CN108069501A - A kind of technique for handling organic wastewater - Google Patents

Abstract

The invention relates to the technical field of wastewater treatment, and specifically discloses a process for treating organic wastewater. The 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 process for treating organic wastewater

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 process for treating organic waste water. The process includes the following contents: a rotating bed reactor is used as a reaction device, the shell of the rotating bed reactor includes an inner rotating bed and an outer rotating bed, and organic waste water 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 catalyst A, the outer rotating bed is composed of a corrosion-resistant frame and catalyst B, the catalyst A is a noble metal supported catalyst, and the catalyst B is composed of a corrosion-resistant frame and a catalyst B. It 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. 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 is a noble metal supported catalyst, including a carrier and an active metal component loaded on the carrier, wherein one or more of activated carbon, molecular sieve or oxide is used as the carrier; the The molecular sieves are 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, di One or more of silicon oxide; one or more of the noble metals Pt, Pd, Rh, Ru, Ir as the active metal component, based on the weight of the catalyst, the content of the noble metal is 0.01% in terms of elements ~5.0%. The active metal component of the catalyst A also includes an auxiliary component, the auxiliary component is a rare earth metal, the content of the rare earth metal is 0.1% to 20.0% in terms of elements, and the rare earth metal is lanthanum, cerium , praseodymium, neodymium in one or more.

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 the noble metal catalyst in the presence of ozone, and the high-concentration ozone converts a part of the organic pollutants under the action of the noble metal catalyst, and the downstream ozone concentration is reduced. Contact with copper-based catalysts with strong ability to give full play to the catalytic effect of copper-based catalysts; through the synergistic effect of noble metal catalysts and copper-based catalysts, not only the treatment effect of organic wastewater is good, but also the loss of metal copper can be effectively reduced, solving the existing problem There is a serious problem of copper metal loss in the use of copper-based catalysts in the technology. 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 of 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 (Ru/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 _RuCl3 to make a solution in the proportion that Ru accounts for 2% of the total catalyst weight. The activated carbon strips were impregnated with an equal volume of Ru solution for 24 h, dried at 100 °C, placed in a tube furnace, reduced with _N2 containing 10% _H2 at 400 °C for 4 h, and passivated with _N2 containing 1% _O2 After 4 hours, the temperature was lowered to room temperature and taken out to obtain catalyst A1.

Preparation of Catalyst A2 (Ru-Ce/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 the dried ZSM-5 carrier, measure a certain amount of RuCl ₃ solution according to the proportion of Ru accounting for 1.0%, and impregnate the carrier with equal volume for 24 hours. After drying at 120 °C, put it into a tube furnace, reduce it with _N2 containing 10% _H2 at 400 °C for 4 hours, and then passivate it with _N2 containing 1% _O2 for 4 hours. A certain amount of Ce(NO ₃ ) ₃ ·6H ₂ O was then weighed to make a solution according to the proportion of Ce accounting for 5.0%, and the sample obtained in the previous step was impregnated with an equal volume of the carrier for another 24 hours. After drying at 120 °C, put it into a tube furnace, bake it with nitrogen at 800 °C for 4 hours, and then passivate it with _N2 containing 1% _O2 for 4 hours. After the temperature dropped to room temperature, it was taken out to obtain catalyst A2.

Preparation of Catalyst A3 (Pt/TiO ₂ )

The strip-shaped TiO ₂ carrier with a diameter of 2.0 mm, a specific surface area of 100 m ² /g, a pore volume of 0.4 cm ³ /g, and an average pore diameter of 3.4 nm was dried at 120°C for use. Weigh 500 g of TiO ₂ carrier, and prepare a solution with chloroplatinic acid (H ₂ PtCl ₆ ·6H ₂ O) according to the ratio of Pt to 2% of the total weight of the catalyst according to its water absorption. The _TiO2 carrier was impregnated with an equal volume of Pt solution for 24 hours, dried at 100 °C, put into _a tube furnace, reduced with _N2 containing 10% _H2 at 400 °C for 4 hours, and then treated with _N2 containing 1% O2 After passivation for 4 hours, 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 583 m ² /g, a pore volume of 0.6 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 2 hours, dry at 80°C, and bake at 550°C for 4 hours in a nitrogen atmosphere. After the temperature dropped to room temperature, take it out to obtain catalyst B1.

Preparation of Catalyst B2 (Cu-La/TS-1)

The TS-1 molecular sieve strip carrier with a diameter of 2.0mm, a specific surface area of 432m ² /g, a pore volume of 0.2 cm ³ /g and an average pore diameter of 3.3nm was dried at 120°C for use. Weigh 500g of TS-1 molecular sieve carrier, use Cu(NO ₃ ) ₂ 3H ₂ O and La(NO ₃ ) ₃ 6H ₂ O according to the ratio of CuO and La ₂ O ₃ to the total catalyst weight of 6% and 1.5% respectively Dubbed 1000 mL solution. The TS-1 carrier was impregnated with Cu-La solution for 3 hours, left to stand in the air for 24 hours, and 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 then taken out after the temperature dropped to room temperature to obtain catalyst A2.

Preparation of Catalyst B3 (Cu-Ce/SiO ₂ )

The strip-shaped SiO 2 carrier with a diameter of 2.0mm, a specific surface area of 207m ² /g, a pore volume of 0.8 cm ³ /g, and an average pore diameter of _5.8nm was dried at 120°C for use. Weigh 500 g of the SiO ₂ carrier, and prepare a solution with Cu(NO ₃ ) ₂ ·3H ₂ O and Ce(NO ₃ ) ₃ ·6H ₂ O according to the ratio of CuO and CeO ₂ to the total catalyst weight of 5% and 1.5%, respectively. Impregnate the _SiO2 carrier with an equal volume of Cu-Ce solution for 2 hours, dry it at 80°C, bake it under nitrogen atmosphere at 550°C for 4 hours, take it out after the temperature drops to room temperature, and obtain catalyst B3.

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 9.0 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 1200 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 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 5

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.

Example 6

Catalysts A2 and B3 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 in Example 1, using the coal chemical industry salty wastewater, and the COD of the original solution is 449.3 mg/L. Intake ozone concentration changed to 14.5 g/m ³ . The results are listed in Table 2.

Example 8

The reaction conditions are the same as in Example 4, 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 2.8 g/m ³ . The results are listed in Table 2.

Example 9

The reaction conditions are the same as in Example 6, 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 12.0 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.

Comparative example 4

Using catalyst B3 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 1-4

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 technique for handling organic wastewater, the technique include herein below：Using rotary drill reactor as consersion unit, Include interior revolving bed and outer revolving bed in the rotary drill reactor housing, using organic wastewater as raw material, in item existing for ozone Oxidation reaction is carried out under part, the interior revolving bed is made of corrosion-resistant frame and catalyst A, and the outer revolving bed is by corrosion-resistant frame Frame and catalyst B are formed, and the catalyst A is noble metal carrier catalyst, and catalyst B is copper system support catalysts.

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

3. the technique of processing organic wastewater described in accordance with the claim 2, it is characterised in that：The reactor shell is cylinder Cylinder, the end socket include upper cover and low head, and cylindrical reactor is vertically arranged.

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

5. the technique of processing organic wastewater described in accordance with the claim 2, it is characterised in that：Between interior revolving bed and outer revolving bed It is with or without gap.

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

7. the technique of processing organic wastewater described in accordance with the claim 1, it is characterised in that：The catalyst A and catalyst B's Volume ratio is 20%~80%：20%~80%.

8. the technique of processing organic wastewater described in accordance with the claim 1, it is characterised in that：The catalyst A and catalyst B's Volume ratio is 40%~70%：30%~60%.

9. the technique of processing organic wastewater described in accordance with the claim 1, it is characterised in that：The catalyst A bears for noble metal Supported catalyst, including carrier and the active metal component being supported on carrier, wherein in activated carbon, molecular sieve, oxide One or more be carrier；The molecular sieve for A types, Y types, one kind in Beta, ZSM-5, TS-1, MCM-41 molecular sieve or Several, the oxide is one or more of aluminium oxide, ceria, zirconium dioxide, titanium dioxide, silica；With One or several kinds in precious metals pt, Pd, Rh, Ru, Ir are active metal component, on the basis of the weight of catalyst, your gold The content of category is 0.01% ~ 5.0% based on the element.

10. according to the technique of the processing organic wastewater described in claim 9, it is characterised in that：The catalyst A includes helping Agent, the auxiliary agent is lanthanum, the one or more in cerium, praseodymium, neodymium, and the auxiliary agent content is 0.1 ~ 20wt%.

11. the technique of processing organic wastewater described in accordance with the claim 1, it is characterised in that：The catalyst B include carrier and The active metal component being supported on carrier, wherein with one or more of activated carbon, molecular sieve, oxide for carrier；Institute Molecular sieve is stated as one or more of A types, Y types, Beta, ZSM-5, TS-1, MCM-41 molecular sieve, 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 technique of the processing organic wastewater described in claim 11, it is characterised in that：The activity gold of the catalyst B Belonging to component includes one or more of iron, nickel, vanadium.

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

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

15. the technique of processing organic wastewater 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. the technique of processing organic wastewater described in accordance with the claim 1, it is characterised in that：The ozone usage is by raw material 0.3~2.0 times of ozone usage needed for the calculating of organic wastewater COD value.

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