CN1611298A - Catalyst for butene olefin disproportionation and its preparing method - Google Patents
Catalyst for butene olefin disproportionation and its preparing method Download PDFInfo
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- CN1611298A CN1611298A CN 200310108175 CN200310108175A CN1611298A CN 1611298 A CN1611298 A CN 1611298A CN 200310108175 CN200310108175 CN 200310108175 CN 200310108175 A CN200310108175 A CN 200310108175A CN 1611298 A CN1611298 A CN 1611298A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000007323 disproportionation reaction Methods 0.000 title claims abstract description 37
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 18
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 title abstract description 7
- -1 butene olefin Chemical class 0.000 title abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 13
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010937 tungsten Substances 0.000 claims abstract description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 32
- 150000001336 alkenes Chemical class 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 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 claims description 4
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011230 binding agent Substances 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 229930195733 hydrocarbon Natural products 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 33
- 238000005303 weighing Methods 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 22
- 229910004298 SiO 2 Inorganic materials 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000009740 moulding (composite fabrication) Methods 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 238000013019 agitation Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 235000011167 hydrochloric acid Nutrition 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004579 marble Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 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
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention relates to a catalyst for olefin hydrocarbon disproportionation reaction, and is mainly aimed at solving the problem of previous technique in which the specific surface area of olefin hydrocarbon disproportionation catalyst is small and the dispersivity of tungsten oxide in catalyst is low. Said invention utilizes the adoption of technical scheme which uses MCM-41 mesohole SiO2 molecular sieve containing tungsten as active component, and uses silica sol as binding agent to form butene disproportionation catalyst, and can utilize the load-supporting process to implement introduction of tungsten component or can directly introduce the tungsten component into MCM-41 mesohole SiO2 molecular sieve skeleton under the acidic or basic condition so as to better solve the above-mentioned problem. Said invention can be used in the industrial production for butene disproportionation reaction.
Description
Technical field
The present invention relates to be used for the Catalysts and its preparation method of olefin dismutation reaction, particularly about the Catalysts and its preparation method of the tungstenic MCM-41 mesopore molecular sieve that is used for butylene disproportionation reaction.
Background technology
Olefin dismutation reaction is a kind of conversion of olefines process.Utilize olefin dismutation reaction, superfluous, that added value is lower relatively alkene can be converted into the high added value olefin product.
The key of olefin dismutation reaction is a catalyst, and catalyst can be homogeneous catalyst and heterogeneous catalyst.Heterogeneous olefin disproportionation catalyst is generally the compound loaded on inert carrier of W, Mo, Re etc.Inert carrier is generally SiO
2, Al
2O
3, TiO
2, SiO
2-Al
2O
3, aluminophosphates.
US 5300718 has reported the technology of butene-2 and ethene generation disproportionated reaction system propylene, and the catalyst that uses is MgO and WO
3/ SiO
2Mixed bed.
EP 0489585 has proposed butylene disproportionation Preparation of catalysts method, and catalyst is WO
3/ inert carrier, wherein carrier is SiO
2With MgO or SiO
2With TiO
2What form is cogelled, and the catalyst by method for preparing can make propylene disproportionation system ethene and butylene; The activity of ethene and butene-2 disproportionation system propylene increases.
US 5138791 has reported the preparation method of olefin disproportionation catalyst, and its catalyst consists of B
2O
3-Re
2O
7/ Al
2O
3-SiO
2, with amorphous aluminum silicide as catalyst carrier, and with Al
2O
3Or SiO
2Compare for the catalyst of carrier, the activity of olefin dismutation reaction improves greatly.
EP 0152112 has reported with Ti and has modified WO
3/ SiO
2Catalyst carrier; US 5905055 has reported with Nb and has modified WO
3/ SiO
2Catalyst carrier, olefin(e) disproportionation activity all obtain to improve.
This shows that the character of carrier has important effect to the performance of olefin disproportionation catalyst, MCM-41 is the crystalline state SiO with homogeneous pore passage structure, bigger serface that synthesizes in generation nineteen ninety
2Mesoporous material is the excellent carrier of catalyst.US 5098684 play-by-play this type of SiO
2The synthetic method of mesoporous material.
US 5672556 has reported a series of transition metal species has been incorporated into synthetic method in the MCM-41 mesoporous material skeleton that these transition metal species comprise Ti, V, Sn, Zr, Zn, Cu, Cr etc.
With mesoporous WO
X/ MCM-41 molecular sieve is that olefin disproportionation catalyst does not appear in the newspapers.
Summary of the invention
One of technical problem to be solved by this invention is to exist the olefin disproportionation catalyst specific area little in the conventional art, and the problem of the bad dispersibility of tungsten oxide in the catalyst provides a kind of new catalyst that is used for olefin dismutation reaction.It is big that this catalyst has specific area, the characteristics of tungsten oxide good dispersion in catalyst.Two of technical problem to be solved by this invention provides a kind of new preparation method who adapts with one of technical problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst that is used for olefin dismutation reaction comprises following component by weight percentage:
A) 50～78% have regular duct, and average pore size is 3～10 nanometers, and specific area is 700～1200 meters
2The mesoporous SiO of MCM-41 of/gram
2Molecular sieve; With carry thereon
B) 2～20% tungsten oxide;
C) 20～48% adhesive silicon sol.
In the technique scheme, the mesoporous SiO of MCM-41 by weight percentage
2The consumption preferable range of molecular sieve is 60～70%, and the specific area preferable range is 700～1000 meters
2/ gram.The consumption preferable range of tungsten oxide is 6～16% by weight percentage, and the consumption preferable range of adhesive silicon sol is 20～30%.
For solve the problems of the technologies described above two, one of the technical solution used in the present invention is as follows: a kind of method for preparing catalyst that is used for olefin dismutation reaction, may further comprise the steps: a) adopt loading method, it is 3～10 nanometers that first tungsten oxide with aequum is carried on average pore size, and specific area is 700～1200 meters
2The mesoporous SiO of MCM-41 of/gram
2Molecular sieve; B) molecular sieve that a) step is made mixes with adhesive silicon sol, gets required catalyst through extrusion modling, roasting.
For solve the problems of the technologies described above two, the technical solution used in the present invention two as follows: a kind of method for preparing catalyst that is used for olefin dismutation reaction may further comprise the steps:
A) with the cationic surfactant being the template agent, is the silicon source with ethyl orthosilicate, Ludox or waterglass, is the tungsten source with ammonium metatungstate, ammonium paratungstate, wolframic acid or tungsten hexachloride, and it is 1SiO that feed molar is formed proportioning
2: 0.08～0.20CTAB: 5～9HCl: 0.001～0.05WO
3: 80～150H
2O is 20～150 ℃ at crystallization temperature, and crystallization pressure is crystallization 6～240 hours under the gel self-generated pressure condition, after 350～800 ℃ of roasting temperatures, must contain the mesoporous SiO of MCM-41 of tungsten oxide
2Molecular sieve, wherein CTAB is a CTAB;
B) molecular sieve that a) step is obtained mixes with the adhesive silicon sol of aequum, gets required catalyst through extrusion modling, roasting.
For solve the problems of the technologies described above two, the technical solution used in the present invention three as follows: a kind of method for preparing catalyst that is used for olefin dismutation reaction may further comprise the steps:
A) with the cationic surfactant being the template agent, is the silicon source with ethyl orthosilicate, Ludox or waterglass, is the tungsten source with ammonium metatungstate, ammonium paratungstate, wolframic acid or tungsten hexachloride, and feed molar is formed proportioning and is: 1SiO
2: 0.08～0.20CTAB: 0.10～1.0C
2H
5NH
2: 0.001～0.05WO
3: 80～150H
2O is 20～150 ℃ at crystallization temperature, and crystallization pressure is crystallization 6～240 hours under the gel self-generated pressure condition, after 350～800 ℃ of mesoporous SiO of MCM-41 that roasting temperature must contain tungsten oxide
2Molecular sieve, wherein CTAB is a CTAB;
B) molecular sieve that a) step is obtained mixes with the adhesive silicon sol of aequum, gets required catalyst through extrusion modling, roasting.
The sintering temperature preferable range is 550～750 ℃ in the technique scheme, and the roasting time preferable range is 1～24 hour.When calcination atmosphere was inert atmosphere, roasting time was 1～20 hour; When calcination atmosphere was oxidizing atmosphere, roasting time was 1～10 hour.
The WO that synthesizes in the technique scheme
X/ MCM-41 can select spin, extruding slivering for use, and method moulding such as compressing tablet should add binding agent in the forming process, and binding agent can be selected Ludox for use.
Adopt the catalyst of technique scheme preparation can use at olefin dismutation reaction, the embodiment of the invention is a butylene disproportionation reaction system propylene.Reaction condition is as follows: in the fixed bed reactors, reaction temperature is 0～550 ℃, reaction pressure is 0～10MPa, and the liquid phase weight space velocity is 0.1～3 hour
-1Under the condition, the butylene disproportionation reaction generates propylene.
Butene feedstock can be the mixture of butene-1, butene-2 or butylene in the such scheme; Or from the C-4-fraction of steam cracking device.
The present invention passes through WO
3Introduce the skeleton of mesopore molecular sieve MCM-41, or adopt the carrier of mesopore molecular sieve MCM-41, the specific area of catalyst is improved, the WO that has increased as catalyst
3Decentralization, thus catalyst olefin dismutation reaction performance improved, obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
WO
X/ MCM-41's is synthetic
Take by weighing CTAB (CTAB) 21.5 grams and place beaker, add 900 ml deionized water and 440 milliliters of concentrated hydrochloric acids, stirring at room is dissolved CTAB fully, wiring solution-forming A.
Other gets a beaker, takes by weighing 104 gram ethyl orthosilicates (TEOS), under room temperature, strong agitation, drip by 2.8 gram ammonium metatungstates, 45 ml deionized water, 10 milliliters of solution that hydrogen peroxide is made into, and after being added dropwise to complete, wiring solution-forming B.
Under the stirring at room,, be added drop-wise in the solution A solution B, after being added dropwise to complete, stirring at room 2 hours; Temperature is risen to 60 ℃, stir after 24 hours, centrifugation, solid sample spends deionised water three times, and sample is 80 ℃ of oven dry, and the gained sample is designated as WSA-1.
[embodiment 2]
WO
X/ MCM-41's is synthetic
Take by weighing CTAB (CTAB) 21.5 grams and place beaker, add 900 ml deionized water and 440 milliliters of concentrated hydrochloric acids, stirring at room is dissolved CTAB fully, wiring solution-forming A.
Other gets a beaker, takes by weighing 104 gram ethyl orthosilicates (TEOS), under room temperature, strong agitation, drip by 4.2 gram ammonium metatungstates, 45 ml deionized water, 10 milliliters of solution that hydrogen peroxide is made into, and after being added dropwise to complete, wiring solution-forming B.
Under the stirring at room,, be added drop-wise in the solution A solution B, after being added dropwise to complete, stirring at room 2 hours; Temperature is risen to 60 ℃, stir after 24 hours, centrifugation, solid sample spends deionised water three times, and sample is 80 ℃ of oven dry, and the gained sample is designated as WSA-2.
[embodiment 3]
WO
X/ MCM-41's is synthetic
Take by weighing CTAB (CTAB) 1.5 grams and place beaker, add 900 ml deionized water and 440 milliliters of concentrated hydrochloric acids, stirring at room is dissolved CTAB fully, wiring solution-forming A.
Other gets a beaker, takes by weighing 104 gram ethyl orthosilicates (TEOS), under room temperature, strong agitation, drip by 5.6 gram ammonium metatungstates, 45 ml deionized water, 10 milliliters of solution that hydrogen peroxide is made into, and after being added dropwise to complete, wiring solution-forming B.
Under the stirring at room,, be added drop-wise in the solution A solution B, after being added dropwise to complete, stirring at room 2 hours; Temperature is risen to 60 ℃, stir after 24 hours, centrifugation, solid sample spends deionised water three times, and sample is 80 ℃ of oven dry, and the gained sample is designated as WSA-3.
[embodiment 4]
WO
X/ MCM-41's is synthetic
Take by weighing CTAB (CTAB) 21.5 grams and place beaker, add 900 ml deionized water and 440 milliliters of concentrated hydrochloric acids, stirring at room is dissolved CTAB fully, wiring solution-forming A.
Other gets a beaker, takes by weighing 104 gram ethyl orthosilicates (TEOS), under room temperature, strong agitation, drip by 4.2 gram ammonium metatungstates, 45 ml deionized water, 10 milliliters of solution that hydrogen peroxide is made into, and after being added dropwise to complete, wiring solution-forming B.
Under the stirring at room,, be added drop-wise in the solution A solution B, after being added dropwise to complete, stirring at room 2 hours; Temperature is risen to 60 ℃, stir after 24 hours, centrifugation, solid sample spends deionised water three times, and sample is 80 ℃ of oven dry, and the gained sample is designated as WSA-4.
[embodiment 5]
WO
X/ MCM-41's is synthetic
Take by weighing CTAB (CTAB) 21.5 grams and place beaker, add 900 ml deionized water and 440 milliliters of concentrated hydrochloric acids, stirring at room is dissolved CTAB fully, wiring solution-forming A.
Other gets a beaker, takes by weighing 107.6 gram waterglass (SiO
2Content 27.43%), under room temperature, strong agitation, drip by 8.4 gram ammonium metatungstates, 45 ml deionized water, 10 milliliters of solution that hydrogen peroxide is made into, after being added dropwise to complete, add 80 milliliters of absolute ethyl alcohols again, the back that stirs becomes solution B.
Under the stirring at room,, be added drop-wise in the solution A solution B, after being added dropwise to complete, stirring at room 2 hours; Temperature is risen to 60 ℃, stir after 24 hours, centrifugation, solid sample spends deionised water three times, and sample is 80 ℃ of oven dry, and the gained sample is designated as WSA-5.
[embodiment 6]
WO
X/ MCM-41's is synthetic
Take by weighing CTAB (CTAB) 21.5 grams and place beaker, add 900 ml deionized water and 440 milliliters of concentrated hydrochloric acids, stirring at room is dissolved CTAB fully, wiring solution-forming A.
Other gets a beaker, takes by weighing 72.8 gram Ludox (SiO
2Content 40%), under room temperature, strong agitation, drip by 8.4 gram ammonium metatungstates, 45 ml deionized water, 10 milliliters of solution that hydrogen peroxide is made into, after being added dropwise to complete, add 80 milliliters of absolute ethyl alcohols again, the back that stirs becomes solution B.
Under the stirring at room,, be added drop-wise in the solution A solution B, after being added dropwise to complete, stirring at room 2 hours; Temperature is risen to 60 ℃, stir after 24 hours, centrifugation, solid sample spends deionised water three times, and sample is 80 ℃ of oven dry, and the gained sample is designated as WSA-6.
[embodiment 7]
The acidity of MCM-41 is synthetic
Take by weighing CTAB (CTAB) 21.5 grams and place beaker, add 900 ml deionized water and 440 milliliters of concentrated hydrochloric acids, stirring at room is dissolved CTAB fully, wiring solution-forming A.
Other gets a beaker, takes by weighing 104 gram ethyl orthosilicates (TEOS), becomes solution B.
Under the stirring at room,, be added drop-wise in the solution A solution B, after being added dropwise to complete, stirring at room 2 hours; Temperature is risen to 60 ℃, stir after 24 hours, centrifugation, solid sample spends deionised water three times, and sample is 80 ℃ of oven dry, and the gained sample is designated as SA.
[embodiment 8]
The alkalescence of MCM-41 is synthetic
Take by weighing CTAB (CTAB) 10.2 grams and place beaker, add the ethylamine solution of 240 ml deionized water and 19.4 grams 65%, stirring at room is dissolved CTAB fully, wiring solution-forming A.
Other gets a beaker, takes by weighing 41.6 gram ethyl orthosilicates (TEOS), becomes solution B.
Under the stirring at room,, be added drop-wise in the solution A solution B, after being added dropwise to complete, stirring at room 2 hours; The material that mixes is put into autoclave, 120 ℃ leave standstill 48 hours after, filter, deionized water washing three times, sample is 80 ℃ of oven dry, the gained sample is designated as SB.
[embodiment 9]
The roasting of synthetic sample
Get above-mentioned dried sample WSA-1, WSA-2, WSA-3, WSA-4, WSA-5, WSA-6, SA, SB placed tube furnace, with gas space velocity 2000 hours
-1Feed nitrogen, rise to 500 ℃ by room temperature, and under the condition that feeds nitrogen, 500 ℃ kept 4 hours, with gas space velocity 2000 hours with 2 ℃/minute programming rates
-1Bubbling air, and 500 ℃ of roastings 6 hours.
Sample after the roasting carries out XRD, low temperature N
2Determining adsorption, measurement result is as follows:
Table 1 WO
X/ MCM-41 properties of samples
XRD low temperature N
2Absorption
Sample
d
100(nanometer) WO
3Characteristic peak S
BET(rice
2/ restrain) V (centimetre
3/ gram) aperture (nanometer)
WSA-1 4.20 does not see 948 0.8266 3.49
WSA-2 4.21 does not see 907 0.7942 3.50
WSA-3 4.19 (weak) is stronger by 742 0.7452 4.01
WSA-4 4.20 (weak) is strong by 684 0.5453 3.19
WSA-5 (weak) does not see 783 0.6692 3.42
WSA-6 (weak) does not see 756 0.6598 3.36
SA 4.22 --- 809 0.7744 3.83
SB 4.91 --- 883 0.8194 3.71
[embodiment 10～11]
Immersion process for preparing WO
X/ MCM-41 sample
Take by weighing the SA sample of 20 grams after the roastings, other takes by weighing ammonium metatungstate 2.89 grams, adds 25 milliliters of deionized waters, under agitation is added drop-wise to respectively in the SA sample, leaves standstill and dries, and 120 ℃ of oven dry 6 hours, places 550 ℃ of roastings of Muffle furnace 6 hours, sample WSA-imp
Take by weighing the SB sample of 20 grams after the roastings, other takes by weighing ammonium metatungstate 2.89 grams, adds 25 milliliters of deionized waters, under agitation is added drop-wise to respectively in the SB sample, leaves standstill and dries, and 120 ℃ of oven dry 6 hours, places 550 ℃ of roastings of Muffle furnace 6 hours, sample WSB-imp.
[comparative example 1]
Immersion process for preparing WO
3/ SiO
2Sample
(15 orders, specific surface are 478 meters to take by weighing 20 gram silica gel samples
2/ gram, SiO
2Content is 99.9%), other takes by weighing ammonium metatungstate 2.89 grams, adds 25 milliliters of deionized waters, under agitation is added drop-wise to respectively in the silica gel sample, leaves standstill and dries, and 120 ℃ of oven dry 6 hours, places 550 ℃ of roastings of Muffle furnace 6 hours, gets sample WO
3/ SiO
2
[embodiment 12]
WO
XThe moulding of/MCM-41 sample and butylene disproportionation
Take by weighing 10 WOs of gram after the above-mentioned roasting
X/ MCM-41 powder sample adds sesbania powder 0.3 and restrains, and behind the adding 10 gram Ludox, mediates evenly, and extruded moulding after room temperature leaves standstill 24 hours, was dried 6 hours, and placed 550 ℃ of roastings of Muffle furnace 6 hours for 120 ℃.
In length is 110 centimetres, and internal diameter is that 2.5 centimetres reactor bottom adding volume is 110 centimetres
3, granularity is 15 order glass marble fillers; The catalyst of 10 gram formings is added reactor, and the catalyst upper end adds 60 centimetres again
3, granularity is 15 order glass marble fillers.Be warming up to 550 ℃ under the condition of nitrogen gas that the reactor feeding is 10 liters/hour, and after keeping 2 hours under this temperature, reduce to 350 ℃ of reaction temperatures.
Reactor stops to feed nitrogen, and feeds 99.5% butene-1 raw material from reactor upper end, and raw material flow rate is the control valve control by reactor outlet of 24 milliliters/hour, reaction system pressure, and pressure is controlled at 0.49MPa.Product after release by the gas-chromatography on-line analysis.React and reach balance, reaction result such as table 2 after 10 hours.
Table 2 WO
XThe reactivity worth of/MCM-41 sample
Product is formed (mole %)
Sample
Ethylene, propylene butene-2 butene-1 isobutene amylene hexene
WSA-1 2.8 20.29 47.65 13.58 0.15 12.55 2.98
WSA-2 4.56 27.77 36.86 10.55 0.15 15.37 4.49
WSA-3 3.30 20.05 46.47 14.22 0.15 12.01 3.80
WSA-4 2.65 11.61 56.40 17.00 0.16 8.81 2.93
WSA-5 3.22 13.77 49.06 19.97 0.12 10.57 3.02
WSA-6 1.26 16.79 51.26 10.74 1.93 10.74 2.52
WSA-imp 4.38 24.58 39.12 11.50 0.15 15.58 4.69
WSB-imp 2.37 22.59 46.47 12.87 0.18 13.25 2.27
WO
3/SiO
2?0.79 11.18 61.11 16.67 0.59 8.49 0.77
Claims (6)
1, a kind of catalyst that is used for olefin dismutation reaction comprises following component by weight percentage:
A) 50～78% have regular duct, and average pore size is 3～50 nanometers, and specific area is 700～1200 meters
2The mesoporous SiO of MCM-41 of/gram
2Molecular sieve; With carry thereon
B) 2～20% tungsten oxide;
C) 20～48% adhesive silicon sol.
2, according to the described catalyst that is used for olefin dismutation reaction of claim 1, it is characterized in that the mesoporous SiO of MCM-41 by weight percentage
2The consumption of molecular sieve is 60～70%, and specific area is 700～1000 meters
2/ gram.
3, according to the described catalyst that is used for olefin dismutation reaction of claim 1, it is characterized in that the tungsten oxide consumption is 6～16% by weight percentage, the consumption of adhesive silicon sol is 20～30%.
4, a kind of method for preparing catalyst that is used for olefin dismutation reaction may further comprise the steps: a) adopt loading method, it is 3～10 nanometers that first tungsten oxide with aequum is carried on average pore size, and specific area is 700～1200 meters
2The mesoporous SiO of MCM-41 of/gram
2On the molecular sieve; B) molecular sieve that a) step is made mixes with adhesive silicon sol, gets required catalyst through extrusion modling, roasting.
5, a kind of method for preparing catalyst that is used for olefin dismutation reaction may further comprise the steps:
A) with the cationic surfactant being the template agent, is the silicon source with ethyl orthosilicate, Ludox or waterglass, is the tungsten source with ammonium metatungstate, ammonium paratungstate, wolframic acid or tungsten hexachloride, and it is 1SiO that feed molar is formed proportioning
2: 0.08～0.20CTAB: 5～9HCl: 0.001～0.05WO
3: 80～150H
2O is 20～150 ℃ at crystallization temperature, and crystallization pressure is crystallization 6～240 hours under the gel self-generated pressure condition, after 350～800 ℃ of roasting temperatures, must contain the mesoporous SiO of MCM-41 of tungsten oxide
2Molecular sieve, wherein CTAB is a CTAB;
B) molecular sieve that a) step is obtained mixes with the adhesive silicon sol of aequum, gets required catalyst through extrusion modling, roasting.
6, a kind of method for preparing catalyst that is used for olefin dismutation reaction may further comprise the steps:
A) with the cationic surfactant being the template agent, is the silicon source with ethyl orthosilicate, Ludox or waterglass, is the tungsten source with ammonium metatungstate, ammonium paratungstate, wolframic acid or tungsten hexachloride, and feed molar is formed proportioning and is: 1SiO
2: 0.08～0.20CTAB: 0.10～1.0C
2H
5NH
2: 0.001～0.05WO
3: 80～150H
2O is 20～150 ℃ at crystallization temperature, and crystallization pressure is crystallization 6～240 hours under the gel self-generated pressure condition, after 350～800 ℃ of mesoporous SiO of MCM-41 that roasting temperature must contain tungsten oxide
2Molecular sieve, wherein CTAB is a CTAB;
B) molecular sieve that a) step is obtained mixes with the adhesive silicon sol of aequum, gets required catalyst through extrusion modling, roasting.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108175 CN1285409C (en) | 2003-10-27 | 2003-10-27 | Catalyst for butene olefin disproportionation and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108175 CN1285409C (en) | 2003-10-27 | 2003-10-27 | Catalyst for butene olefin disproportionation and its preparing method |
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| Publication Number | Publication Date |
|---|---|
| CN1611298A true CN1611298A (en) | 2005-05-04 |
| CN1285409C CN1285409C (en) | 2006-11-22 |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125871A (en) * | 2011-01-14 | 2011-07-20 | 中国石油大学(北京) | Catalyst for olefin metathesis as well as preparation method and application thereof |
-
2003
- 2003-10-27 CN CN 200310108175 patent/CN1285409C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125871A (en) * | 2011-01-14 | 2011-07-20 | 中国石油大学(北京) | Catalyst for olefin metathesis as well as preparation method and application thereof |
| CN102125871B (en) * | 2011-01-14 | 2013-08-14 | 中国石油大学(北京) | Catalyst for olefin metathesis as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1285409C (en) | 2006-11-22 |
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