CN1201862C - Catalyst for preparing propene at low temp. from ethylene and butylene, proparation process and use thereof - Google Patents
Catalyst for preparing propene at low temp. from ethylene and butylene, proparation process and use thereof Download PDFInfo
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- CN1201862C CN1201862C CNB021243883A CN02124388A CN1201862C CN 1201862 C CN1201862 C CN 1201862C CN B021243883 A CNB021243883 A CN B021243883A CN 02124388 A CN02124388 A CN 02124388A CN 1201862 C CN1201862 C CN 1201862C
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- butene
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- ethylene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000005977 Ethylene Substances 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title description 10
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 30
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- 239000010937 tungsten Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 5
- 238000007323 disproportionation reaction Methods 0.000 abstract description 10
- 238000005470 impregnation Methods 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 9
- 238000007796 conventional method Methods 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 7
- 229940010552 ammonium molybdate Drugs 0.000 description 7
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 150000003282 rhenium compounds Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-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)
Abstract
一种用于低温下由乙烯和丁烯通过反歧化反应制丙烯的催化剂，组成为活性组份和载体，活性组份为钼的氧化物和/或钨的氧化物，其重量担载量为0.5-20%，载体为氧化铝或含氧化铝的混合物，载体中氧化铝的重量含量至少为50%。该催化剂的制备方法为：首先用常规方法制备颗粒状混合物载体，然后用提供钼和/或钨元素的溶液浸渍前述粒子，干燥后于400-850℃焙烧，制得所需催化剂。还可以任意重复上述浸渍和焙烧步骤。在压力为0.1-10.0MPa，温度为0-200℃的条件下，该催化剂用于由乙烯和丁烯制丙烯的反歧化反应中，可以在固定床或流化床或浆态床反应器中进行。A catalyst for producing propylene from ethylene and butene through anti-disproportionation reaction at low temperature, consisting of an active component and a carrier, the active component is an oxide of molybdenum and/or an oxide of tungsten, and its weight loading is 0.5-20%, the carrier is alumina or a mixture containing alumina, and the weight content of alumina in the carrier is at least 50%. The preparation method of the catalyst is as follows: firstly, the granular mixture carrier is prepared by a conventional method, and then the particles are impregnated with a solution providing molybdenum and/or tungsten elements, dried and calcined at 400-850° C. to obtain the desired catalyst. It is also possible to arbitrarily repeat the above impregnation and roasting steps. Under the condition of pressure of 0.1-10.0MPa and temperature of 0-200℃, the catalyst is used in the dedisproportionation reaction of producing propylene from ethylene and butene, and can be used in fixed bed, fluidized bed or slurry bed reactor conduct.
Description
Technical field
The present invention relates to a kind of being used under the low temperature by ethene and butylene catalyst by reversal disproportionation preparation of propene, use catalyst provided by the invention can high conversion, high selectivity and high stability ground produces propylene.
The present invention relates to above-mentioned Preparation of catalysts method.
The invention still further relates to above-mentioned Application of Catalyst.
Background technology
Propylene is one of important foundation raw material of development petrochemical industry, also is the fastest industrial chemicals of demand growth in the world, and world's propylene demand from 1,800 ten thousand tons of nearly 5,000 ten thousand tons of increasing to 2000 in 1980, expects 2010 and will reach 7,500 ten thousand tons.It with ethene and butene reaction system propylene one of method that increases propone output, because supply exceed demand for butylene at present, especially the butene-2 shortage is effectively utilized approach, so suit measures to local conditions to adopt this course of reaction can reasonably regulate the product layout of ethene, propylene and butylene.There is part to contain the crude ethylene of methane, ethane and small quantity of hydrogen in addition in the product of heavy oil catalytic pyrolysis, itself and butene reaction are made propylene, both can improve the output of propylene, and can reduce the energy consumption of cryogenic separation again, and this course of reaction is more favourable than propylene disproportionation as can be known by calculation of thermodynamics.This is a process with practicality and novelty, and it is succeeded in developing and can produce remarkable economic efficiency and social benefit.
United States Patent (USP) (USP:5877365) has been reported C
4Cut is converted into polyisobutene and propylene process.This process comprises following three steps: (1) butene-1 tautomerizes to butene-2; (2) isobutene polymerisation becomes polyisobutene; (3) the anti-disproportionation system propylene of butene-2 and ethene.The anti-disproportionation system propylene of butene-2 and ethene catalyst system therefor is the oxide carried on a mixed oxide of rhenium (0.01-20wt%), this mixed oxide comprises at least 75% aluminium oxide, other is a sieve and silica-sesquioxide, one or both in the oxide of molecular sieve and 0.01-30% niobium and tantalum.Reaction temperature is between 0-200 ℃, and pressure is higher than the saturated vapor pressure of gaseous mixture under the respective reaction temperature.
United States Patent (USP) (USP:5120894) has been reported the catalyst of ethene and butene inverse disproportionation system propylene, this catalyst is the oxide carried on silica supports of tungsten, this catalyst is used for the reaction by ethene and butene inverse disproportionation system propylene, and the range of reaction temperature of requirement is 274-360 ℃.
Chinese patent (CN1033246A) has been reported and has been applicable to C
6-C
60Monomer alkene prepares the catalyst of different carbon number alkene by disproportionated reaction, and mainly consisting of of it supports molybdenum oxide on the aluminium oxide, also contain the compound of phosphorus and/or sulphur simultaneously.
Chinese patent (application number is 1104355.5) has been reported the catalyst of ethene and butene inverse disproportionation system propylene, this catalyst is that molybdenum, tungsten and rhenium compound are carried on the molecular sieve carrier, and molecular sieve comprises Silicate-2, Y, HB, SAPO series, ZSM series and MCM series etc.Be reflected in fixed bed or the fluidized-bed reactor and carry out, reaction temperature 0-300 ℃; Weight space velocity is 0.01-3h
-1Ethylene/butylene in the reactor feed gas is than being 0.2-4; Reaction pressure is 0.1-2.0MPa.
Summary of the invention
The object of the present invention is to provide a kind of being used under the low temperature by ethene and butylene system propylene catalyst, use catalyst provided by the invention can high conversion, high selectivity and high stability ground produces propylene.
For achieving the above object, catalyst provided by the invention, it consists of A/D, active constituent A is the oxide of molybdenum and/or the oxide of tungsten, its weight loading is 0.5-20%, is preferably 1-15%, and carrier D is aluminium oxide or aluminium oxide and other hopcalites, the weight content of aluminium oxide is no less than 50% in the carrier, preferably is no less than 60%.Other oxides comprise one or more in silica, clay, alkaline earth oxide or the rare-earth oxide.
Another purpose of the present invention is to provide above-mentioned Preparation of catalysts method, its preparation method is: at first prepare the mixture carrier particle with conventional method, with the solution impregnation aforementioned particles that molybdenum and/or W elements are provided, dry back makes required catalyst in 400-850 ℃ of roasting then.Can also repeatedly repeat above-mentioned dipping and calcination steps.Sintering temperature is preferably 500-800 ℃.
Another object of the present invention is to provide above-mentioned catalyst to be used under the low temperature reaction by ethene and butene inverse disproportionation system propylene.During reaction, C
4Raw material can be a butene-2, can be butene-2 content greater than 50% mixed material, also can be butene-1.When being raw material with the butene-1, butene-1 need at first carry out isomerization reaction, to obtain butene-1, butene-2 mixed material near thermodynamic equilibrium value as anti-disproportionation raw material; Reaction condition is: temperature 0-200 ℃, be preferably 50-150 ℃; Pressure is 0.1-10.0Mpa, is preferably 0.3-6.5MPa; The butene-2 weight space velocity is 0.01-3h
-1Ethylene/butylene in the reaction raw materials-2 molecular proportion is 0.2-10.
The specific embodiment
Below in conjunction with embodiment the present invention is further elaborated, but range of application of the present invention is not produced any restriction.
Embodiment 1
Prepare graininess with conventional method and have Al
2O
3Carrier takes out 10 grams and carries out vacuum impregnation with ammonium molybdate solution, through 120 ℃ of oven dry and 650 ℃ of roastings 3 hours, makes required catalyst A then, and the weight content of Mo is 6%.
Embodiment 2
Prepare graininess with conventional method and have Al
2O
3Carrier takes out 10 grams and carries out vacuum impregnation with ammonium molybdate solution, through 120 ℃ of oven dry and 700 ℃ of roastings 3 hours, makes required catalyst B then, and the weight content of Mo is 9%.
Embodiment 3
Prepare graininess with conventional method and have Al
2O
3Carrier, take out 10 grams and carry out vacuum impregnation with ammonium molybdate solution, then through 120 ℃ of oven dry and 700 ℃ of roastings 3 hours, with this calcining matter is carrier, carry out vacuum impregnation with ammonium molybdate solution once more, through 120 ℃ of oven dry and 700 ℃ of roastings 3 hours, make required catalyst C then, the weight content of Mo is 8%.
Embodiment 4
Prepare graininess with conventional method and have 70Al
2O
3-30SiO
2(70 and 30 represent weight content respectively) carrier takes out 10 grams and carries out vacuum impregnation with ammonium molybdate solution, through 120 ℃ of oven dry and 700 ℃ of roastings 3 hours, makes required catalyst D then, and the weight content of Mo is 9%.
Embodiment 5
The Al that has the certain granules degree with the conventional method preparation
2O
3Carrier takes out 10 grams and carries out vacuum impregnation with ammonium molybdate and ammonium tungstate mixed solution, through 120 ℃ of oven dry and 650 ℃ of roastings 3 hours, makes required catalyst E then, and the weight content of Mo and W is respectively 6% and 3%.
Embodiment 6
The Al that has the certain granules degree with the conventional method preparation
2O
3Carrier takes out 10 grams and carries out vacuum impregnation with ammonium molybdate solution, through 120 ℃ of oven dry and 750 ℃ of roastings 2 hours, makes required catalyst F then, and the weight content of Mo is 6%.
Embodiment 7
Is in the stainless steel fixed bed reactors of 10mm, at N with 5g according to the catalyst of the embodiment method preparation internal diameter of packing into
2Atmosphere in be warmed up to 550 ℃ and kept 1 hour, then at N
2Atmosphere drop to 100 ℃.With nitrogen reacting system pressure is upgraded to 1.0MPa, switching nitrogen is that ethene and butene-2 carry out anti-disproportionated reaction, and keeping the weight space velocity of butene-2 is 0.2, and ethylene/butylene-2 molecular proportion is 3.Switch and begin sample analysis after 20 minutes.The performance that A, B, C, D, E and six kinds of catalyst of F changed with the reaction time 1-table 6 (is criterion calculation propylene selectivity with the butene-2) of tabulating as follows.
The reactivity worth of table 1 catalyst A
| Reaction time (hour) | X C2H4(％) | X C4H8-2 (％) | S C3H6(％) |
| 5 | 29.25 | 82.30 | 91.12 |
| 10 | 26.27 | 76.45 | 90.11 |
| 15 | 24.32 | 70.37 | 88.98 |
| 20 | 22.79 | 64.87 | 91.02 |
The reactivity worth of table 2 catalyst B
| Reaction time (hour) | X C2H4(％) | X C4H8-2(％) | S C3H6(％) |
| 5 | 30.94 | 80.95 | 87.95 |
| 10 | 30.47 | 80.65 | 89.45 |
| 15 | 30.38 | 80.40 | 90.11 |
| 20 | 30.26 | 79.89 | 89.28 |
| 25 | 28.95 | 79.54 | 89.27 |
| 30 | 28.32 | 79.17 | 89.95 |
| 35 | 28.00 | 78.78 | 90.04 |
| 40 | 27.75 | 78.24 | 90.56 |
| 45 | 26.07 | 77.35 | 89.78 |
| 50 | 25.39 | 74.34 | 89.45 |
| 55 | 22.45 | 65.87 | 88.62 |
| 60 | 21.70 | 61.92 | 89.63 |
The reactivity worth (1) of table 3 catalyst C
| Reaction time (hour) | X C2H4(％) | X C4H8-2(％) | S C3H6(％) |
| 5 | 29.45 | 83.65 | 89.91 |
| 10 | 27.68 | 80.15 | 90.18 |
| 15 | 27.53 | 79.42 | 90.00 |
| 20 | 26.43 | 75.98 | 89.69 |
| 25 | 25.87 | 73.42 | 89.35 |
| 30 | 23.46 | 68.51 | 89.18 |
| 35 | 22.65 | 63.27 | 90.24 |
The reactivity worth of table 4 catalyst D
| Reaction time (hour) | X C2H4(％) | X C4H8-2(％) | S C3H6(％) |
| 5 | 28.92 | 83.19 | 89.32 |
| 10 | 27.57 | 81.34 | 88.65 |
| 15 | 26.96 | 79.06 | 90.78 |
| 20 | 25.47 | 74.62 | 89.45 |
| 25 | 24.15 | 69.25 | 89.99 |
| 30 | 22.07 | 64.02 | 89.96 |
The reactivity worth of table 5 catalyst E
| Reaction time (hour) | X C2H4(％) | X C4H8-2(％) | S C3H6(％) |
| 5 | 28.38 | 83.95 | 89.65 |
| 10 | 28.05 | 82.65 | 90.32 |
| 15 | 27.36 | 81.96 | 89.41 |
| 20 | 26.94 | 80.21 | 90.85 |
| 25 | 26.47 | 78.69 | 89.67 |
| 30 | 24.75 | 73.54 | 90.78 |
| 35 | 24.07 | 69.45 | 89.87 |
| 40 | 22.30 | 65.77 | 90.11 |
The reactivity worth of table 6 catalyst F
| Reaction time (hour) | X C2H4(％) | X C4H8-2(％) | S C3H6(％) |
| 5 | 29.82 | 83.40 | 90.14 |
| 10 | 27.96 | 81.07 | 89.66 |
| 15 | 25.74 | 74.90 | 90.30 |
| 20 | 23.61 | 69.88 | 89.99 |
| 25 | 21.96 | 63.2 | 90.36 |
Embodiment 8
Is in the stainless steel fixed bed reactors of 10mm, at N with 5g according to the catalyst C of the embodiment method preparation internal diameter of packing into
2Atmosphere in be warmed up to 550 ℃ and kept 1 hour, then at N
2Atmosphere drop to 50 ℃.With nitrogen reacting system pressure is upgraded to 6.0MPa, switching nitrogen is that ethene and butene-2 carry out anti-disproportionated reaction, and keeping the weight space velocity of butene-2 is 0.05, and ethylene/butylene-2 molecular proportion is 0.9.Switch and begin sample analysis after 20 minutes.The results are shown in Table 7 (are criterion calculation propylene selectivity with the butene-2).
The reactivity worth (2) of table 7 catalyst C
| Reaction time (hour) | X C2H4(％) | X C4H8-2(％) | S C3H6 (％) |
| 5 | 73.46 | 80.24 | 93.42 |
| 10 | 72.18 | 80.07 | 93.59 |
| 15 | 72.00 | 79.80 | 92.87 |
| 20 | 71.87 | 79.65 | 94.00 |
| 25 | 71.28 | 79.04 | 92.98 |
| 30 | 70.94 | 78.56 | 93.24 |
| 35 | 70.37 | 77.99 | 93.00 |
| 40 | 69.74 | 77.32 | 93.57 |
| 45 | 67.28 | 74.57 | 94.20 |
| 50 | 63.57 | 70.37 | 92.98 |
| 55 | 59.42 | 65.83 | 93.00 |
| 60 | 57.00 | 63.17 | 93.87 |
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021243883A CN1201862C (en) | 2002-06-21 | 2002-06-21 | Catalyst for preparing propene at low temp. from ethylene and butylene, proparation process and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021243883A CN1201862C (en) | 2002-06-21 | 2002-06-21 | Catalyst for preparing propene at low temp. from ethylene and butylene, proparation process and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1465435A CN1465435A (en) | 2004-01-07 |
| CN1201862C true CN1201862C (en) | 2005-05-18 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408165C (en) * | 2005-08-15 | 2008-08-06 | 中国石油化工股份有限公司 | Catalyst for preparing ethane and hexane through butene disproportionation |
| CN101148391B (en) * | 2006-09-20 | 2010-10-13 | 中国石油化工股份有限公司 | Method for producing propylene by butylene and ethylene dismutation |
| CN101190869B (en) * | 2006-11-21 | 2010-10-06 | 中国石油化工股份有限公司 | Production increasing method for propylene |
| CN102826948B (en) * | 2011-06-17 | 2015-12-16 | 中国石油化工股份有限公司 | A kind of method of ethylene/butylene disproportionation reaction propylene |
| CN103030509B (en) * | 2011-09-29 | 2015-06-10 | 中国石油化工股份有限公司 | Method for preparing propylene by C4 and ethylene |
| CN102407104B (en) * | 2011-10-14 | 2013-04-17 | 南通职业大学 | Preparation method of mesoporous nano molybdenum-loaded tungsten trioxide highly effective photocatalyst |
| CN103801347A (en) * | 2012-11-12 | 2014-05-21 | 中国科学院大连化学物理研究所 | Catalyst for self-disproportionation of mixed butene, and preparation method and applications of catalyst |
| CN104437525B (en) * | 2013-09-24 | 2017-01-04 | 中国石油化工股份有限公司 | Disproportionation catalyst |
| CN103846084A (en) * | 2014-03-25 | 2014-06-11 | 西安科技大学 | Supported tungsten based catalyst for preparing propylene by 1-butene disproportionation as well as preparation method and application of supported tungsten based catalyst |
-
2002
- 2002-06-21 CN CNB021243883A patent/CN1201862C/en not_active Expired - Fee Related
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