CN103028430B - 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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- CN103028430B CN103028430B CN201310004746.5A CN201310004746A CN103028430B CN 103028430 B CN103028430 B CN 103028430B CN 201310004746 A CN201310004746 A CN 201310004746A CN 103028430 B CN103028430 B CN 103028430B
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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 129
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 128
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 27
- 238000000034 method Methods 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
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 18
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 76
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000011777 magnesium Substances 0.000 claims description 23
- 230000029936 alkylation Effects 0.000 claims description 20
- 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
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 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
- 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
- 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 Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- 238000007598 dipping method Methods 0.000 abstract description 17
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical compound OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 abstract description 12
- 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
- -1 alkaline earth metal salt Chemical class 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical group CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 28
- 230000000694 effects Effects 0.000 description 16
- 230000004048 modification Effects 0.000 description 15
- 238000012986 modification Methods 0.000 description 15
- 239000002253 acid Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 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
- 239000002245 particle Substances 0.000 description 8
- 238000007493 shaping process Methods 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
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 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
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 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 compound 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali 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
- 229910052799 carbon Inorganic materials 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
- 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
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000009413 insulation Methods 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
- 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing 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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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an MWW type molecular sieve carrier catalyst, a preparation method and application thereof, and a catalyst for a toluene methanol side alkylation reaction, a preparation method and application thereof. The MWW type molecular sieve carrier catalyst comprises a body, and boron element and alkaline earth metal loaded on the body. The preparation method comprises the following steps: exchanging ammonium salt, and roasting to obtain an H-type MWW molecular sieve; (b) exchanging alkaline earth metal salt as exchange liquid; (c) roasting, and loading the molecular sieve by a boric acid solution dipping method. The catalyst has excellent hydrothermal stability and special acid center distribution, can enhance the alkalinity of the catalyst and improve the catalytic activity and selectivity. The alkaline-earth metal oxide is adopted to modify the MWW type molecular sieve by an impregnation method, so that the acid-base property of the MWW type molecular sieve can be modulated, and the novel acid-base bifunctional catalyst is prepared.
Description
Technical field
The present invention relates to one is a kind of modified molecular sieve catalyst, its preparation method and application, specifically, 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:
One is ethylbenzene vapor catalytic dehydrogenation preparation of styrene, and this technique is using iron oxide-chromium or zinc oxide as catalyst, adopts many thermal insulation or tubular type isothermal reactor, and styrene is produced in dehydrogenation in the presence of steam.The styrene of 90% obtains all by this method in the world at present, but this technological process is long, and energy consumption consumption is comparatively large, and cost is high, and easily causes environmental pollution;
Two is that this technique is the second largest industrial process inferior to ethylbenzene dehydrogenation with accessory substance when propylene, ethylbenzene peroxidating epoxy ethane;
Three is reclaim styrene with extractive distillation from steam cracking pyrolysis gasoline.It is complicated that above technique ubiquity process, high in cost of production shortcoming.The X utilizing alkali metal to exchange first from Sidorenko Y N in 1967 etc. and y-type zeolite are catalyst, with toluene and methyl alcohol for since raw material successfully synthesizes styrene, 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 creates keen interest, provides new approach for toluene conversion and the C1 utilization of resources simultaneously.And molecular sieve catalyst is conducted extensive research, facilitates the development of base catalyst theory to a great extent.
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 phenyl ring is undertaken by forming carbonium ion intermediate, and catalyst must be acid, and has strong acid center.The X-type molecular sieve that polyvalent cation and the little univalent cation of radius exchange, have obvious activity to this type of reaction, primary product of its reaction is xylene isomer.And side chain alkylation is undertaken by carbanion intermediate, need alkali center successfully to be seized by the proton on Benzyl Side-Chain alpha-carbon atom, form carbanion intermediate, and then the substitution reaction of generation pendant alkyl group obtains styrene and ethylbenzene.
Sidorenko Y N points out this reaction and non-individual completes under alkali central role of zeolite, but to complete under the acting in conjunction of zeolite molecular sieve Acid and basic sites.For the mechanism of methylbenzene methanol side chain alkylation reaction, basically identical viewpoint is: the generation being first formaldehyde, basic center catalysis methanol dehydrogenation can generate formaldehyde, formaldehyde is adsorbed by acid site, toluene is fixed by acid centre absorption and interacts simultaneously, its pendant methyl is activated by alkali center, then reacts by carbanion mechanism generation side chain alkylation the styrene generating ADSORPTION STATE with formaldehyde.Therefore the catalyst for toluene and methanol side chain alkylation reaction should have the character of following three aspects: (1) enough alkalescence is in order to generate methylation reaction intermediate---formaldehyde; (2) toluene the weak L acidic site of its methyl that polarizes is adsorbed; (3) reactant equilibrium adsorption metering.
Molecular sieve owing to there is the adjustable sex change of skeleton composition, controllable acidity or activated centre, cationic interchangeability, good heat endurance and hydrothermal stability and select the character such as shape effect preferably to make it apply more and more extensive.Along with the development of molecular sieve theory and synthetic method etc., have high-ratio surface, large adsorption capacity, the molecular sieve catalyst of many active sites and hydrothermal stability has been widely used in petrochemical industry, the field such as fine chemistry industry and organic synthesis.The modification X reported or y-type zeolite can obtain certain effect when catalysis methylbenzene methanol side chain alkylation, but methanol conversion and cinnamic selective or relatively low, very large gap is also had for reaching demand of industrial production, and these zeolite ubiquities the shortcomings such as acid low, hydrothermal stability difference.
A kind of novel high-silica zeolite MCM-22(of nineteen ninety Mobil company reported first opens up and mends structure is MWW), it has special crystal structure.MCM-22 molecular sieve has larger pore volume compared with the ZSM-5 of ten-ring, and thus MCM-22 molecular sieve has better selective for some reaction.Due to special pore passage structure, MCM-22 is made to have high heat endurance, high surface acidity, what also had when MCM-22 makes carrier in addition selects shape effect, especially have at macromolecular reaction and select shape and catalytic activity preferably, because of but a kind of as toluene and the ideal material of methanol side chain alkylation catalytic reaction agent carrier.And the novel MWW type molecular sieve of this class does not also appear at toluene and methanol side chain alkylation reacts and prepare in cinnamic report.
Patent US5015796 discloses a kind of methylbenzene methanol side chain alkylation Reactive Synthesis ethylbenzene and cinnamic method, the method uses the zeolite molecular sieve material with high thermal stability, through using the basic treatment of alkali metal ion or alkaline-earth metal ions, define the methylbenzene methanol side chain alkylation synthesizing ethyl benzene and cinnamic catalyst material with side chain alkylation catalytic activity.But this patented method can not take into account conversion ratio and the ethylbenzene or cinnamic selective of toluene simultaneously.With the highest K-Mg/LZ-Y52 catalyst of ethylbenzene, selectivity of styrene 450 DEG C of catalytic activitys, its toluene conversion is only 6.6%; And the highest LZ-Y82 catalyst of toluene conversion adds up at the ethylbenzene of 350 DEG C and styrene and selectively only reaches 0.4%.Thus how can take into account the conversion ratio of methylbenzene methanol side chain alkylation reaction and the selective important technology difficult problem becoming this catalysts of design simultaneously.
Patent CN102040457 discloses a kind of reaction for methylbenzene methanol side chain alkylation and prepares ethylbenzene and cinnamic method, and the method uses the meso-porous carbon material of a kind of carrying alkali metal or alkaline-earth metal and boron oxide compound (FDU, CMK) to make catalyst.Raw material toluene and methyl alcohol being gasified to mix in the reactor upper end of nitrogen carrier gas passes in reactor, and final toluene conversion can reach 33.2%, and ethylbenzene and selectivity of styrene can reach 35.2%.
Patent CN102372549 discloses a kind of using 13X molecular sieve as catalyst, and catalyst carries out modification with sylvite before use; Be 5:1 at toluene and methanol molar ratio, reaction temperature is 450 DEG C, and reaction pressure is 0MPa, and raw material weight air speed is 2 hours
-1condition under, methylbenzene methanol side chain alkylation is reacted and generates ethylbenzene and styrene, wherein toluene conversion can reach 35.1%, and ethylbenzene and selectivity of styrene can reach 39.1%.
Although above two kinds of methods improve toluene conversion and selectivity of styrene to a certain extent, the catalyst prepared by above patented method still cannot meet industrial requirements, and there is the shortcomings such as structure destructible, poor catalyst stability.
Summary of the invention
The object of this invention is to provide a kind of MWW type molecular sieve carrier catalyst, the preparation method of this catalyst and this catalyst are used for methylbenzene methanol side chain alkylation Reactive Synthesis styrene, and this catalyst has good conversion ratio and selective and good activity stability.
A kind of MWW type molecular sieve carrier catalyst, described MWW type molecular sieve carrier catalyst is MWW type molecular sieve carrier, with load boron element thereon and alkaline-earth metal, MWW type molecular sieve carrier accounts for 80 ~ 98% of total catalyst weight, boron element with the weight percentage of oxide basis for 0.1 ~ 5%, alkaline-earth metal with the weight percentage of oxide basis for 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 Reactive Synthesis phenylethylene catalyst, and wherein MWW type molecular sieve catalyst used is before use with being first exchanged into NH with ammonium salt
4type MWW molecular sieve, then roasting becomes H type MWW molecular sieve, finally makes modifier with alkaline-earth metal, boric acid, adopts infusion process to carry out modification to it.
The preparation method of catalyst used in the inventive method is as follows:
A () chooses the MWW type molecular sieve of aequum, be first exchanged into NH at 60 ~ 90 DEG C with 0.1 ~ 5mol/L ammonium salt
4type molecular sieve, then becomes H type MWW molecular sieve 400-600 DEG C of roasting;
B the molecular sieve aequum concentration of (a) step process is that the alkali salt of 0.1 ~ 5mol/L exchanges H type MWW molecular sieve for exchanging liquid by (), washing, suction filtration, drying afterwards;
(c) by the molecular sieve of (b) step process 400 ~ 600 DEG C of roastings, then be that 0.1 ~ 5mol/L BAS infusion process loads to after on molecular sieve by aequum concentration, wash again, suction filtration, drying, 400 ~ 600 DEG C of roastings, obtained catalyst of the present invention.
In technique scheme, at least one in MWW type molecular sieve preferred MCM-22, MCM-49, MCM-56, ITQ-1, ITQ-2, its consumption by weight percentage preferable range is 80 ~ 98%; Ammonium salt preferred version for exchanging is be selected from least one in ammonium nitrate or ammonium carbonate; 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 Reactive Synthesis styrene.
Get the flat-temperature zone that 5.0 grams of MWW type molecular sieve catalysts load the miniature continuous flow reactor reactor of fixed bed, reactor top and the bottom are all filled with porcelain ring or bead; Be 0.4MPa at pressure, reaction temperature is at 425 DEG C, is that the toluene of 5:1 mixes with methyl alcohol by the mol ratio of raw material ratio, with micro pump send into preheater to mix with nitrogen vaporize laggard enter reactor upper end, liquid air speed 1.0 hours
-1, nitrogen flow is under the condition of 20 ml/min, flow through beds and carry out catalytic reaction, product ice water condensation is collected, and analyzes its composition by gas-chromatography.
The catalyst prepared as stated above carries out activity rating in the miniature continuous flow reactor of fixed bed, and process is summarized as follows:
Get the flat-temperature zone that appropriate catalyst loads reactor, reactor top and the bottom are all filled with porcelain ring or bead.In low pressure, under the reaction temperature of setting, toluene and methyl alcohol are pressed certain mixed in molar ratio, with micro pump send into preheater to mix with nitrogen vaporize laggard enter reactor upper end, flow through beds and carry out catalytic reaction, product ice water condensation is collected, and analyzes its composition by gas-chromatography.
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, excellent hydrothermal stability and the distribution of special acid site, in multiple reaction, shows good catalytic activity.Alkaline earth oxide is a kind of good solid base catalyst, the alkali-earth metal modified alkalescence that not only can strengthen catalyst, can also improve catalytic activity and selective simultaneously.Alkaline earth oxide modification MWW type molecular sieve is adopted by infusion process, can the soda acid character of modulation MWW type molecular sieve, prepare novel difunction catalyst.
The present invention adopts MWW type molecular sieve to be carrier, such carrier has higher specific area, alkaline element load required for catalysis can be entered in MWW type molecular sieve, and toluene and the side chain alkylation of methyl alcohol to react be a course of reaction needing soda acid position jointly to coordinate catalysis, shape requirement is not selected in reaction, and the characteristic of this bigger serface and macropore greatly can increase toluene and methanol molecules carries out the catalytic efficiency of soda acid concerted catalysis in inside, duct.And the methanol molecules spatial match of reaction needed toluene molecule and activated state reacts, and the styrene that reaction generates needs to remove from catalyst activity surface as soon as possible, vacate reactivity room, so catalyst carrier inside has larger duct, the catalytic activity of this reaction and the raising of selectivity of product are played an important role.Methylbenzene methanol side chain alkylation reaction needed soda acid complex reaction, thus the interpolation of boron element effectively can regulate the acidity of catalyst, and being added in of alkaline-earth metal regulates catalyst alkalescence aspect to have important function.
Figure of description
Fig. 1 is the infrared spectrum of MWW type molecular sieve carrier catalyst of the present invention
Detailed description of the invention
The FT-IR of catalyst characterizes and adopts the test of Thermo Nicolet company NEXUS Series Intelligent type Fourier infrared spectrograph, and test condition is: KBr compressing tablet, and wave-number range is 4000-400cm
-1.
Embodiment 1
A () gets 15 grams of SiO
2/ A1
2o
3mol ratio is the MCM-22 molecular sieve of 15, with the ammonium nitrate solution of 20 milliliters of 0.1mol/L, within 8 hours, is exchanged into NH in 85 DEG C of dippings
4type molecular sieve, then obtains H type MCM-22 molecular sieve in 4 hours 550 DEG C of roastings.
B H type MCM-22 molecular sieve that (a) step obtains by () is exchange liquid to exchange with the salpeter solution of 20 milliliters of 5mol/L alkaline-earth metal magnesium, and be 10 exchange 3 times according to solid-to-liquid ratio at 85 DEG C, each swap time is 2 hours.Wash afterwards, suction filtration, filter cake is dried 4 hours at 110 DEG C.By the roasting 4 hours at 550 DEG C of this molecular sieve, obtain Mg-MCM-22 type molecular sieve.
C () Mg modified MC M-22 molecular sieve is with 0.1mol/L BAS in 25 DEG C of dippings 6 hours, 120 DEG C of dryings 8 hours, 550 DEG C of roastings 3 hours, obtain boric acid and alkali-earth metal modified MCM-22 molecular sieve.Shaping and be broken for 20 ~ 40 object particles, obtain the MCM-22 molecular sieve catalyst of 0.1% boron 10%Mg modification.
5.0 grams of above-mentioned finished catalysts are loaded reactors, pressure be 0.4MPa, methylbenzene methanol raw material ratio is 5:1 (mol ratio), liquid air speed 1.0 hours
-1, 425 DEG C, nitrogen flow is carry out activity rating under the condition of 20 ml/min, test result lists in table l.
Embodiment 2
A () gets 15 grams of SiO
2/ A1
2o
3mol ratio is the MCM-22 molecular sieve of 50, with the ammonium nitrate solution of 20 milliliters of 0.1mol/L, within 8 hours, is exchanged into NH in 85 DEG C of dippings
4type molecular sieve, then obtains H type MCM-22 molecular sieve in 4 hours 550 DEG C of roastings.
B H type MCM-22 molecular sieve that (a) step obtains by () is exchange liquid to exchange with the salpeter solution of 20 milliliters of 5mol/L alkaline-earth metal magnesium, and be 10 exchange 3 times according to solid-to-liquid ratio at 85 DEG C, each swap time is 2 hours.Wash afterwards, suction filtration, filter cake is dried 4 hours at 110 DEG C.By the roasting 4 hours at 550 DEG C of this molecular sieve, obtain Mg-MCM-22 type molecular sieve.
C () Mg modified MC M-22 molecular sieve is with 0.1mol/L BAS in 25 DEG C of dippings 6 hours, 120 DEG C of dryings 8 hours, 550 DEG C of roastings 3 hours, obtain boric acid and alkali-earth metal modified MCM-22 molecular sieve.Shaping and be broken for 20 ~ 40 object particles, obtain the MCM-22 molecular sieve catalyst of 0.5% boron 10%Mg modification.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 1.
Embodiment 3
A () gets 15 grams of SiO
2/ A1
2o
3mol ratio is the MCM-49 molecular sieve of 13, with the ammonium nitrate solution of 20 milliliters of 5mol/L, within 8 hours, is exchanged into NH in 60 DEG C of dippings
4type molecular sieve, then obtains H type MCM-49 molecular sieve in 4 hours 400 DEG C of roastings.
B H type MCM-49 molecular sieve obtained for (a) step is that exchange liquid exchanges with 20 milliliters of 0.1mol/L calcium acetate solutions by (), be 10 exchange 3 times according to solid-to-liquid ratio at 60 DEG C, each swap time is 2 hours.Wash afterwards, suction filtration, filter cake is dried 4 hours at 110 DEG C.By the roasting 4 hours at 400 DEG C of this molecular sieve, obtain Ca-MCM-49 type molecular sieve.
C () Ca modified MC M-49 molecular sieve is with 1mol/L BAS in 25 DEG C of dippings 6 hours, 120 DEG C of dryings 8 hours, 400 DEG C of roastings 3 hours, obtain boric acid and alkali-earth metal modified MCM-49 molecular sieve.Shaping and be broken for 20 ~ 40 object particles, obtain the MCM-49 molecular sieve catalyst of 0.8% boron 1.2%Ca modification.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 1.
Embodiment 4
A () gets 15 grams of SiO
2/ A1
2o
3mol ratio is the MCM-56 molecular sieve of 17, with the sal volatile of 20 milliliters of 1mol/L, within 8 hours, is exchanged into NH in 90 DEG C of dippings
4type molecular sieve, then obtains H type MCM-56 molecular sieve in 4 hours 600 DEG C of roastings.
B H type MCM-56 molecular sieve that (a) step obtains by () is exchange liquid to exchange with the magnesium acetate solution of 20 milliliters of 2mol/L, and be 10 exchange 3 times according to solid-to-liquid ratio at 90 DEG C, each swap time is 2 hours.Wash afterwards, suction filtration, filter cake is dried 4 hours at 110 DEG C.By the roasting 4 hours at 600 DEG C of this molecular sieve, obtain Mg-MCM-56 type molecular sieve.
C () Mg modified MC M-56 molecular sieve is with 5mol/L BAS in 25 DEG C of dippings 6 hours, 120 DEG C of dryings 8 hours, 600 DEG C of roastings 3 hours, obtain boric acid and alkali-earth metal modified MCM-56 molecular sieve.Shaping and be broken for 20 ~ 40 object particles, obtain the MCM-56 molecular sieve catalyst of 5% boron 10%Mg modification.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 1.
Embodiment 5
A () gets 15 grams of SiO
2/ A1
2o
3mol ratio is the ITQ-2 molecular sieve of 38, with the ammonium nitrate solution of 20 milliliters of 0.1mol/L, within 8 hours, is exchanged into NH in 80 DEG C of dippings
4type molecular sieve, then obtains H type ITQ-2 molecular sieve in 4 hours 500 DEG C of roastings.
B H type ITQ-2 molecular sieve obtained for (a) step is that exchange liquid exchanges with 20 milliliters of 5mol/L calcium nitrate solutions by (), be 10 exchange 3 times according to solid-to-liquid ratio at 80 DEG C, each swap time is 2 hours.Wash afterwards, suction filtration, filter cake is dried 4 hours at 110 DEG C.By the roasting 4 hours at 500 DEG C of this molecular sieve, obtain Ca-ITQ-2 type molecular sieve.
C () Ca modification ITQ-2 molecular sieve is with 0.1mol/L BAS in 25 DEG C of dippings 6 hours, 120 DEG C of dryings 8 hours, 500 DEG C of roastings 3 hours, obtain boric acid and alkali-earth metal modified ITQ-2 molecular sieve.Shaping and be broken for 20 ~ 40 object particles, obtain the ITQ-2 molecular sieve catalyst of 0.5% boron 8%Ca modification.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 1.
Embodiment 6
A () gets 15 grams of MCM-22 and ITQ-2 mol ratios is the mixed molecular sieve of 1:1, with the ammonium nitrate solution of 20 milliliters of 0.1mol/L, within 8 hours, is exchanged into NH in 85 DEG C of dippings
4type molecular sieve, then obtains H type mixed molecular sieve in 4 hours 550 DEG C of roastings.
B H type molecular sieve that (a) step obtains by () is exchange liquid to exchange with the salpeter solution of 20 milliliters of 5mol/L alkaline-earth metal magnesium, and be 10 exchange 3 times according to solid-to-liquid ratio at 85 DEG C, each swap time is 2 hours.Wash afterwards, suction filtration, filter cake is dried 4 hours at 110 DEG C.By the roasting 4 hours at 550 DEG C of this molecular sieve, obtain Mg modification mixed molecular sieve.
C () Mg modification mixed molecular sieve is with 0.1mol/L BAS in 25 DEG C of dippings 6 hours, 120 DEG C of dryings 8 hours, 550 DEG C of roastings 3 hours, obtain boric acid and alkali-earth metal modified mixed molecular sieve.Shaping and be broken for 20 ~ 40 object particles, obtain the mixed molecular sieve catalyst of 0.2% boron 10%Mg modification.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 1.
Comparative example 1
A () gets 15 grams of SiO
2/ A1
2o
3mol ratio is the X molecular sieve of 2, with the ammonium nitrate solution of 20 milliliters of 0.1mol/L, within 8 hours, is exchanged into NH in 85 DEG C of dippings
4type molecular sieve, then obtains H type X molecular sieve in 4 hours 550 DEG C of roastings.
B H type X molecular sieve that (a) step obtains by () is exchange liquid to exchange with the salpeter solution of 20 milliliters of 5mol/L alkaline-earth metal magnesium, and be 10 exchange 3 times according to solid-to-liquid ratio at 85 DEG C, each swap time is 2 hours.Wash afterwards, suction filtration, filter cake is dried 4 hours at 110 DEG C.By the roasting 4 hours at 550 DEG C of this molecular sieve, obtain Mg-X type molecular sieve.
C () Mg modified X molecular sieve is with 0.1mol/L BAS in 25 DEG C of dippings 6 hours, 120 DEG C of dryings 8 hours, 550 DEG C of roastings 3 hours, obtain boric acid and alkali-earth metal modified X molecular sieve.Shaping and be broken for 20 ~ 40 object particles, obtain the X molecular sieve catalyst of 0.5% boron 10%Mg modification.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 1.
Comparative example 2
A () gets 15 grams of SiO
2/ A1
2o
3mol ratio is the ZSM-5 molecular sieve of 45, with the ammonium nitrate solution of 20 milliliters of 0.1mol/L, within 8 hours, is exchanged into NH in 85 DEG C of dippings
4type molecular sieve, then obtains H type ZSM-5 molecular sieve in 4 hours 550 DEG C of roastings.
B H type ZSM-5 molecular sieve that (a) step obtains by () is exchange liquid to exchange with the salpeter solution of 20 milliliters of 5mol/L alkaline-earth metal magnesium, and be 10 exchange 3 times according to solid-to-liquid ratio at 85 DEG C, each swap time is 2 hours.Wash afterwards, suction filtration, filter cake is dried 4 hours at 110 DEG C.By the roasting 4 hours at 550 DEG C of this molecular sieve, obtain Mg-ZSM-5 type molecular sieve.
C () Mg modified zsm-5 zeolite is with 0.1mol/L BAS in 25 DEG C of dippings 6 hours, 120 DEG C of dryings 8 hours, 550 DEG C of roastings 3 hours, obtain boric acid and alkali-earth metal modified ZSM-5 molecular sieve.Shaping and be broken for 20 ~ 40 object particles, obtain the ZSM-5 molecular sieve catalyst of 0.5% boron 10%Mg modification.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 1.
Each example performance evaluation of table 1
| Numbering | Toluene conversion % | Selectivity of styrene % |
| 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. a MWW type molecular sieve carrier catalyst, is characterized in that:
Described MWW type molecular sieve carrier catalyst is MWW type molecular sieve carrier, with load boron element thereon and alkaline-earth metal, MWW type molecular sieve carrier accounts for 80 ~ 98% of total catalyst weight, boron element with the weight percentage of oxide basis for 0.1 ~ 5%, alkaline-earth metal with the weight percentage of oxide basis for 1 ~ 10%.
2. catalyst according to claim 1, is characterized in that: described alkaline-earth metal is magnesium or calcium.
3. a preparation method for MWW type molecular sieve carrier catalyst as claimed in claim 1, it comprises the following steps:
A () chooses MWW type molecular sieve, exchange, then become H type MWW molecular sieve 400-600 DEG C of roasting at 60 ~ 90 DEG C with 0.1 ~ 5 mol/L ammonium salt;
B the molecular sieve aequum concentration of (a) step process is that the alkali salt of 0.1 ~ 5mol/L exchanges H type MWW molecular sieve for exchanging liquid by ();
(c) by the molecular sieve of (b) step process 400 ~ 600 DEG C of roastings, then be that 0.1 ~ 5 mol/L BAS infusion process loads to after on molecular sieve by aequum concentration, 400 ~ 600 DEG C of roastings, obtained MWW type molecular sieve carrier catalyst.
4. preparation method according to claim 3, is characterized in that: the percentage by weight consumption of MWW type molecular sieve carrier is 80 ~ 98%; At least one of MWW type molecular screening in MCM-22, MCM-49, MCM-56, ITQ-1, ITQ-2.
5. preparation method according to claim 3, is characterized in that: the ammonium salt for exchanging is selected from ammonium nitrate or ammonium carbonate.
6. preparation method according to claim 3, is characterized in that: the alkali salt for exchanging is nitrate or the acetate of alkaline-earth metal.
7. preparation method according to claim 3, is characterized in that: the element wt percentage composition of the boron of load in catalyst with oxide basis for 0.1 ~ 5%.
8. the preparation method of catalyst according to claim 3, is characterized in that: the alkaline-earth metal of load in catalyst be the weight percentage of Mg or Ca with oxide basis for 1 ~ 10%.
9. the application of the MWW type molecular sieve carrier catalyst according to claim 1-8 any one, is characterized in that: described catalyst is used for toluene and methanol side chain alkylation Reactive Synthesis styrene.
10. the application of MWW type molecular sieve carrier catalyst according to claim 9, it is characterized in that: the catalyst getting 5.0 grams of claim 1 to 8 any one loads the flat-temperature zone of the miniature continuous flow reactor reactor of fixed bed, reactor top and the bottom are all filled with porcelain ring or bead; Be 0.4MPa at pressure, reaction temperature is at 425 DEG C, is that the toluene of 5:1 mixes with methyl alcohol by the mol ratio of raw material ratio, with micro pump send into preheater to mix with nitrogen vaporize laggard enter reactor upper end, liquid air speed 1.0 hours
-1, nitrogen flow is under the condition of 20 ml/min, flow through beds and carry out catalytic reaction, product ice water condensation is collected, and analyzes its composition by gas-chromatography.
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| KR20190040081A (en) * | 2016-10-06 | 2019-04-16 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | Process for the production of para-xylene by methylation of benzene and / or toluene |
| CN109529910B (en) * | 2018-11-29 | 2020-08-07 | 中国科学院大连化学物理研究所 | Catalyst for toluene methanol side-chain alkylation reaction and styrene preparation method |
| US11535578B2 (en) * | 2019-03-28 | 2022-12-27 | Exxonmobil Chemical Patents Inc. | Processes for converting aromatic hydrocarbons using passivated reactor |
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