CN1060755C - Process for producing ethylene and propene by catalytic thermal cracking - Google Patents
Process for producing ethylene and propene by catalytic thermal cracking Download PDFInfo
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- CN1060755C CN1060755C CN98120236A CN98120236A CN1060755C CN 1060755 C CN1060755 C CN 1060755C CN 98120236 A CN98120236 A CN 98120236A CN 98120236 A CN98120236 A CN 98120236A CN 1060755 C CN1060755 C CN 1060755C
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a catalytic thermal cracking method for preparing ethene and propylene by using heavy crude hydrocarbon. Preheated heavy crude hydrocarbon is in contact with a catalyst containing a layered column clay molecular sieve and/or five-ring high-silicon zeolite modified by phosphorus and aluminum or magnesium or calcium in a lift pipe or a downward transfer line reactor under the condition of high-temperature stream; the catalytic thermal cracking reaction is carried out under the conditions that the reaction temperature is from 650 to 750 DEG C, the reaction pressure is from 1.5 to 4*10[5] Pa, the reaction time is from 0.2 to 5 s, the weight ratio of the catalyst to raw oil is 15 to 40:1, and the weight ratio of steam to the raw oil is 0.3 to 1:1. The yield of the ethene and the propene prepared by using the method exceeds 18% by weight.
Description
The invention belongs to the catalytic thermocracking process of heavy petroleum hydrocarbon.More particularly, be the method for heavy petroleum hydrocarbon catalytic thermal cracking process to prepare lower olefine, particularly ethene and propylene under the effect of high-temperature steam and catalyzer.
The traditional method of producing ethene from petroleum hydrocarbon is the steam heat cracking process, and suitable raw material is light petroleum hydrocarbons such as ethane, propane, butane, Sweet natural gas, petroleum naphtha or solar oil.Along with crude oil becomes heavy day by day, the output of light petroleum hydrocarbon is restricted, so people come diversion to the technology of producing ethene from heavy petroleum hydrocarbon.For example adopt the heavy petroleum hydrocarbon pyrolysis method of inert solids such as quartz sand, coke, adopt basic metal or alkaline earth metal oxide catalyzer as the heavy petroleum hydrocarbon pyrolysis method of thermal barrier etc. as thermal barrier.The temperature of reaction of these methods all surpasses 800 ℃.
In recent years, some patent has been introduced the use solid acid catalyst under certain reaction type formula and operational condition, produces the method for low-carbon alkene from heavy petroleum hydrocarbon.For example DD 152356A uses the amorphous silicon Al catalysts, and reactor is fixed bed or moving-bed, when being raw material with the vacuum gas oil, 700 ℃ of temperature of reaction, water vapor is 4.7 o'clock with the stock oil ratio, and ethylene yield is 13.5 heavy %, and productivity of propylene is 6.3 heavy %; In JP 60-222428, then used with the catalyzer of ZSM-5 zeolite, with C as active ingredient
5～C
25Paraffinic hydrocarbon is a raw material, is that 600～750 ℃, feed weight air speed are 20～300 o'clock in temperature of reaction
-1Condition under, the summation of ethene, propylene and butylene productive rate reaches about 30 heavy %.Having introduced a kind of catalytic cracking method of producing propylene and butylene among the ZL CN 87105428.0, adopted fluidized-bed or moving-burden bed reactor and solid acid catalyst, is 500～650 ℃ in temperature of reaction, and the feed weight air speed is 0.2～20 o'clock
-1, agent-oil ratio is to react under 2～12 the condition, as uses ZSM-5 to be active ingredient, the kaolin catalyzer as carrier, with the vacuum gas oil is raw material, and when 580 ℃ of temperature of reaction, ethylene yield is 5.9 heavy %, productivity of propylene is 21.9 heavy %, and the butylene productive rate is 15.6 heavy %.Disclosed among the CN 1069016A and a kind of heavy hydrocarbon has been transformed in fluidized-bed or plug flow reactor, produced C
2 =Hold concurrently and produce C
3 =And C
4 =Method, its principal reaction condition is: 650～900 ℃, 0.13～0.28MPa, agent-oil ratio 5～35,0.1～3 second duration of contact, product C
2 =Yield reaches 17～27%, C
2 =～C
4 =Overall yield reaches 30～40%.Used the five-ring high silica zeolite catalyst that contains clay molecular sieve with layer structure and/or contain rare earth among the CN1083092A, at 680～780 ℃, 1.5～4.0 * 10
5Under the condition of Pa, 0.1～3.0 second reaction times, water-oil ratio 0.2～2.0, agent-oil ratio 5～40 the heavy hydrocarbon cracking can be obtained the C of 23 heavy %
2 =The C of productive rate and 50 heavy %
2 =～C
4 =Productive rate.
The objective of the invention is to provide on the basis of above-mentioned prior art a kind of is raw material with the heavy petroleum hydrocarbon, produces the particularly novel method of ethene and propylene of low-carbon alkene in riser tube or downstriker transfer limes reactor.
The objective of the invention is to reach by following proposal: the heavy crude hydrocarbon feed that makes the process preheating is in riser tube or downstriker transfer limes reactor, with the containing clay molecular sieve with layer structure and/or contact of heat, under the operational condition that thermo-cracking can take place, carry out the catalytic pyrolysis reaction through the catalyzer of phosphorus with the five-ring supersiliceous zeolite of aluminium or magnesium or calcium modification.Reaction product, water vapor and reclaimable catalyst are further isolated gas products and liquid products such as ethene and propylene again from the product that reactor is drawn after quick gas solid separation; Reclaimable catalyst removes stripper, enters revivifier behind the water vapor stripping, contacts with oxygen-containing gas to carry out coke burning regeneration, and regenerated catalyst Returning reactor behind stripping of heat recycles.
Concrete operation method of the present invention is as follows: heavy petroleum hydrocarbon enters after preheating in riser tube or the downstriker transfer limes reactor, with the containing clay molecular sieve with layer structure and/or contact of heat, be that 650～750 ℃, reaction pressure are 1.5～4 * 10 in temperature of reaction through the catalyzer of phosphorus with the five-ring supersiliceous zeolite of aluminium or magnesium or calcium modification
5Handkerchief, reaction times are that the weight ratio (hereinafter to be referred as agent-oil ratio) of 0.2～5 second, catalyzer and stock oil is 15～40: 1, the weight ratio of water vapor and stock oil (hereinafter to be referred as water-oil ratio) is to carry out the catalytic pyrolysis reaction under 0.3～1: 1 the condition.Reaction product, water vapor and reclaimable catalyst are also further isolated gas products and the liquid product that comprises ethene and propylene from the product that reactor is drawn by the light petroleum hydrocarbon chilling after quick gas solid separation; Reclaimable catalyst enters stripper, and the water steam stripped goes out on it hydrocarbon product of absorption, and reclaimable catalyst is admitted to revivifier then, contacts with the oxygen-containing gas of heat such as air and carries out coke burning regeneration.Catalyzer with water steam after the regeneration and/or other rare gas element stripping turn back to the use of reactor internal recycle after removing the non-hydrocarbon gas impurity that adsorbs on it and carry again.The regenerated catalyst of heat is supplied with the needed reaction heat of heavy petroleum hydrocarbon catalytic pyrolysis, and reacted reclaimable catalyst when in revivifier, regenerating liberated heat absorb by regenerated catalyst, during the regenerated catalyst Returning reactor heat that absorbs is resupplied the heavy crude hydrocarbon feed and carries out the catalytic pyrolysis reaction.
The catalyzer that the present invention adopts has following composition: the clay, 5～85% inorganic oxide and 10～70% the active ingredient that account for catalyst weight 1～70%, its medium clay soil is selected from kaolin and/or halloysite, inorganic oxide is selected from amorphous silicon aluminium, silicon oxide or aluminum oxide, and active ingredient is selected from clay molecular sieve with layer structure and/or through the five-ring supersiliceous zeolite of phosphorus and aluminium or magnesium or calcium modification.
One of used active ingredient clay molecular sieve with layer structure is to be the clay with regular interstratified structure of the natural or synthetic that supported of interlayer support thing or the clay of single layer structure with the aluminum contained compound in the catalyzer that the present invention adopts, wherein be preferably aluminum cross-linked rectorite or aluminium cross-linked smectite, preferably aluminum cross-linked rectorite.Can be about the constitutional features of rectorite leng and cross-linked rectorite and Preparation of catalysts method thereof referring to relevant prior art document, as ZL CN86101990, ZLCN87104718.7.
The two five-ring supersiliceous zeolites through phosphorus and aluminium or magnesium or calcium modification of used active ingredient are aluminium or magnesium or the supersiliceous zeolites with ZSM-5, ZSM-8 or ZSM-11 structure type calcium (with zeolite weight is benchmark, in oxide compound), silica alumina ratio preferred 15～60 that contains 2～8% phosphorus and 0.3～3.0%.These supersiliceous zeolites can make with the various known technologies of being reported in the prior art document, but preferred manufacturing procedure is as follows: with water glass, aluminum phosphate and mineral acid was raw material, is crystal seed with the y-type zeolite, 130～200 ℃ of following crystallization 12～60 hours.This preparation method's details can be with reference to CN1058382A, and just crystal seed adopts the y-type zeolite that does not contain rare earth to get final product.Contained phosphorus and aluminium or magnesium or calcium can be that prepare in advance or commercially available five-ring supersiliceous zeolite and aluminum phosphate or trimagnesium phosphate or calcium phosphate colloid are mixed by predetermined proportion on this supersiliceous zeolite, handle 3～6 hours under 400～600 ℃, 60～100% water vapors and introduce; Also can be with that prepare in advance or commercially available five-ring supersiliceous zeolite with to contain the aqueous solution of phosphorus and aluminium or magnesium or calcium cpd even, flood drying, 450～650 ℃ of roastings 1～4 hour and introducing 0.5～4 hour.
Above-mentioned said 0.3～3.0 heavy % nickel (with zeolite weight is benchmark, in oxide compound) that in the five-ring supersiliceous zeolite of phosphorus and aluminium or magnesium or calcium modification, can also contain.On this supersiliceous zeolite contained nickel be with nickel compound and five-ring supersiliceous zeolite that prepare in advance or commercially available and contain phosphorus and the aqueous solution of aluminium or magnesium or calcium cpd even, flooded 0.5～4 hour, drying, 450～650 ℃ of roastings 1～4 hour and introduce.
Can also contain Y zeolite as active ingredient in the catalyzer that the present invention adopts.The Y zeolite that preferably contains rare earth, content of rare earth wherein are that the standard of conventional Industrial products gets final product.
The heavy crude hydrocarbon feed that is suitable in the inventive method can be atmospheric gas oil, vacuum gas oil or its mixture, also can be residual oil or crude oil.The mode of raw material injecting reactor can adopt single-point to inject, and also can adopt multiple spot to inject.
Compared with prior art, the invention has the advantages that:
1. compare with the fluid catalytic cracking of routine, the present invention has adopted that hydrogen transfer activity is low, ethylene selectivity is high contains clay molecular sieve with layer structure and/or through the catalyzer of the five-ring supersiliceous zeolite of phosphorus and aluminium or magnesium or calcium modification, improved temperature of reaction, thereby increased the productive rate of low-carbon alkene, particularly increased the productive rate of ethene and propylene, for petrochemical complex provides more raw materials.
2. compare with the method for the catalytic cracking to prepare lower carbon olefin of prior art, the present invention has adopted the transfer limes reactor and olefine selective is good, lytic activity is high contains clay molecular sieve with layer structure and/or through the catalyzer of the five-ring supersiliceous zeolite of phosphorus and aluminium or magnesium or calcium modification, has improved the particularly productive rate of ethene and propylene of low-carbon alkene.
3, the present invention has been owing to found the operational condition of appropriate catalyst, reactor pattern and catalyzed reaction, thereby obtained than the higher low-carbon alkene productive rate of ethene particularly, and its ethylene yield and productivity of propylene all can surpass 18 heavy %.
4, the wide scope of material of the present invention's use can be atmospheric gas oil, vacuum gas oil or its mixture, also can be residual oil or crude oil.
Following example will give further instruction to the present invention.
Employed catalyzer is as follows in the example:
Catalyst A is to be prepared into according to the method described in the ZL CN87105686.0.Consist of: five-ring supersiliceous zeolite, the 30%Al of 50% cross-linked rectorite, 15% phosphorous and magnesium
2O
3With surplus kaolin.
Catalyst B is that the preparation method according to conventional cracking catalyst is prepared into.Consist of five-ring supersiliceous zeolite, 57% amorphous silicon aluminium and the surplus kaolin of 15% phosphorous and calcium.
Catalyzer C is that the preparation method according to conventional cracking catalyst is prepared into.Consist of five-ring supersiliceous zeolite, 57% amorphous silicon aluminium and the surplus kaolin of 15% phosphorous and magnesium.
Catalyzer D is that the preparation method according to conventional cracking catalyst is prepared into.Consist of the five-ring supersiliceous zeolite of 15% phosphorous and aluminium, 57% yuan of typing sial and surplus kaolin.
Catalyzer E is that the preparation method according to conventional cracking catalyst is prepared into.Consist of the five-ring supersiliceous zeolite of 20% phosphorous and magnesium, 3.5% REY zeolite, 25% aluminum oxide and surplus kaolin.
Catalyzer F is that the preparation method according to conventional cracking catalyst is prepared into.Consist of five-ring supersiliceous zeolite, 25% aluminum oxide and the surplus kaolin of 20% phosphorous, magnesium and nickel.
Wherein used five-ring supersiliceous zeolite be the catalyst plant production of Chang Ling, Hunan, silica alumina ratio is 25 ZSM-5 zeolite.
The main physico-chemical property of above-mentioned catalyzer is listed in table 1.
The main character of used various stock oils is listed in table 2 in the example.
Example 1
Method provided by the invention is adopted in the explanation of this example, and the catalytic pyrolysis of heavy petroleum hydrocarbon in the transfer limes reactor produced the situation of ethene and propylene.
With the vacuum gas oil is raw material, uses catalyzer C, carries out the catalytic pyrolysis test on the small-sized riser arrangement of successive reaction-regenerative operation.The operating method that test adopts one way to pass through, stock oil enters into the inlet of riser reactor after preheating oven is heated to about 350 ℃, all be marked with high-temperature water vapor in preheating oven exit and riser reactor ingress, the weight ratio of water vapor and stock oil is 0.8: 1, stock oil contacts with the catalyzer of heat in riser reactor and carries out the catalytic pyrolysis reaction, the reactor outlet temperature is 685 ℃, and pressure is 2.5 * 10
5Handkerchief, the reaction times is 2.5 seconds, the weight ratio of catalyzer and stock oil is 25: 1.Reaction product and water vapor and reclaimable catalyst enter into settling vessel from reactor outlet, at settling vessel reaction product and catalyzer sharp separation, reaction product is by the diesel oil chilling and further be separated into gaseous product and product liquid, 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 is the water steam stripped in line of pipes, with the non-hydrocarbon gas impurity of removing regenerated catalyst absorption and carrying.Regenerated catalyst behind the stripping turns back in the riser reactor and recycles.The operational condition of test and the results are shown in table 3.
Example 2
This example illustrates that method provided by the invention is produced the situation of ethene and propylene when the different catalysts of using the present invention to select.
With the vacuum gas oil is raw material, is that 680 ℃, agent-oil ratio are that 15: 1, water-oil ratio are that 0.8: 1, weight hourly space velocity are 10h in temperature of reaction
-1Operational condition under, on small fixed flowing bed-tion reacting device, carry out catalytic pyrolysis test, it the results are shown in table 4.As can be seen from Table 4, catalyst A, B, C, D, E and F have higher ethene and productivity of propylene.
Example 3
This example illustrates that method provided by the invention is applicable to the heavy petroleum hydrocarbon of different boiling ranges.The situation that different catalysts is carried out catalytic pyrolysis on the small stationary bed apparatus is listed in table 5.
Example 4
This example illustrates that method provided by the invention is applicable to full cut crude oil.The situation that catalyst A is carried out catalytic pyrolysis on the small stationary bed apparatus is listed in table 6.
Table 1
| Catalyzer | A | B | C | D | E | F |
| Chemical constitution, heavy % Al 2O 3 Na 2O physical properties specific surface area, rice 2/ gram pore volume, milliliter/gram bulk density, the grams per milliliter abrasion index, weigh %/time size composition, 0～40 micron 40～80 microns＞80 microns of heavy % | 50．5 1．03 200 0．16 0．89 3．0 - - - | 40．5 0．05 118 0．12 0．86 1．0 26．5 59．8 13．7 | 40．0 0．05 113 0．11 0．86 1．0 27．2 58．6 14．2 | 41．5 0．05 120 0．13 0．86 1．0 28．2 58．1 13．7 | 46．5 0．05 128 0．12 0．81 2．4 16．6 42．0 41．4 | 45．4 0．05 123 0．12 0．82 1．6 18．8 58．6 22．6 |
Table 2
| Stock oil | Atmospheric gas oil | Vacuum gas oil | Long residuum | Crude oil |
| Density (20 ℃), the grams per milliliter carbon residue, heavy % hydrogen richness, heavy % nickel content, the ppm content of vanadium, the ppm boiling range, ℃ initial boiling point 10% 30% 50% 70% 90% final boiling point | 0．8184 0．01 14．00 - - 242 264 278 290 304 323 347 | 0．8730 0．15 13．54 0．09 ＜0．01 346 411 437 462 489 523 546 | 0．8953 4．17 12．94 4．78 0．08 299 389 480 - - - - | 0．8576 3．75 - 3．36 ＜0．05 - - - - - - - |
Table 3
| Stock oil | Vacuum distillate |
| Catalyst operating condition outlet temperature of riser; ℃ reaction time; Second, oil ratio water-oil factor product yield weighed % cracked gas therein ethylene propylene butene C5 +Gasoline, diesel heavy oil coke ethene+propylene+butylene, heavy % | C 685 2．5 25∶1 0．8∶1 66．67 22．02 20．81 9．51 15．65 6．44 3．56 7．68 52．34 |
Table 4
| Catalyzer | A | B | C | D | E | F |
| Products distribution, heavy % cracked gas therein ethylene propylene butene C 5 +Gasoline, diesel heavy oil coke ethene+propylene+butylene, heavy % | 67．26 19．50 21．58 11．37 15．02 5．74 4．58 7．40 52．45 | 68．61 19．81 22．72 10．53 17．84 3．73 2．64 7．18 53．06 | 69．70 20．77 22．47 10．69 15．22 5．33 3．65 6．10 53．93 | 69．32 20．41 22．52 10．61 15．05 5．16 4．10 6．37 53．54 | 73．97 22．75 25．13 10．86 11．25 3．12 3．03 8．63 58．74 | 70．48 22．26 22．66 10．37 14．36 3．48 3．40 8．28 55．29 |
Table 5
| Stock oil | Atmospheric gas oil | Vacuum gas oil | Long residuum |
| Catalyzer operational condition temperature of reaction, ℃ reaction times, second, agent-oil ratio water-oil ratio product yield weighed ethylene, propylene butylene C in the % cracked gas 5 +Liquid coke ethene+propylene+butylene, heavy % | B 750 2 15 0．3∶1 70．85 18．98 18．69 10．23 21．08 8．07 47．90 | C 700 3 15 0．8∶1 75．03 21．09 23．56 10．47 17．83 7．14 55．12 | A 650 5 25 1．0∶1 62．38 18．07 19．25 9．86 28．10 9．52 47．18 |
Table 6
| Stock oil | Crude oil |
| Catalyst operating condition reaction temperature; ℃ reaction time; Second, oil ratio water-oil factor product yield weighed % cracked gas therein ethylene propylene butene C5 +Liquid coke ethene+propylene+butylene, heavy % | A 700 0．2 40∶1 0．5∶1 61．92 19．35 18．02 10．89 31．02 7．06 48．26 |
Claims (12)
1. catalytic thermocracking process of producing ethene and propylene, comprise that the heavy petroleum hydrocarbon that makes preheating is in reactor, in the presence of high-temperature water vapor, contact and carry out the catalytic pyrolysis reaction with the catalyzer that contains clay molecular sieve with layer structure of heat, reaction product, water vapor is drawn after quick gas solid separation from reactor with the reclaimable catalyst of band coke, the product logistics is removed chilling and is isolated gas products and the liquid product that comprises ethene and propylene, reclaimable catalyst enters revivifier behind the water vapor stripping, coke burning regeneration in the presence of oxygen-containing gas, regenerated catalyst Returning reactor behind stripping of heat recycles, it is characterized in that: heavy petroleum hydrocarbon be in riser tube or downstriker transfer limes reactor with contain clay molecular sieve with layer structure and/or contact through the catalyzer of phosphorus with the five-ring supersiliceous zeolite of aluminium or magnesium or calcium modification, its reaction conditions is: temperature of reaction is 650～750 ℃, reaction pressure is 1.5～4 * 10
5Pa, reaction times are that the weight ratio of 0.2～5 second, catalyzer and stock oil is 15～40: 1, the weight ratio of water vapor and stock oil is 0.3～1: 1, five-ring supersiliceous zeolite wherein contain in zeolite weight be benchmark, with 2～8% phosphorus of oxide compound and 0.3～3.0% aluminium or magnesium or calcium.
2. according to the described method of claim 1, it is characterized in that to contain in the said catalyzer Y zeolite of rare earth.
3. according to the described method of claim 1, it is characterized in that said clay molecular sieve with layer structure is a cross-linked rectorite.
4. according to the described method of claim 1, it is characterized in that the silica alumina ratio of said five-ring supersiliceous zeolite through phosphorus and aluminium or magnesium or calcium modification is 15～60.
5. according to the described method of claim 4, it is characterized in that also can containing in the said modification five-ring supersiliceous zeolite in zeolite weight be benchmark, with 0.3～3.0% nickel of oxide compound.
6. according to the described method of claim 4, it is characterized in that said modification supersiliceous zeolite is that five-ring supersiliceous zeolite and aluminum phosphate or trimagnesium phosphate or calcium phosphate colloid are mixed, under 400～600 ℃, 60～100% water vapors, handle to make in 3～6 hours.
7. according to the described method of claim 4, it is characterized in that said modification supersiliceous zeolite is that the five-ring supersiliceous zeolite is even with the aqueous solution that contains phosphorus and aluminium or magnesium or calcium cpd, flooded 0.5～4 hour, drying, 450～650 ℃ of roastings made in 1～4 hour.
8. according to the described method of claim 5, it is characterized in that nickel in the said modification supersiliceous zeolite be with nickel compound and five-ring supersiliceous zeolite and contain phosphorus and the aqueous solution of aluminium or magnesium or calcium cpd even, flooded 0.5～4 hour, drying, 450～650 ℃ of roastings introducing in 1～4 hour.
9. according to claim 4 or 5 described methods, it is characterized in that said five-ring supersiliceous zeolite is selected from the supersiliceous zeolite of ZSM-5, ZSM-8 or ZSM-11 structure type.
10. according to claim 4 or 5 described methods, it is characterized in that said five-ring supersiliceous zeolite is is raw material with water glass, aluminum phosphate and mineral acid, with the y-type zeolite crystal seed, made in 12～60 hours 130～200 ℃ of following crystallization.
11., it is characterized in that doing the chilling agent from the product that reactor is drawn with light petroleum hydrocarbon injects the quick cooled product logistics in reaction oil gas exit according to the described method of claim 1.
12., it is characterized in that said heavy crude hydrocarbon feed is atmospheric gas oil, vacuum gas oil or its mixture, and residual oil or crude oil according to the described method of claim 1.
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| CN98120236A CN1060755C (en) | 1997-10-15 | 1998-10-06 | Process for producing ethylene and propene by catalytic thermal cracking |
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| CN97119011 | 1997-10-15 | ||
| CN98120236A CN1060755C (en) | 1997-10-15 | 1998-10-06 | Process for producing ethylene and propene by catalytic thermal cracking |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100389100C (en) * | 2002-11-29 | 2008-05-21 | 中国石油化工股份有限公司 | Process for preparing olefin by cracking of kerosene distillate |
| CN102453501A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrocarbon oil conversion method |
| CN102453502A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Conversion method for hydrocarbon oil |
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| CN1098241C (en) * | 1999-07-07 | 2003-01-08 | 中国石化集团齐鲁石油化工公司 | Recovering process for C2 and C3 material from stopped ethylene plant |
| 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 |
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| CN100389100C (en) * | 2002-11-29 | 2008-05-21 | 中国石油化工股份有限公司 | Process for preparing olefin by cracking of kerosene distillate |
| CN102453501A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrocarbon oil conversion method |
| CN102453502A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Conversion method for hydrocarbon oil |
| CN102453502B (en) * | 2010-10-26 | 2014-01-15 | 中国石油化工股份有限公司 | Conversion method for hydrocarbon oil |
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