CN106824296A - A kind of porous graphene zeolite molecular sieve catalyst carrier and preparation method thereof - Google Patents
A kind of porous graphene zeolite molecular sieve catalyst carrier and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 96
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 75
- 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 75
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 68
- 239000010457 zeolite Substances 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- 239000012467 final product Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000012153 distilled water Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 230000004913 activation Effects 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- -1 graphite alkene Chemical class 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method of porous graphene zeolite molecular sieve catalyst carrier, comprise the following steps：(1) zeolitic molecular sieve particle that will have been activated carries out hydro-thermal reaction with the mixture of graphene suspension in hydrothermal reaction kettle；(2) mixture after hydro-thermal reaction filtered, dried, obtained final product porous graphene zeolite molecular sieve catalyst carrier.Preparation method of the invention, it is ensured that the porosity of zeolite molecular sieve, this can lift the effect of gas absorption and separation hole in chemical reaction, and then be conducive to efficiently carrying out for catalytic reaction.
Description
Technical field
The present invention relates to catalyst carrier synthesis field, more particularly to a kind of porous graphene-Zeolite molecular sieve catalysis
Agent carrier and preparation method thereof.
Background technology
Catalyst carrier, also known as carrier, is one of composition of loaded catalyst.Catalyst loading is carried on carrier surface
Body is mainly used in support catalyst, catalyst is had specific physical behavior, and carrier is general in itself and is lived without catalysis
Property.Majority carrier is the product in Catalyst, it is conventional have alumina support, silica-gel carrier, absorbent charcoal carrier and some
Natural products such as float stone, diatomite etc..
Preparing the method for series catalyst agent carrier at this stage mainly has direct-templating synthesis, Self-Assembling of Block Copolymer method, straight
It is bonded into method.
Direct-templating synthesis, including the synthesis, the conversion of the loading, presoma of presoma and template of template four mistakes of removing
Journey.The method will seek template, and preparation is easy, and the most frequently used templated silicas are prepared by the wet chemical etch of HF or NaOH.
Self-Assembling of Block Copolymer method, is primarily adapted for use in long-range order material, and microphase-separated is triggered by incompatible block
So as to produce Mesoscale Structure, and then obtain catalyst carrier.It is bamboo material that the method is mainly with macromolecular compound, is combined with
Machine solvent, through phase separation, poromerics obtains final product catalyst carrier.
Direct synthesis technique, refers to that hole is directly produced in solution polymerization process, and the solvent in hole is then removed again, obtains final product and urges
Agent carrier.
The method of above-mentioned traditional preparation catalyst carrier, proposes the preparation of composite molecular screen material in terms of different
Technology.But there are the following problems --- the above method all refers to a large amount of chemical reagent, if the excessive reagent fails to remove completely,
The exposure of meeting interfering material active site, the carrying out of disturbing reaction influences the product and yield of reaction.
In addition, the material such as the most common active charcoal of adsoption catalysis agent carrier and silica gel, although these inorganic material costs
Cheaply, simple, pollution and interference also in the absence of substantial amounts of chemical reagent are prepared.But their specific surface areas are smaller, thus it is carried
The attachment site of the catalyst of confession is limited, and be available for attachment catalyst type it is few, this causes adsoption catalysis agent carrier application surface
It is narrow.
The content of the invention
Based on this, it is an object of the present invention to provide a kind of porous graphene-zeolite molecular sieve catalyst carrier and its system
Preparation Method, which overcomes the chemical contamination problem in conventional catalyst support preparation process.
A kind of preparation method of porous graphene-zeolite molecular sieve catalyst carrier, comprises the following steps：
(1) zeolitic molecular sieve particle that will have been activated enters water-filling with the mixture of graphene suspension in hydrothermal reaction kettle
Thermal response；
(2) mixture after hydro-thermal reaction filtered, dried, obtained final product porous graphene-zeolite molecular sieve catalyst
Carrier.
The zeolitic molecular sieve particle for having activated has substantial amounts of hole, and the shapes and sizes of hole are various, and this is easy to
Zeolite molecular sieve adsorbs Graphene.Graphene has that physical and chemical stability is high, mass density is low and the characteristic such as hydrophobicity, thus
The long lifespan of the porous graphene of synthesis-zeolite molecular sieve catalyst carrier, and the temperature change come by exothermic/endothermic reaction zone
Influence it is small, thus in catalytic reaction have practical value very high.Preparation method of the invention, is not introduced into organic solvent,
The porosity of zeolite molecular sieve is ensure that, this can lift the effect of gas absorption and separation hole in chemical reaction, and then favorably
In efficiently carrying out for catalytic reaction.In addition, the preparation method letter of porous graphene of the invention-zeolite molecular sieve catalyst carrier
List is easy, and the chemical reagent for using is few, washing is abundant, and the chemical contamination overcome in conventional catalyst support preparation process is asked
Topic, and the porous graphene-zeolite molecular sieve catalyst carrier property for preparing is excellent.
Further, in step (1), the reaction temperature of hydro-thermal reaction is 50 DEG C~70 DEG C, and the reaction time is 8~12 small
When.The reaction temperature and time, be conducive to the hole that Graphene is quick, be sufficiently adhering to zeolitic molecular sieve particle.
Further, in step (1), zeolitic molecular sieve particle is 1 with the mass ratio of graphene suspension:4~1:10.Should
Quality proportioning, advantageously forms the zeolitic molecular sieve particle of appropriate Graphene adhesive rate.
Further, in step (1), the concentration of the graphene suspension is 0.1g/L~1g/L.
Further, in step (1), a diameter of 40 mesh~60 mesh of zeolitic molecular sieve particle.The zeolite molecules of the particle diameter
Sieve particle, comparative surface area is larger, and the hole for being formed is suitable to adsorb Graphene.
Further, in step (1), the zeolitic molecular sieve particle for having activated is obtained as follows：
A, zeolite granular is soaked successively with acid solution, aqueous slkali, stir process；
B, soda acid is processed with distilled water after zeolite granular rinse to neutrality, obtain final product the zeolite molecular sieve for having activated
Grain.
The active zeolite molecular sieve preparation method is not introduced into organic solvent, it is ensured that the hole of the zeolite molecular sieve of activation
Rate.
Further, in step (1), graphene suspension is obtained as follows：
A, graphene oxide powder is placed in distilled water, obtains graphene aqueous solution, it is then water-soluble to the Graphene
Liquid carries out ultrasonically treated；
B, will be ultrasonically treated after graphene aqueous solution heated, then the graphene aqueous solution after heating was carried out
Filter, wash and dry, obtain Graphene；
C, obtained Graphene is mixed with sodium hydroxide powder, then Graphene is put with the mixture of sodium hydroxide powder
Heated in inert gas environment；
D, the Graphene and the mixture of NaOH after heating are washed to neutrality with distilled water；It is sonicated again,
Obtain final product graphene suspension.
The Graphene aaerosol solution preparation method is washed using only chemical reagent NaOH by abundant, thus is avoided
Graphene aaerosol solution is polluted by chemical reagent.
Further, in step c, Graphene is 2 with the mass ratio of sodium hydroxide powder:1~8:1.
Further, in step c, the condition of heating is that heating rate is 3 DEG C/min~5 DEG C/min, then at 550 DEG C
~650 DEG C are kept for 2.5 hours~3.5 hours.
In addition, the present invention also provides a kind of porous graphene-zeolite molecular sieve catalyst carrier, it passes through of the present invention
Porous graphene-zeolite molecular sieve catalyst carrier preparation method be obtained.
For the porous graphene-zeolite molecular sieve catalyst carrier, the chemical reagent that its building-up process is used is few, and
By fully washing, thus this hole Graphene-zeolite molecular sieve catalyst carrier can reduce what catalyst carrier residue brought
Pollution.The Graphene is conducive to combining organic catalyst and providing organic catalyst reaction site, and the molecular sieve is then gold
Category ionic catalyst provides wide attachment platform, thus described porous graphene-Zeolite molecular sieve catalysis carrier can provide
The attachment site of catalyst needed for various reactions, by after repetitious attachment-desorption, adhesive force of the carrier to catalyst
Remain to keep level higher.By this catalytic carrier be used for Various Complex reaction in, can improve reaction conversion ratio while,
The consumption of catalyst is advantageously reduced, the cost of chemical reaction is reduced.
Specific embodiment
The present invention is explained further below in conjunction with specific embodiment, but embodiment does not do any type of limit to invention
It is fixed.
Embodiment 1
The present embodiment provides a kind of method for preparing porous graphene-zeolite molecular sieve catalyst carrier, specifically include as
Lower step.
Step (1) prepares the zeolitic molecular sieve particle of activation：With the hydrochloric acid of 1mol/L, 1mol/L sodium hydroxide solution according to
Secondary that 40 commercially available mesh zeolite granulars are carried out with immersion treatment, soak time is 12 hours, and mechanical agitation simultaneously；Then again with steaming
The zeolite granular that distilled water is rinsed after the hydrochloric acid and sodium hydroxide solution treatment is remained to neutrality to remove the zeolite granular
Hydrochloric acid and NaOH, obtain final product 40 mesh zeolitic molecular sieve particles of activation.
Zeolite is a kind of aluminium silicate mineral containing water rack-like structure, and zeolite loses during activation to be existed originally
The crystallization water, thus form many cavitys of different sizes in zeolite after activation, wherein some apertures are in molecular level, thus
Zeolite after activation is otherwise known as the zeolite molecular sieve of activation.
Step (2) prepares graphene suspension：Commercially available graphite oxide powder is placed in distilled water, Graphene water is obtained
Solution, is then carried out ultrasonically treated 24 hours, with dispersed graphite alkene to graphene aqueous solution；By the graphene aqueous solution after ultrasound
It is placed in and is heated in micro-wave oven 40 minutes, after then the graphene aqueous solution filtering after heating, washing, drying, obtains Graphene；
By obtained Graphene and NaOH powder m in mass ratio (NaOH)：M (Graphene)=2：1 mixing, then the mixture is placed in pipe
Heated in formula stove and under helium protection, heating condition is：3 DEG C/min of heating rate, after being warming up to 550 DEG C, constant temperature keeps
3.5 hours；The Graphene after heating and NaOH mixture of powders are washed to neutrality with distilled water, to remove NaOH, then adds steaming
Distilled water causes that the concentration of Graphene is 1g/L, causes within last ultrasonically treated 6 hours that Graphene is dispersed in distilled water, i.e.,
Obtain graphene suspension.
Step (3) prepares porous graphene-zeolite molecular sieve catalyst carrier：Prepared by step (1) activated 40
The graphene suspension that mesh zeolitic molecular sieve particle is prepared with step (2) mixes, and the mass ratio of mixing is m (zeolite molecular sieve)：m
(graphene suspension)=1:4；Then zeolitic molecular sieve particle and graphene suspension mixture are placed in hydrothermal reaction kettle
Hydro-thermal reaction is carried out, hydrothermal reaction condition is that 50 DEG C of constant temperature are kept for 12 hours；Finally the mixture after hydro-thermal reaction is filtered, is done
After dry, porous graphene-zeolite molecular sieve catalyst carrier is obtained final product.
In the present embodiment, the zeolitic molecular sieve particle for having activated has a substantial amounts of hole, and hole shapes and sizes
Various, this is easy to zeolite molecular sieve to adsorb Graphene.Graphene has that physical and chemical stability is high, mass density is low and hydrophobicity
Etc. characteristic, thus the porous graphene-zeolite molecular sieve catalyst carrier of synthesis long lifespan, and by exothermic/endothermic reaction zone
The influence of the temperature change come is small, thus has practical value very high in catalytic reaction.The preparation method of the present embodiment, not
Introduce organic solvent, it is ensured that the porosity of zeolite molecular sieve, this can lift gas absorption and separation hole in chemical reaction
Effect, and then be conducive to efficiently carrying out for catalytic reaction.In addition, the preparation method of the present embodiment is simple and easy to apply, the chemistry for using
Reagent is few, overcomes the chemical contamination problem in conventional catalyst support preparation process, and the porous graphene-zeolite point for preparing
Sub- sieve catalyst carrier property is excellent.
Embodiment 2
The present embodiment provides another method for preparing porous graphene-zeolite molecular sieve catalyst carrier, specifically includes
Following steps.
Step (1) prepares the zeolitic molecular sieve particle of activation：With the hydrochloric acid of 1mol/L, 1mol/L sodium hydroxide solution according to
Secondary that 60 commercially available mesh zeolite granulars are carried out with immersion treatment, soak time is 20 hours, and mechanical agitation simultaneously；Then again with steaming
The zeolite granular that distilled water is rinsed after the hydrochloric acid and sodium hydroxide solution treatment is remained to neutrality to remove the zeolite granular
Hydrochloric acid and NaOH, obtain final product 60 mesh zeolitic molecular sieve particles of activation.
Step (2) prepares graphene suspension：Commercially available graphite oxide powder is placed in distilled water, Graphene water is obtained
Solution, is then carried out ultrasonically treated 24 hours, with dispersed graphite alkene to graphene aqueous solution；By the graphene aqueous solution after ultrasound
It is placed in and is heated in micro-wave oven 40 minutes, after then the graphene aqueous solution filtering after heating, washing, drying, obtains Graphene；
By obtained Graphene and NaOH powder m in mass ratio (NaOH)：M (Graphene)=8：1 mixing, then the mixture is placed in pipe
Heated in formula stove and under helium protection, heating condition is：4 DEG C/min of heating rate, after being warming up to 650 DEG C, constant temperature keeps
2.5 hours；The Graphene after heating and NaOH mixture of powders are washed to neutrality with distilled water, to remove NaOH, then adds steaming
Distilled water causes that the concentration of Graphene is 0.5g/L, causes within last ultrasonically treated 6 hours that Graphene is dispersed in distilled water, i.e.,
Obtain graphene suspension.
Step (3) prepares porous graphene-zeolite molecular sieve catalyst carrier：Prepared by step (1) activated 60
The graphene suspension that mesh zeolitic molecular sieve particle is prepared with step (2) mixes, and the mass ratio of mixing is m (zeolite molecular sieve)：m
(graphene suspension)=1:4；Then zeolitic molecular sieve particle and graphene suspension mixture are placed in hydrothermal reaction kettle
Hydro-thermal reaction is carried out, hydrothermal reaction condition is that 70 DEG C of constant temperature are kept for 8 hours；Finally the mixture after hydro-thermal reaction is filtered, is done
After dry, porous graphene-zeolite molecular sieve catalyst carrier is obtained final product.
Embodiment 3
The present embodiment provides the method that another prepares porous graphene-zeolite molecular sieve catalyst carrier, specifically includes
Following steps.
Step (1) prepares the zeolitic molecular sieve particle of activation：With the hydrochloric acid of 1mol/L, 1mol/L sodium hydroxide solution according to
Secondary that 40 commercially available mesh zeolite granulars are carried out with immersion treatment, soak time is 24 hours, and mechanical agitation simultaneously；Then again with steaming
The zeolite granular that distilled water is rinsed after the hydrochloric acid and sodium hydroxide solution treatment is remained to neutrality to remove the zeolite granular
Hydrochloric acid and NaOH, obtain final product 40 mesh zeolitic molecular sieve particles of activation.
Step (2) prepares graphene suspension：Commercially available graphite oxide powder is placed in distilled water, Graphene water is obtained
Solution, is then carried out ultrasonically treated 24 hours, with dispersed graphite alkene to graphene aqueous solution；By the graphene aqueous solution after ultrasound
It is placed in and is heated in micro-wave oven 40 minutes, after then the graphene aqueous solution filtering after heating, washing, drying, obtains Graphene；
By obtained Graphene and NaOH powder m in mass ratio (NaOH)：M (Graphene)=2：1 mixing, then the mixture is placed in pipe
Heated in formula stove and under helium protection, heating condition is：5 DEG C/min of heating rate, after being warming up to 600 DEG C, constant temperature keeps 3
Hour；The Graphene after heating and NaOH mixture of powders are washed to neutrality with distilled water, to remove NaOH, then adds distilled water
So that the concentration of Graphene is 0.1g/L, cause within last ultrasonically treated 6 hours that Graphene is dispersed in distilled water, obtains final product stone
Black alkene suspension.
Step (3) prepares porous graphene-zeolite molecular sieve catalyst carrier：Prepared by step (1) activated 40
The graphene suspension that mesh zeolitic molecular sieve particle is prepared with step (2) mixes, and the mass ratio of mixing is m (zeolite molecular sieve)：m
(graphene suspension)=1:10；Then zeolitic molecular sieve particle and graphene suspension mixture are placed in hydrothermal reaction kettle
Hydro-thermal reaction is carried out, hydrothermal reaction condition is that 60 DEG C of constant temperature are kept for 10 hours；Finally the mixture after hydro-thermal reaction is filtered, is done
After dry, porous graphene-zeolite molecular sieve catalyst carrier is obtained final product.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Scope.
Claims (10)
1. a kind of preparation method of porous graphene-zeolite molecular sieve catalyst carrier, comprises the following steps：
(1) that hydro-thermal is carried out in hydrothermal reaction kettle with the mixture of graphene suspension is anti-for the zeolitic molecular sieve particle that will have been activated
Should；
(2) mixture after hydro-thermal reaction filtered, dried, obtained final product porous graphene-zeolite molecular sieve catalyst carrier.
2. the preparation method of porous graphene according to claim 1-zeolite molecular sieve catalyst carrier, its feature exists
In：In step (1), the reaction temperature of hydro-thermal reaction is 50 DEG C~70 DEG C, and the reaction time is 8~12 hours.
3. the preparation method of porous graphene according to claim 1-zeolite molecular sieve catalyst carrier, its feature exists
In：In step (1), zeolitic molecular sieve particle is 1 with the mass ratio of graphene suspension:4~1:10.
4. the preparation method of porous graphene according to claim 1-zeolite molecular sieve catalyst carrier, its feature exists
In：In step (1), the concentration of the graphene suspension is 0.1g/L~1g/L.
5. the preparation method of porous graphene according to claim 1-zeolite molecular sieve catalyst carrier, its feature exists
In：In step (1), a diameter of 40 mesh~60 mesh of zeolitic molecular sieve particle.
6. the preparation method of porous graphene according to claim 1-zeolite molecular sieve catalyst carrier, its feature exists
In：In step (1), the zeolitic molecular sieve particle for having activated is obtained as follows：
A, zeolite granular is soaked successively with acid solution, aqueous slkali, stir process；
B, soda acid is processed with distilled water after zeolite granular rinse to neutrality, obtain final product the zeolitic molecular sieve particle for having activated.
7. the preparation method of porous graphene according to claim 1-zeolite molecular sieve catalyst carrier, its feature exists
In：In step (1), graphene suspension is obtained as follows：
A, graphene oxide powder is placed in distilled water, obtains graphene aqueous solution, then the graphene aqueous solution is entered
Row is ultrasonically treated；
B, will be ultrasonically treated after graphene aqueous solution heated, then the graphene aqueous solution after heating is filtered,
Wash and dry, obtain Graphene；
C, obtained Graphene is mixed with sodium hydroxide powder, then Graphene and the mixture of sodium hydroxide powder are placed in lazy
Heated in property gaseous environment；
D, the Graphene and the mixture of NaOH after heating are washed to neutrality with distilled water；It is sonicated again, obtain final product
Graphene suspension.
8. the preparation method of porous graphene according to claim 7-zeolite molecular sieve catalyst carrier, its feature exists
In：In step c, Graphene is 2 with the mass ratio of sodium hydroxide powder:1~8:1.
9. the preparation method of porous graphene according to claim 7-zeolite molecular sieve catalyst carrier, its feature exists
In：In step c, the condition of heating is that heating rate is 3 DEG C/min~5 DEG C/min, then keeps 2.5 at 550 DEG C~650 DEG C
Hour~3.5 hours.
10. porous graphene-zeolite point that prepared by the preparation method as described in any one claim in claim 1~9
Sub- sieve catalyst carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611256382.XA CN106824296A (en) | 2016-12-30 | 2016-12-30 | A kind of porous graphene zeolite molecular sieve catalyst carrier and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108905966A (en) * | 2018-07-09 | 2018-11-30 | 山东利特纳米技术有限公司 | A kind of preparation method and application of graphene oxide-zeolite moulding material |
| CN116675300A (en) * | 2023-07-18 | 2023-09-01 | 广东省农业科学院设施农业研究所 | Dual-circuit ammonia nitrogen removal method for industrial circulating water culture |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102897751A (en) * | 2012-08-28 | 2013-01-30 | 常州第六元素材料科技股份有限公司 | Method for preparing graphene with high specific surface activity |
| CN103123869A (en) * | 2012-11-28 | 2013-05-29 | 华中科技大学 | Method used for preparing nano titanium dioxide-graphene composite material provided with three-dimensional multi-hole structure and products |
-
2016
- 2016-12-30 CN CN201611256382.XA patent/CN106824296A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102897751A (en) * | 2012-08-28 | 2013-01-30 | 常州第六元素材料科技股份有限公司 | Method for preparing graphene with high specific surface activity |
| CN103123869A (en) * | 2012-11-28 | 2013-05-29 | 华中科技大学 | Method used for preparing nano titanium dioxide-graphene composite material provided with three-dimensional multi-hole structure and products |
Non-Patent Citations (1)
| Title |
|---|
| YANG YU ET AL: "Benzene carboxylic acid derivatized graphene oxide nanosheets on natural zeolites as effective adsorbents for cationic dye removal", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108905966A (en) * | 2018-07-09 | 2018-11-30 | 山东利特纳米技术有限公司 | A kind of preparation method and application of graphene oxide-zeolite moulding material |
| CN116675300A (en) * | 2023-07-18 | 2023-09-01 | 广东省农业科学院设施农业研究所 | Dual-circuit ammonia nitrogen removal method for industrial circulating water culture |
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