CN108069498A - A kind of new organic wastewater treatment process - Google Patents

Abstract

The invention relates to the technical field of wastewater treatment, and specifically discloses a process for treating organic wastewater. The treatment process includes the following content: a rotating bed reactor is used as a reaction device, and the shell of the rotating bed reactor includes an inner rotating bed and an outer rotating bed. The bed uses organic waste water as a raw material and performs oxidation reaction in the presence of ozone. The inner rotating bed is composed of a corrosion-resistant frame and catalyst A, and the outer rotating bed is composed of a corrosion-resistant frame and catalyst B. The invention has simple process and good stability, not only has high COD removal ability, but also can solve the problem of metal loss.

Description

A new type of organic wastewater treatment process

technical field

The invention relates to the field of environmental protection, in particular to a treatment process for organic wastewater.

Background technique

A large amount of organic polluted wastewater caused by industrial production has seriously affected the living conditions of human beings and the ecological environment, and has become an increasingly serious social and economic problem. It is especially difficult to treat organic wastewater that is difficult to biodegrade; Increasingly scarce, the state has become more stringent on the total discharge of pollutants in water, and the formulation of new standards has brought new challenges to the prevention and control of water pollution in my country's refining and chemical enterprises. After the refining and chemical enterprises use the existing secondary biochemical process, the discharge Most of the waste water still cannot meet the discharge requirements of the new standard. Therefore, it is necessary to carry out advanced treatment of external sewage to achieve standard discharge and even reuse, which is of great significance in reducing the discharge of waste water pollutants, reducing the sewage charges of enterprises and reducing the consumption of water resources.

Advanced Oxidation Technology (AOP) means that the oxidation ability exceeds all common oxidants or the oxidation potential is close to or reaches the level of hydroxyl radical·OH, which can undergo a series of free radical chain reactions with organic pollutants, thereby destroying its structure and gradually degrading it into inorganic Harmful low-molecular-weight organic substances are finally degraded into CO ₂ , H ₂ O and other mineral salts. Hydrogen peroxide and ozone are commonly used AOP oxidants. Hydrogen peroxide generates hydroxyl radicals through the Fenton method, but the homogeneous catalyst used has problems such as the use of many chemicals and difficult recovery, which easily causes secondary pollution. The single ozone oxidation technology has disadvantages such as strong selectivity of the direct reaction between ozone molecules and organic matter, low reaction rate constant and refractory pollutants cannot be quickly and completely oxidized and removed. Ozone catalytic wet oxidation technology generates a large number of hydroxyl radicals during the reaction process by adding catalysts to catalyze ozone (the rate constant of hydroxyl radicals reacting with most organic matter is 10 ⁶ ~10 ⁹ M ^-1 s ^-1 , and reacting with the organic matter with ozone The rate constant is at least 7 orders of magnitude higher than that), and it can purify water by oxidizing those organic substances that are difficult to be oxidized or degraded by ozone alone under normal temperature and pressure. Catalytic wet oxidation can overcome the shortcomings of ozone oxidation alone, thus becoming a new advanced oxidation technology with more practical value.

At present, the ozone wet catalytic oxidation technology mostly uses metal oxide-supported catalysts to react with ozone to treat wastewater. Copper-based catalysts have a good catalytic effect, but they are prone to metal loss in wastewater and cause secondary pollution. The national limit (GB8978-1996 ) The content of total copper in the primary standard of sewage discharge should be less than 500 μg/L, and the secondary standard requires less than 1000 μg/L.

Patent CN01135047.4 discloses the preparation and application of a copper-based catalyst for catalytic wet oxidation treatment of industrial wastewater. The main components of the catalyst are oxides of copper, zinc, nickel, magnesium, aluminum, chromium, iron and some rare earth metals. The catalyst is co-precipitated by 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 this catalyst is complicated, and it only has obvious effects in the system of phenol, sodium dodecylbenzenesulfonate and salicylic acid, and its application is greatly limited.

Contents of the invention

Aiming at the deficiencies of the prior art, the present invention provides a process for treating organic wastewater by catalytic wet ozone oxidation. The process is simple and stable, not only has high COD removal capacity, but also can solve the problem of metal loss.

The invention provides a novel organic wastewater treatment process, which includes the following content: a rotating bed reactor is used as a reaction device, and the shell of the rotating bed reactor includes an inner rotating bed and an outer rotating bed, and organic wastewater is used as a raw material , the oxidation reaction is carried out in the presence of ozone, the inner rotating bed is composed of a corrosion-resistant frame and a catalyst A, the outer rotating bed is composed of a corrosion-resistant frame and a catalyst B, and the catalyst A is an iron-based supported catalyst and /or a manganese-based supported catalyst, catalyst B is a copper-based supported catalyst.

In the organic wastewater treatment process of the present invention, the rotating bed reactor includes a rotating bed, a head, a reactor cylinder, a feed pipe and a feed distribution pipe, and the reactor cylinder and the head form a closed shell, and the rotating The bed is vertically arranged in the middle of the shell, the center of the rotating bed is an empty cylinder structure, the feed distribution pipe is arranged in the hollow cylinder structure in the center of the rotating bed, the feed distribution pipe is connected with the feed pipe, and the outlet is arranged in the reactor The lower part of the shell, the upper part of the rotating bed and the reactor shell are fixedly connected by a sealing member, the upper part of the rotating bed and the sealing member are rotatably connected, and the rotating bed is connected to the lower driving device through a rotating shaft. The rotating bed includes an internal A rotating bed and an outer rotating bed, the outer rotating bed is arranged radially outside the inner rotating bed.

In the above rotating bed reactor, the reactor barrel is a cylindrical barrel, the head includes an upper head and a lower head, and the cylindrical reactor is arranged vertically.

In the above-mentioned rotating bed reactor, the shape of the rotating bed is cylindrical, and a suitable gap is set between the rotating bed and the reactor shell to form an annular space; the center of the rotating bed is a cylindrical hollow tube, and the feed distribution pipe is arranged on the cylinder. In the hollow cylinder, there is a suitable gap between the feed distribution pipe and the rotating bed to form an annular space; suitable material distribution holes are set on the feed distribution pipe, and the length of the feed distribution pipe corresponds to the axial length of the rotating bed; The shaft is fixedly connected with the fixed plate at the lower end of the rotating bed, and the rotating shaft is arranged vertically; the rotating shaft is connected with the driving device arranged at the upper or lower part outside the reactor through the head.

In the above rotating bed reactor, there is or is not a gap between the inner rotating bed and the outer rotating bed. When there is a gap, the gap between the inner rotating bed and the outer rotating bed is 5 mm to 300 mm, preferably 10 mm to 50 mm.

In the organic wastewater treatment process of the present invention, when the organic wastewater and ozone enter the rotary bed reactor for reaction, the organic wastewater first contacts with the inner rotary bed for reaction, and then contacts with the outer rotary bed for reaction.

In the organic wastewater treatment process of the present invention, the catalyst A includes a carrier and an active metal component loaded on the carrier, wherein one or more of activated carbon, molecular sieve, and oxide is used as the carrier; the molecular sieve is A type, One or more of Y-type, Beta, ZSM-5, TS-1, MCM-41 molecular sieves, the oxide is one of alumina, ceria, zirconia, titania, silica or several types; iron and/or manganese are used as active metal components, and the content of active metal components is based on oxides, and Fe ₂ O ₃ and/or MnO ₂ is 1~30wt%. The catalyst A may also include an additive component, the additive component is one or more of nickel, zinc, magnesium, lanthanum, cerium, praseodymium, and neodymium, and the additive content is 0.1 to 25wt %.

In the organic wastewater treatment process of the present invention, the catalyst B is a copper-based supported catalyst, including a carrier and an active metal component loaded on the carrier, wherein one or more of activated carbon, molecular sieve, and oxide is used as the carrier; The molecular sieve is one or more of A-type, Y-type, Beta, ZSM-5, TS-1, MCM-41 molecular sieves, and the oxides are alumina, ceria, zirconia, titania, One or more of silicon dioxide; with copper as the active metal component, rare earth metals as additives, based on the weight of the catalyst, the active metal component is calculated based on the content of oxides: CuO is 1~30wt% ; The rare earth metal oxide is 0.1~25wt%. The active metal component of the copper-based supported catalyst may also include one or more of iron, nickel or vanadium.

In the organic wastewater treatment process of the present invention, the rare earth metal is one or more of lanthanum, cerium, praseodymium and neodymium.

In the organic wastewater treatment process of the present invention, the reaction temperature in the reactor is 0-50°C, preferably 20-30°C; the reaction pressure is normal pressure.

In the organic wastewater treatment process of the present invention, the volume ratio of the catalyst A to the catalyst B is 20%-80%: 20%-80%, preferably 40%-70%: 30%-60%.

In the organic wastewater treatment process of the present invention, the rotational speed of the rotary bed is 0-5000 rpm, preferably 150-2000 rpm.

In the organic wastewater treatment process of the present invention, the amount of ozone used is 0.3 to 2.0 times of the required amount of ozone calculated according to the COD value of the original organic wastewater.

In the organic wastewater treatment process of the present invention, 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.

In the organic wastewater treatment process of the present invention, the wastewater is first contacted with iron and/or manganese-based catalysts in the presence of ozone, and high-concentration ozone converts a part of organic pollutants under the action of iron and/or manganese-based catalysts, The ozone concentration in the downstream is reduced, and at this time, it is in contact with a copper-based catalyst with a strong catalytic ability to give full play to the catalytic effect of the copper-based catalyst; through the synergistic effect of the iron and/or manganese-based catalyst and the copper-based catalyst, not only the organic wastewater treatment effect is good , and can effectively reduce the loss of metal copper, and solve the problem of serious loss of copper metal existing in the use of copper-based catalysts in the prior art. Compared with the prior art, the present invention maintains a higher organic wastewater COD removal effect by adopting the catalyst gradation method, reduces the discharge of metal ions, and has higher reactivity and stability in use, and is especially suitable for catalytic Wet ozone oxidation reaction. The process of the method of the invention is simple, convenient, easy to operate and suitable for industrial application.

The organic wastewater treatment process described in the present invention uses a rotary bed reactor as the reaction equipment, and the catalyst is filled into the bed of the rotary bed in the form of filler, which greatly improves the contact efficiency between wastewater, ozone and the catalyst, and greatly shortens the reaction time. Time and efficiency are improved, and the scale of reaction equipment can be greatly reduced, thereby reducing equipment costs and operating expenses.

Description of drawings

Fig. 1 is a structural schematic diagram of a rotating bed reactor in the treatment process of organic wastewater according to the present invention. Among them: 1 is the upper head, 2 is the lower head, 3 is the reactor cylinder, 4 is the outer rotating bed, 5 is the inner rotating bed, 6 is the rotating bed, 7 is the feed distribution pipe, 8 is the feed pipe , 9 is a rotating shaft, 10 is a mechanical seal of the lower head, 11 is a coupling, 12 is a motor, 13 is a discharge port, 14 is organic waste water, 15 is ozone, 16 is a sealing member, and 17 is a fixed plate.

Detailed ways

The preparation method of the present invention will be further described below in conjunction with specific examples, but the scope of the present invention is not limited to the scope of these examples.

The rotary bed reactor used in the treatment process of organic wastewater of the present invention can adopt the existing rotary bed reactor in the art, and can also be prepared according to the method disclosed in the prior art. In the embodiment of the present invention, it is specifically used as shown in Figure 1 The rotating bed reactor shown.

As shown in Fig. 1, the present invention provides a kind of rotating bed reactor, and described rotating bed reactor comprises upper head 1, lower head 2, reactor shell 3, feed pipe 8, feed distribution pipe 7, Rotating bed 6, the reactor body 3, upper head 1, and lower head 2 form a closed shell, the reactor body 3 is a cylindrical body, and the rotating bed 6 is vertically arranged in the middle of the shell, rotating The shape of the bed 6 is cylindrical, and a suitable gap is set between the rotating bed 6 and the reactor shell to form an annular space. The feeding distribution pipe 7 is provided with suitable material distribution holes, and the length of the feeding distribution pipe 7 is the same as that of the rotating bed. The axial length of 6 corresponds; the center of the rotary bed 6 is a cylindrical hollow structure, and the feed distribution pipe 7 is arranged in the cylindrical hollow structure at the center of the rotary bed 6, between the feed distribution pipe 7 and the rotary bed 6 There is a suitable gap to form an annular space; the feed distribution pipe 7 communicates with the feed pipe 8, the discharge port 13 is set at the lower part of the reactor shell, and the upper part of the rotating bed 6 is fixedly connected with the reactor shell through a sealing member 16 , the upper part of the rotating bed 6 is rotatably connected to the sealing member 16, the rotating shaft 9 is fixedly connected to the fixed plate 17 at the lower end of the rotating bed 6, and the rotating bed 6 is connected to the lower driving device 12 through the rotating shaft 9. The rotating bed 6 It includes an inner rotating bed 5 and an outer rotating bed 4 , and the outer rotating bed 4 is arranged radially outside of the inner rotating bed 5 .

When the rotary bed reactor of the present invention is used for organic wastewater treatment, the organic wastewater 14 and ozone 15 enter the feed pipe 8 and then enter the rotary bed 6 after being distributed through the feed distribution pipe 7, and are sequentially combined with the inner rotary bed 5 and the outer rotary bed. Catalyst A and catalyst B in 4 contact and react, and the purified water obtained after the reaction is discharged through the discharge port 13.

Preparation of Catalyst A1 (Fe/AC)

Commercial columnar activated carbon strips with a diameter of 2.0 mm, a specific surface area of 704 m ² /g, a pore volume of 0.7 cm ³ /g, and an average pore diameter of 2.0 nm were dried at 120°C for use. Weigh 500g of dried activated carbon strips, and use Fe(NO ₃ ) ₃ ·9H ₂ O to prepare a solution according to the water absorption rate at a ratio of Fe ₂ O ₃ to 8% of the total weight of the catalyst. The activated carbon strip was impregnated with an equal volume of the solution for 4 hours, dried at 80°C, calcined at 550°C under a nitrogen atmosphere for 4 hours, and taken out after the temperature dropped to room temperature to obtain catalyst A1.

Preparation of Catalyst A2 (Mn/AC)

Commercial columnar activated carbon strips with a diameter of 2.0 mm, a specific surface area of 704 m ² /g, a pore volume of 0.7 cm ³ /g, and an average pore diameter of 2.0 nm were dried at 120°C for use. Weigh 500g of dried activated carbon strips, and prepare a solution with 50% Mn(NO ₃ ) ₂ ·4H ₂ O solution according to the water absorption rate, according to the ratio of MnO ₂ to 8% of the total weight of the catalyst. Impregnate activated carbon strips with an equal volume of the solution for 4 hours, dry at 80°C, and bake at 550°C for 4 hours in a nitrogen atmosphere. After the temperature drops to room temperature, take it out to obtain catalyst A2.

Preparation of Catalyst A3 (Fe-Ce/Al ₂ O ₃ )

The macroporous alumina powder and peptizer are kneaded, rolled, and extruded to make a clover-shaped carrier with a diameter of 2.5mm, and then calcined at 550°C in air to obtain an Al ₂ O ₃ carrier with a specific surface area of 220 m ² /g. The pore volume is 0.7 cm ³ /g, and the average pore diameter is 10.4nm. Weigh 500g of alumina carrier, according to its water absorption, use Fe(NO ₃ ) ₃ 9H ₂ O and Ce(NO ₃ ) ₃ 6H ₂ O to account for 5% and 1.5% of the total weight of the catalyst according to Fe ₂ O ₃ and CeO ₂ respectively. % ratio to make a solution. The alumina carrier was impregnated with an equal volume of Fe-Ce solution for 2 hours, dried at 80°C, then calcined in a muffle furnace at 550°C for 4 hours, and taken out after the temperature dropped to room temperature to obtain catalyst A3.

Preparation of Catalyst A4 (Fe-Mn/ZSM-5)

A commercial ZSM-5 molecular sieve bar carrier with a diameter of 2.0mm, a specific surface area of 320m ² /g, a pore volume of 0.3 cm ³ /g, and an average pore diameter of 2.4nm was dried at 120°C for use. Weigh 500g of ZSM-5 molecular sieve carrier, use Fe(NO ₃ ) ₃ 9H ₂ O and 50% Mn(NO ₃ ) ₂ 4H ₂ O solution to account for 6% of the total catalyst weight by Fe ₂ O ₃ and MnO ₂ And 4% ratio dubbed 1000 mL solution. The ZSM-5 carrier was impregnated with Mn-Ce solution, stirred in a constant temperature water bath at 60°C for 3 hours, left to stand in the air for 24 hours, then evaporated to dryness with a rotary evaporator at 80°C, and the obtained sample was dried in a 100°C drying oven. Then it was calcined in a muffle furnace at 550° C. for 4 hours, and the temperature was lowered to room temperature, and then taken out to obtain catalyst A3.

Preparation of Catalyst B1 (Cu-Ce/AC)

Commercial columnar activated carbon strips with a diameter of 2.0 mm, a specific surface area of 704 m ² /g, a pore volume of 0.7 cm ³ /g, and an average pore diameter of 2.0 nm were dried at 120°C for use. Weigh 500g of dried activated carbon strips, according to its water absorption, use Cu(NO ₃ ) ₂ 3H ₂ O and Ce(NO ₃ ) ₃ 6H ₂ O to account for 5% and 1.5% of the total catalyst weight according to CuO and CeO ₂ respectively ratio to form a solution. Impregnate activated carbon strips with an equal volume of Cu-Ce solution for 4 hours, dry at 80°C, and bake at 550°C under nitrogen atmosphere for 4 hours. After the temperature dropped to room temperature, take it out to obtain catalyst B1.

Preparation of Catalyst B2 (Cu-La/ZSM-5)

A commercial ZSM-5 molecular sieve bar carrier with a diameter of 2.0mm, a specific surface area of 320m ² /g, a pore volume of 0.3 cm ³ /g, and an average pore diameter of 2.4nm was dried at 120°C for use. Weigh 500g of ZSM-5 molecular sieve carrier, use Cu(NO ₃ ) ₂ 3H ₂ O and La(NO ₃ ) ₃ 6H ₂ O to account for 5% and 1.5% of the total catalyst weight by CuO and La ₂ O ₃ respectively Dubbed 1000 mL solution. The ZSM-5 carrier was impregnated with Cu-Ce solution, stirred in a constant temperature water bath at 60°C for 3 hours, left to stand in the air for 24 hours, then evaporated to dryness with a rotary evaporator at 80°C, and the obtained sample was dried in a drying oven at 100°C. Then it was calcined in a muffle furnace at 550° C. for 4 hours, and the temperature was lowered to room temperature and then taken out to obtain catalyst B2.

Example 1

The catalysts A1 and B1 were loaded into the inner rotating bed and the outer rotating bed of the reactor respectively according to volume percentages of 65% and 35%, and the distance between the inner and outer rotating beds was 5 mm. The total catalyst volume is 100 cm ³ . Reaction conditions: the COD of acid scarlet simulated dye wastewater is 286.3 mg/L, the feed rate is 200 mL/h, the ozone concentration is 8.0 g/m ³ , the gas flow rate is 400 mL/min, the rotating bed speed is 600 rpm, The reaction is carried out at normal temperature and pressure. After the reaction, the COD of the liquid is tested, and the catalyst activity is measured according to the removal rate of COD. After the reaction, the content of copper ions in the liquid was tested by inductively coupled plasma mass spectrometry (ICP-MS) to investigate the loss of metals. The results are listed in Table 1.

Example 2

Catalysts A2 and B1 were loaded into the reactor according to volume percentages of 20% and 80% respectively, the rotational speed of the rotating bed was 200 rpm, there was no gap between the inner and outer rotating beds, and other reaction conditions were the same as in Example 1. The results are listed in Table 1.

Example 3

Catalysts A3 and B1 were loaded into the reactor according to volume percentages of 80% and 20% respectively, the rotational speed of the rotating bed was 1000 rpm, there was no gap between the inner and outer rotating beds, and other reaction conditions were the same as in Example 1. The results are listed in Table 1.

Example 4

Catalysts A4 and B1 were loaded into the reactor according to volume percentages of 65% and 35% respectively, and the reaction conditions were the same as in Example 1. The results are listed in Table 1.

Example 5

Catalysts A1 and B2 were loaded into the reactor according to volume percentages of 65% and 35% respectively, and the reaction conditions were the same as in Example 1. The results are listed in Table 1.

Example 6

Catalysts A3 and B2 were loaded into the reactor according to volume percentages of 65% and 35% respectively, and the reaction conditions were the same as in Example 1. The results are listed in Table 1.

Table 1 Comparison of the results of Examples 1-6

Example 7

The reaction conditions are the same as those in Example 1, using coal chemical industry saline wastewater, the COD of the original solution is 449.3 mg/L, and the total dissolved solids TDS is 12000 mg/L. Intake ozone concentration changed to 14.0 g/m ³ . The results are listed in Table 2.

Example 8

The reaction conditions are the same as in Example 1, the wastewater used is the secondary biochemical effluent of Jinling Petrochemical, and the COD of the original solution is 67.6 mg/L. Intake ozone concentration changed to 2.5 g/m ³ . The results are listed in Table 2.

Example 9

The reaction conditions are the same as in Example 1, the waste water model compound used is phenol, and the COD of the original solution is 324.7 mg/L. Intake ozone concentration changed to 11.8 g/m ³ . The results are listed in Table 2.

Table 2 Example 7-9 result comparison

Comparative example 1

Using catalyst A1 alone, the reaction conditions are the same as in Example 1. The results are listed in Table 3.

Comparative example 2

Using catalyst B1 alone, the reaction conditions are the same as in Example 1. The results are listed in Table 3.

Comparative example 3

Using catalyst B2 alone, the reaction conditions are the same as in Example 1. The results are listed in Table 3.

Table 3 Comparison of the results of Comparative Examples 1-3

It can be known from the above examples and comparative examples that the catalyst gradation method of the present invention can significantly reduce the loss of copper ions while maintaining a high COD removal rate.

Claims (17)

1. a kind of new organic wastewater treatment process, the treatment process includes herein below：Using rotary drill reactor as instead Equipment is answered, includes interior revolving bed and outer revolving bed in the rotary drill reactor housing, using organic wastewater as raw material, is deposited in ozone Oxidation reaction is carried out under the conditions, and the interior revolving bed is made of corrosion-resistant frame and catalyst A, and the outer revolving bed is by resistance to Corrode frame and catalyst B is formed, the catalyst A is iron system supported catalyst and/or manganese systems loaded catalyst, is catalyzed Agent B is copper system support catalysts.

2. organic wastewater treatment process described in accordance with the claim 1, it is characterised in that：The rotary drill reactor includes rotation Bed, end socket, reactor shell, feed pipe and charging distributor pipe, the reactor shell and end socket form closing housing, revolving bed Middle part in housing is vertically set on, the revolving bed center is empty barrel structure, and charging distributor pipe is arranged on the sky at revolving bed center In barrel structure, charging distributor pipe is connected with feed pipe, and discharge port is arranged on reactor shell lower part, revolving bed top and reactor It is fixedly connected between housing by containment member, to be rotatably connected between revolving bed top and containment member, revolving bed passes through Rotation axis is connected with lower part driving device, and the revolving bed includes interior revolving bed and outer revolving bed, and outer revolving bed is arranged at inward turning The radial outside of rotated bed.

3. organic wastewater treatment process described in accordance with the claim 2, it is characterised in that：The reactor shell is cylindrical tube Body, the end socket include upper cover and low head, and cylindrical reactor is vertically arranged.

4. organic wastewater treatment process described in accordance with the claim 2, it is characterised in that：Revolving bed shape is cylinder barrel shaped, is revolved It is set between rotated bed and reactor shell suitable for gap, forms annulus；Revolving bed center is cylindrical empty cylinder, and charging is distributed Pipe is arranged in the cylindrical empty cylinder, and feeding between distributor pipe and revolving bed has suitable for gap, forms annulus；Charging point Suitable material distribution hole is set on stringing, and the length for feeding distributor pipe is corresponding with the axial length of revolving bed；Rotation axis and rotation The fixed plate of rotated bed lower end is fixedly connected, and rotation axis is vertically arranged；Rotation axis is set by end socket and top outside reactor or lower part The driving device connection put.

5. organic wastewater treatment process described in accordance with the claim 2, it is characterised in that：Have between interior revolving bed and outer revolving bed It is or very close to each other.

6. according to the organic wastewater treatment process described in claim 5, it is characterised in that：Between interior revolving bed and outer revolving bed Clearance distance is 5mm~300mm, preferably 10mm~50mm.

7. organic wastewater treatment process described in accordance with the claim 1, it is characterised in that：The body of the catalyst A and catalyst B Product is than being 20%~80%：20%~80%.

8. organic wastewater treatment process described in accordance with the claim 1, it is characterised in that：The body of the catalyst A and catalyst B Product is than being 40%~70%：30%~60%.

9. organic wastewater treatment process described in accordance with the claim 1, it is characterised in that：The catalyst A includes carrier and bears The active metal component being loaded on carrier, wherein with one or more of activated carbon, molecular sieve, oxide for carrier；It is described Molecular sieve is one or more of A types, Y types, Beta, ZSM-5, TS-1, MCM-41 molecular sieve, and the oxide is oxidation One or more of aluminium, ceria, zirconium dioxide, titanium dioxide, silica；Using iron and/or manganese as active metal group Point, active metal component is with the content meter of oxide, Fe₂O₃And/or MnO₂For 1 ~ 30wt%.

10. according to the organic wastewater treatment process described in claim 9, it is characterised in that：The catalyst A includes auxiliary agent, The auxiliary agent is nickel, the one or more in zinc, magnesium, lanthanum, cerium, praseodymium, neodymium, and the auxiliary agent content is 0.1 ~ 25wt%.

11. organic wastewater treatment process described in accordance with the claim 1, it is characterised in that：The catalyst B includes carrier and bears The active metal component being loaded on carrier, wherein with one or more of activated carbon, molecular sieve, oxide for carrier；It is described Molecular sieve is one or more of A types, Y types, Beta, ZSM-5, TS-1, MCM-41 molecular sieve, and the oxide is oxidation One or more of aluminium, ceria, zirconium dioxide, titanium dioxide, silica；Active metal component is contained with oxide It measures to calculate：CuO is 1 ~ 30wt%；Rare-earth oxide is 0.1 ~ 25wt%.

12. according to the organic wastewater treatment process described in claim 11, it is characterised in that：The active metal of the catalyst B Component includes one or more of iron, nickel, vanadium.

13. according to the organic wastewater treatment process described in claim 11, it is characterised in that：The rare earth metal for lanthanum, cerium, One or more in praseodymium, neodymium.

14. organic wastewater treatment process described in accordance with the claim 1, it is characterised in that：Reaction temperature in reactor for 0~ 50 DEG C, be preferably 20~30 DEG C；Reaction pressure is normal pressure.

15. organic wastewater treatment process described in accordance with the claim 1, it is characterised in that：The rotating speed of the revolving bed for 0~ 5000 revs/min, be preferably 150~2000 revs/min.

16. organic wastewater treatment process described in accordance with the claim 1, it is characterised in that：The ozone usage is to have by raw material 0.3~2.0 times of ozone usage needed for the calculating of machine COD value of waste water.

17. organic wastewater treatment process described in accordance with the claim 1, it is characterised in that：The COD of the organic wastewater for 10 ~ 10000 mg/L。