CN1234426A - Process for synchronously preparing low-carbon olefines and high aromatic-hydrocarbon gasoline - Google Patents

Process for synchronously preparing low-carbon olefines and high aromatic-hydrocarbon gasoline Download PDF

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Publication number
CN1234426A
CN1234426A CN 98101765 CN98101765A CN1234426A CN 1234426 A CN1234426 A CN 1234426A CN 98101765 CN98101765 CN 98101765 CN 98101765 A CN98101765 A CN 98101765A CN 1234426 A CN1234426 A CN 1234426A
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gasoline
heavy
riser tube
oil
hydrocarbon
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CN1065903C (en
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谢朝钢
刘舜华
王亚民
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Abstract

The method for simutaneously producing low-carbon olefine and high aromatic type gasoline is characterized by that the heavy petroleum hydrocarbon and steam are contacted with catalyst containing zeolite in lower portion of composite reactor formed of lift pipe and dense-phase fluid bed, i. e. in the lower portion of the lift pipe; the light petroleum hydrocarbon is fed into the upper portion of the composite reactor, i. e. bottom portion of the dense-phase fluid bed, and is contacted with the catalyst containing zeolite from lift pipe; the reaction product is separated to obtain dry gas, liquified gas, gasoline, diesel doil and slurry oil; and the catalyst can be stripped and regenerated, and can be cyclically used. Said method possesses the following advantages: using identical catalyst and making reaction in same equipment, raising yield of low-carbon olefine, specially raising yield of propylene, and increasing aromatic hydrocarbon content in gasoline to about 80 wt%.

Description

A kind of method of producing low-carbon alkene and high aromatic-hydrocarbon gasoline simultaneously
The invention belongs to the catalysis conversion method of petroleum hydrocarbon, more particularly, be to use zeolite containing catalyst, is the method that raw material is produced low-carbon alkene and high aromatic-hydrocarbon gasoline simultaneously with heavy and light petroleum hydrocarbon.
The method of producing low-carbon alkene from petroleum hydrocarbon has: be the pyrolysis in tubular furnace of raw material with Sweet natural gas, petroleum naphtha or solar oil; With the heavy petroleum hydrocarbon is the thermal barrier thermo-cracking of raw material; And be the catalyzed conversion of raw material with the low-carbon alcohol.Conventional catalytic cracking also by-product low-carbon alkene when producing gasoline and diesel oil, but its output only accounts for below the 15 heavy % of stock oil.It is that raw material is produced the novel process that propylene and butylene are main low-carbon alkene with the heavy petroleum hydrocarbon that catalytic pyrolysis is one, in patent such as CN87105428.0, USP4980053 and CN1102431A or application Deep Catalytic Cracking process is described in detail.This Deep Catalytic Cracking process adopts riser tube or downstriker transfer limes reactor, fluidized-bed or moving-burden bed reactor pattern, use contains to be selected shape zeolite such as ZSM-5, contain the rare-earth five-membered ring supersiliceous zeolite, contains the solid acid catalyst of the five-ring supersiliceous zeolite etc. of rare earth and phosphorus, optimum reaction condition is: 500~600 ℃ of temperature of reaction, 1~6 second reaction times, agent-oil ratio 6~15: 1, the weight ratio of water vapor and stock oil is 0.05~0.5: 1.Propylene and butylene productive rate amount to about 35 heavy %, and about gasoline yield about 25 heavy %, the aromaticity content in the gasoline is about 35 heavy %.If the non-aromatic component in the catalytic cracking gasoline further can be converted into aromatic hydrocarbons, improve the aromaticity content of catalytic cracking gasoline, just can directly go out aromatic hydrocarbons such as benzene, toluene and dimethylbenzene by the solvent extraction extracting.
Many patents and document are introduced technology of aromatization and catalyzer thereof.As using fixed-bed reactor and the zeolite catalyst that contains ZSM-5 or ZSM-11 among the USP4918256, alkane is changed into aromatic hydrocarbons and alkene; Using X, Y or the zeolite L catalyzer of multistage fixed bed reactor and load VIII family metal among the USP4975178, is that raw material carries out aromatization under hydro condition with gasoline.In addition, N.Y.Chen etc. " Shape Selective Catalysis in Industrial Applications; MarcelDekker; Inc.; 1989 " and Susan Royse in " ECN; Process Review; April1994 " to industrialized Cyclar, Z-Forming, M2-Reforming, Alpha, catalytic aromatization technologies such as Aroforming are introduced, except that the multistage adiabatic radial flow reactors of Cyclar process using, other technology of aromatization all adopts fixed-bed reactor.
The objective of the invention is to provide on the basis of existing technology a kind of use zeolite containing catalyst, is raw material with heavy and light petroleum hydrocarbon, produces the method for low-carbon alkene and high aromatic-hydrocarbon gasoline simultaneously.
Method provided by the invention is: making heavy crude hydrocarbon feed and water vapor after the preheating is that the riser tube bottom contacts with the zeolite containing catalyst of heat in the bottom of a compound reactor of being made up of riser tube and dense phase fluidized bed; Making the low-density oil hydrocarbon feed after the preheating simultaneously is that the dense phase fluidized bed bottom enters bed from the top of compound reactor, contacts with zeolite containing catalyst from riser tube; Reaction product isolated obtains dry gas, liquefied gas, gasoline, diesel oil and slurry oil; Reclaimable catalyst is transported to revivifier behind the water vapor stripping, carry out coke burning regeneration in air, and the regenerated catalyst of heat returns the riser tube bottom cycle and uses.
Method provided by the invention is so concrete enforcement: make water vapor and heavy crude hydrocarbon feed by weight (hereinafter to be referred as water-oil ratio) 0.05~0.5: 1, in the bottom of a compound reactor of being made up of riser tube and dense phase fluidized bed is that the riser tube bottom contacts with the zeolite containing catalyst of heat, the weight ratio of catalyzer and heavy petroleum hydrocarbon (hereinafter to be referred as agent-oil ratio) is 6~15: 1, is 500~600 ℃ in the riser tube temperature out, to promote intraductal retention time be to react under 1~5 second the condition; Making the low-density oil hydrocarbon feed after the preheating simultaneously is that the dense phase fluidized bed bottom enters bed from the top of compound reactor, contacts with zeolite containing catalyst from riser tube, in 500~600 ℃ of bed temperatures, bed weight hourly space velocity 1~6 hour -1Condition under react; Gasoline fraction, diesel oil distillate and the slurry oil of aromatic hydrocarbons such as reaction product isolated obtains dry gas, contains the liquefied gas of propylene and butylene, contains benzene, toluene and dimethylbenzene, wherein the part gasoline fraction turns back to the dense phase fluidized bed bottom and further reacts; Reclaimable catalyst is transported to revivifier behind the water vapor stripping, carry out coke burning regeneration in air, and the regenerated catalyst of heat returns the riser tube bottom cycle and uses.
Zeolite containing catalyst used in the present invention, its active ingredient is made up of the type-Y high silicon zeolite of the five-ring supersiliceous zeolite that contains rare earth and phosphorus of 40~100 heavy % and 0~60 heavy %, and carrier is selected from aluminum oxide, pure aluminium silicate, natural clay and adds aluminum oxide.
The five-ring supersiliceous zeolite that contains rare earth and phosphorus that the present invention is used is to handle obtain phosphorous (with P with aluminum phosphate 2O 5Meter) 2~20 heavy %, the five-ring supersiliceous zeolite that contains rare earth of best 2~10 heavy %.
This five-ring supersiliceous zeolite that contains rare earth prepares by disclosed method among the CN1058382A, promptly be to be raw material with water glass, aluminum phosphate and mineral acid, with Rare Earth Y or rare earth hydrogen Y zeolite is crystal seed, makes in 12~60 hours at 130~200 ℃ of following crystallizations.This zeolite has the x-ray diffraction spectra of ZSM-5 zeolite family, and its anhydrous chemical constitution formula is 0.01~0.30RE 2O 30.4~1.0Na 2OAl 2O 320~60SiO 2, the used crystal seed when synthetic of the rare earth in the composition.This zeolite is 2~4 times of ZSM-5 zeolite to the ratio of normal hexane and hexanaphthene adsorptive capacity.
The method of handling this five-ring supersiliceous zeolite that contains rare earth with aluminum phosphate is as follows: zeolite is exchanged processing in advance with ammonium ion make its sodium content (with Na 2O meter) reduces to and be not more than 0.1 heavy %, will consist of Al 2O 3: P 2O 5=1: 1~3 aluminum phosphate colloid is with P 2O 5: weight ratio and this zeolite of zeolite (butt)=1: 5~99 mix, and roasting is 0.5~6 hour in the presence of 300~600 ℃, 10~100% water vapors.
The used type-Y high silicon zeolite of the present invention is through various chemistry and/or physical method, as the silica alumina ratio that obtains after the processing such as hydrothermal method, acidic treatment, aluminium-eliminating and silicon-replenishing method, silicon tetrachloride method than higher, content of rare earth (with RE 2O 3Meter) 0~3 heavy type-Y high silicon zeolite %, stabilization.
The used heavy crude hydrocarbon feed of the present invention can be a vacuum distillate, also can be long residuum, can also be vacuum distillate and one or more the mixture that is selected from deasphalted oil, wax tailings, the residual oil; Used low-density oil hydrocarbon feed is the part gasoline fraction that obtains from the present invention, also can be one or more the mixture in external catalytically cracked gasoline, pyrolysis gasoline, coker gasoline and the straight-run spirit.The weight ratio of low-density oil hydrocarbon feed and heavy crude hydrocarbon feed is 0.1~0.6: 1.
Below in conjunction with accompanying drawing method provided by the present invention is given further instruction.
Accompanying drawing illustrates the flow process of producing low-carbon alkene and high aromatic-hydrocarbon gasoline simultaneously, and the shape and size of equipment and pipeline are not subjected to the restriction of accompanying drawing, but determines as the case may be.
In the compound reactor of forming by riser tube [2] and dense phase fluidized bed [4], the pre-steam that promotes enters riser tube [2] through pipeline [12] from riser tube [2] bottom, heavy crude hydrocarbon feed after the preheating enters from riser tube [2] bottom by a certain percentage in the riser tube [2] through pipeline [1] and atomized water steam and contacts with the zeolite containing catalyst of heat, reacts under certain conditions; Simultaneously the low-density oil hydrocarbon feed after the preheating enters bed through pipeline [3] and contacts with zeolite containing catalyst from riser tube [2] from dense phase fluidized bed [4] bottom.Reaction product enters separation system [7] through pipeline [6], separates to obtain dry gas, liquefied gas, gasoline, diesel oil and slurry oil, and wherein part gasoline enters dense phase fluidized bed [4] bottom through pipeline [13], [14] with the low-density oil hydrocarbon feed.Stripped vapor enters stripper [5] through pipeline [11], and reaction back reclaimable catalyst after pipeline [8] enters revivifier [9], carries out coke burning regeneration by the water vapor stripping in air, and the regenerated catalyst of heat returns riser tube [2] bottom cycle through pipeline [10] and uses.
The invention has the advantages that: use identical catalyzer in same device, to carry out the catalytic pyrolysis of heavy petroleum hydrocarbon and the catalytic aromatization of light petroleum hydrocarbon simultaneously, improved low-carbon alkene, the productive rate of propylene particularly, the aromaticity content in the gasoline are increased to about 80 heavy %.
Accompanying drawing is a schematic flow sheet of producing low-carbon alkene and high aromatic-hydrocarbon gasoline simultaneously.
Each numbering is described as follows in the accompanying drawing:
[1], [3], [6], [8], [10], [11], [12], [13], [14] all represent pipeline, [2] are riser tube, [4] are dense phase fluidized bed, [5] are stripper, [7] are separation system, [9] are revivifier.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Employed catalyzer is described as follows among the embodiment:
The CRP-1 catalyzer is the catalyzer that contains the five-ring supersiliceous zeolite of rare earth and phosphorus.The CIP-1 catalyzer is to contain the five-ring supersiliceous zeolite of rare earth and phosphorus and the catalyzer of super-stable Y zeolite containing rare-earth elements.These two kinds of catalyzer are by Qilu Petrochemical Co., China Petrochemical Corp.'s catalyst plant industrial production, and its main physico-chemical property is listed in table 1.
Embodiment 1
Method provided by the invention is adopted in the present embodiment explanation, in the compound reactor of being made up of riser tube and dense phase fluidized bed, produces the situation of low-carbon alkene and high aromatic-hydrocarbon gasoline simultaneously.
With density (20 ℃) 0.873 gram per centimeter 3, 350~540 ℃ of boiling ranges vacuum distillate be the heavy petroleum hydrocarbon raw material, with density (20 ℃) 0.745 gram per centimeter that obtains after the reaction 3, 54~198 ℃ of boiling ranges gasoline fraction (hereinafter to be referred as freshening gasoline) be the low-density oil hydrocarbon feed, the weight ratio of freshening gasoline and vacuum distillate is 0.15: 1, uses the CRP-1 catalyzer, tests in compound reactor.
Vacuum distillate after the preheating is through water vapor atomizing back and enter into the bottom of riser tube, vacuum distillate contacts with the catalyzer of heat in riser reactor and carries out catalytic cracking reaction, the riser tube temperature out is 565 ℃, the riser tube residence time is 2.5 seconds, water-oil ratio is 0.25: 1, and agent-oil ratio is 12: 1.
Freshening gasoline enters into the bottom of dense phase fluidized bed, freshening gasoline and contact with catalyzer in the dense fluidized bed bioreactor from the reactant flow of riser tube and to carry out aromatization from riser tube, the bed medial temperature is 555 ℃, and the bed weight hourly space velocity is 4 hours -1
Reaction product isolated obtains dry gas, contains the liquefied gas of propylene and butylene, contains benzene, gasoline, diesel oil and the slurry oil of toluene and dimethylbenzene, and reclaimable catalyst enters into stripper by action of gravity, is gone out the hydrocarbon product that adsorbs on the reclaimable catalyst by the water vapor stripping.Reclaimable catalyst behind the stripping enters into revivifier, contacts with the air that heated and regenerates.Catalyzer after the regeneration turns back to the riser tube bottom cycle again and uses.Test-results is listed in table 2.
Comparative Examples 1
Comparative Examples 1 explanation is adopted independent catalytic cracking method in compound reactor, promptly have only the heavy crude hydrocarbon feed to enter the riser tube reaction from the bottom of compound reactor, produces the situation of aromaticity content in propylene and butylene and the gasoline.
With density (20 ℃) 0.873 gram per centimeter 3, 350~540 ℃ of boiling ranges vacuum distillate be the heavy petroleum hydrocarbon raw material, vacuum distillate contacts with the CRP-1 catalyzer in riser reactor and carries out catalytic cracking reaction, the riser tube temperature out is 565 ℃, the riser tube residence time is 2.5 seconds, water-oil ratio is 0.25: 1, and agent-oil ratio is 12: 1; The logistics of catalytic pyrolysis product then enters dense phase fluidized bed and continues reaction, and the bed weight hourly space velocity is 4 hours -1Reaction product isolated obtains dry gas, contains the liquefied gas of propylene and butylene, contains benzene, gasoline, diesel oil and the slurry oil of toluene and dimethylbenzene, and reclaimable catalyst enters into stripper by action of gravity, is gone out the hydrocarbon product that adsorbs on the reclaimable catalyst by the water vapor stripping; Reclaimable catalyst behind the stripping enters into revivifier, contacts with the air that heated and regenerates; Catalyzer after the regeneration turns back to the riser tube bottom cycle again and uses.Test-results is listed in table 2.
As can be seen from Table 2, compare with independent catalytic pyrolysis, the productivity of propylene of embodiment 1 can improve 2.39 heavy %, and aromaticity content is brought up to 78.84 heavy % by 42.49 heavy % in the gasoline.
Embodiment 2
The present embodiment explanation is when using the catalyzer of different zeolites content, and method provided by the invention is produced the situation of low-carbon alkene and high aromatic-hydrocarbon gasoline simultaneously.
With density (20 ℃) 0.873 gram per centimeter 3, 350~540 ℃ of boiling ranges vacuum distillate be the heavy petroleum hydrocarbon raw material, catalytically cracked gasoline with 58~205 ℃ of boiling ranges is the low-density oil hydrocarbon feed, the weight ratio of catalytically cracked gasoline and vacuum distillate is 0.3: 1, agent-oil ratio is 10: 1, water-oil ratio is 0.25: 1, is that 580 ℃, weight hourly space velocity are 4 hours in temperature of reaction -1Operational condition under, in compound reactor, test, it the results are shown in table 3.
Embodiment 3
The present embodiment explanation is under the different operating condition, and method provided by the invention is produced the situation of low-carbon alkene and high aromatic-hydrocarbon gasoline simultaneously.
With density (20 ℃) 0.873 gram per centimeter 3, 350~540 ℃ of boiling ranges vacuum distillate be the heavy petroleum hydrocarbon raw material, catalytically cracked gasoline with 58~205 ℃ of boiling ranges is the low-density oil hydrocarbon feed, use the CRP-1 catalyzer, the weight ratio of freshening gasoline and vacuum distillate is 0.3: 1, test in compound reactor, operational condition and test-results are listed in table 4.
Table 1
The catalyzer title ????CRP-1 ????CIP-1
Chemical constitution, heavy % Al 2O 3Na 2O physical properties specific surface area, rice 2/ gram pore volume, centimetre 3/ gram tap density, gram per centimeter 3Abrasion index, heavy %/hour burning decrement, heavy % size composition, 0~20 micron 20~40 microns 40~80 microns>80 microns of heavy % ????54.2 ????0.03 ????160 ????0.26 ????0.86 ????1.2 ????12.0 ????5.8 ????20.2 ????60.8 ????13.2 ????52.0 ????0.09 ????210 ????0.30 ????0.80 ????1.6 ????12.3 ????5.2 ????20.4 ????61.8 ????12.6
Table 2
Numbering Embodiment 1 Comparative Examples 1
The reduced pressure distillate oil mass; Kg/hr freshening amount of gasoline; Kg/hr product yield; Heavy % dry gas liquefied gas wherein propylene butene C5+ gasoline, diesel slurry oil coke gasoline forms, and heavy % alkane cycloalkane alkene aromatic hydrocarbons is benzene toluene ethylbenzene dimethylbenzene wherein ????6.0 ????0.9 ????8.68 ????51.58 ????23.42 ????15.51 ????20.63 ????6.62 ????6.08 ????6.41 ????9.63 ????3.85 ????7.68 ????78.84 ????3.46 ????22.27 ????3.86 ????31.78 ????6.0 ????0 ????7.54 ????46.59 ????21.03 ????14.30 ????26.60 ????6.60 ????6.07 ????6.00 ????16.13 ????6.75 ????34.63 ????42.49 ????1.70 ????9.78 ????1.63 ????13.74
Table 3
Catalyzer ????CRP-1 ????CIP-1
Product distributes; Heavy % dry gas liquefied gas wherein propylene butene C5+ gasoline, diesel slurry oil coke gasoline forms, and heavy % alkane cycloalkane alkene aromatic hydrocarbons is benzene toluene ethylbenzene dimethylbenzene wherein ????7.08 ????42.95 ????19.11 ????15.89 ????34.59 ????7.46 ????4.08 ????3.84 ????14.57 ????4.81 ????18.61 ????61.01 ????1.32 ????9.73 ????2.43 ????19.70 ????6.20 ????42.96 ????17.81 ????14.72 ????36.80 ????6.53 ????2.76 ????4.75 ????13.66 ????4.24 ????13.52 ????68.58 ????1.39 ????12.88 ????3.12 ????25.90
Table 4
The operational condition temperature of reaction, ℃ charging air speed, hour -1Oil ratio water-oil factor product distributes; Heavy % dry gas liquefied gas wherein propylene butene C5+ gasoline, diesel slurry oil coke gasoline forms, and heavy % alkane cycloalkane alkene aromatic hydrocarbons is benzene toluene ethylbenzene dimethylbenzene wherein ????500 ????6 ????6 ????0.1 ????2.61 ????30.76 ????11.73 ????10.05 ????41.50 ????11.91 ????11.02 ????2.20 ????21.01 ????7.04 ????36.40 ????35.55 ????1.20 ????5.91 ????1.21 ????9.39 ????600 ????1 ????15 ????0.4 ????8.24 ????42.53 ????19.51 ????14.45 ????32.38 ????8.09 ????4.51 ????4.25 ????13.70 ????4.79 ????13.91 ????67.60 ????2.32 ????14.14 ????3.01 ????23.88

Claims (8)

1, a kind of method of producing low-carbon alkene and high aromatic-hydrocarbon gasoline simultaneously, it is characterized in that making heavy crude hydrocarbon feed and water vapor after the preheating is that the riser tube bottom contacts with the zeolite containing catalyst of heat in the bottom of a compound reactor of being made up of riser tube and dense phase fluidized bed; Making the low-density oil hydrocarbon feed after the preheating simultaneously is that the dense phase fluidized bed bottom enters bed from the top of compound reactor, contacts with zeolite containing catalyst from riser tube; Reaction product isolated obtains dry gas, liquefied gas, gasoline, diesel oil and slurry oil; Reclaimable catalyst is transported to revivifier behind the water vapor stripping, carry out coke burning regeneration in air, and the regenerated catalyst of heat returns the riser tube bottom cycle and uses.
2, according to the method for claim 1, it is characterized in that described zeolite containing catalyst active ingredient is made up of the type-Y high silicon zeolite of the five-ring supersiliceous zeolite that contains rare earth and phosphorus of 40~100 heavy % and 0~60 heavy %, carrier is selected from aluminum oxide, pure aluminium silicate, natural clay and adds aluminum oxide.
3, according to the method for claim 1, it is characterized in that described heavy crude hydrocarbon feed is a vacuum distillate, also can be long residuum, can also be vacuum distillate and one or more the mixture that is selected from deasphalted oil, wax tailings, the residual oil.
4, according to the method for claim 1, the weight ratio that it is characterized in that described water vapor and heavy petroleum hydrocarbon is 0.05~0.5: 1, and the weight ratio of catalyzer and heavy petroleum hydrocarbon is 6~15: 1.
5,, it is characterized in that described heavy petroleum hydrocarbon reaction conditions is 500~600 ℃ of riser tube temperature outs, 1~5 second riser tube residence time according to the method for claim 1.
6, according to the method for claim 1, it is characterized in that the part gasoline fraction that described low-density oil hydrocarbon feed comes autoreaction to obtain, also can be one or more mixture of catalytically cracked gasoline, pyrolysis gasoline, coker gasoline, straight-run spirit.
7,, it is characterized in that described light petroleum hydrocarbon is 500~600 ℃ of bed temperatures, bed weight hourly space velocity 1~6 hour in dense phase fluidized bed internal reaction condition according to the method for claim 1 -1
8, according to the method for claim 1, the weight ratio that it is characterized in that low-density oil hydrocarbon feed and heavy crude hydrocarbon feed is 0.1~0.6: 1.
CN98101765A 1998-05-06 1998-05-06 Process for synchronously preparing low-carbon olefines and high aromatic-hydrocarbon gasoline Expired - Lifetime CN1065903C (en)

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CN1100850C (en) * 2000-04-29 2003-02-05 中国石化集团洛阳石油化工工程公司 Fluidized catalytic process for transforming hydrocarbons
CN100487080C (en) * 2004-03-08 2009-05-13 中国石油化工股份有限公司 Chemical oil-refining method for preparing low carbon olefin and arene
CN101191073B (en) * 2006-11-30 2012-03-07 中国石油化工股份有限公司 Method for producing high octane rating low olefin gasoline
CN102775261A (en) * 2012-07-23 2012-11-14 李小燕 Multifunctional methanol processing method and apparatus
CN106590741A (en) * 2015-10-15 2017-04-26 中国石油化工股份有限公司 Catalytic conversion method for increasing yields of low-carbon olefins and light aromatic hydrocarbons
US11624033B2 (en) 2018-07-16 2023-04-11 China Petroleum & Chemical Corporation Process, reactor and system for catalytic cracking of hydrocarbon oil
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CN1004878B (en) * 1987-08-08 1989-07-26 中国石油化工总公司 Hydrocarbon catalytic conversion method for preparing low-carbon olefin
US4918256A (en) * 1988-01-04 1990-04-17 Mobil Oil Corporation Co-production of aromatics and olefins from paraffinic feedstocks
US4975178A (en) * 1988-05-23 1990-12-04 Exxon Research & Engineering Company Multistage reforming with interstage aromatics removal
CN1034586C (en) * 1993-11-05 1997-04-16 中国石油化工总公司 Catalytic conversion method of low-carbon olefines high-output

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CN1100850C (en) * 2000-04-29 2003-02-05 中国石化集团洛阳石油化工工程公司 Fluidized catalytic process for transforming hydrocarbons
CN100487080C (en) * 2004-03-08 2009-05-13 中国石油化工股份有限公司 Chemical oil-refining method for preparing low carbon olefin and arene
CN101191073B (en) * 2006-11-30 2012-03-07 中国石油化工股份有限公司 Method for producing high octane rating low olefin gasoline
CN102775261A (en) * 2012-07-23 2012-11-14 李小燕 Multifunctional methanol processing method and apparatus
CN106590741A (en) * 2015-10-15 2017-04-26 中国石油化工股份有限公司 Catalytic conversion method for increasing yields of low-carbon olefins and light aromatic hydrocarbons
CN106590741B (en) * 2015-10-15 2018-04-13 中国石油化工股份有限公司 A kind of catalysis conversion method of low-carbon olefines high-output and light aromatic hydrocarbons
US11624033B2 (en) 2018-07-16 2023-04-11 China Petroleum & Chemical Corporation Process, reactor and system for catalytic cracking of hydrocarbon oil
US11891578B2 (en) 2018-07-16 2024-02-06 China Petroleum & Chemical Corporation Process and system for catalytic cracking of hydrocarbon oils

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