CN106362691A - Method for preparing graphene oxide/molecular sieve composite adsorption material - Google Patents
Method for preparing graphene oxide/molecular sieve composite adsorption material Download PDFInfo
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- CN106362691A CN106362691A CN201610928925.1A CN201610928925A CN106362691A CN 106362691 A CN106362691 A CN 106362691A CN 201610928925 A CN201610928925 A CN 201610928925A CN 106362691 A CN106362691 A CN 106362691A
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
A method for preparing a graphene oxide / molecular sieve composite adsorption material, relates to the technical field of adsorption material preparations. A composite material with different content of graphene oxide is simply and rapidly prepared by using a graphene oxide solution and molecular sieve through chemical actions under hydrothermal conditions, and the synergistic effects of the graphene oxide solution and the molecular sieve are used for improving the capacity of adsorption on pollutants.
Description
Technical field
The present invention relates to the preparing technical field of adsorbing material, particularly by molecular sieve and graphene oxide formed new
The preparation method of composite adsorbing material.
Background technology
Waste water from dyestuff is one of industrial wastewater difficult to deal with of currently generally acknowledging both at home and abroad, and is removing the various of pollutant
In technique, the method that adsorption technology is widely regarded as the most purified water of future.Activated carbon class, nanofiber, adsorbent resin,
The adsorbing materials such as CNT are because synthesis material is single, preparation cost is high, bad mechanical strength and the factor such as granule is uneven
Limit its practical application.Therefore, exploitation is simple, recyclable and the high adsorbent of adsorption capacity is significant.
Molecular sieve has as adsorbent that adsorptive selectivity is good, Stability Analysis of Structures, easily regeneration and cheap, environmental protection etc.
Feature, is widely used in adsorbing domain.But single molecular sieve is not high to the adsorption efficiency of Organic substance.In recent years, molecule
Sieve composite adsorbing material initially enters greatly our visual field due to its adsorbance.Liu etc. reports a kind of new modified zeolite/tri-
First EP rubbers composite, the results show modified zeolite/ethylene propylene diene rubber is to cr6+Equilibrium adsorption capacity be far longer than
Natural zeolite and sour modified zeolite [liu x q, xing h q. preparation and cr6+adsorption
property of zeolite/epdm composite[j]. advanced materials research, 2012,
347-353: 2044-2047.].
Graphene oxide is the Novel Carbon Nanomaterials of excellent performance, has high mechanical strength, stable chemical nature, compares table
Area is big to wait outstanding advantages, and the carbonyl that enriches of the hydroxyl that enriches of graphene oxide bottom surface and epoxy-functional and edge and
Carboxyl functional group is conducive to synthesizing graphite alkene composite.In recent years, many scholars also began to study Graphene and its composite wood
Application in water process for the material.Ai etc. is prepared for graphene oxide/CNT (g-cnt) composite using hydro-thermal method, and
Have studied its adsorption effect to aqueous solution of methylene blue, it is demonstrated experimentally that maximal absorptive capacity on g-cnt for the methylene blue up to
81.97 mg/g, and when methylene blue initial concentration is 10 mg/l, removal efficiency is 97% [ai l, jiang j.
removal of methylene blue from aqueous solution with self-assembled
cylindrical rapheme–carbon nanotube hybrid[j]. chemical engineering journal,
2012, 192(2):156-163.].
Although molecular sieve adsorption material has the dye adsorption ability of preferable micro-concentrations, adsorption capacity is relative to material with carbon element
Less, regeneration is more frequent；Although and graphene oxide has good adsorption capacity, for the dye molecule of micro-concentrations
Absorbability is weaker, and cost is too high, and invention can remove micro-concentrations dye molecule and have the suction compared with high-adsorption-capacity again
Enclosure material has wide market prospect.
Content of the invention
It is an object of the invention to provide graphene oxide/molecular sieve that a kind of preparation method is simple, adsorbance is larger is multiple
Close the preparation method of adsorbing material.
The present invention comprises the following steps:
1) high silica alumina ratio molecular sieve is scattered in deionized water, forms molecular sieve suspension；
2) aqueous hydrochloric acid solution is mixed with molecular sieve suspension, after carrying out acid treatment under stirring condition, obtain the molecule of acid treatment
Sieve solution；
3) molecular sieve solution of acid treatment is centrifuged, takes solid phase to be redispersed in after deionized water wash in deionized water, obtain
The molecular sieve suspension of acid treatment；
4) by graphene oxide water solution Deca in the molecular sieve suspension of acid treatment, ultrasonic after be stirred, obtain
Graphene oxide and the mixture of molecular sieve；
5) by the mixture of graphene oxide and molecular sieve after 90～130 DEG C of heat treatment 4～8h, then it is placed in 90～130 DEG C of rings
In border be dried 5～8h, ground become powder body, obtain graphene oxide/molecular sieve novel absorption material.
The present invention uses graphene oxide solution and molecular sieve to pass through the simple and quick preparation of chemical action under hydrothermal conditions
Go out the composite of different graphene oxide contents, improve the absorbability to pollutant using both synergism.
Advantages of the present invention is mainly manifested in:
1. overcome the low shortcoming of single molecular sieve adsorption ability.
2. preparation method is simple, and cost of material is low.
3. the absorbability of composite improves 1.3～3.2 times than simple corresponding molecular sieve.
In addition, being ground after 5～8 h being dried in 90～130 DEG C of environment, molecular sieve and graphene oxide are bonded again
More firm, be conducive to lifting the stability of composite.
Further, high silica alumina ratio molecular sieve described in step 1) of the present invention is 300～500 m for specific surface area2/
The total silicon silicalite-1 molecular sieve of g, or for silica alumina ratio be 10～50: 1, specific surface area be 200～500 m2The beta of/g
Molecular sieve, or for silica alumina ratio be 5～10: 1, specific surface area be 400～600 m2One of y molecular sieve of/g.
Because specific surface area is 300～500 m2The total silicon silicalite-1 of/g has special ten yuan as molecular sieve
Ring pore passage structure, being capable of selective absorption micro-content organism；The present invention is conducive to improving using the high-specific surface area of this molecular sieve
Adsorption capacity to Organic substance.
Due to silica alumina ratio be 10～50: 1, specific surface area be 200～500 m2The beta molecular sieve of/g divides for high silica alumina ratio
Son sieve, has three-dimensional twelve-ring straight channel bore structure, being capable of selective absorption micro-content organism；The present invention adopts this molecule
The high-specific surface area of sieve is conducive to improving the adsorption capacity to Organic substance.
Due to silica alumina ratio be 5～10: 1, specific surface area be 400～600 m2The molecular sieve of/g is high-silica zeolite, pore volume
Amount is larger, being capable of selective absorption micro-content organism；The present invention is conducive to improving to having using the high-specific surface area of this molecular sieve
The adsorption capacity of machine thing.
The number of plies being used for graphene oxide in the described graphene oxide water solution of Deca in step 4) of the present invention is 1～10
Layer, oxygen content is 30%～60%.Under the conditions of being somebody's turn to do, the layer structure of graphene oxide and oxygen-containing functional group are fully utilized, favorably
Fully react in graphene oxide and molecular sieve, lift composite absorbability.
The concentration being used for described graphene oxide (go) aqueous solution of Deca in described step 4) is 0.8～1.5 mg/ml.
Under this concentration, graphene oxide dispersion in aqueous is more uniformly distributed, and is conducive to fully reacting with molecular sieve.
Molecular sieve in graphene oxide and molecular sieve suspension in graphene oxide described in step 5) (go) aqueous solution
Mixing quality than for 1: 10～100.Under this proportioning, the reaction of graphene oxide layer and molecular sieve is more abundant, prepared
Composite is more uniformly distributed, and is conducive to lifting absorption property.
The mass ratio that feeds intake of high silica alumina ratio molecular sieve described in described step 1) and deionized water is 1: 20～100.At this
Under proportioning, the dispersion of molecular sieve is more uniformly distributed, and is conducive to fully reacting with graphene oxide.
Described step 2) described in the speed of stirring be 100～300 r/min, time of stirring is 10～30 min, has
Beneficial to molecular sieve dispersion in aqueous.
In addition, ultrasonic power described in step 4) is 20～50w, the ultrasonic time is 10～30s.Its advantage is:
Under this ultrasound condition, be conducive to graphene oxide and molecular sieve rapid dispersion, graphene oxide layer structure will not be destroyed.
Described step 2) in for mixing described aqueous hydrochloric acid solution percentage by volume be 32%.Under the conditions of being somebody's turn to do, molecular sieve
Surface acidity strengthens, be conducive to graphene oxide layer on enliven group and fully react.
The temperature conditionss of heat treatment described in step 5) are 110 DEG C, and the time is 5～8 h.Under this temperature and time, molecule
The hydroxyl on sieve surface is bonded more firm with the oxygen-containing functional group in graphene oxide layer.
Brief description
Fig. 1 is the sem of the graphene oxide/silicalite-1 molecular sieves compound material made using the inventive method
Figure.
Fig. 2 is the sem figure of the graphene oxide/beta molecular sieves compound material made using the inventive method.
Fig. 3 is the sem figure of the graphene oxide/y molecular sieves compound material made using the inventive method.
Specific embodiment
Embodiment 1:
Preparation technology: power be 50 w ultrasound condition effect under 10 s, by 0.1 g specific surface area be 406.82 m2/ g's
Total silicon silicalite-1 molecular sieve is scattered in 10 ml deionized waters, adds the hydrochloric acid that 0.1 ml percentage by volume is 32%
Aqueous solution, stirs 30 min under 200 r/min stirring conditions to realize acid treatment, takes solid phase to be redispersed in 10 after centrifuge washing
In ml deionized water, obtain the molecular sieve suspension of acid treatment.
To in the molecular sieve suspension of acid treatment, Deca 10 ml graphene oxide concentration is the graphite oxide of 0.8 mg/ml
Aqueous solution, power be 50 w ultrasonic 10 s after be stirred for 30 min.Solution after stirring is placed in 110 DEG C of baking ovens
Carry out heat treatment 5 h, finally 6 hs will be dried at 100 DEG C of reactant, obtain product after grinding, from the sem Electronic Speculum seeing that Fig. 1 provides
Figure understands, graphene oxide successfully loads to silicalite-1 molecular sieve surface.
Absorbing dye is tested: weighs the rhodamine b that the above-mentioned composite adsorbing material of 0.01 g is scattered in 10 ml 50 mg/l
In aqueous solution, at room temperature, ph is to be stirred adsorbing 1 h when 3, and adsorbance is 51.2 mg/g, than simple
Silicalite-1 molecular sieve improves 3 times.
Embodiment 2:
Preparation technology: power be 20 w ultrasound condition effect under 15s, by 0.25 g silica alumina ratio be 18.4, specific surface area be
410.20 m2The beta molecular sieve of/g is scattered in 20 ml deionized waters, adds the salt that 0.1 ml percentage by volume is 32%
Aqueous acid, stirs 30 min to realize acid treatment, takes solid phase to be redispersed in 20 after centrifuge washing under 200 r/min stirring conditions
In ml deionized water, obtain the molecular sieve suspension of acid treatment.
To in the molecular sieve suspension of acid treatment, Deca 2.5 ml concentration containing graphene oxide is the graphite oxide of 1 mg/ml
Aqueous solution, power be 20 w ultrasonic 15s after be stirred for 30 min.Solution after stirring is placed in 110 DEG C of baking ovens
Row heat treatment 6 h, finally will be dried 6 h at 100 DEG C of reactant, obtains product after grinding.
Scheme it can be seen that graphene oxide successfully loads from the sem of Fig. 2 graphene oxide/beta molecular sieves compound material
To beta molecular sieve surface.
Application examples 2: weigh the rhodamine b aqueous solution that the above-mentioned composite adsorbing material of 0.01 g is scattered in 10 ml 80 mg/l
In, at room temperature, ph is to be stirred adsorbing 1 h when 3, and adsorbance is 64.47 mg/g, improves than simple beta molecular sieve
1.3 times.
Embodiment 3:
Preparation technology: power be 25 w ultrasound condition effect under 20 s, by 0.45 g silica alumina ratio be 6, specific surface area be
428.64 m2The y molecular sieve of/g is scattered in 20 ml deionized waters, adds the hydrochloric acid water that 0.1 ml percentage by volume is 32%
Solution, stirs 30 min to realize acid treatment, takes solid phase to be redispersed in 10 ml after centrifuge washing under 200 r/min stirring conditions
In deionized water, obtain the molecular sieve suspension of acid treatment.
To in the molecular sieve suspension of acid treatment, Deca 30 ml concentration containing graphene oxide is the oxidation stone of 1.5 mg/ml
Black aqueous solution, power be 25 w ultrasonic 20s after be stirred for 40 min.Solution after stirring is placed in 110 DEG C of baking ovens
Carry out heat treatment 7 h, finally 6 hs will be dried at 100 DEG C of reactant, after grinding, obtain product.
Scheme it can be seen that graphene oxide successfully loads to y from the sem of Fig. 3 graphene oxide/y molecular sieves compound material
Molecular sieve surface.
Application examples 3: weigh the rhodamine b aqueous solution that the above-mentioned composite adsorbing material of 0.01 g is scattered in 10 ml 80 mg/l
In, at room temperature, ph is to be stirred adsorbing 1 h when 3, and adsorbance is 39.64 mg/g, improves than simple y molecular sieve
3.2 again.
In above example, the number of plies for graphene oxide in each graphene oxide water solution of Deca is 1～10 layer, oxygen-containing
Measure as 30%～60%.
Claims (10)
1. a kind of preparation method of graphene oxide/molecular sieves compound material is it is characterised in that comprise the following steps:
1) high silica alumina ratio molecular sieve is scattered in deionized water, forms molecular sieve suspension；
2) aqueous hydrochloric acid solution is mixed with molecular sieve suspension, after carrying out acid treatment under stirring condition, obtain the molecule of acid treatment
Sieve solution；
3) molecular sieve solution of acid treatment is centrifuged, takes solid phase to be redispersed in after deionized water wash in deionized water, obtain
The molecular sieve suspension of acid treatment；
4) by graphene oxide water solution Deca in the molecular sieve suspension of acid treatment, ultrasonic after be stirred, obtain
Graphene oxide and the mixture of molecular sieve；
5) by the mixture of graphene oxide and molecular sieve after 90～130 DEG C of heat treatment 4～8h, then it is placed in 90～130 DEG C of rings
In border be dried 5～8h, ground become powder body, obtain graphene oxide/molecular sieve novel absorption material.
2. preparation method according to claim 1 is it is characterised in that high silica alumina ratio molecular sieve described in described step 1) is
Specific surface area is 300～500 m2The total silicon silicalite-1 molecular sieve of/g, or be 10～50: 1, specific surface area for silica alumina ratio
For 200～500 m2The beta molecular sieve of/g, or for silica alumina ratio be 5～10: 1, specific surface area be 400～600 m2The y molecule of/g
One of sieve.
3. preparation method according to claim 1 is it is characterised in that be used for the described graphene oxide of Deca in step 4)
In aqueous solution, the number of plies of graphene oxide is 1～10 layer, and oxygen content is 30%～60%.
4. preparation method according to claim 3 is it is characterised in that be used for the described oxidation stone of Deca in described step 4)
The concentration of black aqueous solution is 0.8～1.5 mg/ml.
5. preparation method according to claim 4 is it is characterised in that oxygen in graphene oxide water solution described in step 5)
The mixing quality of the molecular sieve in graphite alkene and molecular sieve suspension is than for 1: 10～100.
6. the preparation method according to claim 1 or 2 or 3 or 4 or 5 is it is characterised in that high silicon described in described step 1)
The mass ratio that feeds intake of aluminum ratio molecular sieve and deionized water is 1: 20～100.
7. preparation method according to claim 1 is it is characterised in that described step 2) described in stirring speed be 100～
300 r/min, the time of stirring is 10～30 min.
8. preparation method according to claim 1 it is characterised in that power ultrasonic described in described step 4) be 20～
50 w, the ultrasonic time is 10～30 s.
9. preparation method according to claim 4 is it is characterised in that described step 2) in for mixing described hydrochloric acid water
The percentage by volume of solution is 32%.
10. preparation method according to claim 1 is it is characterised in that the temperature conditionss of heat treatment described in step 5) are
110 DEG C, the time is 5～8 h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106904630A (en) * | 2017-03-15 | 2017-06-30 | 天津大学 | The preparation method of new MFI molecular sieves/stannic oxide/graphene nano piece composite |
| CN107640829A (en) * | 2017-09-04 | 2018-01-30 | 安徽秀安生态农业有限公司 | A kind of composition for purifying giant salamander water |
| CN107970886A (en) * | 2017-11-09 | 2018-05-01 | 广东工业大学 | A kind of graphene oxide and the composite modified zeolite filler of iron chloride and preparation method thereof |
| CN109351332A (en) * | 2018-12-14 | 2019-02-19 | 大连理工大学 | A kind of three-dimensional magnetic graphene/zeolitic material preparation method of highly efficient regeneration absorption rare earth ion |
| CN111633021A (en) * | 2020-06-08 | 2020-09-08 | 上海大学 | Nano zero-valent iron modified composite mesoporous material and preparation method and application thereof |
| CN113750957A (en) * | 2020-06-05 | 2021-12-07 | 中国石油化工股份有限公司 | Y-type molecular sieve/graphene composite material and preparation method and application thereof |
| CN114558608A (en) * | 2022-02-28 | 2022-05-31 | 中国石油大学(北京) | Graphene-based desulfurization catalyst, preparation thereof and desulfurization method for hydrogen produced by catalytic dehydrogenation of low-carbon alkane |
| CN115353073A (en) * | 2022-07-18 | 2022-11-18 | 安徽东至广信农化有限公司 | Method for purifying hydrogen |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106904630A (en) * | 2017-03-15 | 2017-06-30 | 天津大学 | The preparation method of new MFI molecular sieves/stannic oxide/graphene nano piece composite |
| CN107640829A (en) * | 2017-09-04 | 2018-01-30 | 安徽秀安生态农业有限公司 | A kind of composition for purifying giant salamander water |
| CN107970886A (en) * | 2017-11-09 | 2018-05-01 | 广东工业大学 | A kind of graphene oxide and the composite modified zeolite filler of iron chloride and preparation method thereof |
| CN107970886B (en) * | 2017-11-09 | 2023-10-27 | 广东工业大学 | Graphene oxide and ferric chloride composite modified zeolite filter material and preparation method thereof |
| CN109351332A (en) * | 2018-12-14 | 2019-02-19 | 大连理工大学 | A kind of three-dimensional magnetic graphene/zeolitic material preparation method of highly efficient regeneration absorption rare earth ion |
| CN113750957A (en) * | 2020-06-05 | 2021-12-07 | 中国石油化工股份有限公司 | Y-type molecular sieve/graphene composite material and preparation method and application thereof |
| CN111633021A (en) * | 2020-06-08 | 2020-09-08 | 上海大学 | Nano zero-valent iron modified composite mesoporous material and preparation method and application thereof |
| CN111633021B (en) * | 2020-06-08 | 2021-12-28 | 上海大学 | Nano zero-valent iron modified composite mesoporous material and preparation method and application thereof |
| CN114558608A (en) * | 2022-02-28 | 2022-05-31 | 中国石油大学(北京) | Graphene-based desulfurization catalyst, preparation thereof and desulfurization method for hydrogen produced by catalytic dehydrogenation of low-carbon alkane |
| CN115353073A (en) * | 2022-07-18 | 2022-11-18 | 安徽东至广信农化有限公司 | Method for purifying hydrogen |
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