CN109626486B - Method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater - Google Patents
Method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
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Abstract
A method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater is characterized in that a carbon-containing material is carbonized and activated to prepare a porous carbon material with a high specific surface area and a rich pore structure, and the porous carbon material is used for coupling treatment of high-concentration organic wastewater and heavy metal wastewater and preparation of a hydrogen-rich gas. The porous carbon material prepared from the carbon-containing waste is respectively used for adsorbing and enriching organic matters and heavy metal ions in high-concentration organic wastewater and heavy metal wastewater, so that heavy metals and organic matters are removed. The porous carbon material adsorbed with heavy metal ions is calcined at high temperature to prepare a load type carbon-based catalyst which is used for catalytically reforming organic matters desorbed from the porous carbon adsorbed with organic matters to prepare hydrogen-rich gas. The porous carbon adsorbing and enriching the organic matters is circularly applied to the adsorption of high-concentration organic wastewater after complete desorption, and the inactivated carbon-based catalyst recovers the heavy metals through oxidation and calcination. The water source used in the catalytic reforming experiment is water separated after adsorption is finished, so that the aims of treating waste by waste and regenerating resources are fulfilled.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater.
Background
At present, the problem of water resource pollution in China is increasingly serious, and the problem becomes a great problem which needs to be solved urgently in national economic development. With the development of society, industrial production is continuously increased, industrial sewage discharge is more and more serious, and a large amount of industrial wastewater is directly discharged into rivers or gulfs by a plurality of enterprises, so that not only is the water ecosystem influenced, but also the human health is seriously threatened. Various coking wastewater, pharmaceutical wastewater, textile printing and dyeing wastewater and petrochemical wastewater belong to high-concentration organic wastewater, and the difficulty is high in the treatment process.
The organic matter concentration in the high-concentration organic wastewater is high, the general COD is more than 2000 mg/L, the BOD value is low, the biochemical treatment difficulty is high, the components are complex, the chromaticity of the high-concentration organic wastewater is high, the peculiar smell is large, strong acid and strong alkalinity exist, if the high-concentration organic wastewater is directly discharged, the human sense of discomfort is caused, sunlight is prevented from irradiating the water surface after the high-concentration organic wastewater enters the water body, the photosynthesis rate of microorganisms and aquatic plants in the water is reduced, the aquatic ecology change is caused, and the death of fishes and other aquatic animals in the water is caused.
Heavy metal wastewater is wastewater containing heavy metals (generally containing heavy metals such as nickel, copper, mercury, chromium, cadmium, arsenic, lead, zinc and the like) discharged in industrial production processes such as mining and metallurgy, mechanical manufacturing and the like, and the heavy metals have enrichment property and are difficult to degrade in the environment. Heavy metals discharged along with the heavy metal wastewater can be accumulated in algae and sediment even if the concentration of the heavy metals is low, and the heavy metals are adsorbed by the body surfaces of fishes and shellfishes to generate food chain concentration, thereby causing public nuisance. Heavy metals can strongly interact with proteins and various enzymes in a human body to inactivate the proteins and the enzymes, and can also be enriched in certain organs in the human body, so that acute poisoning, subacute poisoning or chronic poisoning of the human body can be caused and the human body is greatly damaged if the tolerance of the human body is exceeded. For example, water induced in Japan (mercury pollution) and pain (cadmium pollution) are caused by heavy metal pollution. At present, an activated carbon adsorption method is adopted for treating high-concentration organic wastewater and heavy metal wastewater, but the regeneration and elution of activated carbon are difficult. In view of the complexity and the difficult degradability of the components of the high-concentration organic wastewater and the heavy metal wastewater and the limitation of the adopted adsorbent, the method for coupling treatment of the high-concentration organic wastewater and the heavy metal wastewater is researched, and the method has important significance on ecological environment protection and drinking water safety.
Disclosure of Invention
The invention aims to provide a method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater, which utilizes carbon-containing materials such as biomass, waste plastic, waste rubber and the like to prepare porous carbon materials with high specific surface area and rich pore structures, and the porous carbon materials are respectively used for adsorption and enrichment of organic matters and heavy metal ions in the high-concentration organic wastewater and the heavy metal wastewater, and the porous carbon materials adsorbed with the heavy metal ions are calcined at high temperature to prepare a supported carbon-based catalyst which is used for catalytic reforming of organic matters desorbed from the porous carbon adsorbed with the organic matters in the wastewater to prepare hydrogen-rich gas, thereby realizing waste utilization and resource regeneration.
In order to achieve the aim, the method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater comprises the following steps:
firstly, pretreating a carbon-containing raw material, then carrying out carbonization treatment, mixing the obtained carbonized material with an activating agent, and heating and activating in an inert atmosphere to prepare a porous carbon material with a high specific surface area and a rich pore structure;
step two, adsorbing organic matters in the high-concentration organic wastewater by using a porous carbon material, and performing solid-liquid separation on the porous carbon and water to obtain porous carbon adsorbing and enriching the organic matters and first separated water; adsorbing heavy metal ions in the heavy metal wastewater by using a porous carbon material, and performing solid-liquid separation on the porous carbon and water to obtain porous carbon adsorbing and enriching the heavy metal ions and second separated water;
placing the porous carbon adsorbing and enriching the organic matters in a desorption chamber for thermal desorption treatment, desorbing the organic matters adsorbed and enriched on the surface of the porous carbon material and in pore channels in the form of gaseous volatile matters in the heating process to obtain gaseous volatile matters, and recycling the desorbed porous carbon for adsorbing the organic matters in the high-concentration organic wastewater; calcining the porous carbon adsorbing and enriching the heavy metal ions at high temperature in an inert atmosphere to form a supported carbon-based catalyst, wherein the porous carbon material for adsorbing the heavy metal ions is equivalent to a catalyst carrier, and the heavy metal ions adsorbed on the surface and in pore channels of the porous carbon are equivalent to active components;
introducing the gaseous volatile matters into a reforming chamber with a supported carbon-based catalyst, wherein the gaseous volatile matters undergo a reforming reaction, and a reaction water source is obtained from the first separated water and the second separated water and is converted into a hydrogen-rich gas;
and step five, carrying out oxidation and calcination on the carbon-based catalyst inactivated after the reaction to realize the recovery of heavy metals.
The carbon-containing raw material is petroleum coke, biomass, waste rubber or waste plastic, and the biomass comprises fruit shells, straws and wood chips.
The pretreatment in the step one comprises crushing, screening and drying treatment.
The activating agent in the step one is KOH or ZnCl2、H3PO4、NaOH、FeCl3KCl and K2CO3At least one of (1).
The inert atmosphere in the first step is provided by nitrogen, argon or helium, and the activation temperature range is 400-900 ℃.
COD in water of the high-concentration organic wastewater is 2000-30000 mg/L/COD < 0.3.
The heavy metal content of the heavy metal wastewater is 0.1-100 g/L.
And the heating temperature of the third step in the thermal desorption treatment process is 100-300 ℃.
And fifthly, oxidizing and calcining the mixture in an air atmosphere or an oxygen atmosphere at the calcining temperature of 600-900 ℃.
The inert atmosphere in the third step is provided by nitrogen, argon or helium, and the calcining temperature is 500-1000 ℃;
the heavy metal wastewater refers to heavy metal wastewater containing at least one of metal ions of Ni, Cu, Fe, Co, Cd and Au.
The heavy metal ions absorbed on the surface of the porous carbon and in the pore channels of the supported carbon-based catalyst comprise one or more of metal ions of Ni, Cu, Fe, Co, Cd and Au.
Compared with the prior art, the invention has the following beneficial effects: the porous carbon material is prepared from a wide range of raw materials, including petroleum coke, biomass (such as fruit shells, straws, wood chips and the like), waste tires, waste rubber, waste plastics and other carbon-containing materials, and the prepared adsorbing material has the advantages of high specific surface area, high stability, good adsorbing effect and simple preparation process, and can reduce the pollution of wastes to the environment while obtaining the efficient adsorbent. The porous carbon material provided by the invention can be subjected to reduction calcination to obtain the supported carbon-based catalyst after adsorbing heavy metal ions in heavy metal-enriched wastewater, the porous carbon material for adsorbing heavy metals is equivalent to a catalyst carrier, and the heavy metal ions adsorbed on the surface and in pore channels of the porous carbon are equivalent to active components, so that the problems of heavy metal recovery treatment and adsorbent regeneration after traditional activated carbon desorption are reduced to a certain extent, and the solidification and effective recycling of the heavy metals in the wastewater are realized. The coupling treatment method for the high-concentration organic wastewater and the heavy metal wastewater provided by the invention does not relate to a bioreactor, is relatively flexible in operation, simple in process and low in cost, and does not produce secondary pollution. According to the invention, the porous carbon material prepared from the carbon-containing material is used for adsorbing high-concentration organic wastewater and wastewater containing heavy metal ions, so that the heavy metal ions and organic matters in the wastewater can be effectively removed, the cost and time for subsequent water treatment are greatly reduced, and the porous carbon material after heavy metal adsorption can be prepared into the supported carbon-based catalyst through high-temperature calcination.
Drawings
FIG. 1 is a process flow diagram of the present invention for coupling treatment of high concentration organic wastewater and heavy metal wastewater;
in the drawings: 1-a carbonaceous feedstock; 2-a porous carbon material; 3-high concentration organic wastewater; 4-porous carbon for enriching organic matters; 5-first separated water; 6-gaseous volatiles; 7-desorbed porous carbon; 8-a deactivated carbon-based catalyst; 9-supported carbon-based catalyst; 10-second separation of water; 11-porous carbon enriched with heavy metal ions; 12-heavy metal wastewater.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Referring to fig. 1, the method for coupling treatment of high concentration organic wastewater and heavy metal wastewater of the present invention comprises the following steps:
the method comprises the following steps: carrying out pretreatment such as crushing, screening and drying on carbon-containing raw materials 1 such as petroleum coke, biomass, waste rubber and waste plastics, then carrying out carbonization treatment, mixing the obtained carbonized materials with a chemical activating agent, and heating and activating under an inert atmosphere to prepare a porous carbon material 2 with a high specific surface area and a rich pore structure; the activating agent is KOH or ZnCl2、H3PO4、NaOH、FeCl3KCl and K2CO3At least one of them, the activation temperature range is 400-900 ℃.
And secondly, after the porous carbon material 2 prepared in the first step is used for adsorbing organic matters in high-concentration organic wastewater 3, performing solid-liquid separation on the porous carbon and water to obtain porous carbon 4 adsorbing and enriching the organic matters and first decomposed water 5, after the porous carbon material 2 prepared in the first step is used for adsorbing heavy metal ions in heavy metal wastewater 12, performing solid-liquid separation on the porous carbon and water to obtain porous carbon 11 adsorbing and enriching the heavy metal ions and second decomposed water 10, wherein COD in the water of the high-concentration organic wastewater 3 is 2000-30000 mg/L/COD <0.3, and the heavy metal content of the heavy metal wastewater 12 is 0.1-100 g/L.
Step three: and (3) placing the porous carbon 4 which is obtained after solid-liquid separation in the step two and adsorbs the enriched organic matters into a desorption chamber for thermal desorption treatment, so that the organic matters enriched on the surface of the porous carbon material and in the pore channels are desorbed in the form of gaseous volatile matters 6 in the heating process. The heating temperature in the desorption process is generally 100-300 ℃, and the desorbed porous carbon 7 can be cyclically applied to adsorbing organic matters in the high-concentration organic wastewater 3; and (3) calcining the porous carbon 11 which is obtained after solid-liquid separation in the step two and adsorbs and enriches heavy metal ions at high temperature in an inert atmosphere to form the supported carbon-based catalyst 9, wherein the porous carbon material for adsorbing the heavy metal ions is equivalent to a catalyst carrier, and the heavy metal ions adsorbed on the surface and in pore channels of the porous carbon are equivalent to active components. The formed carbon-based catalyst can contain one or more of metal ions such as Ni, Cu, Fe, Co, Cd, Au and the like. The calcination temperature adopted in the preparation process of the catalyst is generally 500-1000 ℃.
In order to prevent the porous carbon from being oxidized in the calcining process, inert gases such as nitrogen, argon, helium and the like are used as protective gases in the calcining process. Meanwhile, the heavy metal ions adsorbed on the porous carbon are solidified on the porous carbon material through calcination;
step four: and introducing the gaseous volatile matter 6 volatilized by desorption into a reforming chamber in which a supported carbon-based catalyst 9 is placed in advance, wherein the gaseous volatile matter 6 is subjected to reforming reaction in the contact process with the supported carbon-based catalyst 9 and is converted into hydrogen-rich gas. The reaction water source is one part of the first separated water 5 and the second separated water 10, and the other part is directly discharged after subsequent treatment;
step five: after the catalytic reforming reaction is finished, the deactivated carbon-based catalyst 8 is oxidized and calcined to realize the recovery of heavy metals. The temperature of the oxidation and calcination is generally 600 to 900 ℃, and the oxidation and calcination are carried out in an air atmosphere or an oxygen atmosphere.
The technical effect of the present invention is illustrated by the following examples:
example 1
The method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater comprises the following steps:
step one, preparing a carbon-containing raw material 1: pine wood chips are taken as a raw material, and are carbonized after being crushed, screened and dried to prepare a carbon-containing raw material 1, wherein the carbonization temperature is 700 ℃, and the carbonization treatment time is 2 hours.
Step two, preparing the porous carbon material 2: mixing the biomass-based carbonized material prepared in the step one with potassium hydroxide in a ratio of 1: 4, reacting in a fixed bed reactor, carrying out acid washing and water washing for multiple times after the reaction is finished, and drying to obtain the porous carbon material 2, wherein the activation temperature of the carbon-containing raw material 1 in the process is 700 ℃, and the reaction time is 2 hours.
And step three, coupling treatment of the high-concentration organic wastewater and the heavy metal wastewater, namely respectively using the porous carbon material 2 prepared in the step two for adsorption of organic matters and heavy metals in the high-concentration organic wastewater 3 and the heavy metal wastewater 12, taking 100ml of the high-concentration organic wastewater with the COD content of 7000 mg/L, adding 0.8g of the porous carbon material 2 prepared in the step two into the wastewater, after the adsorption is completed, the removal rate of the organic matters in the wastewater is 95%, taking the heavy metal wastewater with the nickel ion concentration of 10 g/L, adding 0.8g of the porous carbon material 2 prepared in the step two into the wastewater, and after the adsorption is completed, the removal rate of the heavy metals in the wastewater is 95%.
Step four, preparing a supported carbon-based catalyst 9: the porous carbon material 2 absorbed with Ni ions is reduced and calcined to prepare the supported carbon-based catalyst 9, the calcining temperature is 600 ℃, and the calcining time is 6 hours.
Step five, research of hydrogen production by catalytic reforming: the supported carbon-based catalyst 9 in the fourth step is used for catalytically reforming organic matters absorbed from the porous carbon material 2 which adsorbs the organic matters in the third step, the reforming temperature is 600 ℃, and the hydrogen yield is 73 percent.
Example 2
The method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater comprises the following steps:
step one, preparing a carbon-containing raw material 1: the method comprises the steps of taking petroleum coke as a raw material, crushing, screening and drying the petroleum coke, and then carbonizing the petroleum coke to prepare a carbon-containing raw material 1, wherein the carbonization temperature is 700 ℃, and the carbonization treatment time is 2 hours.
Step two, preparing the porous carbon material 2: mixing the petroleum coke carbonized material prepared in the step one with potassium hydroxide in a ratio of 1: 4, reacting in a fixed bed reactor, carrying out acid washing and water washing for multiple times after the reaction is finished, and drying to obtain the porous carbon material, wherein the activation temperature of the carbonized material in the process is 700 ℃, and the reaction time is 2 hours.
And step three, coupling treatment of the high-concentration organic wastewater and the heavy metal wastewater, namely respectively using the porous carbon material 2 prepared in the step two for adsorption of organic matters and heavy metals in the high-concentration organic wastewater 3 and the heavy metal wastewater 12, taking 100ml of the high-concentration organic wastewater with the COD content of 7000 mg/L, adding 0.8g of the porous carbon material 2 prepared in the step two into the wastewater, wherein after the adsorption is finished, the removal rate of the organic matters in the wastewater is 98%, taking the heavy metal wastewater with the nickel ion concentration of 10 g/L, adding 0.8g of the porous carbon material 2 prepared in the step two into the wastewater, and after the adsorption is finished, the removal rate of the heavy metals in the wastewater is 98%.
Step four, preparing a supported carbon-based catalyst 9: the porous carbon material 2 absorbed with Ni ions is subjected to reduction calcination to prepare the supported carbon-based catalyst 9, wherein the calcination temperature is 700 ℃, and the calcination time is 3 h.
Step five, research of hydrogen production by catalytic reforming: the supported carbon-based catalyst 9 in the fourth step is used for catalytically reforming organic matters absorbed from the porous carbon material 2 which adsorbs the organic matters in the third step, the reforming temperature is 600 ℃, and the yield of the obtained hydrogen is 78%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and it should be understood by those skilled in the art that several modifications or simple substitutions may be made in the technical solution of the present invention without departing from the spirit of the present invention, and these modifications and substitutions also fall within the protection scope defined by the appended claims.
Claims (10)
1. A method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater is characterized by comprising the following steps:
firstly, pretreating a carbon-containing raw material (1), then carrying out carbonization treatment, mixing the obtained carbonized material with an activating agent, and heating and activating in an inert atmosphere to prepare a porous carbon material (2) with a high specific surface area and a rich pore structure;
step two, adsorbing organic matters in the high-concentration organic wastewater (3) by using a porous carbon material (2), and performing solid-liquid separation to obtain porous carbon (4) adsorbing the enriched organic matters and first separated water (5); adsorbing heavy metal ions in the heavy metal wastewater (12) by using a porous carbon material (2), and performing solid-liquid separation to obtain porous carbon (11) adsorbing and enriching the heavy metal ions and second separated water (10);
placing the porous carbon (4) adsorbing and enriching the organic matters in a desorption chamber for thermal desorption treatment, so that the organic matters adsorbed and enriched on the surface of the porous carbon material and in pore channels are desorbed in a gaseous volatile matter (6) form in the heating process, and the desorbed porous carbon (7) is recycled for adsorbing the organic matters in the high-concentration organic wastewater (3); calcining the porous carbon (11) adsorbing and enriching the heavy metal ions at high temperature in an inert atmosphere to form a supported carbon-based catalyst (9), wherein a porous carbon material (2) for adsorbing the heavy metal ions is a catalyst carrier, and the heavy metal ions adsorbed on the surface and in pore channels of the porous carbon are active components;
the heavy metal wastewater (12) is heavy metal wastewater containing at least one of metal ions Ni, Cu, Fe, Co, Cd and Au, and the heavy metal ions adsorbed on the surface and in the pore channels of the porous carbon by the supported carbon-based catalyst (9) comprise one or more of metal ions Ni, Cu, Fe, Co, Cd and Au;
introducing the gaseous volatile matter (6) into a reforming chamber provided with a supported carbon-based catalyst (9), wherein the gaseous volatile matter (6) is subjected to a reforming reaction, and a reaction water source is obtained from the first separated water (5) and the second separated water (10) and is converted into a hydrogen-rich gas;
and step five, carrying out oxidation and calcination on the carbon-based catalyst (8) inactivated after the reaction to realize the recovery of heavy metals.
2. The method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater according to claim 1, wherein the method comprises the following steps: the carbonaceous raw material (1) is petroleum coke, biomass, waste rubber or waste plastic, and the biomass is any one of fruit shell, straw and wood chip.
3. The method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater according to claim 1, wherein the method comprises the following steps: the pretreatment in the step one comprises crushing, screening and drying treatment.
4. The method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater according to claim 1, wherein the method comprises the following steps: the activating agent in the step one is KOH or ZnCl2、H3PO4、NaOH、FeCl3KCl and K2CO3At least one of (1).
5. The method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater according to claim 1, wherein the method comprises the following steps: the inert atmosphere in the first step is provided by nitrogen, argon or helium, and the activation temperature range is 400-900 ℃.
6. The method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater according to claim 1, wherein COD in the high-concentration organic wastewater (3) is 2000-30000 mg/L/COD < 0.3.
7. The method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater according to claim 1, wherein the heavy metal content of the heavy metal wastewater (12) is 0.1-100 g/L.
8. The method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater according to claim 1, wherein the method comprises the following steps: and the heating temperature of the third step in the thermal desorption treatment process is 100-300 ℃.
9. The method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater according to claim 1, wherein the method comprises the following steps: and fifthly, oxidizing and calcining the mixture in an air atmosphere or an oxygen atmosphere at the calcining temperature of 600-900 ℃.
10. The method for coupling treatment of high-concentration organic wastewater and heavy metal wastewater according to claim 1, wherein the method comprises the following steps: and step three, providing an inert atmosphere by nitrogen, argon or helium, wherein the calcining temperature is 500-1000 ℃.
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