CN1189433C - Method for preparing ethene and propylene - Google Patents
Method for preparing ethene and propylene Download PDFInfo
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- CN1189433C CN1189433C CNB021314616A CN02131461A CN1189433C CN 1189433 C CN1189433 C CN 1189433C CN B021314616 A CNB021314616 A CN B021314616A CN 02131461 A CN02131461 A CN 02131461A CN 1189433 C CN1189433 C CN 1189433C
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- Prior art keywords
- oxide
- catalyzer
- zeolite
- ethene
- earth metal
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 41
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims description 34
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 31
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010457 zeolite Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 5
- 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 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 5
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- -1 C 5 monoolefin Chemical class 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 150000005673 monoalkenes Chemical class 0.000 abstract 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 3
- 235000019289 ammonium phosphates Nutrition 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a method for preparing ethene and propene. The method comprises: hydrocarbon compounds of monoolefin containing C4 or C5 are used as raw materials contact catalysts containing zeolite in a fixed bed reactor under the conditions that temperature is from 350 to 500 DGE C, pressure is from 0.6 to 1.0MPa, and the weight hourly space velocity is from 1 to 10<-1>, so reaction compounds containing ethene and propene are obtained. Ethene and propene are obtained after cooling and separation are carried out, wherein the catalysts comprise the components of 20 to 45% of Al2O3 or SiO2, 40 to 70% of high silicon zeolite and 8 to 20% of modified component measured by the total weight of the catalysts, and the modified component is selected from at least one kind in molybdenum oxide, tungsten oxide, phosphorus oxide, alkaline earth metal oxide and rare earth metal oxide. The method of the present invention has the advantages of low reaction temperature, no addition of dilute gas and simple technology.
Description
Technical field
The present invention relates to the preparation method of olefine in low carbon number, specifically, the present invention relates in the presence of zeolite catalyst, prepare the method for ethene and propylene from the hydrocarbon feed of carbon containing four or C 5 monoolefin.
Background technology
As everyone knows, ethene and propylene are the important basic raw materials of organic chemistry and petrochemical complex, are the bases that produces various important organic chemical industry's products.They mainly are to produce by methods such as the catalytic cracking of the dehydrogenation of ethane and propane, petroleum hydrocarbon or catalytic pyrolysiss.
Along with the continuous development of ethylene industry and petroleum refining industry, the output of by product carbon four, C5 fraction constantly increases, and in order to make full use of resource, to reduce production cost of ethylene, it is the focus of people's research in recent years that this huge resource is fully utilized.The carbon four of low value, ethene and the propylene that C5 fraction changes into higher-value are become one of emphasis of research.Carbon four, carbon pentaene hydrocarbon are changed into ethene and propylene, can finish by disproportionation reaction and catalytic cracking reaction.
The disproportionation reaction need make raw material with highly purified 2-butylene or 2-amylene and ethylene reaction just can obtain propylene.If make raw material with mixed c 4 or carbon pentaene hydrocarbon, product also has a lot of by products except that ethene, propylene, is difficult to separate.To contain C
4And C
5The hydrocarbon feed of alkene carries out disproportionation reaction and produces ethene, propylene, has following shortcoming: before (1) reaction, must carry out pre-treatment to raw material; Must use ethene when (2) reacting, just can reduce the generation of by product, the difficulty when alleviating the product separation; (3) ethene of high value degradation is produced the propylene of lesser value, uneconomical.
CN1140794A discloses C
4Olefin fraction changes into the method for polyisobutene and propylene.At first to C
4Diolefine and selective acetylene hydrocarbon hydrogenation in the olefin fraction, 1-butylene is converted into 2-butylene, tells iso-butylene; Making 2-butylene and ethene then is 0.5-10h at 35 ℃, 3.5MPa, air speed
-1Condition under, disproportionation reaction takes place produce propylene.The catalyzer that uses in this method is Re
2O
7/ Al
2O
3, 2-butylene per pass conversion＞60%, propylene selectivity＞90%.
In recent years, the catalytic pyrolysis technology is applied to the conversion reaction of carbon four, carbon pentaene hydrocarbon, has caused the concern of each chemical company.Be characterized in: the degree of freedom of (1) raw material is big; (2) do not need products such as 1-butylene, iso-butylene are carried out pre-treatment; (3) can obtain ethene and propylene simultaneously.But, enter reactive system before, need to handle C to raw material
4-C
5Cut need select hydrogenation to make alkynes and diolefine change into monoolefine, in order to reduce the generation of coking and polymkeric substance, generally will dilute unstripped gas with rare gas element or water vapor.
CN1274342A discloses by catalyzed conversion to contain 20% (weight) or higher (with the weight of hydrocarbon feed) at least a C
4-C
12The straight chain hydrocarbon of alkene is the method that raw material is produced ethene and propylene.Zeolite in the zeolite catalyst that this method is used is not contain proton, SiO substantially
2/ Al
2O
3Mol ratio is 200-5000, contain the zeolite of at least a IB family metal, intermediate pore size, the zeolite of preferred ZSM-5 family.Be reflected under 400-700 ℃ the temperature, a 0.1-10 normal atmosphere and 1-1000h
-1Weight hourly space velocity under carry out, the diluent gas of use comprises hydrogen, methane, steam and rare gas element, can obtain to be up to 6.5% ethylene yield and 22.7% productivity of propylene.
CN1313268A discloses with C
2-C
5Hydrocarbon gas, be the method that raw material is produced ethene as Sweet natural gas, liquefied petroleum gas (LPG) or catalytic cracked gas.Use in this method to contain the clay molecular sieve with layer structure catalyzer, 650-750 ℃, 1.5-4 * 10
5Under the condition of Pa, reaction times 0.2-1 second, can obtain to be up to 15.49% ethylene yield and 25.19% productivity of propylene.
WO 00/26163 discloses to contain C
4And C
5The mixture of alkene is a raw material, prepares the method for ethene and propylene in the presence of zeolite catalyst.The catalyzer that this method is used as the aperture greater than 3.5 dusts, have the not interconnected duct of one dimension, the zeolite of pore volume between 14-28, be reflected under temperature 200-750 ℃ the temperature, a 0.5-10 normal atmosphere and 0.5-1000h
-1Weight hourly space velocity under carry out.
The objective of the invention is on the basis of above-mentioned prior art, provide a kind of to contain C
4And C
5The mixture of alkene is a raw material, does not add diluent gas, and technology is simple, the method long-time, that high yield is stably produced ethene and propylene.
Summary of the invention
The inventor has developed a kind of method for preparing ethene and propylene through a large amount of deep researchs.Method provided by the invention comprises: the hydrocarbon mixture with carbon containing four or C 5 monoolefin is a raw material, in fixed-bed reactor, contact with zeolite containing catalyst, and at 350-500 ℃ temperature, pressure and the 1-10h of 0.6-1.0MPa
-1The processing condition of weight hourly space velocity under react, generate the reaction mixture that contains ethene and propylene, after refrigerated separation, obtain ethene and propylene,
Wherein, described catalyzer comprises following composition: with the total restatement of catalyzer, Al
2O
3Or SiO
2Be 20-45%, be preferably 25-40%, supersiliceous zeolite is 40-70%, is preferably 45-65%, and modified component is 8-20%, is preferably 10-15%.
Described supersiliceous zeolite is selected from commodity ZRP series by name or ZSM-5 class zeolite, and wherein the ZRP series zeolite is the molecular sieve catalyst series of petroleum science research institute exploitation; The SiO of described supersiliceous zeolite
2With Al
2O
3Mol ratio be preferably 50-300,200-300 more preferably.
Described modified component is selected from least a in oxide compound, alkaline earth metal oxide and the rare-earth oxide of molybdenum oxide, Tungsten oxide 99.999, phosphorus; With the total restatement of catalyzer, the content of molybdenum oxide or Tungsten oxide 99.999 is 5-10%, and the content of the oxide compound of phosphorus is 2-5%, and the content of rare-earth oxide is 0-2%, and the content of alkaline earth metal oxide is 1-3%.
Wherein, preferred rare earth metal is a lanthanum, and alkaline-earth metal is a calcium.
The used catalyzer of preferred method of the present invention comprises following composition: with the total restatement of catalyzer, Al
2O
3Be 25-40%, ZRP type zeolite is 45-65%, and the oxide compound of molybdenum, phosphorus, rare earth metal and alkaline-earth metal is 10-20%.
The shape of the catalyzer that method of the present invention is used can be spherical, granular, strip, extrudate etc.
The used catalyzer of method of the present invention adopts kneading method and immersion process for preparing to obtain, and comprises the following steps: that specifically (1) is mixed in proportion supersiliceous zeolite, aluminum oxide, extrusion aid, and that wherein aluminum oxide uses is known specific surface area＞200m
2The high purity aluminium oxide of/g; Used extrusion aid such as sesbania powder, polyacrylamide, silica gel etc.; (2) add nitric acid behind the mixing, stir evenly the back extrusion molding, wherein the weight percent concentration of nitric acid is less than 10%; (3) 60-140 ℃ dry 5-20 hour, 450-650 ℃ roasting 0.5-15 hour; (4) carrier that adopts the solution impregnation step (3) of metal-salt to obtain preferably uses the solution of the compounds such as nitrate of ammonium molybdate, ammonium phosphate, rare earth metal, 80-150 ℃ of baking 10 hours, burns 4-10 hour at 500-600 ℃ then.
The carbon containing four that method of the present invention is used or the raw material of C 5 monoolefin can be selected from
(1) the by product C-4-fraction of cracking petroleum hydrocarbon vapor system ethene removes or selects hydrogenation to make diolefine and alkynes become monoolefine the separate butadiene in the cut;
(2) the by product C5 fraction of cracking petroleum hydrocarbon vapor system ethene after the cyclopentadiene in the cut removed, selects hydrogenation to make diolefine and alkynes become monoolefine;
(3) isolated C-4-fraction or C5 fraction in the product that catalytic cracking obtains;
(4) carbon four raffinate I will remove the resulting cut of whole divinyl in the described C-4-fraction.
The C-4-fraction of preferred use carbon four raffinate I or monoolefine total content＞60% (in the weight of described hydrocarbon feed) or C5 fraction are as raw material of the present invention; Wherein said monoolefine is the alkene that contains the straight or branched of 4 or 5 carbon atoms and two keys, be the isomer of various butylene or amylene, as 1-butylene, suitable-2-butylene, anti--2-butylene, iso-butylene, 1-amylene, suitable-the 2-amylene, anti--the 2-amylene, 3-methyl-1-butene, 2-methyl-2-butene, 2-methyl-1-butene alkene etc.
Method provided by the invention can be used as the independent method for preparing ethene and propylene, also can combine use with the device of preparing ethylene by steam cracking.
The present invention has following advantage:
1, the hydrocarbon mixture with carbon containing four or C 5 monoolefin is a raw material, uses fixed-bed reactor, because therefore used catalyzer anti-coking excellent performance can not add diluent gas, technology is simple;
2, temperature of reaction is lower, catalyzer seldom can be owing to coking inactivation, therefore need not to repeat continually regenerative operation, can prepare ethene and propylene for a long time, efficiently;
3, catalyzer is that supersiliceous zeolite and some metal oxides combine and make, long service life, and the preparation method is simple.
Description of drawings
Fig. 1 is experiment flow figure of the present invention.
Below in conjunction with accompanying drawing method of the present invention is described.
Catalyzer is packed in the fixed-bed reactor 3 into logical N
2Behind the leak test, open process furnace 2 heating, temperature is opened volume pump 1 after rising to temperature of reaction, raw material enters reactor 3 through micro-plunger metering pump 1, reaction product after water cooler 4, gas-liquid separator 5 separates, gas phase wet test meter measurement volumes, liquid phase is collected with Erlenmeyer flask.Analyze the composition of gas phase and liquid phase with gas chromatograph.
Embodiment
Below example will illustrate further the present invention, but not thereby limiting the invention.
Embodiment 1 preparation catalyst A
(provide SiO with 150g ZRP molecular sieve by economic technology trade center, Garden of Ten-Thousand Trees, Beijing
2/ Al
2O
3＞200), 75g aluminum oxide (Luxing Special Catalyst Tech Co., Beijing provides), 8g sesbania powder mix; The nitric acid 120ml of adding 5% is squeezed into the cylindrical type of 2mm, and cuts into 2-3mm behind the mixing after stirring evenly; 80 ℃ and 120 ℃ dry 10 hours respectively,, take out and be cooled to room temperature then 580 ℃ of calcinings 6 hours; The catalyzer of getting the 50g moulding then is respectively with ammonium molybdate, 0.1M lanthanum nitrate and the 0.6M ammonium phosphate solution dipping of 30ml 0.3M, behind the airing respectively 80 ℃ and 120 ℃ of dryings 10 hours, 580 ℃ calcine 6 hours after, it is standby to put into moisture eliminator.
Zhi Bei catalyzer is expressed as catalyst A by this way, has following composition: Al
2O
3Be 29.2%, the ZRP zeolite is 58.4%, MoO
3Be 8.1%, P
2O
5Be 3.2%, La
2O
3Be 1.1%.
Embodiment 2 preparation catalyst B
Repeat embodiment 1, the consumption of aluminum oxide is changed into 150g, the consumption of nitric acid becomes 150ml.Other working method is identical with embodiment 1.
Zhi Bei catalyzer is expressed as catalyst B by this way, has following composition: Al
2O
3Be 43.8%, the ZRP zeolite is 43.8%, MoO
3Be 8.1%, P
2O
5Be 3.2%, La
2O
3Be 1.1%.
Embodiment 3 preparation catalyzer C
Repeat embodiment 1,150g ZRP molecular sieve, 75g aluminum oxide, 10g lime carbonate, 8g sesbania powder are mixed; The consumption of nitric acid is changed into 130ml, and other working method is identical with embodiment 1.
Zhi Bei catalyzer is expressed as catalyzer C by this way, has following composition: Al
2O
3Be 28.5%, the ZRP zeolite is 57.0%, MoO
3Be 8.0%, P
2O
5Be 3.2%, La
2O
3Be 1.2%, CaO is 2.1%.
Embodiment 4 preparation catalyzer D
Repeat embodiment 2, select ZSM-5 molecular sieve (SiO for use
2/ Al
2O
3Be 50, Catalyst Factory, Nankai Univ provides) replace the ZRP zeolite, other working method is identical with embodiment 2.
Zhi Bei catalyzer is expressed as catalyzer D by this way, has following composition: Al
2O
3Be 43.8%, the ZSM-5 molecular sieve is 43.8%, MoO
3Be 8.1%, P
2O
5Be 3.2%, La
2O
3Be 1.1%.
Comparative Examples 1 preparation catalyzer E
Repeat embodiment 2, do not add the ZRP zeolite, other working method is identical with embodiment 2.
Zhi Bei catalyzer is expressed as catalyzer E by this way.
Comparative Examples 2 preparation catalyzer F
Directly, do not flood ammonium molybdate, lanthanum nitrate and ammonium phosphate solution with the catalyzer of moulding among the embodiment 2.
Zhi Bei catalyzer is expressed as catalyzer F by this way.
Embodiment 5
In the small stationary bed bioreactor, be raw material with carbon four raffinates (I), applications catalyst A, B, C, D and comparison catalyzer E, F, at pressure 0.8MPa, weight hourly space velocity 4h
-1Under react, under the differential responses temperature, the yield of primary product is listed in table 1 when reacting 100 hours.
Wherein the weight of raw material consists of: Trimethylmethane 6.36%; Normal butane 4.17%; Instead-2-butylene 5.83%; 1-butylene 50.45%; Iso-butylene 29.18%; Suitable-2-butylene 3.54%.
Reactor is the stainless steel tube of internal diameter φ 14mm, wall thickness 2mm, interior dress 10ml catalyzer, and the particle diameter of catalyzer is about 2.0mm * 3.0mm.
Listed product yield is meant the weight percentage of each component in the gas phase of reaction back in the table.
The transformation efficiency of C 4 olefin is all greater than 65% in 100 hours.
The experiment of embodiment 6 life of catalyst
In temperature is that 450 ℃, pressure are, air speed is 4h under the 0.8MPa condition
-1Being raw material with carbon four raffinates (I) down, is raw material with carbon four raffinates (I), and 200 hours inner catalyst A react the results are shown in table 2.
Listed product yield is meant the weight percentage in the gas phase of reaction back in the table.
Table 1 yield (weight percentage %) of primary product during 100hr under the differential responses temperature
| Catalyzer | Temperature of reaction ℃ | 300℃ | 350℃ | 400℃ | 500℃ | |
| A | Primary product yield % | Ethene | 5.55 | 7.27 | 10.66 | 8.68 |
| Propylene | 23.02 | 29.89 | 34.33 | 27.07 | ||
| B | Ethene | 3.35 | 5.87 | 8.98 | 7.58 | |
| Propylene | 14.02 | 18.19 | 25.68 | 23.07 | ||
| C | Ethene | 6.15 | 8.17 | 11.77 | 9.66 | |
| Propylene | 25.02 | 31.19 | 35.44 | 28.07 | ||
| D | Ethene | 3.28 | 5.26 | 7.03 | 6.11 | |
| Propylene | 11.38 | 15.43 | 19.55 | 18.33 | ||
| E | Ethene | 3.01 | 4.20 | 4.11 | 4.79 | |
| Propylene | 9.03 | 12.57 | 15.50 | 17.75 | ||
| F | Ethene | 2.84 | 5.26 | 5.87 | 5.59 | |
| Propylene | 8.98 | 11.35 | 16.19 | 18.33 | ||
The longevity test result of table 2. catalyst A
| Reaction times (hr) | 25 | 50 | 75 | 100 | 125 | 150 | 175 | 200 | 225 |
| Ethene % | 7.39 | 7.94 | 8.66 | 8.77 | 7.27 | 8.24 | 9.81 | 8.11 | 8.41 |
| Propylene % | 26.61 | 27.46 | 27.77 | 28.83 | 29.92 | 30.29 | 31.13 | 33.98 | 34.39 |
| Transformation efficiency % | 80.2 | 78.3 | 75.1 | 72.6 | 70.3 | 65.4 | 62.1 | 55.6 | 50.5 |
Claims (10)
1, a kind of method for preparing ethene and propylene, this method comprises:
Hydrocarbon mixture with carbon containing four or C 5 monoolefin is a raw material, in fixed-bed reactor, contacts with zeolite containing catalyst, and at 350-500 ℃ temperature, pressure and the 1-10h of 0.6-1.0MPa
-1The condition of weight hourly space velocity under react, generate the reaction mixture that contains ethene and propylene, after refrigerated separation, obtain ethene and propylene,
Wherein, described catalyzer comprises following composition: with the total restatement of catalyzer, Al
2O
3Or SiO
2Be 20-45%, supersiliceous zeolite is 40-70%, and modified component is 8-20%.
2, method according to claim 1, wherein said catalyzer comprises following composition: with the total restatement of catalyzer, Al
2O
3Be 25-40%, supersiliceous zeolite is 45-65%, and modified component is 10-15%.
3, method according to claim 1, wherein said supersiliceous zeolite are selected from commodity ZRP series by name or ZSM-5 class zeolite.
4, method according to claim 3, the SiO of wherein said supersiliceous zeolite
2With Al
2O
3Mol ratio be 50-300.
5, method according to claim 4, the SiO of wherein said supersiliceous zeolite
2With Al
2O
3Mol ratio be 200-300.
6, method according to claim 1, wherein said modified component are selected from least a in oxide compound, alkaline earth metal oxide and the rare-earth oxide of molybdenum oxide, Tungsten oxide 99.999, phosphorus.
7, method according to claim 6, wherein with the total restatement of catalyzer, the content of molybdenum oxide or Tungsten oxide 99.999 is 5-10%, and the content of the oxide compound of phosphorus is 2-5%, and the content of rare-earth oxide is 0-2%, and the content of alkaline earth metal oxide is 1-3%.
8, method according to claim 6, wherein rare earth metal is a lanthanum, alkaline-earth metal is a calcium.
9, method according to claim 1, wherein said catalyzer comprises following composition: with the total restatement of catalyzer, Al
2O
3Be 25-40%, ZRP type zeolite is 45-65%, and the oxide compound of molybdenum, phosphorus, rare earth metal and alkaline-earth metal is 10-20%.
10, according to the described method of one of claim 1-9, wherein said raw material can be selected from the weight in described hydrocarbon feed, the C-4-fraction of monoolefine total content＞60% or C5 fraction, above-mentioned C-4-fraction is removed the resulting carbon four raffinate I of whole divinyl.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460369C (en) * | 2005-09-07 | 2009-02-11 | 中国石油化工股份有限公司 | Method for producing propylene by catalytic cracking of olefins with carbon four and above |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100441554C (en) * | 2005-01-28 | 2008-12-10 | 中国石油化工股份有限公司 | A kind of method utilizing cracking carbon five fractions |
| CN101239878B (en) * | 2007-02-07 | 2010-05-19 | 中国石油化工股份有限公司 | Method for increasing yield of ethylene and propylene from olefin with four carbon or above |
| WO2013034683A1 (en) * | 2011-09-07 | 2013-03-14 | Shell Internationale Research Maatschappij B.V. | Process for preparing ethylene and/or propylene and an iso-olefin-depleted c4 olefinic product |
| CN104557398B (en) * | 2013-10-28 | 2017-08-11 | 中国石油化工股份有限公司 | The method that light dydrocarbon produces propylene |
| CN110813367A (en) * | 2019-11-20 | 2020-02-21 | 延安大学 | Phosphorus and rare earth synergistically modified ZSM-5 and method for increasing propylene yield through catalytic cracking of ZSM-5 |
| CN113041653B (en) * | 2021-03-11 | 2022-05-17 | 浙江杭化科技股份有限公司 | Environment-friendly demulsification water purifier for ethylene device and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100460369C (en) * | 2005-09-07 | 2009-02-11 | 中国石油化工股份有限公司 | Method for producing propylene by catalytic cracking of olefins with carbon four and above |
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