CN1314486C - Catalyst for disproportionation of butylene to produce propylene - Google Patents
Catalyst for disproportionation of butylene to produce propylene Download PDFInfo
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- CN1314486C CN1314486C CNB2003101086995A CN200310108699A CN1314486C CN 1314486 C CN1314486 C CN 1314486C CN B2003101086995 A CNB2003101086995 A CN B2003101086995A CN 200310108699 A CN200310108699 A CN 200310108699A CN 1314486 C CN1314486 C CN 1314486C
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- Prior art keywords
- propylene
- catalyst
- disproportionation
- butene
- butylene
- Prior art date
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000007323 disproportionation reaction Methods 0.000 title claims abstract description 24
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 33
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 24
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 238000000034 method Methods 0.000 abstract description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010955 niobium Substances 0.000 abstract description 6
- 229910052758 niobium Inorganic materials 0.000 abstract description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910019571 Re2O7 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002822 niobium compounds Chemical class 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a catalyst for the disproportionation of butylene to produce propylene, which mainly solves the problems of high consumption of ethene with a high added value, low airspeed, low butylene conversion rate, low propylene selectivity and low propylene yield in the process of the disproportionation to prepare propylene in the prior art. The present invention has the technical scheme that niobium or an oxide thereof is added to a tungsten oxide/silicon dioxide catalyst system; thus, the catalyst favorably solves the problems and can be applied to the industrial production of propylene by the disproportionation of butylene.
Description
Technical Field
The invention relates to a catalyst for preparing propylene by butene disproportionation.
Background
The demand for ethylene is currently growing differently from that for propylene, which is much greater than that for ethylene. The ratio of ethylene to propylene production is limited by existing catalytic cracking technology. On the other hand, the carbon four raw material is excessive to a certain extent along with the popularization of the urban natural gas. Whereas the carbon four feedstock contains a significant amount of carbon four olefins. The existing technology for producing propylene by disproportionation mainly comprises the step of carrying out disproportionation reaction on mixed butene of butene-1, butene-2 and the like to generate propylene and pentene or consuming expensive ethylene to obtain the propylene. Therefore, the direct use of single olefin to produce propylene and the use of butene-1 or butene-2 as a feedstock to obtain high propylene yields have been the goal of pursuit.
Olefin disproportionation is the cleavage and recombination of C ═ C double bonds in olefins over a catalyst to give new olefin products. For example, olefin disproportionation can be represented by the following formula:
wherein R1, R2, R3 and R4 are alkyl substituents. Relatively excessive butene with low added value can be disproportionatedC4The olefin in the raw material is converted into a high value-added propylene product, ethylene and hexene are simultaneously produced, and the pentene can be used for producing alkyl gasoline. Thus olefin disproportionation catalysts are key to the implementation of this process.
Olefin disproportionation catalyst is generally heterogeneous catalyst, and compounds of W, Mo, Re and the like are generally supported on inert carrier SiO2The above.
US6271430 proposes a process for obtaining propylene and pentene by disproportionation of butene-1 and butene-2. The catalyst adopted by the process is Re2O7/Al2O3. With liquid-solid phase reactions, the conversion and selectivity decrease with time. Document US6166279 uses the same Re2O7/Al2O3The catalyst is in a moving bed, and the ethylene and the amylene are adopted to react in two reactors, so that the catalyst has certain difficulty in regeneration.
WO 00014038 describes a process for preparing propylene by disproportionation of butene. The raw material of butylene is butylene-1, butylene-2 or the mixture thereof,and the catalyst is WO3/SiO2Or Cs+、PO4 3-Iso-modified WO3/SiO2The reaction temperature is usually 500 to 550 ℃ and the pressure is 1 atmosphere. The method is a one-step reaction, and no additional ethylene is needed in the reaction. The raw material adopted by the method is a fraction containing butene-1, butene-2 or a mixture thereof. The reaction is carried out in a fixed-bed tubular reactor, the reaction product being divided intoAfter the reaction, the unreacted C4, C5 and C5 hydrocarbon products are recycled to the reaction raw material, and the disproportionation is further carried out, so that the yield of the propylene can be improved. If pure butene-1 is used as the reaction raw material, the proportion of each component in the product is as follows: 8 percent of ethylene, 35 percent of propylene, 20 percent of C4 hydrocarbon, 27 percent of hydrocarbon above C5 and C5, more than 80 percent of C4 conversion rate and the highest yield of propylene can reach 30 percent. However, the weight space velocity of the patent is low, and is generally 0.7 hour-1And the temperature is high.
Disclosure of Invention
The invention aims to solve the technical problems that ethylene with high added value needs to be consumed for obtaining propylene and the space velocity is low, the conversion rate of butylene is low, the selectivity of propylene is low and the yield of propylene is low in the process of preparing propylene by disproportionating butylene in the prior art, and provides a novel catalyst for preparing propylene by disproportionating butylene. The catalyst is used for butene disproportionation reaction, and has the characteristics of suitability for high space velocity operation, high butene conversion rate, high propylene selectivity and high propylene yield.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a catalyst for preparing propylene by butene disproportionation comprises the following components in percentage by weight:
a) 8-12% of tungsten oxide;
b) 0.1-2% niobium oxide;
c)87 to 90.3% of an inorganic oxide carrier containing silica.
In the technical scheme, the preferable range of the using amount of the niobium oxide is 0.1-1%. The catalyst also contains 0.1-2% of magnesium or its oxide.
The preparation method of the catalyst can adopt the methods of dipping, chemical adsorption, chemical deposition, physical mixing and the like, and the preferable scheme is that the soluble tungsten and niobium compound aqueous solution is dipped into a carrier, and the carrier is dried and roasted in the air or inert atmosphere, wherein the roasting temperature is 350-1000 ℃, the preferable range is 500-800 ℃, and the roasting time is 0.5-15 hours.
The precursor of tungsten in the invention can be selected from compounds of tungsten such as sodium tungstate, ammonium metatungstate, ammonium paratungstate, tungstic acid, tungsten hexachloride and the like; the precursor of niobium can be selected from niobium compounds such as niobic acid, niobium nitrate or oxides thereof; the magnesium precursor can be selected from magnesium nitrate, magnesium oxide, etc.
The catalyst prepared by the technical scheme can be used for olefin disproportionation reaction, and in the embodiment of the invention, the catalyst is used for catalyzing butene disproportionation reaction to prepare propylene. The reaction conditions are that the reaction temperature in a fixed bed reactor is 250-550 ℃, the reaction pressure is 0.01-5 MPa, and the weight space velocity of the liquid phase is 0.1-5 hours-1Under the condition, the butene is disproportionated to generate propylene.The preferable range of the reaction temperature is 290-450 ℃, the preferable range of the reaction pressure is 0.2-1.1 MPa, and the preferable range of the liquid weight space velocity is 0.3-3 hours-1。
In the technical scheme, the butene raw material can be butene-1, butene-2 and a mixture thereof or a carbon four-fraction from a steam cracking device.
The niobium or the oxide component thereof is added into the catalyst, so that the acidity and alkalinity of the catalyst are further adjusted, the catalyst can be suitable for the butene disproportionation reaction to generate propylene, experiments prove that ethylene does not need to be consumed in the reaction, the reaction space velocity is greatly improved, the butene conversion rate can be improved by nearly 5 percent and the propylene selectivity can be improved by nearly 5 percent under the same conditions, and better technical effects are achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ COMPARATIVE EXAMPLE 1]
Accurately weighing a certain amount of ammonium metatungstate (A.R. grade, WO)383% by weight), adding deionized water equal in volume to the carrier, and stirring until completely dissolved. Additionally weighing a certain amount of SiO2Carrier (15 mesh) with specific surface area of 478 m2Per g, SiO260% by weight, placing into a roasting furnace for roasting, and roasting the silica gel in air at 550 ℃ for 2 hours before use.
And pouring the ammonium metatungstate solution into a silica gel beaker, adding the ammonium metatungstate solution while stirring, and then putting the mixture into an oven to dry overnight at 120 ℃. Placing the prepared sample in a muffle furnace to be roasted for 8 hours at the temperature of 550 ℃, and obtaining a butene disproportionation reaction catalyst WO3/SiO2，WO3The content is 10%.
In a reactor with a length of 60 cm and an internal diameter of 1.8 cm, 4 g of the prepared catalyst was added to the reactor, 99.5% butene-1 feed was introduced from the upper end of the reactor at 350 ℃, the feed flow rate was 12 g per hour, and the pressure was controlled at 0.55 MPa. The reaction product was analyzed on-line by gas chromatography, and the reaction result was 27.3% propylene yield, 45.1% butene conversion, and 60.5% propylene selectivity.
[ example 1]
The procedure, conditions and evaluation of catalyst conditions of comparative example 1 were conducted except that niobic acid was added to the catalyst preparation, and Nb was added after calcination2O5Accounting for 1.0 percent of the total weight of the catalyst, the reaction result is that the conversion rate of the butylene is 51 percent, the selectivity of the propylene is 72.5 percent, and the yield of the propylene is 37 percent.
[ example 2]
The procedure, conditions and evaluation of catalyst conditions of comparative example 1 were conducted except that niobic acid was added to the catalyst preparation, and Nb was added after calcination2O5Accounting for 0.1 percent of the total weight of the catalyst, the reaction result is that the conversion rate of the butylene is 47 percent, the selectivity of the propylene is 63.8 percent, and the yield of the propylene is 30 percent.
[ example 3]
The procedure, conditions and evaluation of catalyst conditions of comparative example 1 were conducted except that niobic acid and magnesium nitrate were added to the catalyst preparation, and Nb was added after calcination2O5Accounting for 0.5 percent of the total weight of the catalyst, and the MgO accounting for 2 percent of the total weight of the catalyst, the reaction result is that the conversion rate of the butylene is 49.6 percent, the selectivity of the propylene is 67.9 percent, and the yield of the propylene is 33.7 percent.
[ example 4]
The procedures, conditions and evaluation conditions of the catalyst in example 3 were conducted except that WO was used in the amount of the total weight of the catalyst3Content of 12%, Nb2O5The content was 0.5%, the MgO content was 0.5%, the reaction result was 50.4% for butene conversion, 70.6% for propylene selectivity, and 35.6% for propylene yield.
[ example 5]
The procedures, conditions and evaluation conditions of the catalyst in example 3 were conducted except that WO was used in the amount of the total weight of the catalyst3Content of 8% Nb2O5The content was 0.7%, the MgO content was 1.0%, the reaction result was 50% butene conversion, 71.2% propylene selectivity, and 35.6% propylene yield.
Claims (3)
1. A catalyst for preparing propylene by butene disproportionation comprises the following components in percentage by weight:
a) 8-12% of tungsten oxide;
b) 0.1-2% niobium oxide;
c) 87-90.3% of a silica carrier.
2. The catalyst for producing propylene by disproportionation of butene according to claim 1, wherein the amount of niobium oxide is 0.1-1% by weight.
3. The catalyst for producing propylene by disproportionation of butene according to claim 1, wherein the catalyst further contains 0.1-2% by weight of an oxide selected from magnesium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101086995A CN1314486C (en) | 2003-11-19 | 2003-11-19 | Catalyst for disproportionation of butylene to produce propylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101086995A CN1314486C (en) | 2003-11-19 | 2003-11-19 | Catalyst for disproportionation of butylene to produce propylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1618515A CN1618515A (en) | 2005-05-25 |
| CN1314486C true CN1314486C (en) | 2007-05-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101086995A Expired - Lifetime CN1314486C (en) | 2003-11-19 | 2003-11-19 | Catalyst for disproportionation of butylene to produce propylene |
Country Status (1)
| Country | Link |
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| CN (1) | CN1314486C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172925B (en) * | 2006-11-02 | 2010-05-12 | 中国石油化工股份有限公司 | Method for producing propylene with dismutation of ethylene and butylene |
| CN101239879B (en) * | 2007-02-07 | 2010-08-18 | 中国石油化工股份有限公司 | Method for producing propylene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4415480A (en) * | 1981-09-24 | 1983-11-15 | Exxon Research And Engineering Co. | Transition metal oxide Bronsted acid catalysts |
| US5120894A (en) * | 1988-09-19 | 1992-06-09 | Lyondell Petrochemical Company | Olefin conversion process |
| CN1373007A (en) * | 2001-02-28 | 2002-10-09 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by dismutation reaction and its preparing process and application |
| CN1403198A (en) * | 2001-08-29 | 2003-03-19 | 中国科学院大连化学物理研究所 | Catalyst for disproportionation reaction of ethylene and butene to prepare propylene and its prepn |
-
2003
- 2003-11-19 CN CNB2003101086995A patent/CN1314486C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4415480A (en) * | 1981-09-24 | 1983-11-15 | Exxon Research And Engineering Co. | Transition metal oxide Bronsted acid catalysts |
| US5120894A (en) * | 1988-09-19 | 1992-06-09 | Lyondell Petrochemical Company | Olefin conversion process |
| CN1373007A (en) * | 2001-02-28 | 2002-10-09 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by dismutation reaction and its preparing process and application |
| CN1403198A (en) * | 2001-08-29 | 2003-03-19 | 中国科学院大连化学物理研究所 | Catalyst for disproportionation reaction of ethylene and butene to prepare propylene and its prepn |
Non-Patent Citations (1)
| Title |
|---|
| C4烯烃歧化制丙烯技术 瞿勇等，石油化工，第31卷第12期 2002 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1618515A (en) | 2005-05-25 |
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