CN1181163C - Combination type method for catalyzing and transfering hydrocarbon oil - Google Patents

Combination type method for catalyzing and transfering hydrocarbon oil Download PDF

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CN1181163C
CN1181163C CNB02120781XA CN02120781A CN1181163C CN 1181163 C CN1181163 C CN 1181163C CN B02120781X A CNB02120781X A CN B02120781XA CN 02120781 A CN02120781 A CN 02120781A CN 1181163 C CN1181163 C CN 1181163C
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catalyst
oil
reactor
districts
reaction
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CN1462793A (en
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李松年
侯栓弟
许克家
汪燮卿
钟孝湘
武雪峰
何俊
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The present invention relates to a combination method for catalyzing and transforming hydrocarbon oil. The present invention comprises the following procedures that (a) a preheated hydrocarbon oil raw material is injected into a descending reactor (11) to touch a catalyst in the reactor; the hydrocarbon oil raw material and the catalyst react under the catalytic cracking condition, and a generated oil solvent mixture enters a first region of a fluidized bed reactor (13); (b) part of regenerated catalysts enter the first region of the fluidized bed reactor (13) after being cooled to 250 to 350DEGC by a cooler (12) to react with the oil solvent mixture from the procedure (a) under the conditions of the temperature of 300 to 400 DEG C, the pressure of 0.2 to 0.3MPa and a solvent and oil ratio of 10 to 20; (c) the catalyst deposited with carbon overflows to enter a secondary region after reacting in the first region of the fluidized bed reactor (13), and reaction oil gas carried by the catalyst is stripped in the secondary region; (d) the stripped catalyst enters a third region by a bottom of a cambered partition board between the secondary region and the third region of the fluidized bed reactor, the stripped catalyst is led out by the catalyst on the third region to be conveyed to a regenerator (14) to be scorched and regenerated, and the regenerated catalyst is recycled.

Description

A kind of combination type method for catalyzing and transfering hydrocarbon oil
Technical field
The present invention relates to the catalysis conversion method of petroleum hydrocarbon under the situation that does not have hydrogen, more particularly, is a kind of knockdown catalytic conversion method of hydrocarbon oil.
Background technology
In order to make full use of petroleum resources, many countries research and develop the catalytic cracking technology of heavy feed stocks such as handling long residuum, vacuum residuum one after another, and this is an important method that improves the refinery economic benefit.But because the difficult cracking of residual oil, transformation efficiency and raising vapour, diesel yield for improving residual oil all improve temperature of reaction usually.The result who improves temperature of reaction is vapour, diesel oil olefin(e) centent height, the stability variation of oil product; In addition because the sulphur content height of residual oil, so the sulphur content of vapour, diesel oil is also higher.The method of head it off mainly is by the back end hydrogenation processing of oil product or by catalytic cracking and hydrogenation combination technique, as the method for being introduced among the USP6123830 at present.The result who does has like this improved cost, has lost the octane value of gasoline.
Aspect structure of reactor, people such as Zhang Jianfang propose with two up-downgoings (U type) reaction tubes reactors in series technology (CN2214222Y) and two straight riser tube serial connection technologies (CN2380297Y) to improve catalytic cracking reaction, improve yield of light oil, reduce gas, coke productive rate, because what their fluidized-bed reactor all adopted is tubular reactor, and temperature of reaction is higher, its role is to further carry out catalytic cracking reaction, because two reactors are arranged, can control the reaction conditions of two reactors respectively, reach the purpose of best lightweight oil productive rate.
The two-stage catalytic cracking technology (USP5401387) of U.S. Mobil company is that feed stock conversion carries out fractionation below 50% in control first reactor, and the cut of its initial boiling point>650 enters second catalyst cracker, and further cracking is a lightweight oil.Purpose also is to improve the lighter products yield.
The two-stage catalytic cracking technology (ART) that the eighties, Engelhard company proposed is actual to be that heavy feed stock is carried out removing heavy-metal and decarburization, promptly with there not being active thermal barrier to carry out removing heavy-metal and gum-treated substantially, its reacted mink cell focus enters catalyst cracker again and carries out catalytic cracking reaction.
The bottom at riser reactor that American UOP company proposes is provided with a fluidized bed reaction zone, and stock oil is introduced this fluidized-bed, and reaction product is drawn by this fluidized-bed top and entered the back tripping device in step.The catalyzer of this fluidized bed reaction zone is directly come by revivifier or introduces the part reclaimable catalyst, but temperature of reaction is all than higher, and purpose improves oil product and as the yield (USP5965012) of the light olefin of industrial chemicals.
What U.S. Texaco company proposed draws a part of regenerated catalyst with the preheating of part material oil, catalyst reaction after the part of vaporization enters this and is cooled product is later delivered to fractionation plant, and Qi Hua raw material does not enter riser reactor as the main reaction region of device with catalyzer and hot regenerated catalyst.The purpose of this double-reaction area all is for improving catalytic cracking reaction handiness and selectivity (USP4725408).
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of knockdown petroleum hydrocarbon catalytic conversion method, distribute, improve product quality to improve product.
Method provided by the invention may further comprise the steps:
(a) hydrocarbon oil crude material after the preheating injects down-flow reactor 11, contacts with catalyzer in it, and reacts under catalytic cracking condition, and the finish mixture that is generated enters a district of fluidized-bed reactor 13;
(b) the partial regeneration catalyzer is cooled to a 250-350 ℃ of laggard district of going into fluidized-bed reactor 13 through water cooler 12, mixes to be incorporated under the condition that 300-400 ℃, 0.2-0.3MPa, agent-oil ratio are 10-20 with finish mixture from step (a) and reacts;
(c) the catalyzer overflow of carbon deposit enters two districts behind fluidized-bed reactor 13 1 district's internal reactions, and the reaction oil gas that stripping catalyst is carried secretly in two districts;
(d) catalyzer behind the stripping enters three districts by the bottom of the arc-shaped partition between the He San district, fluidized-bed reactor two district, draws, sends into revivifier 14 coke burning regenerations by the catalyst outlet on top, three districts again, and the catalyst recirculation after the regeneration is used.
Compared with prior art, adopt method provided by the invention can make dry gas yied reduce 8.87%, liquefied gas yield reduces 2.71%, vapour, diesel yield increase by 1.45 units, diesel and gasoline ratio improves, coke yield reduces, content of olefin in gasoline is reduced to 24.28% by 42.59%, aromaticity content is increased to 27.33% by 22.16%, gasoline octane rating reduces all in 1 unit, breakdown time is increased to 587 minutes, and sulfur in gasoline content drops to 52ppm by 141ppm, and the solar oil sulphur content drops to 158ppm by 312ppm.
Enter the cold catalyzer in 250~350 ℃ in fluidized-bed reactor one district, its objective is the contact, the reinforcement reaction that reduce temperature of reaction, rising agent oil ratio, increase finish.The main effect of fluidized-bed reactor is at a lower temperature, mainly petroleum naphtha, solar oil cut are carried out selectivity hydrogen transference and isomerization, aromatization and desulphurization reaction, to reduce olefin(e) centent and the sulphur content in vapour, the diesel oil, improve the quality and the stability of vapour, diesel oil.The catalytic cracking reaction that carries out in first reactor is typical thermo-negative reaction, need the catalyzer of comparatively high temps that more heat is provided, and the selectivity hydrogen transfer reactions that fluidized-bed reactor carries out is thermopositive reaction, requirement is than demulcent temperature and less heat, and two reactors adapt to different reaction requirements respectively.
Two reactors directly closely link to each other, under different reaction conditionss, finish two and require different reaction contents, promptly regulate and control temperature, catalyst in reactor reserve, the density of two reactors independently, the different agent-oil ratio that the different reaction times is required with reaction.
Add in the fluidized-bed reactor through cooled regenerated catalyst (250~350 ℃), temperature of reaction is reduced to 300~400 ℃, stop catalytic cracking reaction rapidly, realize the selectivity hydrogen transfer reactions of vapour, diesel oil and vapour, diesel fuel desulfurization reaction simultaneously, to improve the lightweight oil productive rate and to improve vapour, diesel quality, reduce olefin(e) centent and sulphur content.This fluidized-bed reactor is to reduce temperature by introducing cooled regenerated catalyst, has strengthened the agent-oil ratio of selectivity hydrogen transfer reactions in the fluidized-bed reactor simultaneously, improves reaction efficiency.
Description of drawings
Fig. 1 is the structural representation of down-flow reactor involved in the present invention.
Fig. 2 is the schematic flow sheet that the invention provides method.
Fig. 3 is the structural representation of fluidized-bed reactor involved in the present invention.
Embodiment
The structure of down-flow reactor of the present invention as shown in Figure 1.This reactor mainly comprises with lower member: catalyst transport (1), reactor head (2), raw material nozzles (3), reactor outer cylinder body (6), promote dielectric distribution device (8), descending reaction tubes (9) in advance; Wherein, descending reaction tubes (9) and the vertically coaxial setting of reactor outer cylinder body (6); The upper end of outer cylinder body is connected with top cover (2) is along the circumferential direction airtight, and the cavity that is positioned at descending reaction tubes inlet top that is constituted is atomizing raw materials chamber (5), and the bottom of outer cylinder body is connected with the outer wall of descending reaction tubes is airtight; Descending reaction tubes epimere is positioned at reactor outer cylinder body inside, and its hypomere is stretched out by the bottom of outer cylinder body; Raw material nozzles (3) is arranged on the top cover (2); Catalyst transport (1) is fixedlyed connected with outer cylinder body, and is connected with the pre-lifting zone of ring catalyst (7) that outer cylinder body and descending reaction tubes are constituted; Pre-lifting dielectric distribution device (8) is arranged on the bottom of the pre-lifting zone of catalyzer.This down-flow reactor has been applied for Chinese patent, and application number is 02116925.X.
With arc-shaped partition this reactor is divided into as shown in Figure 3 three zones that interconnect, i.e. a district, He San district, two districts in the fluidized-bed reactor of the present invention.One district is a reaction zone, and two districts are stripping zone, and three districts are for flowing out the district.The ratio of the cross-sectional area in one district, He San district, two districts is 20-16: 6-4: 1, and preferred 18-16: 5-4: 1.Arc-shaped partition between one district and two districts separates fully from bottom Jiang Yi district and two districts, and the top is submerged in the fluidized-bed, is connected by the fluidized-bed top.The bottom of the arc-shaped partition between two districts and three districts is connected, and this dividing plate exceeds fluidized-bed top bed surface, is connected with two districts with a district from this arc-shaped partition top to prevent catalyzer, and the catalyzer short circuit takes place.The surfaces externally and internally of two arc-shaped partitions all sprays nonmetal wear-resisting thermofin.
Catalyzer of the present invention can be selected from the catalytic cracking catalyst of any routine, and the activity of such catalysts component can be selected from: ZSM-5 series zeolite, REY, REHY, REUSY, USY and they one or more the mixture in the zeolite of physics or chemical process modification.For example, can adopt with zeolites such as rare-earth five-membered ring supersiliceous zeolite, REY and high silicon Y is the catalyzer of active ingredient.
Hydrocarbon oil crude material of the present invention is selected from: the mixture of one or more in decompressed wax oil, wax tailings, hydrocracking tail oil, deasphalted oil, long residuum, vacuum residuum and the crude oil.The present invention is specially adapted to heavy catalytically cracked materials such as long residuum, vacuum residuum.
In down-flow reactor of the present invention, the reaction conditions of hydrocarbon oil crude material is as follows: temperature of reaction 490-600 ℃, and preferred 500-530 ℃; Reaction pressure 0.2-0.3Mpa, preferred 0.2-0.25Mpa; The weight ratio of catalyzer and stock oil is 3-10, preferred 6-8; Reaction times 1-5 second, preferred 2-4 second.
In fluidized-bed reactor of the present invention one district, the reaction conditions of hydrocarbon oil crude material is as follows: temperature of reaction is 300-400 ℃, preferred 350-400 ℃; Reaction pressure is 0.2-0.3Mpa, preferred 0.2-0.25Mpa; The weight ratio of catalyzer and stock oil is 10-30, preferred 14-25; Weight hourly space velocity is 10-50h -1Preferred 12-30h -1
The operational condition of revivifier of the present invention is as follows: 670-750 ℃ of revivifier dense-phase bed temperature, regeneration pressure 0.26-0.34MPa.
Further specify method provided by the present invention below in conjunction with accompanying drawing, but therefore the present invention is not subjected to any restriction.
As shown in Figure 2, hydrocarbon oil crude material after the preheating injects in the down-flow reactor 11, contact, react with the regenerated catalyst in it, reaction oil gas and mixture of catalysts enter a district of fluidized-bed reactor 13 through descending reaction tubes, and reduce to 250-350 ℃ regenerated catalyst with temperature after catalyst cooler 12 coolings and mix, react in a district.Described mass rate through catalyst cooler 12 cooled regenerated catalyst is 0.6-1.5 with the ratio of the mass rate of the regenerated catalyst that enters down-flow reactor: 1, and preferred 0.8-1.2: 1.In addition, can also introduce inferior patrols such as part coker gasoline, straight-run spirit in the district,, improve low-quality quality of gasoline simultaneously to reduce temperature of reaction, for example, the olefin(e) centent of reduction coker gasoline and sulphur content etc.The injection rate of low-quality gasoline is 0.1-0.3 with the ratio of the mass rate of the hydrocarbon oil crude material that enters down-flow reactor: 1, and preferred 0.15-0.25: 1.The top overflow of the arc-shaped partition of the catalyzer of carbon deposit between a district and two districts enters two districts behind one district's internal reaction.The catalyzer of stripping reaction back carbon deposit in two districts.In order to guarantee Srteam Stripping effect, preferably introduce one hot regenerated catalyst in two districts, with the catalyst mix of reaction back carbon deposit, to improve the stripping temperature, to improve steam stripping efficiency.The mass rate of the regenerated catalyst of the heat in described introducing two districts is 0.8-1.4 with the ratio of the mass rate of the regenerated catalyst that enters down-flow reactor: 1, and preferred 0.9-1.2: 1.Enter three districts through the catalyzer behind two district's strippings by the bottom of the arc-shaped partition between two districts and three districts, the catalyst outlet by top, three districts is drawn out to revivifier 14 coke burning regenerations again.Catalyzer Returning reactor after the regeneration recycles.Reaction oil gas is sent into subsequent separation system and further is separated into various products after the cyclonic separator at fluidized-bed reactor top separates.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.The character of employed stock oil and catalyzer is listed in table 1 and table 2 respectively in the test.
Comparative Examples
This Comparative Examples adopts conventional riser catalytic cracking middle-scale device to test the test-results conduct
The benchmark of embodiment.
Main testing sequence is as follows: in the stock oil injecting lift pipe after the preheating, contacts with regenerated catalyst and reacts, and separating reaction oil gas and mixture of catalysts, reaction oil gas enters through settling vessel and further is separated into various products in the subsequent separation system.Reclaimable catalyst is sent into the revivifier coke burning regeneration behind stripping, the catalyzer Returning reactor after the regeneration recycles.Various products are measured, separate.
Main operational condition sees Table 3, and product distributes and sees Table 4.
Embodiment
This embodiment explanation: adopt method provided by the present invention can improve product and distribute, improve the quality of products.
Main testing sequence is as follows: as shown in Figure 2, hydrocarbon oil crude material after the preheating injects in the down-flow reactor 11, contact, react with the regenerated catalyst in it, reaction oil gas and mixture of catalysts enter a district of fluidized-bed reactor 13 through descending reaction tubes, and reduce to 250 ℃ regenerated catalyst with temperature after catalyst cooler 12 coolings and mix, react in a district.Ratio through the mass rate of catalyst cooler 12 cooled regenerated catalyst and the mass rate of the regenerated catalyst that enters down-flow reactor is 1: 1.The top overflow of the arc-shaped partition of the catalyzer of carbon deposit between a district and two districts enters two districts behind one district's internal reaction.The catalyzer of stripping reaction back carbon deposit in two districts.In order to guarantee Srteam Stripping effect, introduce one hot regenerated catalyst in two districts, its mass rate is 1: 1 with the ratio of the mass rate of the regenerated catalyst that enters down-flow reactor.Enter three districts through the catalyzer behind two district's strippings by the bottom of the arc-shaped partition between two districts and three districts, the catalyst outlet by top, three districts is drawn out to revivifier 14 coke burning regenerations again.Catalyzer Returning reactor after the regeneration recycles.Reaction oil gas is sent into subsequent separation system and further is separated into various products after the cyclonic separator at fluidized-bed reactor top separates.
The stock oil that embodiment adopted is all identical with Comparative Examples with catalyzer, and the concrete operations condition sees Table 3, and product distributes and to see Table 4, and table 5 and table 6 have been listed the character of product gasoline and light oil in the table 4 respectively.
Compare with Comparative Examples, under the identical situation of raw material, embodiment adopts method provided by the invention to make dry gas yied reduce 8.87%, liquefied gas yield reduces 0.41 unit (2.71%), vapour, diesel yield increases by 1.45 units, diesel and gasoline ratio brings up to 0.81 by 0.68, coke yield reduces by 0.29 unit, content of olefin in gasoline is reduced to 24.28% by 42.59%, saturated hydrocarbon content is increased to 48.20% by 34.97%, aromaticity content is increased to 27.33% by 22.16%, gasoline octane rating (MON, RON) reduce all in 1 unit, breakdown time is increased to 587 minutes, and content of sulfur in gasoline drops to 52ppm by 141ppm, and the solar oil sulphur content drops to 158ppm by 312ppm.
Table 1
Stock oil Mixing raw material
Density (20 ℃), kilogram/rice 3 906.0
Kinematic viscosity (100 ℃), millimeter 2/ second 48.09
Zero pour, ℃ 36
Carbon residue, heavy % 4.68
Elementary composition, heavy %
S/N 0.12/0.21
C/H 86.6/12.9
Heavy metal content, ppm
Nickel/iron 4.6/3.7
Copper/vanadium 0.03/0.01
Boiling range, ℃
Initial boiling point/5% 355/443
10%/30% 482/-
500 ℃ distillate v% 29.0
Table 2
Chemical constitution, heavy %
Aluminum oxide 54.2
Sodium oxide 0.03
Apparent density, kilogram/rice 3 860
Pore volume, milliliter/gram 0.26
Specific surface area, rice 2/ gram 160
Abrasion index, %/hour 1.2
Nickel contamination, ppm 469
Activity index (800 ℃, 4 hours) 63.0
Size composition, heavy %
<20 microns 3.1
The 20-40 micron 21.1
The 40-80 micron 55.5
The 80-110 micron 13.8
>110 microns 6.5
Table 3
Operational condition: Comparative Examples Embodiment
Reaction pressure, MPa (cutting off) 0.18 0.18
Regeneration pressure, MPa (cutting off) 0.22 0.22
The cracking reaction temperature, ℃ 500 500
Regeneration temperature, ℃ 705 706
The cracking reaction agent-oil ratio 6.0 6.0
Recycle ratio 0.28 0.25
Riser tube inlet flow velocity, meter per second 4.12 --
The riser tube exit velocity, meter per second 9.6 --
The fluidized-bed reaction actuator temperature, ℃ -- 350
The agent-oil ratio of fluidized-bed reactor -- 24.5
Table 4
Product distributes, heavy % Comparative Examples Embodiment
Dry gas 3.27 2.98
Liquefied gas 15.11 14.70
Gasoline 40.38 38.43
Light oil 27.54 31.03
Slurry oil 4.08 3.54
Coke 9.09 8.80
Loss 0.53 0.52
Add up to 100.00 100.00
Table 5
Character Comparative Examples Embodiment
Density (20 ℃), kilogram/rice 3 718.8 720.8
RON/MON 90.2/80.1 89.7/79.4
Inductive phase, minute 268 587
Existent gum, milligram/100 milliliters <2.0 <2.0
Sulphur content, ppm 141 52
Nitrogen content, ppm 57 39
Group composition, heavy %
Stable hydrocarbon 34.97 48.20
Alkene 42.59 24.28
Aromatic hydrocarbon 22.16 27.33
Boiling range, ℃
Initial boiling point/10% 39/58 40/57
50%/90% 97/176 98/175
Do 198 201
Table 6
Character Comparative Examples Embodiment
Density (20 ℃) kilogram/rice 3 869.4 871.2
Zero pour ℃ -13.0 -11.0
Existent gum, milligram/100 milliliters 241.0 163.0
Sulphur content, ppm 312 158
Basic nitrogen, ppm 144 101
Boiling range, ℃
Initial boiling point 201 203
10% 223 226
50% 268 271
90% 329 331
Do 341 343

Claims (10)

1, a kind of combination type method for catalyzing and transfering hydrocarbon oil, it is characterized in that this method may further comprise the steps: (a) hydrocarbon oil crude material after the preheating injects down-flow reactor (11), contact with the catalyzer in it, and under catalytic cracking condition, react, the finish mixture that is generated enters a district of fluidized-bed reactor (13);
(b) the partial regeneration catalyzer is cooled to a 250-350 ℃ of laggard district of going into fluidized-bed reactor (13) through water cooler (12), mixes to be incorporated under the condition that 300-400 ℃, 0.2-0.3MPa, agent-oil ratio are 10-20 with finish mixture from step (a) and reacts;
(c) the catalyzer overflow of carbon deposit enters two districts behind fluidized-bed reactor (13) one district's internal reactions, and the reaction oil gas that stripping catalyst is carried secretly in two districts;
(d) catalyzer behind the stripping enters three districts by the bottom of the arc-shaped partition between the He San district, fluidized-bed reactor two district, draws, sends into revivifier (14) coke burning regeneration by the catalyst outlet on top, three districts again, and the catalyst recirculation after the regeneration is used.
2, according to the method for claim 1, it is characterized in that described down-flow reactor comprises with lower member: catalyst transport (1), reactor head (2), raw material nozzles (3), reactor outer cylinder body (6), promote dielectric distribution device (8), descending reaction tubes (9) in advance; Wherein, descending reaction tubes (9) and the vertically coaxial setting of reactor outer cylinder body (6); The upper end of outer cylinder body is connected with top cover (2) is along the circumferential direction airtight, and the cavity that is positioned at descending reaction tubes inlet top that is constituted is atomizing raw materials chamber (5), and the bottom of outer cylinder body is connected with the outer wall of descending reaction tubes is airtight; Descending reaction tubes epimere is positioned at reactor outer cylinder body inside, and its hypomere is stretched out by the bottom of outer cylinder body; Raw material nozzles (3) is arranged on the top cover (2); Catalyst transport (1) is fixedlyed connected with outer cylinder body, and is connected with the pre-lifting zone of ring catalyst (7) that outer cylinder body and descending reaction tubes are constituted; Pre-lifting dielectric distribution device (8) is arranged on the bottom of the pre-lifting zone of catalyzer.
3,, it is characterized in that the ratio of the cross-sectional area in described fluidized-bed reactor Nei Yi district, He San district, two districts is 20-16: 6-4: 1 according to the method for claim 1.
4,, it is characterized in that the arc-shaped partition between a described district and two districts separates fully from bottom Jiang Yi district and two districts, and the top is submerged in the fluidized-bed according to the method for claim 1 or 3; The bottom of the arc-shaped partition between two districts and three districts is connected, and this dividing plate exceeds fluidized-bed top bed surface.
5,, it is characterized in that the surfaces externally and internally of described arc-shaped partition sprays nonmetal wear-resisting thermofin according to the method for claim 4.
6, according to the method for claim 1, it is characterized in that described activity of such catalysts component is selected from: ZSM-5 series zeolite, REY, REHY, REUSY, USY and they one or more the mixture in the zeolite of physics or chemical process modification.
7,, it is characterized in that described hydrocarbon oil crude material is selected from: the mixture of one or more in decompressed wax oil, wax tailings, hydrocracking tail oil, deasphalted oil, long residuum, vacuum residuum and the crude oil according to the method for claim 1.
8, according to the method for claim 1, it is characterized in that the reaction conditions of described hydrocarbon oil crude material in down-flow reactor is temperature of reaction 490-600 ℃, reaction pressure 0.2-0.3Mpa, the weight ratio of catalyzer and stock oil is 3-10, reaction times 1-5 second.
9, according to the method for claim 1, the operational condition that it is characterized in that described revivifier is 670-750 ℃ of a revivifier dense-phase bed temperature, regeneration pressure 0.26-0.34MPa.
10,, it is characterized in that in described step (c), entering by bottom, two districts, with the catalyst mix of reaction back carbon deposit without the refrigerative regenerated catalyst according to the method for claim 1.
CNB02120781XA 2002-05-31 2002-05-31 Combination type method for catalyzing and transfering hydrocarbon oil Expired - Lifetime CN1181163C (en)

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CN1309804C (en) * 2004-09-03 2007-04-11 中国石油化工集团公司 Down pipe type catalytic cracking method and apparatus
CN100351016C (en) * 2004-09-28 2007-11-28 中国石油化工股份有限公司 Multiple segment steam stripping method for catalyst
US8241583B2 (en) * 2008-03-07 2012-08-14 Shell Oil Company Process for cracking a hydrocarbon feed
CN101665714B (en) * 2009-09-01 2012-09-05 青岛京润石化设计研究院有限公司 Method and equipment for cooling catalyst for gas-solid reaction
CN102443435A (en) * 2010-10-13 2012-05-09 中国石油化工股份有限公司 Heavy oil hydrogenation method utilizing partition plate type reactor
CN110540860B (en) * 2018-05-28 2021-08-06 中国石油化工股份有限公司 Process and system for catalytic cracking by adopting double descending pipes

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