CN101966467B - Catalyst for carbon eight aromatic hydrocarbon isomerization reaction process and preparation method thereof - Google Patents
Catalyst for carbon eight aromatic hydrocarbon isomerization reaction process and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910052799 carbon Inorganic materials 0.000 title abstract description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title abstract description 6
- 230000008569 process Effects 0.000 title abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims abstract description 106
- 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 106
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 22
- 238000007598 dipping method Methods 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- 229910000765 intermetallic Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 6
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910002796 Si–Al Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229940008099 dimethicone Drugs 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 238000005137 deposition process Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 abstract description 74
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 37
- 239000008096 xylene Substances 0.000 abstract description 30
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 abstract description 20
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000020335 dealkylation Effects 0.000 abstract description 8
- 238000006900 dealkylation reaction Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 2
- 229940078552 o-xylene Drugs 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- 230000006204 deethylation Effects 0.000 abstract 1
- 238000003541 multi-stage reaction Methods 0.000 abstract 1
- 150000003738 xylenes Chemical class 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000012159 carrier gas Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000007767 bonding agent Substances 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000001404 mediated effect Effects 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010555 transalkylation reaction Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- RJOOTDIYJNEGLP-UHFFFAOYSA-N [3-(ethoxycarbonylamino)phenyl] n-phenylcarbamate;[3-(methoxycarbonylamino)phenyl] n-(3-methylphenyl)carbamate Chemical compound CCOC(=O)NC1=CC=CC(OC(=O)NC=2C=CC=CC=2)=C1.COC(=O)NC1=CC=CC(OC(=O)NC=2C=C(C)C=CC=2)=C1 RJOOTDIYJNEGLP-UHFFFAOYSA-N 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
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst for a carbon-eight aromatic hydrocarbon isomerization reaction process and a preparation method thereof, wherein the composite reaction catalyst is formed by compounding two different molecular sieve components modified by different methods in a certain ratio, wherein one component has a high-selectivity catalysis effect of xylene isomerization, and the other component has a shape-selective catalysis effect of ethylbenzene deethylation. The high-efficiency catalytic action of the composite molecular sieve catalyst can simultaneously realize the dealkylation of ethylbenzene in carbon-eight mixed aromatics and the high-selectivity catalysis of isomerization of m-xylene and o-xylene into p-xylene. In the reaction process of isomerization and dealkylation of the carbon eight mixed aromatics, a fixed bed reactor is adopted, the carbon eight mixed aromatics are used as raw materials (a mixture of aromatics mainly comprising m-xylene, o-xylene and ethylbenzene), the reaction temperature is 350-460 ℃, the reaction pressure is 0.5-3.0 MPa, and the reaction space velocity is 2.0-15 h-1The reaction catalyst of the present invention has high reaction activity, high selectivity and high stability, and the reaction process is simplified, and has obviously lowered power consumption and production cost.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used for the isomerization of C-8 aromatics reaction process.
Background technology
Paraxylene (p-X) is one of main basic organic of petrochemical industry, in numerous chemical production field such as chemical fibre, synthetic resin, agricultural chemicals, medicine, plastics purposes is widely arranged.At present, through with C8 aronmatic C
8Meta-xylene m-X, ortho-xylene o-X isomery turn to paraxylene among the A, and are that the major technique of producing paraxylene is gone up in industry with the method that ethylbenzene (EB) transforms xylenes or benzene.In recent years, along with the swift and violent increase of terephthalic acid (TPA) (PTA) production capacity, demonstrate the paraxylene situation that supply falls short of demand in China, the isomerization catalysis technique that this shows xylenes is an important topic in the chemical production field.
At present, the isomerization of C-8 aromatics catalyst technology can be divided into two types according to the effect difference that ethylbenzene (EB) is transformed: one type is the EB dealkylation catalyst, and promptly m-X, o-X carry out isomerization reaction in the reaction, and ethylbenzene EB takes off alkyl generation benzene and transformed; The another kind of EB of being isomerization bifunctional catalyst (noble metal that all contains higher amount), xylenes and EB participate in isomerization reaction; The advantage of latter's double-function catalyzing isomerate process is that reaction process is simple, and ethylbenzene can be converted into xylenes, but that major defect is the low loss ratio with the open loop of xylenes hydrogenation of conversion ratio of ethylbenzene is higher.Desirable C
8The A arene isomerization catalyst can have high xylene isomerization rate and low aromatic hydrocarbons cracking loss under high EB activity of conversion.
From present circumstances and technology trends from now on, because energy prices go up and energy-saving and cost-reducing increase in demand, and EB takes off the restriction that alkyl does not receive chemical balance, can under high conversion, convert it into benzene, and make C
8The concentration of PX increases in the aromatic hydrocarbons, helps the separation of PX.Therefore, adopt EB to take off alkyl type isomerization catalyst at present and be obvious ascendant trend, become mainstream development direction now, it is very fast that EB is taken off the increase in demand of alkyl type isomerization catalyst.
EB is taken off alkyl to be transformed the key technical problem that type catalyst need solve and be: catalyst should be able to adapt to EB content high in the raw material, product is at utmost formed keeping near the thermodynamical equilibrium of xylenes.Simultaneously catalyst should suppress side reactions such as incident xylenes disproportionation, xylenes transalkylation, xylenes demethylation and hydrocracking, under the least possible condition of xylene loss, has stability preferably.
The ZSM-5 molecular sieve that MHAI (high activity isomery) method of Mobil company exploitation in recent years adopts two kinds of Different Silicon aluminum ratios to form is processed two kinds of different catalysts with binding agent respectively again, fills in two positions up and down of reactor.Its catalyst of separating reactor top mainly is to make ethylbenzene dealkylation and Fei Fang cracking, and the lower catalytic agent act as xylene isomerization.Though MHAI method activity is high, selectivity is better; But before using, must handle by these two kinds of catalyst through the presulfurization of reactor original position; And catalyst can not use on radial reactor and shell and tube reactor; Regeneration behind the catalyst coking inactivation is also than difficult and complicated, so limited its commercial Application simultaneously.
CN200680022943.8 relate to a kind of in two order districts with the isomerized method of the non-equilibrium mixture of alkylaromatic hydrocarbon, wherein first district uses not catalyst made from platonic and under the condition that does not have hydrogen, operates, the use of second district comprises the catalyst of molecular sieve and platinum group metal component; Thereby from mixture, obtain comparing the paraxylene of productive rate raising with existing method; But catalyst regeneration is difficult, and technological operation is complicated, and is high to equipment requirements; Once investment is big, and energy consumption is high.
EP 0923512 releases three xylene isomerization catalyst systems and is applicable to xylene isomerization and EB conversion reaction process; This system is made up of the catalyst of three kinds of series connection: first catalyst is used for Transformed E B; Second catalyst is used for hydrogenation (adopting with the aluminium oxide is the molybdenum catalyst of carrier), and the 3rd catalyst is used for xylene isomerization.This invention has solved the quick coking problem of catalyst, and coking especially takes place when EB accomplishes the transalkylation reaction conversion easily, has developed three bed process paths of less expensive simultaneously.Traditional double bed xylene isomerization catalyst is made up of EB reforming catalyst component and xylene isomerization catalyst component; Owing to produce ethene on the EB reforming catalyst; Cause the xylene isomerization catalyst deactivation rate too high; This invention is provided with hydrogenation catalyst and has solved the inactivation problem between EB reforming catalyst component and xylene isomerization catalyst component, hydrogenation catalyst can be converted into ethane in a large number with ethene, and other components in the product are not had any harmful effect; But this exists the antigravity system flow process complicated difficult with regeneration, and the technological operation trouble is high to equipment requirements, and the high deficiency of energy consumption.
Hence one can see that, and present existing double bed xylene isomerization catalyst technology all exists reaction process and catalyst complicacy, difficult, high to consersion unit and operation requirement, the high higher distinct disadvantage of plant energy consumption of catalyst regeneration.So the exploitation of the efficient integer catalyzer of carbon eight BTX aromatics high selectivity isomerization and dealkylation has very important actual demand.
Summary of the invention
In order to solve above-mentioned the problems of the prior art, the object of the present invention is to provide a kind of Catalysts and its preparation method that is used for the isomerization of C-8 aromatics reaction process.This catalysts is made up of by certain ratio is compound two kinds of different molecular sieve compositions through the distinct methods modification; Wherein a kind of composition has the high selectivity catalytic action of xylene isomerization; Another kind of composition has the shape selective catalysis effect that ethylbenzene takes off ethyl; Thereby make in two kinds of dissimilar molecular sieves that are reflected at different catalytic properties and obtained optimization respectively, and be presented as a kind of typical catalyst again with using in the operation on the mode of appearance.Through the efficient catalytic effect of composite molecular sieve catalyst of the present invention, can realize simultaneously that dealkylation and the meta-xylene of ethylbenzene in carbon eight BTX aromatics, the isomery of ortho-xylene turn to the high selectivity catalysis of paraxylene reaction; Catalysts also has the catalytic action of ethylene hydrogenation reaction simultaneously, to suppress the catalyst coking, to increase the service life.Carbon eight BTX aromatics isomerization with take off in the reaction process of alkyl, reaction molecular sieve catalyst of the present invention can be suitable for all types of axially, radially, use on the fixed bed reactors such as shell and tube.
A kind of catalyst that is used for the isomerization of C-8 aromatics reaction process that the present invention proposes, this catalyst is made up of two kinds of molecular sieve composition and binding agents through the distinct methods modification; Comprise following component in parts by weight:
(1) one of molecular sieve composition is SiO
2/ Al
2O
3Mol ratio is 10～80 parts of the Hydrogen Si-Al molecular sieves of 20～200 ten-ring pore structure, and this molecular sieve is modified the back use through liquid-phase silicone deposition processes and metallic compound load;
(2) two of the molecular sieve composition is SiO
2/ Al
2O
3Mol ratio is 10～80 parts of the Hydrogen Si-Al molecular sieves of 3～150 ten-ring or ten binary pore structures, and this molecular sieve uses behind modified metal oxide;
(3) all the other are adhesive oxides, and its gross weight umber satisfies 100 parts.
Among the present invention; One of said molecular sieve composition adopts in ZSM-5, NU-87, ZSM-11 or the EU-1 molecular sieve any; And to adopt dimethicone or polymethylphenyl siloxane fluid be that the liquid-phase silicone sedimentation that dressing agent carries out molecular sieve is modified, and its silica deposit amount is 2～10wt% of molecular sieve; Again above-mentioned siliceous deposits molecular sieve is further carried out the metallic compound load and modify, metallic compound adopts in molybdenum, nickel, platinum, palladium, rhodium, chromium, ruthenium or the cobalt arbitrary to multiple, and its content is counted 0.05～9wt% of molecular sieve with metal.
Among the present invention; Two of said molecular sieve composition adopts in Beta, ZSM-5, NU-87, ZSM-35, MCM-22, MOR, EU-1 or the Y molecular sieve any; And the load that at least a metal oxide in being selected from zinc, copper, iron, lanthanum, cerium, barium, magnesium or calcium carries out molecular sieve modifies, and its content is counted 0.1～12wt% of molecular sieve with metal.
Among the present invention, said adhesive oxides adopts aluminium oxide or silica.
The reaction process of catalysts of the present invention is: adopt fixed bed reactors; The C8 aronmatic raw material is to be a kind of aromatic hydrocarbons mixture of master with meta-xylene, ortho-xylene and ethylbenzene; At 350～460 ℃ of reaction temperatures, reaction pressure 0.5～3.0MPa, reaction velocity is under 2.0～15h-1; And using hydrogen as the reaction carrier gas, carrier gas/reactant ratio is 1～6: 1 (mol/mol).
The Preparation of catalysts method that is used for the isomerization of C-8 aromatics reaction process that the present invention proposes, concrete steps are following:
(1) one of molecular sieve composition in the catalysts: the petroleum ether solution of a kind of employing 8～25wt% dimethicone or polymethylphenyl siloxane fluid in ZSM-5, NU-87, ZSM-11 or the EU-1 zeolite is flooded; Benzinum is removed in the volatilization of dipping back; Again 500～530 ℃ of following roastings, promptly accomplish the liquid-phase silicone sedimentation of molecular sieve and modify after 120 ℃ of dryings; Behind at least a metallic compound in above-mentioned siliceous deposits molecular sieve molybdenum, nickel, platinum, palladium, rhodium, chromium, ruthenium or the cobalt or nitrate solution dipping; Molecular sieve is following dry 2 hours at 120 ℃; Then 450～560 ℃ of following roastings 2 hours; Promptly accomplish the further metal oxide supported modification of molecular sieve, obtain one of molecular sieve composition;
(2) two of the molecular sieve composition in the catalysts: will be selected from SiO
2/ Al
2O
3Mol ratio be among 20～200 Beta, ZSM-5, NU-87, ZSM-35, MCM-22, MOR, EU-1 or the Y any molecular sieve with at least a metal-nitrate solutions dipping that is selected from zinc, copper, iron, lanthanum, cerium, barium, magnesium, the calcium after; Molecular sieve is following dry 2 hours at 120 ℃; Then 480～550 ℃ of following roastings 2 hours; Promptly accomplish the metal oxide supported modification of molecular sieve, obtain two of molecular sieve composition;
(3) with above-mentioned two kinds mixing with the 1/10-1/1 weight ratio through modifying different molecular sieve composition; Method through bonding oxide agent and molecular sieve mixing granulation or extrusion modling is carried out moulding; Following dry 2 hours after the moulding at 120 ℃; 480～550 ℃ of following roastings 2 hours, promptly get required product then.
The present invention adopts fixed bed reactors, uses hydrogen as the reaction carrier gas, carries out the isomerized reaction of taking off ethyl reaction and meta-xylene, ortho-xylene of ethylbenzene in the C8 aronmatic.Reactor used internal diameter 20mm, length 600mm, stainless steel; The bead that it is 5mm that reactor bottom is filled one section diameter is as support, and the about 11cm of catalyst that fill at the middle part, the bead that fill on top play the effect of preheating and vaporization raw material; Mixed xylenes in the raw material (containing meta-xylene and ortho-xylene) and ethylbenzene mix with hydrogen, react through beds from top to bottom.
Raw material uses C
8BTX aromatics in mass fraction at meta-xylene 35-65wt%, ortho-xylene 15-30wt%, in the proportion of ethylbenzene 5-30wt%, experimental data adopts following formula calculating:
The present invention adopts fixed bed reactors, and through the efficient catalytic effect of catalyst of the present invention, simultaneously the highly selective isomery that carries out dealkylation and meta-xylene, the ortho-xylene of ethylbenzene in carbon eight BTX aromatics turns to paraxylene and reacts.This catalysts has that reaction process is simple, reactivity and selectivity height and the good characteristics of reaction stability.
Technical method of the present invention uses the catalyst of the composite molecular screen of a kind of compositing formula and preparation method's uniqueness as active component in single reactor; This catalyst is fit to the replacement catalyst and the transformation of existing process units easily; Both can improve carbon eight BTX aromatics isomerization and dealkylation activity and selectivity, and can promote the yield of product again.Above-mentioned technical characterictic makes in this invention catalyst and the present commercial production employed catalyst compare, and have following remarkable advantages: not only make production technology and simplified equipment, more convenient operation reduces production costs; And under higher reaction velocity, paraxylene isomerization rate and conversion of ethylbenzene are higher, and xylene loss is also less, and reaction stability is good, and the catalyst runs cycle is long.
The specific embodiment
Further specify the present invention through embodiment below.
Embodiment 1:
1) gets SiO
2/ Al
2O
3Mol ratio is 50 parts in 60 a Hydrogen ZSM-11 molecular sieve; Adopt the petroleum ether solution of 8% polymethylphenyl siloxane fluid to carry out the molecular sieve dipping, behind the dipping volatilization of solvent benzinum is removed, 120 ℃ of dry backs are 530 ℃ of following roastings; Promptly accomplish ZSM-11 liquid-phase silicone sedimentation and modify, obtain 3.1wt%SiO
2/ ZSM-11; Above-mentioned molecular sieve further again with 3.0wt% ammonium molybdate solution dipping, 480 ℃ of following roastings 2 hours, is promptly accomplished the burning molybdenum load of molecular sieve and modified after under 120 ℃ dry 2 hours, obtain 1.8wt%Mo/3.1wt%SiO
2/ ZSM-11; 2) get SiO
2/ Al
2O
3Mol ratio is 40 parts in 24 a Hydrogen Beta molecular sieve, with molecular sieve with 4.0wt% lanthanum nitrate hexahydrate dipping back 120 ℃ dry 2 hours down, then 500 ℃ of following roastings 2 hours, promptly accomplish the load of burning lanthanum and modify, obtain 2.3wt%La/Beta.3) with above-mentioned two kinds after modification different molecular sieve composition ZSM-11 and Beta mix; Adding the aluminium oxide bonding agent mixes with molecular sieve for 10 parts again; Add then and carry out extruded moulding after the rare nitric acid of a certain amount of 3wt% is fully mediated evenly, descended dry 2 hours at 120 ℃ then, again 550 ℃ of following roastings 2 hours; Promptly accomplish the preparation process of entire reaction molecular sieve catalyst, be designated as catalyst I.
Embodiment 2:
1) gets SiO
2/ Al
2O
3Mol ratio is 30 parts in 25 a Hydrogen ZSM-5 molecular sieve; Adopt the petroleum ether solution of 15% methyl-silicone oil to carry out the molecular sieve dipping, behind the dipping volatilization of solvent benzinum is removed, 120 ℃ of dry backs are 500 ℃ of following roastings; Promptly accomplish ZSM-5 liquid-phase silicone sedimentation and modify, obtain 5.7wt%SiO
2/ ZSM-5; Above-mentioned molecular sieve further again with 1.2wt% palladium nitrate solution dipping, 550 ℃ of following roastings 2 hours, is promptly accomplished the burning palladium load of molecular sieve and modified after under 120 ℃ dry 2 hours, obtain 0.58wt%Pd/6.7wt%SiO
2/ ZSM-5; 2) get SiO
2/ Al
2O
3Mol ratio is 50 parts in 20 a Hydrogen MCM-22 molecular sieve, with molecular sieve with 7.0wt% magnesium nitrate solution dipping back 120 ℃ dry 2 hours down, then 480 ℃ of following roastings 2 hours, promptly accomplish the magnesium-supported modification of burning, obtain 3.9wt%Mg/MCM-22.3) with above-mentioned two kinds after modification different molecular sieve composition ZSM-5 and MCM-22 mix; Adding the silica bonding agent mixes with molecular sieve for 20 parts again; Add then and carry out extruded moulding after the rare nitric acid of a certain amount of 3wt% is fully mediated evenly, descended dry 2 hours at 120 ℃ then, again 510 ℃ of following roastings 2 hours; Promptly accomplish the preparation process of entire reaction molecular sieve catalyst, be designated as catalyst I I.
Embodiment 3:
1) gets SiO
2/ Al
2O
3Mol ratio is 10 parts in 20 a Hydrogen EU-1 molecular sieve; Adopt the petroleum ether solution of 20% methyl-silicone oil to carry out the molecular sieve dipping, behind the dipping volatilization of solvent benzinum is removed, 120 ℃ of dry backs are 490 ℃ of following roastings; Promptly accomplish EU-1 liquid-phase silicone sedimentation and modify, obtain 8.2wt%SiO
2/ EU-1; Above-mentioned molecular sieve further again with 12.5wt% nickel nitrate solution dipping, 510 ℃ of following roastings 2 hours, is promptly accomplished the burning Ni of molecular sieve and modified after under 120 ℃ dry 2 hours, obtain 8.7wt%Ni/6.7wt%SiO
2/ EU-1; 2) get SiO
2/ Al
2O
3Mol ratio is 50 parts in 8 a Hydrogen MOR molecular sieve, with molecular sieve with 1.0wt% cerous nitrate solution dipping back 110 ℃ dry 2 hours down, then 490 ℃ of following roastings 2 hours, promptly accomplish the load of burning cerium and modify, obtain 0.19wt%Ce/MOR.3) with above-mentioned two kinds after modification different molecular sieve composition MOR and EU-1 mix; Adding the silica bonding agent mixes with molecular sieve for 40 parts again; Add then and carry out extruded moulding after the rare nitric acid of a certain amount of 3wt% is fully mediated evenly, descended dry 2 hours at 120 ℃ then, again 480 ℃ of following roastings 2 hours; Promptly accomplish the preparation process of entire reaction molecular sieve catalyst, be designated as catalyst I II.
Embodiment 4:
1) gets SiO
2/ Al
2O
3Mol ratio is 45 parts in 198 a Hydrogen NU-87 molecular sieve; Adopt the petroleum ether solution of 25% polymethylphenyl siloxane fluid to carry out the molecular sieve dipping, behind the dipping volatilization of solvent benzinum is removed, 120 ℃ of dry backs are 520 ℃ of following roastings; Promptly accomplish NU-87 liquid-phase silicone sedimentation and modify, obtain 12.0wt%SiO
2/ NU-87; Above-mentioned molecular sieve further again with 0.25wt% platinum acid chloride solution dipping, 550 ℃ of following roastings 2 hours, is promptly accomplished the compound loaded modification of metal platinum of molecular sieve after under 120 ℃ dry 2 hours, obtain 0.08wt%Pt/12.0wt%SiO
2/ NU-87; 2) get SiO
2/ Al
2O
3Mol ratio is 45 parts in 149 a Hydrogen ZSM-5 molecular sieve, with molecular sieve with 18.0wt% zinc nitrate solution dipping back 120 ℃ dry 2 hours down, then 520 ℃ of following roastings 2 hours, promptly accomplish the metal zinc oxide load and modify, obtain 11.9wt%Zn/ZSM-5.3) with above-mentioned two kinds after modification different molecular sieve composition NU-87 and ZSM-5 mix; Adding the silica bonding agent mixes with molecular sieve for 10 parts again; Add then and carry out extruded moulding after the rare nitric acid of a certain amount of 3wt% is fully mediated evenly, descended dry 2 hours at 120 ℃ then, again 480 ℃ of following roastings 2 hours; Promptly accomplish the preparation process of entire reaction molecular sieve catalyst, be designated as catalyst I V.
Embodiment 5:
Adopt fixed bed reactors, use hydrogen, carry out the isomerized reaction of taking off ethyl reaction and meta-xylene, ortho-xylene of ethylbenzene in the C8 aronmatic as the reaction carrier gas.Reactor used internal diameter 20mm, length 600mm, stainless steel; The bead that it is 5mm that reactor bottom is filled one section diameter is as support, and the about 11cm of catalyst height that fill at the middle part, the bead that fill on top play the effect of preheating and vaporization raw material; Include mixed xylenes in the raw material (containing meta-xylene 55.2wt% and ortho-xylene 23.7wt%) and ethylbenzene 21.1wt%; Raw material with after hydrogen mixes from top to bottom through beds, reaction condition is that 350～460 ℃ of reaction temperatures, reaction pressure 0.5～3.0MPa, reaction velocity are 2.0～15h
-1Down, and use hydrogen as the reaction carrier gas, carrier gas/reactant ratio is 1～6: 1 (mol/mol), and concrete catalyst system therefor and reaction condition are seen table 1.To design temperature, feed reaction raw materials with measuring pump through temperature programming in 100 minutes, sample calculates reaction conversion ratio and selectivity, xylene loss through gas chromatographic analysis.
Table 1. practical implementation reaction condition and catalytic reaction result
The reaction result data show in the table 1; Use composite molecular sieve catalyst of the present invention the isomerization reaction of xylenes and ethylbenzene to take off the catalytic activity that not only has two reactions in the ethyl reaction all higher; And the loss late of xylenes is also less in the reaction; Explain that catalyst can suppress side reaction such as xylenes disproportionation dramatically, make whole selectivity high, and can simplify production technology, the purpose of reached energy-saving and cost-reducing, practicing thrift cost; It is the high-performance paraxylene isomerization catalyst of new generation that meets the commercial Application demand.
Claims (3)
1. one kind is used for the isomerization of C-8 aromatics catalyst for reaction, it is characterized in that said catalyst is made up of two kinds of molecular sieve composition and binding agents through the distinct methods modification; Comprise following component in parts by weight:
(1) one of molecular sieve composition is SiO
2/ Al
2O
3Mol ratio is 10～80 parts of the Hydrogen Si-Al molecular sieves of 20～200 ten-ring pore structure, and this molecular sieve is modified the back use through liquid-phase silicone deposition processes and metallic compound load;
(2) two of the molecular sieve composition is SiO
2/ Al
2O
3Mol ratio is 10～80 parts of the Hydrogen Si-Al molecular sieves of 3～150 ten-ring or ten binary pore structures, and this molecular sieve uses behind modified metal oxide;
(3) all the other are adhesive oxides, and its gross weight umber satisfies 100 parts;
Wherein: one of said molecular sieve composition adopts in ZSM-5, NU-87, ZSM-11 or the EU-1 molecular sieve any; And to adopt dimethicone or polymethylphenyl siloxane fluid be that the liquid-phase silicone sedimentation that dressing agent carries out molecular sieve is modified, and its silica deposit amount is 2～10wt% of molecular sieve; Again above-mentioned siliceous deposits molecular sieve is further carried out the metallic compound load and modify, metallic compound adopts in molybdenum, nickel, platinum, palladium, rhodium, chromium, ruthenium or the cobalt arbitrary to multiple, and its content is counted 0.05～9wt% of molecular sieve with metal; Two of said molecular sieve composition adopts in Beta, ZSM-5, NU-87, ZSM-35, MCM-22, MOR, EU-1 or the Y molecular sieve any; And the load that at least a metal oxide in being selected from zinc, copper, iron, lanthanum, cerium, barium, magnesium or calcium carries out molecular sieve modifies, and its content is counted 0.1～12wt% of molecular sieve with metal.
2. the isomerization of C-8 aromatics catalyst for reaction that is used for according to claim 1 is characterized in that said adhesive oxides adopts aluminium oxide or silica.
3. preparation method who is used for the isomerization of C-8 aromatics catalyst for reaction as claimed in claim 1 is characterized in that concrete steps are following:
(1) one of molecular sieve composition in the catalysts: the petroleum ether solution of a kind of employing 8～25wt% dimethicone or polymethylphenyl siloxane fluid in ZSM-5, NU-87, ZSM-11 or the EU-1 molecular sieve is flooded; Benzinum is removed in the volatilization of dipping back; Again 500～530 ℃ of following roastings, promptly accomplish the liquid-phase silicone sedimentation of molecular sieve and modify after 120 ℃ of dryings; Behind at least a metal compound solution dipping in above-mentioned siliceous deposits molecular sieve molybdenum, nickel, platinum, palladium, rhodium, chromium, ruthenium or the cobalt; Molecular sieve is following dry 2 hours at 120 ℃; Then 450～560 ℃ of following roastings 2 hours; Promptly accomplish the further metal oxide supported modification of molecular sieve, obtain one of molecular sieve composition;
(2) two of the molecular sieve composition in the catalysts: will be selected from SiO
2/ Al
2O
3Mol ratio be among 3～150 Beta, ZSM-5, NU-87, ZSM-35, MCM-22, MOR, EU-1 or the Y any molecular sieve with at least a metal-nitrate solutions dipping that is selected from zinc, copper, iron, lanthanum, cerium, barium, magnesium, the calcium after; Molecular sieve is following dry 2 hours at 120 ℃; Then 480～550 ℃ of following roastings 2 hours; Promptly accomplish the metal oxide supported modification of molecular sieve, obtain two of molecular sieve composition;
(3) with above-mentioned two kinds mixing with 1/1 weight ratio through modifying different molecular sieve composition; Method through bonding oxide agent and molecular sieve mixing granulation or extrusion modling is carried out moulding; Descended dry 2 hours at 120 ℃ after the moulding,, promptly get required product then 480～550 ℃ of following roastings 2 hours.
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| CN102909058B (en) * | 2011-08-01 | 2014-08-20 | 中国石油化工股份有限公司 | Catalyst containing modified EUO type molecular sieve, and preparation method and application thereof |
| CN102909057B (en) * | 2011-08-01 | 2014-08-20 | 中国石油化工股份有限公司 | Catalyst comprising EUO type zeolite, preparation method and applications thereof |
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| CN110218142B (en) * | 2019-06-26 | 2020-07-28 | 北京化工大学 | Method for preparing p-xylene by isomerizing m-xylene and/or o-xylene |
| CN112299435B (en) * | 2019-07-29 | 2022-06-03 | 中国石油天然气股份有限公司 | Hydrogen type ZSM-35/EU-1 eutectic zeolite, aromatic isomerization catalyst, preparation method and application |
| CN113042097B (en) * | 2019-12-26 | 2023-09-26 | 中国石油天然气股份有限公司 | Molecular sieve catalyst, preparation method and application thereof |
| CN113117740B (en) * | 2019-12-31 | 2023-08-22 | 中国石油天然气股份有限公司 | Shape selective catalyst, method for the production thereof and use thereof |
| CN113663718A (en) * | 2020-05-15 | 2021-11-19 | 中国石油天然气股份有限公司 | Ethylbenzene dealkylation type xylene isomerization reaction catalyst and preparation method thereof |
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