JPS6154838B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the production of atmospheric hydrocarbon oil distillates from one or more hydrocarbon residues obtained by vacuum distillation.

In the atmospheric distillation of crude mineral oils, which are applied on a large scale in refineries for the production of atmospheric distillates, residual oil is obtained as a by-product. In order to increase the yield of atmospheric distillate from the crude oil concerned, the vacuum distillate can be separated from the residual oil by vacuum distillation, but this vacuum distillate can be separated by a relatively simple method. to one or more atmospheric distillates, for example by catalytic cracking or hydrogenolysis. Just as in atmospheric distillation, residual oil is obtained as a by-product of vacuum distillation. In some cases, this residual oil is suitable for use as a starting material for the production of residual lubricating oils, but usually the oils have high vanadium and high nickel contents and high Conradson Carbon Test Values (CCT). and is only marginally suitable for use as a fuel oil component.

In view of the increasing demand for atmospheric distillates, attempts have been made in the past to convert vacuum residues to atmospheric distillates, for example by catalytic cracking or hydrogenolysis. The use of vacuum residues produced as feeds for these processes has significant drawbacks that make their application on a commercial scale out of the question. Thus, for example, the main drawbacks of catalytic cracking of vacuum residues are that the catalyst consumption is very high and, due to the very high coke and gas yields, low yields of atmospheric distillate are obtained. Hydrogenolysis of vacuum residues involves very rapid catalyst deactivation, very high gas outputs and very high hydrogen consumption.

Considering the above aspects and the fact that in the atmospheric distillation of crude mineral oils and their processing to atmospheric distillate via vacuum distillation in combination with the conversion of the vacuum distillate, considerable amounts of vacuum residue are obtained as by-products. It will become clear that there is an urgent need for a process that provides the possibility of converting these vacuum residues into atmospheric distillates, such as gasoline, in an economically justified manner.

Since catalytic cracking has in practice proven to be an excellent process for the conversion of heavy hydrocarbon oil distillates, such as vacuum gas oil, to light distillates, such as gasoline, the applicant has carried out research to We sought to discover how widespread catalytic cracking applications can be achieved in the conversion of vacuum residues. It has been found that a suitable combination of catalytic cracking as the main step and catalytic hydrogenation and deasphalting as auxiliary steps makes it possible to realize a process that is very suitable for this purpose. The present patent application relates to such a method.

In the method of the invention, the hydrocarbon oil residue obtained by vacuum distillation is subjected to a catalytic hydrogenation treatment,
The hydrotreated product is separated by distillation into one or more atmospheric distillates and a residue. At least a portion of the residue is separated by deasphalting into deasphalted oil and asphalt. The deasphalted oil is converted to one or more atmospheric distillates by catalytic cracking, and at least 50% by weight of asphalt is redirected to a catalytic hydrogenation process. Fresh feed for catalytic cracking is 10ppmw
It must have a lower total palladium and nickel content and a CCT lower than 3% by weight. The catalytic hydrogenation treatment has an average temperature of 375 to 475
°C, hydrogen partial pressure 25 to 300 bar, space velocity 0.1 to 3.0 kg. 1 ^-1 .h ^-1 and hydrogen/feed ratio 250
to 2500 N1.Kg ^-1 , in which case the above hydrogenation conditions result in (a) more than 50% by weight of the asphalt present in the catalytic hydrogenation feed being non-asphaltic compounds (hydrogenated (b) the liquid reaction product of the catalytic hydrogenation process is , a total vanadium and nickel content of less than 25% of that of the feed for catalytic hydrogenation and less than 50% of that of said feed.
Has CCT.

In the process of the present invention, catalytic cracking of deasphalted oil is used as the main method. This process converts a significant portion of the oil to the desired atmospheric distillate. One or more atmospheric distillates are separated from the decomposition products as a final product by distillation. In order to increase the yield of atmospheric distillate, preferably at least a portion of the residue obtained from the distillation is recycled to the catalytic cracker. Although the catalytic cracking process is preferably carried out in the presence of a zeolite type catalyst, coke is deposited on the catalyst. This coke is removed from the catalyst by combustion during a catalyst regeneration stage combined with catalytic cracking, resulting in an exhaust gas comprising carbon monoxide and carbon dioxide. Catalytic cracking is preferably carried out at an average temperature of 400 to 550°C, in particular 450 to 525°C, a pressure of 1 to 10 bar, in particular 1.5 to 7.5 bar, 0.25 to 4 Kg/Kgh, in particular 0.5 to 2.5 Kg/Kgh. and a catalyst feed rate of 0.1 to 5, in particular 0.2 to 2, tons per 1000 tons of feed. In the process of the invention, the fresh feed to the catalytic cracker consists of at least a portion of the oil obtained by deasphalting the distillation residue of the hydrotreated product, which
It has a total vanadium nickel content and CCT of less than 10 ppmw and 3% by weight.

In the process of the invention, the distillation residue of the hydrotreated product is subjected to deasphalting as an auxiliary step. Deasphalting is preferably carried out at high temperature and pressure in the presence of lower hydrocarbons such as propane, butane or pentane. At least 50% by weight of the asphalt separated from the oil during deasphalting is redirected to a catalytic hydrogenation process.

In the process of the invention, the mixture of vacuum residue and asphalt is subjected to a catalytic hydrogenation treatment as a further auxiliary step. The catalytic hydrogenation process (a) converts more than 50% by weight of the asphalt present in the catalytic hydrogenation feed to non-asphaltic compounds; and (b) the catalytic hydrogenation process converts the feed into must be carried out under conditions such that more than 75% of the total amount of vanadium nickel is removed from the feed and the reduction in CCT of the feed is more than 50%. The catalytic hydrogenation treatment is preferably carried out in a two-stage process, and the actual conversion of asphalt carried out in the second stage is preceded by a catalytic hydrogenation treatment mainly aimed at reducing the metal content of the feed to be converted. urge Suitable catalysts for use in the one-stage catalytic hydrogenation process as well as the second stage of the two-stage catalytic hydrogenation process include a metal having one or more hydrogenation activities on a support consisting of 40% by weight or more of alumina. It is a catalyst consisting of Suitable catalysts for use in the first stage of the two-stage catalytic hydrogenation process are catalysts comprising 80% by weight or more of silica. Contact hydrogenation treatment at average temperature as much as possible
390 to 450°C, hydrogen partial pressure 50 to 200 bar,
Space velocity 0.2 to 1.0Kg/lh and hydrogen supply rate
It is recommended to carry out at 500 to 2000N/Kg.

The hydrotreated product is separated by distillation into one or more atmospheric distillate and atmospheric residue suitable as the final product. Catalytically cracked deasphalted oil can be produced from the atmospheric residue.
The atmospheric residue is preferably separated by distillation into a vacuum distillate and a vacuum residue, and the deasphalted oil is separated from the vacuum residue. An atmospheric residue can be produced from the vacuum distillate by catalytic cracking or hydrogenolysis. If an atmospheric distillate is to be produced from a vacuum distillate of a hydrogenated product by catalytic cracking, the cracking operation is preferably carried out in an apparatus in which deasphalted oil is also cracked.

The process of the invention is highly suitable for use as part of a broader process for producing atmospheric hydrocarbon oil distillates from atmospheric distillation residues. Such a method may be implemented as follows. The atmospheric distillation residue is separated by vacuum distillation into a vacuum distillate and a vacuum residue. The desired atmospheric hydrocarbon oil distillate is prepared from the vacuum distillate by catalytic cracking or hydrogenolysis and from the vacuum residue of the present invention. If an atmospheric distillate is to be produced from a vacuum distillate by catalytic cracking, the cracking operation is preferably carried out in an apparatus in which the deasphalted oil and optionally the vacuum distillate of the hydrogenated product are also cracked. It's good to do that. If desired, the two vacuum distillates may be hydrogenolyzed together.

The process according to the invention can be used exclusively for the production of one or more light atmospheric distillates as the final product, or also for the production of one or more light atmospheric distillates together with one or more intermediate distillates as the final product. Both are also suitable for producing distillates. If the purpose is to produce exclusively one or more light distillates as the final product, the initial boiling point is greater than or equal to the final boiling point of the heaviest light distillate desired to be separated from the cracked products. Intermediate atmospheric distillates having . In addition to the vacuum distillate of the hydrogenated product, there are intermediate atmospheric distillates to be separated from the hydrogenated product that have an initial boiling point higher than the final boiling point of the desired heaviest and lightest distillate. In this case too, it is suitable for use as a feed component for a single cracker.

The process scheme for the conversion of atmospheric hydrocarbon oil residues into light hydrocarbon oil distillates is explained in more detail below with reference to the accompanying drawings, to which the invention is not limited.

The method sequentially comprises a first vacuum distillation section 1, a catalytic hydrogenation section 2, a first atmospheric distillation section 3, a second vacuum distillation section 4, a deasphalting section 5, a catalytic cracking section 6 and a second atmospheric distillation section. It is carried out in an apparatus comprising part 7. The hydrocarbon oil residue 8 obtained by atmospheric distillation is separated into a vacuum distillate 9 and a vacuum residue 10 by vacuum distillation. vacuum residue 10
is mixed with asphalt 11 and the mixture 12 is directed to a catalytic hydrogenation process along with a hydrogen stream 13. substantially
After separation of the gas stream 14 consisting of C ₄ -hydrocarbons and H ₂ S, the liquid reaction product 15 is separated by atmospheric distillation into a gasoline fraction 16 and a medium distillate fraction 17.
and residue 18. Residue 18 is separated by vacuum distillation into vacuum distillate 19 and vacuum residue 20. Vacuum residue 20 is separated by deasphalting into deasphalted oil 21 and asphalt 22. The asphalt 22 separates into two parts having the same composition 11 and 23. Deasphalted oil 21 consists of two vacuum distillates 9
and 19 and intermediate distillate fraction 17 to form fresh cracked feed 24. The fresh cracked feed 24 is mixed with the intermediate distillate cut 25 and the mixture is catalytically cracked. Catalyst regeneration in the catalytic cracker results in a waste gas 26 containing carbon monoxide and carbon dioxide. Catalytic cracking product 27 is separated by atmospheric distillation into C ₄ - fraction 28, gasoline fraction 29, intermediate distillate fraction 25, and residue 30 is a mixture of heavy cycle oil and slurry oil. .

The invention will now be further illustrated by the following examples without limiting the invention.

EXAMPLE The method of the invention was applied to the atmospheric distillation residue of crude oil from the Middle East. The atmospheric distillation residue has an initial boiling point of 370℃
It had The method was carried out according to the attached process plan. The following conditions were applied in various parts.

Catalytic cracking uses a zeolite catalyst and
It was carried out at 490° C., a pressure of 2.2 bar and a space velocity of 2 Kg/Kgh.

The catalytic hydrogenation process uses a Ni/V/SiO ₂ catalyst comprising 0.5 pbw nickel and 2 pbw vanadium per 100 pbw silica in the first stage and in the second stage.
The stage consists of Ni/containing 4 pbw nickel and 11 pbw molybdenum per 100 pbw alumina.
It was carried out in two steps using Mo/Al ₂ O ₃ . The first stage of the catalytic hydrogenation process was carried out at an average temperature of 407° C., a hydrogen partial pressure of 150 bar, a space velocity of 0.5 Kg/lh and a hydrogen feed ratio of 1000 N/Kg. The second stage of catalytic hydrogenation treatment has an average temperature of 425°C, hydrogen partial pressure of 150 bar, space velocity of 0.65 Kg/lh and hydrogen supply ratio of 1500 N/Kg.
It was carried out in

Deasphalting was carried out at 145° C. and 41 bar with butane as solvent and a solvent/oil weight ratio of 4:1.

370℃ ⁺ atmospheric distillation residue 8 as starting material
For 100 pbw, the amounts of the various streams were: 56.0 pbw 370-520°C vacuum distillate 9, 44.0 pbw 520°C vacuum residue 10, from this
21.0 pbw asphalt at 145 °C and 41 bar with butane as solvent and solvent/oil weight ratio 4:
It could be obtained by removing asphalt in step 1.

51.2 pbw mixture 12 with a total vanadium and nickel content and CCT of 125 ppmw and 26% by weight respectively, 1.3 pbw hydrogen 13, 3.8 pbw C ₄ ^- - fraction + H ₂ S 14, 48.7 pbw liquid product 15, with a total vanadium and nickel content and CCT of 4.1 ppmw and 9.2% by weight, respectively; 4.6 pbw C ₅ -200 °C gasoline fraction 16; 6.7 pbw 200-300 °C intermediate distillate fraction 17; 37.4pbw370℃ ⁺ residue 18, 7.7pbw370~520℃ vacuum distillate 19, 29.7pbw520℃ residue 20, 22.1pbw deasphalted oil 21, 7.6pbw asphalt 22, 7.2pbw part 11, 0.4pbw part 23, 92.5p bw Fresh cracked feed 24, for which total vanadium and nickel content and CC
T. with 1.2 ppmw and 1.4 wt% respectively, 51.4 pbw _C5-200 °C gasoline fraction 29, 15.0 pbw 200-370°C intermediate distillate fraction 25, and 14.5 pbw 370°C residue 30.

[Brief explanation of the drawing]

The figure is a process diagram of the present invention. 1, 4...Vacuum distillation section, 3, 7...Normal pressure distillation section, 2...Catalytic hydrogenation treatment section, 5...Deasphalt removal section, 6...Catalytic cracking section.

Claims (1)

[Scope of Claims] 1. Subjecting the vacuum residue to a catalytic hydrogenation treatment, separating the hydrogenated product by distillation into one or more atmospheric distillates and a residue, at least a portion of the residue. into deasphalted oil and asphalt by deasphalting, converting the deasphalted oil to one or more atmospheric distillates by catalytic cracking, and converting at least one of the asphalts into one or more atmospheric distillates by catalytic cracking.
50 wt.% is again subjected to catalytic hydrogenation treatment, the fresh feed for the catalytic cracker has a total vanadium and nickel content of less than 10 ppmw and a CCT of less than 3 wt.%, and the catalytic hydrogenation treatment is carried out at an average temperature of 375
to 475°C, hydrogen partial pressure 25 to 300 bar, space velocity 0.1 to 3.0 kg. 1 ^-1 .h ^-1 and a hydrogen/feed ratio of 250 to 2500 N1.Kg ^-1 , in which case the above hydrogenation conditions result in (a) asphalt present in the catalytic hydrogenation feed; (b) the liquid reaction product of the catalytic hydrogenation contains less than 25% of that of the catalytic hydrogenation feed of vanadium and nickel; A process for the production of one or more atmospheric hydrocarbon oil distillates, characterized in that they have a total content and a CCT of less than 50% of that of the feed. 2. The method according to claim 1, wherein at least a portion of the residue obtained by atmospheric distillation of the catalytic cracking product is recycled to the catalytic cracking apparatus. 3 Catalytic cracking at an average temperature of 400 to 550℃ and a pressure of 1
to 10 bar, space velocity 0.25 to 4 Kg/Kgh,
3. Process according to claim 1, characterized in that it is carried out with 0.1 to 5 tons of catalyst per 1000 tons of catalytic make-up rate feed. 4 80% by weight in the first stage of catalytic hydrogenation treatment
In the second stage of the catalyst made of the above silica,
It is carried out as a two-step process using a catalyst comprising one or more metals with hydrogenation activity on a support consisting of more than 40% by weight of alumina. The method described in any of paragraph 3. 5 Separation of the hydrotreated product into one or more atmospheric distillate, vacuum distillate and vacuum residue by distillation, and separation of the vacuum residue into a deasphalted oil and asphalt by deasphalting. death,
Claims 1 to 4 are characterized in that the atmospheric distillate is produced from deasphalted oil by catalytic cracking, and the vacuum distillate is produced by catalytic cracking or hydrogen cracking. the method of. 6 Hydrogenated product - production of atmospheric distillate from vacuum distillate is carried out in an apparatus which also performs deasphalting oil cracking by catalytic cracking. Method. 7 producing one or more atmospheric distillates from an atmospheric hydrocarbon oil residue, separating the atmospheric distillate by vacuum distillation into a vacuum distillate and a vacuum residue; and further producing one or more atmospheric distillates by vacuum distillation. 7. The method according to claim 1, wherein the atmospheric distillate is produced from the vacuum distillate by catalytic cracking or hydrogen cracking. 8. Claim 7, characterized in that the production of the atmospheric distillate from the vacuum distillate is carried out by catalytic cracking in an apparatus that also cracks deasphalted oil.
The method described in section. 9. The method according to claim 7, characterized in that the vacuum distillate is hydrogenolyzed together with the vacuum distillate of the hydrogenated product.