CN111377519A - Method for treating organic wastewater - Google Patents

Method for treating organic wastewater Download PDF

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Publication number
CN111377519A
CN111377519A CN201811618219.2A CN201811618219A CN111377519A CN 111377519 A CN111377519 A CN 111377519A CN 201811618219 A CN201811618219 A CN 201811618219A CN 111377519 A CN111377519 A CN 111377519A
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catalyst
hours
roasting
calcium
pore
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CN111377519B (en
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蒋广安
赵越
李宝忠
王雪清
马传军
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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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
    • C02F1/72—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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/618—Surface area more than 1000 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

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

Abstract

The invention relates to the technical field of wastewater treatment, and particularly discloses a method for treating organic wastewater, which comprises the following steps: the organic wastewater and ozone enter a reactor to react, a catalyst A and a catalyst B are sequentially filled in the reactor according to the contact sequence of the organic wastewater, the catalyst A is a supported catalyst, the active component of the catalyst A is one or more of copper, chromium, nickel, silver and zinc, and the carrier of the catalyst A is one or more of activated carbon, a molecular sieve and an oxide; the catalyst B comprises an active metal component and a composite carrier. The method has simple process and good stability, not only has high COD removal capability, but also can solve the problem of metal loss.

Description

Method for treating organic wastewater
Technical Field
The invention belongs to the field of environmental protection, relates to a method for treating organic wastewater, and particularly relates to a method for treating wastewater by adopting ozone catalytic wet oxidation.
Background
With the rapid development of the petrochemical industry, the discharge of a large amount of waste water of refractory organic pollutants causes serious harm to human health and environment, and the sustainable development of social economy is restricted. With the increasing concern of national policy and regulation on environmental problems, the treatment of organic wastewater has become a hot spot in the wastewater treatment field of China at the present stage. The sewage is deeply treated to achieve standard discharge and even can be recycled, which has important significance in reducing the discharge amount of discharged pollutants of the wastewater, reducing the sewage discharge cost of enterprises, reducing the consumption of water resources and the like.
Advanced oxidation technology (AOP) refers to the oxidation capacity of all common oxidants or oxidation potential approaching or reaching hydroxyl radical2、H2O and other mineral salts. Hydrogen peroxide and ozone are commonly used AOP oxidants. The hydrogen peroxide generates hydroxyl radicals by a Fenton method, but the used homogeneous catalyst has the problems of more used medicaments, difficult recovery and the like, and is easy to cause secondary pollution. The traditional ozone single oxidation technology has the defects of strong direct reaction selectivity of ozone molecules and organic matters, low reaction rate constant, incapability of quickly and completely oxidizing and removing pollutants difficult to degrade and the like, and the best treatment effect is difficult to achieve. The catalytic ozonation technology developed on the basis takes ozone gas as an oxidant, utilizes a catalyst to promote ozonolysis to generate OH for free radical reaction to remove COD in wastewater, and is a high-grade oxidation technology with simple process and wide applicability. The ozone catalytic oxidation technology can convert ozone in the aqueous solution into hydroxyl radical (. OH) with higher oxidation potential through the action of a catalyst, and the OH is nearly indiscriminateSelectively react with most organic matters, and the reaction rate is 106～1010M-1•s-1Compared with the reaction rate of ozone and organic matters, the reaction rate is about 7 orders of magnitude higher, and the defect of single ozone oxidation is overcome, so that the method becomes a novel advanced oxidation technology with more practical value.
The catalytic ozonation technology is mainly used for treating wastewater by adopting a metal oxide supported catalyst to react with ozone. Ozone is generated by decomposing OH, and OH further passes through the OH to carry out series of free radical chain reactions with organic pollutants, thereby destroying the structure of the ozone, gradually degrading the ozone into harmless low molecular weight organic matters and finally degrading the organic matters into CO2、H2O and other mineral salts. Metals such as copper, chromium, nickel, silver, zinc and the like have good catalytic effect when being used as active components of the catalyst, but the metals are easy to lose in waste water to cause secondary pollution. The discharge standards of pollutants for municipal wastewater treatment plants (GB 18918-2002) have strict limits on the discharge of metals such as copper, chromium, nickel, silver, zinc and the like, which are respectively 0.5mg/L, 0.1 mg/L, 1 mg/L, 0.05 mg/L and 0.1 mg/L, and greatly limit the application of the metals in the field of wastewater treatment.
Patent CN01135047.4 discloses a preparation and application of a copper-based catalyst for catalytic wet oxidation treatment of industrial wastewater. The main components of the catalyst are copper, zinc, nickel, magnesium, aluminum, chromium, iron and a part of rare earth metal oxides. The catalyst is prepared by coprecipitation of salts containing various metals to obtain a catalyst with a hydrotalcite-like structure, so that the loss of copper ions is controlled. However, the preparation method of the catalyst is complex, and the catalyst has obvious effect only in a system of phenol, sodium dodecyl benzene sulfonate and salicylic acid, and is greatly limited in application.
Patent 201310576895.9 discloses an ozone catalyst and a method for preparing the same. The catalyst comprises the following components in percentage by weight: modified activated carbon carrier: 70% -80%; the active components are Fe2O3 and MnO 2; the modified activated carbon carrier is prepared by cleaning activated carbon with a sodium hydroxide solution, then soaking the activated carbon with dilute nitric acid, cleaning the activated carbon with deionized water and drying the activated carbon. The preparation method comprises the following steps: the active component is loaded on the modified active carbon carrier according to the using amount, and the ozone catalyst is prepared after drying and roasting. The catalyst has good stability, and reduces the dissolution of active components of metal oxides. However, the range of the applicable active metal is narrow, and the application cannot be widely realized.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for treating organic wastewater by catalytic oxidation of ozone, which has the advantages of simple process, good stability, high COD removal capacity and capability of solving the problem of metal loss.
The invention provides a method for treating organic wastewater, which comprises the following steps: the method comprises the following steps that organic wastewater and ozone enter a reactor to react, and a catalyst A and a catalyst B are sequentially filled in the reactor according to the contact sequence of the organic wastewater, wherein the catalyst A is a supported catalyst, the active component of the supported catalyst is one or more of copper, chromium, nickel, silver and zinc, and the carrier is one or more of activated carbon, a molecular sieve and an oxide; the catalyst B comprises an active metal component and a composite carrier, wherein the active metal component is a transition metal, the composite carrier comprises active carbon and basic calcium phosphate, and the basic calcium phosphate is mainly distributed on the outer surface of the active carbon, wherein the active carbon accounts for 35-90% of the total weight of the composite carrier, and preferably 40-80%; the basic calcium phosphate accounts for 10-65% of the total weight of the composite carrier, and preferably 20-60%.
In the method, the volume ratio of the catalyst A to the catalyst B is 20-80%: 20% to 80%, preferably 40% to 70%: 30 to 60 percent.
In the method, an activated carbon bed layer is also filled in the reactor, a catalyst A, a catalyst B and the activated carbon bed layer are sequentially filled in the reactor according to the contact sequence of the activated carbon bed layer and the organic wastewater, and the volume ratio of the catalyst A to the catalyst B to the activated carbon bed layer is 10-40%: 20% -70%: 20 to 40 percent; preferably 20% to 30%: 40% -60%: 20 to 30 percent. The activated carbon in the activated carbon bed layer can be selected from conventional activated carbon commodities, and the specific surface area is 500-3000 m2A pore volume of 0.2-1.8 cm3(ii)/g, the average pore diameter is 1 to 10 nm.
In the method, the molecular sieve in the catalyst A is one or more of A-type, Y-type, Beta, ZSM-5, TS-1 and MCM-41 molecular sieves, and the oxide is one or more of alumina, cerium dioxide, zirconium dioxide, titanium dioxide and silicon dioxide.
In the method, the content of the active metal component in the catalyst A is 1-30 wt% in terms of oxide based on the weight of the catalyst.
In the method, the catalyst A can also comprise an auxiliary agent, wherein the auxiliary agent is rare earth metal, and the rare earth metal accounts for 0.1-25 wt% of the oxide by taking the weight of the catalyst as a reference.
In the method, the transition metal in the catalyst B is one or more of Fe, Cu, Mn, Ti and Zn, and the transition metal accounts for 0.1-20.0% of the total mass of the catalyst in terms of oxide.
In the method, the catalyst B comprises an auxiliary agent component, wherein the auxiliary agent component is a rare earth metal, and the rare earth metal is one or more of lanthanum, cerium, praseodymium and neodymium; the rare earth metal accounts for 0.1 to 15.0 percent of the total mass of the catalyst by oxide.
In the method, the composite carrier in the catalyst B has two-stage pore channels, the pore diameter of the first-stage pore channel is 0.5-2 nm, the pore diameter of the second-stage pore channel is 2-50 nm, wherein the pore volume of the pore with the pore diameter of 0.5-2 nm accounts for less than 85% of the total pore volume, preferably 60-80%, and the pore volume of the pore with the pore diameter of 2-50 nm accounts for more than 15% of the total pore volume, preferably 20-40%.
In the method of the invention, the properties of the composite carrier in the catalyst B are as follows: the specific surface area is 150-1500 m2A pore volume of 0.1 to 1.2 cm/g3(ii)/g, the average pore diameter is 1-12 nm.
In the method, the activated carbon used in the catalyst B is powdered activated carbon, the granularity is 150-300 meshes, and the specific surface area is 500-3000 m2A pore volume of 0.5-1.8 cm3(ii) a pore volume of pores having an average pore diameter of 0.5 to 4.0nm and a pore diameter of 0.5 to 2.0nm accounts for 90% or more of the total pore volume.
In the method, the active carbon in the catalyst B can be selected from conventional powdered active carbon commodities, such as various wood active carbons, shell active carbons and coal-based active carbons; or can be selected from various activated carbon products obtained by conventional preparation methods of wood materials, mineral materials, plastics and wastes, such as wood, sawdust, charcoal, coconut shells, fruit pits, fruit shells, coal carbon, coal gangue, petroleum coke, petroleum pitch, polyvinyl chloride, polypropylene, organic resin, waste tires, residual sludge and the like.
In the method of the invention, the specific properties of the catalyst B are as follows: the specific surface area is 120-1600 m2A pore volume of 0.1 to 2.0cm3G, abrasion Rate<3wt% and a side pressure strength of 80 to 250N/cm.
In the method of the invention, the preparation method of the catalyst B comprises the following steps:
(1) mixing activated carbon and a soluble organic calcium salt solution uniformly to obtain a material A;
(2) introducing a carbonate solution or an alkaline solution into the material A obtained in the step (1), uniformly mixing, and standing to obtain a material B;
(3) performing solid-liquid separation on the material B obtained in the step (2), and drying and roasting a solid phase obtained by separation to obtain a material C;
(4) mixing the material C obtained in the step (3) with water, then adding phosphoric acid, adjusting the pH value to 9.0-12.0, preferably 9.5-11.0, uniformly mixing, and then carrying out solid-liquid separation, drying and roasting to obtain a composite carrier material;
(5) and (4) impregnating the active metal component and the optional auxiliary agent component on the composite carrier material obtained in the step (4), and then drying and roasting to obtain the ozone catalytic oxidation catalyst.
In the preparation method of the catalyst B, the activated carbon in the step (1) is powdered activated carbon, the granularity is 150-300 meshes, and the specific surface area is 500-3000 m2A pore volume of 0.5-1.8 cm3(ii) a pore volume of pores having an average pore diameter of 0.5 to 4.0nm and a pore diameter of 0.5 to 2.0nm accounts for 90% or more of the total pore volume. The activated carbon can be selected from conventional powdered activated carbon commodities, such as various wood activated carbonShell activated carbon, coal-based activated carbon; or can be selected from various activated carbon products obtained by conventional preparation methods of wood materials, mineral materials, plastics and wastes, such as wood, sawdust, charcoal, coconut shells, fruit pits, fruit shells, coal carbon, coal gangue, petroleum coke, petroleum pitch, polyvinyl chloride, polypropylene, organic resin, waste tires, residual sludge and the like.
In the preparation method of the catalyst B, the soluble organic calcium salt in the step (1) is one or more of calcium gluconate, calcium acetate, calcium lactate, calcium amino acid, calcium L-aspartate, calcium L-threonate and calcium protein, and preferably adopts calcium gluconate or calcium lactate; when two or more soluble organic calcium salts are used, the two or more soluble organic calcium salts may be mixed in any suitable ratio.
In the preparation method of the catalyst B, the activated carbon and the soluble organic calcium salt in the step (1) are mixed according to the weight ratio of C: ca2+The molar ratio is 4.5-75.3: 1, and the ratio of C: ca2+The molar ratio is 15-60: 1.
In the preparation method of the catalyst B, the carbonate in the step (2) is one or more of ammonium carbonate, potassium carbonate and sodium carbonate, preferably ammonium carbonate; the concentration of the carbonate solution is 0.1-1.0 mol/L.
In the preparation method of the catalyst B, the carbonate is used in the step (2) in an amount of CO3 2-：Ca2+The molar ratio is 1-1.2: 1, and CO is preferably selected3 2-：Ca2+The molar ratio is 1:1
In the preparation method of the catalyst B, the alkaline solution in the step (2) is an inorganic alkaline solution, and specifically may be ammonia, sodium hydroxide or potassium hydroxide.
In the preparation method of the catalyst B, in the step (2), an alkaline solution is introduced into the material A obtained in the step (1), and then the pH value is adjusted to 8-9.
In the preparation method of the catalyst B, the dosage of the alkaline solution in the step (2) is OH-：Ca2+The molar ratio is 2-4: 1, and OH is preferred-：Ca2+The molar ratio is 2-2.5: 1.
In the preparation method of the catalyst B, the drying temperature in the step (3) is 70-110 ℃, preferably 80-100 ℃, and the drying time is 2-6 hours, preferably 3-4 hours.
In the preparation method of the catalyst B, the calcination in the step (3) is carried out in nitrogen or inert atmosphere, wherein the inert atmosphere is one of argon and helium. In the step (3), the roasting temperature is 500-1200 ℃, preferably 600-900 ℃, and the roasting time is 2-8 hours, preferably 3-5 hours.
In the preparation method of the catalyst B, the material C in the step (4) is mixed with water at the temperature of 60-90 ℃.
In the preparation method of the catalyst B, the amount of the phosphoric acid in the step (4) is PO4 3-：Ca2+The mol ratio is 3-4: 5, and PO is preferably used4 3-：Ca2+The molar ratio was 3: 5.
In the preparation method of the catalyst B, the drying temperature in the step (4) is 50-100 ℃, preferably 60-70 ℃, and the drying time is 3-24 hours, preferably 6-8 hours.
In the preparation method of the catalyst B, the calcination in the step (4) is carried out in nitrogen or inert atmosphere, wherein the inert atmosphere is one of argon and helium. In the step (4), the roasting temperature is 100-220 ℃, the roasting time is preferably 150-190 ℃, and the roasting time is 2-12 hours, preferably 3-8 hours.
In the above preparation method of the catalyst B, the solid-liquid separation in the step (3) and the step (4) may adopt any scheme capable of realizing solid-liquid separation in the field, such as solid-liquid separation by filtration.
In the preparation method of the catalyst B, when the active metal component and the optional auxiliary component are impregnated on the composite carrier material obtained in the step (4) in the step (5), the composite carrier material obtained in the step (4) is preferably prepared and molded first, and then the active metal component and the optional auxiliary component are impregnated on the composite carrier material, the molding technology of the composite carrier adopts any technology which can realize molding in the prior art, and the shape of the molded carrier is any one of a cylinder, a hollow cylinder, a clover shape and a sphere.
In the preparation method of the catalyst B, in the step (5), the active metal component is one or more of transition metals Fe, Cu, Mn, Ti and Zn, and the transition metals account for 0.1-20.0% of the total mass of the catalyst in terms of oxides.
In the preparation method of the catalyst B, the auxiliary component in the step (5) is rare earth metal, and the rare earth metal is one or more of lanthanum, cerium, praseodymium and neodymium; the rare earth metal accounts for 0.1 to 15.0 percent of the total mass of the catalyst by oxide.
In the preparation method of the catalyst B, the carrier impregnation of the active metal and the auxiliary agent component in the step (5) can be spray impregnation, saturated impregnation or supersaturated impregnation.
In the preparation method of the catalyst B, in the step (5), the drying condition is drying at 70-100 ℃ for 1-15 hours, the roasting temperature is 150-220 ℃, the roasting time is 1-10 hours, and the roasting is performed in nitrogen or inert atmosphere.
In the method, the reaction temperature in the reactor is 0-50 ℃, and preferably 20-30 ℃; the reaction pressure was normal pressure.
In the method, the retention time of the organic wastewater in the catalyst bed layer is 10-300 minutes.
In the method, the dosage of the oxidant is 0.3-2.0 times of the dosage of the oxidant required by calculation according to the COD value of the original organic wastewater.
In the method, the COD of the organic wastewater is 10-10000 mg/L, and the wastewater can be any one or more of dye wastewater, petrochemical wastewater and coal chemical wastewater.
Compared with the prior art, the method for treating the organic wastewater has the following advantages:
in the method for treating the organic wastewater, the wastewater is firstly contacted with a supported catalyst A taking copper, chromium, nickel, silver and/or zinc as active metal components in the presence of ozone, the catalytic action of the active metals such as copper, chromium, nickel, silver and/or zinc and the like is fully exerted to decompose and generate part of ozone; the concentration of downstream ozone is reduced, and then the downstream ozone is contacted with a catalyst B loaded by an active carbon composite carrier with stronger catalytic ozone decomposition capability, so that the catalytic action of the active carbon, the metal active component and hydroxyl on the surface of the basic phosphate for catalyzing the decomposition of ozone to generate OH is fully exerted; the unique pore channel distribution of the carrier and the active carbon and the basic metal salt in the carrier can recover active metal ions dissolved out from the upstream catalyst in an adsorption and ion exchange mode, thereby avoiding secondary pollution caused by the active metal ions. The activated carbon bed layer not only has the catalytic action of catalyzing ozone to generate hydroxyl radicals, but also has the adsorption action of adsorbing organic pollutants and metal ions, can further remove the organic pollutants and adsorb the metal ions lost in upstream reaction, and has double functions. Compared with the prior art, the method maintains higher COD removal effect of the organic wastewater by adopting a catalyst grading method, reduces the loss of metal ions, has higher reaction activity and use stability, and is particularly suitable for catalytic ozonation reaction. The method has simple and convenient process, is easy to operate and is suitable for industrial application.
In the method for treating the organic wastewater, the catalyst B adopts a novel composite carrier, and the basic calcium phosphate is introduced into the outer surface of the active carbon in the composite carrier, so that compared with a pure active carbon carrier, the relative content of the active carbon in the carrier is reduced, the utilization rate of free radicals can be improved, and the problems that the generation of hydroxyl free radicals is accelerated due to overhigh content of the active carbon in the existing pure active carbon catalyst, the collision probability among the free radicals is increased, and the concentration of the free radicals is weakened are solved. The composite carrier has the characteristic that the pore size distribution contains microporous and mesoporous two-stage pore channels, compared with a pure activated carbon carrier, the proportion of mesopores in the carrier is greatly increased, and the adsorption and activation of organic pollutants are facilitated due to the increase of the mesopores. And hydroxyl contained in the basic calcium phosphate is introduced into the outer surface of the composite carrier, so that the decomposition of ozone is promoted to generate hydroxyl free radicals, a free radical chain reaction is further initiated, and the utilization efficiency of the hydroxyl free radicals can be improved to the greatest extent by controlling the content of the hydroxyl through adjusting the content of the basic calcium phosphate. When the activated carbon composite carrier loaded with the active metal forms the catalyst for wastewater treatment, calcium ions in the apatite and active metal ions dissolved out from the catalyst can form M apatite (M represents metal ions replacing the calcium ions) corresponding to the metal ions through ion exchange reaction, so that secondary pollution caused by the active metal ions is avoided.
According to the preparation method of the composite carrier, the macromolecular organic calcium salt solution is mixed with the active carbon, and molecules of the macromolecular organic calcium salt are difficult to enter into the pore channels of the active carbon, so that almost all calcium ions can be attached to the surface of the active carbon, the organic calcium salt solution is prevented from entering into the pore channels of the active carbon, and the generated basic calcium phosphate can be prevented from blocking the pore channels and influencing the performance of the carrier. The preparation process of the composite carrier is an in-situ generation process of organic calcium salt-calcium carbonate (calcium hydroxide) -calcium oxide-calcium hydroxide-basic calcium phosphate, the basic calcium phosphate is firmly attached to the outer surface of the active carbon, the mechanical mixing of the active carbon and the basic calcium phosphate is more uniform and firm, and the defect that pore channels are blocked due to in-situ generation in pores is avoided. Meanwhile, the organic component in the organic calcium salt can generate carbon in the roasting stage, and the carbon can organically connect the generated calcium salt with the original activated carbon carrier, so that the firmness between the alkali calcium phosphate and the activated carbon in the composite carrier is improved, the strength of the formed carrier is enhanced, and the abrasion is reduced.
Detailed Description
The method for treating organic wastewater according to the present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited to these examples.
Preparation of catalyst A1
The diameter of the mixture is 2.0mm, the specific surface area is 704m2G, pore volume 0.7cm3Per gram, commercial cylindrical activated carbon strips with an average pore size of 2.0nm were dried at 120 ℃ for future use. 500g of dried activated carbon strips are weighed and Cu (NO) is used according to the water absorption rate3)2·3H2O is prepared into solution according to the proportion that CuO accounts for 4.5 percent of the total weight of the catalyst. Soaking the activated carbon strips in the solution for 2 hours in the same volume, drying at 80 ℃, roasting for 4 hours at 550 ℃ in a nitrogen atmosphere, cooling to room temperature, and taking out to obtain the catalyst A1.
Preparation of catalyst A2
Kneading, rolling and extruding macroporous alumina powder and peptizing agent to prepare clover-shaped carrier with the diameter of 2.5mm, and roasting in air at 550 ℃ to prepare Al2O3Support, specific surface area 220m2G, pore volume 0.7cm3G, average pore diameter of 10.4 nm. 500g of alumina carrier is weighed and Cu (NO) is used according to the water absorption rate3)2·3H2O and Zn (NO)3)2·6H2O is prepared into solution according to the proportion that CuO and ZnO respectively account for 4 percent and 1.5 percent of the total weight of the catalyst. Soaking the activated carbon strip with Cu-Zn solution in the same volume for 2 hours, drying at 80 ℃, roasting at 550 ℃ for 4 hours in a nitrogen atmosphere, cooling to room temperature, and taking out to obtain the catalyst A2.
Preparation of catalyst A3
Kneading, rolling and extruding macroporous alumina powder and peptizing agent to prepare clover-shaped carrier with the diameter of 2.5mm, and roasting in air at 550 ℃ to prepare Al2O3Support, specific surface area 220m2G, pore volume 0.7cm3G, average pore diameter of 10.4 nm. 500g of alumina carrier is weighed and Cr (NO) is used according to the water absorption3)3·9H2O and Ce (NO)3)3·6H2O is Cr2O3And CeO2The catalyst is prepared into solution respectively accounting for 5 percent and 1 percent of the total weight of the catalyst. And (3) soaking the alumina carrier by using Cr-Ce solution in the same volume for 2 hours, drying at 80 ℃, then roasting in a muffle furnace at 550 ℃ for 4 hours, cooling to room temperature, and taking out to obtain the catalyst A3.
Preparation of catalyst A4
The diameter of the mixture is 2.0mm, the specific surface area is 320m2G, pore volume 0.3 cm3The commercial ZSM-5 molecular sieve strip carrier with the average pore diameter of 2.4nm is dried at 120 ℃ for standby. Weighing 500g of ZSM-5 molecular sieve carrier and adding Ni (NO)3)2·6H2O is calculated by NiO based on the total weight of the catalyst5% to prepare 1000 mL of solution. The ZSM-5 carrier is soaked by the solution, stirred for 3 hours in a constant temperature water bath at 60 ℃, kept stand in the air for 24 hours, evaporated to dryness in a rotary evaporator at 80 ℃ in vacuum, and the obtained sample is dried in a drying box at 100 ℃. Then, the catalyst was calcined at 550 ℃ for 4 hours in a muffle furnace, and the temperature was lowered to room temperature and taken out to obtain a catalyst A4.
Preparation of catalyst A5
The diameter of the mixture is 2.0mm, the specific surface area is 207m2G, pore volume 0.8 cm3(g) SiO in the form of strips with an average pore diameter of 5.8nm2The carrier is dried at 120 ℃ for standby. Weighing SiO2Carrier 500g, with AgNO3The solution is prepared according to the proportion that Ag accounts for 1.5 percent of the total weight of the catalyst. Isovolumic impregnation of SiO with this solution2And (3) drying the carrier for 2 hours at 80 ℃, roasting the carrier for 4 hours at 550 ℃ in a nitrogen atmosphere, cooling the temperature to room temperature, and taking out the carrier to obtain the catalyst A5.
Preparation of catalyst B1
Adding 100g of activated carbon powder into 300g of calcium gluconate solution with the mass fraction of 16%, slowly stirring, and soaking for 4 hours; slowly dripping 225mL of ammonium carbonate solution with the concentration of 0.5mol/L under stirring to generate calcium carbonate precipitate, stirring, standing for 2 hours, filtering, drying at 80 ℃ for 12 hours, and roasting at 900 ℃ for 3 hours under the protection of nitrogen to obtain the activated carbon-calcium oxide compound. Adding the obtained compound into 200g of distilled water, heating to 90 ℃ in a water bath, quickly dropwise adding 0.067moL of phosphoric acid, adding ammonia water to adjust the pH value to 9.5, stirring for 2 hours, and standing for 2 hours; filtering, drying at 70 ℃ for 8h, and roasting at 180 ℃ for 4h under the protection of nitrogen to obtain the active carbon and basic calcium phosphate composite carrier material. The obtained carrier material is made into a clover shape with the diameter of 1.7mm, dried at 70 ℃, and roasted under the protection of nitrogen to obtain the catalyst forming carrier. With Cu (NO)3)2·3H2O and La (NO)3)3·6H2O as CuO and La2O3Respectively accounting for 5.0 percent and 1.0 percent of the total weight of the catalyst to prepare 1000 mL of solution. And supersaturating and dipping the carrier strip by using a Cu-La solution, stirring for 3 hours at 60 ℃ in a constant-temperature water bath, standing for 24 hours in air, then evaporating to dryness in vacuum at 80 ℃ by using a rotary evaporator, and drying the obtained sample in a drying box at 100 ℃. Then is atRoasting for 4 hours at 200 ℃ under the protection of nitrogen, cooling the temperature to room temperature, and taking out to obtain the catalyst B1.
Preparation of catalyst B2
Adding 100g of activated carbon powder into 300g of L calcium lactate solution with the mass fraction of 16%, slowly stirring, and soaking for 4 hours; slowly dropwise adding 200mL of 0.8mol/L sodium carbonate solution under stirring to generate calcium carbonate precipitate, stirring, standing for 2 hours, filtering, drying at 80 ℃ for 12 hours, and roasting at 1100 ℃ for 3 hours under the protection of nitrogen to obtain the activated carbon-calcium oxide compound. Adding the obtained compound into 200g of distilled water, heating to 90 ℃ in a water bath, quickly dropwise adding 0.1moL of phosphoric acid, adding sodium hydroxide to adjust the pH value to 10, stirring for 2 hours, and standing for 2 hours; filtering, drying at 70 ℃ for 8h, and roasting at 170 ℃ for 4h under the protection of helium to obtain the active carbon and basic calcium phosphate composite carrier material. The obtained carrier material is made into clover shape with the diameter of 2.5mm, dried at 70 ℃, and roasted under the protection of nitrogen to obtain the catalyst carrier. According to its water absorption rate, Fe (NO)3)3·9H2O and Ce (NO)3)3·6H2O is Fe2O3And CeO2The catalyst is prepared into solution respectively accounting for 5.0 percent and 1.5 percent of the total weight of the catalyst. And (3) soaking the carrier strip with Fe-Ce solution in the same volume for 2 hours, drying at 80 ℃, roasting for 6 hours at 180 ℃ in a nitrogen atmosphere, cooling to room temperature, and taking out to obtain the catalyst B2.
Preparation of catalyst B3
Adding 50g of activated carbon powder into 200g of a 10 mass percent L-calcium aspartate solution, slowly stirring, and soaking for 4 hours; slowly dropwise adding 220mL of ammonium carbonate solution with the concentration of 0.3mol/L under stirring to generate calcium carbonate precipitate, stirring, standing for 2 hours, filtering, drying at 80 ℃ for 12 hours, and roasting at 900 ℃ for 3 hours under the protection of nitrogen to obtain the activated carbon-calcium oxide compound. Adding the obtained compound into 200g of distilled water, heating to 90 ℃ in a water bath, quickly dropwise adding 0.04moL of phosphoric acid, adding ammonia water to adjust the pH value to 10.0, stirring for 2 hours, and standing for 2 hours; filtering, drying at 70 ℃ for 8h, and roasting at 180 ℃ for 4h under the protection of nitrogen to obtain the active carbon and basic calcium phosphate composite carrier material. Making the obtained carrier material into cylindrical shape with diameter of 3.0mm, 80 deg.CAnd drying, and roasting under the protection of nitrogen to obtain the catalyst carrier. Zn (NO) according to its water absorption3)2·6H2O and Nd (NO)3)3·6H2O as ZnO and Nd2O3Respectively accounting for 8.0 percent and 4.5 percent of the total weight of the catalyst to prepare solutions. Soaking the carrier strip with the solution in the same volume for 2 hours, drying at 80 ℃, roasting for 4 hours at 180 ℃ in a nitrogen atmosphere, cooling to room temperature, and taking out to obtain the catalyst B3.
Preparation of catalyst B4
Adding 50g of activated carbon powder into 200g of calcium gluconate solution with the mass fraction of 13.5%, slowly stirring, and soaking for 4 hours; slowly dripping 210mL of 0.3mol/L potassium carbonate solution under stirring to generate calcium carbonate precipitate, stirring, standing for 2 hours, filtering, drying at 80 ℃ for 12 hours, and roasting at 900 ℃ for 3 hours under the protection of nitrogen to obtain the activated carbon-calcium oxide compound. Adding the obtained compound into 200g of distilled water, heating to 90 ℃ in a water bath, quickly dropwise adding 0.038moL of phosphoric acid, adding sodium hydroxide to adjust the pH value to 11.5, stirring for 2 hours, and standing for 2 hours; filtering, drying at 70 ℃ for 8h, and roasting at 180 ℃ for 4h under the protection of nitrogen to obtain the active carbon and basic calcium phosphate composite carrier material. The obtained carrier material is made into a hollow cylinder shape with the diameter of 3.0mm, dried at 70 ℃, and roasted under the protection of nitrogen to obtain the catalyst carrier. Cu (NO) according to its water absorption3)2·3H2O and Ce (NO)3)3·6H2O as CuO and CeO2Respectively accounting for 15.0 percent and 1.5 percent of the total weight of the catalyst to prepare solutions. And (3) soaking the carrier strip with a Cu-Ce solution in the same volume for 2 hours, drying at 80 ℃, roasting at 175 ℃ for 6 hours in a nitrogen atmosphere, cooling to room temperature, and taking out to obtain a catalyst B4.
The activated carbon has a diameter of 2.0mm and a specific surface area of 704m2G, pore volume 0.7cm3A commercial activated carbon in the form of a column having an average pore diameter of 2.0nm, dried at 120 ℃ for use.
Example 1
Catalysts A1 and B1 were loaded in a cylindrical reactor in proportions of 60% and 40% by volume, respectively, with a total volume of 100cm3. Reverse osmosis concentrateWater (COD: 261.8 mg/L) enters the reactor from the bottom of the reactor, the retention time of the water in the catalyst bed layer is 30 minutes, the ozone dosage is 300mg/L, and the water and the wastewater enter the bottom of the reactor together. The reaction is carried out at normal temperature and pressure. The liquid after the reaction was tested for its COD and the catalyst activity was measured as the removal rate of COD. After the reaction, the liquid is tested for the content of metal ions by inductively coupled plasma mass spectrometry (ICP-MS) to examine the loss condition of the metal. The results are shown in Table 1.
Example 2
The catalysts A3 and B2 were loaded into the reactor in the proportions of 60% and 40% by volume, respectively, and the flow rate of the wastewater was adjusted so that the residence time in the catalyst bed was 40 minutes, and the ozone addition was 200mg/L, and the other reaction conditions were the same as in example 1. The results are shown in Table 1.
Example 3
The catalysts A5 and B3 were loaded into the reactor in the proportions of 20% and 80% by volume, respectively, and the flow rate of the wastewater was adjusted so that the residence time in the catalyst bed was 12 minutes, and the ozone addition was 600mg/L, and the other reaction conditions were the same as in example 1. The results are shown in Table 1.
Example 4
The catalysts A2 and B4 were loaded into the reactor in proportions of 80% and 20% by volume, respectively, and the flow rate of the wastewater was adjusted so that the residence time in the catalyst bed was 300 minutes and the ozone addition was 80mg/L, the other reaction conditions being the same as in example 1. The results are shown in Table 1.
Example 5
Catalysts A4 and B2 were charged into the reactor in proportions of 60% and 40% by volume, respectively, and the ozone addition was adjusted to 400mg/L, under the same reaction conditions as in example 1. The results are shown in Table 1.
Example 6
Catalysts A1, B1 and activated carbon were charged into the reactor in proportions of 30%, 50% and 20% by volume, respectively, under the same reaction conditions as in example 1. The results are shown in Table 1.
Example 7
The catalysts A3, B2 and activated carbon were loaded into the reactor in the proportions of 10%, 50% and 40% by volume, respectively, and the flow rate of wastewater was adjusted so that the residence time of the wastewater in the catalyst bed was 20 minutes, the ozone addition amount was 400mg/L, and the other reaction conditions were the same as in example 1. The results are shown in Table 1.
Example 8
The catalysts A5, B3 and activated carbon were loaded into the reactor in the proportions of 40%, 40% and 20% by volume, respectively, and the flow rate of wastewater was adjusted so that the residence time of the wastewater in the catalyst bed was 120 minutes and the ozone addition amount was 100mg/L, and the other reaction conditions were the same as in example 1. The results are shown in Table 1.
Example 9
Catalysts A2, B4 and activated carbon were charged into the reactor in proportions of 30%, 50% and 20% by volume, respectively, under the same reaction conditions as in example 1. The results are shown in Table 1.
Example 10
Catalysts A4, B2 and activated carbon were charged into the reactor in proportions of 30%, 50% and 20% by volume, respectively, under the same reaction conditions as in example 1. The results are shown in Table 1.
TABLE 1 comparison of results from examples 1-10
Figure 425640DEST_PATH_IMAGE001
Example 11
The reaction conditions were the same as in example 6, and the COD of the raw solution was 78.5 mg/L using the biochemical effluent from a sewage treatment plant. The ozone dosage is changed to 120 mg/L. The results are shown in Table 2.
Example 12
The reaction conditions were the same as in example 6, and the used wastewater was medical wastewater, and the COD of the original solution was 436.1 mg/L. The ozone dosage is changed to 600 mg/L. The results are shown in Table 2.
Example 13
The reaction conditions were the same as in example 6, the waste water used was municipal sewage, and the COD of the raw solution was 3186 mg/L. The adding amount of ozone is changed to 3200 mg/L. The results are shown in Table 2.
TABLE 2 comparison of results from examples 11-13
Figure DEST_PATH_IMAGE002
Comparative example 1
Catalyst A1 was used alone and the reaction conditions were the same as in example 1. The results are shown in Table 3.
Comparative example 2
Catalyst A2 was used alone and the reaction conditions were the same as in example 1. The results are shown in Table 3.
Comparative example 3
Catalyst a3 and activated carbon were charged to the reactor in proportions of 60% and 40% by volume, respectively, under the same reaction conditions as in example 1. The results are shown in Table 3.
Comparative example 4
Catalyst a4 and activated carbon were charged to the reactor in proportions of 60% and 40% by volume, respectively, under the same reaction conditions as in example 1. The results are shown in Table 3.
TABLE 3 comparison of results of comparative examples 1-4
Figure 31196DEST_PATH_IMAGE003
From the above examples and comparative examples it can be seen that: the catalyst grading mode of the invention can obviously reduce the loss of active metal ions and simultaneously keep higher COD removal rate.

Claims (33)

1. A method of treating organic wastewater, the method comprising: the method comprises the following steps that organic wastewater and ozone enter a reactor to react, and a catalyst A and a catalyst B are sequentially filled in the reactor according to the contact sequence of the organic wastewater, wherein the catalyst A is a supported catalyst, the active component of the supported catalyst is one or more of copper, chromium, nickel, silver and zinc, and the carrier is one or more of activated carbon, a molecular sieve and an oxide; the catalyst B comprises an active metal component and a composite carrier, wherein the active metal component is a transition metal, the composite carrier comprises active carbon and basic calcium phosphate, and the basic calcium phosphate is mainly distributed on the outer surface of the active carbon, wherein the active carbon accounts for 35-90% of the total weight of the composite carrier, and preferably 40-80%; the basic calcium phosphate accounts for 10-65% of the total weight of the composite carrier, and preferably 20-60%.
2. The method of claim 1, wherein: the volume ratio of the catalyst A to the catalyst B is 20-80%: 20% to 80%, preferably 40% to 70%: 30 to 60 percent.
3. The method of claim 1, wherein: the reactor is filled with an active carbon bed layer, a catalyst A, a catalyst B and the active carbon bed layer are sequentially filled in the reactor according to the contact sequence of the active carbon bed layer and the organic wastewater, and the volume ratio of the catalyst A to the catalyst B to the active carbon bed layer is 10-40%: 20% -70%: 20 to 40 percent; preferably 20% to 30%: 40% -60%: 20 to 30 percent.
4. The method of claim 1, wherein: the molecular sieve in the catalyst A is one or more of A-type, Y-type, Beta, ZSM-5, TS-1 and MCM-41 molecular sieves, and the oxide is one or more of alumina, cerium dioxide, zirconium dioxide, titanium dioxide and silicon dioxide.
5. The method of claim 1, wherein: the catalyst A comprises an auxiliary agent, the auxiliary agent is rare earth metal, and the rare earth metal accounts for 0.1-25 wt% of the catalyst in terms of oxide.
6. The method of claim 1, wherein: the transition metal in the catalyst B is one or more of Fe, Cu, Mn, Ti and Zn, and accounts for 0.1-20.0% of the total mass of the catalyst in terms of oxide.
7. The method of claim 1, wherein: the catalyst B comprises an auxiliary agent component, wherein the auxiliary agent component is rare earth metal, and the rare earth metal is one or more of lanthanum, cerium, praseodymium and neodymium; the rare earth metal accounts for 0.1 to 15.0 percent of the total mass of the catalyst by oxide.
8. The method of claim 1, wherein: the composite carrier in the catalyst B is provided with two-stage pore channels, the pore diameter of the first-stage pore channel is 0.5-2 nm, the pore diameter of the second-stage pore channel is 2-50 nm, wherein the pore volume of the pore with the pore diameter of 0.5-2 nm accounts for less than 85% of the total pore volume, preferably 60-80%, and the pore volume of the pore with the pore diameter of 2-50 nm accounts for more than 15% of the total pore volume, preferably 20-40%.
9. The method of claim 1, wherein: the properties of the composite carrier in the catalyst B are as follows: the specific surface area is 150-1500 m2A pore volume of 0.1 to 1.2 cm/g3(ii)/g, the average pore diameter is 1-12 nm.
10. The method of claim 1, wherein: the active carbon used in the catalyst B is powdery active carbon with the granularity of 150-300 meshes and the specific surface area of 500-3000 m2A pore volume of 0.5-1.8 cm3(ii) a pore volume of pores having an average pore diameter of 0.5 to 4.0nm and a pore diameter of 0.5 to 2.0nm accounts for 90% or more of the total pore volume.
11. The method of claim 1, wherein: the specific properties of catalyst B are as follows: the specific surface area is 120-1600 m2A pore volume of 0.1 to 2.0cm3G, abrasion Rate<3wt% and a side pressure strength of 80 to 250N/cm.
12. A method according to any of claims 1-11, characterized by: the preparation method of the catalyst B comprises the following steps:
(1) mixing activated carbon and a soluble organic calcium salt solution uniformly to obtain a material A;
(2) introducing a carbonate solution or an alkaline solution into the material A obtained in the step (1), uniformly mixing, and standing to obtain a material B;
(3) performing solid-liquid separation on the material B obtained in the step (2), and drying and roasting a solid phase obtained by separation to obtain a material C;
(4) mixing the material C obtained in the step (3) with water, then adding phosphoric acid, adjusting the pH value to 9.0-12.0, preferably 9.5-11.0, uniformly mixing, and then carrying out solid-liquid separation, drying and roasting to obtain a composite carrier material;
(5) and (4) impregnating the active metal component and the optional auxiliary agent component on the composite carrier material obtained in the step (4), and then drying and roasting to obtain the ozone catalytic oxidation catalyst.
13. The method of claim 12, wherein: in the step (1), the activated carbon is powdered activated carbon, the granularity is 150-300 meshes, and the specific surface area is 500-3000 m2A pore volume of 0.5-1.8 cm3(ii) a pore volume of pores having an average pore diameter of 0.5 to 4.0nm and a pore diameter of 0.5 to 2.0nm accounts for 90% or more of the total pore volume.
14. The method of claim 12, wherein: in the step (1), the soluble organic calcium salt is one or more of calcium gluconate, calcium acetate, calcium lactate, calcium amino acid, calcium L-aspartate, calcium L-threonate and calcium proteinate, and preferably adopts calcium gluconate or calcium lactate.
15. The method of claim 12, wherein: in the step (1), the activated carbon and the soluble organic calcium salt are mixed according to the ratio of C: ca2+The molar ratio is 4.5-75.3: 1, and the ratio of C: ca2+The molar ratio is 15-60: 1.
16. The method of claim 12, wherein: the carbonate in the step (2) is one or more of ammonium carbonate, potassium carbonate and sodium carbonate, preferably ammonium carbonate; the concentration of the carbonate solution is 0.1-1.0 mol/L.
17. The method of claim 12, wherein: the carbonate dosage in the step (2) is CO3 2-：Ca2+The molar ratio is 1-1.2: 1, and CO is preferably selected3 2-：Ca2+The molar ratio is 1: 1.
18. The method of claim 12, wherein: in the step (2), the alkaline solution is an inorganic alkaline solution, specifically ammonia water, sodium hydroxide or potassium hydroxide.
19. The method of claim 12, wherein: and (3) introducing an alkaline solution into the material A obtained in the step (1) in the step (2), and then adjusting the pH value to 8-9.
20. The method of claim 12, wherein: the dosage of the alkaline solution in the step (2) is OH-：Ca2+The molar ratio is 2-4: 1, and OH is preferred-：Ca2+The molar ratio is 2-2.5: 1.
21. The method of claim 12, wherein: in the step (3), the drying temperature is 70-110 ℃, preferably 80-100 ℃, and the drying time is 2-6 hours, preferably 3-4 hours.
22. The method of claim 12, wherein: in the step (3), the roasting is carried out in nitrogen or inert atmosphere, wherein the inert atmosphere is one of argon and helium; the roasting temperature is 500-1200 ℃, preferably 600-900 ℃, and the roasting time is 2-8 hours, preferably 3-5 hours.
23. The method of claim 12, wherein: and (4) mixing the material C with water at the temperature of 60-90 ℃.
24. A method according to claim 12, characterized in thatThe method comprises the following steps: the dosage of the phosphoric acid in the step (4) is PO4 3-：Ca2+The mol ratio is 3-4: 5, and PO is preferably used4 3-：Ca2+The molar ratio was 3: 5.
25. The method of claim 12, wherein: in the step (4), the drying temperature is 50-100 ℃, preferably 60-70 ℃, and the drying time is 3-24 hours, preferably 6-8 hours.
26. The method of claim 12, wherein: in the step (4), the roasting is carried out in nitrogen or inert atmosphere, wherein the inert atmosphere is one of argon and helium; the roasting temperature is 100-220 ℃, the roasting time is 2-12 hours, and the roasting time is 3-8 hours.
27. The method of claim 12, wherein: in the step (5), the active metal component is one or more of transition metals Fe, Cu, Mn, Ti and Zn, and the transition metals account for 0.1-20.0% of the total mass of the catalyst in terms of oxides.
28. The method of claim 12, wherein: in the step (5), the auxiliary agent component is rare earth metal, and the rare earth metal is one or more of lanthanum, cerium, praseodymium and neodymium; the rare earth metal accounts for 0.1 to 15.0 percent of the total mass of the catalyst by oxide.
29. The method of claim 12, wherein: in the step (5), the drying condition is drying at 70-100 ℃ for 1-15 hours, the roasting temperature is 150-220 ℃, the roasting time is 1-10 hours, and the roasting is carried out in nitrogen or inert atmosphere.
30. The method of claim 1, wherein: the reaction temperature in the reactor is 0-50 ℃, and preferably 20-30 ℃; the reaction pressure was normal pressure.
31. The method of claim 1, wherein: the retention time of the organic wastewater in the catalyst bed layer is 10-300 minutes.
32. The method of claim 1, wherein: the dosage of the oxidant is 0.3-2.0 times of the dosage of the oxidant calculated according to the COD value of the original organic wastewater.
33. The method of claim 1, wherein: the COD of the organic wastewater is 10-10000 mg/L.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1149287A (en) * 1994-05-27 1997-05-07 希巴-盖吉股份公司 Process for the preparation of unsaturated amino compounds
JP2001205277A (en) * 1999-11-19 2001-07-31 Hitachi Zosen Corp Method and apparatus for removing hardly decomposable organic compound in water
CN108069501A (en) * 2016-11-11 2018-05-25 中国石油化工股份有限公司抚顺石油化工研究院 A kind of technique for handling organic wastewater
CN108069500A (en) * 2016-11-11 2018-05-25 中国石油化工股份有限公司抚顺石油化工研究院 A kind of method of ozone catalytic wet oxidation processing organic wastewater
CN108069496A (en) * 2016-11-11 2018-05-25 中国石油化工股份有限公司抚顺石油化工研究院 A kind of technique using catalytic wet ozone Oxidation Treatment organic wastewater
CN108069499A (en) * 2016-11-11 2018-05-25 中国石油化工股份有限公司抚顺石油化工研究院 Using the method for ozone catalytic wet oxidation processing waste water
CN108069502A (en) * 2016-11-11 2018-05-25 中国石油化工股份有限公司抚顺石油化工研究院 A kind of processing method of organic wastewater

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1149287A (en) * 1994-05-27 1997-05-07 希巴-盖吉股份公司 Process for the preparation of unsaturated amino compounds
JP2001205277A (en) * 1999-11-19 2001-07-31 Hitachi Zosen Corp Method and apparatus for removing hardly decomposable organic compound in water
CN108069501A (en) * 2016-11-11 2018-05-25 中国石油化工股份有限公司抚顺石油化工研究院 A kind of technique for handling organic wastewater
CN108069500A (en) * 2016-11-11 2018-05-25 中国石油化工股份有限公司抚顺石油化工研究院 A kind of method of ozone catalytic wet oxidation processing organic wastewater
CN108069496A (en) * 2016-11-11 2018-05-25 中国石油化工股份有限公司抚顺石油化工研究院 A kind of technique using catalytic wet ozone Oxidation Treatment organic wastewater
CN108069499A (en) * 2016-11-11 2018-05-25 中国石油化工股份有限公司抚顺石油化工研究院 Using the method for ozone catalytic wet oxidation processing waste water
CN108069502A (en) * 2016-11-11 2018-05-25 中国石油化工股份有限公司抚顺石油化工研究院 A kind of processing method of organic wastewater

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