CN106179473B - Nano zero valence iron/carbon nanotube/zeolite hybridization mesoporous molecular sieve composite material preparation method - Google Patents
Nano zero valence iron/carbon nanotube/zeolite hybridization mesoporous molecular sieve composite material preparation method Download PDFInfo
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- CN106179473B CN106179473B CN201610524313.6A CN201610524313A CN106179473B CN 106179473 B CN106179473 B CN 106179473B CN 201610524313 A CN201610524313 A CN 201610524313A CN 106179473 B CN106179473 B CN 106179473B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 36
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 30
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 30
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 30
- 239000010457 zeolite Substances 0.000 title claims abstract description 30
- 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 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 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 17
- 238000009396 hybridization Methods 0.000 title claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 64
- 239000010703 silicon Substances 0.000 claims abstract description 64
- 239000000017 hydrogel Substances 0.000 claims abstract description 29
- 239000012690 zeolite precursor Substances 0.000 claims abstract description 20
- 239000000499 gel Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000000034 method Methods 0.000 description 7
- 239000005416 organic matter Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001652 electrophoretic deposition Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- -1 molecular sieves compound Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- B01J35/39—
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of preparation methods of nano zero valence iron/carbon nanotube/zeolite hybridization mesoporous molecular sieve composite material.The specific steps of the present invention are as follows: (1) individually by zeolite, or after the mixture of silicon source and silicon source is sufficiently mixed in aqueous slkali, zeolite precursor body being made at a temperature of 90-140 DEG C；(2) by zeolite precursor body, silicon source, silicon source and C16TMABr is mixed in aqueous slkali, and hydrogel is prepared；(3) nano zero valence iron and carbon nanotube are added in hydrogel, mixed gel is made；(4) mixed gel is successively carried out to Crystallizing treatment and high-temperature calcination processing obtains nano zero valence iron/carbon nanotube/zeolite hybridization mesoporous molecular sieve composite material.Preparation process of the present invention is simple, and flexibility is high；Zeolite is introduced to the hole wall of mesopore molecular sieve, and adds nano zero valence iron and carbon nanotube, the efficiency of composite material separation and degradable organic pollutant can be effectively improved.
Description
Technical field
The invention belongs to technical field of composite materials, specifically, are related to a kind of nano zero valence iron/carbon nanotube/zeolite
The preparation method of hybrid mesoporous molecular sieves compound material.
Background technique
With the fast development of agricultural and industry, a large amount of waste water of generation cause greatly natural environment and human body etc.
Harm.Agricultural and industrial wastewater are rich in organic pollutant, for example, antibiotic, humic acid etc..High concentration organic contaminant results in
Environmental disruption.Animal husbandry, city and agricultural effluent, industrial wastewater can all increase the organic concentration in water environment.Rich in highly concentrated
The wastewater source of degree organic matter is more, discharge amount is big, and the unprocessed or incomplete waste water of processing can cause greatly to endanger to environment
Evil.Therefore, by the concern of people, organic matter is included in " 12th Five-Year Plan " by China for the processing of high concentration organic contaminant
In overall control index.
A kind of load carbon is prepared in view of the above-mentioned problems, disclosing application No. is 201410049887.3 Chinese invention patent
The method of the Iron-complex-filling of nanotube, using waste iron filing and multi-walled carbon nanotube as raw material, by iron plate together with carbon nanotube
It is put into the aqueous isopropanol dissolved with 0.003mol/L magnesium chloride, is carried out with ultrasonic treatment, under 160V voltage, 1mA electric current
Electrophoretic deposition 1-3h, so that carbon nanotube is attached on iron plate；At a temperature of drying 2-3h by compounded mix obtained at 40 DEG C,
Then it, in 600 DEG C of roasting temperatures, is finally obtained into the compounded mix of sizing as in argon gas stream.The patented technology is made
Filler there is higher good specific surface area, mass transfer rate is high, is capable of the plate of the passivation of effectively preventing filler surface and filler
Knot；The biodegradability of dyeing waste water can be improved in a short time, and reduce the CODcr and coloration of waste water.
Application No. is 200710052555.0 Chinese invention patent, to disclose a kind of iron carbon for microwave water process multiple
Nanocatalyst and preparation method thereof is closed, main group of the catalyst becomes source of iron and carbon source, and source of iron and carbon source mass ratio are 10
~1: 1.Wherein the source of iron is nano zero valence iron or nanometer di-iron trioxide；The carbon source is carbon nanotube or carbon nanometer
Fibrous material.Preparation method is: using carbon source, source of iron and ptfe emulsion for raw material, it is mixed by composition and ratio
Uniformly, after molding under nitrogen protection air drying to get to can be used for microwave water process ferro-carbon composite nano catalysis material.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide one kind to be conducive to variety classes in degradation water
Organic matter nano zero valence iron/carbon nanotube/zeolite hybridization mesoporous molecular sieve composite material preparation method.
The present invention by Zero-valent Iron and carbon nanotube in conjunction with zeolite hybridization mesopore molecular sieve, adjustable mesoporous hole
Diameter adsorbs the organic matter of different molecular radius, and has ion-exchange performance, is conducive to remove cationic organic matter.In addition
By nanoscale photocatalyst on the carrier of mesopore molecular sieve, be conducive to the recycling of photochemical catalyst avoiding nanometer
Secondary pollution of the particle to water.
The purpose of the present invention can be achieved through the following technical solutions.
The present invention provides a kind of preparation side of nano zero valence iron/carbon nanotube/zeolite hybridization mesoporous molecular sieve composite material
Method, the specific steps are as follows:
(1) individually by zeolite, or after the mixture of silicon source and silicon source is sufficiently mixed in aqueous slkali, 90-140 DEG C of temperature
Degree lower reaction 5-12 hours, zeolite precursor body is made；
(2) zeolite precursor body, silicon source, silicon source and C16TMABr are mixed again in aqueous slkali, hydrogel is prepared；
(3) nano zero valence iron and carbon nanotube are added in hydrogel, are uniformly mixed, mixed gel is made；
(4) mixed gel is subjected to Crystallizing treatment, to Crystallizing treatment after, be separated, washed, dried, 300-700 DEG C
At a temperature of high-temperature calcination 1-15 hours, obtain nano zero valence iron/carbon nanotube/zeolite hybridization mesoporous molecular sieve composite material.
In above-mentioned steps (1), (2), aqueous slkali is the sodium hydroxide solution or potassium hydroxide that molar concentration is 1-10mol/L
Solution.
In above-mentioned steps (1), the additional amount of zeolite in the aqueous slkali are as follows: 0.005- is added in every milliliter of aqueous slkali
The zeolite of 0.5g.
In above-mentioned steps (1), the molar ratio of silicon source, silicon source and alkali is (1-15): (1-18): (150-550).
Silicon source includes one of silica solution or waterglass or a variety of.Silicon source includes sodium metaaluminate, boehmite or different
One of aluminium propoxide is a variety of.
In above-mentioned steps (2), zeolite precursor body, silicon source, silicon source, aqueous slkali and C16The molar ratio of TMABr is (0.1-3):
(1-50):(1-5):(0.1-5):(100-600)。
In above-mentioned steps (3), the mass ratio of nano zero valence iron and hydrogel is 1:1~1:10, the carbon nanotube with
The mass ratio of hydrogel is 1:1~1:10.
In above-mentioned steps (4), the condition of Crystallizing treatment are as follows: at a temperature of 90-180 DEG C, crystallization is carried out under self-generated pressure, is controlled
Time is 5-96 hours.
The present invention combines micro-pore zeolite with mesopore molecular sieve, has bigger specific surface area and stronger adsorption energy
Power can adsorb different size of organic molecule, and combine with nano zero valence iron and carbon nanotube, under visible light conditions,
It is good to the removal effect of organic pollutant.
Detailed description of the invention
Fig. 1 is embodiment 1, embodiment 2, embodiment 3 and the material of the preparation of embodiment 4 to 70mL 1 × 10-5mol L-1It is sub-
The removal rate map of methyl blue.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
(1) natural zeolite is mixed with sodium hydroxide solution, wherein the concentration of sodium hydroxide solution is 10mol/L, every milli
The zeolite that 0.2g is added in aqueous slkali is risen, is reacted 6 hours at 100 DEG C after being sufficiently mixed and zeolite precursor body is prepared；
(2) zeolite precursor body, silicon source, silicon source and C16TMABr are mixed again in aqueous slkali, hydrogel is prepared；Silicon
Source is silica solution, and silicon source is sodium metaaluminate, and aqueous slkali is the sodium hydroxide solution that molar concentration is 10mol/L；Zeolite precursor body,
Silicon source, silicon source, the molar ratio of aqueous slkali and C16TMABr are 0.5:30:4:3:350；
(3) nano zero valence iron and carbon nanotube are uniformly mixed with hydrogel, the quality of nano zero valence iron and hydrogel
Than for 1:2, the mass ratio of carbon nanotube and hydrogel is 1:4；
(4) Crystallizing treatment will be carried out, to Crystallizing treatment after, be separated, washed, dried, high-temperature calcination is obtained and received
Rice Zero-valent Iron/carbon nanotube/zeolite hybridization mesoporous molecular sieve composite material.Under 115 DEG C and self-generated pressure, mixed gel crystallization
20 hours, then separated, washed, dried, under the conditions of normal pressure and 500 DEG C, calcines 5 hours, obtain sample.
Embodiment 2
The present embodiment nano zero valence iron/carbon nanotube-zeolite hybridization mesoporous molecular sieve composite material preparation method, specifically
The following steps are included:
(1) it after being sufficiently mixed the mixture of silicon source and silicon source in aqueous slkali, reacts at a certain temperature, zeolite is made
Presoma；
(2) zeolite precursor body, silicon source, silicon source and C16TMABr are mixed again in aqueous slkali, hydrogel is prepared；
(3) nano zero valence iron and carbon nanotube are added in hydrogel, are uniformly mixed, mixed gel is made；
(4) mixed gel is subjected to Crystallizing treatment, to Crystallizing treatment after, be separated, washed, dried, high-temperature calcination,
Obtain sample.
Above-mentioned silicon source is silica solution, and silicon source is sodium metaaluminate, and aqueous slkali is that the sodium hydroxide that molar concentration is 5mol/L is molten
Liquid.
In step (1), silicon source and silicon source are added in aqueous slkali, are sufficiently mixed, and react 8 hours at 120 DEG C, i.e.,
Zeolite precursor body is made.
In step (2), zeolite precursor body, silicon source, silicon source, aqueous slkali and C16The molar ratio of TMABr is 0.8:20:3:4:
450 are prepared hydrogel.
In step (3), the mass ratio of nano zero valence iron and hydrogel is 1:3, and the mass ratio of carbon nanotube and hydrogel is
1:6。
In step (4), the condition of Crystallizing treatment are as follows: crystallization is carried out under 98 DEG C and self-generated pressure, the control time is 12 small
When.The condition of calcining are as follows: calcined under 500 DEG C and condition of normal pressure, the control time is 8 hours.
Embodiment 3
The present embodiment nano zero valence iron/carbon nanotube-zeolite hybridization mesoporous molecular sieve composite material preparation method, specifically
The following steps are included:
(1) it after being sufficiently mixed the mixture of silicon source and silicon source in aqueous slkali, reacts at a certain temperature, zeolite is made
Presoma；
(2) zeolite precursor body, silicon source, silicon source and C16TMABr are mixed again in aqueous slkali, hydrogel is prepared；
(3) nano zero valence iron and carbon nanotube are added in hydrogel, are uniformly mixed, mixed gel is made；
(4) mixed gel is subjected to Crystallizing treatment, to Crystallizing treatment after, be separated, washed, dried, high-temperature calcination,
Obtain sample.
Above-mentioned silicon source is silica solution, and silicon source is sodium metaaluminate, and aqueous slkali is that the sodium hydroxide that molar concentration is 8mol/L is molten
Liquid.
In step (1), silicon source and silicon source are added in aqueous slkali, are sufficiently mixed, and react 6 hours at 130 DEG C, i.e.,
Zeolite precursor body is made.Wherein, the molar ratio of silicon source, silicon source and alkali is 10:7:350.
In step (2), zeolite precursor body, silicon source, silicon source, aqueous slkali and C16The molar ratio of TMABr is 1.2:30:5:3:
500 are prepared hydrogel.
In step (3), the mass ratio of nano zero valence iron and hydrogel is 1:5, and the mass ratio of carbon nanotube and hydrogel is
1:3。
In step (4), the condition of Crystallizing treatment are as follows: crystallization is carried out under 125 DEG C and self-generated pressure, the control time is 10 small
When.The condition of calcining are as follows: calcined under 480 DEG C and condition of normal pressure, the control time is 10 hours.
Embodiment 4
The present embodiment nano zero valence iron/carbon nanotube-zeolite hybridization mesoporous molecular sieve composite material preparation method, specifically
The following steps are included:
(1) it after being sufficiently mixed the mixture of silicon source and silicon source in aqueous slkali, reacts at a certain temperature, zeolite is made
Presoma；
(2) zeolite precursor body, silicon source, silicon source and C16TMABr are mixed again in aqueous slkali, hydrogel is prepared；
(3) nano zero valence iron and carbon nanotube are added in hydrogel, are uniformly mixed, mixed gel is made；
(4) mixed gel is subjected to Crystallizing treatment, to Crystallizing treatment after, be separated, washed, dried, high-temperature calcination,
Obtain sample.
Above-mentioned silicon source is silica solution, and silicon source is sodium metaaluminate, and aqueous slkali is that the sodium hydroxide that molar concentration is 9mol/L is molten
Liquid.
In step (1), silicon source and silicon source are added in aqueous slkali, are sufficiently mixed, and react 7 hours at 110 DEG C, i.e.,
Zeolite precursor body is made.Wherein, the molar ratio of silicon source, silicon source and alkali is 9:10:250.
In step (2), zeolite precursor body, silicon source, silicon source, aqueous slkali and C16The molar ratio of TMABr is 1.7:35:4:2:
450 are prepared hydrogel.
In step (3), the mass ratio of nano zero valence iron and hydrogel is 1:8, and the mass ratio of carbon nanotube and hydrogel is
1:6。
In step (4), the condition of Crystallizing treatment are as follows: crystallization is carried out under 108 DEG C and self-generated pressure, the control time is 10 small
When.The condition of calcining are as follows: calcined under 600 DEG C and condition of normal pressure, the control time is 10 hours.
As shown in Figure 1, the material prepared for the embodiment of the present invention 1, embodiment 2, embodiment 3 and embodiment 4 to 70mL1 ×
10-5mol L-1The removal rate map of methylene blue, dosage 1g/L, reaction time are 2 hours；It can be seen from the map
Composite material produced by the present invention is to 70mL 1 × 10-5mol L-1The removal rate of methylene blue can reach 90% or more, degradation
Organic pollutant it is high-efficient, have a good application prospect.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (9)
1. a kind of preparation method of nano zero valence iron/carbon nanotube/zeolite hybridization mesoporous molecular sieve composite material, feature exist
In, the specific steps are as follows:
(1) individually by zeolite, or after the mixture of silicon source and silicon source is sufficiently mixed in aqueous slkali, at a temperature of 90-140 DEG C
Zeolite precursor body is made in reaction 5-12 hours；
(2) again by zeolite precursor body, silicon source, silicon source and C16TMABr is mixed in aqueous slkali, and hydrogel is prepared；
(3) nano zero valence iron and carbon nanotube are added in hydrogel, are uniformly mixed, mixed gel is made；
(4) mixed gel is subjected to Crystallizing treatment, to Crystallizing treatment after, be separated, washed, dried, 300-700 DEG C of temperature
Lower high-temperature calcination 1-15 hours obtains nano zero valence iron/carbon nanotube/zeolite hybridization mesoporous molecular sieve composite material, uses
In visible light conditions go down water removal in methylene blue.
2. preparation method according to claim 1, which is characterized in that in step (1) and step (2), aqueous slkali is mole
Concentration is the sodium hydroxide solution or potassium hydroxide solution of 1-10mol/L.
3. preparation method according to claim 1, which is characterized in that in step (1), be added in every milliliter of aqueous slkali
The zeolite of 0.005-0.5g.
4. preparation method according to claim 1, which is characterized in that in step (1), the molar ratio of silicon source, silicon source and alkali
For (1-15): (1-18): (150-550).
5. preparation method according to claim 1, which is characterized in that in step (2), zeolite precursor body, silicon source, silicon source,
Aqueous slkali and C16The molar ratio of TMABr is (0.1-3): (1-50): (1-5): (0.1-5): (100-600).
6. preparation method according to claim 4 or 5, which is characterized in that silicon source includes in zeolite, silica solution or waterglass
It is one or more.
7. preparation method according to claim 4 or 5, which is characterized in that silicon source includes zeolite, sodium metaaluminate, intends thin water
One of aluminium stone or aluminium isopropoxide are a variety of.
8. preparation method according to claim 1, which is characterized in that in step (3), the matter of nano zero valence iron and hydrogel
Ratio is measured as 1:1~1:10, the mass ratio of carbon nanotube and hydrogel is 1:1~1:10.
9. preparation method according to claim 1, which is characterized in that in step (4), the condition of Crystallizing treatment are as follows: 90-
At a temperature of 180 DEG C, crystallization is carried out under self-generated pressure, the control time is 5-96 hours.
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| CN110102255B (en) * | 2019-04-03 | 2021-10-19 | 广东工业大学 | Molecular sieve-doped magnetic carbon nanotube composite material and preparation method and application thereof |
| CN110040875A (en) * | 2019-05-06 | 2019-07-23 | 上海应用技术大学 | A kind of minimizing technology of the useless Organic substance in water of coating material production |
| CN111559748A (en) * | 2020-04-02 | 2020-08-21 | 广东轻工职业技术学院 | Preparation method of silicon-aluminum molecular sieve |
| CN116474747B (en) * | 2023-03-24 | 2023-10-31 | 北京师范大学珠海校区 | Lanthanum-loaded iron carbon nanotube composite molecular sieve film and preparation method and application thereof |
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