CN109663606A - A kind of preparation method of P Modification graphene oxide, molecular sieve/graphene composite material and preparation method thereof - Google Patents
A kind of preparation method of P Modification graphene oxide, molecular sieve/graphene composite material and preparation method thereof Download PDFInfo
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- CN109663606A CN109663606A CN201710958363.XA CN201710958363A CN109663606A CN 109663606 A CN109663606 A CN 109663606A CN 201710958363 A CN201710958363 A CN 201710958363A CN 109663606 A CN109663606 A CN 109663606A
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- molecular sieve
- graphene oxide
- modification
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 176
- 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 153
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 152
- 230000004048 modification Effects 0.000 title claims abstract description 131
- 238000012986 modification Methods 0.000 title claims abstract description 131
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 45
- 238000002425 crystallisation Methods 0.000 claims abstract description 39
- 230000008025 crystallization Effects 0.000 claims abstract description 39
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 38
- 239000010439 graphite Substances 0.000 claims abstract description 38
- -1 graphite alkenes Chemical class 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000012805 post-processing Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 42
- 229910052710 silicon Inorganic materials 0.000 claims description 42
- 239000010703 silicon Substances 0.000 claims description 42
- 239000006185 dispersion Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 238000000638 solvent extraction Methods 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 4
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 4
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005819 Potassium phosphonate Substances 0.000 claims description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 3
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
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- 230000008569 process Effects 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
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- 239000007864 aqueous solution Substances 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
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- 238000000967 suction filtration Methods 0.000 description 4
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- 238000006482 condensation reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
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- 206010054949 Metaplasia Diseases 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
The present invention provides a kind of preparation methods of P Modification graphene oxide, include the following steps, after first mixing phosphorus source, alkali and organic solvent, obtain mixture；It states after graphene oxide water solution is added in the mixture that step obtains and is reacted then up, after post-processing, obtain P Modification graphene oxide.The present invention also provides a kind of molecular sieve/P Modification graphene composite materials.The present invention is prepared for P Modification graphene oxide using specific step, P Modification graphene oxide increases the active site of later period graphite alkenes material surface, improve the growth activity of graphite alkenes material surface, and bigger advantage is that alkalinity is presented in its surface, be conducive to first crystallization stage -- the formation of surface crystal seed of the system with molecular sieve for preparing for during, promote the formation of little crystallite size molecular sieve, to substantially increase molecular sieve pore passage diffuser efficiency, to obtain molecular sieve/P Modification graphene composite material of the better two-dimensional slice stratiform of performance.
Description
Technical field
The invention belongs to technical field of molecular sieve, are related to preparation method, the molecular sieve/stone of a kind of P Modification graphene oxide
Black alkene composite material and preparation method more particularly to a kind of preparation method of P Modification graphene oxide, molecular sieve/P Modification
Graphene composite material and preparation method thereof.
Background technique
Molecular sieve (also known as synthetic zeolite) refers to uniform micropore, aperture and the comparable one kind of general molecular size
Substance is a kind of more microporous crystals of alumino-silicate.It is made of basic skeleton structure silicon oxygen, aluminum-oxygen tetrahedron, in crystalline substance
There is metal cation (such as Na+, K+, Ca2+, Li+ etc.) in lattice, to balance negative electrical charge extra in crystal.The class of molecular sieve
Type is broadly divided by its crystal structure: A type, X-type, Y type etc..
Molecular sieve is very widely used, can make efficient drying agent, selective absorbent, catalyst, ion-exchanger
Deng.Common molecular sieve is the silicate or alumino-silicate of crystalline state, is to pass through oxygen bridge key by oxygen-octahedron or aluminum-oxygen tetrahedron
It is connected and is formed duct and the cavity system of molecular dimension size (usually 0.3~2nm), not because of binding molecule size and shape
Same and ability with screening fluid molecule of different sizes.International Union of Pure and Applied Chemistry is big according to molecular sieve bore diameter
It is small, they are defined as 3 grades: be known as micro porous molecular sieve of the aperture less than 2nm, aperture being known as between 2~50nm it is mesoporous or
Mesoporous molecular sieve, aperture are known as large pore molecular sieve greater than 50nm's.Since molecular sieve has, adsorption capacity is high, selectivity is strong, resistance to
The features such as high temperature, is widely used in the superior adsorbent of organic chemical industry and petrochemical industry and dehydration of gas, on waste gas purification
Also it is paid more and more attention, especially molecular sieve catalyst has extensive in various fields such as industrial petroleum refining, catalysis and separation
Application.If ZSM-5 type catalyst has three-dimensional network microcellular structure, with its unique cellular structure and good catalytic
Energy, excellent hydrothermal stability and thermal stability become indispensable solid acid catalyst, have good selective activization.
However, the aperture of tradition ZSM-5 is single, since the microcellular structure of molecular sieve leads to the limited transportation route of molecule,
Cause its existing defects in terms of catalytic applications.In addition, the only microcellular structure of traditional ZSM-5, limits macromolecular substances
Diffusion so that it is difficult to the big molecule of conversion volume.Also have in prior art by using special structure directing agent, soft mode
Their pore structure of the methods of plate and desiliconization expansion.But these methods make synthesis process complicated, and to produce
Object becomes unstable.
Graphene has many excellent characteristics, these characteristics make it be highly suitable for a variety of subjects and field,
In energy storage material, environmental project, sensing sensitive aspect is widely used, referred to as " dark fund " or " king of new material ", and
Potential application prospect is vast, has become global focus and research hotspot at present, but graphene with molecular sieve
Binding in, although existing relevant report of the graphene in conjunction with molecular sieve, since graphene itself is easy to reunite, easy
Curling and have stronger chemical inertness, thus with molecular sieve it is compound after, the effect is unsatisfactory, so in industry but not
It is common, hinder the expansion of graphene application field.
Therefore, how molecular sieve is modified, synthesizing a kind of molecular sieve catalyst has meso-hole structure abundant, simultaneously
With efficient catalytic efficiency and long service life cycle, it has also become many production firms and downstream application field urgently solve
One of major issue certainly.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of preparation side of P Modification graphene oxide
Method, molecular sieve/P Modification graphene composite material and preparation method thereof, molecular sieve provided by the invention/P Modification graphene are multiple
Condensation material has the molecular sieve uniform load of nano-scale in P Modification graphene surface, and molecular sieve can be in graphite alkenes material
On be uniformly distributed, catalytic performance is excellent, and preparation method is simple, be suitable for large-scale industrial production.
The present invention provides a kind of preparation methods of P Modification graphene oxide, comprising the following steps:
1) after mixing phosphorus source, alkali and organic solvent, mixture is obtained；
2) mixture obtained to above-mentioned steps is reacted after graphene oxide water solution is added, and after post-processing, is obtained
P Modification graphene oxide.
Preferably, phosphorus source includes triphenyl phosphite, triethyl phosphite, sodium phosphite, potassium phosphite, phosphorous
One of acid, Trimethyl phosphite and triisopropyl phosphite are a variety of；
The alkali includes one of sodium hydroxide solution, potassium hydroxide solution and ammonium hydroxide or a variety of；
The organic solvent includes methylene chloride, ethyl alcohol, acetone, ethyl alcohol, isopropanol, toluene, dimethylbenzene, n-butanol, different
One of butanol, ethylene glycol and glycerine are a variety of；
The mass concentration of the graphene oxide water solution is 0.1%~0.9%；
The organic solvent and the mass ratio of the graphene oxide water solution are (1~100): 1；
The mass ratio of phosphorus source and the graphene oxide is (0.5~20): 1.
The present invention provides a kind of molecular sieve/P Modification graphene composite materials, including P Modification graphite alkenes material；
And it is compounded in the molecular sieve of the P Modification graphite alkenes material surface.
Preferably, the partial size of the molecular sieve is 50~500nm；
The mesopore diameter of the molecular sieve is 2~10nm；
The piece diameter of the P Modification graphite alkenes material is 10~30 μm.
Preferably, the mass ratio of the graphite alkenes material and the molecular sieve is 1:(15~300)；
The graphite alkenes material includes one of graphene, graphene oxide and redox graphene or a variety of；
The molecular sieve includes in type ZSM 5 molecular sieve, ZSM-11 type molecular sieve, beta molecular sieve and HY type molecular sieve
It is one or more.
The present invention also provides a kind of molecular sieve/P Modification graphene composite material preparation methods, comprising the following steps:
A) P Modification graphene oxide dispersion, silicon source, template and silicon source are mixed after carrying out crystallization, using
Post-processing, obtains powder；
B after) powder for obtaining above-mentioned steps removes template, molecular sieve/P Modification graphene composite material is obtained.
Preferably, the molar ratio of the template and the silicon source is 1:(20~300)；
The mass concentration of the P Modification graphene oxide dispersion is 0.3%~8%；
The mass ratio of the silicon source and the P Modification graphene oxide is (15~1000): 1；
The molar ratio of source of aluminium and the silicon source is 1:(10~500).
Preferably, the step A) specifically:
A1 it after) mixing P Modification graphene oxide dispersion, silicon source and template for the first time, obtains mixed liquor, carries out the
After one stage crystallization, a step product is obtained；
A2 the step product) obtained to above-mentioned steps is added silicon source and mixes again, after carrying out second stage crystallization, then passes through
Later it handles, obtains powder；
The silicon source includes in tetraethyl orthosilicate, positive tetrabutyl silicate, white carbon black, waterglass, silica solution and sodium metasilicate
It is one or more；
Source of aluminium includes one of sodium aluminate, sodium metaaluminate, boehmite, aluminum sulfate, aluminium chloride and aluminum nitrate
Or it is a variety of；
The template includes tetrapropylammonium hydroxide, tetraethyl oxyammonia, polybutadiene rubber, tetraethyl amine and tetrapropyl ammonium
One of or it is a variety of.
Preferably, the temperature of the first stage crystallization is 60~120 DEG C；The time of the first stage crystallization be 8~
24h；
The temperature of the second stage crystallization is 170~200 DEG C；The time of the second stage crystallization is 16~72h；
The time mixed for the first time is 30~180min；The time mixed again is 30~240min.
Preferably, the post-processing includes one of washing, separation and drying or a variety of；
The mode for removing template includes alcohols solvent extraction and/or roasting；
The temperature of the extraction is 60~160 DEG C；
The temperature of the roasting is 400~600 DEG C.
The present invention provides a kind of preparation methods of P Modification graphene oxide, additionally provide a kind of molecular sieve/P Modification
Graphene composite material, including P Modification graphite alkenes material；And it is compounded in the P Modification graphite alkenes material surface
Molecular sieve.Compared with prior art, the present invention is single for traditional molecular sieve bore diameter, leads to the limited transportation route of molecule,
Cause its existing defects in terms of catalytic applications.And modified method is complicated, and product becomes unstable.The present invention abandons
Traditional method of modifying especially uses graphene and is combined with molecular sieve, and prepares graphene/molecular sieve for existing
In material, since graphene itself is easy to reunite, easy curling and has stronger chemical inertness, cause composite material load uneven
It is even, many undesirable effects such as easy curling, and then hinder the yoke of graphene application field expansion.
The present invention is few from graphene surface active site amount, and surface growth activity is low, and composite material surface is unevenly distributed,
The problem of easily crimping, creative is prepared for P Modification graphene, and P Modification graphene oxide increases later period graphite alkenes material
The active site for expecting surface, improves the growth activity of graphite alkenes material surface, and bigger advantage is that its surface is in
Existing alkalinity is conducive to first crystallization stage -- the formation of surface crystal seed of the system with molecular sieve for preparing for during, promotes little crystallite size point
The formation of son sieve, so that molecular sieve pore passage diffuser efficiency is substantially increased, to obtain the better two-dimensional slice stratiform of performance
Molecular sieve/P Modification graphene composite material.
The experimental results showed that molecular sieve prepared by the present invention/P Modification graphene composite material is in benzene ethylene alkylation
Good catalytic effect is shown, the catalytic performance of molecular sieve is effectively raised, is 5% in P Modification graphene additional amount
When, the conversion ratio of ethylene improves 30%, and the selectivity of ethyl is 95% or more.This is because the graphene of P Modification is fine
Induced synthesis nano-ZSM-5 molecular sieve, effectively raise the specific surface area of molecular sieve, improve diffuser efficiency.
Detailed description of the invention
Fig. 1 is metallograph of the P Modification graphene oxide of the preparation of the embodiment of the present invention 1 in water phase；
Fig. 2 is the EDS energy spectrum diagram of P Modification graphene oxide prepared by the embodiment of the present invention 1；
Fig. 3 is the preparation process flow schematic diagram that the embodiment of the present invention 1 provides；
Fig. 4 is molecular sieve/P Modification graphene composite material stereoscan photograph prepared by the embodiment of the present invention 1；
Fig. 5 is the stereoscan photograph of ZSM-5 molecular sieve prepared by same procedure and condition；
Fig. 6 is molecular sieve/P Modification graphene composite material graph of pore diameter distribution prepared by the embodiment of the present invention 1；
Fig. 7 is molecular sieve/P Modification graphene composite material stereoscan photograph prepared by the embodiment of the present invention 2；
Fig. 8 is molecular sieve/P Modification graphene composite material stereoscan photograph prepared by the embodiment of the present invention 3.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyzing, pure or graphene is compound
The conventional purity that Material Field uses.
The present invention provides a kind of preparation methods of P Modification graphene oxide, comprising the following steps:
1) after mixing phosphorus source, alkali and organic solvent, mixture is obtained；
2) mixture obtained to above-mentioned steps is reacted after graphene oxide water solution is added, and after post-processing, is obtained
P Modification graphene oxide.
After the present invention first mixes phosphorus source, alkali and organic solvent, mixture is obtained.
Phosphorus source is not particularly limited in the present invention, with conventional phosphorus source well known to those skilled in the art, originally
Field technical staff can select and adjust according to practical condition, product requirement and quality requirement, of the present invention
Phosphorus source preferably include triphenyl phosphite, triethyl phosphite, sodium phosphite, potassium phosphite, phosphorous acid, Trimethyl phosphite and
One of triisopropyl phosphite is a variety of, more preferably triphenyl phosphite, triethyl phosphite, sodium phosphite, phosphorous
Sour potassium, phosphorous acid, Trimethyl phosphite or triisopropyl phosphite, more preferably triphenyl phosphite, triethyl phosphite, Asia
Trimethyl phosphate or triisopropyl phosphite.
The additional amount of phosphorus source is not particularly limited in the present invention, with the amount of being routinely added to well known to those skilled in the art
, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The mass ratio of bright phosphorus source and the graphene oxide is (0.5~20): 1, more preferably (0.5~20): 1, more preferably
(0.5~20): 1.
The alkali is not particularly limited in the present invention, with conventional alkali well known to those skilled in the art, this field
Technical staff can select and adjust according to practical condition, product requirement and quality requirement, and alkali of the present invention is excellent
Choosing includes the aqueous solution of alkali, more specifically preferably includes one of sodium hydroxide solution, potassium hydroxide solution and ammonium hydroxide or a variety of,
More preferably sodium hydroxide solution, potassium hydroxide solution or ammonium hydroxide.
The additional amount of the alkali is not particularly limited in the present invention, is with the amount of being routinely added to well known to those skilled in the art
Can, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, the present invention
The pH value of the mixture is preferably greater than or equal to 12, is more preferably greater than equal to 13, is more preferably higher than equal to 14.
The organic solvent is not particularly limited in the present invention, with conventional organic solvent well known to those skilled in the art
, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright organic solvent is preferably the organic solvent that can dissolve phosphorus source, more preferably includes methylene chloride, ethyl alcohol, acetone, second
One of alcohol, isopropanol, toluene, dimethylbenzene, n-butanol, isobutanol, ethylene glycol and glycerine are a variety of, more preferably dichloro
Methane, ethyl alcohol, acetone, ethyl alcohol, isopropanol, toluene, dimethylbenzene, n-butanol, isobutanol, ethylene glycol or glycerine.
The additional amount of the organic solvent is not particularly limited in the present invention, is added with routine well known to those skilled in the art
Entering amount, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement,
Organic solvent of the present invention and the mass ratio of the graphene oxide water solution are preferably (1~100): 1, more preferably (5~
80): 1, more preferably (10~60): 1, more preferably (20~40): 1.
The mixed mode is not particularly limited in the present invention, with conventional hybrid mode well known to those skilled in the art
, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright mixing is preferably stirred.
The present invention is to improve the performance of P Modification graphene oxide, guarantees the effect of subsequent reaction, complete and optimization work
Skill route, the step 1) are particularly preferred as:
After first mixing phosphorus source and organic solvent, phosphorus source solution is obtained, then with after the aqueous solution strong stirring of alkali, mixed
Close object.
The mixture that the present invention is obtained then to above-mentioned steps reacts after graphene oxide water solution is added, and post-processes
Afterwards, P Modification graphene oxide is obtained.
The concentration of the graphene oxide water solution is not particularly limited in the present invention, with well known to those skilled in the art
The concentration of graphite alkenes material solution, those skilled in the art can be according to practical condition, product requirement and matter
Amount requires to be selected and adjusted, and the mass concentration of graphene oxide water solution of the present invention is preferably 0.1%~0.9%,
More preferably 0.3%~0.8%, more preferably 0.4%~0.7%, more preferably 0.5%~0.6%.
The temperature of the reaction is not particularly limited in the present invention, with the temperature of such reaction well known to those skilled in the art
Degree, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement,
The temperature of reaction of the present invention is preferably 35~60 DEG C, more preferably 40~55 DEG C, more preferably 45~50 DEG C.
The time of the reaction is not particularly limited in the present invention, with such reaction well known to those skilled in the art when
Between, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement,
The time of reaction of the present invention is preferably 4~for 24 hours, more preferably 8~20h, more preferably 12~16h.
The mode of the reaction is not particularly limited in the present invention, with the anti-of such reaction well known to those skilled in the art
Answer mode, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, reaction of the present invention are preferably hot back flow reaction.
The detailed process of the post-processing is not particularly limited in the present invention, with such mistake well known to those skilled in the art
The conventional post-processing step of journey, those skilled in the art can carry out according to the condition of production, product requirement and quality requirement
It selects and adjustment, post-processing of the present invention preferably includes one of washing, separation and drying or a variety of, more preferably separate
And washing, it is specifically as follows revolving Separation of Organic and eccentric cleaning, the temperature for rotating separation is preferably 60 DEG C, eccentric cleaning
To be cleaned multiple times.
Above-mentioned steps of the present invention are prepared for P Modification graphene oxide, and present invention employs specific steps and raw material group
It closes, P Modification graphene oxide has been prepared, be subsequent grapheme material, provide more surface-active sites, enhance
The growth activity of graphene surface, solves the problems, such as that subsequent molecular sieve is unevenly distributed on the surface of graphene.
The present invention provides a kind of molecular sieve/P Modification graphene composite materials, including P Modification graphite alkenes material；
And it is compounded in the molecular sieve of the P Modification graphite alkenes material surface.
In the above-mentioned molecular sieve/graphene composite material of the present invention, the optimum principle of P Modification graphite alkenes material used and
Additional amount is consistent with the optimum principle and additional amount of material in aforementioned P Modification graphite alkenes material preparation method, herein no longer
It repeats one by one.
The definition of the graphite alkenes material is not particularly limited in the present invention, with graphite well known to those skilled in the art
The concept of alkene and its derivative, those skilled in the art can want according to practical situations, product requirement and quality
It asks and is selected and adjusted, the graphene concept of graphite alkenes material, that is, broad sense of the present invention preferably includes graphene, oxidation
One of graphene and redox graphene are a variety of, more preferably single-layer graphene, multi-layer graphene, graphene oxide
Or redox graphene, most preferably one of graphene, redox graphene and graphene oxide or a variety of.
The design parameter of graphene in the P Modification graphite alkenes material is not particularly limited in the present invention, with this field
The conventional parameter of graphene known to technical staff, those skilled in the art can want according to practical condition, product
It asks and quality requirement is selected and adjusted, the size of graphene of the present invention, is i.e. the piece of P Modification graphite alkenes material
Diameter is preferably 10~30 μm, more preferably 12~28 μm, more preferably 15~25 μm, most preferably 18~23 μm.
The ratio of the graphite alkenes material and molecular sieve is not particularly limited in the present invention, ripe with those skilled in the art
The conventional ratio known, those skilled in the art can carry out according to practical situations, product requirement and quality requirement
The mass ratio of selection and adjustment, graphite alkenes material of the present invention and the molecular sieve is preferably 1:(15~300), more preferably
For 1:(15~200), more preferably 1:(20~100), more preferably 1:(20~50), or 1:(15~30).
The specific choice of the molecular sieve is not particularly limited in the present invention, with molecular sieve well known to those skilled in the art
Type, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement
Whole, molecular sieve of the present invention preferably includes type ZSM 5 molecular sieve, ZSM-11 type molecular sieve, beta molecular sieve and HY type molecular sieve
One of or a variety of, more preferably type ZSM 5 molecular sieve, ZSM-11 type molecular sieve, beta molecular sieve or HY type molecular sieve, more
Preferably type ZSM 5 molecular sieve.
The design parameter of the molecular sieve is not particularly limited in the present invention, with molecular sieve well known to those skilled in the art
Conventional parameter, those skilled in the art can select according to practical condition, product requirement and quality requirement
It selects and adjusts, the partial size (size) of molecular sieve of the present invention is preferably 50~500nm, and more preferably 150~400nm is more excellent
It is selected as 250~300nm.The mesopore diameter of molecular sieve of the present invention is preferably 2~10nm, more preferably 3~9nm, more preferably
For 4~8nm, more preferably 5~7nm.
The present invention also provides a kind of molecular sieve/P Modification graphene composite material preparation methods, comprising the following steps:
A) P Modification graphene oxide dispersion, silicon source, template and silicon source are mixed after carrying out crystallization, using
Post-processing, obtains powder；
B after) powder for obtaining above-mentioned steps removes template, molecular sieve/P Modification graphene composite material is obtained.
In the preparation method of the above-mentioned molecular sieve/P Modification graphene composite material of the present invention, the optimum principle of material therefor
With additional amount in previous molecular sieve/P Modification graphene composite material material optimum principle and additional amount it is consistent, herein
No longer repeat one by one.
P Modification graphene oxide dispersion, silicon source, template and silicon source are mixed carry out crystallization first by the present invention
Afterwards, using post-processing, powder is obtained.
The silicon source is not particularly limited in the present invention, is used to prepare zeolite molecular sieve with well known to those skilled in the art
Conventional silicon source, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, silicon source of the present invention preferably include tetraethyl orthosilicate, positive tetrabutyl silicate, white carbon black, waterglass, silica solution and
One of sodium metasilicate is a variety of, more preferably tetraethyl orthosilicate, white carbon black, waterglass, silica solution or sodium metasilicate.
The additional amount of the silicon source is not particularly limited in the present invention, is used to prepare point with well known to those skilled in the art
The silicon source amount of being routinely added to of son sieve, those skilled in the art can want according to practical condition, product requirement and quality
Ask and selected and adjusted, the mass ratio of silicon source of the present invention and the P Modification graphene oxide be preferably (15~
1000): 1, more preferably (20~800): 1, more preferably (25~500): 1, more preferably (35~200): 1, more preferably
(45~100): 1.
Source of aluminium is not particularly limited in the present invention, is used to prepare zeolite molecular sieve with well known to those skilled in the art
Conventional silicon source, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, silicon source of the present invention preferably include sodium aluminate, sodium metaaluminate, boehmite, aluminum sulfate, aluminium chloride and aluminum nitrate
One of or a variety of, more preferably sodium metaaluminate, boehmite, aluminum sulfate, aluminium chloride or aluminum nitrate.
The additional amount of source of aluminium is not particularly limited in the present invention, is used to prepare point with well known to those skilled in the art
The silicon source amount of being routinely added to of son sieve, those skilled in the art can want according to practical condition, product requirement and quality
Ask and selected and adjusted, the molar ratio of silicon source of the present invention and the silicon source is preferably 1:(10~500), more preferably 1:
(50~450), more preferably 1:(150~350), more preferably 1:(200~300).
The template is not particularly limited in the present invention, is used to prepare zeolite molecules with well known to those skilled in the art
Conventional template is sieved, those skilled in the art can carry out according to practical condition, product requirement and quality requirement
Selection and adjustment, template of the present invention preferably include tetrapropylammonium hydroxide, tetraethyl oxyammonia, polybutadiene rubber, tetrem
One of base amine and tetrapropyl ammonium are a variety of, more preferably tetrapropylammonium hydroxide, tetraethyl oxyammonia, polybutadiene rubber, four
One of ethylamine or tetrapropyl ammonium are a variety of, more preferably tetrapropylammonium hydroxide or tetraethyl oxyammonia.
The additional amount of the template is not particularly limited in the present invention, is used to prepare with well known to those skilled in the art
The conventional mould agent additional amount of molecular sieve, those skilled in the art can be according to practical condition, product requirement and matter
Amount requires to be selected and adjusted, and the molar ratio of template of the present invention and the silicon source is preferably 1:(20~300), it is more excellent
It is selected as 1:(70~250), more preferably 1:(120~200).
The concentration of the P Modification graphene oxide solution is not particularly limited in the present invention, ripe with those skilled in the art
The concentration for the graphite alkenes material solution known, those skilled in the art can according to practical condition, product requirement with
And quality requirement is selected and is adjusted, the mass fraction of P Modification graphene oxide solution of the present invention is preferably 0.3%
~8%, more preferably 1%~7%, more preferably 2%~6%, more preferably 3%~5%.
The dispersing method of the P Modification graphene oxide dispersion or source is not particularly limited in the present invention, with ability
The dispersing method of graphene dispersing solution known to field technique personnel or source, those skilled in the art can be according to practical lifes
It produces situation, product requirement and quality requirement to be selected and adjusted, P Modification graphene oxide dispersion of the present invention is excellent
Choosing is obtained after dispersion by P Modification graphene oxide and water.Dispersion of the present invention is preferably ultrasonic disperse processing, more excellent
It is selected as ultrasonic agitation processing.
The time of the dispersion is not particularly limited in the present invention, is with jitter time well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The time of the bright dispersion is preferably 30~240min, more preferably 60~180min, most preferably 90~150min.
The frequency of the ultrasound is not particularly limited in the present invention, is with supersonic frequency well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The frequency of the bright ultrasound is preferably 10~40Hz, more preferably 15~35Hz, most preferably 20~30Hz.
The rate of the stirring is not particularly limited in the present invention, is with stirring rate well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The rate of the bright stirring is preferably 150~450r/min, more preferably 200~400r/min, most preferably 250~350r/
min。
The detailed process that the present invention carries out crystallization to the mixing is not particularly limited, ripe with those skilled in the art
The mixed process known, those skilled in the art can carry out according to practical condition, product requirement and quality requirement
Selection and adjustment, the present invention is to further increase the effect of crystallization, can choose an aforementioned crystallization, can also be preferably
Two crystallizations, guarantee the evenly dispersed of graphite alkenes material, and the mixing carries out the specific steps of crystallization, i.e. step A) tool
Body is preferred are as follows:
A1 it after) mixing P Modification graphene oxide dispersion, silicon source and template for the first time, obtains mixed liquor, carries out the
After one stage crystallization, a step product is obtained；
A2 the step product) obtained to above-mentioned steps is added silicon source and mixes again, after carrying out second stage crystallization, then passes through
Later it handles, obtains powder.
The mode mixed for the first time is not particularly limited in the present invention, with hybrid mode well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
The first mixing is invented to preferably include to be stirred.
The time mixed for the first time is not particularly limited in the present invention, with incorporation time well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
The time that invention mixes for the first time is preferably 30~180min, more preferably 60~120min, most preferably 80~100min.
The design parameter being stirred is not particularly limited in the present invention, with mixing well known to those skilled in the art
Parameter, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the revolving speed of the present invention being stirred is preferably 150~450r/min, more preferably 200~400r/min, most preferably
For 250~350r/min.
The temperature of the first stage crystallization is not particularly limited in the present invention, with crystallization well known to those skilled in the art
Parameter, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the temperature of first stage crystallization of the present invention is preferably 60~120 DEG C, more preferably 70~110 DEG C, more preferably 80
~100 DEG C.
The time of the first stage crystallization is not particularly limited in the present invention, with crystallization well known to those skilled in the art
Parameter, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the time of first stage crystallization of the present invention is preferably 8~for 24 hours, more preferably 12~20h, more preferably 14~
18h。
The mode that silicon source is added is not particularly limited in the present invention, with adding manner well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
The mode that silicon source is added is invented preferably to be slowly added to, it is more specific to be preferably added dropwise.
The mode mixed again is not particularly limited in the present invention, with hybrid mode well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
The invention mixing again preferably includes to be stirred.
The time mixed again is not particularly limited in the present invention, with incorporation time well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
The time that invention mixes again is preferably 30~240min, more preferably 60~180min, most preferably 90~150min.
The design parameter being stirred is not particularly limited in the present invention, with mixing well known to those skilled in the art
Parameter, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the revolving speed of the present invention being stirred is preferably 150~450r/min, more preferably 200~400r/min, most preferably
For 250~350r/min.
The temperature of the second stage crystallization is not particularly limited in the present invention, with crystallization well known to those skilled in the art
Parameter, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the temperature of second stage crystallization of the present invention is preferably 170~200 DEG C, and more preferably 175~195 DEG C, more preferably
180~190 DEG C.
The time of the second stage crystallization is not particularly limited in the present invention, with crystallization well known to those skilled in the art
Parameter, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the time of second stage crystallization of the present invention is preferably 16~72h, more preferably 28~60h, more preferably 30~
48h。
The present invention is to further increase the performance of final products, optimized process flow, is preferably also wrapped after the crystallization
Include post-processing step.
The detailed process of the post-processing step is not particularly limited in the present invention, with it is well known to those skilled in the art this
The conventional post-processing step of class process, those skilled in the art can be according to the condition of production, product requirement and quality requirements
It is selected and is adjusted, post-processing step of the present invention preferably includes one of washing, separation and drying or a variety of, more excellent
It is selected as separation and drying, is specifically as follows suction filtration and drying.The temperature of the drying is preferably 40~120 DEG C, more preferably 60
~100 DEG C, more preferably 70~90 DEG C.
The present invention has obtained the powder of grey black by above-mentioned steps, then will after powder removes template, obtain molecular sieve/
P Modification graphene composite material.
The mode for removing template is not particularly limited in the present invention, with removing mould well known to those skilled in the art
The usual manner of plate agent, those skilled in the art can according to practical condition, product requirement and quality requirement into
Row selection and adjustment, the mode of the present invention for removing template preferably include under alcohols solvent extraction and/or protective atmosphere
Roasting, more preferably roasts under alcohols solvent extraction heat or protective atmosphere.
The temperature of the extraction is not particularly limited in the present invention, with removing template well known to those skilled in the art
Extraction temperature, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, the temperature of extraction of the present invention are preferably 60~160 DEG C, more preferably 80~140 DEG C, more preferably 100~120
℃。
The temperature of the roasting is not particularly limited in the present invention, with removing template well known to those skilled in the art
Maturing temperature, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, the temperature of roasting of the present invention are preferably 400~600 DEG C, more preferably 420~580 DEG C, more preferably 450~
550℃。
The selection of the protective atmosphere is not particularly limited in the present invention, with protectiveness well known to those skilled in the art
Atmosphere, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement
Whole, protective atmosphere described in the present invention preferably includes one of nitrogen, inert gas, hydrogen and ammonia or a variety of.
In the present invention, graphene oxide can also be reduced to stone while removing template agent removing by extraction heat and roasting
Graphene oxide partial reduction can be grapheme material by black alkene material, and the extraction heat process of specific temperature, thus, this
It invents in the molecular sieve/P Modification graphene composite material being prepared, can include graphite alkenes material, that is, there is graphite
Alkene, graphene oxide and redox graphene.
The present invention also provides a kind of molecular sieve described in above-mentioned technical proposal any one/P Modification graphene composite woods
Molecular sieve/P Modification graphene composite material prepared by material or above-mentioned technical proposal any one is in benzene and vinyl alkyl metaplasia
Produce ethylbenzene, benzaldehyde and the condensation reaction of glycerine, the esterification of caproic acid and benzyl alcohol, the methylation reaction of cyclohexanone, first
Benzene and benzyl chloride it is Benzylation react and the condensation reaction of benzaldehyde and 2- hydroxy acetophenone in application.
Molecular sieve, if ZSM-5 molecular sieve has unique microcellular structure, so ZSM-5 molecular sieve is wide as catalyst
It is general to be applied to benzene and ethylene alkylation production ethylbenzene, but micropore also limits the diffusion of molecule in the catalyst.The present invention mentions
The molecular sieve of confession/P Modification graphene composite material not only has the unique microcellular structure of molecular sieve, also compares table with biggish
The advantages that area, shorter duct, diffusional resistance is substantially reduced, therefore the catalytic performance of molecular sieve catalyst can be improved,
Good catalytic activity can be embodied in benzene ethylene alkylated reaction.
Above-mentioned steps of the present invention provide a kind of preparation method of P Modification graphene oxide, molecular sieve/P Modification graphite
Alkene composite material and preparation method, the present invention use the P Modification graphene of particular step preparation, P Modification graphene oxide
The active site for increasing later period graphite alkenes material surface, improves the growth activity of graphite alkenes material surface, Er Qiegeng
Big advantage is that alkalinity is presented in its surface, is conducive to first crystallization stage -- the shape of surface crystal seed of the system with molecular sieve for preparing for during
At the formation of promotion little crystallite size molecular sieve, to substantially increase molecular sieve pore passage diffuser efficiency.The present invention especially will again
P Modification graphene oxide is added at system with molecular sieve for preparing standby initial stage, in molecular sieve preparation process, in-situ reducing, in crystallization mistake
Cheng Zhong, in conjunction with the mode of different template agent removings, is selected so that molecular sieve is directly loaded in the surface of graphite alkenes material
To molecular sieve/P Modification graphite alkenes composite material or molecular sieve/P Modification graphene composite material.
The experimental results showed that molecular sieve prepared by the present invention/P Modification graphene composite material is in benzene ethylene alkylation
Good catalytic effect is shown, the catalytic performance of molecular sieve is effectively raised, is 5% in P Modification graphene additional amount
When, the conversion ratio of ethylene improves 30%, and the selectivity of ethyl is 95% or more.This is because the graphene of P Modification is fine
Induced synthesis nano-ZSM-5 molecular sieve, effectively raise the specific surface area of molecular sieve, improve diffuser efficiency.
In order to further illustrate the present invention, with reference to embodiments to a kind of P Modification graphene oxide provided by the invention
Preparation method, molecular sieve/graphene composite material and preparation method thereof is described in detail, but it is to be understood that these realities
Applying example is to be implemented under the premise of the technical scheme of the present invention, gives detailed embodiment and specifically operated
Journey is only further explanation the features and advantages of the present invention, rather than limiting to the claimed invention, guarantor of the invention
Shield range is also not necessarily limited to following embodiments.
Embodiment 1
1] 3g triphenyl phosphite and 300ml methylene chloride are mixed, after adding the NaOH stirring of 1.5g, is mixed
Object；Then the aqueous dispersions for the graphene oxide containing 1g that mass concentration is 5 ‰ are added, strong stirring, at 40~65 DEG C, heat is returned
Stream reaction 16h, obtains reaction system；
By above-mentioned reaction system after methylene chloride is evaporated off in 60 DEG C of backspins, three times (twice of body is added in eccentric cleaning every time
Ponding), obtain P Modification graphene oxide.
Aqueous solution is dispersed into P Modification graphene oxide prepared by the embodiment of the present invention 1 to characterize.
Referring to metallograph of the P Modification graphene oxide that Fig. 1, Fig. 1 are the preparation of the embodiment of the present invention 1 in water phase.
As shown in Figure 1, P Modification graphene oxide is reunited without obvious, evenly dispersed in water.
EDS energy spectrum analysis detection is carried out to P Modification graphene oxide prepared by the embodiment of the present invention 1.
Referring to fig. 2, Fig. 2 is the EDS energy spectrum diagram of P Modification graphene oxide prepared by the embodiment of the present invention 1.
Referring to table 1, table 1 is each element in the P Modification graphene oxide EDS spectroscopy detection of the preparation of the embodiment of the present invention 1
Content.
Table 1
| Element | Wt% | Wt%Sigma |
| C | 53.76 | 0.46 |
| O | 31.85 | 0.44 |
| Na | 10.47 | 0.17 |
| P | 3.81 | 0.09 |
| Si | 0.12 | 0.04 |
| Tatal: | 100.00 |
2] P Modification graphene oxide slurry (solid content 4%) 6.55g is taken, the dispersion liquid of 5 ‰ concentration is made into.To P Modification
Tetraethyl orthosilicate 20.8g and tetrapropylammonium hydroxide 32.536g is added in graphene oxide dispersion, seals hydro-thermal (oil bath
Under), while stir process, 16h, mixing speed 450r/min obtain mixed liquor A；
3] to step 2] obtained in mixed liquor A after cooling, be added dropwise sodium metaaluminate aqueous solution, silicon source and silicon source are rubbed
Your ratio is 1:50, and mixing speed 450r/min, mixing time 120min obtain mixed liquid B；
4] by step 3] obtained in mixed liquid B carry out hydro-thermal process, temperature obtains in 180 DEG C, mixing speed 450r/min
To mixed liquor C；
5] by step 4] obtained in mixed liquor C carry out suction filtration drying, obtain grey black powder A, 60 DEG C of drying temperature；
6] by step 5] obtained in powder A carry out calcination process under nitrogen atmosphere up to compound point of ZSM-5/ graphene
Sub- sieve catalyst, 550 DEG C of maturing temperature.
Referring to Fig. 3, Fig. 3 is the preparation process flow schematic diagram that the embodiment of the present invention 1 provides.
Molecular sieve/P Modification the graphene composite material prepared to the embodiment of the present invention 1 characterizes.
Referring to fig. 4, Fig. 4 is molecular sieve/P Modification graphene composite material scanning electron microscope prepared by the embodiment of the present invention 1
Photo.
It is the stereoscan photograph of ZSM-5 molecular sieve prepared by same procedure and condition referring to Fig. 5, Fig. 5.
By Fig. 4 and Fig. 5 it is found that molecular sieve/P Modification graphene composite material, molecule has successfully been prepared in the present embodiment
Sieve is successfully supported on P Modification graphene surface, and is evenly distributed.
The molecular sieve prepared to the embodiment of the present invention 1/P Modification graphene composite material carries out Pore Diameter Detection.
It is molecular sieve/P Modification graphene composite material pore-size distribution prepared by the embodiment of the present invention 1 referring to Fig. 6, Fig. 6
Figure.
It will be appreciated from fig. 6 that molecular sieve/P Modification graphene composite material BET specific surface prepared by the embodiment of the present invention 1
Product is 728.78m2/g。
Performance detection is carried out to molecular sieve/P Modification graphene composite material of preparation of the embodiment of the present invention.
Molecular sieve evaluation procedure:
Molecular sieve is needed before using as catalyst through ammonium exchange-activation process.Ammonium exchange system is for H-type nano-ZSM-5 point
Son sieve: compound concentration is the ammonium chloride solution of 0.5mol/L, takes about 20mL solution in three-necked flask, will be passed through made from reaction
It roasts obtained nano molecular sieve and carries out ion exchange under 90 DEG C, the mixing speed of 300r/min, exchange three times, exchanges every time
It 2 hours, filters and is washed with deionized for several times while hot after having exchanged every time, handed over after dry at 110 DEG C next time
It changes.Third time exchanged after, filtrate is examined with silver nitrate solution, washing into filtrate without chloride ion until.Molecule after exchange
Sieve is dried overnight at 110 DEG C, passes through 2 DEG C/min temperature programming to 550 DEG C of high-temperature calcinations, 4 hours removing NH4+, obtain Hydrogen and receive
Rice ZSM-5 molecular sieve.
The above-mentioned Hydrogen nano molecular sieve and binder boehmite powder, mass ratio 3:7 for weighing certain mass are put
Enter in agate mortar, mixes, then make extrusion aid with the nitric acid solution of 0.5mol/L, glue is ground to when extrusion aid is added dropwise
Shape, extrusion are air-dried to be placed in Muffle furnace and be calcined 4 hours at 550 DEG C, obtain molding ZSM-5 molecular sieve and urge at normal temperature
Agent.
Detailed process is as follows for evaluation: reaction temperature is 350 DEG C, system pressure 1MPa, forms nano-ZSM-5 molecular sieve
Amount of fill be 3.0g, quartz sand is filler.It is sequentially loaded into filler, catalyst, filler in the reactor before reaction, must make to urge
Agent is in the flat-temperature zone of reactor.Then make protection gas with N2, the speed purging of 300mL/min, and by vaporizer, preheater
It is warming up to 180,200 and 350 DEG C respectively with reactor, opens the feed pump of benzene, benzene is fed with the speed of 0.5mL/min, is led to
After 20min, nitrogen is closed, opens ethylene, the raw materials components mole ratio of benzene and ethylene is 5.After logical ethylene about 5min, will be with ethylene
System pressure is quickly charged to 1MPa, and after pressure stablizes half an hour, reaction solution is released, and then proceedes to reaction 2h, and pass through electronics
The flow of cmf record ethylene.After completion of the reaction, it is depressured after first termination of pumping, closes ethylene and open nitrogen, blown to system
It sweeps and cools down.Product is analyzed into the amount of benzene and the flow velocity of ethylene, and with gas-chromatography in record 2h.In reaction product
The content of benzene, ethylbenzene and diethylbenzene is both needed to be measured by gas-chromatography, passes through peak area and internal standard method (internal standard compound is normal heptane)
Mass Calculation obtains.
Referring to table 2, table 2 is the molecular sieve/P Modification graphene composite material and blank ZSM-5 of preparation of the embodiment of the present invention
Catalytic activity of the molecular sieve in benzene ethylene alkylated reaction.
Table 2
| Sample serial number | Graphene content | Conversion of ethylene (%) | Ethyl selectivity (%) |
| Blank ZSM-5 | 0% | 50.4 | 91.2 |
| Embodiment 1 | 5% | 65.6 | 95.5 |
| Embodiment 2 | 10% | 55.8 | 93.1 |
| Embodiment 3 | 20% | 44.3 | 92.1 |
As shown in Table 2, molecular sieve prepared by the present invention/P Modification graphene composite material is in benzene ethylene alkylated reaction
In embody good catalytic activity.
Embodiment 2
1] P Modification graphene oxide slurry (solid content 4%) 13.1g prepared by Example 1 is made into point of 5 ‰ concentration
Dispersion liquid.Tetraethyl orthosilicate 20.8g and tetrapropylammonium hydroxide 32.536g is added into P Modification graphene oxide dispersion,
It seals hydro-thermal (under oil bath), while stir process, 16h, mixing speed 450r/min obtain mixed liquor A；
2] to step 2] obtained in mixed liquor A after cooling, be added dropwise sodium metaaluminate aqueous solution, silicon source and silicon source are rubbed
Your ratio is 1:50, and mixing speed 450r/min, mixing time 120min obtain mixed liquid B；
3] by step 3] obtained in mixed liquid B carry out hydro-thermal process, temperature obtains in 180 DEG C, mixing speed 450r/min
To mixed liquor C；
4] by step 4] obtained in mixed liquor C carry out suction filtration drying, obtain grey black powder A, 60 DEG C of drying temperature；
5] by step 5] obtained in powder A carry out calcination process under nitrogen atmosphere up to compound point of ZSM-5/ graphene
Sub- sieve catalyst, 550 DEG C of maturing temperature.
Molecular sieve/P Modification the graphene composite material prepared to the embodiment of the present invention 2 characterizes.
It is molecular sieve/P Modification graphene composite material scanning electron microscope prepared by the embodiment of the present invention 2 referring to Fig. 7, Fig. 7
Photo.
Molecular sieve/P Modification graphene composite material of preparation of the embodiment of the present invention is detected.
Referring to table 2, table 2 is the molecular sieve/P Modification graphene composite material and blank ZSM-5 of preparation of the embodiment of the present invention
Catalytic activity of the molecular sieve in benzene ethylene alkylated reaction.
Embodiment 3
1] P Modification graphene oxide slurry (solid content 4%) 26.2g for taking Example 1 to prepare, is made into 5 ‰ concentration
Dispersion liquid.Tetraethyl orthosilicate 20.8g and tetrapropylammonium hydroxide are added into P Modification graphene oxide dispersion
32.536g is sealed hydro-thermal (under oil bath), while stir process, 16h, mixing speed 450r/min obtain mixed liquor A；
2] to step 2] obtained in mixed liquor A after cooling, be added dropwise sodium metaaluminate aqueous solution, silicon source and silicon source are rubbed
Your ratio is 1:50, and mixing speed 450r/min, mixing time 120min obtain mixed liquid B；
3] by step 3] obtained in mixed liquid B carry out hydro-thermal process, temperature obtains in 180 DEG C, mixing speed 450r/min
To mixed liquor C；
4] by step 4] obtained in mixed liquor C carry out suction filtration drying, obtain grey black powder A, 60 DEG C of drying temperature；
5] by step 5] obtained in powder A carry out calcination process under nitrogen atmosphere up to compound point of ZSM-5/ graphene
Sub- sieve catalyst, 550 DEG C of maturing temperature.
Molecular sieve/P Modification the graphene composite material prepared to the embodiment of the present invention 3 characterizes.
It is molecular sieve/P Modification graphene composite material scanning electron microscope prepared by the embodiment of the present invention 3 referring to Fig. 8, Fig. 8
Photo.
Molecular sieve/P Modification graphene composite material of preparation of the embodiment of the present invention is detected.
Referring to table 2, table 2 is the molecular sieve/P Modification graphene composite material and blank ZSM-5 of preparation of the embodiment of the present invention
Catalytic activity of the molecular sieve in benzene ethylene alkylated reaction.
Above to a kind of preparation method of P Modification graphene oxide provided by the invention, molecular sieve/P Modification graphene
Composite material and preparation method is described in detail, and specific case used herein is to the principle of the present invention and implementation
Mode is expounded, and the above description of the embodiment is only used to help understand the method for the present invention and its core ideas, including
Best mode, and but also any person skilled in the art can practice the present invention, including any dress of manufacture and use
It sets or system, and implements the method for any combination.It should be pointed out that for those skilled in the art, not
, can be with several improvements and modifications are made to the present invention under the premise of being detached from the principle of the invention, these improvement and modification are also fallen into
In the protection scope of the claims in the present invention.The range of the invention patent protection is defined by the claims, and may include this
Field technical staff it is conceivable that other embodiments.If these other embodiments, which have, is not different from claim text
The structural element of statement, or if they include the equivalent structural elements with the character express of claim without essence difference,
So these other embodiments should also be included in the scope of the claims.
Claims (10)
1. a kind of preparation method of P Modification graphene oxide, which comprises the following steps:
1) after mixing phosphorus source, alkali and organic solvent, mixture is obtained；
2) mixture obtained to above-mentioned steps is reacted after graphene oxide water solution is added, and after post-processing, is obtained phosphorus and is changed
Property graphene oxide.
2. preparation method according to claim 1, which is characterized in that phosphorus source includes triphenyl phosphite, phosphorous acid
One of triethyl, sodium phosphite, potassium phosphite, phosphorous acid, Trimethyl phosphite and triisopropyl phosphite are a variety of；
The alkali includes one of sodium hydroxide solution, potassium hydroxide solution and ammonium hydroxide or a variety of；
The organic solvent include methylene chloride, ethyl alcohol, acetone, ethyl alcohol, isopropanol, toluene, dimethylbenzene, n-butanol, isobutanol,
One of ethylene glycol and glycerine are a variety of；
The mass concentration of the graphene oxide water solution is 0.1%~0.9%；
The organic solvent and the mass ratio of the graphene oxide water solution are (1~100): 1；
The mass ratio of phosphorus source and the graphene oxide is (0.5~20): 1.
3. a kind of molecular sieve/P Modification graphene composite material, which is characterized in that including P Modification graphite alkenes material；
And it is compounded in the molecular sieve of the P Modification graphite alkenes material surface.
4. composite material according to claim 3, which is characterized in that the partial size of the molecular sieve is 50~500nm；
The mesopore diameter of the molecular sieve is 2~10nm；
The piece diameter of the P Modification graphite alkenes material is 10~30 μm.
5. composite material according to claim 1, which is characterized in that the matter of the graphite alkenes material and the molecular sieve
Amount is than being 1:(15~300)；
The graphite alkenes material includes one of graphene, graphene oxide and redox graphene or a variety of；
The molecular sieve includes one of type ZSM 5 molecular sieve, ZSM-11 type molecular sieve, beta molecular sieve and HY type molecular sieve
Or it is a variety of.
6. a kind of molecular sieve/P Modification graphene composite material preparation method, which comprises the following steps:
A) P Modification graphene oxide dispersion, silicon source, template and silicon source are mixed after carrying out crystallization, using rear place
Reason, obtains powder；
B after) powder for obtaining above-mentioned steps removes template, molecular sieve/P Modification graphene composite material is obtained.
7. preparation method according to claim 6, which is characterized in that the molar ratio of the template and the silicon source is 1:
(20~300)；
The mass concentration of the P Modification graphene oxide dispersion is 0.3%~8%；
The mass ratio of the silicon source and the P Modification graphene oxide is (15~1000): 1；
The molar ratio of source of aluminium and the silicon source is 1:(10~500).
8. preparation method according to claim 6, which is characterized in that the step A) specifically:
A1 after) mixing P Modification graphene oxide dispersion, silicon source and template for the first time, mixed liquor is obtained, carries out the first rank
After Duan Jinghua, a step product is obtained；
A2 the step product) obtained to above-mentioned steps is added silicon source and mixes again, after carrying out second stage crystallization, using rear
Processing, obtains powder；
The silicon source includes one in tetraethyl orthosilicate, positive tetrabutyl silicate, white carbon black, waterglass, silica solution and sodium metasilicate
Kind is a variety of；
Source of aluminium includes one of sodium aluminate, sodium metaaluminate, boehmite, aluminum sulfate, aluminium chloride and aluminum nitrate or more
Kind；
The template includes tetrapropylammonium hydroxide, in tetraethyl oxyammonia, polybutadiene rubber, tetraethyl amine and tetrapropyl ammonium
It is one or more.
9. preparation method according to claim 8, which is characterized in that the temperature of the first stage crystallization is 60~120
℃；The time of the first stage crystallization be 8~for 24 hours；
The temperature of the second stage crystallization is 170~200 DEG C；The time of the second stage crystallization is 16~72h；
The time mixed for the first time is 30~180min；The time mixed again is 30~240min.
10. preparation method according to claim 8, which is characterized in that the post-processing includes in washing, separation and drying
It is one or more；
The mode for removing template includes alcohols solvent extraction and/or roasting；
The temperature of the extraction is 60~160 DEG C；
The temperature of the roasting is 400~600 DEG C.
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|---|---|---|---|---|
| CN112503494A (en) * | 2020-10-30 | 2021-03-16 | 江西森通新材料科技有限公司 | Radiating fin for LED radiator and preparation method thereof |
| CN114590818A (en) * | 2022-02-25 | 2022-06-07 | 厦门大学 | Lamellar MOR molecular sieve, preparation method thereof, catalyst for preparing ethanol by using synthesis gas and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864057A (en) * | 2012-12-07 | 2014-06-18 | 北京大学 | Phosphor-doped graphene, its preparation method and its application |
| CN106475131A (en) * | 2016-10-11 | 2017-03-08 | 中国科学院山西煤炭化学研究所 | A kind of Graphene/molecular sieve composite catalyst and preparation method thereof |
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- 2017-10-16 CN CN201710958363.XA patent/CN109663606A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864057A (en) * | 2012-12-07 | 2014-06-18 | 北京大学 | Phosphor-doped graphene, its preparation method and its application |
| CN106475131A (en) * | 2016-10-11 | 2017-03-08 | 中国科学院山西煤炭化学研究所 | A kind of Graphene/molecular sieve composite catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112503494A (en) * | 2020-10-30 | 2021-03-16 | 江西森通新材料科技有限公司 | Radiating fin for LED radiator and preparation method thereof |
| CN112503494B (en) * | 2020-10-30 | 2023-05-23 | 裕鑫丰(广东)照明科技有限公司 | Radiating fin for LED radiator and preparation method thereof |
| CN114590818A (en) * | 2022-02-25 | 2022-06-07 | 厦门大学 | Lamellar MOR molecular sieve, preparation method thereof, catalyst for preparing ethanol by using synthesis gas and method |
| CN114590818B (en) * | 2022-02-25 | 2023-08-08 | 厦门大学 | Lamellar MOR molecular sieve and preparation method thereof, catalyst for preparing ethanol by using synthesis gas and preparation method thereof |
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Application publication date: 20190423 |