CN106278801A - Side chain alkylation produces ethylbenzene, cinnamic method - Google Patents
Side chain alkylation produces ethylbenzene, cinnamic method Download PDFInfo
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- CN106278801A CN106278801A CN201510324785.2A CN201510324785A CN106278801A CN 106278801 A CN106278801 A CN 106278801A CN 201510324785 A CN201510324785 A CN 201510324785A CN 106278801 A CN106278801 A CN 106278801A
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- Prior art keywords
- side chain
- molecular sieve
- chain alkylation
- catalyst
- ethylbenzene
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 25
- 230000029936 alkylation Effects 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 79
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000002808 molecular sieve Substances 0.000 claims abstract description 58
- 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 58
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 25
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 20
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 15
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 10
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 10
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 10
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 53
- 238000005342 ion exchange Methods 0.000 claims description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- 229910052681 coesite Inorganic materials 0.000 claims description 18
- 229910052593 corundum Inorganic materials 0.000 claims description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims description 18
- 229910052682 stishovite Inorganic materials 0.000 claims description 18
- 229910052905 tridymite Inorganic materials 0.000 claims description 18
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 18
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 10
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 10
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 8
- 229910001414 potassium ion Inorganic materials 0.000 claims description 8
- 229910001419 rubidium ion Inorganic materials 0.000 claims description 8
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical group OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 abstract description 17
- 230000009849 deactivation Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 239000000463 material Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- JMNDBSWHIXOJLR-UHFFFAOYSA-N ethylbenzene;styrene Chemical compound CCC1=CC=CC=C1.C=CC1=CC=CC=C1 JMNDBSWHIXOJLR-UHFFFAOYSA-N 0.000 description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 13
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 13
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 13
- 229910001415 sodium ion Inorganic materials 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 230000002779 inactivation Effects 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- 150000001340 alkali metals Chemical class 0.000 description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005352 clarification Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 6
- 230000007717 exclusion Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- -1 MgO Chemical class 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical group C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GEIGXJHXQWKQAT-UHFFFAOYSA-N europium;nitric acid Chemical compound [Eu].O[N+]([O-])=O GEIGXJHXQWKQAT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of side chain alkylation and produce ethylbenzene, cinnamic method, mainly solve prior art and have that catalysqt deactivation is fast, the problem of poor stability.The present invention, by using with toluene and methanol as raw material, under conditions of being enough to make the reaction of raw material generation side chain alkylation, makes raw material contact with catalyst and obtains ethylbenzene and styrene；Described catalyst includes in terms of parts by weight: a) 98～99.5 parts of particle sizes are the X molecular sieve of 20～900 nanometers；B) technical scheme of 0.5～2 part of at least one auxiliary agent in europium, gadolinium, ytterbium or lutecium preferably solves this problem, can be used for methylbenzene methanol side chain alkylation and prepares in ethylbenzene and cinnamic commercial production.
Description
Technical field
The present invention relates to a kind of side chain alkylation and produce ethylbenzene, cinnamic method.
Background technology
Styrene monomer is a kind of important Organic Chemicals, is mainly used in polystyrene, ABS
The production of the products such as resin, butadiene-styrene rubber, unsaturated-resin.Additionally, can be additionally used in pharmacy, dye
Expecting or produce farm chemical emulgent and dressing agent etc., purposes is quite varied.Styrene series resin
Yield is only second to PE, PVC in synthetic resin and comes in third.Major part technical benzene ethylene at present
It is to be generated ethylbenzene by benzene and ethylene through Friedel-Craft reaction, then gets through catalytic dehydrogenation.This method stream
Journey compared with long, side reaction is many, energy consumption is high, cost of material account for produce variable cost 85%, produce into
This is higher.Toluene and methanol alkylation are to produce a cinnamic route having potential application foreground.
X-type and y-type zeolite that Sidorenko in 1967 etc. exchange with alkali metal ion first are catalyst
Success is by toluene and methanol-fueled CLC ethylbenzene and styrene.Compared with traditional handicraft, the method has
There are the advantages such as raw material sources are wide, low cost, energy consumption are low, pollution is few.Thus this reacts once report
Just being subject to the people's attention, the research about this respect also begins to increase.
The reaction of methylbenzene methanol side chain alkylation once conducted extensive research on multiple catalysts.Permitted
Polymolecular sieve such as X, Y, L, β, ZSM-5, and some basic anhydride such as MgO, MgO-TiO2、
And CaO-TiO2The research that is all in the news is applied to be catalyzed in the reaction of methylbenzene methanol side chain alkylation, as
JOURNAL OF CATALYSIS 173,490 500 (1998) and CN101623649A,
CN101623650A.Result of study finds, wants to reach preferable side chain alkylation catalytic effect,
Catalyst must is fulfilled for following 4 requirements: catalyst is it is necessary to have enough basic center activate first
Alcohol is changed into methylating reagent formaldehyde；There is weak Lewis acid site to stablize toluene and to polarize it
Methyl；Toluene and methanol to have a good stoichiometric adsorption equilibrium on a catalyst；Urge
Agent must have micropore canals structure.Therefore, the result of study of some zeolite catalysis activity is shown,
The X-type zeolite of alkali metal cation-exchanged is the catalyst of relative efficiency.The reaction of y-type zeolite is lived
Property inferior to X-type zeolite.And other reactivity such as zeolites such as L, β, ZSM-5 types is the most undesirable,
And some do not have the basic anhydride of microcellular structure, such as MgO, MgO-TiO2And CaO-TiO2Deng
The lowest activity.Although X and Y molecular sieve catalyst are the catalysis materials that activity is higher, but
It is X and Y molecular sieve is belonging to the molecular sieve that silica alumina ratio is relatively low, course of reaction exists molecular sieve
The easy dealuminzation of catalyst, the shortcoming that catalyst easily inactivates.Therefore, this kind of catalyst how is solved
Stability problem become methylbenzene methanol and prepare the cinnamic key point of ethylbenzene.
Summary of the invention
The technical problem to be solved is that prior art exists that catalysqt deactivation is fast, stability
The problem of difference, it is provided that a kind of new side chain alkylation produces ethylbenzene, cinnamic method.The method
There is use ratio of methanol high, the feature that catalyst stability is good.
For solving above-mentioned technical problem, the technical scheme that the present invention takes is as follows: a kind of pendant alkyl group
Metaplasia produces ethylbenzene, cinnamic method, with toluene and methanol as raw material, makes raw material occur being enough to
Under conditions of side chain alkylation reaction, make raw material contact with catalyst and obtain ethylbenzene and styrene；Institute
State catalyst to include in terms of parts by weight:
A) 98～99.5 parts of particle sizes are the X molecular sieve of 20～900 nanometers；
B) 0.5～2 part of at least one auxiliary agent in europium, gadolinium, ytterbium or lutecium.
In technique scheme, it is preferable that the particle size of described catalyst is 50～700 nanometers.
In technique scheme, it is preferable that the particle size of described catalyst is 80～500 nanometers.
In technique scheme, it is preferable that the particle size of described catalyst is 80～250 nanometers.
In technique scheme, it is preferable that described X molecular sieve SiO2/Al2O3It is 2～3.
In technique scheme, it is preferable that described X molecular sieve be make X molecular sieve and alkali metal from
Component contacts and carries out the method for ion exchange and obtain；Described method includes making nanometer X molecule
Sieve at least contacts step once with at least one in potassium ion source, rubidium ion source or Ces Ium Ion Sources.
It is highly preferred that described method include making nanometer X molecular sieve and potassium ion source, rubidium ion source or caesium from
At least two in component the most at least contacts step once.Most preferably, described method includes
Nanometer X molecular sieve is made the most at least to contact once with potassium ion source, rubidium ion source and Ces Ium Ion Sources
Step.It is particularly preferred that described method include making nanometer X molecular sieve successively with potassium ion source, rubidium
Ion source the most at least contacts step once with Ces Ium Ion Sources.
In technique scheme, it is preferable that described in be enough to make raw material generation side chain alkylation react
Condition is: toluene and methanol molar ratio are (2～7): 1, and reaction temperature is 350～500 DEG C, reaction pressure
Power is 0～0.5MP, and raw material weight air speed is 1～8 hour-1。
In the inventive method, as described ion source, these alkali-metal hydrogen such as can be enumerated
Oxide, inorganic acid salt (such as halide salts, nitrate etc.) and acylate (such as vinegar
Hydrochlorate etc.) etc., it is not particularly limited.To described molecular sieve and described alkali metal ion source
Contact and carry out the mode of ion exchange there is no particular limitation, can be conventional according to this area
Mode is carried out.Such as, temperature is 50～90 DEG C, and each time of contact is 1～3 hour, liquid-solid
Weight ratio is 5～10.
In the inventive method, the mode making rare earth element be carried on nanometer X molecular sieve is for ability
Infusion process known in territory, use the saline solution containing europium, gadolinium, ytterbium or lutecium by europium, gadolinium, ytterbium or
Lutecium element loads on X molecular sieve.Dipping temperature is between 40～80 DEG C, and dip time is 3～8
Hour.
The evaluation of the inventive method can be carried out in continuous flow reactor of fixed bed, its process letter
State as follows: take the desired amount of catalyst and put into the flat-temperature zone of reactor, catalyst bottom quartz sand
Fill.Under the temperature set, pressure, by toluene and methanol mixed, deliver to preheating with micro pump
Enter reactor upper end after device and nitrogen mixture, flow through beds and carry out catalytic reaction,
Product directly enters gas chromatogram with valve injection and is analyzed.
The activity and selectivity of catalyst calculates according to below equation:
The inventive method selects nano X-type molecular sieve to be that catalyst material, beneficially reaction molecular exist
Diffusion in molecular sieve catalyst duct, decreases the decomposition of methanol, thus is effectively increased methanol
Utilization rate；Europium, gadolinium, ytterbium or lutecium element are loaded on catalyst, catalyst can be greatly improved steady
Qualitative.It addition, according to ionic radius increase order (potassium, rubidium, caesium), with containing potassium, rubidium,
The solution continuous process of caesium carries out ion exchange successively to nanometer X molecular sieve, improves ion exchange
Degree, substantially increases catalytic effect.Use the inventive method, be 5: 1 at toluene and methanol molar ratio,
Reaction temperature is 425 DEG C, and reaction pressure is normal pressure, and raw material weight air speed is 2.5 hours-1Condition
Lower reaction, use ratio of methanol can be up to 37%, and ethylbenzene styrene overall selectivity is up to 97%；Urge
Agent stability can keep 200 hours activity constant, achieves preferable technique effect.
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
[embodiment 1]
Sodium hydroxide is dissolved in distilled water, then sodium aluminate is joined in sodium hydroxide solution, stir
Mix to clarification.Then Ludox is joined in above-mentioned solution, the mol ratio of each material in mixture
For n (Na2O):n(SiO2):n(Al2O3):n(H2O)=2.92:2:1:96.Stir after addition, finally
Put in the stainless steel autoclave with teflon lined, 80 DEG C of water bath sonicator crystallization 2.5
Hour, synthetic product obtains nanometer X molecular sieve through filtration washing.Synthesizing nano X molecular sieve
SiO2/Al2O3Ratio is 2.10, and average particle size particle size is 800nm.
Take above-mentioned nanometer X molecular sieve, use KNO3Solution, RbNO3Solution and CsNO3Solution depends on
Secondary carry out ion exchange, filter latter 100 DEG C and be dried 10 hours.After exchange, alkali metal in catalyst
In Ion exchange-Size exclusion, the ion-exchange degree of sodium ion is more than 85%.(ion-exchange degree uses
ICP method measures).Then by europium nitrate wiring solution-forming, europium is impregnated into above-mentioned modified molecular screen
On material.In load rear catalyst, the content of europium is 1%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Stream
Speed is to carry out activity rating under conditions of 10 ml/min.
Result: use ratio of methanol 36.1%, ethylbenzene styrene overall selectivity 96.6%, reaction 200 is little
Time non-inactivation.
[embodiment 2]
Sodium hydroxide is dissolved in distilled water, then sodium aluminate is joined in sodium hydroxide solution, stir
Mix to clarification.Then Ludox is joined in above-mentioned solution, the mol ratio of each material in mixture
For n (Na2O):n(SiO2):n(Al2O3):n(H2O)=3.57:2:1:96.Stir after addition, finally
Put in the stainless steel autoclave with teflon lined, 80 DEG C of water bath sonicator crystallization 2.5
Hour, synthetic product obtains nanometer X molecular sieve through filtration washing.Synthesizing nano X molecular sieve
SiO2/Al2O3Ratio is 2.07, and average particle size particle size is 650nm.
Take above-mentioned nanometer X molecular sieve, use KNO3Solution, RbNO3Solution and CsNO3Solution depends on
Secondary carry out ion exchange, filter latter 100 DEG C and be dried 10 hours.After exchange, alkali metal in catalyst
In Ion exchange-Size exclusion, the ion-exchange degree of sodium ion is more than 85%.Then europium nitrate is made into
Solution, is impregnated into europium on above-mentioned modified molecular screen material.The content of load rear catalyst europium is 1%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Stream
Speed is to carry out activity rating under conditions of 10 ml/min.
Result: use ratio of methanol 36.3%, ethylbenzene styrene overall selectivity 97.4%, reaction 200 is little
Time non-inactivation.
[embodiment 3]
Sodium hydroxide is dissolved in distilled water, then sodium aluminate is joined in sodium hydroxide solution, stir
Mix to clarification.Then Ludox is joined in above-mentioned solution, the mol ratio of each material in mixture
For n (Na2O):n(SiO2):n(Al2O3):n(H2O)=4.71:2:1:96.Stir after addition, finally
Put in the stainless steel autoclave with teflon lined, 80 DEG C of water bath sonicator crystallization 2.5
Hour, synthetic product obtains nanometer X molecular sieve through filtration washing.Synthesizing nano X molecular sieve
SiO2/Al2O3Ratio is 2.12, and average particle size particle size is 400nm.
Take above-mentioned nanometer X molecular sieve, use KNO3Solution, RbNO3Solution and CsNO3Solution depends on
Secondary carry out ion exchange, filter latter 100 DEG C and be dried 10 hours.After exchange, alkali metal in catalyst
In Ion exchange-Size exclusion, the ion-exchange degree of sodium ion is more than 85%.Then europium nitrate is made into
Solution, is impregnated into europium on above-mentioned modified molecular screen material.The content of load rear catalyst europium is 1%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Stream
Speed is to carry out activity rating under conditions of 10 ml/min.
Result: use ratio of methanol 36.4%, ethylbenzene styrene overall selectivity 97.5%, reaction 200 is little
Time non-inactivation.
[embodiment 4]
Sodium hydroxide is dissolved in distilled water, then sodium aluminate is joined in sodium hydroxide solution, stirring
To clarification.Then being joined by Ludox in above-mentioned solution, in mixture, the mol ratio of each material is
n(Na2O):n(SiO2):n(Al2O3):n(H2O)=5.85:2.8:1:105.Stir after addition, finally
Put in the stainless steel autoclave with teflon lined, 80 DEG C of water bath sonicator crystallization 2.5
Hour, synthetic product obtains nanometer X molecular sieve through filtration washing.Synthesizing nano X molecular sieve
SiO2/Al2O3Ratio is 2.88, and average particle size particle size is 250nm.
Take above-mentioned nanometer X molecular sieve, use KNO3Solution, RbNO3Solution and CsNO3Solution depends on
Secondary carry out ion exchange, filter latter 100 DEG C and be dried 10 hours.After exchange, alkali metal in catalyst
In Ion exchange-Size exclusion, the ion-exchange degree of sodium ion is more than 85%.Then europium nitrate is made into
Solution, is impregnated into europium on above-mentioned modified molecular screen material.The content of load rear catalyst europium is 1%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Stream
Speed is to carry out activity rating under conditions of 10 ml/min.
Result: use ratio of methanol 37.2%, ethylbenzene styrene overall selectivity 97.2%, reaction 200 is little
Time non-inactivation.
[embodiment 5]
Sodium hydroxide is dissolved in distilled water, then takes sodium aluminate and join in sodium hydroxide solution, stir
Mix to clarification.Then Ludox is joined in above-mentioned solution, the mol ratio of each material in mixture
For n (Na2O):n(SiO2):n(Al2O3):n(H2O)=5.85:2:1:105.Stir after addition, finally
Put in the stainless steel autoclave with teflon lined, 80 DEG C of water bath sonicator crystallization 2.5
Hour, synthetic product obtains nanometer X molecular sieve through filtration washing.Synthesizing nano X molecular sieve
SiO2/Al2O3Ratio is 2.10, and average particle size particle size is 120nm.
Take above-mentioned nanometer X molecular sieve, use KNO3Solution, RbNO3Solution and CsNO3Solution depends on
Secondary carry out ion exchange, filter latter 100 DEG C and be dried 10 hours.After exchange, alkali metal in catalyst
In Ion exchange-Size exclusion, the ion-exchange degree of sodium ion is more than 85%.Then europium nitrate is made into
Solution, is impregnated into europium on above-mentioned modified molecular screen material.The content of load rear catalyst europium is 1%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Stream
Speed is to carry out activity rating under conditions of 10 ml/min.
Result: use ratio of methanol 38.9%, ethylbenzene styrene overall selectivity 97%, react 200 hours
Non-inactivation.
[embodiment 6]
Sodium hydroxide is dissolved in distilled water, then sodium aluminate is joined in sodium hydroxide solution, stir
Mix to clarification.Then Ludox is joined in above-mentioned solution, the mol ratio of each material in mixture
For n (Na2O):n(SiO2):n(Al2O3):n(H2O)=5.85:2.25:1:105.Stir after addition,
After put in the stainless steel autoclave with teflon lined, 80 DEG C of water bath sonicator crystallization 2.5
Hour, synthetic product obtains nanometer X molecular sieve through filtration washing.Synthesizing nano X molecular sieve
SiO2/Al2O3Ratio is 2.31, and average particle size particle size is 85nm.
Take above-mentioned nanometer X molecular sieve, use KNO3Solution, RbNO3Solution and CsNO3Solution depends on
Secondary carry out ion exchange, filter latter 100 DEG C and be dried 10 hours.After exchange, alkali metal in catalyst
In Ion exchange-Size exclusion, the ion-exchange degree of sodium ion is more than 85%.Then europium nitrate is made into
Solution, is impregnated into europium on above-mentioned modified molecular screen material.The content of load rear catalyst boron is
0.5%, the content of phosphorus is 0.8%, and the content of europium is 1%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Stream
Speed is to carry out activity rating under conditions of 10 ml/min.
Result: use ratio of methanol 40.5%, ethylbenzene styrene overall selectivity 97.2%, reaction 200 is little
Time non-inactivation.
[embodiment 7]
Take the nanometer X molecular sieve in [embodiment 6], use KNO3Solution, RbNO3Solution and
CsNO3Solution carries out ion exchange successively, filters latter 100 DEG C and is dried 10 hours.After exchange, urge
In agent, in alkali metal ion exchange molecular sieve, the ion-exchange degree of sodium ion is more than 85%.Then
By Ytterbium(III) nitrate. wiring solution-forming, ytterbium is impregnated on above-mentioned modified molecular screen material.Load rear catalyst
The content of ytterbium is 1%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Stream
Speed is to carry out activity rating under conditions of 10 ml/min.
Result: use ratio of methanol 39.8%, ethylbenzene styrene overall selectivity 97%, react 200 hours
Non-inactivation.
[embodiment 8]
Take the nanometer X molecular sieve in [embodiment 6], use KNO3Solution, RbNO3Solution and
CsNO3Solution carries out ion exchange successively, filters latter 100 DEG C and is dried 10 hours.After exchange, urge
In agent, in alkali metal ion exchange molecular sieve, the ion-exchange degree of sodium ion is more than 85%.Then
By Gadolinium trinitrate wiring solution-forming, gadolinium is impregnated on above-mentioned modified molecular screen material.Load rear catalyst
The content of gadolinium is 1%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Stream
Speed is to carry out activity rating under conditions of 10 ml/min.
Result: use ratio of methanol 40.1%, ethylbenzene styrene overall selectivity 97.8%, reaction 200 is little
Time non-inactivation.
[embodiment 9]
Take the nanometer X molecular sieve in [embodiment 6], use KNO3Solution, RbNO3Solution and
CsNO3Solution carries out ion exchange successively, filters latter 100 DEG C and is dried 10 hours.After exchange, urge
In agent, in alkali metal ion exchange molecular sieve, the ion-exchange degree of sodium ion is more than 85%.Then
By lutecium nitrate wiring solution-forming, lutecium is impregnated on above-mentioned modified molecular screen material.Load rear catalyst
The content of lutecium is 1%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Stream
Speed is to carry out activity rating under conditions of 10 ml/min.
Result: use ratio of methanol 39.2%, ethylbenzene styrene overall selectivity 97.8%, reaction 200 is little
Time non-inactivation.
[comparative example 1]
Take silica alumina ratio SiO2/Al2O3The common X molecular sieve (particle size is 3-5 μm) of=2.1, uses
KNO3Solution, RbNO3Solution and CsNO3Solution carries out ion exchange successively, filters latter 100 DEG C
It is dried 10 hours.After exchange, the ion of sodium ion in alkali metal ion exchange molecular sieve in catalyst
Exchange degree is more than 85%.(ion-exchange degree uses ICP method to measure).Then by nitric acid
Europium wiring solution-forming, is impregnated into europium on above-mentioned modified molecular screen material.Europium in load rear catalyst
Content is 1%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Stream
Speed is to carry out activity rating under conditions of 10 ml/min.
Result: use ratio of methanol 33.8%, ethylbenzene styrene overall selectivity 97.8%, reaction 200 is little
Time non-inactivation.
[comparative example 2]
Take silica alumina ratio SiO2/Al2O3The common X molecular sieve (particle size is 3-5 μm) of=2.1, uses
KNO3Solution, RbNO3Solution and CsNO3Solution carries out ion exchange successively, filters latter 100 DEG C
It is dried 10 hours.After exchange, the ion of sodium ion in alkali metal ion exchange molecular sieve in catalyst
Exchange degree is more than 85%.Then by Ytterbium(III) nitrate. wiring solution-forming, ytterbium is impregnated into above-mentioned modified molecules
On sieve material.The content of load rear catalyst ytterbium is 1%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Stream
Speed is to carry out activity rating under conditions of 10 ml/min.
Result: use ratio of methanol 32.5%, ethylbenzene styrene overall selectivity 97.8%, reaction 200 is little
Time non-inactivation.
[comparative example 3]
Take silica alumina ratio SiO2/Al2O3The common X molecular sieve (particle size is 3-5 μm) of=2.1, uses
KNO3Solution, RbNO3Solution and CsNO3Solution carries out ion exchange successively, filters latter 100 DEG C
It is dried 10 hours.After exchange, the ion of sodium ion in alkali metal ion exchange molecular sieve in catalyst
Exchange degree is more than 85%.Then by Gadolinium trinitrate wiring solution-forming, gadolinium is impregnated into above-mentioned modified molecules
On sieve material.The content of load rear catalyst gadolinium is 1%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Stream
Speed is to carry out activity rating under conditions of 10 ml/min.
Result: use ratio of methanol 32.7%, ethylbenzene styrene overall selectivity 97.8%, reaction 200 is little
Time non-inactivation.
[comparative example 4]
Take silica alumina ratio SiO2/Al2O3The common X molecular sieve (particle size is 3-5 μm) of=2.1, uses
KNO3Solution, RbNO3Solution and CsNO3Solution carries out ion exchange successively, filters latter 100 DEG C
It is dried 10 hours.After exchange, the ion of sodium ion in alkali metal ion exchange molecular sieve in catalyst
Exchange degree is more than 85%.Then by lutecium nitrate wiring solution-forming, lutecium is impregnated into above-mentioned modified molecules
On sieve material.The content of load rear catalyst lutecium is 1%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5, at 2.5 hours-1Liquid air speed, 425 DEG C, N2Stream
Speed is to carry out activity rating under conditions of 10 ml/min.
Result: use ratio of methanol 32.2%, ethylbenzene styrene overall selectivity 97.8%, reaction 200 is little
Time non-inactivation.
Claims (10)
1. side chain alkylation produces ethylbenzene, a cinnamic method, with toluene and methanol as raw material,
Under conditions of being enough to make the reaction of raw material generation side chain alkylation, make raw material contact with catalyst and obtain
Ethylbenzene and styrene；Described catalyst includes in terms of parts by weight:
A) 98～99.5 parts of particle sizes are the X molecular sieve of 20～900 nanometers；
B) 0.5～2 part of at least one auxiliary agent in europium, gadolinium, ytterbium or lutecium.
The most according to claim 1, side chain alkylation produces ethylbenzene, cinnamic method, and it is special
Levy and be that the particle size of described catalyst is 50～700 nanometers.
The most according to claim 2, side chain alkylation produces ethylbenzene, cinnamic method, and it is special
Levy and be that the particle size of described catalyst is 80～500 nanometers.
The most according to claim 3, side chain alkylation produces ethylbenzene, cinnamic method, and it is special
Levy and be that the particle size of described catalyst is 80～250 nanometers.
The most according to claim 1, side chain alkylation produces ethylbenzene, cinnamic method, and it is special
Levy and be described X molecular sieve SiO2/Al2O3It is 2～3.
The most according to claim 1, side chain alkylation produces ethylbenzene, cinnamic method, and it is special
Levy and be that described X molecular sieve is to make X molecular sieve contact with alkali metal ion source and carry out ion exchange
Method and obtain；Described method includes making nanometer X molecular sieve and potassium ion source, rubidium ion source
Or at least one in Ces Ium Ion Sources at least contacts step once.
The most according to claim 6, side chain alkylation produces ethylbenzene, cinnamic method, and it is special
Levy and be that described method includes making nanometer X molecular sieve and potassium ion source, rubidium ion source or Ces Ium Ion Sources
In at least two the most at least contact step once.
The most according to claim 7, side chain alkylation produces ethylbenzene, cinnamic method, and it is special
Levy and be that described method includes making nanometer X molecular sieve and potassium ion source, rubidium ion source and Ces Ium Ion Sources
The most at least contact step once.
The most according to claim 8, side chain alkylation produces ethylbenzene, cinnamic method, and it is special
Levy be described method include making nanometer X molecular sieve successively with potassium ion source, rubidium ion source and caesium from
Component the most at least contacts step once.
The most according to claim 1, side chain alkylation produces ethylbenzene, cinnamic method, its
The condition that be enough to described in being characterised by make raw material generation side chain alkylation react is: toluene rubs with methanol
Your ratio is (2～7): 1, and reaction temperature is 350～500 DEG C, and reaction pressure is 0～0.5MP, raw material
Weight space velocity is 1～8 hour-1。
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