CN101362961B - Catalytic conversion method for preparing aromatic hydrocarbons and light olefins - Google Patents
Catalytic conversion method for preparing aromatic hydrocarbons and light olefins Download PDFInfo
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Abstract
The invention provides a catalysis conversion method used for preparing arene and low carbon olefin; the raw material with the distilling range of 160-260 DEG C contacts a catalytic cracking catalyst, so as to carry out the cracking reaction inside a fluidized bed reactor under the conditions of 450-750 DEG C of temperature, 0.1-800h<-1> of weight hourly space velocity, 0.10-1.0MPa of pressure, 1-150 of weight ratio of catalyst to raw material and 0.05-1.0 of weight ratio of water vapour to raw material; a spent catalyst and reaction oil gas are separated, and the spent catalyst is returned to the reactor after regeneration; the reaction oil gas is separated so as to gain the object outcome: low carbon olefin and arene. The method greatly increases the yield and selectivity of the ethane and propylene, the yield of the gasoline and the yield of the arene in the gasoline are extremely high, only little heavy oil is generated; furthermore, the yield of coke is low.
Description
Technical field
The invention belongs in the situation that there is not the catalysis conversion method of hydrogen hydrocarbon ils, more particularly, be a kind of be short chain aromatic hydrocarbons and low-carbon alkene with feedstock conversion, especially alkene is take ethene and propylene as main, short chain aromatic hydrocarbons take toluene, dimethylbenzene, isopropyl benzene as main catalysis conversion method.
Background technology
Low-carbon alkene such as ethene, propylene etc. are important Organic Chemicals, and as long as therein ethylene is for the production of polyethylene (HDPE, LDPE, LLDPE), oxyethane (EO), ethylene dichloride/vinyl chloride monomer (EDC/VCM) and ethylbenzene (EB).Whole world ethylene requirements amount is roughly from 7,300 ten thousand tons of 11,500 ten thousand tons of rising to 2006 of 1996.Analyze 2006-2010 ethylene requirements annual growth according to the chemical market combination meeting (CMAI) of houston, u.s.a and will be about 4.3%; And propylene is the synthon of the products such as polypropylene, vinyl cyanide.Along with increasing rapidly of the derivative demands such as polypropylene, the demand of propylene is also all being increased year by year.The demand in World Propylene market is 1,520 ten thousand tons of 5,120 ten thousand tons of being increased to 2000 before 20 years, and average growth rate per annum reaches 6.3%.The demand that expects propylene in 2010 will reach 8,600 ten thousand tons, and average growth rate per annum is about 5.6% therebetween.The present catalytically cracked gasoline quality of China is compared with the clean gasoline standard that is about to upgrading, olefin(e) centent is too high and aromaticity content is lower, the octane values such as the toluene in the short chain aromatic hydrocarbons of by-product, dimethylbenzene, isopropyl benzene are higher, can be used as the blend component of stop bracket gasoline, solve the effective way of present quality of gasoline problem, also can carry out in addition the BTX of Aromatics Extractive Project production high added value.
The method of producing ethene, propylene is mainly steam cracking and catalytic cracking (FCC), wherein steam cracking is produced ethene, propylene take mink cell focuses such as petroleum naphthas as raw material by thermo-cracking, but the productive rate of propylene is only that about 15 heavy %, FCC is take mink cell focuses such as vacuum gas oils (VGO) as raw material.At present, 66% propylene is produced the byproduct of ethene from steam cracking in the world, and 32% produces the byproduct of vapour, diesel oil from refinery FCC, a small amount of (approximately 2%) is obtained by dehydrogenating propane and ethene-butylene metathesis reaction.
If petrochemical complex is walked traditional preparing ethylene by steam cracking, propylene route, will face several large restraining factors such as the shortage of lightweight material oil, inefficiency of production and high cost.
FCC is because the advantages such as its adaptability to raw material is wide, flexible operation come into one's own day by day.In the U.S., almost 50% of the propylene market demand all derive from FCC apparatus.It is very fast that the catalytic cracking of propylene enhancing improves technical development.
US4,980,053 disclose a kind of hydrocarbon conversion processes of preparing low-carbon olefins, and raw material is petroleum fractions, residual oil or the crude oil of different boiling ranges, uses solid acid catalyst in fluidized-bed or moving-burden bed reactor, temperature 500-650 ℃, pressure 1.5-3 * 10
5Pa, weight hourly space velocity 0.2-2.0h
-1, agent-oil ratio 2-12 condition under carry out catalytic conversion reaction, reacted catalyzer Returning reactor internal recycle after coke burning regeneration uses.The overall yield of the method ethene, propylene and butylene can reach 50% left and right, and the therein ethylene productive rate is 7.37, and productivity of propylene is up to 26.34%.Aromatic Hydrocarbon in Gasoline content is up to 50.46%
WO00/31215A1 discloses a kind of catalyst cracking method of producing alkene, the method adopts ZSM-5 and/or ZSM-11 zeolite to do active component, catalyzer take a large amount of inert substances as matrix, take VGO as raw material, the productive rate of ethene and propylene closes can surpass at most 20 heavy %.
US4,422,925 disclose the method that multiple hydro carbons with different cracking performances contacts and transforms with hot regenerated catalyst, the described hydro carbons of the method contains a kind of gas alkane raw material and a kind of liquid hydrocarbon raw material at least, the method has different cracking performances according to different hydrocarbon molecules, reaction zone is divided into a plurality of reaction zones carries out cracking reaction, with voluminous low-molecular olefine.
Cracking reaction designs still Shortcomings to above-mentioned prior art to alkane molecule, causing is increasing in the productivity of propylene situation, dry gas yied increases considerably, simultaneously, the product of prior art distributes and is that routinely FCC fractionating system is cut, arene underwater content in gasoline or diesel oil and low-carbon alkene potential content are underused, and cause ethene, propylene, aromatics yield is on the low side.In order to satisfy the demand of growing propylene, aromatic hydrocarbons industrial chemicals, be necessary to develop a kind of catalysis conversion method of a large amount of production propylene.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology the catalysis conversion method of a kind of preparing aromatic hydrocarbon and low-carbon alkene, wherein low-carbon alkene is take ethene, propylene as main, and the toluene of aromatic hydrocarbons in the mononuclear aromatics, dimethylbenzene, isopropyl benzene are as main.
Method of the present invention is so concrete enforcement: boiling range is that the raw material of 160 ℃-260 ℃ contacts with catalytic cracking catalyst, at 450 ℃-750 ℃ of temperature, weight hourly space velocity 0.1h
-1-800h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 1-150, the weight ratio of water vapor and raw material is under the 0.05-1.0 condition, carry out cracking reaction in fluidized-bed reactor, separate reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after regeneration, and separating reaction oil gas is isolated to purpose product low-carbon alkene and aromatic hydrocarbons.
Described raw material is that boiling range is 160 ℃-260 ℃ preferred cuts of 170 ℃-250 ℃, is selected from one or more the mixture in straight run petrol and diesel oil, coker gasoline and diesel, coking gasoline and diesel, thermally splitting petrol and diesel oil, hydrogenation petrol and diesel oil, gelatin liquefaction petrol and diesel oil." petrol and diesel oil " of the present invention refers to meet the mixed fraction of heavy petrol and the solar oil of above-mentioned boiling range.
Described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, and each component accounts for respectively total catalyst weight: the heavy % of the heavy %-50 of zeolite 1, the heavy % of the heavy %-99 of inorganic oxide 5, the heavy % of the heavy %-70 of clay 0.
Its mesolite is selected from mesopore zeolite and optional large pore zeolite as active ingredient, and mesopore zeolite accounts for the 50 heavy % of heavy %-100 of zeolite gross weight, and the preferred 70 heavy % of heavy %-100, large pore zeolite account for the 0 heavy % of heavy %-50 of zeolite gross weight, the preferred 0 heavy % of heavy %-30.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also can carry out modification with transition metals such as the non-metallic elements such as phosphorus and/or iron, cobalt, nickel to above-mentioned mesopore zeolite, the more detailed description of relevant ZRP is referring to US5,232,675, the ZSM series zeolite is selected from one or more the mixture among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, the more detailed description of relevant ZSM-5 is referring to US3,702,886.Large pore zeolite selects one or more the mixture in this group zeolite that super steady Y, high silicon Y that free Rare Earth Y (REY), rare earth hydrogen Y (REHY), different methods obtain consist of.
Inorganic oxide is selected from silicon-dioxide (SiO as caking agent
2) and/or aluminium sesquioxide (Al
2O
3).
Clay is selected from kaolin and/or halloysite as matrix (being carrier).
Described fluidized-bed reactor be selected from riser tube, etc. fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, one or both series combinations of downstriker transfer limes of linear speed.Riser tube can be conventional isodiametric riser tube, can be also the riser tube of various forms reducing.Wherein the gas speed of fluidized-bed is 0.1 meter per second-2 meter per second, and the gas speed of riser tube is 2 meter per seconds-30 meter per second (disregarding catalyzer).
Preferred reaction conditions is: 500 ℃-700 ℃ of temperature, weight hourly space velocity 0.5h
-1-500h
-1, reaction pressure 0.2MPa-0.8MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 5-120, the weight ratio of water vapor and raw material is 0.1-0.8.
The mononuclear aromatics that this technical scheme is larger with the content in raw material effectively utilizes, and the present invention compared with prior art has following unforeseeable technique effect:
1, ethene, productivity of propylene and its respectively the selectivity in dry gas, liquefied gas increase considerably.Wherein in dry gas, the productive rate of ethene can be up to 60 heavy %; In liquefied gas, the productive rate of propylene is up to 49 heavy %;
2, in the situation that productivity of low carbon olefin hydrocarbon increases considerably, the yield of gasoline is up to 66 heavy %, and more than the Aromatic Hydrocarbon in Gasoline productive rate can weigh % up to 63, and wherein C6-C9 aromatic hydrocarbons accounts for the heavy % of gasoline 50;
3, only have a small amount of heavy oil to generate, and coke yield is lower.
Description of drawings
Accompanying drawing is the catalysis conversion method schematic flow sheet of preparing aromatic hydrocarbon provided by the invention and low-carbon alkene.
Embodiment
Below in conjunction with accompanying drawing, method provided by the present invention is further detailed, but does not therefore limit the present invention.
Accompanying drawing is the catalysis conversion method schematic flow sheet of preparing aromatic hydrocarbon provided by the invention and low-carbon alkene.
Its technical process is as follows:
The pre-lift medium is entered by riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 11 under the castering action of pre-lift medium along the riser tube accelerated motion that makes progress, boiling range is that the stock oil of 160 ℃-260 ℃ is through pipeline 3 and injecting lift pipe 2 together with the atomizing steam of pipeline 4, mix with the existing logistics of riser reactor, cracking reaction occurs in raw material on the catalyzer of heat, and upwards accelerated motion.The oil gas that generates and the reclaimable catalyst of inactivation enter the cyclonic separator in settling vessel 5, realize separating of reclaimable catalyst and oil gas, and oil gas enters subsequent separation system through pipeline 6, separates to obtain low-carbon alkene and aromatic hydrocarbons.Catalyst fines returns to settling vessel 5 by dipleg.In settling vessel, reclaimable catalyst flows to stripping stage 7, contacts with steam from pipeline 8.The oil gas that stripping goes out from reclaimable catalyst enters subsequent separation system after cyclonic separator separates.Reclaimable catalyst after stripping enters revivifier 10 through inclined tube 9, and main air enters revivifier 10 through pipeline 11, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters the cigarette machine through pipeline 12.Catalyzer after regeneration enters riser tube through inclined tube 13 and recycles.
The following examples will be further described present method, but therefore not limit present method.
In embodiment, raw material used is the catalytic diesel oil cut, and its character is as shown in table 1.
Catalytic cracking catalyst preparation method used in embodiment is summarized as follows:
1), with 20gNH
4Cl is dissolved in 1000g water, adds 100g (butt) crystallization product ZRP-1 zeolite (production of Qilu Petrochemical Company catalyst plant, SiO in this solution
2/ Al
2O
3=30, content of rare earth RE
2O
3=2.0 heavy %), after 90 ℃ of exchange 0.5h, filter to get filter cake; Add 4.0gH
3PO
4(concentration 85%) and 4.5gFe (NO
3)
3Be dissolved in 90g water, dry with the filter cake hybrid infusion; Then process at 550 ℃ of roasting temperatures and obtained phosphorous and MFI structure mesopore zeolite iron in 2 hours, its elementary analytical chemistry consists of
0.1Na
2O·5.1AI
2O
3·2.4P
2O
5·1.5Fe
2O
3·3.8RE
2O
3·88.1SiO
2。
2), with 250kg decationized Y sieve water with 75.4kg halloysite (Suzhou china clay company Industrial products, solid content 71.6m%) making beating, add again 54.8kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63m%), with hydrochloric acid, its PH is transferred to 2-4, stir, under 60-70 ℃ standing aging 1 hour, maintenance PH was 2-4, cools the temperature to below 60 ℃, add 41.5Kg aluminium colloidal sol (Qilu Petrochemical Company catalyst plant product, Al
2O
3Content is 21.7m%), stirred 40 minutes, obtain mixed serum.
3), with step 1) MFI structure mesopore zeolite (butt is 22.5kg) and DASY zeolite (the Qilu Petrochemical Company catalyst plant Industrial products of the phosphorous and iron of preparation, lattice constant is 2.445-2.448nm, butt is 2.0kg) join step 2) in the mixed serum that obtains, stir, spray drying forming, with ammonium dihydrogen phosphate (phosphorus content is 1m%) washing, wash away free Na
+, being drying to obtain the catalytic cracking catalyst sample, phosphorous MFI structure mesopore zeolite, 3 heavy %DASY zeolites, the 32 heavy % pseudo-boehmites, 6 with iron of 15 heavy % that consist of of this catalyzer weigh % aluminium colloidal sol and surplus kaolin.
Method provided by the invention is adopted in the present embodiment explanation, and catalyzed conversion is produced the situation of aromatic hydrocarbons and low-carbon alkene in the small-sized fluidized bed reactor.
The listed initial boiling point of table 1 is greater than the distillate A of the 165 ℃ raw material as catalytic pyrolysis, use the catalytic cracking catalyst of the present embodiment preparation, react in the small-sized fluidized bed of successive reaction regenerative operation and carry out the experiment that the distillate catalyzed conversion is produced aromatic hydrocarbons and low-carbon alkene in it.Distillate A mixes with the preheating high-temperature water vapor laggardly to enter in fluidized-bed reactor, is 545 ℃ in temperature of reaction, and reacting its top pressure is 0.3MPa, and weight hourly space velocity is 13h
-1, agent-oil ratio is 9, water vapor and raw material weight are than being to contact with catalyzer under 0.15 condition to carry out preparing low carbon alkene by catalytic conversion and aromatic hydrocarbons.Reaction product, steam and reclaimable catalyst separate in settling vessel, and reaction product isolated obtains gaseous product and product liquid, and reclaimable catalyst enters stripper, is gone out the hydrocarbon product that adsorbs on reclaimable catalyst by the water vapor stripping.Catalyzer after stripping enters into revivifier, contacts regeneration with the warm air that heated, and the catalyzer after life turns back to reactor cycles again and uses.Operational condition and product distribute and list in table 2.
As can be seen from Table 2, in dry gas, the productive rate of ethene weighs % up to 60.12; In liquefied gas, the productive rate of propylene is up to 49.91 heavy %; In gasoline, the productive rate of high-octane rating aromatic hydrocarbons is up to 63.53 heavy %; The yield of gasoline is up to 66.53 heavy %, and research octane number (RON) (RON) is up to 94.8; Only there is the heavy oil of 1.23 heavy % to generate.
Comparative Examples 1
Comparing the grease separation of this reaction raw materials with embodiment 1 is full range diesel oil B, and concrete experimental procedure is identical with embodiment 1, and operational condition and product distribute and list in table 2.As can be seen from Table 2, although in dry gas, the productive rate of ethene is up to 48.20 heavy %, in liquefied gas, the productive rate of propylene is up to 45.83 heavy %, in gasoline, the productive rate of high-octane rating aromatic hydrocarbons is up to 44.33 heavy %, but the yield of gasoline is only 29.48 heavy %, RON is 93.20, and has the heavy oil up to 13.02 heavy % to generate, and coke yield is also higher.
Method provided by the invention is adopted in the present embodiment explanation, uses the situation of different boiling range raw materials preparing low carbon alkene by catalytic conversion and aromatic hydrocarbons in the small-sized fluidized bed reactor.
The preparing low carbon alkene by catalytic conversion that the listed initial boiling point of table 1 carries out in the small-sized fluidized bed reactor of successive reaction regeneration condition as the raw material of catalytic pyrolysis greater than the distillate C of 171 ℃ and the experiment of aromatic hydrocarbons.Concrete experimental procedure is identical with embodiment 1.Operational condition and product distribute and list in table 2.
As can be seen from Table 2, in dry gas, the productive rate of ethene weighs % up to 58.36; In liquefied gas, the productive rate of propylene is up to 47.38 heavy %; In gasoline, the productive rate of high-octane rating aromatic hydrocarbons is up to 59.85%; The yield of gasoline is up to 64.41 heavy %; RON is up to 94.40; Only there is the heavy oil of 1.02 heavy % to generate.
Table 1
| |
Comparative Examples 1 | |
|
| The stock oil numbering | A | B | C |
| Stock oil character | |||
| Density (20 ℃), g/cm 3 | 0.8536 | 0.9056 | 0.8659 |
| Group composition, w% | |||
| Stable hydrocarbon | 28.9 | 41.5 | 34.2 |
| Paraffinic hydrocarbons | 16.2 | 25.3 | 20.8 |
| Naphthenic hydrocarbon | 12.7 | 16.2 | 13.4 |
| Aromatic hydrocarbons | 70.6 | 57.6 | 64.8 |
| Mononuclear aromatics | 53.2 | 19.6 | 45.6 |
| Dicyclo and polycyclic aromatic hydrocarbons | 17.4 | 38.0 | 19.2 |
| Colloid | 0.5 | 0.9 | 1.0 |
| Boiling range (ASTM D-1160), ℃ | |||
| IBP | 165 | 165 | 171 |
| 30％ | 175 | 235 | 180 |
| 50％ | 185 | 270 | 209 |
| 70％ | 202 | 319 | 235 |
| EP | 223 | 352 | 254 |
Table 2
| |
Comparative Examples 1 | |
|
| The stock oil numbering | A | B | C |
| Operational condition | |||
| Temperature of reaction, ℃ | 545 | 545 | 500 |
| Reaction pressure, MPa | 0.3 | 0.3 | 0.2 |
| Weight hourly space velocity, |
13 | 13 | 15 |
| Agent-oil ratio, m/ |
9 | 9 | 8 |
| Water vapor/raw material weight ratio | 0.15 | 0.15 | 0.10 |
| Product distributes, heavy % | |||
| Dry gas | 1.24 | 3.26 | 1.97 |
| Ethene | 60.12 | 48.20 | 58.36 |
| Liquefied gas | 8.89 | 12.87 | 9.62 |
| Propylene | 49.91 | 45.83 | 47.38 |
| Gasoline | 66.53 | 29.48 | 64.41 |
| Alkane | 24.59 | 37.68 | 26.30 |
| Alkene | 9.12 | 13.12 | 9.98 |
| Naphthenic hydrocarbon | 2.76 | 4.87 | 3.87 |
| Aromatic hydrocarbons | 63.53 | 44.33 | 59.85 |
| C6-C9 aromatic hydrocarbons | 50.82 | 34.58 | 49.68 |
| Diesel oil | 19.30 | 37.04 | 20.25 |
| Heavy oil | 1.23 | 13.02 | 1.02 |
| Coke | 2.60 | 4.12 | 2.52 |
| Loss | 0.21 | 0.21 | 0.21 |
| Octane value (RON) | 94.8 | 93.2 | 94.4 |
Claims (5)
1. the catalysis conversion method of a preparing aromatic hydrocarbon and low-carbon alkene is characterized in that boiling range is that the raw material of 160 ℃-260 ℃ contacts with catalytic cracking catalyst, at 450 ℃-750 ℃ of temperature, weight hourly space velocity 0.1h
-1-800h
-1, reaction pressure 0.10MPa-1.0MPa, catalytic cracking catalyst and raw material weight ratio 1-150, the weight ratio of water vapor and raw material is under the 0.05-1.0 condition, carry out cracking reaction in fluidized-bed reactor, separate reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after regeneration, reaction oil gas is isolated to purpose product aromatic hydrocarbons, and described raw material is selected from one or more the mixture in straight run petrol and diesel oil, coker gasoline and diesel, coking gasoline and diesel, thermally splitting petrol and diesel oil, hydrogenation petrol and diesel oil, gelatin liquefaction petrol and diesel oil.
2. according to the method for claim 1, it is characterized in that described raw material is that boiling range is the cut of 170 ℃-250 ℃.
3. according to the method for claim 1, it is characterized in that described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, each component accounts for respectively total catalyst weight: the heavy % of the heavy %-50 of zeolite 1, the heavy % of the heavy %-99 of inorganic oxide 5, the heavy % of the heavy %-70 of clay 0, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for the 50 heavy % of heavy %-100 of zeolite gross weight, large pore zeolite accounts for the 0 heavy % of heavy %-50 of zeolite gross weight, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from the Y-series zeolite.
4. according to the method for claim 1, it is characterized in that reactor used be selected from riser tube, etc. the fluidized-bed, one or both series combinations in isodiametric fluidized-bed of linear speed, wherein riser tube is conventional isodiametric riser tube or the riser tube of various forms reducing.
5. according to the method for claim 1, it is characterized in that reaction conditions is: 500 ℃-700 ℃ of temperature, weight hourly space velocity 0.5h
-1-500h
-1, reaction pressure 0.2MPa-0.8MPa, catalytic cracking catalyst and raw material weight ratio 5-120, the weight ratio of water vapor and raw material is 0.1-0.8.
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| JP2012503038A (en) * | 2008-09-15 | 2012-02-02 | ユーオーピー エルエルシー | Method to increase propylene yield and reduce benzene in the resulting naphtha fraction from cracked hydrocarbon feed |
| CN102031140B (en) * | 2009-09-29 | 2014-04-30 | 中国石油化工股份有限公司 | Combination method of gasification and coke processing from inferior heavy oil |
| KR101545073B1 (en) * | 2011-05-24 | 2015-08-17 | 제이엑스 닛코닛세키에너지주식회사 | Method for producing monocyclic aromatic hydrocarbon and plant for producing monocyclic aromatic hydrocarbon |
| CN104419459B (en) * | 2013-08-30 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of catalysis conversion method producing propylene and oil fuel |
| CN104726131B (en) * | 2015-03-17 | 2016-06-08 | 东南大学 | The pre-carbon distribution of a kind of catalyst increases the apparatus and method of hydro carbons productivity |
| CN112745932B (en) * | 2019-10-30 | 2022-07-15 | 中国石油化工股份有限公司 | Method for producing light aromatic hydrocarbon |
| CN113620768B (en) * | 2020-05-08 | 2024-02-09 | 中国石油化工股份有限公司 | Method for producing ethylene, propylene and aromatic hydrocarbon and catalytic reaction system |
| CN114686252B (en) * | 2021-12-26 | 2024-02-09 | 中海油天津化工研究设计院有限公司 | Method for preparing chemicals from crude oil |
Citations (1)
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|---|---|---|---|---|
| CN1031834A (en) * | 1987-08-08 | 1989-03-22 | 中国石油化工总公司石油化工科学研究院 | Produce the hydrocarbons catalytic conversion method of low-carbon alkene |
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2007
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031834A (en) * | 1987-08-08 | 1989-03-22 | 中国石油化工总公司石油化工科学研究院 | Produce the hydrocarbons catalytic conversion method of low-carbon alkene |
Non-Patent Citations (1)
| Title |
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| 邹仁鋆.《石油化工裂解原理与技术》.《石油化工裂解原理与技术》.化学工业出版社,1986,正文第38-40页. * |
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