CN101380591A - Preparation method of alkali treatment modified ZSM-5 zeolite toluene disproportionation catalyst - Google Patents
Preparation method of alkali treatment modified ZSM-5 zeolite toluene disproportionation catalyst Download PDFInfo
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- CN101380591A CN101380591A CNA2008101558999A CN200810155899A CN101380591A CN 101380591 A CN101380591 A CN 101380591A CN A2008101558999 A CNA2008101558999 A CN A2008101558999A CN 200810155899 A CN200810155899 A CN 200810155899A CN 101380591 A CN101380591 A CN 101380591A
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 239000003513 alkali Substances 0.000 title claims abstract description 48
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 31
- 239000010457 zeolite Substances 0.000 title claims abstract description 31
- 238000007323 disproportionation reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 230000008021 deposition Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 24
- 238000000465 moulding Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 241001494479 Pecora Species 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 235000009508 confectionery Nutrition 0.000 claims description 7
- 239000002689 soil Substances 0.000 claims description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 abstract description 52
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 238000000034 method Methods 0.000 abstract description 21
- 230000004048 modification Effects 0.000 abstract description 15
- 238000012986 modification Methods 0.000 abstract description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract 1
- 239000002808 molecular sieve Substances 0.000 description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 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
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of an alkali treatment modified ZSM-5 zeolite toluene disproportionation catalyst. Adding a binder into raw zeolite powder with an active component of ZSM-5 for forming, treating the raw zeolite powder with 0.01 to 0.4mol/L of alkali solution at the temperature of between 25 and 75 ℃ to exchange the raw zeolite powder into hydrogen type zeolite, washing the hydrogen type zeolite powder with organic acid, drying the catalyst, performing chemical liquid phase deposition modification by using a cyclohexane solution of ethyl orthosilicate, and drying and roasting the catalyst to obtain the catalyst. The obtained catalyst is especially suitable for preparing benzene and p-xylene by shape-selective disproportionation of toluene, and can obviously enhance the conversion rate of toluene, and after the catalyst used for toluene disproportionation reaction is used by said method, the conversion rate of toluene can be raised by 6-10%, and the side reaction can be reduced.
Description
Technical field
The present invention relates to a kind of preparation method of ZSM-5 molecular sieve modified catalyst and the application in toluene disproportionation process thereof, relate in particular to a kind of preparation method of modified ZSM-5 zeolite toluene disproportionation catalyst by soda treatment.
Background technology
Toluene disproportionation is the important course of reaction in the petroleum chemical industry, and it can change into toluene higher benzene of value and dimethylbenzene, and wherein dimethylbenzene has three isomers, is worth the highest paraxylene (PX) and accounts for 24%.Therefore there is the people to propose the new technology of selective disproportionation, makes reaction system optionally generate paraxylene.
Paraxylene is a primary raw material of producing the p-phthalic acid in the polyester industrial, and its demand continues to increase at a high speed always.Industrial utilization reformation gasoline, drippolene, toluene, C
9Aromatic hydrocarbons and mixed xylenes are raw material, make C by disproportionation, transalkylation and isomerization
8Aromatic hydrocarbons makes paraxylene through adsorbing separation or Crystallization Separation.Usually use catalyst such as Y zeolite, modenite, can only obtain the dimethylbenzene (contraposition a: position: ortho position=24%:53%:23%), isolate paraxylene with expensive fractional crystallization or adsorbing separation then that thermodynamical equilibrium is formed.The utilization rate of toluene is relatively low, except that part is used as solvent, and most of toluene and C
9Aromatic hydrocarbons is produced dimethylbenzene by traditional disproportionation and alkylation process, and the paraxylene concentration in the product is controlled by thermodynamics, and productive rate is lower.
In toluene disproportionation process, a lot of patents all claim their catalyst can access higher paraxylene selectivity, but toluene conversion declines to a great extent before all more unmodified.
Among the CN 1362390, metals such as load bismuth, chromium, nickel on low silica-alumina ratio HZSM-5 zeolite, unmodified preceding HZSM-5 zeolite, toluene conversion is 50%, the paraxylene selectivity is 24%.After the modification, the paraxylene selectivity rises to 90%, and toluene conversion then reduces to 20%.
Among the CN 1765497, utilize ZSM-5 as active component, silicone oil is modifier, carries out dystopy siliceous deposits molecular sieve by dipping-roasting method.Before unmodified, toluene conversion is 51%, and the paraxylene selectivity is 24%.After silicon oil modified, the paraxylene selectivity rises to 90%, and toluene conversion drops to 30%.
Among the CN 1762593, as active component, ethyl orthosilicate is a modifier, carries out steam treatment after the modification again with the ZSM-5 zeolite.Before the modification, toluene conversion is 48 heavy %, and the paraxylene selectivity is 24 heavy %.After the modification, the paraxylene selectivity rises to 96.5 heavy %, and toluene conversion drops to 23 heavy %.
US 4137195, and the middle ZSM-5 zeolite of using carries out load as active component with ammonium phosphate salt and magnesium compound.Before the modification, toluene conversion is 49%, and the paraxylene selectivity is 24%.After the modification, the paraxylene selectivity rises to 96%, and toluene conversion drops to 11%.
Among the WO 2008052445, as active component, drop to 19% with the metal-modified catalyst that obtains toluene conversion after modification with ZSM-5, the paraxylene selectivity rises to 96%.
Activity descends before all more unmodified significantly in the given example of relevant various patents, therefore at high paraxylene optionally under the prerequisite, seek a kind of easy method and improve toluene conversion, select the application of disproportionation processes promoting toluene, significant.
With naoh treatment ZSM-5 zeolite be preparation to contain mesoporous ZSM-5 zeolite be a kind of simple and easy to do method, its principle is that alkali removes the part silicon on the skeleton, causes the part framework local to subside, it is mesoporous to produce part.
T.Suzuki etc. (T.Suzuki, T.Okuhara.Micropor Mesopor Mater.2001,43,83) adopt the NaOH of 0.05mol/L, under different temperatures, are that 37 ZSM-5 molecular sieve is handled to the mol ratio of silica and aluminium oxide.Experimental result shows that alkali treatment can increase the total specific area and the external surface area of ZSM-5 molecular sieve.
(J.C.Groen, L.A.A.Peffer, J.A.Moulijn.et al.Micropor mesoporMater.2004 such as J.C.Groen, 69,29) handle the ZSM-5 zeolite with the 0.25mol/L sodium hydroxide solution, find that alkali treatment can produce mesoporous under suitable condition.
In toluene disproportionation process, mesoporous by the intracrystalline that alkali treatment produced, help the diffusion of molecule in geode of reaction system, make the easier inner surface activated centre that touches molecular sieve of reactant, also make product deviate from catalyst faster, thereby improve the conversion ratio of reaction.Because mesoporous generation, the time of staying of reactant and product shortens, and has reduced the generation of side reaction.It is a kind of feasible method in theory that this explanation is used to improve reaction conversion ratio with the alkali treatment modifying toluene disproportionation catalyst.In the existing document, though provided various powder alkali treatment methods, but in the toluene disproportionation catalyst preparation process, moulding need add various auxiliary agents and the moulding rear catalyst must be through repeatedly modification processing, because the adding of alkali treatment process, auxiliary agent kind, amount of auxiliary and modification procedure of Jia Ruing and method all need change before, thus provide alkali treatment condition and impracticable in the document, but can guide direction.Behind alkali treatment method improvement toluene disproportionation catalyst, (the paraxylene selectivity is 95% level at high selectivity, low-conversion, conversion ratio is 23% level, and CN 1762593 Wang Jun appoint universe dawn) the basis on improved the toluene conversion 6-10% of toluene disproportionation process and reduced the mol ratio of benzene and dimethylbenzene.
Summary of the invention
The objective of the invention is to improve in the prior art and to cause conversion ratio to descend significantly owing to modification and the problem of side reaction degree aggravation catalyst, and a kind of preparation method of modified ZSM-5 zeolite toluene disproportionation catalyst by soda treatment proposed, it is active and reduce side reaction that prepared catalyst can effectively improve toluene disproportionation process.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of modified ZSM-5 zeolite toluene disproportionation catalyst by soda treatment, and concrete steps are as follows:
A) the ZSM-5 zeolite powder is carried out molding bonded with the binding agent of the heavy % of 10-60, dry then, dry, roasting, make the moulding sample;
B) with above-mentioned moulding sample under 25-75 ℃, add in the aqueous slkali and carry out alkali treatment, wherein the concentration of aqueous slkali is 0.01-0.4mol/L, the addition of moulding sample is 1:5-1:20 for the control solid-to-liquid ratio, alkali treatment time 0.3-4h; Oven dry, roasting obtain the alkali treatment sample then;
C) the alkali treatment sample with step b gained carries out ammonium ion exchange, washing then, centrifugation, drying, roasting in ammonium salt solution; Sample after the roasting is carried out pickling at oxalic acid solution, wash then, filter, drying, carry out chemical liquid deposition with the cyclohexane solution of ethyl orthosilicate, suction filtration, drying makes catalyst after the roasting.
Above-mentioned ZSM-5 zeolite is preferably the HZSM-5 zeolite.The silica alumina ratio of ZSM-5 zeolite is preferably 25-70.
Above-mentioned binding agent is Ludox, aluminium oxide, the sweet soil of sheep, kaolin or attapulgite.Be preferably the sweet soil of Ludox or sheep.
The described alkali of alkali treatment modifying is organic or inorganic alkali, preferred TPAOH, NaOH, ammoniacal liquor, n-butylamine or potassium hydroxide; More preferably alkali is NaOH or ammoniacal liquor.
Its alkali purification temp in the step b) is preferably 45-65 ℃; Alkali concn is 0.08-0.3mol/L, and the alkali treatment time is 0.5-3h.
Commercially available ammonium chloride or the ammonium nitrate solution of the general selection of above-mentioned ammonium salt solution.Above-mentioned ammonium ion exchange is generally 4-6 time.
The described preparation catalyst of the inventive method can directly mix Hydrogen ZSM-5, extrusion aid and Ludox in the bar shaped catalyst alkali treatment, drying and roasting after the moulding.General forming method is extrusion molding, compression forming, rotational forming.That the shape of moulding can be is cylindrical, spherical, bar shaped or cloverleaf pattern.In the fine catalyst alkali treatment, the catalyst after the processing mixes moulding then after exchanging through ammonium again with extrusion aid, Ludox.Drying and roasting after the moulding.General forming method is extrusion molding, compression forming, rotational forming.That the shape of moulding can be is cylindrical, spherical, bar shaped or cloverleaf pattern.
Beneficial effect:
1. the organic base of modified zeolite molecular sieve that the present invention is used for or inorganic base are commercial organic base or the inorganic base that is easy to obtain.
2. the used alkali treatment of the present invention: step is simple, treatment conditions are gentle, experimental facilities is not had specific (special) requirements, can effectively improve the toluene conversion of catalyst and effectively reduces the generation of side reaction.
The present invention not only comprised catalyst carried out powder modification but also comprises moulding after the granular solids modification.
The specific embodiment
The following examples will be further specified the present invention, but not thereby limiting the invention.
[embodiment 1]
With the former powder of 30g HZSM-5 zeolite molecular sieve (Catalyst Factory, Nankai Univ system, the mol ratio of silica and aluminium oxide are 38) and 25g Ludox, 1.2g sesbania powder mixes, and extruded moulding makes binder content and be 20% strip catalyst solid particle.Above-mentioned catalyst is carried out ammonium ion exchange, washing then, centrifugation, drying, roasting in ammonium chloride solution (ammonium chloride is 1:1 with the solid weight ratio).Catalyst is carried out pickling at the 0.5mol/L oxalic acid solution, solid-to-liquid ratio 1:5, wash then, filter, drying, cyclohexane solution with ethyl orthosilicate carries out chemical liquid deposition 2 times, modification 5h, depositing temperature is 45 ℃, and 120 ℃ of following dry 6h, 1 ℃/min are warming up to 550 ℃ of roastings and make final catalyst A after after 4 hours.
Toluene disproportionation process carries out on the high pressure micro-reaction equipment.Get the 2g catalyst A and be seated in 500mm length, internal diameter is the stainless steel reaction pipe stage casing of 14mm, fills quartz sand up and down.Pure toluene charging, mass space velocity are 3.0h
-1, reaction temperature is 440 ℃, and reaction pressure is 1.2MPa, and hydrogen and toluene mole ratio are 2.The toluene feed procatalyst is nitrogen activation 1h under 440 ℃ of temperature, and product is cooled to liquid phase through cold-trap, gets liquid-like behind the reaction 4h, analyzes it by gas chromatograph and forms toluene conversion X
T(%), paraxylene selectivity S
P(%) and the computing formula of B/X as follows:
Formula (1), X represents the mole fraction of each component in product in (2), (3), subscript is explained as follows:
B--------------------------benzene
T--------------------------toluene
The PX------------------------paraxylene
The MX-----------------------meta-xylene
The OX-----------------------ortho-xylene
X-------------------------dimethylbenzene is that the result of summation sample A of PX, MX, OX is as shown in table 1.
[embodiment 2]
With former powder (the Catalyst Factory, Nankai Univ system of 30g HZSM-5 zeolite molecular sieve, silica is 38 with the mol ratio of aluminium oxide) mix with the 0.2mol/L sodium hydroxide solution and be made into suspension, solid-to-liquid ratio 1:10, stir 0.5h down at 65 ℃, filtration, washing, dry 2-5h in 100-120 ℃ of baking oven, in Muffle furnace, be warming up to 550 ℃, at this roasting temperature 3-5h with 2 ℃/min.
After the powder that obtains thus carries out ammonium exchange, by binder content 20% carry out that extruded moulding, drying, roasting exchange then, pickling, deposition, obtain catalyst sample B.
[embodiment 3]
The former powder of 30g HZSM-5 zeolite molecular sieve (Catalyst Factory, Nankai Univ system, the mol ratio of silica and aluminium oxide are 38) is added 25g Ludox, 1.2g sesbania powder moulding (binder content 20%).With solid drying, roasting after the moulding.
Get the above-mentioned solid of 5g in the 0.05mol/L sodium hydroxide solution, under 45 ℃, at the uniform velocity shake 2h under the condition of solid-to-liquid ratio 1:10.Washing then, dry, roasting.After the gained solid carries out 6 ammonium exchanges, pickling, secondary deposition.Obtain bar shaped alkali treatment catalyst sample C after the deposition.
Get the above-mentioned catalyst of 2 grams and carry out toluene disproportionation process.
[embodiment 4]
Change hydrogen and toluene mole ratio are original 2 times on the basis of embodiment 3, obtain catalyst D.
Table 1 catalyst activity evaluation result
| Numbering | Catalyst modification | X T/％ | S P/％ | B/X |
| A | Former state is untreated | 22.5 | 94.1 | 1.6 |
| B | The powder alkali treatment | 29.1 | 96.5 | 1.4 |
| C | The strip catalyst alkali treatment | 28.3 | 95.3 | 1.3 |
| D | The strip catalyst alkali treatment | 24.1 | 95.1 | 1.3 |
Table 1 presentation of results: no matter be powder alkali treatment catalyst or strip alkali treatment catalyst, toluene conversion all obviously improves than the sample of not alkali treatment, and the paraxylene selectivity still remains on the high level more than 94%, and B/X has obvious decline.
Embodiment 5-10 investigated in Different Silicon aluminum ratio, temperature, concentration, solid-to-liquid ratio, processing time, final sample activity of such catalysts and selectivity under the aqueous slkali.
[embodiment 5]
The ZSM-5 molecular sieve powder of silica alumina ratio 25 is at 45 ℃, and in the 0.3mol/L sodium hydroxide solution, solid-to-liquid ratio is 1:5, handles 2h, obtains sample E.
[embodiment 6]
The ZSM-5 molecular sieve powder of silica alumina ratio 70 is at 75 ℃, and in the 0.1mol/L potassium hydroxide solution, solid-to-liquid ratio is 1:20, handles 0.5h, obtains sample F.
[embodiment 7]
The ZSM-5 molecular sieve powder of silica alumina ratio 70 is at 55 ℃, and in the 0.15mol/L TPAOH solution, solid-to-liquid ratio is 1:10, handles 1h, obtains sample G.
[embodiment 8]
The ZSM-5 molecular sieve strip solid of silica alumina ratio 25 is at 25 ℃, and in the 0.08mol/L sodium hydroxide solution, solid-to-liquid ratio is 1:5, handles 3h, obtains sample H.
[embodiment 9]
The ZSM-5 molecular sieve powder of silica alumina ratio 70 is at 45 ℃, and in the 0.1mol/L potassium hydroxide solution, solid-to-liquid ratio is 1:20, handles 0.5h, obtains sample I.
[embodiment 10]
The ZSM-5 molecular sieve powder of silica alumina ratio 38 is at 35 ℃, and in the 0.15mol/L ammonia spirit, solid-to-liquid ratio is 1:10, handles 1h, obtains sample J.
Embodiment 11-13 changes the kind of alkali on the basis of embodiment 7, select TPAOH, ammoniacal liquor, n-butylamine successively for use.
[embodiment 11]
The ZSM-5 molecular sieve strip solid of silica alumina ratio 25 is at 25 ℃, and in the 0.08mol/L TPAOH solution, solid-to-liquid ratio is 1:5, handles 3h, obtains sample L.
[embodiment 12]
The ZSM-5 molecular sieve strip solid of silica alumina ratio 25 is at 25 ℃, and in the 0.08mol/L ammonia spirit, solid-to-liquid ratio is 1:5, handles 3h, obtains sample M.
[embodiment 13]
The ZSM-5 molecular sieve strip solid of silica alumina ratio 25 is at 25 ℃, and in the 0.08mol/L n-butylamine solution, solid-to-liquid ratio is 1:5, handles 3h, obtains sample N.Toluene disproportionation performance such as table 2.
Table 2 catalyst activity evaluation result
| Numbering | Treatment temperature/℃ | Concentration of treatment/mol/L | Processing time/h | Solid-to-liquid ratio | Silica alumina ratio | X T /％ | S P /％ | B/X |
| A | \ | \ | \ | \ | 38 | 22.5 | 94.1 | 1.6 |
| E | 45 | 0.3 | 2 | 1：5 | 25 | 33.2 | 94.5 | 1.3 |
| F | 75 | 0.1 | 0.5 | 1：20 | 70 | 30.3 | 95.1 | 1.4 |
| G | 55 | 0.15 | 1 | 1：10 | 70 | 32.3 | 94.3 | 1.4 |
| H | 25 | 0.08 | 3 | 1：5 | 25 | 28.2 | 95.1 | 1.3 |
| I | 45 | 0.1 | 0.5 | 1：20 | 70 | 29.1 | 95.5 | 1.5 |
| J | 35 | 0.15 | 1 | 1：10 | 38 | 28.3 | 95.3 | 1.4 |
| L | 25 | 0.08 | 3 | 1：5 | 25 | 26.5 | 94.5 | 1.4 |
| M | 25 | 0.08 | 3 | 1：5 | 25 | 28.1 | 94.1 | 1.3 |
| N | 25 | 0.08 | 3 | 1：5 | 25 | 25.1 | 93.3 | 1.5 |
As shown in Table 2, prepared alkali treatment modifying toluene disproportionation catalyst all can more significantly improve toluene conversion and reduce B/X, and the preferred NaOH of the used alkali of alkali treatment, ammoniacal liquor.
[embodiment 14]
Replace Ludox to carry out molding bonded with the sweet soil of sheep on the basis of case 3, binding agent accounts for 10 heavy %, handles 4h with the ammoniacal liquor of 0.01mol/L down at 65 ℃, and solid-to-liquid ratio 1:5 obtains sample O.
[embodiment 15]
Replace Ludox to carry out molding bonded with the attapulgite hybrid rod on the basis of case 3, binding agent accounts for 60 heavy %, handles 0.3h with the sodium hydroxide solution of 0.4mol/L down at 35 ℃, and solid-to-liquid ratio 1:10 obtains sample P.
[embodiment 15]
Replace Ludox to carry out molding bonded with aluminium oxide on the basis of case 3, binding agent accounts for 30 heavy %, handles 1h with the n-butylamine solution of 0.08mol/L down at 55 ℃, and solid-to-liquid ratio 1:20 obtains sample Q.
[embodiment 16]
Replace Ludox to carry out molding bonded with kaolin on the basis of case 3, binding agent accounts for 40 heavy %, handles 1.5h with the TPAOH solution of 0.1mol/L down at 25 ℃, and solid-to-liquid ratio 1:15 obtains sample R.The results are shown in Table 3.
Table 3 catalyst activity evaluation result
| Numbering | The binding agent kind | Binder content/weight % | Treatment temperature/℃ | Concentration of treatment/mol/L | Processing time/h | Solid-to-liquid ratio | X T /％ | S P /％ | B/X |
| C | Ludox | 20 | 45 | 0.05 | 2 | 1:10 | 28.3 | 95.3 | 1.3 |
| O | The sweet soil of sheep | 10 | 65 | 0.01 | 4 | 1:5 | 27..6 | 95.6 | 1.4 |
| P | The attapulgite hybrid rod | 60 | 35 | 0.4 | 0.3 | 1:10 | 25.5 | 95.1 | 1.4 |
| Q | Aluminium oxide | 30 | 55 | 0.08 | 1 | 1:20 | 23.33 | 94.3 | 1.3 |
| R | Kaolin | 40 | 25 | 0.1 | 1.5 | 1:15 | 24.1 | 94.5 | 1.3 |
Table 3 presentation of results, the preferred Ludox of used binding agent or the sweet soil of sheep.
Claims (9)
1, a kind of preparation method of modified ZSM-5 zeolite toluene disproportionation catalyst by soda treatment, concrete steps are as follows:
A) the ZSM-5 zeolite powder is carried out molding bonded with the binding agent of the heavy % of 10-60, dry then, dry, roasting, make the moulding sample;
B) with above-mentioned moulding sample under 25-75 ℃, add in the aqueous slkali and carry out alkali treatment, wherein the concentration of aqueous slkali is 0.01-0.4mol/L, the addition of moulding sample is 1:5-1:20 for the control solid-to-liquid ratio, alkali treatment time 0.3-4h; Oven dry, roasting obtain the alkali treatment sample then;
C) the alkali treatment sample with step b gained carries out ammonium ion exchange, washing then, centrifugation, drying, roasting in ammonium salt solution; Sample after the roasting is carried out pickling at oxalic acid solution, wash then, filter, drying, carry out chemical liquid deposition with the cyclohexane solution of ethyl orthosilicate, suction filtration, drying makes catalyst after the roasting.
2, preparation method according to claim 1, the silica alumina ratio that it is characterized in that the ZSM-5 zeolite is 25-70.
3, preparation method according to claim 1 is characterized in that the ZSM-5 zeolite is the HZSM-5 zeolite.
4, preparation method according to claim 1 is characterized in that binding agent is Ludox, aluminium oxide, the sweet soil of sheep, kaolin or attapulgite.
5, preparation method according to claim 4 is characterized in that described binding agent is Ludox or the sweet soil of sheep.
6, preparation method according to claim 1 is characterized in that the described alkali of alkali treatment modifying is TPAOH, NaOH, ammoniacal liquor, n-butylamine or potassium hydroxide.
7, preparation method according to claim 6 is characterized in that described alkali is NaOH or ammoniacal liquor.
8, preparation method according to claim 1 is characterized in that described its alkali purification temp is 45-65 ℃.
9, according to the preparation method of the described alkali treatment modifying toluene disproportionation zeolitic catalyst of claim 1, it is characterized in that described alkali concn is 0.08-0.3mol/L, the alkali treatment time is 0.5-3h.
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