CN103028430A - MWW type molecular sieve carrier catalyst and preparation method and application thereof - Google Patents
MWW type molecular sieve carrier catalyst and preparation method and application thereof Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 129
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 79
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 27
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 22
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000011777 magnesium Substances 0.000 claims description 23
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 17
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 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 9
- 239000011575 calcium Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001802 infusion Methods 0.000 claims description 4
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 238000009834 vaporization Methods 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 10
- 239000004327 boric acid Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 3
- -1 alkaline-earth metal salt Chemical class 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 28
- 238000007598 dipping method Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 230000004048 modification Effects 0.000 description 15
- 238000012986 modification Methods 0.000 description 15
- 230000029936 alkylation Effects 0.000 description 14
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical group OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- ZOXJGFHDIHLPTG-BJUDXGSMSA-N Boron-10 Chemical compound [10B] ZOXJGFHDIHLPTG-BJUDXGSMSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- QEFDIAQGSDRHQW-UHFFFAOYSA-N [O-2].[Cr+3].[Fe+2] Chemical compound [O-2].[Cr+3].[Fe+2] QEFDIAQGSDRHQW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an MWW type molecular sieve carrier catalyst and a preparation method and an application thereof, namely a catalyst for the alkylation reaction of toluene and carbinol side chains and a preparation method and an application of the same. The MWW type molecular sieve carrier catalyst comprises a carrier body, and a boron element and alkali-earth metal which are loaded on the carrier body. The preparation method comprises the following steps of: (a) exchanging ammonium salt, and baking into an H-type MWW type molecular sieve; (b) exchanging alkaline-earth metal salt by exchange liquid; and (c) baking, and loading on the molecular sieve by a boric acid solution impregnation method to obtain the MWW type molecular sieve carrier catalyst. The catalyst prepared by the method has excellent hydrothermal stability and special acid site distribution, the alkalinity of the catalyst can be enhanced, and the catalytic activity and selectivity can be improved. The MWW type molecular sieve is modified by alkaline-earth metal oxide through the impregnation method, the acid-alkali property of the MWW type molecular sieve can be modulated, and the novel catalyst having acid-alkali double functions is prepared.
Description
Technical field
The present invention relates to a kind of is a kind of modified molecular sieve catalyst, its preparation method and application, specifically, is used for catalyst, its preparation method and the application of the reaction of methylbenzene methanol side chain alkylation.
Background technology
Styrene is as the important basic material of petrochemical industry, and purposes is very extensive, and mainly for the production of styrene series resin and butadiene-styrene rubber, it also can be used for the industries such as pharmacy, agricultural chemicals, dyestuff and ore dressing simultaneously.Along with the fast development of China's building materials, household electrical appliances and auto industry, China also will maintain sustained and rapid growth to cinnamic demand.Cinnamic production line mainly contains three:
The one, ethylbenzene vapor catalytic dehydrogenation preparation of styrene, this technique be with iron oxide-chromium or zinc oxide as catalyst, adopt many thermal insulation or tubular type isothermal reactor, styrene is produced in dehydrogenation in the presence of steam.90% styrene all makes by this method in the world at present, but this technological process is long, and energy consumption consumption is larger, and cost is high, and easily causes environmental pollution;
The 2nd, the accessory substance during with propylene, ethylbenzene peroxidating epoxy ethane, this technique is the second largest industrial process inferior to ethylbenzene dehydrogenation;
The 3rd, from the steam cracking pyrolysis gasoline, reclaim styrene with extractive distillation.It is complicated that above technique ubiquity process, the high in cost of production shortcoming.Utilize first X and the y-type zeolite of alkali metal exchange to be catalyst from Sidorenko Y N in 1967 etc., since successfully synthesizing styrene take toluene and methyl alcohol as raw material, researchers are simple to this technique, flow process is short, energy consumption is low, raw material sources are wide, and the production line that cost is low has produced keen interest, transform for toluene simultaneously and the C1 utilization of resources provides new approach.And molecular sieve catalyst is conducted extensive research, promoted to a great extent the development of base catalyst theory.
Alkylation of toluene reaction has two kinds of forms, and one, the alkylation of phenyl ring generates dimethylbenzene or trimethylbenzene, two, the alkylation of benzene ring side chain generates styrene and ethylbenzene.The reaction of these two kinds of forms is all relevant with the Acidity of Aikalinity of catalyst surface.Alkylation on the phenyl ring is undertaken by forming the carbonium ion intermediate, and catalyst must be acid, and has strong acid center.The X-type molecular sieve that the univalent cation that polyvalent cation and radius are little exchanges has obvious activity to this type of reaction, and the primary product of its reaction is xylene isomer.And side chain alkylation is undertaken by the carbanion intermediate, needs the alkali center successfully the proton on the Benzyl Side-Chain alpha-carbon atom to be seized, and forms the carbanion intermediate, and then generation side chain alkyl substitution obtains styrene and ethylbenzene.
Sidorenko Y N points out that this reaction is not to finish separately under alkali central role of zeolite, but under the center acting in conjunction of zeolite molecular sieve soda acid, finish.For methylbenzene methanol side chain alkylation mechanism, basically identical viewpoint is: the generation that at first is formaldehyde, basic center can the catalysis methanol dehydrogenation generate formaldehyde, formaldehyde is adsorbed by the acid site, simultaneously toluene fixing and interaction by acid centre absorption, its pendant methyl is activated by the alkali center, generates the styrene of ADSORPTION STATE by the reaction of carbanion mechanism generation side chain alkylation with formaldehyde again.Therefore the catalyst that is used for the reaction of toluene and methanol side chain alkylation should have the character of following three aspects: (1) enough alkalescence is in order to generate methylation reaction intermediate---formaldehyde; (2) the weak L acidic site of absorption toluene and its methyl that polarizes; (3) reactant equilibrium adsorption metering.
Molecular sieve is owing to have the adjustable sex change that skeleton forms, controllable acidity or activated centre, cationic interchangeability, good heat endurance and hydrothermal stability and select preferably the character such as shape effect and make its application more and more extensive.Development along with molecular sieve theory and synthetic method etc. has high-ratio surface, large adsorption capacity, and the molecular sieve catalyst of many active sites and hydrothermal stability has been widely used in petrochemical industry, the fields such as fine chemistry industry and organic synthesis.The modification X that has reported or y-type zeolite can have been obtained certain effect when catalysis methylbenzene methanol side chain alkylation, but methanol conversion and cinnamic selective or relatively low, also has very large gap for reaching demand of industrial production, and these zeolite ubiquities acid low, the shortcoming such as hydrothermal stability is poor.
Nineteen ninety Mobil company reported first a kind of novel high-silica zeolite MCM-22(open up that to mend structure be MWW), it has special crystal structure.The MCM-22 molecular sieve has larger pore volume than the ZSM-5 of ten-ring, thereby the MCM-22 molecular sieve has better selective for some reaction.Because special pore passage structure, so that MCM-22 has high heat endurance, high surface acidity, the good shape effect of selecting is also arranged when MCM-22 makes carrier in addition, especially have at macromolecular reaction and select preferably shape and catalytic activity, thereby be a kind of as the ideal material of toluene and methanol side chain alkylation catalytic reaction agent carrier.And the novel MWW type molecular sieve of this class does not also appear in the cinnamic report of toluene and methanol side chain alkylation reaction preparation.
Patent US5015796 discloses a kind of methylbenzene methanol side chain alkylation reaction synthesizing ethyl benzene and cinnamic method, the method is used the zeolite molecular sieve material with high thermal stability, through using the basic treatment of alkali metal ion or alkaline-earth metal ions, methylbenzene methanol side chain alkylation synthesizing ethyl benzene and cinnamic catalyst material with side chain alkylation catalytic activity have been formed.But this patented method can not be taken into account conversion ratio and the ethylbenzene or cinnamic selective of toluene simultaneously.450 ℃ of catalytic activitys, its toluene conversion only is 6.6% with the highest K-Mg/LZ-Y52 catalyst of ethylbenzene, selectivity of styrene; And the highest LZ-Y82 catalyst of toluene conversion adds up at 350 ℃ ethylbenzene and styrene and selectively only reaches 0.4%.Thereby how can take into account simultaneously the conversion ratio of methylbenzene methanol side chain alkylation reaction and selectively become an important technology difficult problem that designs this catalysts.
Patent CN102040457 has announced a kind of for methylbenzene methanol side chain alkylation reaction preparation ethylbenzene and cinnamic method, and the method uses the meso-porous carbon material (FDU, CMK) of a kind of carrying alkali metal or alkaline-earth metal and boron oxide compound to make catalyst.Gasification on the reactor of nitrogen carrier gas mixes and passes in the reactor with raw material toluene and methyl alcohol, and final toluene conversion can reach 33.2%, and ethylbenzene and selectivity of styrene can reach 35.2%.
Patent CN102372549 announced a kind of with the 13X molecular sieve as catalyst, catalyst carries out modification with sylvite before use; Be 5:1 at toluene and methyl alcohol mol ratio, reaction temperature is 450 ℃, and reaction pressure is 0MPa, and the raw material weight air speed is 2 hours
-1Condition under, make methylbenzene methanol side chain alkylation reaction generate ethylbenzene and styrene, wherein toluene conversion can reach 35.1%, ethylbenzene and selectivity of styrene can reach 39.1%.
Although above two kinds of methods have improved toluene conversion and selectivity of styrene to a certain extent, the prepared catalyst of above patented method still can't satisfy industrial requirements, and has the shortcomings such as structure destructible, poor catalyst stability.
Summary of the invention
The purpose of this invention is to provide the molecular sieve supported body catalyst of a kind of MWW type, the preparation method of this catalyst and this catalyst are used for methylbenzene methanol side chain alkylation reaction synthesizing styrene, and this catalyst has preferably conversion ratio and activity stability selectively and preferably.
The molecular sieve supported body catalyst of a kind of MWW type, the molecular sieve supported body catalyst of described MWW type is MWW type molecular sieve carrier, with load boron element and alkaline-earth metal thereon, MWW type molecular sieve carrier accounts for 80 ~ 98% of total catalyst weight, boron element is take the weight percentage of oxide as 0.1 ~ 5%, and alkaline-earth metal is take the weight percentage of oxide as 1 ~ 10%.
Described alkaline-earth metal is Mg or Ca.
The technical solution used in the present invention is as follows: a kind of preparation method for methylbenzene methanol side chain alkylation reaction synthesizing styrene catalyst, wherein used MWW type molecular sieve catalyst is before use with being exchanged into NH with ammonium salt first
4Type MWW molecular sieve, roasting becomes H type MWW molecular sieve again, makes modifier with alkaline-earth metal, boric acid at last, adopts infusion process that it is carried out modification.
The preparation method of used catalyst is as follows in the inventive method:
(a) choose the MWW type molecular sieve of aequum, be exchanged into NH at 60 ~ 90 ℃ with 0.1 ~ 5mol/L ammonium salt first
4Then the type molecular sieve becomes H type MWW molecular sieve 400-600 ℃ of roasting;
(b) be that the alkali salt of 0.1 ~ 5mol/L exchanges afterwards washing, suction filtration, drying for exchange liquid to H type MWW molecular sieve with aequum concentration with the molecular sieve of (a) step process;
(c) with the molecular sieve of (b) step process 400 ~ 600 ℃ of roastings, then be after 0.1 ~ 5mol/L BAS loads on the molecular sieve with infusion process with aequum concentration, again washing, suction filtration, drying 400 ~ 600 ℃ of roastings, make catalyst of the present invention.
In technique scheme, at least a among the preferred MCM-22 of MWW type molecular sieve, MCM-49, MCM-56, ITQ-1, the ITQ-2, its consumption by weight percentage preferable range is 80 ~ 98%; The ammonium salt preferred version that is used for exchange is be selected from ammonium nitrate or ammonium carbonate at least a; Alkaline earth oxide consumption by weight percentage preferable range is 1 ~ 10%, the alkaline-earth metal preferably magnesium of its load, calcium; The oxide consumption of boron by weight percentage preferable range is 0.1 ~ 5%.
Described catalyst is used for toluene and methanol side chain alkylation reaction synthesizing styrene.
Get pack into the flat-temperature zone of the miniature continuous flow reactor reactor of fixed bed of 5.0 gram MWW type molecular sieve catalysts, all fill with porcelain ring or bead the reactor top and the bottom; Be 0.4MPa at pressure, reaction temperature is under 425 ℃, is that the toluene of 5:1 mixes with methyl alcohol with the mol ratio of raw material ratio, sends into preheater with micro pump and mixes with nitrogen that vaporization is laggard to enter reactor upper end, liquid air speed 1.0 hours
-1, nitrogen flow is under the condition of 20 ml/min, the beds of flowing through carries out catalytic reaction, product is collected with ice water condensation, with gas-chromatography its composition is analyzed.
The catalyst of preparation carries out activity rating in the miniature continuous flow reactor of fixed bed as stated above, and process is summarized as follows:
Get pack into the flat-temperature zone of reactor of an amount of catalyst, all fill with porcelain ring or bead the reactor top and the bottom.In low pressure, under the reaction temperature of setting, toluene and methyl alcohol are pressed certain mixed in molar ratio, send into preheater with micro pump and mix with nitrogen that vaporization is laggard to enter the reactor upper end, the beds of flowing through carries out catalytic reaction, product is collected with ice water condensation, with gas-chromatography its composition is analyzed.
The activity and selectivity of catalyst calculates as follows:
Beneficial effect:
MWW type molecular sieve is the novel catalysis material of a class, has unique ten-ring duct and twelve-ring pore passage structure, good hydrothermal stability and special acid site and distributes, and shows good catalytic activity in multiple reaction.Alkaline earth oxide is a kind of good solid base catalyst, and the alkali-earth metal modified alkalescence that not only can strengthen catalyst can also improve catalytic activity and selective simultaneously.Adopt alkaline earth oxide modification MWW type molecular sieve by infusion process, soda acid character that can modulation MWW type molecular sieve prepares novel difunction catalyst.
It is carrier that the present invention adopts MWW type molecular sieve, such carrier has higher specific area, alkaline element load that can catalysis is essential enters in the MWW type molecular sieve, and the reaction of the side chain alkylation of toluene and methyl alcohol is a course of reaction that needs the soda acid position jointly to cooperate catalysis, the shape requirement is not selected in reaction, and the characteristic of this bigger serface and macropore can increase toluene and methanol molecules are carried out the soda acid concerted catalysis in inside, duct catalytic efficiency greatly.And the methanol molecules space of reaction needed toluene molecule and activated state coupling reacts, and the styrene that reaction generates needs to remove from the catalyst activity surface as soon as possible, vacate the reactivity room, so catalyst carrier inside has larger duct, play an important role for the catalytic activity of this reaction and the raising of selectivity of product.Methylbenzene methanol side chain alkylation reaction needed soda acid complex reaction, thereby the interpolation of boron element can effectively regulate the acidity of catalyst, being added in of alkaline-earth metal are regulated catalyst alkalescence aspect and are had important function.
Figure of description
Fig. 1 is the infrared spectrum of the molecular sieve supported body catalyst of MWW type of the present invention
The specific embodiment
The FT-IR of catalyst characterizes and adopts the test of the Thermo Nicolet NEXUS of company Series Intelligent type Fourier infrared spectrograph, and test condition is: KBr compressing tablet, wave-number range are 4000-400cm
-1
(a) get 15 gram SiO
2/ A1
2O
3Mol ratio is 15 MCM-22 molecular sieve, with the ammonium nitrate solution of 20 milliliters of 0.1mol/L, is exchanged into NH in 8 hours in 85 ℃ of dippings
4Then the type molecular sieve got H type MCM-22 molecular sieve in 4 hours 550 ℃ of roastings.
(b) being that exchange liquid exchanges with the H type MCM-22 molecular sieve that makes of (a) step with the salpeter solution of 20 milliliters of 5mol/L alkaline-earth metal magnesium, is 10 exchanges 3 times according to solid-to-liquid ratio under 85 ℃, and be 2 hours swap time at every turn.Afterwards washing, suction filtration, filter cake was 110 ℃ of lower oven dry 4 hours.This molecular sieve 550 ℃ of lower roastings 4 hours, is got Mg-MCM-22 type molecular sieve.
(c) Mg modified MC M-22 molecular sieve with the 0.1mol/L BAS in 25 ℃ of dippings 6 hours, 120 ℃ of dryings 8 hours, 550 ℃ of roastings 3 hours obtain boric acid and alkali-earth metal modified MCM-22 molecular sieve.Moulding also is broken for 20 ~ 40 purpose particles, namely gets the MCM-22 molecular sieve catalyst of 0.1% boron 10%Mg modification.
With the above-mentioned finished catalyst of the 5.0 grams reactor of packing into, be that 0.4MPa, methylbenzene methanol raw material ratio are 5:1 (mol ratio), liquid air speed 1.0 hours at pressure
-1, 425 ℃, nitrogen flow are to carry out activity rating under the condition of 20 ml/min, test result is listed in table l.
Embodiment 2
(a) get 15 gram SiO
2/ A1
2O
3Mol ratio is 50 MCM-22 molecular sieve, with the ammonium nitrate solution of 20 milliliters of 0.1mol/L, is exchanged into NH in 8 hours in 85 ℃ of dippings
4Then the type molecular sieve got H type MCM-22 molecular sieve in 4 hours 550 ℃ of roastings.
(b) being that exchange liquid exchanges with the H type MCM-22 molecular sieve that makes of (a) step with the salpeter solution of 20 milliliters of 5mol/L alkaline-earth metal magnesium, is 10 exchanges 3 times according to solid-to-liquid ratio under 85 ℃, and be 2 hours swap time at every turn.Afterwards washing, suction filtration, filter cake was 110 ℃ of lower oven dry 4 hours.This molecular sieve 550 ℃ of lower roastings 4 hours, is got Mg-MCM-22 type molecular sieve.
(c) Mg modified MC M-22 molecular sieve with the 0.1mol/L BAS in 25 ℃ of dippings 6 hours, 120 ℃ of dryings 8 hours, 550 ℃ of roastings 3 hours obtain boric acid and alkali-earth metal modified MCM-22 molecular sieve.Moulding also is broken for 20 ~ 40 purpose particles, namely gets the MCM-22 molecular sieve catalyst of 0.5% boron 10%Mg modification.
Appreciation condition by embodiment 1 carries out activity rating, and test result is listed in table 1.
Embodiment 3
(a) get 15 gram SiO
2/ A1
2O
3Mol ratio is 13 MCM-49 molecular sieve, with the ammonium nitrate solution of 20 milliliters of 5mol/L, is exchanged into NH in 8 hours in 60 ℃ of dippings
4Then the type molecular sieve got H type MCM-49 molecular sieve in 4 hours 400 ℃ of roastings.
(b) being that exchange liquid exchanges with the H type MCM-49 molecular sieve that makes of (a) step with 20 milliliters of 0.1mol/L calcium acetate solutions, is 10 exchanges 3 times according to solid-to-liquid ratio under 60 ℃, and be 2 hours swap time at every turn.Afterwards washing, suction filtration, filter cake was 110 ℃ of lower oven dry 4 hours.This molecular sieve 400 ℃ of lower roastings 4 hours, is got Ca-MCM-49 type molecular sieve.
(c) Ca modified MC M-49 molecular sieve with the 1mol/L BAS in 25 ℃ of dippings 6 hours, 120 ℃ of dryings 8 hours, 400 ℃ of roastings 3 hours obtain boric acid and alkali-earth metal modified MCM-49 molecular sieve.Moulding also is broken for 20 ~ 40 purpose particles, namely gets the MCM-49 molecular sieve catalyst of 0.8% boron 1.2%Ca modification.
Appreciation condition by embodiment 1 carries out activity rating, and test result is listed in table 1.
Embodiment 4
(a) get 15 gram SiO
2/ A1
2O
3Mol ratio is 17 MCM-56 molecular sieve, with the sal volatile of 20 milliliters of 1mol/L, is exchanged into NH in 8 hours in 90 ℃ of dippings
4Then the type molecular sieve got H type MCM-56 molecular sieve in 4 hours 600 ℃ of roastings.
(b) being that exchange liquid exchanges with the H type MCM-56 molecular sieve that makes of (a) step with the magnesium acetate solution of 20 milliliters of 2mol/L, is 10 exchanges 3 times according to solid-to-liquid ratio under 90 ℃, and be 2 hours swap time at every turn.Afterwards washing, suction filtration, filter cake was 110 ℃ of lower oven dry 4 hours.This molecular sieve 600 ℃ of lower roastings 4 hours, is got Mg-MCM-56 type molecular sieve.
(c) Mg modified MC M-56 molecular sieve with the 5mol/L BAS in 25 ℃ of dippings 6 hours, 120 ℃ of dryings 8 hours, 600 ℃ of roastings 3 hours obtain boric acid and alkali-earth metal modified MCM-56 molecular sieve.Moulding also is broken for 20 ~ 40 purpose particles, namely gets the MCM-56 molecular sieve catalyst of 5% boron 10%Mg modification.
Appreciation condition by embodiment 1 carries out activity rating, and test result is listed in table 1.
Embodiment 5
(a) get 15 gram SiO
2/ A1
2O
3Mol ratio is 38 ITQ-2 molecular sieve, with the ammonium nitrate solution of 20 milliliters of 0.1mol/L, is exchanged into NH in 8 hours in 80 ℃ of dippings
4Then the type molecular sieve got H type ITQ-2 molecular sieve in 4 hours 500 ℃ of roastings.
(b) being that exchange liquid exchanges with the H type ITQ-2 molecular sieve that makes of (a) step with 20 milliliters of 5mol/L calcium nitrate solutions, is 10 exchanges 3 times according to solid-to-liquid ratio under 80 ℃, and be 2 hours swap time at every turn.Afterwards washing, suction filtration, filter cake was 110 ℃ of lower oven dry 4 hours.This molecular sieve 500 ℃ of lower roastings 4 hours, is got Ca-ITQ-2 type molecular sieve.
(c) Ca modification ITQ-2 molecular sieve with the 0.1mol/L BAS in 25 ℃ of dippings 6 hours, 120 ℃ of dryings 8 hours, 500 ℃ of roastings 3 hours obtain boric acid and alkali-earth metal modified ITQ-2 molecular sieve.Moulding also is broken for 20 ~ 40 purpose particles, namely gets the ITQ-2 molecular sieve catalyst of 0.5% boron 8%Ca modification.
Appreciation condition by embodiment 1 carries out activity rating, and test result is listed in table 1.
Embodiment 6
(a) getting 15 gram MCM-22 and ITQ-2 mol ratio is the mixed molecular sieve of 1:1, with the ammonium nitrate solution of 20 milliliters of 0.1mol/L, is exchanged into NH in 8 hours in 85 ℃ of dippings
4Then the type molecular sieve got H type mixed molecular sieve in 4 hours 550 ℃ of roastings.
(b) being that exchange liquid exchanges with the H type molecular sieve that makes of (a) step with the salpeter solution of 20 milliliters of 5mol/L alkaline-earth metal magnesium, is 10 exchanges 3 times according to solid-to-liquid ratio under 85 ℃, and be 2 hours swap time at every turn.Afterwards washing, suction filtration, filter cake was 110 ℃ of lower oven dry 4 hours.This molecular sieve 550 ℃ of lower roastings 4 hours, is got Mg modification mixed molecular sieve.
(c) Mg modification mixed molecular sieve with the 0.1mol/L BAS in 25 ℃ of dippings 6 hours, 120 ℃ of dryings 8 hours, 550 ℃ of roastings 3 hours obtain boric acid and alkali-earth metal modified mixed molecular sieve.Moulding also is broken for 20 ~ 40 purpose particles, namely gets the mixed molecular sieve catalyst of 0.2% boron 10%Mg modification.
Appreciation condition by embodiment 1 carries out activity rating, and test result is listed in table 1.
Comparative example 1
(a) get 15 gram SiO
2/ A1
2O
3Mol ratio is 2 X molecular sieve, with the ammonium nitrate solution of 20 milliliters of 0.1mol/L, is exchanged into NH in 8 hours in 85 ℃ of dippings
4Then the type molecular sieve got H type X molecular sieve in 4 hours 550 ℃ of roastings.
(b) being that exchange liquid exchanges with the H type X molecular sieve that makes of (a) step with the salpeter solution of 20 milliliters of 5mol/L alkaline-earth metal magnesium, is 10 exchanges 3 times according to solid-to-liquid ratio under 85 ℃, and be 2 hours swap time at every turn.Afterwards washing, suction filtration, filter cake was 110 ℃ of lower oven dry 4 hours.This molecular sieve 550 ℃ of lower roastings 4 hours, is got Mg-X type molecular sieve.
(c) the Mg modified X molecular sieve with the 0.1mol/L BAS in 25 ℃ of dippings 6 hours, 120 ℃ of dryings 8 hours, 550 ℃ of roastings 3 hours obtain boric acid and alkali-earth metal modified X molecular sieve.Moulding also is broken for 20 ~ 40 purpose particles, namely gets the X molecular sieve catalyst of 0.5% boron 10%Mg modification.
Appreciation condition by embodiment 1 carries out activity rating, and test result is listed in table 1.
Comparative example 2
(a) get 15 gram SiO
2/ A1
2O
3Mol ratio is 45 ZSM-5 molecular sieve, with the ammonium nitrate solution of 20 milliliters of 0.1mol/L, is exchanged into NH in 8 hours in 85 ℃ of dippings
4Then the type molecular sieve got H type ZSM-5 molecular sieve in 4 hours 550 ℃ of roastings.
(b) being that exchange liquid exchanges with the H type ZSM-5 molecular sieve that makes of (a) step with the salpeter solution of 20 milliliters of 5mol/L alkaline-earth metal magnesium, is 10 exchanges 3 times according to solid-to-liquid ratio under 85 ℃, and be 2 hours swap time at every turn.Afterwards washing, suction filtration, filter cake was 110 ℃ of lower oven dry 4 hours.This molecular sieve 550 ℃ of lower roastings 4 hours, is got Mg-ZSM-5 type molecular sieve.
(c) the Mg modified zsm-5 zeolite with the 0.1mol/L BAS in 25 ℃ of dippings 6 hours, 120 ℃ of dryings 8 hours, 550 ℃ of roastings 3 hours obtain boric acid and alkali-earth metal modified ZSM-5 molecular sieve.Moulding also is broken for 20 ~ 40 purpose particles, namely gets the ZSM-5 molecular sieve catalyst of 0.5% boron 10%Mg modification.
Appreciation condition by embodiment 1 carries out activity rating, and test result is listed in table 1.
Each example performance evaluation of table 1
| Numbering | Toluene conversion % | Selectivity of |
| Embodiment | ||
| 1 | 77.2 | 57.0 |
| Embodiment 2 | 82.0 | 66.4 |
| Embodiment 3 | 83.9 | 63.5 |
| Embodiment 4 | 81.5 | 52.2 |
| Embodiment 5 | 83.6 | 62.0 |
| Embodiment 6 | 81.2 | 65.4 |
| Comparative example 1 | 65.6 | 29.1 |
| Comparative example 2 | 37.4 | 60.3 |
Claims (10)
1. molecular sieve supported body catalyst of MWW type is characterized in that:
The molecular sieve supported body catalyst of described MWW type is MWW type molecular sieve carrier, with load boron element and alkaline-earth metal thereon, MWW type molecular sieve carrier accounts for 80 ~ 98% of total catalyst weight, boron element is take the weight percentage of oxide as 0.1 ~ 5%, and alkaline-earth metal is take the weight percentage of oxide as 1 ~ 10%.
2. catalyst according to claim 1, it is characterized in that: described alkaline-earth metal is magnesium or calcium.
3. the preparation method of the molecular sieve supported body catalyst of MWW type as claimed in claim 1, it may further comprise the steps:
(a) choose MWW type molecular sieve, exchange with 0.1 ~ 5 mol/L ammonium salt at 60 ~ 90 ℃, then become H type MWW molecular sieve 400-600 ℃ of roasting;
(b) be that the alkali salt of 0.1 ~ 5mol/L exchanges H type MWW molecular sieve for exchange liquid with aequum concentration with the molecular sieve of (a) step process;
(c) with the molecular sieve of (b) step process 400 ~ 600 ℃ of roastings, then be after 0.1 ~ 5 mol/L BAS loads on the molecular sieve with infusion process, 400 ~ 600 ℃ of roastings, to make the molecular sieve supported body catalyst of MWW type with aequum concentration.
4. preparation method according to claim 3, it is characterized in that: the percentage by weight consumption of MWW type molecular sieve carrier is 80 ~ 98%; At least a in MCM-22, MCM-49, MCM-56, ITQ-1, ITQ-2 of MWW type molecular screening.
5. preparation method according to claim 3 is characterized in that: be selected from ammonium nitrate or ammonium carbonate for the ammonium salt that exchanges.
6. preparation method according to claim 3 is characterized in that: the alkali salt that is used for exchange is nitrate or the acetate of alkaline-earth metal.
7. preparation method according to claim 3, it is characterized in that: the element wt percentage composition of the boron of load counts 0.1 ~ 5% with oxide in the catalyst.
8. the preparation method of described catalyst according to claim 3 is characterized in that: the alkaline-earth metal of load is that the weight percentage of Mg or Ca counts 1 ~ 10% with oxide in the catalyst.
9. according to claim 1-8 application of the molecular sieve supported body catalyst of the described MWW type of any one is characterized in that: described catalyst is used for toluene and methanol side chain alkylation reaction synthesizing styrene.
10. the application of the molecular sieve supported body catalyst of MWW type according to claim 9, it is characterized in that: the catalyst of getting 5.0 gram claim 1 to the 8 any one flat-temperature zone of the miniature continuous flow reactor reactor of fixed bed of packing into, all fill with porcelain ring or bead the reactor top and the bottom; Be 0.4MPa at pressure, reaction temperature is under 425 ℃, is that the toluene of 5:1 mixes with methyl alcohol with the mol ratio of raw material ratio, sends into preheater with micro pump and mixes with nitrogen that vaporization is laggard to enter reactor upper end, liquid air speed 1.0 hours
-1, nitrogen flow is under the condition of 20 ml/min, the beds of flowing through carries out catalytic reaction, product is collected with ice water condensation, with gas-chromatography its composition is analyzed.
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| CN117619429A (en) * | 2023-10-23 | 2024-03-01 | 中国科学院青岛生物能源与过程研究所 | Preparation method and application of metal sub-nanocluster catalyst |
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