CN110639599A - Copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst and preparation method and application thereof - Google Patents
Copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN110639599A CN110639599A CN201910996463.0A CN201910996463A CN110639599A CN 110639599 A CN110639599 A CN 110639599A CN 201910996463 A CN201910996463 A CN 201910996463A CN 110639599 A CN110639599 A CN 110639599A
- Authority
- CN
- China
- Prior art keywords
- fly ash
- molecular sieve
- copper
- composite catalyst
- modified fly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000010881 fly ash Substances 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 28
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000002351 wastewater Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003245 coal Substances 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 230000015556 catabolic process Effects 0.000 claims abstract description 5
- 238000006731 degradation reaction Methods 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 230000004927 fusion Effects 0.000 claims abstract description 3
- 239000000725 suspension Substances 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 230000000593 degrading effect Effects 0.000 claims description 7
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000000203 mixture Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910017827 Cu—Fe Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst, a preparation method thereof and application thereof in degradation of quinoline wastewater in coal chemical industry. The invention adds fly ash into sodium hydroxide solution, assists alkali fusion under microwave irradiation, then adds precursor salt solution containing copper and iron and cetyl trimethyl ammonium bromide, then puts into hydrothermal reaction kettle for crystallization, finally obtains modified fly ash-molecular sieve composite catalyst doped with copper and iron bimetal through washing, filtering, drying and roasting. The catalyst of the invention has simple preparation process, no waste material is generated in the preparation process, and the obtained composite catalyst is utilized to activate H2O2The degradation of quinoline wastewater in coal chemical industry has excellent catalytic activity and stability.
Description
Technical Field
The invention belongs to the field of waste recycling, and particularly relates to a copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst, and a preparation method and application thereof.
Background
The fly ash is mainly a product formed by burning coal dust in coal-fired power plants, smelting, chemical industries and other industries at high temperature, and is one of industrial solid wastes with the largest discharge amount in China. The building material industry is the most main comprehensive utilization field of the fly ash in China, and once the fly ash disposal problem caused by the rapid growth of the thermal power industry is greatly relieved. However, as the economic development of China enters a new normal state, the requirements of the building industry and infrastructure on traditional building materials such as cement and concrete are further reduced, and the fly ash treatment and utilization of China face more severe challenges.
Based on the self-properties and chemical components of the fly ash (containing more than 70 percent of Al)2O3And SiO2) The preparation of high value-added products by proper modification is of more realistic significance. In the existing research, people modify fly ash by acid-base modification, synthesis of molecular sieve and loading of metal oxide to improve activity. Wherein, acid-base modification can generate liquid waste, and has limited effect of improving the activity of the fly ash; the process of synthesizing the molecular sieve is complicated and complicated, and the yield is low; the way of loading metal is mostly stopped in the dipping method, the steps are more, and the dispersion of the metal is not facilitated. Therefore, there is a need to develop an environmentally friendly and efficient improved method for treating fly ash and expanding its application range.
Disclosure of Invention
The invention aims to provide a preparation method of a copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst and application of the copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst in degradation of quinoline wastewater in coal chemical industry. By utilizing the technical scheme of the invention, the problems of complex process, harsh modification conditions and uneven metal dispersion in other methods for preparing the molecular sieve by utilizing the fly ash can be solved, the purposes of preparing the modified fly ash catalyst with more stable structure, higher metal dispersion degree and better catalytic effect are realized, and the preparation process is simple.
In order to realize the purpose of the invention, the invention adopts the following technical scheme to realize:
the invention provides a preparation method of a copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst, which specifically comprises the following steps:
(1) adding the fly ash into a sodium hydroxide solution with the mass concentration of 10-30% to obtain a suspension A;
(2) transferring the suspension A into a microwave reactor, assisting alkali fusion under microwave irradiation, and then adjusting the pH value to about 9 by using an HCl solution to obtain a suspension B, wherein the suspension B consists of insoluble modified fly ash and a solution containing a silicon element and an aluminum element;
(3) weighing hexadecyl trimethyl ammonium bromide, dissolving the hexadecyl trimethyl ammonium bromide in water, and adding the hexadecyl trimethyl ammonium bromide into the suspension B with the well adjusted pH value under the stirring condition;
(4) weighing Fe (NO)3)3·9H2O and Cu (NO)3)2·3H2Preparing a metal precursor salt solution from O, adding the solution into a suspension B containing hexadecyl trimethyl ammonium bromide, carrying out ultrasonic treatment for 40min, and then stirring for 2h to obtain a suspension C;
(5) transferring the suspension C dispersed with the metal precursor into a hydrothermal reaction kettle lined with polytetrafluoroethylene, putting the hydrothermal reaction kettle into an oven for hydrothermal crystallization, wherein the crystallization temperature is 60-100 ℃, and the time is 12-24 hours;
(6) and after the crystallization reaction is finished, filtering and washing the metal-doped modified fly ash-molecular sieve compound to be neutral, drying and then transferring the compound into a muffle furnace for roasting for 3 hours.
Further: the mass ratio of the fly ash to the sodium hydroxide in the step (1) is 1: 1.2.
Further: in the step (2), the microwave power is 160-320W, and the irradiation time is 15-30 min.
Further: the mass ratio of the hexadecyl trimethyl ammonium bromide to the fly ash in the step (3) is 1: 6-8.
Further: in the step (4), the mass ratio of copper to iron in the metal precursor salt solution is 1:1.
Further: the roasting temperature in the step (6) is 300-500 ℃.
The invention also provides the copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst prepared by the preparation method.
The invention also provides application of the copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst in degradation of quinoline wastewater in coal chemical industry.
Further: the copper-iron bimetal doped modified fly ash-moleculeThe combined oxidant of the sieve composite catalyst in the process of degrading quinoline wastewater is H2O2。
Compared with the prior art, the invention has the advantages and beneficial effects that:
the invention adopts a microwave irradiation auxiliary alkali fusion method to modify the fly ash, simultaneously obtains a solution containing silicon element and aluminum element, adds a template agent and a metal precursor salt solution after adjusting the pH value, and obtains the modified fly ash-molecular sieve composite catalyst with highly dispersed metal by one step of hydrothermal crystallization. The catalyst has simple preparation process and mild conditions, does not need to add a silicon source or an aluminum source, and has high utilization rate of the fly ash.
The copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst prepared by the invention is used for H2O2Has good activation effect and can efficiently degrade quinoline in the coal chemical industry wastewater.
Drawings
FIG. 1 is a TEM image of the Cu-Fe bimetal doped modified fly ash-molecular sieve composite catalyst prepared in example 1 of the present invention.
FIG. 2 shows the efficiency of the catalysts prepared in examples 1-3 of the present invention and comparative example 1 for degrading quinoline wastewater.
Detailed Description
The technical solutions of the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments, and the present invention is not limited to these embodiments.
The fly ash used in the examples of the present invention has the following chemical composition:
| components | SiO2 | Al2O3 | Fe2O3 | CaO | SO3 | CuO | Others |
| Composition (wt%) | 41.07 | 17.69 | 8.58 | 13.44 | 7.72 | 0.05 | 11.45 |
Example 1
The preparation method of the copper-iron bimetal modified fly ash-molecular sieve composite catalyst comprises the following steps:
1. weighing 2.5g of fly ash and 3g of sodium hydroxide, and adding the fly ash and the sodium hydroxide into 25mL of deionized water to obtain a suspension A;
2. transferring the suspension A into a microwave reactor, irradiating for 15min at the power of 320W, cooling, and adjusting the pH to about 9 by using 6mol/L HCl solution to obtain a suspension B;
3. dissolving 0.4g of hexadecyl trimethyl ammonium bromide in 5mL of deionized water, and adding the deionized water into the suspension B with the well adjusted pH value under the stirring condition;
4. weighing 0.9155gFe (NO)3)3·9H2O and 0.5018g Cu (NO)3)2·3H2Dissolving O in 10mL deionized water to obtain a metal precursor solution, and adding into a solution containing cetyltrimethylammonium bromideIn the suspension B, carrying out ultrasonic treatment for 40min, and then stirring for 2h to obtain a suspension C;
5. transferring the suspension C dispersed with the metal precursor to a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven, heating to 80 ℃, and carrying out hydrothermal crystallization for 12 hours;
6. after the crystallization reaction is finished, filtering and washing the modified fly ash-molecular sieve compound doped with metal to be neutral, drying for 12 hours at the temperature of 80 ℃, putting the compound into a muffle furnace, raising the temperature by program for 1 to 400 ℃, and roasting for 2 hours at constant temperature to obtain the modified fly ash-molecular sieve composite catalyst doped with copper and iron bimetal.
The composition of the copper-iron bimetallic doped modified fly ash-molecular sieve composite catalyst prepared in this example is shown in the following table.
| Components | SiO2 | Al2O3 | Fe2O3 | CaO | SO3 | CuO | Others |
| Composition (wt%) | 35.82 | 23.19 | 15.11 | 8.78 | 1.30 | 4.21 | 11.59 |
Fig. 1 shows a TEM image of the cu-fe bimetallic doped modified fly ash-molecular sieve composite catalyst prepared in this example, and it can be seen that the prepared catalyst has a partially regular molecular sieve structure and a lattice structure of metal oxide.
Secondly, the application of the copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst in degrading quinoline wastewater is as follows:
500mL of 50mg/L quinoline solution is prepared, the catalyst dosage is 0.25g, and H is2O2The amount of (2) was 1.5mL, and the mixture was stirred in a water bath at a constant temperature of 80 ℃ to degrade quinoline as shown in FIG. 2.
Example 2
The preparation method of the copper-iron bimetal modified fly ash-molecular sieve composite catalyst comprises the following steps:
1. weighing 2.5g of fly ash and 3g of sodium hydroxide, and adding the fly ash and the sodium hydroxide into 25mL of deionized water to obtain a suspension A;
2. transferring the suspension A into a microwave reactor, irradiating for 15min at the power of 320W, cooling, and adjusting the pH to about 9 by using 6mol/L HCl solution to obtain a suspension B;
3. dissolving 0.4g of hexadecyl trimethyl ammonium bromide in 5mL of deionized water, and adding the deionized water into the suspension B with the well adjusted pH value under the stirring condition;
4. weighing 0.9155gFe (NO)3)3·9H2O and 0.5018g Cu (NO)3)2·3H2Dissolving O in 10mL of deionized water to prepare a metal precursor solution, adding the metal precursor solution into a suspension B containing hexadecyl trimethyl ammonium bromide, carrying out ultrasonic treatment for 40min, and then stirring for 2h to obtain a suspension C;
5. transferring the suspension C dispersed with the metal precursor to a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven, heating to 80 ℃, and carrying out hydrothermal crystallization for 24 hours;
6. after the crystallization reaction is finished, filtering and washing the modified fly ash-molecular sieve compound doped with metal to be neutral, drying for 12 hours at the temperature of 80 ℃, putting the compound into a muffle furnace, raising the temperature by program for 1 to 400 ℃, and roasting for 2 hours at constant temperature to obtain the modified fly ash-molecular sieve composite catalyst doped with copper and iron bimetal.
Secondly, the application of the copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst in degrading quinoline wastewater is as follows:
500mL of 50mg/L quinoline solution is prepared, the catalyst dosage is 0.25g, and H is2O2The amount of (2) was 1.5mL, and the mixture was stirred in a water bath at a constant temperature of 80 ℃ to degrade quinoline as shown in FIG. 2.
Example 3
The preparation method of the copper-iron bimetal modified fly ash-molecular sieve composite catalyst comprises the following steps:
1. weighing 2.5g of fly ash and 3g of sodium hydroxide, and adding the fly ash and the sodium hydroxide into 25mL of deionized water to obtain a suspension A;
2. transferring the suspension A into a microwave reactor, irradiating for 15min at the power of 320W, cooling, and adjusting the pH to about 9 by using 6mol/L HCl solution to obtain a suspension B;
3. dissolving 0.4g of hexadecyl trimethyl ammonium bromide in 5mL of deionized water, and adding the deionized water into the suspension B with the well adjusted pH value under the stirring condition;
4. weighing 0.9155gFe (NO)3)3.9H2O and 0.5018g Cu (NO)3)2.3H2Dissolving O in 10mL of deionized water to prepare a metal precursor solution, adding the metal precursor solution into a suspension B containing hexadecyl trimethyl ammonium bromide, carrying out ultrasonic treatment for 40min, and then stirring for 2h to obtain a suspension C;
5. transferring the suspension C dispersed with the metal precursor to a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven, heating to 80 ℃, and carrying out hydrothermal crystallization for 12 hours;
6. after the crystallization reaction is finished, filtering and washing the modified fly ash-molecular sieve compound doped with metal to be neutral, drying for 12 hours at the temperature of 80 ℃, putting the compound into a muffle furnace, raising the temperature by program for 1 to 300 ℃, and roasting for 2 hours at constant temperature to obtain the modified fly ash-molecular sieve composite catalyst doped with copper and iron bimetal.
Secondly, the application of the copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst in degrading quinoline wastewater is as follows:
500mL of 50mg/L quinoline solution is prepared, the catalyst dosage is 0.25g, and H is2O2The amount of (2) was 1.5mL, and the mixture was stirred in a water bath at a constant temperature of 80 ℃ to degrade quinoline as shown in FIG. 2.
Comparative example 1
The preparation method of the loaded bimetal modified fly ash-molecular sieve composite catalyst comprises the following steps:
1. weighing 2.5g of fly ash and 3g of sodium hydroxide, and adding the fly ash and the sodium hydroxide into 25mL of deionized water to obtain a suspension A;
2. transferring the suspension A into a microwave reactor, irradiating for 15min at the power of 320W, cooling, and adjusting the pH to about 9 by using 6mol/L HCl solution to obtain a suspension B;
3. dissolving 0.4g of hexadecyl trimethyl ammonium bromide in 5mL of deionized water, adding the deionized water into the suspension B with the well adjusted pH value under the stirring condition, transferring the suspension B to a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven, heating the suspension B to 80 ℃, and carrying out hydrothermal crystallization for 24 hours;
4. after the crystallization reaction is finished, filtering and washing the modified fly ash-molecular sieve compound to be neutral, and drying for 12 hours at 80 ℃;
5. weighing 0.9155gFe (NO)3)3.9H2O and 0.5018g Cu (NO)3)2.3H2Dissolving O in 10mL of deionized water to prepare a metal precursor solution, soaking the modified fly ash-molecular sieve composite in the same volume, drying, placing the mixture into a muffle furnace, raising the temperature by program for 1h to 400 ℃, and roasting at constant temperature for 2h to prepare the modified fly ash-molecular sieve composite catalyst loaded with the copper-iron bimetal.
500mL of 50mg/L quinoline solution is prepared, the catalyst dosage is 0.25g, and H is2O2The amount of (2) was 1.5mL, and the mixture was stirred in a water bath at a constant temperature of 80 ℃ to degrade quinoline as shown in FIG. 2.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (9)
1. A preparation method of a copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) adding the fly ash into a sodium hydroxide solution with the mass concentration of 10-30% to obtain a suspension A;
(2) transferring the suspension A into a microwave reactor, assisting alkali fusion under microwave irradiation, and then adjusting the pH value to about 9 by using an HCl solution to obtain a suspension B, wherein the suspension B consists of insoluble modified fly ash and a solution containing a silicon element and an aluminum element;
(3) weighing hexadecyl trimethyl ammonium bromide, dissolving the hexadecyl trimethyl ammonium bromide in water, and adding the hexadecyl trimethyl ammonium bromide into the suspension B with the well adjusted pH value under the stirring condition;
(4) weighing Fe (NO)3)3·9H2O and Cu (NO)3)2·3H2Preparing a metal precursor salt solution from O, adding the solution into a suspension B containing hexadecyl trimethyl ammonium bromide, carrying out ultrasonic treatment for 40min, and then stirring for 2h to obtain a suspension C;
(5) transferring the suspension C dispersed with the metal precursor into a hydrothermal reaction kettle lined with polytetrafluoroethylene, putting the hydrothermal reaction kettle into an oven for hydrothermal crystallization, wherein the crystallization temperature is 60-100 ℃, and the time is 12-24 hours;
(6) and after the crystallization reaction is finished, filtering and washing the metal-doped modified fly ash-molecular sieve compound to be neutral, drying and then transferring the compound into a muffle furnace for roasting for 3 hours.
2. The preparation method of the copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst according to claim 1, which is characterized by comprising the following steps of: the mass ratio of the fly ash to the sodium hydroxide in the step (1) is 1: 1.2.
3. The preparation method of the copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst according to claim 1, which is characterized by comprising the following steps of: in the step (2), the microwave power is 160-320W, and the irradiation time is 15-30 min.
4. The preparation method of the copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst according to claim 1, which is characterized by comprising the following steps of: the mass ratio of the hexadecyl trimethyl ammonium bromide to the fly ash in the step (3) is 1: 6-8.
5. The preparation method of the copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst according to claim 1, which is characterized by comprising the following steps of: in the step (4), the mass ratio of copper to iron in the metal precursor salt solution is 1:1.
6. The preparation method of the copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst according to claim 1, which is characterized by comprising the following steps of: the roasting temperature in the step (6) is 300-500 ℃.
7. The copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst prepared by the preparation method of any one of claims 1 to 6.
8. The use of the copper-iron bimetallic doped modified fly ash-molecular sieve composite catalyst of claim 7 in the degradation of quinoline wastewater in coal chemical industry.
9. The application of the copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst in degrading quinoline wastewater in coal chemical industry according to claim 8 is characterized in that: the oxidant jointly used by the copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst in the process of degrading quinoline wastewater is H2O2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910996463.0A CN110639599A (en) | 2019-10-19 | 2019-10-19 | Copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910996463.0A CN110639599A (en) | 2019-10-19 | 2019-10-19 | Copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110639599A true CN110639599A (en) | 2020-01-03 |
Family
ID=69013116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910996463.0A Pending CN110639599A (en) | 2019-10-19 | 2019-10-19 | Copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110639599A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112340750A (en) * | 2020-11-11 | 2021-02-09 | 贵州理工学院 | Green and efficient activation method for fly ash |
| CN113751053A (en) * | 2021-10-11 | 2021-12-07 | 中国环境科学研究院 | Catalyst suitable for low-concentration large-air-volume organic volatile matters and preparation method thereof |
| CN114471449A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Adsorbing material, preparation method thereof and application of adsorbing material in treatment of printing and dyeing wastewater |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586010A (en) * | 2013-10-30 | 2014-02-19 | 中国科学院过程工程研究所 | Method for preparing molecular sieve by using fly ash and mercury removal use of prepared molecular sieve |
| CN105967203A (en) * | 2016-05-10 | 2016-09-28 | 吴迪 | Preparation method of pulverized fly ash MFI zeolite molecular sieve |
| CN107020146A (en) * | 2017-04-20 | 2017-08-08 | 河海大学 | A kind of composite catalyst for handling phenolic waste water and preparation method thereof |
| CN107983395A (en) * | 2017-11-30 | 2018-05-04 | 青岛科技大学 | Using flyash as silicon source and the class fenton catalyst of source of iron and application |
-
2019
- 2019-10-19 CN CN201910996463.0A patent/CN110639599A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586010A (en) * | 2013-10-30 | 2014-02-19 | 中国科学院过程工程研究所 | Method for preparing molecular sieve by using fly ash and mercury removal use of prepared molecular sieve |
| CN105967203A (en) * | 2016-05-10 | 2016-09-28 | 吴迪 | Preparation method of pulverized fly ash MFI zeolite molecular sieve |
| CN107020146A (en) * | 2017-04-20 | 2017-08-08 | 河海大学 | A kind of composite catalyst for handling phenolic waste water and preparation method thereof |
| CN107983395A (en) * | 2017-11-30 | 2018-05-04 | 青岛科技大学 | Using flyash as silicon source and the class fenton catalyst of source of iron and application |
Non-Patent Citations (2)
| Title |
|---|
| 张新华，等: ""Cu/Fe掺杂Silicalite-1合成及其Fenton氧化含酚废水的试验研究"", 《环境科学与技术》 * |
| 梁杰，等: "《粉煤灰资源化研究与实用技术》", 31 August 2017 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471449A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Adsorbing material, preparation method thereof and application of adsorbing material in treatment of printing and dyeing wastewater |
| CN114471449B (en) * | 2020-10-23 | 2023-07-14 | 中国石油化工股份有限公司 | Adsorption material, preparation method thereof and application thereof in treatment of printing and dyeing wastewater |
| CN112340750A (en) * | 2020-11-11 | 2021-02-09 | 贵州理工学院 | Green and efficient activation method for fly ash |
| CN113751053A (en) * | 2021-10-11 | 2021-12-07 | 中国环境科学研究院 | Catalyst suitable for low-concentration large-air-volume organic volatile matters and preparation method thereof |
| CN113751053B (en) * | 2021-10-11 | 2022-08-12 | 中国环境科学研究院 | Catalyst suitable for low-concentration large-air-volume organic volatile matters and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110639599A (en) | Copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst and preparation method and application thereof | |
| CN107824210B (en) | Titanium dioxide composite photocatalyst coated by nitrogen-doped mesoporous carbon and preparation method and application thereof | |
| CN104998672B (en) | A kind of g C3N4/{001}TiO2Composite visible light catalyst and preparation method and application | |
| CN111054417B (en) | High-efficiency iron monatomic Fenton catalyst, and synthesis method and application thereof | |
| CN109650484B (en) | Wastewater treatment agent and preparation method thereof | |
| CN106582673A (en) | Solid phase reaction preparation method for iron-molybdenum process catalyst used for methanol oxidation to formaldehyde | |
| CN105664902A (en) | Trivalent titanium ion self-doped titanium dioxide nanosheet catalyst | |
| CN113877599B (en) | Cobalt manganese spinel material and preparation method and application thereof | |
| CN104843770A (en) | Method of resource utilization of tin sludge | |
| CN106475089A (en) | A kind of TiO with surface Lacking oxygen2/WO3 Visible light catalyst and its preparation method and application | |
| CN110152671A (en) | A kind of metal composite oxide diatomite catalyst and its preparation method and application | |
| CN107572635A (en) | A kind of preparation method of waste water light electrolysis iron carbon filler | |
| CN104148099A (en) | Preparation method for MoS2-BiPO4 composite photocatalyst | |
| CN106582722A (en) | Composite photocatalysis system, and preparation method and application thereof | |
| CN110237855A (en) | A kind of preparation method and application of visible light-responded oxidation Fe2O3 doping nitrogen defect nitridation carbon composite | |
| CN108816266B (en) | YF/g-C3N4Composite material and application thereof in photocatalysis | |
| CN100594976C (en) | Preparation method of purificant in nano titanic oxide photochemical catalyst chamber | |
| CN113351226B (en) | Petal-shaped loaded ZnIn 2 S 4 Preparation method of bismuth oxide composite visible light catalytic material and product prepared by same | |
| CN107416852B (en) | Method for preparing sodium silicate from coal gangue | |
| CN111686767B (en) | Microspherical Bi3O4Preparation and application of Cl/BiOI compound | |
| CN103007980A (en) | Metal doped type visible light denitrification photocatalyst and preparation method and application thereof | |
| CN109012730B (en) | Visible light response boron-nitrogen co-doped photocatalyst and preparation method and application thereof | |
| CN106268746A (en) | A kind of high activity compound oxidizing zinc photocatalyst | |
| CN113477267B (en) | Application of nitrogen oxidation phosphorescence catalytic reduction uranium-containing wastewater | |
| CN103964659A (en) | Method for solidifying lead-containing sludge by utilizing iron-containing sludge generated by Fenton reagent method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200103 |