JPH0829251B2 - Porous solid phosphoric acid catalyst and method of using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] In the present invention, 25.0% or less of the total pore volume of a catalyst has a diameter of 10,0.
The present invention relates to a porous solid phosphoric acid catalyst composition characterized by comprising pores of 00Å or more.

Solid phosphoric acid consists of phosphoric acid and diatomaceous earth (diatomaceouseart
h), the name used for the calcined mixture with porous binders such as nematodes. Traditionally, solid phosphoric acid catalysts have been the only catalysts that are effective in actually polymerizing normally gaseous olefins to produce normally liquid hydrocarbons. Mixtures of propane and propylene, butane and butylene, and ethane and ethylene are the main raw materials for this polymerization process. Further, the solid phosphoric acid catalyst is extremely useful as a catalyst for producing cumene by alkylation of aromatic hydrocarbons with aliphatic hydrocarbons, particularly alkylation of benzene with propylene.

[Conventional technology]

Solid phosphoric acid catalysts, additives, formulations, etc. having several capabilities are well known in the art as providing more powerful, active and durable catalysts. However, a solid phosphoric acid catalyst characterized in that 25.0% or less of the total pore volume of the catalyst composition is composed of pores having a diameter of 10,000 Å or more and it has not been known so far that it exhibits excellent stability in catalytic condensation reaction. .

The basic formulation of solid phosphoric acid catalyst compositions is well known, for example US Pat. No. 2,586,852 discloses kaolin crystalline silica and phosphoric acid based solid phosphoric acid.

Porous binders are known for improving the properties of solid phosphoric acid catalyst compositions. US Pat. No. 3,044,964 describes solid phosphoric acid catalyst compositions based on phosphoric acid and natural porous silica materials. In addition, the catalyst can contain a binder that is not naturally porous.

Controlling the stability of solid phosphoric acid catalyst systems based on the limitations of available pore volume is not well known in the art. U.S. Pat. No. 3,661,801 discloses a solid phosphoric acid catalyst composition prepared to obtain a particular pore volume distribution. However, the disclosed catalyst has pores with a diameter greater than 350Å.
0.07 to 0.2-0.4cc / g and hole with diameter larger than 9,000Å
I have 0.20cc / g. Therefore, the ratio of the pore volume where the pore diameter of this prior art catalyst exceeds 9,000Å is at least 17.5% or more or 0.07 cc / g in absolute amount. It is further disclosed that such catalysts are produced in a way that only spherical catalysts are obtained. All of these factors distinguish between the catalyst made by the method disclosed in the aforementioned U.S. Pat. No. 3,661,801 and the catalyst of the present invention.

[Problems to be Solved by the Invention]

The main object of the present invention is to provide an improved porous solid phosphoric acid catalyst. This improved catalyst exhibits superior stability compared to similar catalysts of the prior art. The improved stability is due to the unique pore volume distribution of the catalyst of the present invention.

Accordingly, a broad embodiment of the present invention is a porous solid phosphoric acid catalyst system. The solid phosphoric acid catalyst composition is a combination of solid phosphoric acid and a binder. This catalyst is characterized in that less than 17.5% of the total pore volume of the catalyst composition consists of pores with a diameter of 10,000 liters or more. Further, in this solid phosphoric acid catalyst composition, the binder is preferably an inorganic oxide material, most preferably a siliceous material such as diatomaceous earth, or artificially made silica, or mixtures thereof. Characterize.

In a preferred embodiment, the porous solid phosphoric acid catalyst composition is in the form of an extrudate and is based on phosphoric acid and an inorganic oxide binder. This preferred catalyst is characterized in that no more than 17.5% of the catalyst composition extrudate consists of pores with a diameter of 10,000 liters or more. Furthermore, this catalyst is characterized in that the total pore volume of the catalyst composition molded article is about 0.24 cc / g or less, and the absolute pore volume for pores having a diameter of 10,000 Å or more is 0.07 cc / g or less.
Finally, the catalyst composition of the present invention preferably contains at least 60 wt% P ₂ O ₅ .

In another embodiment, the present application describes a method for converting hydrocarbons in the presence of said solid phosphoric acid catalyst by contacting a hydrocarbon feedstock with the solid phosphoric acid catalyst composition under hydrocarbon conversion conditions. .

It is well known that solid phosphoric acid catalysts are useful in a variety of important hydrocarbon conversion processes. However, these methods always have problems associated with the use of a solid phosphoric acid catalyst, such as dissolution of the catalyst, weak physical strength of the catalyst, and poor stability of the catalyst. Therefore, strong catalysts exhibiting high activity and stability are constantly being sought. Pore volume is now an important factor for the stability of solid phosphoric acid as it approaches the goal of producing strong, highly active and long-lived catalysts, and coarse pores, that is, pores with diameters greater than 10,000Å. It has been found that reduction in volume is important.

It is an important aspect of the present invention that 25% or less of the pore volume of the catalyst is 10,000 Å or more in diameter. Most preferably, pores of 10,000 liters or more compensate for less than 17.5% of the total pore volume of the catalyst. A large volume of coarse pores not only weakens the strength of the extrudate, but also increases carbon deposition during use due to increased pore diffusion due to coarse porosity. A large amount of carbon deposited during the reaction may promote deactivation and bulking of the catalyst, resulting in lower than normal reactor pressures.

It was also observed that the total pore volume of the catalyst is also related to the stabilization of the catalyst. Therefore, the maximum total pore volume of the catalyst is 0.24 cc / g
It is preferred that

The necessary and active component of the solid phosphoric acid catalyst referred to herein is phosphorus, preferably a phosphorus acid having a valence of +5. This phosphoric acid is about 60 to 60% of the final catalyst mixture.
It can constitute about 80 wt%. Among various phosphoric acids, orthophosphoric acid (H ₃ PO ₄ ) and metaphosphoric acid (H ₄ P ₂ O ₇ ) are generally used in this main mixture because they are mainly inexpensive and easily available. Not only the phosphoric acid mentioned above can be used in the resulting catalyst composition, but also any other phosphoric acid, if compatible. However, other available phosphoric acids make catalysts that have the same effect on a given organic reaction as do the catalysts made with various phosphoric acids, or have their own characteristic actions due to slightly modified methods. It does not mean to indicate to do. However, it is believed that the catalysts made as disclosed herein have superior hydrocarbon conversion performance as compared to the catalysts disclosed herein without the pore volume distribution.

When orthophosphoric acid is used as the main component, the concentration of this aqueous solution can be used in the range of about 75-100%. Acids containing some free phosphorus pentoxide can be used as well. This means that orthophosphoric acid may contain a certain proportion of pyrophosphoric acid corresponding to its main dehydrated phase. In this concentration range, the acid is a viscosity-changing liquid and mixes readily with the adsorbent. In fact, the pyrophosphoric acid corresponding to the formula H ₄ P ₂ O ₇ can be mixed with the binder at a temperature slightly above its melting point (61 ° C),
Also, the heating time to the pyrophosphoric acid-adsorbent mixture may be different than when orthophosphoric acid is used in this way.

Triphosphoric acid, which can be represented by the formula H ₅ P ₃ O ₁₀ , can also be used as a starting material for the preparation of the catalyst of the invention. These catalyst compositions can also be prepared from the siliceous materials described herein and phosphoric acid mixtures including orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, and other polyphosphoric acids.

The binder that can be used as a component of the solid phosphoric acid catalyst composition can be any material that can adsorb or bind the phosphoric acid component in the catalyst composition. One group of such materials are refractory inorganic oxides such as alumina, silica, or other metal oxides (eg, magnesium, calcium, phosphorus, titanium, or mixtures of several of these designated).

The binder is preferably a siliceous material. Specific examples of these siliceous materials, ie, SiO ₂ -containing materials, which are useful as the binding component of the solid phosphoric acid catalyst of the present invention include diatomaceous earth, dropworm soil, kaolin, fuller's earth, or artificially produced porous materials. Silica or mixtures thereof may be mentioned. The most preferred siliceous binder is Keith Lager. But dripworm soil,
It is noted that the terms and and siliceous materials and generally naturally occurring porous siliceous materials are used interchangeably and are generally referred to by the same criteria in connection with the present invention.

One method that can be used to make a solid phosphoric acid catalyst composition having the desired pore volume characteristics of the catalyst of the present invention is to tightly control the particle size of the binder. Most typical binders contain particles of very different sizes. By using a binder consisting of very small particles, the resulting solid phosphoric acid catalyst composition is more compact and therefore has fewer pores larger than 10,000 Å in diameter compared to catalysts made with particles larger than said particles. Is expected.

Binders of small particle size can be obtained in various ways. The binder can be screened to capture only the smallest particles. Alternatively, the binder can be mechanically sized using an Eiger mill, ball mill, etc. to break up the large particles into smaller particles useful in the solid phosphoric acid catalyst composition of the present invention. When the binder classification method is used to prepare the catalyst of the present invention, the binder particle size is preferably in the range of 1 to about 150 μm.

In preparing the catalyst composition used in the present invention, the oxygen acid of phosphorus and the solid binder are about 10 ~.
Mix to form a composition at a temperature of about 232 ° C, preferably about 95-180 ° C. Thus the satisfactory result is polyphosphoric acid (P ₂ O ₅
Content of 82%) was heated at a temperature of about 170 ° C. and then this hot phosphoric acid was mixed with diatomaceous earth at room temperature beforehand. The polyphosphoric acid and diatomaceous earth produce a composition having a weight ratio of phosphorus pentoxide to siliceous adsorbent of about 1.5 to about 7.5. Although the composition is slightly wet or almost dry in appearance, the composition is pressed in a hydraulic or helical extruder that forms into pieces that are cut into the shape of particles. Time becomes plastic.

Extrusion of the phosphoric acid / binder mixture is another step in the catalyst preparation process that can easily reduce the porosity of the catalyst composition to pore sizes above 10,000Å in diameter. Extrusion can be used to control the porosity of the catalyst in a number of ways, essentially by controlling the extrusion back pressure. Generally, the higher the extrusion pressure, the more compact or lower the porosity, pore volume and pore size of the catalyst. The extrusion back pressure can be changed in various ways. One way is to change the cross-sectional area of the holes in the die plate of the extruder. Another method is to change the moisture content of the dough that is extruded by the dryer dough which also creates back pressure. Yet another method relates to the strength or energy used in extruding the catalyst composition of the present invention. The extrudate is made in an extruder with a rotating screw or ram. Both types of equipment are compacted before the dough is extruded through a die plate. By changing the screw rotation or the ram strength, along with other extrusion variables such as clearance between screw and barrel, screw pitch, etc., the catalyst precursor dough can be made compact and more energy is required for extrusion. Can be consumed.

What is important about the variables such as extrusion that affect the catalyst is (1) the porosity distribution of the desired catalyst is known, and (2) the variables such as the extrusion method that affect the finished catalyst are known and controlled. It is possible. Those familiar with extrusion will understand the contribution of the above variables in controlling the porosity of the expanded catalyst, and thus control these variables in order to consistently produce the solid phosphoric acid catalysts of the present invention. Could be

After all, the solid phosphoric acid catalyst of the present invention is preferably produced in the form of an extruded product. It is considered that the present catalyst can be produced in various shapes according to the required pore size / pore volume distribution. However, these important properties may be more controllable if the catalyst composition is in extruded form. Extrusion is also an efficient and inexpensive method for producing the formed catalyst particles.

For example, the catalyst composition formed by extrusion is amorphous (or green) and needs to undergo a crystallization step to bring the catalyst composition into a crystalline form for use in hydrocarbon conversion processes. Generally, this crystallization process is performed by baking. Amorphous extrudates are fired by conventional firing methods that control the temperature and time in the zone and, if necessary, the water level. Therefore the crystallization of the catalyst is a single zone,
It can occur in a baking device that includes two or more than two bands. The strips are characterized in that the strip temperature can be controlled at least independently of other strips.

The above calcining variables are believed to directly impact the type and amount of pores and the pore volume in the calcined solid phosphoric acid catalyst. As described above, the finished solid phosphoric acid catalyst is characterized in that 25.0% or less of the total pore volume of the catalyst is composed of pores having a diameter of 10,000 Å or more. Furthermore, this catalyst has a total pore volume of 0.28 cc / g.
The following is preferred.

Temperature is the first important baking condition. Temperature is important in controlling the type of crystallites that result from dehydration and firing of amorphous materials. When the baking temperature is as high as 500 ° C. or higher, a solid phosphoric acid catalyst essentially having only crystallites of silicon pyrophosphate is obtained. If a catalyst having both orthosilicon and silicon pyrophosphate crystallites is desired, a calcination temperature of 100
A range of ~ 450 ° C, especially 350-450 ° C, has been determined to be most desirable.

In connection with controlling the firing temperature, it is known to tightly control the water vapor or water content of the firing zone to produce a finished solid phosphoric acid catalyst composition exhibiting the desired porosity and pore volume. The amount of water vapor in the vapor of the burning zone is preferably more than 5.0 mol% based on the total amount of vapor to the calciner in order to introduce the desired porosity characteristics into the catalyst.

It should be noted that controlling the amount of water vapor in the vapor of the calciner does not necessarily mean that all or part of the vapor must be added to the calciner from an external source. It is entirely possible that a large amount of water vapor is present in the vapor of the tempering zone during firing as a result of the evaporation of water from the catalyst. Although there may be additions to the zone, the variables can also be controlled by controlling variables such as total steam flow through the zone, temperature, and water content of the biocatalyst.

Time in the broiler is also an important variable. Generally the total baking time can vary from 20 to 120 minutes. If more than one burning strip is used, the total burning time for each strip is 20 ~
It can be changed to be in the range of 120 minutes.

Furthermore, a preferred aspect of the present invention is that if there are more than one zone, at least one zone needs to be operated at the above conditions. Further, the end (or final) zone of a multi-zone burner is preferably operated under the desired process conditions detailed above. That is, other zones than the end zones cannot be operated under favorable operating conditions, and operating this final zone at maximum temperature is the most efficient method of making the catalysts disclosed herein. it is conceivable that.

Further, the water level in the edge zone is preferably 5.0% or more. The solid phosphoric acid catalyst calcined by the above method generally has the desired porosity as described above. As a result, 25.0% or less of the total pore volume of the present catalyst composition has pores of 10,000 Å or more as analyzed by the mercury infiltration method.

The catalyst surface area and pore volume distribution are typically determined by mercury insertion and extrusion methods. Mercury insertion and extrusion methods are widely used in catalytic science for the pore nature of catalysts.
A detailed discussion can be found in A Review of Mercury Porosimetry, HM Rotare, A Review of Mer, pp225-252 Plenum Publishing, 1970, for advanced experimental techniques in powder metallurgy.
Curry Porosimetry, Powder Technology, 33 (1982) pp201-209, A Generalized Analysis fo by RWSmithmick.
r Mercury Porosimetry, Surface Colloid Science, vol
In 13, Advance in Experimenta by DN Winslow
It can be found in literature such as Techniques for Mercury Intrusion Porosimetry.

The catalysts of this invention are used where it is known to use solid phosphoric acid catalysts in catalytic conditions, aromatic alkylation and other hydrocarbon conversion processes. When used to convert olefinic hydrocarbons to oligomers or polymers, catalysts of the above type are preferably used as the particulate bed in the heated reactor, which is generally made of steel, and pass the preheated hydrocarbon fraction directly. Thus, the solid catalyst in this method can use the olefin-containing hydrocarbon mixed vapor for the treatment of olefin oligomerization or polymerization. However, the same catalyst is also used to operate under suitable conditions to maintain a liquid phase during the oligomerization or polymerisation of olefinic hydrocarbons such as butylene, producing a gasoline fraction.

When used in the polymerisation of conventional gaseous olefins, the catalyst particles are generally placed in a vertical tubular processing column or in a fixed bed in the reactor or column and the gas containing olefins is fed to this reactor or column. Through 140 ℃ to 290 ℃
These conditions are particularly suitable when treating olefin-containing feeds containing about 10 to 50% or more propylene and butylene, at a temperature of 6 to 102 atmospheres and a downward pressure. When operating a mixture consisting essentially of propylene and butylene, the catalyst is from about 140 ° C to about 2 ° C.
A pressure of about 34 to about 102 atmospheres at a temperature of 50 ° C is effective.

The catalyst of the present invention is also used for alkylating alkylating agents and aromatic hydrocarbons. The alkylating agent introduced into the alkylation reaction zone is a group of various substances including mono-olefins, di-olefins, polyolefins, acetylene hydrocarbons and alkali halides, alcohols, ethers and the like, the latter of which is alkyl sulfates and alkyl phosphates. It is selected from the group comprising salts and various esters of carboxylic acids. Preferred olefin-acting compounds are olefinic hydrocarbons consisting of monoolefins containing one double bond in the molecule.

Monoolefins which can be used as olefin-acting compounds in the process of the present invention are either normally gaseous or normally liquid and include ethylene, propylene, 1-butene, 2-butene, isobutene, and various pentenes, hexenes. High molecular weight normal liquid olefins and higher molecular weight liquid olefins, such as heptene, octene, and mixtures thereof, the latter including propylene trimer, propylene tetramer, propylene pentamer, etc. in about 9 to about one molecule. Included are various olefin polymers having 18 carbon atoms. Cycloolefins such as cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene and the like can also be used but do not necessarily give equivalent results. Other hydrocarbons such as paraffins, naphthenes and those containing from 2 to 18 carbon atoms can also be present in the alkylating agent. When the catalyst of the present invention is used in an aromatic alkylation reaction,
Monoolefins containing at least not more than 2 and 14 carbon atoms are preferred. More particularly preferably, the monoolefin is propylene.

Aromatic substances mixed with an alkylating agent and charged into the alkylation reaction zone are benzene and R is methyl, ethyl or a combination thereof, and n is an integer from 1 to 5 and can be selected from the group of monocyclic substituted benzenes having 7 to 12 carbon atoms. In other words, the starting aromatic substituents are alkylaromatics containing 1 to 5 methyl and / or ethyl group substituents and mixtures thereof. Such raw materials are not limited, for example, benzene, toluene, xylene, ethylbenzene, mesitylene (1,3,
5-trimethylbenzene) and mixtures thereof. A particularly preferred aromatic based material is benzene.

In a continuous process for the alkylation of aromatic hydrocarbons with olefins, the above-described reactants are continuously charged into a pressure tube containing the solid phosphoric acid catalyst of the present invention. The raw material mixture is introduced into the alkylation reaction zone containing the alkylation catalyst at a constant or variable rate. Normally, the fragrance and the olefinic alkylating agent are contacted in a molar ratio of about 1: 1 to 20: 1 and preferably about 2: 1 to 8: 1. The optimum feedstock molar rate helps to prolong catalyst life by minimizing catalyst inactivity due to the deposition of solids and heavy materials on the catalyst. The catalyst is either contained in one bed in the reactor or is placed in many separate beds in the reactor. The alkylation reaction system can include a series of one or more reaction tubes. The charge to the reaction zone can flow vertically upwards or downwards through the catalyst bed of a typical Pragg Flow reactor or horizontally across the catalyst bed of a radial Flow reactor.

In some cases, keeping the reaction temperature in a suitable range,
And thereby reducing the formation of unwanted polyalkylaromatics, which makes cooling of the reactants by the heat of reaction desirable. A cooling stream comprising an alkylating agent olefin, an alkylating agent or a reactor effluent stream or a mixture thereof is injected into an alkylation reactor system to disperse heat, and an additional amount of olefin alkylating agent and in the reactor. The unreacted aromatic-based material at is supplied to the reaction zone.
This is accomplished by the example of a single-stage reactor in which the cooling stream components described below are injected in multiple stages into the reaction zone through conduits introduced into the reaction zone.

In either the single stage reaction system or the multi stage reaction system, the amount and composition of the cooled raw material to be injected into this system can be changed as necessary. Multi-stage cooling-
Injection can eliminate costly cooling equipment in this process, and large amounts of surface heat equipment and molar rates of olefins to aromatics are most effective throughout the reaction zone to improve formation of the desired alkyl aromatics. The result is improved selectivity and thus an increased yield of the desired monoalkylated aromatic compound.

The preferred temperature used in this process is the particular olefin used to selectively produce the aromatic base material and the desired monoalkylaromatic compound from 100 ° C to about 390 ° C, especially about 150 ° C.
It is preferable to use a temperature of from to 275 ° C. The preferred pressure used is not less than about 1 pressurization, but not more than about 130 atmospheres. A particularly preferred pressure range is about 10 to about 40 atmospheres. Space velocity per hour of the liquid in which the benzene feed rate based on (LHSV) from about 0.5 to 50 hr ^-1, and especially from about 1 to about 10 hr ^-1. It should be noted that the combination of temperature and pressure used herein essentially causes the liquid phase alkylation reaction to occur. In the liquid phase process for the production of alkylaromatics, the catalyst is continuously washed with the reactants,
Thus, it is possible to prevent the solids from rising on the catalyst. As a result of the reduction in the amount of carbon formed on the catalyst in this case, the catalyst life is extended compared to gas phase alkylation processes, where solids formation and catalyst deactivation are major problems. It

In addition, the amount of water can be adjusted by appropriately adding it to the alkylation reaction zone. Virtually prevent the loss of water from the catalyst,
And, as a result, in order to prevent a reduction in catalyst activity, an amount of water vapor, such as water or steam, is added to substantially equilibrate the vapor pressure of the alkylation catalyst. The amount of water is in the range of about 0.01 to 6% of the volume of raw material fed to the alkylation zone. Water is later removed by the large by-product stream recovered in the first separation phase.

Most of the aromatic hydrocarbons and essentially all of the olefin alkylating agent react in the alkylation reaction zone in the presence of a solid phosphoric acid catalyst to form monoalkyl aromatic compounds and polyalkyl aromatic compounds. The preferred product of the alkylation process using the solid phosphoric acid catalyst composition of the present invention is cumene.

The following examples are provided to illustrate the catalyst compositions of the present invention and the use of the catalysts and are not intended to limit the general broad scope of the invention as defined by the claims.

〔Example〕

Example I This example illustrates the general method of amorphous phosphoric acid catalyst extrusion, that is, crystals of solid phosphoric acid catalyst with different coarse pore volumes by the various calcination methods of the following examples. Converted to form.

Diatomaceous earth and phosphoric acid having a P ₂ O ₅ content of 82% or more are mixed in a weight ratio of 1: 2 at a temperature of 170 ° C. This raw material is extruded by an extruder through an extrusion production mold having a diameter of about 5 mm.
Only materials with amorphous properties were detected by X-ray analysis of the green extrudate. The extrudates produced in this way are
Used in the burning examples described in II or V. Baked condition is 100
C. to 500.degree. C., humidity of 0 to 25 mol% based on total vapor level in the furnace, total time in the range of 20 to 120 minutes. The final catalyst is analyzed for porosity and pore volume distribution.
Pore volume distribution is measured on a Micromeritic Autopore 9220 by mercury insertion.

Example II This example highlights the effect of various firing conditions on the porosity and pore volume distribution of solid phosphoric acid catalysts. Example 1
100 batches of amorphous solid phosphoric acid green extrudate from
Subject to a baking process in a small furnace in batches of up to 150 g.
The furnace is vented at one time and steam is equipped with closing means for adjusting the furnace temperature as well as means for adding at a controlled rate. After about 50 minutes under only 3% steam level in the furnace preheated to 392 ° C furnace temperature, the catalyst was removed and its porosity was analyzed. The calcined catalyst had a total pore volume of 0.236 cc / g and a coarse pore volume (pore volume above 10,000) of 0.071 cc / g was measured by mercury insertion. This gives a coarse pore volume of 30% of the total pore volume. This catalyst does not meet the definition of catalyst of the invention.

A second batch of amorphous solid phosphoric acid green extrudate from Example I was subjected to the firing process in a small kiln similar to that in Example II. Approximately 5% at 14% steam in a furnace preheated to 430 ° C
The catalyst was removed and analyzed for porosity with 0 minutes followed by 22% steam addition for 20 minutes. The total pore volume of 0.239 cc / g and the coarse pore volume (pore volume of 10,000 or more) 0.035 cc / g were measured by the mercury insertion method. This coarse pore volume represented 15% of the total pore volume. This catalyst falls within the porosity / pore volume distribution of the catalyst of the present invention. As is apparent from this example, the ratio of steam to burnt area is necessary for the production of the catalyst of the present invention having porosity and pore volume distribution.

Example III A number of solid phosphoric acid catalysts were prepared as described in Example I and analysis of total pore volume and pore volume distribution was performed by the mercury insertion method. The results of this analysis can be found in Table 1 below.

The analyzed catalysts were run under pressure by placing the catalyst in an olefin polymerisation process with a post propylene feed, hydrocarbon feed air velocities of 1.8 to 2.1, and temperatures of 150 to 230 ° C. The tests were carried out in a normally operating plant producing commercial products. All catalyst life values were recorded in comparison with catalyst E, the catalyst with the shortest life. The end of the catalyst life is determined by when the pressure drops across the catalyst bed and the continuous process becomes too large.

The above data show that there is a clear correlation between catalyst life and volume percentage of pores of 10,000 or more in the solid phosphoric acid catalyst. This correlation indicates that the lower the percentage of catalyst volume containing 10,000 or more pores in diameter, the longer the catalyst life.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (8)

[Claims] 1. A pore volume of all catalysts containing phosphoric acid and an inorganic oxide binder characterized in that the pore volume of pores having a diameter of 10,000 liters or more is 17.5% or less of the total pore volume of the catalyst. Is 0.
A porous solid phosphoric acid catalyst for converting hydrocarbons of 24 cc / g or less. 2. The porous solid phosphorus for hydrocarbon conversion according to claim 1, wherein the inorganic oxide binder is a siliceous substance selected from diatomaceous earth, artificially produced porous silica and a mixture thereof. Acid catalyst. 3. Hydrocarbons are obtained by contacting the porous solid phosphoric acid catalyst according to claim 1 or 2 with a hydrocarbon raw material in the presence of a porous solid phosphoric acid catalyst under hydrocarbon conversion conditions under hydrocarbon conversion conditions. How to convert. 4. The method of claim 3 wherein the hydrocarbon conversion is a method of alkylating an aromatic hydrocarbon with an olefinic agent. 5. Hydrocarbon conversion at a temperature of 100 ° to 390 ° C.,
4. The method according to claim 3, wherein the conditions include a pressure of 1 to 130 atm and a space velocity of the liquid of 0.5 to 50 hr ⁻¹ per hour. 6. A process according to claim 4, characterized in that the alkylation of the aromatic hydrocarbons takes place in liquid phase with the olefin-acting agent. 7. A process according to claim 3, wherein the hydrocarbon conversion is carried out under catalytic conditions such that the feed stream olefinic hydrocarbons control the production of oligomeric products. 8. Process according to claim 7, characterized in that the hydrocarbon conversion conditions comprise a temperature of 140 to 290 ° C. and a pressure of 6 to 102 atm.