CN103120949B - Methylbenzene methylation catalyst for increasing production of o-xylene and p-xylene and preparation method thereof - Google Patents
Methylbenzene methylation catalyst for increasing production of o-xylene and p-xylene and preparation method thereof Download PDFInfo
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 89
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 title claims abstract description 78
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000007069 methylation reaction Methods 0.000 title claims abstract description 20
- 230000011987 methylation Effects 0.000 title claims abstract description 18
- 229940078552 o-xylene Drugs 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 11
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 14
- 239000002808 molecular sieve Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000005804 alkylation reaction Methods 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 230000029936 alkylation Effects 0.000 description 8
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical compound OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 238000007323 disproportionation reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- 150000003738 xylenes Chemical class 0.000 description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- -1 hydrogen hydrocarbon Chemical class 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NANSARKGFCEFOF-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Al+3].[Al+3] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Al+3].[Al+3] NANSARKGFCEFOF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a methylbenzene methylation catalyst for increasing production of o-xylene and p-xylene and a preparation method thereof, and is mainly used for solving the problems that in the prior art, the methylbenzene methylation catalyst only generates dimethylbenzene products in balanced distribution, and selectivity of o-xylene and p-xylene is lower. The catalyst comprises the components in parts by weight as follows: a) 5-95 parts of hydrogen mordenite (NaHMor) containing 0.8-2.8% of sodium ions; and b) 95-5 parts of bonder. The problems are better solved by adopting the technical scheme, and the catalyst can be applied to industrial production of o-xylene and p-xylene.
Description
Technical field
The present invention relates to toluene methylation catalysts of a kind of Increasing o-Xylene Output and paraxylene and preparation method thereof.
Background technology
Ortho-xylene is important chemical intermediate, mainly for the production of phthalic anhydride (being commonly called as phthalic anhydride).Phthalic anhydride is mainly used in the production of plasticizer and alkyd resins, unsaturated-resin, PEPA, polyester resin, also can be used for the intermediate of asccharin, pigment, dyestuff, medicine, pesticide producing.Along with the continuous expansion of phthalic anhydride downstream product application, particularly along with the development of Building Trade in China and traffic, electronics, aircraft industry, the extensive use of anti-corrosion material, a large amount of uses of unsaturated polyester resin and alkyd resins, market also presents increasing trend to its raw material ortho-xylene demand.
At present, the production capacity of domestic ortho-xylene can not be met the need of market far away, although ortho-xylene manufacturer expands energy in Technologies in Petrochemical Industry comprehensively, but still can not meet the need of market, ortho-xylene still needs a large amount of import, and import volume presents growth trend, and price is high, within 2009, import total amount reaches 67.3 ten thousand tons, and unit price also increases to the 9400-9500 unit/t at the beginning of 2011 by 5950 yuan/t at the beginning of 2004.
At present, the source of ortho-xylene mainly contains: 1. coal tar, the accessory substance of mainly coal industry and metallurgical industry.2. catalytic reforming.3. drippolene, the co-product of liquid material when preparing ethylene by steam cracking.4. toluene disproportionation and transalkylation.
In several ortho-xylene production method, with paraxylene joint production process for the best, adopt the aromatics seperation technique of combining with isomerization, disproportionation, first with rectification method, ortho-xylene separated before p-xylene separation.This method is two tower operations, and the first tower realizes ortho-xylene and other C8 isomer separation.Generate oil for raw material with catalytic reformate, drippolene and disproportionation, Joint Production ortho-xylene is also the common method of producing ortho-xylene abroad.Benzene, toluene, mixed xylenes and paraxylene all can be produced simultaneously.Production procedure is flexible, can adjust product proportion, resource fully and is reasonably utilized according to the market demand.
CN 1752057A with benzene, toluene and carbon nine and above aromatic hydrocarbons thereof for mixed xylenes produced by raw material, first be separated neighbour, paraxylene respectively, unreacted feedstock circulation enters technique unit, when solving the production ortho-xylene existed in accordance transfer techniques in the past, in a large amount of benzene of by-product, raw material, carbon nine and above heavy virtue thereof obtain the higher neighbour of purity, paraxylene through the low problem of content, but the one way distribution of reaction products involved by patent does not break thermodynamical equilibrium, thus this patent be only to a certain extent improve its production capacity.
Paraxylene is also a kind of important Organic Chemicals, is mainly used in synthesis terephthalic acid (TPA) or dimethyl terephthalate (DMT), all has purposes extremely widely in fields such as polyester fiber, medicine, agricultural chemicals, dye well solvents.At present, it is raw material that paraxylene produces main employing mixed xylenes, produced by isomerization, adsorbing separation or Crystallization Separation, owing to controlling by thermodynamical equilibrium, paraxylene content in mixed xylenes only accounts for about 24%, in technical process, Matter Transfer treating capacity is large, and equipment is huge, and operating cost is high.Also can adopt selective disproportionation of toluene technique, can generate high concentration paraxylene, but toluene conversion be only 30%, solid circulating rate is also larger.
Along with the development of C1 chemistry, the output of methyl alcohol increases, cost reduces, if can react by toluene and methanol alkylation cheap and easy to get the paraxylene directly synthesizing high concentration, separation and isomerized workload can be reduced, economic benefit is considerable, thus utilizes alkylation of toluene methanol to select the research generating paraxylene to cause the great interest of people.Alkylation of toluene methanol reacts the high concentration paraxylene that can using value be become higher toluene conversion, and decrease separation and isomerized workload, its economic benefit is by considerable.
Also do not have large-scale alkylation of toluene methanol to react commodity production device at present in the world to come out, mainly whether the economic benefit of this kind of device will depend on supporting with large-scale methanol device.The focus that people pay close attention to is to prepare paraxylene by methylbenzene methanol shape selective alkylation reaction to molecular sieve (mainly ZSM-5 molecular sieve) modification, existing document has done and has summarized (Ge Xin etc., " Chinese Journal of Inorganic Chemistry ", 2001,17 (1): 17-26; Cao Dean, " Chemical Reaction Engineering and technique ", 2007,23 (4): 359-364).Also there is the problem of catalyst preparation process complexity, easily coking deactivation.And modification is not carried out to molecular sieve, can only obtain the mixed xylenes of thermodynamical equilibrium, wherein paraxylene accounts for about 24%, ortho-xylene accounts for about 22%, and the less meta-xylene of purposes accounts for 54%, and follow-up isomerization, separation of material circular treatment amount are large, energy consumption is high, and the easy coking deactivation of catalyst.
In recent years, the patent of many products for the purpose of paraxylene is also disclosed both at home and abroad.Patent CN 1762593A, US4067920, US 4011276, in US 5367099 and US 5607888, propose the modification to ZSM-5 molecular sieve structure, namely port size and shielding outer surface acidity active sites is reduced, prepare selective toluene disproportionation or methylation catalyst, above-mentioned patent is all to improve product for the purpose of Selectivity for paraxylene, there is loaded down with trivial details, the used organosilicon modifier price of processing step high, complex structure or consumption is many, solvent for use is expensive, or need to add precious metal etc. in catalyst and to have much room for improvement part.
Zeolite molecular sieve has uniform composition and regular structure, and conventional zeolite molecular sieve (aluminosilicate zeolite molecular sieve) is hydrated aluminosilicate crystal, has uniform aperture, by SiO
4and AlO
4tetrahedron (is referred to as TO
4tetrahedron) to share oxygen atom be basic skeleton structure unit, composition shortrange order and the crystal structure of long-range order.By SiO
4tetrahedron and AlO
4the aluminosilicate zeolite molecular sieve that tetrahedron is formed has anion frame structure, and skeleton negative electrical charge is by extra cation balance.For synthetic zeolite, these cations are all sodium ions usually.These sodium ions can carry out reversible exchange with other cations, after exchange, the electrostatic field of crystals can be made to change, thus changing its performance, it is different with the difference of cationic property and exchange degree that it changes degree, after adopting ammonium salt solution to carry out ion-exchange to sodium form molecular sieve, molecular sieve just changes ammonium type into, again through roasting, just change hydrogen type molecular sieve into, become solid acid.The zeolite molecular sieve being typically used as acid catalyst is all hydrogen type molecular sieve, and its sodium content is less than 0.02%.
Summary of the invention
One of technical problem to be solved by this invention there is the xylene products that toluene methylation catalysts used can only be balanced distribution in alkylation of toluene methanol technology in the past, ortho-xylene and Selectivity for paraxylene problem on the low side, provide the toluene methylation catalysts of a kind of new Increasing o-Xylene Output and paraxylene.This catalyst is used for toluene methylation reaction, has ortho-xylene and the high advantage of Selectivity for paraxylene; Two of technical problem to be solved by this invention is to provide a kind of preparation method of the catalyst corresponding with one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the toluene methylation catalysts of a kind of Increasing o-Xylene Output and paraxylene, comprises following component with weight parts: a) h-mordenite (NaHMor) containing sodium ion 0.08-2.8% weight of 5 ~ 95 parts; B) binding agent of 95 ~ 5 parts.
In technique scheme, the mol ratio [n (SiO of silica and aluminium oxide in modenite
2)/n (Al
2o
3), be called for short silica alumina ratio, as follows] preferable range is 8-80.Binding agent preferred version is selected from least one in Ludox, boehmite or aluminium oxide.H-mordenite (NaHMor) is 0.10-2.0% weight containing the preferable range of sodium ion.Organic acid preferred version is selected from least one in citric acid, oxalic acid or tartaric acid.Ammonium salt preferred version is selected from least one in ammonium nitrate, ammonium chloride or ammonium sulfate.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the preparation method of the toluene methylation catalysts of a kind of Increasing o-Xylene Output and paraxylene, comprise the following steps: a) at 20 DEG C ~ 95 DEG C, concentration sodium form modenite being joined aequum is process 0.5-24 hour in the organic acid soln of 0.05-5mol/L, washing after filtering, drying; B) concentration above-mentioned modenite being joined aequum is in the ammonium salt solution of 0.05-5mol/L, constant temperature process 0.5-24 hour under 40 DEG C ~ 100 DEG C conditions, washing after filtering, drying; C) above-mentioned modenite and binding agent are mixed in proportion aftershaping, under 300-600 DEG C of condition, constant temperature calcining 1-12 hour obtains catalyst.
In technique scheme, ammonium salt preferred version is selected from least one in ammonium nitrate, ammonium chloride or ammonium sulfate.
Because the methyl on toluene phenyl ring is ortho para location base when alkylated reaction, toluene methylation reaction only generates ortho-xylene and paraxylene in theory, and the ratio of ortho-product and contraposition product is 2: 1, meta-xylenes a large amount of in actual product is from the isomerization reaction of ortho-xylene and paraxylene.According to the preparation method of the toluene methylation catalysts of Increasing o-Xylene Output provided by the invention and paraxylene, the sodium ions content of modenite is controlled by controlling ammonium ion exchange condition, thus after roasting becomes hydrogen type molecular sieve, change sour density and the acid site distribution of modenite.Which reduce the probability of methyl alcohol generation side reaction in modenite 8 ring side opening (because the little toluene molecule in aperture cannot enter), also reduce sour density, be conducive to suppressing isomerization reaction, thus improve the selective of ortho-xylene and paraxylene.
By catalyst of the present invention, for alkylation of toluene methanol reaction, at reaction temperature 400 DEG C, reaction pressure 1.0MPa, air speed (WHSV) 6h
-1with under hydrogen hydrocarbon mol ratio 1.0 condition, its ortho-xylene is selective reaches 50%, higher than prior art more than 22% 1 times; Its Selectivity for paraxylene can reach 30%, higher than prior art with 24%, achieve good technique effect.
Illustrate embodiment of the present invention below by embodiment, but the present invention is not limited to this.
Detailed description of the invention
[embodiment 1-6]
Get respectively 30 grams of silica alumina ratios be 15 sodium form modenite (industrial goods) join in the certain density organic acid soln of aequum process after certain hour filter, washing, dry, joined in the certain density ammonium salt solution of aequum again, the certain hour of constant temperature process at a certain temperature carries out ion-exchange, washing after filtering, drying, obtain the modenite of different sodium exchange degree; The modenite exchanged and binding agent are mixed in proportion aftershaping, obtains catalyst A-F after constant temperature calcining certain hour, specifically in table 1.
Table 1 catalyst preparing
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Organic acid | Citric acid | Oxalic acid | Tartaric acid | Citric acid | Citric acid | Citric acid |
| Organic acid concentration, mol/L | 0.1 | 0.5 | 0.5 | 4 | 0.5 | 1 |
| Acid treatment temperature, DEG C | 90 | 90 | 90 | 30 | 80 | 50 |
| The acid treatment time, hour | 24 | 6 | 6 | 1 | 18 | 12 |
| Ammonium salt | Ammonium nitrate | Ammonium nitrate | Ammonium nitrate | Ammonium chloride | Ammonium chloride | Ammonium sulfate |
| Ammonium salt concentration, mol/L | 4 | 1 | 1 | 0.1 | 2 | 1 |
| Ammonium exchange temperature, DEG C | 50 | 90 | 90 | 95 | 90 | 80 |
| Ammonium swap time, hour | 4 | 6 | 6 | 24 | 1 | 4 |
| Sodium ions content in NaHMor, % weight | 0.10 | 0.36 | 0.34 | 2.3 | 0.60 | 0.92 |
| Binding agent | Aluminium oxide | Aluminium oxide | Aluminium oxide | Ludox | Aluminium oxide | Boehmite |
| Catalyst forms, modenite/binding agent | 15/85 | 50/50 | 30/70 | 90/10 | 70/30 | 80/20 |
| Sintering temperature, DEG C | 320 | 500 | 500 | 580 | 500 | 550 |
| Roasting time, hour | 2 | 4 | 4 | 10 | 6 | 6 |
| Catalyst is numbered | A | B | C | D | E | F |
[embodiment 7-11]
At 60 DEG C, the concentration that the sodium form modenite (industrial goods) getting 30 grams of Different Silicon aluminum ratios respectively joins aequum is process 6 hours in the citric acid solution of 0.5mol/L, washing after filtering, dry; Joined in the certain density ammonium nitrate solution of aequum again, the certain hour of constant temperature process at a certain temperature carries out ion-exchange, and washing after filtering, drying, obtain the modenite of different sodium exchange degree; The modenite exchanged and alumina binder are mixed in proportion aftershaping, and 500 DEG C of constant temperature calcinings obtain catalyst G-K after 6 hours, specifically in table 2.
Table 2 catalyst preparing
| Embodiment | 7 | 8 | 9 | 10 | 11 |
| Modenite silica alumina ratio | 10 | 10 | 25 | 30 | 72 |
| Concentration of ammonium nitrate solution, mol/L | 1 | 0.5 | 1 | 0.5 | 0.2 |
| Ammonium exchange temperature, DEG C | 60 | 60 | 80 | 90 | 90 |
| Ammonium swap time, hour | 1 | 2 | 2 | 4 | 2 |
| Sodium ions content in NaHMor, % weight | 0.58 | 0.71 | 0.50 | 1.10 | 0.82 |
| Catalyst forms, modenite/binding agent | 40/60 | 60/40 | 70/30 | 90/10 | 80/20 |
| Catalyst is numbered | G | H | I | J | K |
[comparative example]
Get 30 grams of silica alumina ratios be 10 sodium form modenite (industrial goods) concentration that joins aequum be in the ammonium nitrate solution of 1mol/L, at 95 DEG C, constant temperature process carries out ion-exchange in 4 hours, washing after filtering, dry; Repeat 3 ammoniums under the same terms again to exchange, in the h-mordenite (HM) obtained, sodium ions content is 0.02% weight; HM is mixed aftershaping with alumina binder by 70/30, and 500 DEG C of constant temperature calcinings obtained comparative catalyst L after 6 hours.
[embodiment 12-23]
Fixed bed reaction evaluating apparatus has been investigated the performance of catalyst A-L catalysis alkylation of toluene methanol reaction, the mol ratio of raw material toluene and methyl alcohol is 2: 1, and loaded catalyst is 5g, reaction temperature 400 DEG C, reaction pressure 1.0MPa, Feed space velocities (WHSV) 6.0h
-1, hydrogen hydrocarbon mol ratio 1.0.React 2 hours post analysis product compositions, the results are shown in table 3.
Table 3 different catalysts catalysis alkylation of toluene methanol reactivity worth
| Catalyst | Toluene conversion | OX is selective | PX is selective | MX is selective |
| A | 18.6 | 24 | 25 | 51 |
| B | 20.1 | 32 | 25 | 43 |
| C | 18.2 | 29 | 25 | 46 |
| D | 13.6 | 35 | 26 | 39 |
| E | 15.4 | 41 | 27 | 32 |
| F | 17.3 | 48 | 30 | 22 |
| G | 16.2 | 41 | 26 | 33 |
| H | 17.5 | 40 | 26 | 34 |
| I | 18.4 | 39 | 25 | 36 |
| J | 18.8 | 41 | 26 | 33 |
| K | 16.3 | 50 | 26 | 24 |
| L | 19.8 | 22 | 24 | 54 |
Claims (7)
1. a toluene methylation catalysts for Increasing o-Xylene Output and paraxylene, comprises following component with weight parts:
A) h-mordenite containing sodium ion 0.08-2.8% weight of 5 ~ 95 parts;
B) binding agent of 95 ~ 5 parts;
The preparation method of described catalyst, comprises the following steps:
A) at 20 DEG C ~ 95 DEG C, concentration sodium form modenite being joined aequum is process 0.5-24 hour in the organic acid soln of 0.05-5mol/L, washing after filtering, drying;
B) concentration above-mentioned modenite being joined aequum is in the ammonium salt solution of 0.05-5mol/L, constant temperature process 0.5-24 hour under 40 DEG C ~ 100 DEG C conditions, washing after filtering, drying;
C) above-mentioned modenite is mixed aftershaping with binding agent in required ratio, under 300-600 DEG C of condition, constant temperature calcining 1-12 hour obtains catalyst.
2. the toluene methylation catalysts of Increasing o-Xylene Output according to claim 1 and paraxylene, is characterized in that the mol ratio of silica and aluminium oxide in modenite is 8-80.
3. the Increasing o-Xylene Output according to claim l and the toluene methylation catalysts of paraxylene, is characterized in that binding agent is selected from least one in Ludox, boehmite, aluminium oxide.
4. the toluene methylation catalysts of Increasing o-Xylene Output according to claim 1 and paraxylene, is characterized in that h-mordenite sodium ions content scope is 0.10-2.0% weight.
5. the toluene methylation catalysts of Increasing o-Xylene Output according to claim 1 and paraxylene, is characterized in that organic acid is selected from least one in citric acid, oxalic acid, tartaric acid.
6. the preparation method of the toluene methylation catalysts of Increasing o-Xylene Output according to claim 1 and paraxylene, comprises the following steps:
A) at 20 DEG C ~ 95 DEG C, concentration sodium form modenite being joined aequum is process 0.5-24 hour in the organic acid soln of 0.05-5mol/L, washing after filtering, drying;
B) concentration above-mentioned modenite being joined aequum is in the ammonium salt solution of 0.05-5mol/L, constant temperature process 0.5-24 hour under 40 DEG C ~ 100 DEG C conditions, washing after filtering, drying;
C) above-mentioned modenite is mixed aftershaping with binding agent in required ratio, under 300-600 DEG C of condition, constant temperature calcining 1-12 hour obtains catalyst.
7. the preparation method of the toluene methylation catalysts of Increasing o-Xylene Output according to claim 6 and paraxylene, is characterized in that ammonium salt is selected from least one in ammonium nitrate, ammonium chloride or ammonium sulfate.
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| US6525234B1 (en) * | 2000-11-21 | 2003-02-25 | Exxonmobil Oil Corporation | Process for liquid phase aromatics alkylation comprising in-situ catalyst reactivation with polar compounds |
| CN1662485A (en) * | 2002-06-27 | 2005-08-31 | 三菱丽阳株式会社 | Production method of dimethylamine |
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| US5993642A (en) * | 1994-11-23 | 1999-11-30 | Exxon Chemical Patents Inc. | Hydrocarbon conversion process using a zeolite bound zeolite catalyst |
| US6525234B1 (en) * | 2000-11-21 | 2003-02-25 | Exxonmobil Oil Corporation | Process for liquid phase aromatics alkylation comprising in-situ catalyst reactivation with polar compounds |
| CN1662485A (en) * | 2002-06-27 | 2005-08-31 | 三菱丽阳株式会社 | Production method of dimethylamine |
| CN101340976A (en) * | 2005-12-22 | 2009-01-07 | 法国石油公司 | Bi-zeolite catalysts comprising Group VIII metals and Group IIIA metals and their use in the isomerization of aromatic C8 compounds |
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