JPH0238626B2 - KOKINZOKUGANJUSHOKUBAINYORUSEKITAN * ABURAKONGOBUTSUNOZENSHINRYUBUNKAI - Google Patents

Description

[Detailed description of the invention]

The search for technically possible and economically viable techniques to convert coal into suitable liquid fuels has been ongoing for over 100 years. Recent political and economic developments have driven research in this area. The soaring price of crude oil has triggered and increased research into coal liquefaction and gasification. US Patent No.
As exemplified in No. 3607718, No. 3652446, No. 3870621, and No. 4054504, it has been suggested that liquefied coal can be improved into a useful fuel by fluid catalytic cracking and hydrocracking methods. . Riser cracking of coal liquefaction liquids was suggested in US Pat. No. 4,081,351 and US Pat. No. 4,108,758. Effective riser cracking methods generally involve careful pretreatment of the coal before its introduction into the cracking zone, e.g., by completely dissolving the coal and separating out undesirable components. include. Furthermore, it has been proposed to hydrogenate the carbon upstream of the riser, ie during solubilization. The present invention aims to provide a process in which at least a portion of the hydrogenation of coal can be accomplished within the riser itself, while at the same time making use of catalyst-containing metal deposits that were generally considered harmful in the past. One object of the present invention is to provide a method for cracking coal/oil mixtures that can use a wide variety of coal types. Another object of the present invention is to provide a process for coal/oil cracking that can proceed without or with complete dissolution of the coal before introduction into the progressive flow cracking zone. Yet another object is to provide a method that does not require one or more pretreatments of coal, such as desulfurization, denitrification, deaeration, deashing, etc. Yet another object is a process in which coal can be introduced mixed with a petroleum feedstock for catalytic cracking, the feedstock being suitable or not suitable for complete dissolution of the coal with which it is mixed. The goal is to provide the following. Another objective is to crack the coal/oil mixture in a progressive flow cracking operation in the presence of hydrogen generated in the cracking zone, thereby increasing the yield of liquid products from the coal. It is. Another purpose is to progressively crack the coal/oil mixture by contacting it with a particulate catalyst having substantial cracking activity and substantial dehydrogenation activity. The present invention comprises introducing a feedstock consisting of slurried and/or at least partially dissolved coal and metal-contaminated hydrocarbon residue into a gradual flow catalytic cracking zone, e.g., a riser cracking zone. Become. Therein, the feedstock mixture, in an at least partially vaporized and/or atomized state, is introduced into the cracking zone, providing a linear velocity of at least about 25 feet (7.6 m)/sec. hydrocarbon cracking catalyst formed into a stream or suspension. The present invention uses a cracking catalyst that has a sufficient accumulation of heavy metal deposits of at least about 1500 nickel equivalents. Heavy metal deposition is carried out by contacting the catalyst in the reaction zone with the oil-coal mixture and optionally with the hydrogen donor material under conditions in which hydrogen forms in the stream due to dehydrogenation of the oil and/or the supplied hydrogen donor material. It occurs when The hydrogen generated under the conditions of the progressive flow reaction zone feeds hydrogen into the mixture to promote the production of liquid product from the coal. In the cracking operation of the present invention, mobile hydrogen is formed under a combination of steam conditions. The combination of this steam condition is about 900 to about 1400〓 (about 482 to about
760°C) and a total pressure of about 10 to about 50 psig in the catalytic cracking zone.
Consists of vapor residence times ranging up to 10 seconds. The operating conditions selected are intended to be sufficient to convert the oil in a single pass through the cracking zone to the extent of at least about 50% by volume. Claim 1
``Conversion of at least 50% by volume/pass of said residual oil'' means conversion based on said residual oil (not including slurried and/or at least partially dissolved coal); Percentage of residual oil (not including slurried and/or at least partially dissolved coal) is indicated. This value is one of the operating conditions known to those skilled in the art. The resulting products of coal liquefaction, hydrogenation and cracking, as well as the products of cracking of the fed oil, are separated from the cracking catalyst after traversing the cracking zone. In the practice of this invention, coals of a lower grade than anthracite, e.g. sub-anthracite,
Bituminous coal, subbituminous coal, lignite or lignite, and peat (which is subsumed within the term "coal" as used herein) generally tend to give liquid products in somewhat higher yields than anthracite. Therefore, it is preferable. However, for purposes of the present invention the choice of coal is less critical than in other prior art methods, and the use of anthracite is contemplated as well. Since complete dissolution of the coal is not a critical requirement of the present invention, the coal can be introduced into the progressive flow cracking zone in substantially undissolved, partially solid form or in completely dissolved form. Preferably, the coal-oil mixture is introduced into the reaction zone at least partially in solid form after the initial contact of the coal with the oil feed.
It is introduced within a period of 10 minutes or less, preferably 5 minutes or less, even more preferably 1 minute or less. Generally, when coal is fed to a cracking zone in a form containing substantial ash, and when the ash is recovered from the cracking catalyst by washing, it is desirable that the coal also be ground to a smaller particle size than the fluidized catalyst used in the cracking zone. . For example, a coal particle size of about 200 mesh or less is preferred. The present invention allows treatments of coal such as hydrogenation, denitrification, desulphurization, degassing and deashing to be carried out before the coal is introduced into the riser, and the prior art patents mentioned above (as well as in Although other cited documents detail such processes, it is an advantage of the present invention that the present invention may be practiced without one or more or even all of the foregoing processes. This is considered an advantage. Various hydrocarbon oils, such as crude oil, crude oil fractions, shale oil, etc., as well as certain non-hydrocarbon substances, such as sulfur or its compounds, nitrogen compounds, heavy metal compounds and alkali metal or alkaline earth metal compounds. , but these do not deprive the oils of their essential hydrocarbon properties. Moreover, it should be understood that such oils can be subjected to various pretreatments necessary to reduce the amount of the aforementioned non-hydrocarbon materials present therein. Examples of preferred hydrocarbon oils for practicing the present invention are desalinated crude oil, the 400° ⁺ (204°C ⁺ ) fraction of desalted crude oil, and relatively low residual carbon upon pyrolysis (e.g., less than about 1 It is a common FCC gas oil characterized by a relatively low heavy metal content (low) and relatively low heavy metal content. However, certain benefits are realized by hydrocarbon oils containing metal and Conradson carbon (hereinafter referred to as carbon metal oils) characterized by a pyrolysis residual carbon of at least about 1 and a heavy metal content of at least 4. can do. Such carbon metal oil will be described in detail below. There are a number of non-hydrocarbon components in crude oil that can affect implementation of the FCC Act. Some of these, for example light metals, can be removed economically by desalting operations, which are part of the normal procedure for pretreating crude oil for fluid catalytic cracking. Other materials, such as coke precursors, asphaltenes, etc., tend to decompose during the cracking operation into carbonaceous precipitates, which deposit on the catalyst and
It interferes with contact between the carbon feedstock and the catalyst and generally reduces the level of efficiency or activity of the catalyst. Generally, the coke forming tendency or coke precursor content of an oil can be determined by determining the weight percent of carbon remaining after pyrolyzing a sample of the oil. This value is an industry-accepted measurement of the degree to which a given oil tends to form non-catalyzed coke when used as a feed to a catalytic cracker. Two types of established tests are recognized. They are the Conradson Carbon Test and the Ramsbottom Carbon Test, the former described in ASTM D189-76 and the latter described in ASTM Test No. D524-76. In normal FCC implementation, about 0.05 to about 1.0
A Conradson carbon value of approximately 100% is considered an indication of acceptable feed. Certain embodiments of the present invention relate to the use of hydrocarbon feedstocks that have higher Conradson carbon values and therefore have a substantially greater potential for coke formation than conventional feeds. For the purposes of this invention, the term "heavy metals" means nickel, vanadium, copper and iron, although trace amounts of other heavy metal elements may sometimes be present.
During the cracking process, the heavy metals contained in the feed are transferred almost quantitatively from the feed to the catalyst particles. Although heavy metals initially tend to deposit and aggregate near the surface of the porous catalyst matrix, a significant proportion of these metals migrate to the interior of the catalyst matrix and
There, crystalline decomposition components or other catalyst components carried within the matrix can be precipitated. From the point of view of most operators of FCC units, the buildup of vanadium and other metals, especially nickel, is considered catalyst "poison". They promote dehydrogenation and aromatic condensation to varying degrees, resulting in what has traditionally been generally regarded as excessive production of carbon and gas, thereby degrading the yield of liquid fuel. Topped crudes or crude oil fractions of whole crude oils, such as bottom oils and residues or other oils that are particularly rich in nickel and/or other metals that behave similarly, but contain relatively large amounts of coke precursors. Such oils, referred to herein as carbon metal oils, represent a particular challenge to oil refiners. Since different heavy metals do not have equal catalyst inhibitory activity, it is convenient to express the inhibitory activity of an oil containing a given inhibitory metal in terms of the amount of a single metal that is estimated to have equivalent inhibitory activity. . Thus, the heavy metal content of a certain oil is determined by the following formula (WLNelson, Oil
(patterned from the formula on page 143 of Gas Journal, October, 1961), in which the content of each metal present is based on the weight of the feed, on a weight basis: As metals, expressed in ppm of such metals: Nickel equivalent = Ni + V / 4.8 + Fe / 7.1 + Cu / 1.23 According to conventional FCC practices, the heavy metal content of the feedstock for the FCC method is at a relatively low level, e.g. , limited to approximately 0.25 ppm nickel equivalent or less. The present invention provides a supply containing dehydrogenation-promoting heavy metals in amounts exceeding the above values, which under given operating conditions has a significant potential to inhibit the activity selectivity properties of the catalyst and to accumulate on the catalyst. Concerning processing of raw materials. The above equation can also be used as a measure of heavy metal accumulation on the cracking catalyst, except that the amount of metal used in this equation is based on the weight of the catalyst (moisture-free basis) instead of the weight of the feed. Based on. Traditional
In FCC practice, a recycled amount of catalyst is used many times to treat fresh feed, small amounts of fresh catalyst are added periodically or continuously and spent catalyst is withdrawn, and the metal content of the catalyst is For example, about
Maintain a level that is within the range of 200 to about 600 ppm nickel equivalent. However, the method of the present invention
It relates to the use of catalyst compositions which have a substantially higher content of deactivated metals and therefore have a greater tendency than normal to promote dehydrogenation, aromatic condensation, gas production or coke formation. Such high metal build-up is usually considered highly undesirable in FCC processing. The present invention can be practiced with any hydrocarbon cracking catalyst having the required heavy metal content, and under the conditions described herein, from about 3 to about 18
At a catalyst to oil weight ratio of , progressive flow catalytic cracking can produce a feedstock conversion of at least 50% by volume/pass. Particularly preferred are cracking catalysts conventionally used in fluid catalytic cracking, such as silica-alumina cracking catalysts, which can be used alone or in admixture with other catalysts. However, regardless of whether the feedstock contains carbon-metal oil or not, the most preferred catalysts are crystalline aluminosilicates made from natural or synthetic zeolites, especially through feeder pores and matrices with large minimum diameters. , a zeolite catalyst characterized by a matrix with large openings that promote the diffusion of high molecular weight molecules to the entrance surface area of the molecular sieve molecules within the matrix. Such catalysts will be described in detail below. The heavy metal content of the catalyst will tend to dehydrogenate the components of the feedstock (including feed, product, or both) and/or hydrogen donor substances (other than hydrogen itself) that come into contact with the catalyst as well. be. Examples of hydrogen donor substances are: water in liquid water or steam form (which can be introduced into the reaction zone and/or into the feed upstream of the reaction zone), naphtha, tetralin, decalin and/or Gaseous donors (eg, _C1 - _C5 materials and low molecular weight fractions of crude oil) that contribute non-molecular transferred hydrogen and/or carbon-hydrogen fragments. Additional information about hydrogen donor materials and techniques for using them can be found in the following U.S. patents: U.S. Pat.
No. 3168459 (issued February 2, 1965), No. 3849291
No. 3856659 (issued November 9, 1974)
Issued on December 24, 1975), No. 3886060 (May 27, 1975)
(issued on April 20, 1976), No. 3951781 (issued on April 20, 1976),
Same No. 3974062 (issued August 10, 1976), Same No.
No. 4002557 (issued January 11, 1977), No. 4035285
No. 4090949 (issued on July 12, 1977) and No. 4090949 (issued on May 23, 1978). The relative amounts of coal and oil used in this process can vary widely, making the resulting mixture of coal and oil easy to pump and sufficiently homogeneous to interfere with operation of the cracking unit, at least when preheated. All that is required is that there is enough oil to avoid this. Thus, the oil to coal weight ratio is at least about 1:1, more particularly at least about 3:1, even more particularly at least about 5:1. When the coal is at least partially in solid form as it enters the cracking zone, the oil to coal ratio is preferably at least 7:1, most preferably at least about 9:1. The aforementioned ratios have no particular upper limit, since progressively lower amounts of coal in the oil require progressively less dispersion effort. However, in most cases the oil to coal ratio is approximately
up to 1000:1, more typically up to about 100:1,
Preferably up to about 33:1. As previously mentioned, the present invention can be practiced with a wide variety of oils. Some of these oils have low enough heavy metal content that the cracking unit equipment can be
When operating at catalyst displacement rates typical of FCC operations, it will not accumulate the necessary heavy metals on the catalyst. In such cases, the necessary heavy metals are
It can be fed onto the catalyst by suitable means, for example by pre-impregnation of the catalyst before introduction into the cracking zone or by injection of heavy metal-containing additives into the cracking zone. Although the invention can thus be practiced with a wide variety of oils, catalysts and operating conditions, relatively high nickel equivalent content oils and crystalline zeolite-containing cracking catalysts under selected cracking conditions such as those used in the RCC process are preferred. A combination of these constitutes advantageous conditions for implementing the invention. For example, an oil can be provided that contains at least about 4 ppm of nickel equivalent heavy metals and is characterized by a pyrolysis carbon residue of less than 1.
Such oil should contain at least about 1500
The aforementioned heavy metal content of nickel equivalent can be supplied and maintained. However, it is an advantage of the present invention that this process can be carried out using carbon metal oils having the aforementioned metal levels in combination with a carbon residual greater than 1. Therefore, other preferred embodiments of the carbon metal oil, zeolite decomposition catalyst and RCC decomposition conditions will be detailed. Carbon metal conversion equipment feed is approximately 650〓 (343℃)
Consists of or consists of boiling oil. Such oil, or at least 650〓
+ (343°C +) portion has a heavy metal content of at least 4, preferably greater than about 5, most preferably at least 5.5 weight ppm nickel equivalent and at least about 1% by weight, more preferably at least about 2
Characterized by weight percent carbon residue upon pyrolysis. According to the present invention, a carbon metal feed is contacted in pumpable liquid form with a hot conversion catalyst at a catalyst to feed weight ratio ranging from about 3 to about 18, preferably greater than about 6. . The feed in the mixture undergoes a conversion step, including cracking, during which the mixture of feed and catalyst passes through a progressive flow reactor. The reactor includes an elongated reaction chamber that is at least partially vertical or inclined and in which the feed, the resulting product and the catalyst are maintained in contact with each other while the dilute phase or about 0.5 as current
Flow with a well-determined residence time before the riser in the range of ~10 seconds. Feeds, catalyst and other materials can be introduced into the reaction chamber at one or more points along its length. The reaction is about 900 to about 1400〓 measured at the reaction chamber outlet.
50% under a total pressure of about 10 to about 50 psia (pounds per square inch absolute) at a temperature of (about 482 to about 760 degrees Celsius)
giving a conversion/passage range of more than
0.3 to about 3% by weight, preferably at least about 0.5%
The process is carried out under sufficiently severe conditions to deposit an amount of coke on the catalyst. The overall rate of coke production is based on the new feed:
It ranges from about 4 to about 14% by weight. At the end of a predetermined residence time, the catalyst is separated from the product and then stripped to remove high-boiling entrained hydrocarbon components and other entrained or adsorbed hydrocarbons, and then regenerated. less than about 0.25% by weight of carbon on the catalyst,
Regeneration with an oxygen-containing combustion support gas under sufficient time, temperature, and atmospheric conditions to reduce the oxygen content, preferably to about 0.05% by weight or less. Depending on how the method of the invention is implemented, one or more of the following additional advantages may be realized. Optionally, preferably, the process is performed without prior hydrotreating the feed and/or without using methods to remove asphaltenes, porphyrins and metals from the feed.
and that the carbon metal oil contains a total of greater than about 4, or greater than about 5, or even greater than about 5.5 weight ppm of heavy metals and about 1% by weight.
This is true even when having a pyrolysis residual carbon of greater than about 1.4 weight percent or greater than about 2 weight percent. Moreover, the aforementioned converter feeds can be decomposed within one and the same conversion chamber. The cracking reaction was carried out using a catalyst previously used (recycled, but excluding necessary replacement to compensate for normal losses and deactivation) to crack the carbon-metal oil-containing feed under the conditions described above. Can be implemented. Heavy hydrocarbons that are not cracked into gasoline in the first pass, with or without hydrotreatment, are treated in the same manner as the same type of feed in which they were contained and initially exposed to cracking conditions. It can be recycled for further decomposition upon contact under various conditions. A substantially single-pass or single-pass mode of operation (eg, less than about 15 volume percent recirculation based on the volume of fresh feed) is preferred. The present invention provides a process for the continuous catalytic conversion of a wide variety of carbon metal oils to low molecular weight products, while maximizing the production of highly valuable liquid products, and optionally Distillation and other expensive treatments, such as hydro-processing, can be eliminated. The term "oil" refers not only to primarily hydrocarbon compositions that are liquid at room temperature (i.e., 68°C, 20°C), but also to asphalts or tars at ambient temperature.
It includes primarily hydrocarbon compositions that liquefy when heated to temperatures in the range of up to about 800°C (427°C). The present invention applies to
Applicable to carbon metal oil. For example, as long as they have the necessary boiling range, residual carbon and heavy metal content upon pyrolysis, the present invention is applicable to the treatment of a wide range of materials such as: heavy residues from crude oil, heavy residual oils, Blue crude oil, reduced crude oil
Crude oils known as “heavy crudes” similar in nature to shale oil, tar sands extracts, atmospheric and vacuum extracted crude oils, extracts and/or roughinates from solvent deasphalting, lubricating oils. Aromatic extracts from refining, tar residues, heavy cycle oils, slop oils, other refining waste streams and mixtures thereof. Such a mixture is
For example, the available hydrocarbon fractions, e.g.
It can be prepared by mixing oil, tar, pitch, etc. Although those skilled in the art know how to demetalize carbon metal oils, and demetalized oils can be converted by the present invention, the present invention allows the use of feedstock carbon metal oils that have not been previously demetalized. is one advantage of the present invention. Similarly, although the present invention is applicable to hydrogenated feedstocks, it is an advantage of the present invention that the present invention can effectively convert carbon metal oils that have not undergone substantial prior hydrotreatment. be. However, the preferred application of this method is to use residual oils and extracted crude oils, i.e. parts or fractions of crude oil boiling above 650㎓ (343°C) alone or in vacuum gas oils or FCC.
It is applied to a mixture with column residual oil. Although the use of materials that have undergone vacuum distillation is contemplated, the present invention can satisfactorily process materials that have not been vacuum distilled, thus eliminating the need for conventional FCCs that require vacuum distillation.
One advantage of the present invention is that capital investment and operating costs can be saved compared to conventional methods. According to the invention, at least about 70%, more preferably at least about 85%, even more preferably about
Prepare carbon metal oil whose 100% (volume) boils at about 650㎓ (343℃) or higher. All boiling temperatures herein are based on standard atmospheric pressure conditions.
In carbon-metallic oils that are partially or completely composed of materials that boil at about 650° or higher, such materials are preferably referred to herein as 650° materials;
And the 650〓 ⁺ material that is the part of the oil containing components boiling above and below 650〓 or separated therefrom is called the 650〓 fraction. The terms "boils above" and "650 ⁺ " are not intended, however, to mean that all of the materials characterized by said terms have the ability to boil. The carbon-metal oils contemplated in the present invention may contain substances that do not boil under any conditions, for example, certain asphalts and asphaltenes do not clearly boil during distillation, but can be thermally decomposed. . Thus, for example, when we say that the feed consists of at least 70% by volume of a material that boils above about 650°C, it is understood that the 70% in question may contain some material that does not boil or volatilize at any temperature. Should. These non-boiling substances, when present, have temperatures below about 1000㎓ (538℃)
or may be often or mostly concentrated in the portion of the feed that does not boil above 1025°C (552°C). Thus, at least about 10%, more preferably about 15%, even more preferably at least about
20% (volume) of 650〓 ⁺ distillate is about 1000〓 or 1025
〓When you say that it will not boil at a lower temperature than 1000
It is to be understood that all or a portion of a substance that does not boil at temperatures below 0 or 1025 may or may not volatilize at the indicated temperature or higher. Preferably, the contemplated feed or at least ⁶⁵⁰⁺ material therein has a pyrolysis carbon residue of at least about 2 or more. For example, the Conradson carbon content can range from about 2 to about 12, most often at least about 4. A particularly common range is from about 4 to about 8. Feeds with Conradson carbon content greater than about 6 require special measures to control excess heat within the regenerator. Preferably, the feed has an average composition characterized by an atomic hydrogen to carbon ratio ranging from about 1.2 to about 1.9, preferably from about 1.3 to about 1.8. The carbon metal feed, or ⁶⁵⁰⁺ material therein, used in accordance with the present invention contains at least about 4 ppm nickel equivalents defined above, of which at least about 2 ppm is nickel (as metal, by weight by). Carbon metal oil within the above range is
Can be prepared from a mixture of two or more oils,
Some of them contain nickel equivalents and nickel in the amounts described above, and some do not. The above values for the nickel equivalent and nickel will allow the conversion equipment to operate for a substantial period of time, e.g.
It should be noted that the time-weight average is expressed over one month of operation. It should also be noted that heavy metals, in some environments, have somewhat reduced inhibiting tendencies after repeated oxidation and reduction of catalysts, and the criteria for establishing "effective metal" values are not described in the literature. ing. for example,
Cimbalo.elal., “Deposited Metals Poison
FCC Catalyst”. Oil and Gas Journal ,
See May 15, 1972, pages 112-122. If deemed necessary or desirable, the nickel equivalent and nickel content in the carbon metal oil treated according to the invention can be expressed in terms of "effective metal" values.
Despite the gradual decrease in inhibitory activity described in the above literature, regeneration of the catalyst under normal FCC regeneration conditions significantly reduces the dehydrogenation, demethanization and aromatic condensation activities of heavy metals accumulated on the cracking catalyst. There is no way to reduce it, and it is not within the normal range. From about 0.2% to about 5% by weight of "sulfur" in the form of elemental sulfur and/or its compounds (but reported as elemental sulfur based on the weight of the feed); and modified forms of sulfur enter the resulting gasoline product, and when lead is added,
It is known to tend to reduce lead's ability to increase octane. Sulfur in gasoline products requires modification when processing high sulfur content crude oils. To the extent that sulfur is present in the coke, the regenerator burns the sulfur to produce SO ₂ and
Sulfur potentially contaminates the air since _SO3 . However, in the process of the invention, sulfur in the feed on the other hand suppresses the activity of heavy metals by keeping metals such as Ni, V, Cu and Fe in the reactor in the form of sulfides. That's what we discovered. These sulfides are much less active than the metals themselves in promoting dehydrogenation and coking reactions. Thus, the present invention provides at least about 0.3%, satisfactorily greater than about 0.8%, and more satisfactorily at least 1.5% in the 650〓 ⁺ fraction.
% (by weight) of sulfur is acceptable. The carbon metal oils useful in this invention typically can and do contain significant amounts of heavy, high-boiling nitrogen-containing compounds, a substantial proportion of which are basic nitrogen. For example, the total nitrogen content of the carbon metal oil can be at least about 0.05% by weight. Since cracking catalysts rely on acid sites on the catalyst surface or in the pores for their activity, basic nitrogen-containing compounds can temporarily neutralize these sites and inhibit the catalyst. However, the catalyst is not permanently damaged since the nitrogen can be burned off and removed from the catalyst during regeneration, so that the acidity of the active sites is restored. The carbon metal oil may also contain a significant amount of pentane insoluble materials, such as at least about 0.5% by weight, more typically 2% or more, and even about 4% or more. This may include, for example, asphaltenes and other substances. Alkali metals and alkaline earth metals are
There is generally no tendency for significant evaporation under the distillation conditions used in the distillation of crude oil to prepare vacuum gas oils commonly used as FCC feedstocks. Rather, these metals remain largely in the "residual" fraction (the high-boiling fraction that does not evaporate), which can be used, for example, in the production of asphalt or other by-products. However, reduced oils and other carbon metal oils are often residual oil products and therefore can contain significant amounts of alkali and alkaline earth metals, such as sodium. These metals are deposited on the catalyst during decomposition. Depending on the composition of the catalyst and the magnitude of the regeneration temperature to which it is exposed,
These metals interact and react with the catalyst (including the catalyst support), and they
Under processing conditions not normally experienced when processing VGO. If catalyst properties and regeneration conditions require,
Precautions are of course required to limit the amount of alkali metals and alkaline earth metals in the feed. The metals may enter the feed not only as brine associated with crude oil in its natural state, but also as a component of the water or steam fed to the cracking unit. Thus, careful desalination of the crude oil used in the preparation of the carbon metal feed can be important when the catalyst is particularly sensitive to alkali metals and alkaline earths. In such cases, the content of such metals (hereinafter collectively referred to as "sodium") in the feed may be maintained at about 1 ppm or less, based on the feedstock. Alternatively, the sodium level of the feed may be adjusted to match the sodium level of the catalyst in order to maintain the sodium level of the catalyst being used at substantially the same level or lower than the sodium level of the catalyst replacement fed to the cracker. It must be very important. In accordance with certain preferred embodiments of the invention, the carbon metal oil feed comprises at least about 70% by volume of about
Consists of substances that boil at a temperature higher than 650〓 (343℃) and at least about 10% of substances that boil at a temperature higher than about 650〓 and do not boil at a temperature lower than about 1025〓 (552℃). . The average composition of this 650〓 ⁺ substance is characterized by: (a)
a nickel equivalent, of which at least about 2 ppm is nickel ( (as a metal, by weight), and (d) at least one of the following: (i) at least about 0.3% sulfur;
(ii) at least about 0.05% by weight nitrogen, and (iii) at least about 0.5% by weight pentane-insoluble material. Most commonly, preferred feeds will include all of (i), (ii) and (iii), and other components found in petroleum and non-petroleum source oils will be included as long as they do not interfere with the process. , can also exist in varying amounts. Although there is no intention to preclude the possibility of using feedstocks that have undergone some prior cracking, it is possible to produce liquid hydrocarbon fuels at high conversion and very The present invention has the distinct advantage that it can be successfully prepared in substantial yields. Thus, for example, preferably about 85%, more preferably at least 90%, and most preferably substantially all of the carbon metal feed introduced into the process of the invention is contacted with the cracking catalyst under cracking conditions. This is oil that I had not come into contact with before. Moreover, the method of the invention is suitable for being carried out in a substantially one-pass or single-pass manner. Thus, if recycled, the volume is preferably about 15% or less, more preferably about 10% or less, based on the new feed volume. Generally, the weight ratio of catalyst to fresh feed (feed that has not been previously exposed to the cracking catalyst under cracking conditions) used in the present invention is from about 3 to about 18. This weight ratio is preferably about 4 to about 12, more preferably about 5 to about 10, even more preferably about 6
~10, and a ratio of about 10 is currently considered to be the closest to the optimal value. Within limits of product quality, adjusting the catalyst to oil ratio to relatively low levels within the aforementioned ranges tends to reduce the coke yield of this process based on fresh feed. In conventional VGO FCC processing, the number of barrels per day of plant processing and the total tonnage of catalyst circulated through all stages of the process can vary widely. For purposes of this disclosure, daily plant throughput is defined as a liquid product with a boiling point of about 650°C (343°C) that the plant processes in an average day of operation to have a boiling point below about 430°C (221°C). °C) is defined as the number of barrels of new feed. The present invention can be practiced with catalyst residuals of about 2 to about 30 tons per 1000 barrels of daily plant throughput. In order to maximize the contact between the feed and the fresh catalyst, from about 2 to about 5 per 1000 barrels of daily plant throughput when carried out with carbon metal oil.
It has been suggested that it is desirable to operate with less than a ton or 2 tons of catalyst remaining. However, “Deposited Metals Poison FCC
1 of 1000 barrels at the desired catalyst displacement rate.
Effective metal levels on the catalyst can be reduced by operating at higher residual amounts, for example in the range of about 12 to about 20 tons per day of throughput. In the practice of the invention, catalyst can be added continuously or periodically, for example, to replenish normal losses of catalyst from the system. Moreover, the addition of catalyst can be carried out in conjunction with the withdrawal of catalyst, for example, to maintain or increase the average activity level of the catalyst within the unit device. For example, the rate at which new catalyst is added to the unit is 1
from about 0.1 to about 3 pounds, more preferably from about 0.15 to about 2 pounds, and most preferably from about 0.2 to about 3 pounds per barrel.
Approximately 1.5 pounds range. On the other hand, the FCC
When utilizing off-line equilibrium catalyst, displacement rates as high as about 5 pounds per barrel can be achieved. If the average amount of catalyst used in the unit is less than the deactivation tolerance and/or the conditions prevailing in the unit are such that they promote faster deactivation,
Addition rates greater than those mentioned above can be used, but in the opposite case, smaller addition rates can be used. To illustrate, if the unit is run at a metal content of 5000 ppm Ni+V (parts by weight) on equilibrium catalyst, for example, about 2.7 pounds of introduced catalyst displacement per barrel (42 gallons) of feed throughput. Speed can be used. However, higher levels on the catalyst e.g.
10000 ppm Ni+V can substantially reduce the displacement rate, e.g.
Can be reduced to 1.3 pounds of catalyst. Thus, the level of metal on the catalyst and the rate of displacement of the catalyst can be increased and decreased, respectively, to values that are effective and consistent with the desired activity of the catalyst for carrying out the process. Without wishing to be bound by any theory, a number of features of the methods detailed hereinafter, such as residence time and optional mixing of the steam and feedstock, indicate that the carbon metals and regeneration conditions reduce the amount of heavy metals deposited onto the catalyst particles. It appears that decomposition conditions tend to limit the extent to which metals are produced in reduced form on catalysts from sulfides, sulfates or oxides. thus,
This method appears to significantly suppress the effects of heavy metal inhibition on the catalyst, even when the accumulation of such metals is very substantial. Therefore, this method can convert heavy metals into elemental metals, oxides, sulfides or conventional FCC-VGO.
It can be carried out with catalysts that have accumulated in the form of other compounds that have hitherto been considered highly unacceptable in operations. Thus, on average about
It is contemplated to implement this process using catalysts with heavy metal accumulations in the range of nickel equivalents of 3000 ppm or more. The nickel equivalent concentration of the metal on the catalyst can be up to about 50,000 ppm or more.
More specifically, the accumulation is about 3000 to about 30000 ppm,
Preferably, it can range from about 3,000 to 20,000 ppm, more preferably from about 3,000 to about 12,000 ppm.
Within these ranges just mentioned, practice at metal levels greater than about 4000 ppm, greater than about 5000 ppm, or greater than about 7000 ppm tends to reduce the rate of catalyst displacement required. The ranges are based on and based on regenerated equilibrium catalysts and are based on ppm of nickel equivalent by weight, with metals expressed as metals. However, catalysts of suitable activity are available at very low cost;
If this allowed very high rates of catalyst displacement, catalysts with less than 3000 ppm of nickel equivalents of heavy metals could be used to convert carbon metal oils to low boiling liquid products. for example,
From other units, e.g. FCC units,
Used for cracking feeds, e.g. vacuum gas oil, with residual carbon of less than 1 and about 4 ppm during pyrolysis
Equilibrium lithium catalysts containing fewer nickel equivalents of heavy metal could be used. All inventions described in this specification are
Co-pending U.S. Patent Applications No. 94091, No. 94092, No. 94217, and No. 94217 filed on November 14, 1979
No. 94277, and co-pending U.S. Patent Application No. 246751, No. 246782, and No. 246791, all filed March 23, in the methods and apparatus for converting carbon metal oils. Although the methods described in these applications can handle crude oils or crude oils containing high metal values and Conradson carbon values that cannot be subjected to prior direct processing, certain crude oils, e.g.
Mexican Mayan or Venezuelan and certain other types of oil feeds contain unusually high heavy metal values and Conradson carbon values. When these very low grade oils are processed by carbon-metal processes, they are It can make operation uneconomical. Very poor low grade oils, for example oils containing more than 50 ppm heavy metals and/or more than 8% by weight Conradson carbon value, preferably more than 100 ppm heavy metals and/or more than 10% by weight Conradson carbon value. For improvement, these oils can be pretreated with sorbents to reduce the levels of these contaminants to the aforementioned low levels. Such a method of upgrading is described in US Pat. No. 4,263,128, dated April 21, 1981. In any case, the average concentration of heavy metals in the circulating catalyst can be adjusted (maintained or varied as necessary) by adjusting the aforementioned catalyst addition rate. Thus, for example, the addition of catalyst can be maintained at a rate that adjusts the accumulation of heavy metals on the catalyst to one of the aforementioned ranges. generally has a relatively high level of degradative activity;
It is preferred to use catalysts that provide relatively high conversion levels and productivity with short residence times. The conversion capacity of a catalyst can be expressed by the conversion produced during the actual implementation of the process and/or by the conversion produced in standard catalyst activity tests. For example, it is possible to use a catalyst that is sufficiently active to maintain a level of conversion of at least about 50%, more preferably at least about 60%, when run over an extended period of time under the prevailing process conditions. preferable. In this context, conversion is expressed in % by volume of liquid, based on fresh feed. Also, for example, preferred catalysts have a specific activity expressed as a percentage in their fresh or equilibrium state by MAT (Micro Activity Test) conversion. For the purposes of the invention, said percentages are volume % of a standard feedstock, which is
The evaluation catalyst was calculated and weighed at 900〓 (482℃), 16WHSV (weight hourly space velocity, 1100〓 (593℃),
using the conditioned, clean catalyst for at least 8 hours at about 25° C. and 50% relative humidity until no more than about 1 hour before contact with the feed;
(calculated on a moisture-free basis) and 3C/O (catalyst to oil weight ratio) according to ASTM D-32MAT test D-3907-80, using a suitable standard feed, e.g. the following analytical values and properties: 430° (221°C) end point gasoline, lighter products and coke using a corrosive-free (Sweet) light primary gas oil used by Davison, Division of WRGrace. Will convert: API gravity, 60〓 (15.6℃), degrees 31.0 Specific gravity, 60〓 (15.6℃), g/cc 0.8708 Ramsbottom carbon, wt% 0.09 Conradson carbon, wt% 0.04 carbon, wt% 84.92 hydrogen, Weight % 12.94 Sulfur, weight % 0.68 Nitrogen, ppm 305 Viscosity, 100〓 (37.8°C), centistokes 10.36 Watson K factor 11.93 Aniline point 182 Bromine number 2.2 Paraffin, volume % 31.7 Olefin, volume % 1.6 Naphthene, volume % 44.0 Aroma Group, volume % 22.7 Average molecular weight % 284 Nickel Trace vanadium 〃 Iron 〃 Sodium 〃 Chloride 〃 BS&W 〃 Distillation ASTM D-1160 IBP 445 10% 601 30% 664 50% 701 70% 734 90% 787 FBP 83 4 above MAT Conversion Test Description and ASTM D-
In the 32MAT test D-3907-80, the conversion rate was
430〓 (221°C) end point gasoline, lighter products and volume percentage of feedstock converted to coke. For standard supplies, light primary gas oils or equivalents as described above may be used. For the purpose of determining relative activity, a “standard catalyst”
2 is a chart or graph of conversion (as defined above) versus round trip WHSV for a standard catalyst and feedstock. A sufficient number of experiments were conducted using a standard feedstock at varying levels of WHSV under ASTM D-3907-80 conditions (modified as above) to determine the Create an accurate “curve” of conversion versus WHSV. This curve should encompass all or substantially all of the various levels of conversion, including the range of conversions one would expect to test the catalyst used. From this curve, a standard value of round trip WHSV corresponding to a level of conversion selected to represent 100% relative activity in the standard WHSV and standard catalyst for test comparison can be established. For purposes of this disclosure, the aforementioned round trip WHSV and conversion are 0.0625 and 75%, respectively. When testing a used catalyst of unknown relative activity, conduct a sufficient number of experiments using the catalyst under D-3907-80 conditions (modified as above) to determine which catalyst is used. Standard round trip using
Establish the level of conversion that is or will be produced in the WHSV. Then, using the standard catalyst curve described above, calculate the required round trip WHSV
A hypothetical round trip WHSV consisting of a WHSV is established using a standard catalyst to obtain the same level of conversion that the catalyst used exhibits or would exhibit in a standard WHSV. The relative activity is then 1/16 or
A virtual round trip with a standard WHSV of a round trip that is 0.0625
It can be calculated by dividing WHSV. The result is a relative activity expressed as a decimal, which can then be converted to a percentage relative activity by multiplying by 100. When applying the results of this measurement,
A relative activity of 0.5 or 50% indicates that it is necessary to use twice the amount to obtain the same conversion as the standard catalyst, i.e. the manufactured catalyst is 50% of the activity of the reference catalyst. means. The catalyst can be introduced into the process in its virgin form or, as previously indicated, in a form other than virgin. For example, equilibrium catalysts drawn from other units, eg catalysts used for cracking different feeds, can be used. Preferred catalysts, whether characterized on the basis of MAT conversion activity or relative activity, are
It can be described on the basis of activity, or on the basis of "as drawn" or equilibrium activity in the method of the invention, or on the basis of both of these criteria. Preferred activity levels of fresh and non-fresh catalysts "as introduced" into the process of the invention are at least about 60% by MAT conversion, and preferably at least about 20%, more preferably at least about 20% relative activity. is at least about 40%, even more preferably at least about 60
%. However, lower activity levels may be tolerated, especially in the case of unused catalyst fed at high addition rates. The "as drawn" or equilibrium acceptable activity level of the catalyst used in the process of the present invention is at least 20% or more, but about 40% or more, preferably about 60% or more on a relative activity basis. A preferred value and activity levels of 60% or higher based on MAT conversion are also contemplated. More preferably, it is desirable to use a catalyst that establishes equilibrium activity at or above the indicated level under the conditions used in the unit device. The activity of the catalyst is carried out using a catalyst with less than 0.01 coke, for example a regenerated catalyst. Any hydrocarbon catalyst having the conversion capabilities indicated above can be used. A particular class of catalysts are those with a pore structure that allows molecules of the feed material to enter for adsorption and/or for contact with active catalyst sites within or adjacent to the pores. Various types of catalysts falling within this category are available, such as layered silicates, such as smethites. The most widely available catalysts within this class are the well-known zeolite-containing catalysts, although non-zeolite catalysts are also contemplated. Examples of preferred zeolite-containing catalysts are natural, semi-synthetic or synthetic zeolites, either alone or in admixture with other substances, which do not significantly reduce the appropriate properties of the catalyst. However, the resulting catalyst must have the aforementioned activity and pore structure. For example, when the virgin catalyst is a mixture, it can include a zeolite component associated with or dispersed within a porous refractory inorganic oxide support, in which case the catalyst is e.g. From about 1 to about 60% by weight, more preferably from about 15 to about 60% by weight, based on total weight (water-free basis)
It contains 50% by weight zeolite, most typically from about 20% to about 45% by weight, with the balance of the catalyst being a catalyst that promotes various desired reactions or inhibits undesirable reactions, alone or with the porous refractory inorganic oxide. in combination with known auxiliary substances that inhibit A general description of the genus of zeolite, molecular sieve catalysts useful in the present invention is found in the following document: “Refinery Catalysts Are a Fluid
Business” and “Making Cat Crachers”
Work On Varied Diet”, respectively, July 1978
Chemical published on September 26, 1978 and September 13, 1978
Featured in Week magazine. For the most part, the zeolite component of the zeolite-containing catalyst will be one known to be useful in FCC cracking processes. In general, these are crystalline aluminosilicates, typically composed of four-coordinated aluminum atoms associated with adjacent silicon atoms in the crystal structure via oxygen atoms. However, the term "zeolite" as used in this disclosure refers not only to aluminum silicates, but also to materials in which aluminum is partially or fully substituted with, for example, gallium and/or other metal atoms, and Furthermore, substances in which all or part of the silicon is replaced by, for example, germanium are included. Substitution of titanium and zirconium can also be carried out. Since most zeolites are manufactured or naturally occurring in the sodium form, sodium cations are associated with electronegative sites in the crystal structure. Sodium cations tend to render zeolites inert and very poorly stable under hydrocarbon conversion conditions, especially when exposed to high temperatures. Thus, when the zeolite can be ion-exchanged, and the zeolite is a component of the catalyst composition, such ion exchange can be performed before or after adding the zeolite to the catalyst composition. Examples of cations suitable for replacing sodium in the zeolite crystal structure are ammonium (which can be decomposed to hydrogen), hydrogen, rare earth metals,
These include alkaline earth metals. Various ion exchange methods and exchangeable cations into zeolite crystal structures are well known in the art. Examples of naturally occurring zeolites that can be used or included as catalysts in the present invention are hawkiasite, mordenite, clinoptilote, chiabazite, analcite, kryonite, as well as levinite, gucciardite,
paulingite, nocellite, ferriolite, heulandite, scorcite, stivite, halmotome, philipsite, breustellite, fullerite, datolite, gumerite,
They are caumnite, leucite, lazurite, scaprite, mesolite, putolite, nephrin, matolite, offretite and sodalite. Examples of synthetic crystalline aluminosilicate zeolites useful as or included as catalysts in the practice of this invention are: Zeolite X, U.S. Pat. No. 2,882,244;
Zeolite Y, U.S. Pat. No. 3,130,007; and Zeolite A, U.S. Pat. No. 2,882,243; and Zeolite B, U.S. Pat. No. 3,008,803; Zeolite D, Canadian Patent No. 661,981; Zeolite E, Canadian Patent No. 614,495; Zeolite F, US Patent No. 2996358; Zeolite H, US Patent No. 3010789
Zeolite J, US Patent No. 3011869; Zeolite L, Belgian Patent No. 575177; Zeolite M, US Patent No. 2995423; Zeolite O, US Patent No. 3140252; Zeolite Q, US Patent No.
No. 2991151; Zeolite S, US Patent No. 3054657
Zeolite T, US Patent No. 2950952; Zeolite W, US Patent No. 3012853; Zeolite Z,
Canadian Patent No. 614495; and Zeolite Omega, Canadian Patent No. 817915. Also, ZK−4HJ,
Alpha beta and ZSM-type zeolites are useful. Moreover, U.S. Patent No. 3,140,249;
Also useful are the zeolites described in No. 3140253, No. 3944482, and No. 4137151. Crystalline aluminosilicate zeolites with a faujasite-type crystal structure are particularly suitable for use in the present invention. This includes in particular natural faujasite and zeolite X and zeolite Y. Crystalline aluminosilicate zeolites, such as synthetic phasiasite, will crystallize under normal conditions as discrete particles of size from about 1 to about 10 microns in an ordered pattern. Therefore, this is the range of sizes often found in commercial catalysts that can be used in the present invention. Preferably, the size of the particles of this zeolite is about
It ranges from 0.1 to about 10 microns, more preferably from about 0.1 to about 2 microns or less. for example,
Zeolite produced in situ from calcined kaolin is characterized by smaller microcrystals. Crystalline zeolites exhibit both internal and external surface areas, with the external surface being defined as the "inlet" surface area. The majority of the total surface area is the internal surface area. By inlet surface area we refer to the external surface of the zeolite crystal, through which the reactants are considered to pass in order to be converted to low-boiling products. For example, blockage of internal channels by coke formation, blocking of internal channel inlets by deposition of coke in the inlet surface area, and contamination by metal toxicity greatly reduce the total zeolite surface area. Therefore, in order to minimize the effects of contamination and pore clogging, crystals larger than the normal sizes cited above are preferably not used in the catalyst of the present invention. Commercial zeolite-containing catalysts are available as carriers containing a wide variety of metal oxides and combinations thereof, such as silica, alumina, magnesia and mixtures thereof and such oxides as described in, for example, U.S. Pat. No. 3,034,948. including mixtures with clays such as For example, any zeolite-containing molecular sieve fluid cracking catalyst suitable for vacuum gas oil to gasoline products may be selected. However, careful selection of catalysts with notable resistance to metals may certainly be advantageous. Metal-resistant zeolite catalysts are, for example, as described in U.S. Pat. No. 3,944,482, where the catalyst contains 1-40% by weight of rare earth-exchanged zeolite, the balance being a refractory metal with a particular pore volume and size distribution. It is an oxide. "metal-
Other catalysts described as "acceptable" are described in the editorial by Cimbala, et al., supra. Generally, from about 5 to about 160, more preferably from about 40 to
A catalyst having an overall particle size in the range of about 120, most preferably about 40 to about 80 microns may be used. For example, useful catalysts have a skeletal density of about 150 pounds per cubic foot, and about 60 to about 70
May have an average particle size of microns, with no more than 10% of particles having a size smaller than about 40 microns, and about
Less than 80% of the particles are smaller than 50-60 microns in size. A wide range of other catalysts can be used in the practice of this invention, including zeolite-containing and zeolite-free catalysts. The following table is a useful example on a commercial scale that may be implemented with the present invention.

[Table] AGZ-290, GRZ-1, CCZ-220 and
and Super DX catalysts are products of WR Grace and Co.
Yes, F-87 and FOC-90 are Filtrol products.
Yes, while HFZ-20 and HEZ-55
It is a product of Engelhard/Houdry. the above
is the property of the virgin catalyst, and the zeolite content
With the exception of waterless standards, i.e. 1750〓
Based on a substance that ignites. Zeolite content
“Determination of the Faujasite Content
of a Catalyst”
The proposed ASTM standard method entitled
Catalyst according to draft #6 dated January 9, 1978
From sample and high purity sodium Y zeolite.
It is derived from the comparison of the X-ray intensity of standard samples.
Ru. Among the commercially useful catalysts mentioned above, Super
D class and especially the catalyst called GRZ-1
preferable. For example, Super DX is an Arabian light
Particularly good with tocrude (Arabian light crude)
The result is out. GRZ-1 is now better than Super DX.
Also substantially more expensive, but somewhat more metal-acceptable
Show your gender. Although not utilized on a commercial scale, the present invention
The best catalyst for implementing
The matrix is passed through the surface area of the entrance of the Lasieve particles.
to facilitate the diffusion of high molecular weight molecules.
feeder with a minimum diameter and a large mouth
Characterized by a matrix with pores.
Such a matrix is a carbon-metal oil-fed, non-evaporated
A relatively large pore volume is used to immerse the eruption area.
It is also preferable to have one. In this way, liquid hydrocarbon content
A significant number of children of the matrix and
Activates catalytic sites both within the sieve particles on the surface
can be spread to become Generally, 0.2cc/gm
It is better to use a catalyst with a larger total pore volume.
stomach. Preferably at least 0.4cc/gm, more preferably
preferably at least 0.6cc/gm and most preferably
The range is 0.7-1.0cc/gm. matrix
said total pore volume is at least 0.1 cc/gm, preferably
or at least 0.2 cc/gm, about 400 to about 6000 ohms.
range of ngstrom units, preferably approx.
1000 – approximately 6000 angstrom unit range
It consists of feeder pores with a diameter. these catalysts
And the manufacturing method for this is “Large Pore
Catalysts for Heavy Hydrocarbon
Filed on April 10, 1981 entitled “Conversion”
Jointly filed international application No. PCT/US81/00492
(Ashland oil O, Inc, et al).
It is. Catalysts for carrying out the invention include:
“Immobilization of Vanadia Deposited on
Catalytic Materials During Carbo―Metallio
Filed on March 19, 1981 entitled “oil Conversion”
PCT International Application No. PCT/US81/00356
Banerjee listed in (Ashland oil, Inc, et al)
Using other metal additives to control the opposite effect of
may be used. These other metal additives
This method is believed to interact with
is stated in the said PCT international application, and the entire
The disclosure of the same is incorporated herein by reference. child
Some of the additive metal compounds disclosed in the PCT applications of
In particular, titanium and zirconium are also
Immobilizes Kel, iron and copper. titanium and
and zirconium immobilizes nickel, iron and copper
The mechanism for this is that of aluminum and silicon.
i.e. oxide coating and/or spinel coating
It is believed that this is similar to the formation of
If this additive is introduced directly into the conversion process,
i.e. riser, regenerator tube or intermediate configuration
When introduced into the element, this additive provides hydrocarbon
Oil supply or hydrocarbon solvents that are miscible with the supply oil.
Titanium or zirconium dissolved in medium
Preferably, it is an organic-metallic compound. this
Preferred organo-metallic compounds of these metals include
Tetraisopropyltanate, Ti(C ₃ H ₇ O) _Four , Du
Used by Pont Company as TYZOR
Zirconium isopropoxide, Zr
(C ₃ H ₇ O) _Four and zirconium 2,4-pentane
Geonate-Zr(C _Five H ₇ O ₂ ) _Four It is. these organic
Metal is just one example of the wide variety of types available.
and other alcoholates, esters, and phenols.
Naphthenates, carboxylates, diene
Contains Rusanderutsch compounds and others. other
Preferred additives include titanium tetrachloride.
zirconium tetrachloride and zirconium
nium acetate and the water-soluble nature of these metals.
Machine salts, their sulphates, nitrates and chlorides
is relatively inexpensive. Atomic weights of nickel and vanadium and zirco
The atomic weight of titanium is different, while that of titanium is different.
They are the same, with an atomic ratio of 1:1, and nickel and banana.
Weight of titanium plus dium
ratio, approximately equal to 1.0, and vanadium is added to nickel.
Weight ratio of zirconium to that obtained, approximately 2.0
be equivalent to. The number of parts with an atomic ratio of 1:1 is the weight ratio
Requires the same multiple. For example, an atomic ratio of 2:1
is a titanium weight ratio of approximately 2.0 and a zirco weight ratio of approximately 4.0.
weight ratio. Non-selective catalytic activity of heavy metals deposited on conversion catalysts
Riser and regenerate additives to immobilize
Introduced into pipes or other conversion system components
good. Preferred additives for carrying out the invention are
“Passivating Heavy Hetals In Carbo―
William P. titled “Metallic Oic Conversion”.
Concurrently filed herein in the name of Hetlinger, Jr.
Contains additives disclosed in the US application. Said U.S.
The entire disclosure of the application is incorporated herein by reference. William P. Hetzingarge, et al.
Filed on April 10, 1981 under the name "Carbon-Gold
Capture of metals deposited on catalyst materials during metal oil conversion
Disclosed in U.S. Patent Application No. 252,967
Particularly preferred catalysts also include vanadium, as shown in
Contains trap. William Pea Hetz
April 20, 1981 under the name of Chingaji Uniyar etc.
Application, entitled ``Precipitation in Catalyst Materials During Carbon-Metal Oil Conversion.''
“Immobilization of Accumulated Vanadium”
Application for permission, filed on April 28, 1981
As also disclosed in the continuation-in-part of the same application of
Determining the valence state of vanadium accumulation on the live catalyst
Preferably controlled. United States of America above
All patent application disclosures are hereby incorporated by reference.
It has been incorporated. The method of the present invention is characterized in that tin and/or antimony is
qualitatively absent, or at least substantially
of catalysts lacking either or both of these metals in
It is considered an advantage that it can be carried out in the presence of
Ru. Although charging of additional substances is not allowed, the reaction
as substantially the only material charged to the zone.
Even with the carbon-metal oil and catalyst described above, the present invention
The method can be operated. Charging recirculated oil to the reaction zone
has already been mentioned. As described in more detail below.
However, other materials that perform different functions may also be included in the charge.
can. In such cases, carbon-metal oil and catalyst
is usually the majority of the weight of the total material charged to the reaction zone.
equivalent to minutes. Some additional substances that can be used are carbon-metal
Significant benefits such as those achieved with oil and catalyst alone
It functions to add benefits to the process. Among these features
control the effects of heavy metals and other catalyst contaminants;
control; enhancement of catalytic activity;
absorption of excess heat in media; disposal of contaminants or
From products that are more easily disposed of and/or
Transfer of one or more forms of waste that can be separated
oxidation; control of catalyst temperature; diluting carbon-metal oil vapor
to lower these partial pressures and increase the yield of the desired product.
Addition: Adjustment of raw material/catalyst contact time; Hydrogen-deficient coal
Hydrogenation of base metal oil raw materials, e.g.
Filed on March 23, 1981 in the name of Dehmeyer, marked
Titled “Use of Naphtha in Carbon-Metal Oil Conversion”
As disclosed in Co-pending Patent Application No. 246791
This application is hereby incorporated by reference.
promotes dispersion of supply; and perhaps
There is also distillation of the product. Heavy metal accumulation on the catalyst
Some of the metals are derived from these metals.
If in the form of elementary metals, they are
In its oxidized form, formed on contact with oxygen.
more active in promoting undesirable reactions.
It is. However, in the past conventional catalytic cracking
In this case, the contact time between the catalyst, raw material, and product vapor is
was sufficient, so it was released in the decomposition reaction.
hydrogen reconverts a significant portion of the less harmful oxides.
can be converted back to more harmful elemental heavy metals.
came. gaseous (including vapor) in the reaction zone.
Adding additional substances to the mixture of catalyst, feedstock and product vapors
Take advantage of this situation by introducing
Can be done. In the reaction zone, such additions
The increased capacity of matter brought about by the presence of quality
product tends to increase the velocity of flow through the reaction zone
There is a reaction and the resulting oxidized heavy
Reduces metal residence time. At this reduced residence time
oxidized heavy metals are reduced to elemental form due to
Elemental metals that are less likely and therefore harmful
The low amount of water helps in contact between raw material and product. Substances added may be added to the process in any suitable manner.
Some examples are as follows.
For example, before the feedstock comes into contact with the catalyst, these substances
can be mixed with carbon-metal oil feedstocks. Instead,
If desired, the added substance is the catalyst that is the raw material.
Can be mixed with catalyst before contacting oil. added
The separated parts of the substance are both the catalyst and the carbon-metal oil.
may be mixed separately. In addition, feedstock oil, catalyst
and the added substances, if desired,
They may be collected qualitatively simultaneously. The additional parts are
as mentioned above, insofar as they are introduced into the mixture as a result.
In either method, the substance added
Partly mixed with catalyst and/or carbon-metal oil
good. For example, some of the substances to be added to the reaction zone
carbon-to-metal oil and/or catalyst before reaching
may be added to, while other substances of the added substance may be added to
The portion is introduced directly into the reaction zone. things added
quality in many open spaces in the reaction zone or even
If it is long and narrow, introduce it along the length of the reaction zone.
stomach. Supply oil, catalyst or the above functions and others
The amount of additive that may be present in the reaction zone in which the
can be made into the desired amount. But the amount
is preferably in an amount that is sufficient for the practical heat balance of the method.
Delicious. These substances can e.g.
It is introduced at a ratio of up to about 0.4. Preferably,
A range of about 0.02 to about 0.4 is good, more preferably
Approximately 0.03 to approximately 0.3 is good and most preferable is approximately 0.05 to
It is approximately 0.25. For example, many of the desirable features listed above.
or all about 0.04 or more relative to the feed oil,
or more preferably from about 0.05 to about 0.1 or more,
in the form of steam or liquid water or a combination thereof in the ratio of
H in combination ₂ By introducing O into the reaction zone
It can be achieved. Don't be bound by any theory
H without desire ₂ When using O catalytic burden oxide,
Reduces sulfites and sulfides to free metals
tend to prevent it from happening. And it ends
resulting in coke and hydrogen yields and associated products.
Enrichment with accelerated loss of - promoting dehydrogenation
It is believed. More H ₂ O is also touched to some extent.
Reduces metal deposition on media surfaces. nitrogen
catalytic particles and other heavy contaminant-containing molecules
have a tendency to desorb from the surface of the
Both catalysts tend to prevent their absorption.
be. Added H ₂ O forms Brønsted acid
This tends to increase the acidity of the catalyst, which in turn tends to increase the acidity of the catalyst.
It is believed to increase the activity of the catalyst. Supplement
supplied H ₂ O is the regenerated catalyst and/or reaction zone
Assuming that the reaction zone is colder than the temperature of
The temperature of the water decreases due to contact with catalysts located elsewhere.
The heat felt as it rises absorbs excess heat from the catalyst.
It can be accommodated. This H ₂ If O is dissolved in it for example
Approximately 500-5000ppm H ₂ With recirculated water containing S
If present or included, there are many additional benefits.
A point occurs. Ecologically unattractive H ₂ S is in the atmosphere
There is no need to vent to the H ₂ S
H without requiring further processing to remove ₂ S is for heavy metal
Aids in reducing catalyst coking by immobilization
In other words, heavy metals are converted to sulfides and
free gas and hydrogen products tend to increase.
smaller than metal. In the reaction zone, H ₂ Existence of O
The present can dilute the carbon metal oil vapor, and this
of the desired products so as to reduce their partial pressure
It tends to increase yield. H ₂ O with other substances
The combination is beneficial in generating hydrogen during decomposition.
It turns out that there is. In this way, insufficient hydrogen
Carbon as hydrogen donor for metal oil feedstock
It is possible to work. This H ₂ O is like
It also serves a purely mechanical function. (1) Atomization or dispersion of feed oil; (2) Adsorption of high molecular weight molecules on the surface of the catalyst.
(3) Steaming the evaporable products from the non-evaporable feed material, thus preventing coke formation.
vapor distill. (4) releasing products from the catalyst as a result of the decomposition reaction;
Ru, H ₂ Refining O, catalyst and carbon metal oil
It is particularly preferable to introduce them simultaneously. For example,
H during fog nozzle ₂ Mix the supply oil with O and add it to the reaction zone.
Spray the catalyst and the resultant at the downstream end of the zone.
I can touch it. Regarding adding a flow to the reaction zone, the fluid
Often mentioned in the catalytic cracking literature. reaction
supply oil compared to introducing the flow directly into the zone.
Adding liquid water to the water is relatively and occasionally discussed.
It will be done. However, according to the present invention, liquid water is
Approximately when or before introducing oil into the reaction zone.
Mix intimately with carbon metal oil at a weight ratio of 0.04 to about 0.25.
It is particularly preferable that By this, water (parable)
In the form of liquid water or in contact with oil, liquid water evaporates.
(in the form of vapor) enters the reaction zone.
It enters the reaction zone as part of the oil stream. whatever
I don't want to be bound by theory, but the above
It is advantageous to promote the dispersion of the supplied oil
It is believed that Also, the heat of evaporation of water is
absorbed from the solvent, feed oil, or both.
If water is a more effective cooling radiator than steam alone
It's tight. Preferably liquid water to feed oil
The weight ratio of about 0.04 to about 0.2, more preferably about
0.05-about 0.15 is good. Of course, liquid water can be prepared using the above method or other methods.
can be introduced into the process by
The introduction of water adds additional water as steam to the same reaction zone.
or by introducing it into different parts or by touching it.
by introducing it into the fluid and/or feed oil.
accompanied by For example, the additional amount of steam is added to the feed oil.
On the other hand, if the weight ratio is between about 0.01 and about 0.25,
If the total H for the supplied oil ₂ O (vapor and liquid
The weight ratio (as water) may be less than about 0.3. liquid water
When using this combination of and steam,
The weight ratio imposed on liquid water to vapor is e.g.
The preferred range is from about 15 to about 0.2. this
such a ratio is maintained at a predetermined level within such a range.
or to maintain or regulate heat balance.
change as desired or needed.
can be done. reaction zone to perform one or more of the functions listed above;
Other substances may be added to the area. For example, reaction zone
Dehydrogenation of heavy metals by introducing hydrogen sulfide gas into
- Can block concentration activity. Heavy naphtha in the reaction zone
Ordinary hydrogen donating diluents such as e.g.
Itoparaffins, low molecular weight alcohols and molecules
Other compounds that allow or prefer hydrogen transfer between
and carbon monoxide and water or alcohol.
of or with olefin or other things
such as reactions with qualities or with mixtures of the former.
Chemically combines in the reaction zone to generate hydrogen
Relatively low molecular weight carbon-hydrocarbon fragments, including compounds
By introducing contributors, hydrogen becomes hydrogen insufficient
Available for carbon metal oil supply oil. All additional substances mentioned above (including water)
alone or in combination with each other or nitrogen or
Combination with other substances such as inert gases, light hydrocarbons, etc.
achieves some of the functionality mentioned above and
Because of their ability to reduce the supply partial pressure without limitation
as a diluent and/or from the regeneration process.
Absorbs excess heat present in that catalyst as received
Suitable as a heat sink for storage. The above mentioned
Catalyst and carbon metal oil introduced into the reaction zone
Some of the functions performed by substances other than raw materials
This is a discussion. and departing from the spirit of the invention.
Other substances can be added without and other functions can be performed.
You should understand that. The invention can be implemented in a wide variety of devices.
However, the preferred device is
Rapidly vaporizes the feedstock and catalyst
mix efficiently (although order is unnecessary)
The resulting mixture is then diluted into suspension in the forward flow.
For liquid flow and predetermined residence time
Decomposed products and undegraded or parts at the end of
for separating the catalyst from the decomposed feed
Contains means. All or a little of the product
at least a substantial amount from at least a portion of the catalyst
Preferably, the separation should be abrupt. For example, the device may run along its long reaction chamber.
one or more catalyst inlets;
one or more additional substance inlets, one or more
Product outlet and one or more catalysts
It may have an outlet. for introducing catalysts, feeds and other materials
The means is to remove complex jets or spouts from open pipes.
range of nozzles and finely distributes its liquid feed.
Use any means that can produce a clear dispersion.
is preferred. Preferably the catalyst, liquid water (use
) and fresh supplies as of December 14, 1978.
The device described in U.S. Patent Application No. 969,601 issued by
It is brought together with similar equipment. Stephen
It is understood that it came from Mr. M. Kovacs.
According to a particularly preferred embodiment based on the suggestion that
that liquid water and carbon before its introduction into the riser
For metal oil, use a propeller, opening plate, or suitable high-shear agitation.
The oil and/or oil present as a continuous phase passes through the means.
or a small amount of fine oil and/or water with water.
Form a homogeneous mixture containing drops. The reaction chamber, or at least a large part of it, is horizontal
Also close to vertical and at least about 10 length to diameter
It is preferable to have a ratio. The ratio is about 20-25.
It is preferable that vertical riser type reactor
It is preferable to use If it is tube-shaped,
The reactor is of uniform diameter throughout and
continuously along its flow path or directly from step to step.
The diameter can be increased. Generally, a packing means for catalyst and feed and
Its reactor geometry allows for relatively high velocity flow and catalyst
is made to yield a dilute suspension of. for example
The steam or catalyst velocity in the riser is usually low.
both about 25 and typically more than about 35 feet/second
be. This speed is approximately 55 feet per second, or approximately 75 feet per second.
up to 100 feet/second or about 100 feet/second or so.
It can change to more than that. Steaming at the top of the reactor
The air velocity may be higher than the flow velocity at the bottom of it.
and about 80 feet/second at the top, for example.
At the bottom, it is about 40 feet/second. the reactor
The speed capability of the riser is generally
sufficient to prevent catalyst build-up during the
and thereby the upstream (bottom) of that riser.
) and downstream (top) of the catalyst in its riser.
The load is less than 4 or 5 pounds per cubic foot, e.g.
if kept below 0.5, 2 or 0.8 lb/ft.
held. The progressive flow type is e.g. catalyst, feed,
and product streams. The flow is long and long
The adjusted and maintained orientation of the reactor
Ru. However, this is not a strictly linear flow.
does not imply that it must be done. Are known
As such, turbulence and slippage of the catalyst will affect the vapor velocity and
and to some extent especially in certain ranges of certain catalyst loadings.
but it causes slip and back mixing
Using a catalyst load low enough to limit
was reported. If the reactor is one or more along the riser
The decomposition products vaporized from the catalyst at more than
rapidly separate a substantial portion or all of the
vaporized from the catalyst at the downstream end of the riser.
virtually all of the decomposition products can be separated.
Both are preferable. The preferred type of reactor is that
includes ballistic separation of catalyst and products, i.e.
established by catalytic riser movement
General as launched and established in the direction
Happens to continue its movement in the direction. On the other hand
Products with less movement create abrupt changes in direction
This occurs due to rapid and substantial loss of product from the catalyst.
resulting in immediate separation. ventilation lie
In a preferred embodiment referred to as the
The riser tube is virtually protected downstream of it.
There are no openings to remove the catalyst. at its downstream end
An outlet near the adjacent tube outlet discharges the product.
Accept. The outlet is connected to the catalyst flow path.
The passageways are equipped with regular strippers and strippers.
connected to the catalytic converter, while the outlet is essentially its catalyst passage.
product that is completely or substantially separated from
It is connected to the road. Its product passage is relatively small
connected to a means of separating the product from the catalyst of
ing. Optionally obtain an inlet to its product outlet
Manage for. The best way to carry out the invention
The catalyst/product separation embodiment is shown in FIG. It communicates with the inside of the cup, but inside the riser tube.
product vapor conduits that do not communicate with the
Located inside the cup upstream of the riser pipe outlet
emitted from the riser pipe by
Product vapor that changes direction and enters the cup is
to separate the catalyst and product downstream of the cup.
carried away by auxiliary equipment for use. Such an arrangement
When placed in the vented riser pipe outlet.
Highly complete separation of catalyst from product vapor in
and, as a result, an aid for catalyst separation.
equipment such as cyclones, which require a large capacity.
resulting in lower capital investment and operational costs.
It is possible to save a large amount of industrial costs. Preferred conditions for carrying out the method are listed below.
vinegar. These conditions include feedstock, catalyst and
Reaction temperature, reaction and feed pressure, residence time
and conversion levels, coke formation and catalysts
There is coke adhesion to the top. In conventional FCC operation using VGO,
The feedstock is customarily preheated and the pumping of the feedstock is
In order to make it possible to transport and introduce into the reactor,
For the purpose of improving the fluidity of raw materials to a certain extent
Preheat to a temperature much higher than required
There are many cases where it happens. For example, about 700〓(371
℃) or high preheating temperature of 800〓(427℃)
has also been reported. However, the main project currently being carried out
In this method, preheating of the feedstock is limited.
It is preferable. Thereby the feedstock is transferred from the catalyst
This is because it can absorb a large amount of heat. thus the catalyst
raises the feedstock to the conversion temperature and simultaneously adds the feedstock.
Minimum amount of external fuel used for heating
It can be suppressed. Therefore, it is possible due to the nature of the feedstock oil.
If so, it can be supplied at ambient temperature. Relatively heavy raw material
temperatures up to about 600°C (316°C), typically about
Serve at a preheat temperature of 200〓 (93℃) to 500〓 (260℃).
I can provide. However, if a higher preheating temperature is used,
That doesn't mean you shouldn't. The temperature of the catalyst fed to the reactor varies over a wide range
can. For example, about 1100〓 (593℃) to about 1600〓
(871℃), more preferably about 1200〓(649℃)~
1500〓(816℃), most preferably about 1300〓(704℃)
℃) to approximately 1400〓(760℃)
It can be adopted, but currently it is about 1325〓 (718℃)
~1375〓 (746℃) is considered to be the optimum temperature.
It will be done. As shown earlier, low molecular weight products of carbon metal oil
The conversion to is approximately 900 °C at the temperature measured at the outlet of the reaction chamber.
〓(482℃)～1400〓(760℃)
I can do it. The reaction temperature measured at the outlet is
More preferably about 965〓 (518℃) to about 1300〓
(704℃), more preferably about 975〓
(524℃) to approximately 1200〓(649℃), and further
Most preferably about 980〓((527℃)~about 1150〓
(621℃). selected temperature and
depending on the nature of the feedstock and feedstock.
When it is okay to vaporize the feedstock and when all of the feedstock is vaporized
There are cases in which you should not do so. As indicated above, the reactor pressure ranges from about 10 to about
Variations in the range of 50 psia are acceptable but preferred
The range and more preferred range are each about 15
~about 35 psia and about 20 to about 35 psia. generally supplied
The partial pressure (or total pressure) of the raw material is about 3 to about 30, or more.
Preferably from about 7 to about 25, and most preferably
Values can range from about 10 to about 17 psia.
The partial pressure of the feedstock is such that the gaseous (vaporous)
(including) substances such as water vapor, water and other substances mentioned above.
Control or suppression by introducing additives
can do. The method includes, for example, a riser
fraction of the feedstock relative to the total pressure in the
pressure, about 0.2 to 0.8, more typically about 0.3 to about 0.7,
and further typically ranges from about 0.4 to about 0.6.
It is operated as a fence. However, within the riser
added gaseous material relative to the total pressure at
quality (this includes recirculating gas and/or riser
-H in the form of water vapor ₂ This was created as a result of introducing O.
Contains water vapor and/or liquid water. )
The ratio of, corresponding to each case above, is approximately
0.8 to about 0.2, more typically about 0.7 to about 0.3, even
It is typically about 0.6 to about 0.4. Example above
For the operations indicated, the fraction of added gaseous substances
The ratio of pressure to feedstock partial pressure is about 0.25 to about 4.0, and
typically about 0.4 to about 2.3;
was within the range of about 0.7 to about 1.7. Feedstock and product vapor in the riser
The residence time of is, as mentioned above, about 0.5 to about 10
may be in the range of seconds, but preferred and even more preferred.
The preferred times are about 0.5 to about 6 seconds and
It is about 1 to about 4 seconds, and currently about 1.5 to about 3.0 seconds.
Seconds are considered to be almost optimal. For example,
The method is to raise large amounts of gaseous substances.
By introducing within the riser steam residence time
It operates in about 2.5 seconds or less. That value is
For example, added gaseous substances vs. hydrocarbon feedstock
The partial pressure ratio of approximately 0.8 or more is allowed. difference
To better illustrate, the residence time is approximately 2 seconds.
and the ratio is within the range of about 1 to about 2.
The method has been implemented. Low feedstock content
products from pressure, very short residence times and catalysts
The combination of conditions such as ballistic separation of carbon metal oil
It is considered to be particularly advantageous for the conversion of added
Gaseous substances, especially the H ₂ The effective partial pressure of O is
Sometimes, in the above combination, additional benefits
may be obtained. In the riser, the catalyst and hydrocarbon vapor
Catalytic riser stagnation depends on whether there is slippage between
In some cases, the residence time can be made equal to the residence time of steam.
There are cases where it is not possible. Therefore, the average catalytic reactor stagnation
The ratio of residence time to steam reactor residence time, i.e.
is about 1 to about 5, more preferably about 1 to about 4,
Most preferably within the range of about 1 to about 3
can. Currently, we believe that approximately 1 to 2 is optimal.
It will be done. In actual operation, a small amount of slippage, e.g.
There should normally be a slip of at least about 1.05 to 1.2.
Dew. When the unit is in operation, e.g.
The slippage is about 1.1 at the bottom of the iser and about 1.05 at the top.
can occur. For certain types of known FCC units,
The catalyst and product vapors are usually kept in one part of the reactor.
Riser is sent into a large room that is thought to be the
in which the catalyst is separated from the products.
Can be collected. Catalysts in such large chambers, undisclosed
The decomposition feed materials (if any) and decomposition products are
Continuous contact in a large room like the one shown below generally causes
The contact time between catalyst and feed material is
It clearly exceeds the retention time. Meyer mentioned above
As taught in the patent of Myer et al.
Catalyst at the downstream (e.g., upper) tip of the riser
The method of the invention by ballistic separation of the vapor and
Implement. Riser residence time and catalyst contact time
is for most of the feed and product vapors above.
will be virtually the same. Steam riser residence time and
total feed through the riser and steam catalyst contact time
at least about 80% by volume of material and product vapors,
preferably at least about 90% by volume and at least
Preferably about 95% by volume are substantially the same.
It is considered to be advantageous if touch like that
Avoid continuous contact with steam catalyst in medium removal recovery chamber
This reduces the tendency towards re-degradation and reduced selectivity.
It can be stopped. In general, the catalyst to oil ratio, temperature, pressure and stagnation
Residence time is the effective
They must be combined in such a way that a transformation can be achieved.
stomach. A very high level of conversion is achieved in a single pass.
It is an advantage of the method of the present invention that parable
In some cases, the conversion rate ranges from 50% to about 90% or more. Conversion
level from about 60 to about 90%, more preferably from about 70 to about
Maintain each of the above conditions at a level sufficient to maintain the
It is preferable to hold it. Is the above conversion level 100%?
Liquid capacity of new feed material from 221℃ (430〓)
(tbp. standard atmospheric pressure) or higher boiling point production
Percentage obtained by dividing the volume of the object by 100 times
Calculated by subtracting . These substantial level transformations have resulted in relatively large
yield, e.g. from about 4 to about 14
% by weight, more commonly about 6% to about 13%, but most commonly
About 10% to about 13% coke is produced. This
The particles are deposited more or less quantitatively on the catalyst.
Coal obtained at expected catalyst to petroleum ratio
The carbonaceous deposits are added to the weight of the regenerated catalyst without moisture.
Generally greater than about 0.3% by weight, more commonly about
More than 0.5% by weight, very often more than about 1%
ing. Such coke deposition is approximately 2% or
Or it can be as high as about 3% or more.
be. Similar to traditional FCC operations for VGO,
This invention provides for use after removal of catalyst from product vapors.
It consists of stripping the finished catalyst. A person skilled in the art is appropriate
stripping agent and used catalyst.
Although the conditions for pinging are well known, there are some
In this case, the method of the present invention is somewhat more
Requires strict conditions. This is for example a reaction
Contains components that do not volatilize under favorable conditions in the container.
This is achieved through the use of carbon metal oil. the ingredient
is at least partially deposited on the catalyst. like that
Adsorbed unevaporated materials can be evaluated from at least two perspectives.
It's a tough thing. First, remove the catalyst
Gases (including steam) used for
It can be put into the catalyst removal and recovery chamber connected to the end of the flow.
Preferably, and the accumulation of catalyst in such a chamber
If available, remove these unevaporated hydrocarbon strippers.
evaporation in the chamber followed by adsorption onto the catalyst bed in the chamber.
can be done. More specifically, stripper
The catalyst within the adsorbed feedstock is removed from the adsorbed feedstock.
As time passes, the resulting feed vapor is used for catalyst recovery and
and/or through a bed of catalyst accumulated in the removal chamber.
to remove coke and/or concentrated material.
Deposit onto the catalyst in the bed. such deposition
The catalyst supporting the substance is removed from the above catalyst bed by a stripper.
from there to the regenerator, concentrating
The product has greater stripping capacity.
while coke requires regeneration temperature
tend to increase and require greater regeneration capacity.
There is a direction. For the above reasons, the catalyst removal or recovery chamber is
Contact between stripping vapor and catalyst build-up
This can be done by preventing or limiting. parable
essentially falling out of circulation and being removed and/or
or large amounts that may remain at the bottom of the collection chamber.
Prevention by eliminating the catalyst. circulating catalyst
As soon as it is deposited at the bottom of the chamber, it is immediately removed from the chamber.
removed. In addition, the regeneration temperature and regeneration capacity requirements
In order to minimize the
Volatile hydrocarbon materials produced by removed catalyst
Effective for less than approximately 10% by weight of the total carbon loaded on the catalyst.
of sufficient time, temperature and atmosphere to reduce
It is preferable to use conditions. such a strip
Tupping can be caused by, for example, reheating the catalyst or using steam.
For long-time stripping and FCC/VGO operations.
gas at a temperature higher than that considered normal for
Flue gas and hydro from regenerators, e.g.
Rieter off gas (H ₂ S containing), other products such as hydrogen
Consists of the use of oil plant gas. For example about 150 psig
Use pressure steam and a steam-to-catalyst weight ratio of approx.
Stripper at a temperature of about 350〓 at 0.002~0.003
Can be operated. On the other hand, strippers are about 1025〓 or more.
Can be operated at temperatures of According to the present invention, carbon metal oil can be charged into light products.
With fractionalization, significantly higher coke yields and catalyst
tends to cause coke deposits on the catalyst
Requires some care when playing. Zeolite and non
To maintain appropriate activity of zeolite catalyst
is caused by the accumulation of large amounts of heavy metals on the catalyst.
However, the weight percent of carbon remaining on the catalyst is approximately 0.25%.
% or less for a sufficient time, temperature, and atmosphere.
It is desirable to regenerate the catalyst under ambient conditions. child
The weight percent is approximately 0.1 especially for zeolite catalysts.
% or less, more preferably about 0.05% or less.
Ru. Therefore, when processing carbon metal oil, contact
The amount of coke that must be burnt off from the medium is
The amount is much larger than when disassembling VGO normally.
In the present invention, "coke" refers to residual unevaporated coke.
is understood to encompass feed materials or decomposition products.
If it exists, the string
Present on the catalyst after topping. For example, by adding a combustion modifier to the decomposition catalyst, it can be regenerated.
Carbon dioxide and/or monoacid in coke in vessel
It is possible to lower the combustion temperature for carbon dioxide.
Ru. Additionally, heat exchange means, e.g.
installed heat exchanger (e.g. steam coil)
heat can be removed from the catalyst during regeneration by
I can do it. Heat exchanger transfers catalyst from regenerator to reactor
Is it possible to install the regenerated catalyst in the catalyst transfer path to be transferred?
heat can be removed from the to the catalyst in the regenerator
The amount of heat given increases the amount of insulation of the regenerator to the surrounding atmosphere.
by somewhat tolerably reducing the heat loss of
In particular, the amount of raw material used to make coke is limited.
Once supplied; generally heat loss to the atmosphere is
It is preferable from an economic point of view compared to the other methods mentioned above.
It is thought that there is no such thing. Also, in the regenerator, dense
floors, e.g. water and/or steam
By injecting cooling fluid into the area, the regenerator
an inert gas used for heat absorption and removal in
can increase the amount of Feedstock fed via recycled regenerated catalyst
other suitable for controlling or limiting the heat transferred to
The preferred technology is that the CO2 formed in the regenerator
Maintains a specific ratio between carbon and carbon monoxide
However, the gas is not in heat exchange contact with the catalyst during regeneration.
or be brought into some kind of relationship. general
is the weight of coke present in the catalyst just before regeneration.
All or most of the above ratios are controlled as described below.
removed in at least one controlled combustion zone.
It will be done. More specifically, the coke on the catalyst
at least a major amount, preferably at least about 65%, and
preferably at least about 80% by weight CO ₂ /CO's
a level where the molar ratio is substantially less than 5, e.g. less than about 4;
is removed in the combustion zone, which is maintained at a constant temperature. Reverse
CO from the point of view ₂ /CO When looking at the relationship, CO ₂ /CO
The molar ratio is at least about 0.25, and more preferably
at least about 0.3 and more preferably about 1 or more
should be greater than or equal to 1.5. A person skilled in the art should know that CO ₂ technology to prevent combustion of
Although I am familiar with it, CO:CO ₂ The molar ratio of carbon-
Catalyzed by heavy metal deposits produced from the processing of metallic oils
should be kept below 0.2 when playing
It has been taught (e.g., Zrinscak et al.
(see U.S. Pat. No. 4,162,213). However, this invention
in which the catalyst contains less than about 0.1% C, more preferably about
During regeneration below 0.05% C, CO production increases.
Further, in accordance with a preferred method of carrying out this invention
Therefore, the regeneration sub-process as a whole is carried out under oxygen-deficient conditions.
Reduce the level of carbon on the regenerated catalyst to the low levels described above.
carried out up to the bell; more specifically, there is one
The total oxygen supplied to the regeneration process is
All the hydrogen in the ₂ Burns into O and coke
CO ₂ chemical amount required to burn to
It can be and is preferably less than the stoichiometric amount. If,
If the coke contains other combustible materials,
The stated stoichiometry is the amount required to burn them.
can be adjusted to contain a suitable amount of oxygen. The recycler applied to the feedstock via the recycled catalyst
Other preferred techniques for controlling or limiting raw heat include circulating
A portion of the heat generated by the ring-shaped catalyst is transferred to the reactor.
Additives introduced into the system, e.g. water, steam, naph
other hydrogen donors, flue gas, inert gases and
and other gaseous or volatile substances that may be introduced into the reactor.
quality. The amount of coke burned from a given amount of catalyst
The higher the temperature, the more the catalyst is exposed to excessive temperatures.
more likely to occur. Many useful cracking catalysts are
It is easily deactivated at high temperatures, and among these, it is expensive.
molecular sieve or zeolite type catalyst.
Zeolite crystals, which are often similar to
The structure and pore structure of the catalyst are typically
or susceptible to hydrothermal denaturation. carbon-metal feedstock
The use of such catalysts in catalytic conversion processes is extremely
Destroys catalyst even when exposed to severe temperatures and steam
It is necessary to create a regeneration technology that does not Like this
The need is to transport the spent catalyst to the first regeneration zone.
and the process of introducing oxidizing gas therein.
can be satisfied by multi-step regeneration methods including
Ru. The amount of oxidizing gas introduced into this first region
The concentration of oxygen and oxygen introduced therein is
The desired conversion of coke to carbon dioxide gas on the medium
In other words, it is sufficient if it is even partially effective. Next, the department
The partially regenerated catalyst is removed from the first regeneration zone.
and transferred to the second playback area. Oxidizing gas is the
Introduced into the second regeneration area, higher concentration than the first area
Oxygen or oxygen-containing gas is supplied to the desired carbon
remove it to the level that Then it was played
Catalyst is removed from the second zone and recycled to the reactor.
is recycled and contacted with fresh feedstock. multiple like this
An example of the process regeneration method is included for reference in the present invention.
George D. Myers, et al., 1978, 12
Described in U.S. Patent Application No. 969602 filed on April 14th
has been done. Other examples can be found in U.S. Patent 2938739
Ru. Burns off coke deposited on catalyst during feedstock conversion
Regeneration of the catalyst by
Approximately 1000 to 1600〓 when measured at the mouth.
It can be carried out at any suitable temperature. This temperature is approximately
It is preferably within the range of 1200 to about 1500〓.
More preferably, it is about 1275 to about 1425〓, which is optimal.
It is about 1325〓 to about 1375〓. For example, this person
The method ranges from about 1300 to about 1400〓 depending on the fluid regenerator.
It was carried out at the temperature of the catalytic dense phase. One or more flows in one or more flow chambers
It is preferable to perform regeneration while maintaining the catalyst in the bed.
Delicious. For example, such fluidized bed operation
For example, a floor density of about 25 to about 50 pounds per cubic foot.
characterized by one or more fluidized dense beds of boiling particles with
do. The flow is based on the gas flow, including the combustion sustaining gas.
Maintain by passing. Gas moves particles into a fluid state
velocity is sufficient to keep the particles in
at a speed sufficient to prevent gas entrainment.
I am sent to the hospital. For example, the linear velocity of the fluidizing gas is
from about 0.2 to about 4 feet/second, preferably from about 0.2 to about 4 feet/second
Within 0.3 feet/second. One or more of the particles
The average total time spent on the floor above is approximately 5
to about 0, more preferably 5 to about 20, even more preferably
Usually about 5 to about 10 minutes. From the above description, the book
The fluidized bed regeneration method of the invention is implemented with the FCC operation method.
A short-contact, low-density entrainment regeneration method and easily distinguishable
We can separate. For example, approximately 0.1
% or less, or about 0.05% or less
Regenerates the catalyst to an extremely low level of carbon content
If the gas produced by combustion contains excessive amounts of oxygen,
at least the last of the coke in contact with the
about 10% or at least about the last 5% before playing
Incinerate (based on the total weight of coke on the catalyst)
can be done. In this case, the last 5% by weight
or the entire range of coke reduced to 10% by weight.
A particular coke portion selected from the
It is thought that it can be combusted with oxygen.
“Excess amount of oxygen” means all the hydrogen in water, all the
Carbon to carbon dioxide and coke just before regeneration
may be present in the selected portion of. Other
Its most stable oxidation under regeneration conditions for all combustible materials
in excess of the stoichiometric amount required to combust to
It means surplus. in the presence of excess amounts of oxygen
The gaseous products of the combustion that take place are usually
contains an amount of free oxygen. This kind of play
Oxygenation is supplemented by means or methods other than regeneration.
removed from raw gas or in other forms
If you do not convert it to
Appears as free oxygen in flue gases. excessive amount
Necessary for complete combustion of coke by oxygen
In order to obtain sufficient power, the amount of free oxygen must be
Usually, it is not just something that can be detected, but something that is significant.
It is. That is, from the entire completed regeneration operation
The concentration of free oxygen in the total regenerated flue gas recovered is
The amount is such that it is at least about 2 mole percent. child
Techniques such as
Although it is effective in increasing the level of
The boundaries and difficulties will become clear from the following explanation. Generated by the combustion of coke in the regenerator
The generated heat is absorbed by the catalyst and then regenerated.
The heat remains until the material is brought into contact with new material.
It can be easily retained by medium. Carbometallic
The relatively high conversion level of oils included in the present invention
When processing up to
The regenerator heat amount transferred to the raw material is
Heat the other materials, vaporize them, and
Provides endothermic heat for the packing reaction and
Thermal equipment required in the riser to compensate for heat losses
The level of input can be greatly increased.
For example, with the present invention, new raw materials can be transferred
The regenerator heat capacity may be adjusted within an appropriate specified range if necessary.
Can be clause or limited. The amount of heat transferred in this way
For example, about 500 to about 1 pound of new raw material.
1200, preferably about 600 to about 900, more preferably
is in the range of about 650 to about 850 BTU. said fever
The quantity range is the combined heat (in units of new raw materials)
BTU per pound). this union
The generated heat is used for reactions (e.g. cracking).
heat and enthalpy between the product and the new raw material
Feedstock and reaction by catalyst to supply the difference
The product is produced from the catalyst after the feedstock comes into contact with the catalyst.
This is communicated until the product is separated. the above
Heat causes coke to be adsorbed on the catalyst surface.
The heat thus made available in the reactor,
and extinguished by heating, vaporization, or reaction circulation.
expended heat, water, steam naphtha and other
such as hydrogen donors, flue gas and inert gases.
heat or radiation consumed by such additives.
and other losses. The amount of reaction heat transferred to the new raw material by the catalyst
one of the above techniques for the regulation or restriction of
or a combination of these may be used in the present invention.
Ru. Multi-stage regeneration is CO:CO ₂ along with control of the molar ratio of
Provides the possibility of regenerating bonded oxygen vacancies. Hidden
te, CO:CO ₂ The molar ratio of
regeneration during one or more stages of regeneration
About 50% by weight or less of coke on the catalyst just before
or more, more preferably about 65 to about 95% by weight, and
more preferably about 80 to about 95% by weight.
I can do it. The previously existing coke
The last 5% or more by weight of or 10% by weight of
Pre-stage or
All coke remaining after multiple stages is removed.
The next regeneration until a larger amount of oxygen is present
Can be removed in stages. This kind of method
All flue gas collected when the full regeneration operation is completed.
contains little or no excess oxygen.
No, i.e. 2 mol% as proposed elsewhere.
substantially less than about 0.2 mol% or less;
or a small amount of about 0.1 mol% or less
allows operation in such a way that it contains
do. Thus, multi-stage regeneration depends on the regenerated catalyst.
to limit the regeneration heat transferred to the feedstock oil and
and/or heat deactivation potential and at the same time
The carbon level on the regenerated catalyst specifically determines the catalytic activity.
A very low percentage of improvement (e.g. less than about 0.1%)
Another convenience that gives the opportunity to lower the
It is particularly useful in providing a good method for example
For example, in the two-stage recycling method, approximately 80% of the coke is removed in the first stage.
CO/CO by burning at a bed temperature of about 1300〓 ₂ and
CO and CO in 1 molar ratio ₂ The second step is to generate
About 20% of the coke is burned at a bed temperature of about 1350〓.
and CO mixed with free oxygen ₂ virtually all generated
You can do as you like. on the first stage floor
Combustion support gas with additional air introduced
and using the gas from the second stage, CO vs.
C.O. ₂ The overall ratio of these two is approximately 0.6, and the
The total residence time of the catalyst in the zone is approximately 5-15 minutes.
becomes. Additionally, the regeneration conditions, e.g. temperature or atmosphere.
The atmosphere is substantially more severe in the second zone than in the first zone.
(e.g. at least about 10〓, preferably
(up to at least about 20〓), the most severe conditions
That part of the regeneration sequence that includes
This is done as long as a certain amount of coke is present.
Such operations expose the catalyst to more severe conditions.
Protect to the extent possible. Particularly preferred embodiments of the invention
is the dense phase of the second stage compared to the dense phase of the first stage.
In the phase, reduce the temperature by at least about 10 or 20
Thus, the carbon on the catalyst is also reduced in the second zone to about
0.05% by weight or less, or about 0.025%
Or even lower it to a maximum of about 1500〓.
It is a two-stage fluidization regeneration carried out at high temperatures.
In fact, catalysts can be used even if the amount of carbon on them is
According to this method, even if the amount is as large as about 1%,
Easily regenerated to levels as low as 0.01%
Can be done. In most cases, adsorbed oxygen-containing gas is
ensure that they are not carried to the riser by
This is very important. Thus, such an effect
Refurbishment whenever deemed necessary.
The catalyst discharged from the plant removes oxygen-containing gases.
Stripping with suitable stripping gas
You can tsping. Streets like this
For example, stripping gas or gas
Steam, nitrogen gas or other inert gas
Using gas at a relatively high temperature, for example about 1350° to about
It can be carried out at a temperature of 1370㎓. Nitrogen gas or
When using steam, the use of other inert gases
In this case, the tendency of catalyst deactivation due to hot water derived from
Useful from an avoidance perspective. Next on metal management, carbon management and thermal management
The findings and considerations are the most important when implementing the present invention.
It will help you get good results. these
Opinions are mostly on what is considered the best driving mode
Since the present invention is directed to
is not limited to the particular driving mode being studied.
It should be obvious. Furthermore, those with these opinions
Since it is necessarily based on theoretical considerations,
Regarding the operation mentioned here or below.
whether such a theory is included in the proposal of
There is no chance that it will be linked to this. Although each will be considered separately below, metal pipes
carbon management and thermal management in both theory and practice.
interrelated and interdependent issues
One thing will become immediately clear. coke
The formation of carbon and its deposition on the catalyst are mainly observed in carbon-metallic oil.
The presence of relatively large amounts of coke precursors
As a result, coke formation is caused by a high accumulation of metals.
and high accumulation of this metal.
It also has a considerable effect on catalyst performance. moreover,
The degree of success experienced in metals and carbon management
thermal management has a direct impact on the degree of thermal management required.
vinegar. Furthermore, it is also
Some of the steps that can be taken include carbon management and thermal management.
proved to be of great help. As mentioned above, large amounts of heavy metals accumulate on the catalyst.
When present, it is responsible for dehydrogenation and aromatic compounds.
This tends to cause condensation problems as well.
For feedstock oil with a certain fixed Ramsbottom coal residue value
increases gas and coke production. water vapor
or H in the form of either liquid water ₂ o substantial
Introducing heavy metals into the reactor in small amounts is less harmful.
form, i.e. oxide form rather than metal form.
This is extremely advantageous from the standpoint of storage. this is
Assists in maintaining the desired selectivity. In addition, catalyst regeneration can be performed by selecting system components and residence time.
The residence time of the catalytic reactor relative to the residence time of the
The design of the equipment to reduce the ratio is such that the catalyst
of time under sub- and oxidative conditions, respectively.
There is a tendency to lower the ratio. This also desired selectivity
This can help maintain the level of Is the metal content of the catalyst well controlled?
The sum of hydrogen and methane produced in the reactor is
and/or the ratio of hydrogen to methane thus produced.
can be observed by monitoring.
Generally, the molar ratio of hydrogen to methane is less than about 1, preferably
or should be about 0.6 or less.
possible, and about 0.4 or less is about the best.
considered suitable. in actual implementation
The hydrogen to methane ratio ranges from about 0.5 to about 1.5, on average
can range from about 0.8 to about 1. Selectivity by carefully controlling carbon
(functionality that maximizes production of effective products) and
Both thermal productivity can be improved. general
In addition, the metal control technology described above also applies to carbon control.
Helpful. Utility of water addition in relation to carbon control
is a specification describing the additives introduced into the reaction zone.
That part of the specification has already been explained in considerable detail.
did. Generally, the distribution of the feed into the reaction zone
Techniques to improve supply are also effective, e.g.
Spraying or misting equipment that helps disperse materials
Includes use. Catalyst to oil ratio is also a factor in thermal control.
be. Prior art fluid catalytic cracking for VGO
Similar to the (FCC) method, for riser type reactors,
drop in reactor temperature, typically outlet temperature
and rising hot regenerated catalyst to the reactor.
by increasing or decreasing the flow of
In the practice of this invention, the temperature of the reactor is controlled.
You can control it. Excess catalyst to oil ratio
Automatic control of catalyst introduction is set to maintain
If the new feed was added to the reaction zone,
Production of carbon that is unnecessarily large in proportion to the weight of the object
Predictable speed and heat release. The relatively high reaction temperature also has implications for carbon control.
preferred. Such higher temperatures are supplied
More complete vaporization and separation of product from catalyst
Facilitate. Appropriately limiting the reactor total pressure and feed partial pressure
It also makes carbon control easier.
can be done. Generally, for a given level of conversion
, with a relatively small decrease in said pressure.
Coke formation can be substantially reduced. this thing
reduces the high boiling point of the feed by limiting the total pressure
Enhances vaporization of components, promotes decomposition, and reduces unconverted feed
and high-boiling decomposition products from the catalyst.
This is thought to be due to the fact that it tends to make it easier to
available. It is downstream of reactor equipment and reaction
Helps limit pressure drop in connection with vessel
It can be. However, for example, operating limits (e.g.
For example, due to pressure drop in downstream equipment),
Is it desirable to operate the reaction system at a higher total pressure?
or, if necessary, limit the partial pressure of the feed.
By doing so, the above advantages can be obtained.
Wear. Appropriate range of reactor total pressure and feed partial pressure
As mentioned above, in general, these ranges
It is desirable to minimize the pressure within. Product gas and unconverted feed (if any)
Rapid separation of the catalyst from the
be. For this reason, ballistic separation equipment
is the preferred type to carry out this process
This is the device. For the same reason, the catalyst is removed from the product gas.
The elapsed time between separation and the start of stripping is
It is advantageous to reduce it as much as possible. Katsupu
Type vented riser and rapid stripping
reducing the chance of coking of unconverted feed.
and reduce high-boiling decomposition products adsorbed on the catalyst.
There is a tendency to Particularly desirable aspects of operation from the perspective of carbon control
is a bend-type lamp with hydrogen donation if necessary.
The first step is to operate this process in a thermal chamber. same
At times, feed partial pressures and total reactor pressures should be kept as low as possible.
Keep low water, steam and as needed.
Other diluents are added in relatively large amounts. to do so
A very large number of the advantages mentioned above in great detail by
is obtained. In addition, liquid water, hydrogen donors, hydrogen
and other gaseous or vaporizable substances
When fed to the reaction zone, these materials
Gives you the opportunity to exercise additional control over oil ratios.
I can do it. Thus, for example, at the reactor temperature
catalyst vs. oil for a given value of fall or rise.
To increase or decrease the ratio, use water, steam and
and other gaseous or vaporizable substances.
Appropriately reduce or increase the feeding ratio to the area, or
Alternatively, the water vs. steam and
and/or other gaseous substances.
By substituting either less or more
Can be transformed or eliminated. Heat control releases in various parts of the process
measures taken or released to control the amount of heat produced.
Means of successfully handling such heat that may be emitted
including. Sufficient while regenerating the reactor heat balance
Using VGO, which usually has problems generating high heat,
Unlike the traditional FCC method, which uses carbon metal oil
(carbo-metallic oils) should be treated with careful control.
Generally generates large amounts of heat that requires
Ru. Thermal control is related to the substances introduced into the reactor,
This can be easily done by various techniques. write
The heat absorption by the feed is due to the preheating of the feed.
can be maximized by minimizing
Ru. It can be pumped well in reactors.
and ensure that the supply is sufficiently liquid to allow dispersion.
It is only necessary that the feed temperature be high enough.
Ru. coke so that higher conversion is achieved
Highly active state with suppression of (metallic control)
When holding the catalyst at
Higher conversion and greater selectivity reduce the heat absorption of the reaction.
Revenue can be increased. Generally high coke
High boiling point components that are very difficult to suppress and have the potential for oxidation.
Regardless of the
Facilitate. The rate of catalyst deactivation thus increases, but
Higher operating temperatures offset this loss in activity
There is a tendency to The higher temperature in the reactor is
It also contributes to an increase in octane number, thus increasing the
Offsets the octane-suppressing effects of primary deposition. heat absorption
Other techniques of collection also include adding water, steam,
and other gaseous or vaporizable substances.
As mentioned above in connection with the introduction of This invention also allows for “single unit RCC”
Named Dwight F. Barger U.S. Patent Application No.
Crude oil and crude oil distillate described in No. 06/263397
Applicable to RCC conversion of minutes. The entire content of the patent application
The content is included here for reference. Which of the above oils is useful in the present invention - whether it is charcoal or
Coal containing - whether or not it is a base oil/
Oil mixtures contain relatively large amounts of accumulated or deposited heavy
Metals (including their reduced states) and hydrogen donors
PCT Application No. 81/00662 containing a catalyst with a given substance
It can be decomposed by the technique described in . This PCT
The application was filed by Assurand Oil Inc.
Ted (Ashland Oil Inc.), Oliver J.
Zandona (Oliver J.Zandona), George Dei
George D. Myers, William
William P.
Hettingcr. Jr.) and Steven M. Kovacs
Co-authored with the invention under the name of Steven M. Kovach.
The application was filed in
shall be included herein. This PCT application
for cracking coal/oil mixtures according to the invention
Favorable conditions are disclosed. As noted above, the present invention provides a method and a method described above.
It can be carried out by another method. descriptive, non-restrictive
A preferred embodiment is shown in the attached schematic diagram in FIG.
This will be explained by the explanation of the figure shown below. To explain FIG. 1 in detail, the cold storage container 10
Stored pulverized coal (e.g. 100-200 meth)
) is passed through the pipe 16 at a predetermined speed by the metering device 14.
The mixture is then supplied to the mixer 22. Atmospheric distillation residual oil
The eel hydrocarbon oil is introduced through the inlet pipe 12.
Ru. The velocity introduced into mixer 22 through tube 20
The degree of
A desired oil-to-coal ratio can also be provided.
In the case of the present invention, the range is from about 9:1 to about 1000:1.
It is surrounded. The coal is completely melted in the mixer 14.
However, in the embodiment of the present invention, the
At least some of the coal is solid and suspended in oil.
Mix and drain quickly. coal and
The oil mixture is then passed through pipe 24 to pump 26
The mixture is then passed through tube 28 to a control valve.
30. control valve is open
The coal/oil mixture is flowed into the feed pipe 82 while
vinegar. The above coal/oil mixture is fed along feed pipe 82.
The water is sent to the joint with the water supply pipe that has the control valve 83.
Ru. suitable metering and control means (not shown))
through liquid water and 650〓+carbon metal oil.
It can be supplied to the pump 79 at a predetermined ratio. This pon
The water and converter feed mixture
, a control valve 80, a heat exchanger for preheating the feed material
81 and the riser through an extension of the supply pipe 82.
-type reactor 91. During operation of the riser type reactor 91, the catalyst is
It is sent to the reactor through a medium pipe 86. catalyst
The flow rate is controlled by the control valve 87 and the riser type clamp.
To those skilled in the art of designing and operating king equipment.
is a known suitable automatic control device (not shown)
Adjusted by. Decomposition and desorption of feed material in riser 91
After separation of product and catalyst in chamber 92, the catalyst is
removed from the desorption chamber 92 by the tripper 94.
Ru. The spent catalyst is removed by a slider to control the flow rate.
a spent catalyst transport pipe 97 with a valve 98;
Then, it is sent from the stripper 94 to the regenerator 101.
It will be done. The regenerator 101 is located between the top and bottom of the regeneration chamber.
A dividing panel 104 separates the upper chamber 102 and the lower chamber.
It is divided into a chamber 103. Transport pipe 97?
These spent catalysts are supplied to the upper chamber 102, where they are
partially played. Partially regenerated catalyst
is a funnel-shaped collection with a diagonally cut upper edge.
The dense catalyst phase in the upper chamber 102
is collected from the upper surface of the
High density in the lower chamber 103 through one falling leg 107
sent below the surface of the catalyst phase. Internal catalyst falling leg 10
Use an external drop leg (not shown) in place of 7.
You can also do that. Valves in such external falling legs
The residence time in the upper and lower chambers is
and the flow rate between both chambers can be controlled. replenishment
Catalyst and/or catalyst or regeneration additives
A dosing tube (not shown) connects the upper chamber 102 and/or
Alternatively, it can be added to the lower chamber 103. Supply air to the regenerator through the air supply pipe 113
do. A portion of the air is sent through the branch supply pipe 114.
It is sent to the inlet pipe 115. This insertion pipe 115 is filled with air.
extending upward into the chamber 111 along its central axis.
Ru. The catalyst in the lower chamber 103 is
Enter the space between the wall and the spigot. Inside this space
A small spigot (not shown) suspends the catalyst and
The top of the plenum chamber 111 communicating with the lower chamber 103
Horizontally arranged annular distributor adjacent to the opening (Fig.
(not shown). Air supply pipe 11
The remainder of the air passing through 3 is air heater 117,
At least during initiation by VGO, heated and then
It is introduced into the inlet 118 of the annular distributor. this
Partially regenerated air in the lower chamber 103 is inserted into the inlet.
Provide an upward flow of gas to suspend the catalyst.
A hole, nozzle or gap can be provided.
Ru. The air in the lower chamber 103 causes the falling leg 107 to
Regeneration of the partially regenerated catalyst introduced through
be completed. The amount of air supplied depends on the combustion that occurs
The gas reaches the top of the lower chamber 103 and the upper chamber
102.
The falling leg 107 fills the expanded gap in the panel 104.
This panel has drop legs and coaxial
and the gas distributor 120 surrounding it is fixed.
has been established. Pre-partially discharged lower chamber
Combustion support gas from 103 passes through gas distributor 120
The coke is then introduced into the upper regenerator 102 where the coke
Coal coming in from the contaminated catalyst transport pipe 97
contact with a carbonation catalyst. in the gas distributor 120
The open tube 121 contains partially discharged combustion support gas.
promotes uniform distribution of gas into the upper chamber 102. Supplementary
Charge air or cooling fluid is supplied through supply pipe 122.
It can be introduced into the upper chamber 102. Also supply
Tube 122 can be vented through gas distributor 120.
You can also do it. less than about 0.25% carbon, preferably less than about 0.1%,
More preferably, the carbon content is less than about 0.05%.
The regenerated catalyst is discharged from the lower regeneration chamber 103.
and passes through the regenerated catalyst stripper 128 to the catalyst stand.
It is fed into a dopipe 86. In this way,
The live catalyst is returned to riser 91 where it is fed with fresh raw material.
further contact with the material. The reproducing device is an upper reproducing chamber 102 and a lower reproducing chamber 10.
Since it is divided into 3 parts, it can be used in the catalyst regeneration device.
It is possible to eliminate fluctuations in residence time due to
or limit the amount of regeneration heat imparted to fresh raw materials;
Produces regenerated catalyst with low carbon levels and returns it to the riser.
It has the unique effect of being useful for sending messages. Since the playback device is configured as above,
The relatively high carbon content supplied from the transfer line 97
The coking catalyst is used to sustain combustion in the upper regeneration chamber 102
Contact with gas. This gas is partially recycled
The carbon in the medium burns in the lower regeneration chamber 103.
At least some of the oxygen has been removed.
There is. Therefore, the carbon combustion and upper regeneration chamber 102
controlling both the amount of carbon dioxide produced in
Can be done. Air supply pipe 113 and branch path 11
The regeneration gas introduced through 4 contains a relatively large amount of acid.
Although there is a possibility that it contains elements, the lower regeneration chamber 10
The partially regenerated catalyst in 3 contains most of its carbon content.
has already been removed. High inside lower regeneration chamber 103
The effects of oxygen concentration and high temperature combine to reduce the amount of residue in the catalyst.
quickly removes carbon and cleans with minimal heat dissipation.
A highly regenerated catalyst can be obtained. Therefore, here again, below
Combustion temperature and CO in the regeneration chamber ₂ Control of CO ratio
can be easily controlled. Regeneration off gas is in upper regeneration chamber 1
From 02 to gas pipe 123, control valve 124, powdering
Discharge via catalyst trap 125 and outlet 126
be done. The gaseous product from desorption vessel 92 can be removed from any convenient
For example, steam line 1
31 to the fractionating column 132.
Wear. The fractionating column 132 has a pot residual oil outlet 133 and a side line.
Oil outlet 134, flash oil stripper
135, and stripper bottom line 136.
The bottom line 136 of the strip is a flash
It is connected to the oil discharge pump 137. Stoli
The overhead product from Zupah 135 takes line 138.
After that, it returns to the fractionating column 132. The main line 139 for discharging top oil of the fractionating column is
Connected to the top oil receiving tank 142, and further connected to the pot residual oil line 1
43, the gasoline product is discharged through the pump 144.
It will be done. Line 145 for recirculating a portion of gasoline products
It can also be sent back to the fractionation tower via
A valve 146 serves as a control valve for the recirculation amount. Tower top oil pan
The tank 142 further includes a water receiving tank 147 and a water discharge line 1.
Contains 48. Gas outlet 150 of the tower oil receiving tank
are mainly C _Five Less flow is discharged, but other
C _Five ,C ₆ and C ₇ It also includes a small amount. If necessary,
C included in the stream _Five The above ingredients are compressed, cooled and
It is separated by fractional distillation and returned to the top oil receiving tank 142.
Good too. introduced into the regeneration zone 103 via line 114.
Oxidizing gas such as air is supplied from management 109.
Can be mixed with spray cooling water. Oxidizing
The mixture of gas and spray water passes through the spigot 115.
and finally fed to the lower granular catalyst bed. The aperture diameter of the acid separator 120 allows it to flow upwardly.
flow easily passes through and enters the upper regeneration chamber 102.
It has sufficient size. However, this opening
The diameter is increased due to the pressure difference between the upper and lower regeneration chambers.
of catalyst particles flow into the bottom through the distributor.
The size is such that it prevents Plug tube 1
The aperture diameter of 15 is the same as that of the distributor. reproduction
The gas components coming out of the device are combustion products, nitrogen,
Steam formed by the reaction and/or regenerator
Water vapor derived from vaporized water added to
are oxides of other trace elements. These gases are
A cyclone separator (not shown) eliminates floating contact.
It is separated from the medium particles and passes through the discharge pipe 123 to the regeneration chamber.
is discharged from. The present invention also applies to single-stage regenerators and combustion gas
Multi-stage where the catalyst is basically in a forward flow relationship rather than a counter flow relationship.
It can also be used in formula regenerators, especially as shown in Figure 2.
This is effective for such types of playback devices. This is countercurrent
Low CO in formula ₂ Obtain combustion generated gas with a CO ratio
This CO is suitable for ₂ It has a low CO ratio
This helps lower regeneration temperatures under high carbon content.
One. The temperature of the zeolite in the catalyst is too high or
If the residence time is too long, it may deteriorate.
Playback with two or more stages or zones due to
Preferably using a device. Reinstall as shown in Figure 2.
Dividing the storage into upper and lower regeneration chambers is the regeneration process.
control of coke adhering to the surface of the regenerated catalyst.
reduce the amount without exposing the catalyst to excessive temperatures
It has a special effect of being helpful. Figure 2 shows the upper part of the desorption chamber 92, and the inside of the desorption chamber 92.
The upper end 164 of the iser 91 and the gas solid therein
An enlarged vertical cross-section of the separation device (this is in detail).
Ru. That is, hydrocarbon conversion from suspended solid catalyst particles
The cross section of the separation device for separating the components is numbered 16.
Inclusively indicated by 0. The separation device includes a discharge section. As this discharge part
It forms part of the elongated reaction chamber itself and its discharge
a hollow member forming a passageway including an end or a reaction chamber;
an extension or branch from the reaction chamber in direct communication with
and receives a stream containing catalyst particles suspended in the product.
any hollow member forming a passageway through which
good. In some cases, the discharge and the upstream part of the reaction chamber
There is no clear distinction between the two, and both have the same predetermined length.
It can form part of a pipe. That is, the second
As shown, the separator 160 has a hollow discharge section.
166, this discharge is connected to the downstream cylindrical riser
91 with the same diameter as the tube end flange 162 at the upper end 164.
and by bolting or welding (not shown) thereto.
It has a fixed tube end flange 168. Exclusion
The protrusion 166 is an extension that is integrated with the cylindrical riser 91.
You can make it into a long shape or butt weld the top end 164.
Alternatively, flanges 162 and 168 may be omitted. As shown, the passageway 170 starts from the inlet section 172A.
Outlet section 172 with starting end lip 173
substantially over most of its length ending in B
It has a uniform circular cross section. As described below, the exit
The cross-sectional area of the portion 172B and the lip 173 is the same as that of the inlet portion 17.
Same as internal cross-sectional area of 2A and/or riser 91
or may be larger or smaller. Furthermore,
Passage 170, lip 173, inlet and outlet 17
The cross sections of 2A and 172B do not necessarily have to be circular.
stomach. Other regular or irregular shapes are also considered.
can be used in the present invention. Its upstream end (lower in the drawing) and downstream end (lower in the drawing)
contains one or more bends in the middle of
Risers can be successfully used and therefore lever
invention can be used with this type of riser. La
The sharp bend in the iser substantially reduces catalyst particles.
It can be made faster. Therefore upstream of outlet section 172B
There is a noticeable bend over a short distance (downward in the drawing).
If there is a reduction in the catalytic velocity obtained,
If the curvature significantly reduces the separation efficiency of the
When increasing the radius of curvature is desirable or necessary
and/or its flexure at the exit portion 1
Further upstream (downward in the drawing) relative to 72B
Transfer may be desirable or necessary.
In this way, the catalyst particles reach the outlet part
can be re-accelerated (in this case in a vapor/solids stream)
steam flows downstream of the bend (upward in the drawing).
Over a qualitative distance, the catalyst particle leaves its curvature.
Something that continues to move faster than the speed at which it moves
). However, in this embodiment, the exit
Section 166 and its discharge channel 170 are
The flow path that exists over the entire length of the line riser 91
It has a vertical axis XX that coincides with the vertical axis. like that
Figure 2 shows only the downstream end (upper side in the drawing) of the riser.
Shown below. The inlet portion 172A and the outlet portion 172B are
The tubular risers 164 are substantially coaxial with each other.
Hydrocarbon conversion products and solid catalyst particles flowing out from
Provide a continuous discharge flow path for the child.
Both are preferable. For best results, exit section 170
so that its vertical axis X-X is vertical or nearly vertical.
For example, if desired,
The vertical axis is less than about 30° from vertical, preferably less than about 20°.
more preferably by an angle of less than about 10°.
It's okay. The use of angles larger than these
However, as the above angle increases,
There is a loss in efficiency. But vertical or
Reverse operation in approximately vertical arrangement, i.e. exit section 17
It is also possible to operate with 2B opened downward,
Such operations may in some cases be affected by the effects of gravity.
It can bring some benefits. Separation device 160 includes an outlet portion 166 at least
siege assembly 180, which is partially surrounding
Also included. In a preferred embodiment, the exit section
When viewed in a cross section perpendicular to the axis X-X of the
Boot 180 follows the outline of exit section 166.
It is a ring-shaped body that can be rolled up. However, within the scope of this invention
and the substance of the outline of the exit section 166 mentioned above.
extended adjacent to (sometimes all)
It is considered possible to use existing enclosure assemblies.
It will be done. The enclosure assembly 180 includes an exit section.
166 substantially parallel to the longitudinal axis X-X.
It includes an extending outer wall portion 182. Also the encirclement area
The assembly 180 has an exit section from the outer wall 182.
Extending inward towards the exterior wall of the building 166
It also includes a connecting wall 184. However, siege 1
Upstream end of 80 (compared to flow direction in riser 91)
be at least partially closed to
is preferred (but this is not the case). deer
Gaps and openings in the connecting wall 184 are
Harmony of different expansions and contractions of the surrounding and outlet areas
This is useful from the viewpoint of
Stripping device located upstream of the tube 166
used stripping steam if it contains
It is also possible to provide a means to extract the for example,
Such a stripping device uses riser 91.
It can be provided so as to surround it. Outer wall part 18
2 and the connecting wall (if any) substantially
Define the envelope of the cup shape. shape like this
is a preferred embodiment. Does it have a connecting wall 184?
The outer wall portion 182 with or without an exit section
166, and a collection channel 186 is formed between the two.
stipulates. In a preferred embodiment of this invention
In other words, the collection channel 186 extends along the entire length of the outer wall portion 182.
Figure 2 shows an extended annular cross section. However, other cross sections
Any shape is also possible. At least one outlet hole 190 is surrounded by 180
preferably through a portion of the outer wall 182.
Provided through. However, the exit hole is in the connecting wall 184.
may be provided. The outlet hole 190 is the collection channel 1
86 and hollow outlet conduit 192.
It functions in such a way that it can The outlet conduit 192 is connected to the enclosure 1
80 to a second stage separation such as a conventional cyclone device
It can extend to a device (not shown). As shown in FIG.
The attached downstream end portion of the riser 164 is connected to the desorption chamber 9.
Located within 2. Second stage separation of the type mentioned above
Or, even if the cleaning device is placed inside the desorption chamber 92,
You don't have to leave it there. According to a preferred embodiment, the light
of the hydrocarbon conversion products discharged from the
The only outlet from the desorption chamber 92 for
and into outlet conduit 192 through. For clarity, FIG. 2 shows a single exit hole 190.
Although only shown, a plurality of exit holes 190 surround
Extending through the separation of the outer wall 182 includes:
It is within the scope of this invention. The exit hole 190 is located at the edge 1
70 (not shown).
Alternatively, it may be located upstream of the edge 170.
(as shown). Exit hole 1 adjacent edge 170
90, the height of the surrounding outer wall 182, i.e.
In other words, the downstream extension is the downstream extension of the edge 173.
It can be lengthened. of the tubular riser 164 and the desorption chamber.
Any number of separation exit holes 190 depending on size
are provided around the outer wall portion 182 at intervals from each other.
and each exit hole also has its own exit conduit.
I can do it as much as I want. Alternatively, multiple exit holes
190 through one common manifold or equivalent
may be introduced into a single outlet conduit 192. Adhering to the following advice is to
Can help achieve high levels of operational efficiency
Ru. More specifically, the end 196 of the shroud 180
Approximately 2DD upstream or approximately 3D below the lip portion 173
Preferably, it is located in a zone extending up to the flow. Like
Specifically, end 196 is approximately D upstream from lip 173.
and D downstream. More preferably,
The above band is approximately D/3 upstream of the lip portion 172B.
It spreads approximately D/6 downstream. Now, the optimal position of edge 196
The location seems to be practically upstream of D/5, and here
, D is the effective downstream end of exit section 166.
It is the diameter. As shown, end 196
There is a space outward from the exit section 166.
Inlet 19 for the collected flow passage 186
form 7. In the above discussion, D is the exit section 166
indicates the effective diameter of the cross-sectional opening area at the downstream end of
Ru. The opening end may or may not be circular.
It can be divided into two or more openings.
In any case here
is also not a diameter in the ordinary sense of the term. opening
The effective diameter of the total opening area of the
For example, the formula: D=√4
(In the formula, A is the plane of the inner cross section that combines the above openings.
product). According to the above particularly preferred embodiment, the lip portion 1
73 projects downstream of the shroud end 196. like this
and the edge 196 of the shroud is about D/20 to about 2D;
Preferably from D/12 to about D, more preferably
Lip portions 1 separated by a range of about D/3 to about D/8
Upstream of 73 is preferred. Exit section as shown in Figure 2
166 discharges the catalyst into the space downstream of its outlet end.
Ru. In this embodiment, at the exit section 166
downstream based on the direction of movement of the catalyst and decomposition products.
The discharge path P has a motion component in the direction ₁ catalyst along
Particles are released. Such a passage P ₁ is generally
It expands in the downstream extension direction of the exit cross-sectional axis XX. Sara
, catalyst passage P ₁ branch out from and axis X-X
of the exit cross section 166 as a flow S branching out from
Product vapors are released from the downstream end. The lip portion 173 protrudes downstream of the shroud end 196.
If gaseous transition occurs due to hydrocarbon cracking,
The conversion products are routed through the arrows before entering the collective flow path 186.
It is formed by a lip portion 173 as shown by S.
It may be flown around curved corners. At the same time, raw
The momentum of the catalyst particles is much larger than the momentum of the product vapor.
The momentum of these particles is the curve shown by the arrow S.
Ivy makes it difficult to swerve along the flow path. This embodiment allows for discharge from the downstream end of the outlet section 166.
The majority of the product vapor produced is at an angle of at least about 45°.
How does it diverge from the vertical axis X-X at the opening angle?
and adjacent the downstream end of the outlet section 166.
This product evaporates in a predetermined portion of the desorption chamber 92.
Consistent method for collection and removal
It explains how it is formed in the flow. of said angle
Preferred embodiments are at least about 90° and more preferred
Preferably, it is at least about 105°. This aspect is also
In addition, at a position Z downstream of the planned portion of the release chamber 92.
How does the catalyst point outward from axis X-X?
Streamline P ₂ on the side in the desorption chamber as shown in
and then the catalyst particles move along the predetermined portion.
Passage P placed outside from ₃ and P _Four along top
It shows that it is carried away in the direction of the flow. A preferred and advantageous variant of the separation device is the
It is disclosed in Figure 3. For example, a variation is the exit
Intersects the vertical axis X-X of the cross section and is at a higher level
Signage that can help you achieve the efficiency of
together with everything previously stated with respect to Figure 2.
It may also include a part. bound by theory
There is no forest, but the signboard indicates that you can enter via Entrance 197.
the probability that a particle will proceed to the entrance to the opening 190
more regular or consistent in reducing
Helps form a separate catalyst in the stream.
It seems that The signboard should be flat as shown in Figure 3.
board, inside and opposite the top edge of the hemisphere as shown in Figure 2.
When a catalyst is released into a pair of spheres, or other
Suitable shape and shape to promote rectification of catalyst particles
It can be any size. Generally, the catalyst flow is from the downstream end of the outlet section 166.
The marking is at least about 3 times the total width of the catalyst stream.
Preferably, it is twice as large. Name the sign in the previous sentence.
approximately 1/2 to 5 times the overall width applied, more preferably
about 1.5 to about 3 times, and most preferably about 1.5
or twice the distance downstream of the catalyst release location.
It would be advantageous to place a signboard at signboard
When in use, the
touching at least the space downstream of the open outlet section 166.
The medium is thrown out. In some embodiments, the sign is
Annular or circumferential orifice in cooperation with lip 173
It may be considered as providing a chair. Figure 3 state
, the sign 200 is aligned with the longitudinal axis of the exit section 166.
It intersects X-X, and is also suspended by the hanging rod 202.
It is provided within the desorption chamber 92. Signboard 200 is good
Preferably, the catalyst flow extending downstream from the outlet cross section 166
intersects the road and extends substantially at right angles to the axis
Includes an impact surface 204. During operation, catalyst particles and lip portion 173
A small amount of decomposition products released from the surface 204
collide with The catalyst and gas flow approaches plate 200.
Then, as shown by the catalyst flow path T, the gravity
eventually separated from the outer part of the sign 200 under the influence.
As the catalyst particles leave, the flow reaches signboard 200.
deviate radially and outwardly along the When the sign is sufficiently close to the downstream end of the exit section 166,
As shown in Figure 3, when the flow leaves the exit cross section,
The catalyst immediately begins to separate from axis XX. this
has a component moving in the downstream direction, and the exit cross section
emission that extends in one or more directions deviating outward from the axis of
How catalyst particles are thrown out along the path
This is an example. Furthermore, this aspect
How can it be thrown out from the downstream end of the exit cross section?
Catalyst flow deflected downstream or outward
It shows a deviation in the upstream direction from the passage. Both this embodiment and the embodiment described above involve the connection between the catalyst and the product stream.
closely adjacent to the downstream end of the elongated reaction chamber, between
Figure 3 is an illustration of interposing barriers at locations. the catalyst particles at a sufficient velocity, e.g. about 60-100 ft.
exit 166 at a speed of
Due to their momentum at 4, most catalyst particles
target until it fully exceeds the outer wall 182 of enclosure 180.
It is preferable to move it outward along the
Delicious. Within this velocity range, the flow exits outlet 166.
exit and direct the flow along the target impact surface 204.
Forms a pressure cone that helps direct
Is possible. Catalyst particles are the final target
When leaving the G-200, it is necessary to leave under the influence of gravity.
Collection flow path 18 as it passes downwardly through chamber 92
Much more likely to pass 6. With this
In contrast, the air flow impacting the target 200
The reaction product does not exhibit the momentum of the solid catalyst particles. So
Therefore, this gaseous product is quickly removed from the target 200.
the adjacent area until it separates and enters the collection flow path 186.
It turns and falls. For example, about 60 feet/second or more.
At riser speeds like below, the target 200 surface
Attach an eccentric assembly such as cone 206 to
the direction of the flow emitted from the outlet 166
Start making gentle changes. For example, 45 feet/second
At lower speeds, the tip of the cone 206
It may be advantageous to have the end slightly protrude into the downstream end of the outlet.
There is. The target 200 and the cone 206 are
Separation efficiency can be significantly increased, but they
The use of is optional. Hydrocarbon gases (including steam) are generated during fluid catalytic cracking operations.
) and solid catalyst at a flow rate of approximately 25 to 100 (or
or more) through the tubular riser at a speed of feet per second.
It can be flowed downward. The flow is at the outlet 16
6 through the downstream end of passageway 170.
Adjust the flow velocity in the downstream direction by increasing or decreasing the surface
Sometimes it is desirable. through the riser
The flow velocity is relatively low, with a flow velocity of about 45 feet/second.
If it is made, reduce the cross section of the passage 170 and
It is desirable to increase the velocity of the flow before discharge from
There is. Alternatively, e.g. about 80-100 feet
The flow moves over the riser at relatively high speeds, such as
If it passes, increase the cross-sectional area of the passage 170,
It is desirable to reduce the velocity of the flow before discharge from the outlet.
There is something interesting. In a similar manner, at least in part, outlet 166
An enclosure entrance 197 or collection passageway 186 surrounding the
Ratio of the cross section of the riser outlet to the downstream open end of the riser outlet
It was made small enough to be mistakenly targeted.
Minimizes the chance of catalyst particles entering enclosure 180.
At the same time, the cross-sectional area of the enclosure collection passageway 186 is
To prevent excessive increase in speed when entering the enclosure
be large enough to prevent excessive pressure drop in the flow.
should be stopped and significant abrasion of enclosure passage surfaces should be avoided.
be. Effective riser release velocity of 45 feet/second
When the enclosure collection area is e.g. about 0.7
If the ratio is to the riser discharge area, the flow through the enclosure is
The speed is not excessive. At the same time, riser release
When the speed is 80 feet/second, it is approximately 1
The ratio of discharge area to collection area is
This is an exemplary value to avoid excessive flow velocity. these
The ratio of abrasive wear and overload on the downstream side of the enclosure assembly
Non-excessive flow rate required to avoid excessive pressure drop
of a range of values that can be demonstrated to be effective in maintaining
This is an example. Due to the need to achieve these objectives,
It is within the scope of this invention to increase or decrease the product ratio. outfit
In designing the equipment, it is natural to consider appropriate equipment components.
size, adjust downstream processing equipment and riser
Achieve sufficient pressure drop from the outlet to the outlet 192.
The generated steam is passed from outlet 166 to outlet 192.
The flow, and from there, the downstream side like a cyclone
Facilitate flow of the steam to processing equipment. Flow enters outlet 190 from enclosure collection passage 186.
and the speed does not increase excessively while passing through it.
It is also desirable to have an enclosure and exit in a variety of shapes. one
In an exemplary embodiment, the area of the outlet(s) is equal to the flow rate
sufficient to maintain approximately the same value as in the enclosed collection aisle.
make it a thing.

[Brief explanation of drawings]

FIG. 1 shows the apparatus used in the method of the invention.
Figures 2 and 3 are detailed views of the upper part of the riser. 10...Cold storage container, 14...Measuring device, 91
...Riser, 94...Stripper.

Claims (1)

Claims: 1. () A feedstock consisting of slurried and/or at least partially dissolved coal and metal-contaminated hydrocarbon residue is introduced into a progressive flow catalytic cracking zone where the coal is ,
forming a stream having a linear velocity of at least 25 ft/sec (7.6 m/sec) consisting of the resid and a hydrocarbon cracking catalyst; () dehydrogenating the resid without addition of molecular hydrogen; to provide mobile hydrogen in the stream to facilitate the dehydrogenation to provide mobile hydrogen to promote the production of liquid product from the coal; of heavy metals in contact with a well-deposited cracking catalyst; () steam in said catalytic cracking zone for a period of up to 10 seconds sufficient to cause a conversion of said resid of at least 50% by volume per pass; Residence time,
forming said mobile hydrogen under a combination of temperatures in the range of 900-1400㎓ (482-760°C) and total pressures of 10-50 psi absolute (7031-35155 Kg/ ^m2 ), and () separating from said cracking catalyst. and recovering the products of liquefaction and/or conversion and cracked oil. 2. The method of claim 1, wherein the hydrocarbon cracking catalyst has a surface area in the range 40-250 m ^<2> /g and a total pore volume in the range 0.2-0.5 cm ^<3> /g. 3. Liquid water, steam or a combination of liquid water and steam is introduced into said zone, wherein the ratio of the partial pressure of said water, steam or combination thereof to said feedstock oil is in the range 1-14. The method described in paragraph 1. 4. The liquid water, steam or a combination thereof
A method according to claim 3 containing hydrogen sulfide in the range of 500-5000 ppm. 5. The method of claim 1, wherein the vapor residence time is in the range of 0.5-3 seconds. 6. The method of claim 1, wherein the vapor residence time is in the range of 1.0-2.0 seconds. 7. said coal is selected from the class consisting of sub-anthracite, bithyuminous, sub-bithuminous, lignite, lignite or peat and mixtures thereof, wherein said hydrocarbon oil containing said metal and Conradson carbon contains at least 2 ppm nickel equivalent. The method according to claim 1, which contains nickel. (8) introducing a feedstock consisting of a slurried and/or at least partially dissolved coal- and metal-contaminated hydrocarbon residue and a hydrogen donor into a progressive-flow catalytic cracking zone;
Accordingly, at least 25% of the total
forming a stream with a linear velocity of feet per second (7.6 m/sec); The resid and the hydrogen donating material are combined in an amount of at least 1500 nickel equivalents to provide mobile hydrogen to the coal and to facilitate the dehydrogenation to provide mobile hydrogen and promote the production of liquid product from the coal. contacting heavy metals with a well-deposited cracking catalyst; () vapor retention in said catalytic cracking zone for a period of up to 10 seconds sufficient to cause a conversion of said resid of at least 50% by volume per pass; time,
forming said mobile hydrogen under a combination of a temperature in the range of 900-1400㎓ (approximately 482-760°C) and a total pressure of 10-50 psi absolute (7031-35155 Kg/ ^m2 );
and () separating from said cracking catalyst and recovering the products of liquefaction and/or conversion and cracked oil. (9) introducing a feedstock consisting of a slurried and/or at least partially dissolved (a) coal and (b) a hydrocarbon oil containing metals and Conradson carbon into a progressive flow catalytic cracking zone; The oil has at least 1-2% by weight of residual carbon upon pyrolysis and at least 4-2% by weight of residual carbon.
characterized by containing 5.5 ppm nickel equivalent of a heavy metal, said metal comprising nickel, and a linear velocity of at least 25 ft/s (7.6 m/s) to promote dehydrogenation of said feedstock; forming a stream in said zone having said feedstock and said hydrocarbon cracking catalyst, said catalyst characterized by having a heavy metal deposit of at least 1500 ppm nickel equivalent, () up to 10 seconds; Steam residence time in the range of 900−
Temperatures in the range of 1400〓(482−760℃) and 10−
forming mobile hydrogen in said zone under a combination of total pressures in the range of 50 psi absolute (7031-3.5155 Kg/ ^m2 ); Introducing the mobile hydrogen into the stream by dehydrogenation of the feedstock without adding hydrogen, thereby producing a liquid product from the feedstock and at the same time adding hydrogen in the range of 0.3-3%. A method for economically producing a liquid fuel product comprising the steps of: depositing coke on a hydrocarbon cracking catalyst, thereby producing a spent catalyst; and () separating the liquid product from the spent catalyst. . 10 () introducing a feedstock consisting of a slurried and/or at least partially dissolved (a) coal and (b) a hydrocarbon oil containing metals and Conradson carbon into a progressive flow catalytic cracking zone; The oil has a residual carbon of at least about 2 or more upon pyrolysis, and at least 4
−5.5 ppm nickel equivalent of heavy metals, said metals including nickel, to promote dehydrogenation of said feedstock. ), the stream comprises the feedstock and a hydrocarbon cracking catalyst, and the catalyst has a linear velocity of at least 1500 ppm.
Characterized by having heavy metal and water deposits of nickel equivalent (), vapor residence times ranging up to 10 seconds, 900−
Temperatures in the range of 1400〓(482−760℃) and 10−
forming mobile hydrogen in said zone under a combination of total pressures in the range of 50 psi absolute (7031-35155 Kg/ ^m2 ); () contacting said feedstock with said hydrocarbon cracking catalyst to form molecular hydrogen; introducing the mobile hydrogen into the stream by dehydrogenation of the feedstock, thereby producing a liquid product from the feedstock and at the same time reducing the carbonization in the range of 0.3-3%. depositing coke on a hydrocracking catalyst, thereby producing a spent catalyst; () separating the liquid product from the spent catalyst; and () depositing coke on the spent catalyst in one or more regeneration zones. maintaining one or more fluidized catalyst regeneration beds consisting of the spent catalyst regenerated by combustion of the coke and a combustion supporting gas such as oxygen;
supplying additional spent catalyst to one or more such fluidized regeneration beds () sufficient for combustion of the coke on the spent catalyst to bring the level of carbon on the spent catalyst to 0.25% by weight; maintaining the spent catalyst in the regeneration zone in contact with the combustion support gas flow under conditions of temperature, pressure and average total residence time in the zone that are sufficient to reduce the , CO and/or CO ₂
and a regenerated catalyst, said regenerated catalyst characterized by a deposited nickel content in an at least partially oxidized state, () at least one of said oxidized nickel; () contacting the regenerated catalyst with the reduced nickel deposits with fresh feedstock oil under reducing conditions sufficient to reduce nickel to a reduced state; for
recycling said water to said progressive flow catalytic cracking zone at a temperature in the range of 1100-1600㎓ (593-871°C) to form a mixture of said water and catalyst and feedstock stream; introducing into the progressive flow catalytic cracking zone, the amount of water introduced into the progressive flow catalytic cracking zone and the amount of reduced nickel on the regenerated catalyst providing reforming reaction vapor to the catalytic cracking zone; A method of economically producing a liquid fuel product comprising steps sufficient for 11 the regenerated catalyst contains deposited nickel with a nickel equivalent in the range of 3000-50000 ppm, the ratio of the partial pressure of the water to the partial pressure of the feedstock in the catalytic cracking zone is less than or equal to 14; −
containing H ₂ S in the range of 5000 ppm, and the nickel content of the regenerated catalyst is based on the weight of the regenerated catalyst.
Claim 1 in the range of 0.5-3.0% by weight
The method described in item 0.