CN114632524A - Copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment and preparation method thereof - Google Patents

Copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment and preparation method thereof Download PDF

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CN114632524A
CN114632524A CN202210536692.6A CN202210536692A CN114632524A CN 114632524 A CN114632524 A CN 114632524A CN 202210536692 A CN202210536692 A CN 202210536692A CN 114632524 A CN114632524 A CN 114632524A
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precursor
manganese
copper
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aluminum oxide
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吴昌永
付丽亚
王辉
王盼新
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Henan Anyi Environmental Protection Technology Co ltd
Chinese Research Academy of Environmental Sciences
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Henan Anyi Environmental Protection Technology Co ltd
Chinese Research Academy of Environmental Sciences
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • 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
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)

Abstract

A copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment and a preparation method thereof belong to the technical field of catalyst preparation. The paint comprises the following components in parts by weight: 50-80 parts of Al2O3The composite activating agent comprises an activating composite carrier, 10-20 parts of a first active component, 10-20 parts of a second active component and 3-5 parts of a competitive adsorption auxiliary agent. The invention uses Al2O3The activated composite carrier is used as a catalyst carrier, and the metal active component is impregnated on the surface of the activated composite carrier, so that the prepared catalyst particles have large specific surface area, more active sites and adsorption effectGood in the same properties, and Al2O3The composite carrier is activated by adding Al to the existing Al2O3On the basis, a rough structure is formed on the surface of the composite material through low-temperature plasma etching, and then the composite material is placed in PTFE emulsion for soaking to form a nano-scale whisker structure, and meanwhile, the composite material is activated by matching with a radio frequency plasma energy supply mode, so that Al is added2O3The surface area of the activated composite carrier improves the active sites, so that the prepared catalyst has large and uniform loading capacity and good catalytic performance.

Description

Copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment and preparation method thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment and a preparation method thereof.
Background
The method comprises the following steps of (1) carrying out thermal cracking on the raw materials of light oil or heavy oil such as naphtha and byproduct gas in oil refining production to produce chemical raw materials such as ethylene and the like, and further reacting to synthesize various organic chemical products, wherein the waste water discharged in the process is named petrochemical waste water; the waste water discharged in the production process of synthetic rubber, synthetic plastics, fibers, detergents and other products and chemical raw materials such as benzene, Cai, methanol, glycerol, acetaldehyde and the like is petrochemical waste water.
The petrochemical wastewater has large water quantity and complex components, and the nature of the wastewater is complex and variable due to the complexity of petrochemical products, complex reaction process and unit operation; the waste water has high content of organic matters, especially hydrocarbons and derivatives thereof, and contains various heavy metals. Petrochemical wastewater has a plurality of sources and different components, and is closely related to a production flow, so that the quality and the quantity of the wastewater are difficult to determine.
The petrochemical wastewater treatment difficulty is high, the investment cost is high, and the pollution to the environment forms serious pollution and the like; with the continuous deepening of the national sustainable development strategy, the problem of improving and solving the environmental pollution caused by petrochemical wastewater is a problem which needs to be solved urgently.
Heterogeneous catalytic ozonation generates more oxidative hydroxyl radical free radicals by catalytic ozonation, and can degrade and thoroughly mineralize organic pollutants which are difficult to be subjected to independent ozonation in water. The method has strong dependence on the catalyst, but the existing catalyst for treating petrochemical wastewater has small specific surface area and low surface active sites, so that the catalytic performance is low, and meanwhile, the binding force between the surface of carrier particles and active components of the prepared catalyst is not strong, so that the prepared catalyst has small and not uniform load, and the consumption of impregnation liquid is large during impregnation treatment, thereby causing resource waste.
Disclosure of Invention
Aiming at the problems, the invention provides a copper-manganese/aluminum oxide catalyst with good active sites and catalytic performance for petrochemical wastewater treatment and a preparation method thereof.
The technical scheme of the invention is as follows: a copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment comprises the following components in parts by weight: 50-80 parts of Al2O3The composite material comprises an activated composite carrier, 10-20 parts of a first active component, 10-20 parts of a second active component and 3-5 parts of a competitive adsorption auxiliary agent, wherein the first active component is CuO and Cu in a mass ratio of 1:22O, the second active component is MnO, the competitive adsorption auxiliary agent is any one of citric acid, tartaric acid, trichloroacetic acid or oxalic acid, and the two active components can be uniformly distributed on Al by adding the competitive adsorption auxiliary agent2O3Activating the composite carrier.
Further, the Al2O3The specific surface area of the activated composite carrier is 430-450m/g, and the pore volume is 0.5-0.9 mL/g.
Further, the Al2O3The preparation method of the activation composite carrier comprises the following steps:
s1, mixing Al (NO) according to the mass ratio of 1:33)3·9H2Dissolving O in anhydrous ethanol, heating at 50-70 deg.C, stirring, adjusting pH to 6-7, reacting for 2-3 hr to obtain mixed base solution, and adding concentrated HNO with molar concentration of 13.4mol/L and 0.8-1wt% of the mixed base solution3Then, Al is generated2O3Gelling;
s2, heating the Al at 40-50 DEG C2O3Drying the gel for 20-24h to obtain Al2O3A precursor;
s3, etching Al by using low-temperature plasma2O3Precursor, forming rough structure on the surface of the precursor, and then adding Al according to the solid-to-liquid ratio of 1:22O3Soaking the precursor in PTFE emulsion, and inducing Al by doping F element2O3Growing a nano-scale whisker structure on the surface of the precursor, and finally, adopting a radio frequency plasma energy supply mode to enable the Al to pass through2O3Activating the precursor to obtain Al2O3Activating the composite support by Al2O3The rough structure on the surface of the precursor ensures that the contact area between the PTFE emulsion and the surface of the PTFE emulsion is large, the nano-scale whisker structure is formed, and meanwhile, the activation treatment is carried out by matching with the mode of radio frequency plasma energy supply, so that the Al content is increased2O3The surface area of the composite carrier is activated, and simultaneously, the active sites are improved, so that the prepared catalyst has large and uniform loading capacity and good catalytic performance.
Further, in step S3, during the low temperature plasma etching, the etching gas is SF with a flow rate of 40-45sccm6And O at a flow rate of 8 to 10sccm2The power of the upper electrode is 350-370W, the power of the lower electrode is 6-8W, and the etching result with higher selection ratio is obtained by controlling the relevant parameters, so that the etching effect is improved.
Further, the power output power of the radio frequency plasma is 80-90W.
Further, the copper-manganese/aluminum oxide catalyst is applied to the aspect of advanced treatment of petrochemical wastewater biochemical effluent.
The preparation method of the copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment comprises the following steps:
(1) dissolving the first active component, the second active component and the competitive adsorption auxiliary agent in parts by weight in 50-60 parts of deionized water to obtain an impregnation solution;
(2) taking the immersion liquid to react with Al2O3Activating the composite carrier to perform pre-soaking treatment when Al is contained2O3When the water content of the activated composite carrier reaches 15-20wt%, adding Al2O3The activated composite carrier is uniformly dispersed into the circulating fluidized bed, and simultaneously, the impregnated carrier after pre-soaking treatment is impregnatedAtomizing the solution, continuously spraying the atomized impregnation solution into the circulating fluidized bed in a mode of changing the spraying height, and continuing for 30-40min to obtain a precursor of the copper-manganese/aluminum oxide catalyst, wherein the spraying amount of the atomized impregnation solution is 900-1000 g/m-2；
(3) Drying the precursor of the copper-manganese/aluminum oxide catalyst for 1-2h at the temperature of 90-100 ℃, then placing the precursor in a tubular furnace, and roasting the precursor for 5-6h at the temperature of 450-500 ℃ to obtain the copper-manganese/aluminum oxide catalyst.
Further, in the step (2), when the atomized impregnation liquid is sprayed into the circulating fluidized bed in a manner of changing the spraying height, the spraying amount of the impregnation liquid is sequentially reduced along with the reduction of the spraying height, wherein the height difference between two adjacent heights is 50-70cm, and the spraying amount difference between two adjacent heights is 50-100 g.
Further, in the step (2), Al is added2O3When the activated composite carrier is uniformly dispersed into the circulating fluidized bed, Al2O3The addition rate of the activated composite carrier was 150-180 mg/s.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention uses Al2O3The activated composite carrier is used as a catalyst carrier, and the metal active component is impregnated on the surface of the activated composite carrier, so that the prepared catalyst particles have the characteristics of large specific surface area, many active sites, good adsorption effect and the like, are widely applied in various fields, and Al2O3The composite carrier is activated by adding Al to the existing Al2O3On the basis, a rough structure is formed on the surface of the composite material through low-temperature plasma etching, and then the composite material is placed in PTFE emulsion for soaking to form a nano-scale whisker structure, and meanwhile, the composite material is activated by matching with a radio frequency plasma energy supply mode, so that Al is added2O3The surface area of the activated composite carrier improves the active sites, so that the prepared catalyst has large and uniform loading capacity and good catalytic performance;
(2) when the catalyst is prepared, the invention is used for Al2O3Pre-soaking the activated composite carrier to obtain Al2O3The activated composite carrier can maintain a certain humidity, and can avoid Al2O3The activated composite carrier particles are mutually collided and crushed to ensure that Al2O3The surface area and active sites of the activated composite carrier are reduced, thus reducing the activity of the catalyst, the impregnating solution is sprayed into the circulating fluidized bed at different heights after being atomized, and the spraying amount of the impregnating solution is reduced along with the reduction of the height, because Al2O3The surface of the activated composite carrier can be repeatedly sprayed with the impregnation liquid in the descending process, and only a small amount of impregnation liquid is needed to be sprayed when the activated composite carrier is positioned at a lower position, so that Al is ensured2O3The part of the surface of the activated composite carrier, which is not sprayed in place, is completely soaked, so that the impregnation liquid can be fully sprayed by controlling the spraying of the impregnation liquid, the use amount of the impregnation liquid can be saved, and the method has the advantages of energy conservation and emission reduction.
Detailed Description
In order to further understand the contents of the present invention, the present invention is described in detail by examples below.
Example 1
A copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment comprises the following components in parts by weight: 50 parts of Al2O3The catalyst comprises a carrier, 10 parts of a first active component, 10 parts of a second active component and 3 parts of citric acid, wherein the first active component is CuO and Cu in a mass ratio of 1:22O, and the second active component is MnO;
the preparation method of the copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment comprises the following steps:
(1) dissolving the first active component, the second active component and the competitive adsorption auxiliary agent in parts by weight in 50 parts of deionized water to obtain an impregnation solution;
(2) taking the immersion liquid to react with Al2O3Pre-wetting the carrier to Al2O3When the water content of the carrier reached 15wt%, Al was added at an addition rate of 150mg/s2O3The carrier is uniformly dispersed to the circulating fluidizationIn the bed, simultaneously atomizing the impregnation liquid after the pre-wetting treatment, continuously spraying the atomized impregnation liquid into the circulating fluidized bed in a mode of changing the spraying height for 30min to obtain a copper-manganese/aluminum oxide catalyst precursor, wherein the spraying amount of the atomized impregnation liquid is 900g/m2The spraying amount of the impregnation liquid is reduced in sequence along with the reduction of the spraying height, wherein the height difference between two adjacent heights is 50cm, and the spraying amount difference of the impregnation liquid between two adjacent heights is 50 g;
(3) drying the precursor of the copper-manganese/aluminum oxide catalyst for 1h at the temperature of 90 ℃, then placing the precursor in a tubular furnace, and roasting the precursor for 5h at the temperature of 450 ℃ to obtain the copper-manganese/aluminum oxide catalyst.
Example 2
A copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment comprises the following components in parts by weight: 60 parts of Al2O3The catalyst comprises a carrier, 15 parts of a first active component, 15 parts of a second active component and 4 parts of citric acid, wherein the first active component is CuO and Cu in a mass ratio of 1:22O, and the second active component is MnO;
the preparation method of the copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment comprises the following steps:
(1) dissolving the first active component, the second active component and the competitive adsorption auxiliary agent in parts by weight in 55 parts of deionized water to obtain an impregnation solution;
(2) taking the immersion liquid to react with Al2O3Pre-wetting the carrier to Al2O3When the water content of the carrier reached 18wt%, Al was added at an addition rate of 165mg/s2O3Uniformly dispersing the carrier into a circulating fluidized bed, atomizing the presoaked impregnation liquid, continuously spraying the atomized impregnation liquid into the circulating fluidized bed in a mode of changing the spraying height for 35min to obtain a copper-manganese/aluminum oxide catalyst precursor, wherein the spraying amount of the atomized impregnation liquid is 950g/m2Dipping with decreasing spray heightThe spraying amount of the liquid is reduced in sequence, wherein the height difference between two adjacent heights is 60cm, and the spraying amount difference of the impregnating solution between two adjacent heights is 80 g;
(3) drying the precursor of the copper-manganese/aluminum oxide catalyst for 1.5h at the temperature of 95 ℃, then placing the precursor in a tubular furnace, and roasting the precursor for 5.5h at the temperature of 480 ℃ to obtain the copper-manganese/aluminum oxide catalyst.
Example 3
A copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment comprises the following components in parts by weight: 80 parts of Al2O3The catalyst comprises a carrier, 20 parts of a first active component, 20 parts of a second active component and 5 parts of citric acid, wherein the first active component is CuO and Cu in a mass ratio of 1:22O, and the second active component is MnO;
the preparation method of the copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment comprises the following steps:
(1) dissolving the first active component, the second active component and the competitive adsorption auxiliary agent in parts by weight in 60 parts of deionized water to obtain an impregnation solution;
(2) taking the immersion liquid to react with Al2O3Pre-wetting the carrier to Al2O3When the water content of the carrier reaches 20wt%, Al is added at an addition rate of 180mg/s2O3Uniformly dispersing the carrier into a circulating fluidized bed, simultaneously atomizing the impregnation liquid after the pre-wetting treatment, continuously spraying the atomized impregnation liquid into the circulating fluidized bed in a mode of changing the spraying height for 40min to obtain a copper-manganese/aluminum oxide catalyst precursor, wherein the spraying amount of the atomized impregnation liquid is 1000g/m2The spraying amount of the impregnation liquid is reduced in sequence along with the reduction of the spraying height, wherein the height difference between two adjacent heights is 70cm, and the spraying amount difference of the impregnation liquid between two adjacent heights is 100 g;
(3) drying the precursor of the copper-manganese/aluminum oxide catalyst for 2 hours at the temperature of 100 ℃, then placing the precursor in a tubular furnace, and roasting the precursor for 6 hours at the temperature of 500 ℃ to obtain the copper-manganese/aluminum oxide catalyst.
Example 4
This example is substantially the same as example 3, except that:
by using Al2O3Substitution of Al by activated composite carrier2O3Support, Al2O3The specific surface area of the activated composite carrier is 430m/g, and the pore volume is 0.5 mL/g;
Al2O3the preparation method of the activated composite carrier comprises the following steps:
s1, mixing Al (NO) according to the mass ratio of 1:33)3·9H2Dissolving O in absolute ethyl alcohol, heating at 50 ℃, stirring, adjusting pH to 6, continuing to react for 2h to obtain a mixed base liquid, and adding concentrated HNO with a molar concentration of 13.4mol/L and 0.8wt% of the mixed base liquid relative to the weight of the mixed base liquid into the mixed base liquid3Then, Al is generated2O3Gelling;
s2, heating the Al at 40 DEG C2O3Drying the gel for 20h to obtain Al2O3A precursor;
s3, etching Al by using low-temperature plasma2O3Precursor, forming rough structure on the surface of the precursor, and then adding Al according to the solid-to-liquid ratio of 1:22O3Soaking the precursor in PTFE emulsion, and inducing Al by doping F element2O3Growing a nano-scale whisker structure on the surface of the precursor, and finally supplying the Al by adopting a radio frequency plasma energy supply mode with the power output of 80W2O3Activating the precursor to obtain Al2O3Activating the composite carrier, wherein the etching gas is SF with a flow rate of 40sccm6And O at a flow rate of 8sccm2The upper electrode power was 350W, and the lower electrode power was 6W.
The copper-manganese/aluminum oxide catalyst is applied to the aspect of advanced treatment of petrochemical wastewater biochemical effluent.
Example 5
This example is substantially the same as example 3, except that:
by using Al2O3Substitution of Al by activated composite carrier2O3Support, Al2O3The specific surface area of the activated composite carrier is 440m/g, and the pore volume is 0.7 mL/g;
Al2O3the preparation method of the activated composite carrier comprises the following steps:
s1, mixing Al (NO) according to the mass ratio of 1:33)3·9H2Dissolving O in absolute ethyl alcohol, heating at 60 ℃, stirring, adjusting pH to 6.5, continuing to react for 2.5h to obtain a mixed base liquid, and adding concentrated HNO with the molar concentration of 13.4mol/L and the weight of 0.9wt% of the mixed base liquid into the mixed base liquid3Then, Al is generated2O3Gelling;
s2, heating the Al at 45 DEG C2O3Drying the gel for 22h to obtain Al2O3A precursor;
s3, etching Al by using low-temperature plasma2O3Precursor, forming rough structure on the surface of the precursor, and then adding Al according to the solid-to-liquid ratio of 1:22O3Soaking the precursor in PTFE emulsion, and inducing Al by doping F element2O3Growing a nano-scale whisker structure on the surface of the precursor, and finally supplying the Al by adopting a radio frequency plasma energy supply mode with the power output power of 85W2O3Activating the precursor to obtain Al2O3Activating the composite carrier, wherein the etching gas is SF with a flow rate of 43sccm6And O at a flow rate of 9sccm2The upper electrode power is 360W, and the lower electrode power is 7W.
The copper-manganese/aluminum oxide catalyst is applied to the aspect of advanced treatment of petrochemical wastewater biochemical effluent.
Example 6
This example is substantially the same as example 3, except that:
by using Al2O3Substitution of Al by activated composite carrier2O3Support, Al2O3The specific surface area of the activated composite carrier is 450m/g, and the pore volume is 0.9 mL/g;
Al2O3the preparation method of the activated composite carrier comprises the following steps:
s1, mixing Al (NO) according to the mass ratio of 1:33)3·9H2Dissolving O in anhydrous ethanol, heating at 70 deg.C, stirring, adjusting pH to 7, reacting for 3 hr to obtain mixed base solution, and adding concentrated HNO with a molar concentration of 13.4mol/L (1 wt% relative to the weight of the mixed base solution)3Then, Al is generated2O3Gelling;
s2, heating the Al at 50 DEG C2O3Drying the gel for 24 hours to obtain Al2O3A precursor;
s3, etching Al by using low-temperature plasma2O3Precursor, forming rough structure on the surface of the precursor, and then adding Al according to the solid-to-liquid ratio of 1:22O3Soaking the precursor in PTFE emulsion, and inducing Al by doping F element2O3Growing a nano-scale whisker structure on the surface of the precursor, and finally supplying the Al by adopting a radio frequency plasma energy supply mode with power output power of 90W2O3Activating the precursor to obtain Al2O3Activating the composite carrier, wherein the etching gas is SF with a flow rate of 45sccm6And O at a flow rate of 10sccm2The upper electrode power is 370W, and the lower electrode power is 8W.
The copper-manganese/aluminum oxide catalyst is applied to the aspect of advanced treatment of petrochemical wastewater biochemical effluent.
Test examples
The catalyst for treating petrochemical wastewater in the prior art and the catalyst prepared by the method of examples 1 to 6 were used to treat petrochemical wastewater to obtain performance index parameters of the treated water body, which are specifically shown in table 1.
Table 1: performance index parameter Table for Water after petrochemical wastewater treatment with Prior Art catalysts and catalysts of examples 1-6
Figure DEST_PATH_IMAGE002
As can be seen from Table 1, when the catalysts of the prior art and examples 1-6 are used for treating petrochemical wastewater, the methods of examples 1-6 have higher removal rates for COD, BOD, TOC, SS, TN and ammonia nitrogen, which indicates that the desalting effect of the method of the examples of the present invention is better than that of the prior art.
As can be seen from comparative examples 1 to 3, the parameters related to example 3 are most effective in treating petrochemical wastewater during the treatment of petrochemical wastewater, and thus, the scheme of example 3 is superior to examples 1 and 2.
As can be seen from comparing example 3 with examples 4 to 6, examples 4 to 6 are superior to example 3 in the effect of treating petrochemical wastewater, and illustrate that Al prepared by the present invention2O3The effect of the activated composite carrier is better than that of Al2O3Carrier, and wherein the relevant parameters of example 6 are optimal for petrochemical wastewater treatment, therefore, example 6 is the best example.

Claims (9)

1. The copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment is characterized by comprising the following components in parts by weight: 50-80 parts of Al2O3The composite material comprises an activated composite carrier, 10-20 parts of a first active component, 10-20 parts of a second active component and 3-5 parts of a competitive adsorption auxiliary agent, wherein the first active component is CuO and Cu in a mass ratio of 1:22O, the second active component is MnO, and the competitive adsorption auxiliary agent is any one of citric acid, tartaric acid, trichloroacetic acid or oxalic acid.
2. The copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment according to claim 1, wherein the Al is2O3The specific surface area of the activated composite carrier is 430-450m/g, and the pore volume is 0.5-0.9 mL/g.
3. A method according to claim 1The copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment is characterized in that the Al is2O3The preparation method of the activated composite carrier comprises the following steps:
s1, mixing Al (NO) according to the mass ratio of 1:33)3·9H2Dissolving O in anhydrous ethanol, heating at 50-70 deg.C, stirring, adjusting pH to 6-7, reacting for 2-3 hr to obtain mixed base solution, and adding concentrated HNO with a molar concentration of 13.4mol/L (0.8-1 wt% relative to the weight of the mixed base solution)3Then, Al is generated2O3Gelling;
s2, heating the Al at 40-50 deg.C2O3Drying the gel for 20-24h to obtain Al2O3A precursor;
s3, etching Al by using low-temperature plasma2O3Precursor, forming rough structure on the surface of the precursor, and then adding Al according to the solid-to-liquid ratio of 1:22O3Soaking the precursor in PTFE emulsion, and inducing Al by doping F element2O3Growing a nano-scale whisker structure on the surface of the precursor, and finally, adopting a radio frequency plasma energy supply mode to enable the Al to pass through2O3Activating the precursor to obtain Al2O3And (4) activating the composite carrier.
4. The Cu-Mn/Al oxide catalyst as claimed in claim 3, wherein in step S3, the etching gas is SF gas with a flow rate of 40-45sccm during low temperature plasma etching6And O at a flow rate of 8-10sccm2The power of the upper electrode is 350-370W, and the power of the lower electrode is 6-8W.
5. The copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment according to claim 3, wherein the power output of the radio frequency plasma is 80-90W.
6. The copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment according to claim 1, wherein the copper-manganese/aluminum oxide catalyst is applied to advanced treatment of biochemical effluent of petrochemical wastewater.
7. The method of claim 1, wherein the method comprises the following steps:
dissolving the first active component, the second active component and the competitive adsorption auxiliary agent in parts by weight in 50-60 parts of deionized water to obtain an impregnation solution;
taking the immersion liquid to react with Al2O3Activating the composite carrier to perform pre-soaking treatment when Al is contained2O3When the water content of the activated composite carrier reaches 15-20wt%, adding Al2O3Uniformly dispersing the activated composite carrier into a circulating fluidized bed, simultaneously atomizing the impregnation liquid subjected to pre-wetting treatment, continuously spraying the atomized impregnation liquid into the circulating fluidized bed in a mode of changing the spraying height, and continuing for 30-40min to obtain a copper-manganese/aluminum oxide catalyst precursor, wherein the spraying amount of the atomized impregnation liquid is 900-1000 g/m-2；
Drying the precursor of the copper-manganese/aluminum oxide catalyst for 1-2h at the temperature of 90-100 ℃, then placing the precursor in a tubular furnace, and roasting the precursor for 5-6h at the temperature of 450-500 ℃ to obtain the copper-manganese/aluminum oxide catalyst.
8. The method according to claim 7, wherein in the step (2), when the atomized impregnation liquid is sprayed into the circulating fluidized bed in a manner of varying the spraying height, the spraying amount of the impregnation liquid is sequentially reduced as the spraying height is reduced, wherein the height difference between two adjacent heights is 50 to 70cm, and the spraying amount difference between two adjacent heights is 50 to 100 g.
9. Root of herbaceous plantThe method of claim 7, wherein in the step (2), Al is added2O3When the activated composite carrier is uniformly dispersed into the circulating fluidized bed, Al2O3The addition rate of the activated composite carrier was 150-180 mg/s.
CN202210536692.6A 2022-05-18 2022-05-18 Copper-manganese/aluminum oxide catalyst for petrochemical wastewater treatment and preparation method thereof Pending CN114632524A (en)

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CN110302796A (en) * 2019-07-09 2019-10-08 中北大学 A kind of Mn-Fe-Cu/ γ-Al of hypergravity fluidisation spray-stain method preparation2O3Catalyst and its application
CN110302797A (en) * 2019-07-09 2019-10-08 中北大学 A kind of bi-component manganese base supported catalyst of hypergravity spray-stain method preparation and its application
CN111282577A (en) * 2020-03-30 2020-06-16 中国环境科学研究院 Supported bi-component metal oxide catalyst for advanced treatment of petrochemical wastewater and preparation method thereof

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Publication number Priority date Publication date Assignee Title
WO2006006702A1 (en) * 2004-07-15 2006-01-19 Nikki-Universal Co., Ltd. Catalyst for purifying exhaust gas containing organic nitrogen compound and method for purifying such exhaust gas
CN110152682A (en) * 2018-03-30 2019-08-23 铜仁学院 A kind of organic wastewater ozone oxidation catalyst and its preparation method and application
CN108772056A (en) * 2018-06-14 2018-11-09 南京信息工程大学 A kind of preparation of support type cordierite catalyst and photo-thermal synergistic oxidation VOCs
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Application publication date: 20220617