CN106865860A - Energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit and method of wastewater treatment - Google Patents

Energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit and method of wastewater treatment Download PDF

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Publication number
CN106865860A
CN106865860A CN201710164498.9A CN201710164498A CN106865860A CN 106865860 A CN106865860 A CN 106865860A CN 201710164498 A CN201710164498 A CN 201710164498A CN 106865860 A CN106865860 A CN 106865860A
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reaction
heat exchanger
gas
reaction tower
liquid
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CN106865860B (en
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王维
孙承林
卫皇曌
李先如
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Zhangjiagang Institute Of Industrial Technology Dalian Institute Of Chemical Physics China Academy Of Sciences
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Zhangjiagang Institute Of Industrial Technology Dalian Institute Of Chemical Physics China Academy Of Sciences
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048Purification of waste water by evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/10Energy recovery

Abstract

The invention discloses a kind of energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit, waste water storage tank connects First Heat Exchanger simultaneously with catalyst carrier, First Heat Exchanger connects the first reaction tower, first reaction tower connects the second heat exchanger, second heat exchanger connects the second reaction tower, the heat exchange water out connection turbine generators of the second heat exchanger, second reaction tower connects the first gas-liquid separator, the gaseous phase outlet of the first gas-liquid separator is communicated with the first tail gas absorber, liquid-phase outlet is communicated with MVR evaporators, MVR evaporators connect the 3rd heat exchanger, 3rd heat exchanger connects the 3rd reaction tower, 3rd reaction tower connects the second gas-liquid separator, the gaseous phase outlet of the second gas-liquid separator connects the import of the second tail gas absorber;Air compressor machine is the first reaction tower, the second reaction tower and the 3rd reaction tower provide reaction air.The method have the advantages that:High concentration high salinity waste water can directly be processed, environmental protection, low cost, effect is good, floor space is small, recoverable energy.

Description

Energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit and method of wastewater treatment
Technical field
The present invention relates to a kind of industrial organic waste water processing technology field, and in particular to one kind is used to process that high concentration is high to be contained The apparatus and method of salt industrial organic wastewater.
Background technology
Water pollution is the major issue that a China needs to address at present.Solving water pollution problems should just solve first The generation in the source certainly polluted, i.e. sewage and discharge, and the industrial organic waste water that factory produces be water pollution main source it One.Pollutant component is complicated in industrial wastewater, bio-toxicity is big, COD is high, salinity is high, color is deep, taste weight, processes very tired It is difficult.Processing method main at present has:Bioanalysis, extraction, burning method, Fenton process and Ozone etc., but these methods lack Putting is:(1)Processing cost is high and poor processing effect;(2)COD contents cannot directly be processed more than 100,000 mg/L and high salinity Waste water, before high slat-containing wastewater is processed, it is necessary to which first diluting the COD contents and salt content of high concentration high slat-containing wastewater reduces, place Reason step complexity is cumbersome;(3)The occupation area of equipment applied is big;(4)Exist to the secondary of environment in wastewater treatment process Pollution and a large amount of wastes of energy, not energy-conserving and environment-protective.
The content of the invention
Can directly and efficiently process high concentration highly salt containing organic waste water it is an object of the invention to provide one kind, in waste water The energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit of non-secondary pollution and energy effective recycling energy in processing procedure And method of wastewater treatment.
To achieve the above object, present invention employs following technical scheme:A kind of described energy recovery type waste water catalysis Wet oxidation processing unit, including be used to store the waste water storage tank of waste water, be used to store the catalyst carrier of catalyst, Yi Jikong Press, the delivery port of the waste water storage tank is communicated with the charging aperture of First Heat Exchanger simultaneously with the discharging opening of catalyst carrier, the The discharging opening of one heat exchanger is communicated with the import of the first reaction tower, the first reaction tower outlet and the second heat exchanger charging aperture phase Logical, the discharging opening of the second heat exchanger is communicated with the import of the second reaction tower, and the heat exchange water out connection of second heat exchanger is saturating Flat generator, the outlet of second reaction tower is connected through First Heat Exchanger with the import of the first gas-liquid separator, the first gas The gaseous phase outlet of liquid/gas separator is connected with the import of the first tail gas absorber, the liquid-phase outlet and MVR of the first gas-liquid separator The charging aperture of evaporator is connected, and the condensation-water drain of MVR evaporators is connected with the charging aperture of the 3rd heat exchanger, the 3rd heat exchange The discharging opening of device is connected with the import of the 3rd reaction tower, and the outlet of the 3rd reaction tower is through the 3rd heat exchanger and the second gas-liquid separation The import of device is connected, and the gaseous phase outlet of the second gas-liquid separator is connected with the import of the second tail gas absorber;The pneumatics Machine is by pipeline simultaneously for the first reaction tower, the second reaction tower and the 3rd reaction tower carry available for reaction air.
Further, foregoing a kind of energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit, wherein:Second reaction tower Outlet be connected with the shell of First Heat Exchanger, cold material and thermal material adverse current by First Heat Exchanger, First Heat Exchanger Shell outlet is connected with the import of the first gas-liquid separator.
Further, foregoing a kind of energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit, wherein:3rd reaction tower Outlet be connected with the shell of the 3rd heat exchanger, cold material and thermal material adverse current by the 3rd heat exchanger, the 3rd heat exchanger Shell outlet is connected with the import of the second gas-liquid separator.
Further, foregoing a kind of energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit, wherein:First gas-liquid point Liquid-phase outlet from device is connected with the charging aperture of the first dashpot, the discharging opening of the first dashpot and the charging of MVR evaporators Mouth is connected.
Further, foregoing a kind of energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit, wherein:MVR evaporators Steaming more than mother liquor reflux to catalyst carrier.
A kind of method of wastewater treatment, comprises the following steps:
(1)Heated up again after first homogeneous catalyst is mixed with waste water and be passed through the first reaction tower, be mixed with homogeneous catalyst waste water and The reaction provided by air compressor machine in first reaction tower carries out first time homogeneous catalysis wet type in the first reaction tower together with air Oxidation reaction, first road treatment water of the generation comprising homogeneous catalyst;
(2)Then by step(1)The second reaction tower is passed through after the first road treatment water cooling of generation, then Shi Chu roads treatment water and the The reaction provided by air compressor machine in two reaction towers carries out second homogeneous catalysis wet type oxygen with air in the second reaction tower together Change reaction, two roads treatment water of the generation comprising homogeneous catalyst;
(3)Then by step(2)Being passed through the first gas-liquid separator after the two roads treatment water cooling of generation carries out gas-liquid separation, generates Gas phase and the liquid phase containing homogeneous catalyst;
(4)Then by step(3)The liquid phase of generation is passed through MVR evaporators and is evaporated, and generates colourless crystallization salt, condensed water and contains There is mother liquor more than the steaming of homogeneous catalyst;
(5)Then by step(4)The condensed water of generation is passed through the 3rd reaction tower, multiphase in condensed water and the 3rd reaction tower after heating up Catalyst and by air compressor machine provide reaction carry out heterogeneous catalysis wet oxidation reaction in the 3rd reaction tower together with air, Generate three roads treatment water;
(6)Then by step(5)Being passed through the second gas-liquid separator after the three roads treatment water cooling of generation carries out gas-liquid separation, generates Gas phase and meet the liquid phase of discharge standard.
Described homogeneous catalyst is ferric sulfate, ferric nitrate, copper sulphate, copper nitrate, manganese sulfate, manganese nitrate, cobaltous sulfate, nitre One or more in sour cobalt, zinc sulfate, zinc nitrate, nickel sulfate, nickel nitrate.
Described heterogeneous catalyst is noble metal carrier catalyst, and its carrier is activated carbon, titanium dioxide, titanium dioxide One or more in zirconium, alundum (Al2O3), silica and molecular sieve combination, its active component be ruthenium, rhodium, palladium, silver, platinum, One or more in cerium, lanthanum, neodymium.
Further, foregoing a kind of method of wastewater treatment, wherein:Step(1)Middle Characteristic of Homogenous Catalytic Wet Air Oxidation reaction Reaction condition is:Reaction temperature is(250~300)DEG C, reaction pressure is(4.5~9)MPa, liquid hourly space velocity (LHSV) is(0.5~3) h-1, The dosage of wherein homogeneous catalyst is that every liter of waste water is added(50~500)mg(With metal ion gauge).
Further, foregoing a kind of method of wastewater treatment, wherein:Step(2)Middle Characteristic of Homogenous Catalytic Wet Air Oxidation reaction Reaction condition is:Reaction temperature is(220~290)DEG C, reaction pressure is(2.5~8)MPa, liquid hourly space velocity (LHSV) is(0.5~3) h-1, The dosage of wherein homogeneous catalyst is that every liter of waste water is added(50~500)mg(With metal ion gauge).
Further, foregoing a kind of method of wastewater treatment, wherein:Step(4)The evaporation conditionses of middle MVR evaporators are: Evaporating temperature is(50~100)DEG C, remaining mother liquor amount control is steamed in step(3)The amount of liquid phase of generation(1~10)%.
Further, foregoing a kind of method of wastewater treatment, wherein:Step(5)Middle heterogeneous catalysis wet oxidation reaction Reaction condition is:Reaction temperature is(180~280)DEG C, reaction pressure is(2.0~7.5)MPa, liquid hourly space velocity (LHSV) is(0.5~3) h-1
By the implementation of above-mentioned technical proposal, the advantage of wastewater treatment equipment of the present invention is:(1)Processing cost is low, treatment Effect is good, floor space is small and high degree of automation;(2)Waste water need not be diluted, it is possible to directly process COD contents more than 100,000 The waste water of mg/L and high salinity;(3)In the absence of the secondary pollution to environment in wastewater treatment process;(4)By heat exchanger Waste heat is reclaimed, and the steam that heat exchanger is produced generates electricity for turbine generators, has reached the purpose that energy regenerating is utilized, Not only realize environmental benefit but also obtain economic benefit;The advantage of method of wastewater treatment of the present invention is:Good treatment efficiency, COD clearances Height, COD clearances are more than 95.5%, in the absence of the secondary pollution to environment in wastewater treatment process and useless without dilution Water, it is possible to directly process COD contents more than 100,000 mg/L and the waste water of high salinity, it is especially volatile to treatment organic principle Waste water have more advantage, MVR steams the reuse of remaining mother liquor and prepares that homogeneous catalyst had not only solved the problems, such as concentrate and to reach circulation sharp Purpose, and salt is separated out for colourless clean salt, recyclable recycling.
Brief description of the drawings
Fig. 1 is that a kind of structural principle of energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit of the present invention is illustrated Figure.
Specific embodiment
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
As shown in figure 1, a kind of described energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit, including be used to store useless The waste water storage tank 1 of water, it is used to store the catalyst carrier 2 and air compressor machine 3 of catalyst, the delivery port of the waste water storage tank 1 leads to Cross and be provided with the first pipeline 5 of the first membrane pump 4 and be connected with the import of pipe-line mixer 6, the discharging opening of catalyst carrier 2 passes through Second pipeline 7 is connected with the import of pipe-line mixer 6, the outlet of pipe-line mixer 6 and the charging aperture phase of First Heat Exchanger 9 Logical, the discharging opening of First Heat Exchanger 9 is communicated with the import of the first reaction tower 10, and the outlet at the top of the first reaction tower 10 passes through the 4th Pipeline 12 is communicated with the charging aperture of the second heat exchanger 11, the import phase of the discharging opening of the second heat exchanger 11 and the second reaction tower 13 It is logical, the heat exchange water out connection turbine generators 14 of the second heat exchanger 11, the top exit of the second reaction tower 13 is by the 5th pipe Road 15 is connected with the heat exchange water inlet of First Heat Exchanger 9, and the heat exchange water out of First Heat Exchanger 9 is by the 6th pipeline 16 and the The import of one gas-liquid separator 17 is connected, and two roads that the second reaction tower 13 can so generated process the waste heat pair of water Heat temperature raising is carried out by the high concentration highly salt containing organic waste water of First Heat Exchanger 9, homogeneous catalyst and air three mixture, So as to reclaim heat, the energy has been saved;
The gaseous phase outlet of the first gas-liquid separator 17 is connected by the 7th pipeline 18 with the import of the first tail gas absorber 19, the The liquid-phase outlet of one gas-liquid separator 17 is connected by the 8th pipeline 20 with the charging aperture of the first dashpot 21, the first dashpot 21 discharging opening is connected by being provided with the 9th pipeline 23 of the second membrane pump 22 with the charging aperture of MVR evaporators 24, MVR evaporations The condensation-water drain of device 24 is connected by being provided with the tenth pipeline 26 of the 3rd membrane pump 25 with the charging aperture of the 3rd heat exchanger 27, The discharging opening of the 3rd heat exchanger 27 is connected with the import of the 3rd reaction tower 28, and the top exit of the 3rd reaction tower 28 passes through the tenth One pipeline 29 is connected with the heat exchange water inlet of the 3rd heat exchanger 27, and the heat exchange water out of the 3rd heat exchanger 27 is by the 12nd pipe Road 30 is connected with the import of the second gas-liquid separator 31, and three roads that the 3rd reaction tower 28 can so generated process many of water Waste heat amount carries out heat temperature raising to the condensed water by the 3rd heat exchanger 27, so as to reclaim heat, has saved the energy;
The gaseous phase outlet of the second gas-liquid separator 31 is connected by the 13rd pipeline 32 with the import of the second tail gas absorber 33, The liquid-phase outlet of the second gas-liquid separator 31 is connected by the 14th pipeline 34 with the charging aperture of the second dashpot 35;The sky Press 3 is connected by the 3rd pipeline 8 with the import of pipe-line mixer 6, so that for the first reaction tower 10 carries available for reaction air, And by the 15th pipeline 36 that is connected with the 4th pipeline 12 for the second reaction tower 13 carries available for reaction air, while passing through The 16th pipeline 37 being connected with the tenth pipeline 26 is for the 3rd reaction tower 28 carries available for reaction air;
In the present embodiment, catalyst stored in catalyst carrier 2 is homogeneous catalyst, and the homogeneous catalyst is sulfuric acid Iron, ferric nitrate, copper sulphate, copper nitrate, manganese sulfate, manganese nitrate, cobaltous sulfate, cobalt nitrate, zinc sulfate, zinc nitrate, nickel sulfate, nitric acid One or more in nickel, at can be preferably to high concentration highly salt containing organic waste water after above-mentioned homogeneous catalyst Reason, high treating effect;
In the present embodiment, heterogeneous catalyst is filled with the 3rd reaction tower 28, described heterogeneous catalyst is noble-metal-supported Type catalyst, its carrier be activated carbon, titanium dioxide, zirconium dioxide, alundum (Al2O3), SiO 2 molecular sieve in one kind or Multiple combination, its active component is one or more in ruthenium, rhodium, palladium, silver, platinum, cerium, lanthanum, neodymium, using above-mentioned heterogeneous catalyst After preferably high concentration highly salt containing organic waste water can be processed, high treating effect;
The operation principle of wastewater treatment equipment of the present invention is as follows:
The high concentration highly salt containing organic waste water that the first membrane pump 4 will be stored in waste water storage tank 1 is first passed through to be passed through through the first pipeline 5 Pipe-line mixer 6, while the homogeneous catalyst stored in catalyst carrier 2 is also passed into pipe-line mixer through the second pipeline 7 6, while making air compressor machine 3 that reaction air is also passed into pipe-line mixer 6 by the 3rd pipeline 8, now high concentration saliferous high has Machine waste water, homogeneous catalyst and air three enter the after mixing in the pipe-line mixer 6 from the charging aperture of First Heat Exchanger 9 One heat exchanger 9, then from the discharging opening of First Heat Exchanger 9 into the first reaction tower 10 in carry out sufficient Characteristic of Homogenous Catalytic Wet Air Oxidation Reaction, the first road treatment water that the first reaction tower 10 will can be formed after reaction enters the 4th pipe from the top exit of the first reaction tower 10 Road 12, then enter the charging aperture of the second heat exchanger 11 from the 4th pipeline 12, now reaction can be passed through the tenth by air compressor machine 3 with air Five pipelines 36 are also passed into the charging aperture of the second heat exchanger 11, and the first reaction tower 10 first road treatment water out can be with air second Mix in heat exchanger 11 and sufficiently exchanged heat with the water in the second heat exchanger 11, the water in the second heat exchanger 11 is through heat exchange After can become steam and generated electricity for turbine generators, and treatment water in two roads is then entered and carried out in the second reaction tower 13 after heat exchange cooling Second Characteristic of Homogenous Catalytic Wet Air Oxidation reacts, and two roads that the second reaction tower 13 will can be formed after reaction process water from the second reaction tower 13 top exit enters the 5th pipeline 15, then enters First Heat Exchanger 9, Ran Houzai from the heat exchange water inlet of First Heat Exchanger 9 Enter the 6th pipeline 16 from the heat exchange water out of First Heat Exchanger 9, the discharge of the second reaction tower 13 two roads treatment water by the During one heat exchanger 9, two roads treatment water waste heat can by the high concentration highly salt containing organic waste water by First Heat Exchanger 9, Homogeneous catalyst and air three absorb, so as to high concentration highly salt containing organic waste water, the homogeneous catalysis by First Heat Exchanger 9 Agent and air three mixture carry out heat temperature raising, and itself then gradually cools after heat exchange;
Now gas-liquid can be carried out in the 6th pipeline 16 into the first gas-liquid separator 17 by the roads of the Hou bis- treatment water that cools Separate, the first gas-liquid separator 17 two roads is processed the gas phase generated after water gas-liquid separation and enters the first tail gas through the 7th pipeline 18 Absorption tower 19, is carried out being discharged after treatment is up to standard through the first tail gas absorber 19, and two roads are processed water by the first gas-liquid separator 17 The liquid phase generated after gas-liquid separation can enter the first dashpot 21 through the 8th pipeline 20, then by the second membrane pump 22 through the 9th pipeline 23 squeeze into MVR evaporators 24 is processed, and the remaining mother liquor of steaming and condensed water can be formed after the treatment of MVR evaporators 24, wherein steaming remaining female Liquid can be used for reuse and prepare homogeneous catalyst, and condensed water then squeezes into the 3rd heat exchanger by the 3rd membrane pump 25 through the tenth pipeline 26 Reaction air be also passed into the charging of the 3rd heat exchanger 27 by the 16th pipeline 37 for 27 charging aperture, the now meeting of air compressor machine 3 Mouthful, condensed water is passed through the 3rd reaction tower after mixing in the 3rd heat exchanger 27 with air from the discharging opening of the 3rd heat exchanger 27 28, and sufficient heterogeneous catalysis humidifying oxidation reaction is carried out together with the heterogeneous catalyst in the 3rd reaction tower 28, the 3rd reaction The three roads treatment water that tower 28 will can be formed after reaction enters the 11st pipeline 29, then changing from the 3rd heat exchanger 27 from top exit Hot water inlet enters the 3rd heat exchanger 27, and then the heat exchange water out again from the 3rd heat exchanger 27 enters the 12nd pipeline 30, During three roads formed after the CWO reaction of the discharge of the 3rd reaction tower 28 process water by the 3rd heat exchanger 27, The waste heat of three road treatment water can be absorbed by the condensed water of the 3rd heat exchanger 27 with air, so as to by the 3rd heat exchange Condensed water and air in device 27 carry out heat temperature raising, and itself then gradually cools after heat exchange;At cooling Hou tri- roads Reason water can enter the 12nd pipeline 30 from the heat exchange of the 3rd heat exchanger 27 mouth, then enter the second gas-liquid separation from the 12nd pipeline 30 Device 31, the second gas-liquid separator 31 generates gas phase and liquid phase, the gas phase meeting for being generated after three roads treatment water is carried out into gas-liquid separation Entered through the 13rd pipeline 32 after second tail gas absorber 33 carries out treatment up to standard and discharged, and the liquid phase for being generated can be through the 14th Pipeline 34 enters the second dashpot 21, then is directly discharged into extraneous from the second dashpot 21 or enters biochemical system treatment, by upper Operation is stated, that is, completes the treatment to high concentration highly salt containing organic waste water.
The advantage of wastewater treatment equipment of the present invention is:(1)Processing cost is low, high treating effect, floor space are small and automatic Change degree is high;(2)Waste water need not be diluted, it is possible to directly process COD contents more than 100,000 mg/L and the waste water of high salinity; (3)In the absence of the secondary pollution to environment in wastewater treatment process;(4)Waste heat is reclaimed by heat exchanger, and will heat exchange The steam that device is produced generates electricity for turbine generators, has reached the purpose that energy regenerating is utilized.
A kind of method of wastewater treatment, comprises the following steps:
(1)A kind of organic intermediate production waste water is processed, the waste water mainly contains 1, the composition such as hydroresorcinol, sodium chloride, COD It is 125360 mg/L, pH=3.5, salinity is 12.5%;Heated up again after first homogeneous catalyst is mixed with waste water and be passed through the first reaction Tower, is mixed with the waste water and the first reaction tower of homogeneous catalyst by the reaction of air compressor machine offer with air together in the first reaction tower Inside carry out first time Characteristic of Homogenous Catalytic Wet Air Oxidation reaction, first road treatment water of the generation comprising homogeneous catalyst;Wherein homogeneous catalysis The reaction condition of wet oxidation reaction is:Reaction temperature is(250~300)DEG C, reaction pressure is(4.5~9)MPa, liquid hourly space velocity (LHSV) For(0.5~3) h-1, the dosage of wherein homogeneous catalyst is that every liter of waste water is added(50~500)mg;
(2)Then by step(1)The second reaction tower is passed through after the first road treatment water cooling of generation, then Shi Chu roads treatment water and the The reaction provided by air compressor machine in two reaction towers carries out second homogeneous catalysis wet type oxygen with air in the second reaction tower together Change reaction, two roads treatment water of the generation comprising homogeneous catalyst, the reaction condition of wherein Characteristic of Homogenous Catalytic Wet Air Oxidation reaction is:Instead The temperature is answered to be(220~290)DEG C, reaction pressure is(2.5~8)MPa, liquid hourly space velocity (LHSV) is(0.5~3) h-1, wherein homogeneous catalyst Dosage be that every liter of waste water is added(50~500)mg;
(3)Then by step(2)Being passed through the first gas-liquid separator after the two roads treatment water cooling of generation carries out gas-liquid separation, generates Gas phase and the liquid phase containing homogeneous catalyst;
(4)Then by step(3)The liquid phase of generation is passed through MVR evaporators and is evaporated, and generates colourless crystallization salt, condensed water and contains The evaporation conditionses for having mother liquor more than the steaming of homogeneous catalyst, wherein MVR evaporators are:Evaporating temperature is(50~100)DEG C, steam remaining female Liquid measure is controlled in step(3)The amount of liquid phase of generation(1~10)%;
(5)Then by step(4)The condensed water of generation is passed through the 3rd reaction tower, multiphase in condensed water and the 3rd reaction tower after heating up Catalyst and by air compressor machine provide reaction carry out heterogeneous catalysis wet oxidation reaction in the 3rd reaction tower together with air, Three roads treatment water is generated, the reaction condition of wherein heterogeneous catalysis wet oxidation reaction is:Reaction temperature is(180~280)DEG C, instead The pressure is answered to be(2.0~7.5)MPa, liquid hourly space velocity (LHSV) is(0.5~3) h-1
(6)Then by step(5)Being passed through the second gas-liquid separator after the three roads treatment water cooling of generation carries out gas-liquid separation, generates Gas phase and meet the liquid phase of discharge standard.
Described homogeneous catalyst is ferric sulfate, ferric nitrate, copper sulphate, copper nitrate, manganese sulfate, manganese nitrate, cobaltous sulfate, nitre One or more in sour cobalt, zinc sulfate, zinc nitrate, nickel sulfate, nickel nitrate.
Described heterogeneous catalyst is noble metal carrier catalyst, and its carrier is activated carbon, titanium dioxide, titanium dioxide One or more in zirconium, alundum (Al2O3), silica and molecular sieve combination, its active component be ruthenium, rhodium, palladium, silver, platinum, One or more in cerium, lanthanum, neodymium.
Following table is raw wastewater by after the reaction of Characteristic of Homogenous Catalytic Wet Air Oxidation twice and anti-by heterogeneous catalysis wet oxidation Should after COD, COD clearance, salt content and pH value in the treatment water that obtains, and it can be seen that this wastewater treatment side from table The high treating effect of method.
The advantage of method of wastewater treatment of the present invention is:Good treatment efficiency, COD clearances are high, and COD clearances are more than 95%, in waste water In the absence of the secondary pollution to environment in processing procedure, and waste water need not be diluted, it is possible to directly process COD contents more than 10 The waste water of ten thousand mg/L and high salinity, especially has more advantage to the treatment volatile waste water of organic principle, and MVR steams remaining mother liquor reuse Homogeneous catalyst is prepared not only to have solved the problems, such as concentrate and reached the purpose that recycles, and it is colourless cleaning to separate out salt Salt, recyclable recycling.

Claims (10)

1. energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit, it is characterised in that:Waste water storage including being used to store waste water Groove, it is used to store the catalyst carrier and air compressor machine of catalyst, the delivery port of the waste water storage tank and going out for catalyst carrier Material mouth is communicated with the charging aperture of First Heat Exchanger simultaneously, and the discharging opening of First Heat Exchanger is communicated with the import of the first reaction tower, the The outlet of one reaction tower is communicated with the charging aperture of the second heat exchanger, the import phase of the discharging opening of the second heat exchanger and the second reaction tower It is logical, the heat exchange water out connection turbine generators of second heat exchanger, the outlet of second reaction tower is through First Heat Exchanger Import with the first gas-liquid separator is connected, the import phase of the gaseous phase outlet of the first gas-liquid separator and the first tail gas absorber Connection, the liquid-phase outlet of the first gas-liquid separator is connected with the charging aperture of MVR evaporators, the condensation-water drain of MVR evaporators Charging aperture with the 3rd heat exchanger is connected, and the discharging opening of the 3rd heat exchanger is connected with the import of the 3rd reaction tower, and the 3rd is anti- Answer the outlet of tower to be connected with the import of the second gas-liquid separator through the 3rd heat exchanger, the gaseous phase outlet of the second gas-liquid separator with The import of the second tail gas absorber is connected;The air compressor machine is simultaneously the first reaction tower by pipeline, the second reaction tower and the Three reaction towers carry available for reaction air.
2. energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit according to claim 1, it is characterised in that:Second is anti- The outlet of tower is answered to be connected with the shell of First Heat Exchanger, with thermal material adverse current by First Heat Exchanger, first exchanges heat cold material The shell outlet of device is connected with the import of the first gas-liquid separator.
3. energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit according to claim 1, it is characterised in that:3rd is anti- The outlet of tower is answered to be connected with the shell of the 3rd heat exchanger, cold material is with thermal material adverse current by the 3rd heat exchanger, the 3rd heat exchange The shell outlet of device is connected with the import of the second gas-liquid separator.
4. energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit according to claim 1, it is characterised in that:First gas The liquid-phase outlet of liquid/gas separator is connected with the charging aperture of the first dashpot, discharging opening and the MVR evaporators of the first dashpot Charging aperture is connected.
5. energy recovery type Catalytic Wet Air Oxidation for Wastewater processing unit according to claim 1, it is characterised in that:MVR steams Mother liquor reflux is sent out more than the steaming of device to catalyst carrier.
6. a kind of method of wastewater treatment, it is characterised in that:Using the device as described in any one of Claims 1 to 5, and including such as Lower step:
(1)Heated up again after first homogeneous catalyst is mixed with waste water and be passed through the first reaction tower, be mixed with homogeneous catalyst waste water and The reaction provided by air compressor machine in first reaction tower carries out first time homogeneous catalysis wet type in the first reaction tower together with air Oxidation reaction, first road treatment water of the generation comprising homogeneous catalyst;
(2)Then by step(1)The second reaction tower is passed through after the first road treatment water cooling of generation, then Shi Chu roads treatment water and the The reaction provided by air compressor machine in two reaction towers carries out second homogeneous catalysis wet type oxygen with air in the second reaction tower together Change reaction, two roads treatment water of the generation comprising homogeneous catalyst;
(3)Then by step(2)Being passed through the first gas-liquid separator after the two roads treatment water cooling of generation carries out gas-liquid separation, generates Gas phase and the liquid phase containing homogeneous catalyst;
(4)Then by step(3)The liquid phase of generation is passed through MVR evaporators and is evaporated, and generates colourless crystallization salt, condensed water and contains There is mother liquor more than the steaming of homogeneous catalyst;
(5)Then by step(4)The condensed water of generation is passed through the 3rd reaction tower, multiphase in condensed water and the 3rd reaction tower after heating up Catalyst and by air compressor machine provide reaction carry out heterogeneous catalysis wet oxidation reaction in the 3rd reaction tower together with air, Generate three roads treatment water;
(6)Then by step(5)Being passed through the second gas-liquid separator after the three roads treatment water cooling of generation carries out gas-liquid separation, generates Gas phase and meet the liquid phase of discharge standard;
Described homogeneous catalyst is ferric sulfate, ferric nitrate, copper sulphate, copper nitrate, manganese sulfate, manganese nitrate, cobaltous sulfate, nitric acid One or more in cobalt, zinc sulfate, zinc nitrate, nickel sulfate, nickel nitrate;
Described heterogeneous catalyst is noble metal carrier catalyst, and its carrier is activated carbon, titanium dioxide, zirconium dioxide, three One or more in Al 2 O, silica and molecular sieve combination, its active component be ruthenium, rhodium, palladium, silver, platinum, cerium, lanthanum, One or more in neodymium.
7. a kind of method of wastewater treatment according to claim 6, it is characterised in that:Step(1)Middle homogeneous catalysis wet type oxygen Changing the reaction condition for reacting is:Reaction temperature is(250~300)DEG C, reaction pressure is(4.5~9)MPa, liquid hourly space velocity (LHSV) is(0.5 ~3) h-1, the dosage of wherein homogeneous catalyst is that every liter of waste water is added(50~500)mg.
8. a kind of method of wastewater treatment according to claim 6, it is characterised in that:Step(2)Middle homogeneous catalysis wet type oxygen Changing the reaction condition for reacting is:Reaction temperature is(220~290)DEG C, reaction pressure is(2.5~8)MPa, liquid hourly space velocity (LHSV) is(0.5 ~3) h-1, the dosage of wherein homogeneous catalyst is that every liter of waste water is added(50~500)mg.
9. a kind of method of wastewater treatment according to claim 6, it is characterised in that:Step(4)The evaporation of middle MVR evaporators Condition is:Evaporating temperature is(50~100)DEG C, remaining mother liquor amount control is steamed in step(3)The amount of liquid phase of generation(1~10)%.
10. a kind of method of wastewater treatment according to claim 6, it is characterised in that:Step(5)Middle heterogeneous catalysis wet type oxygen Changing the reaction condition for reacting is:Reaction temperature is(180~280)DEG C, reaction pressure is(2.0~7.5)MPa, liquid hourly space velocity (LHSV) is (0.5~3) h-1
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CN108383231A (en) * 2018-03-09 2018-08-10 涂学炎 A method of based on MVR system two-phase catalytic treatments high concentrated organic wastewater with high salt
CN109179791A (en) * 2018-11-16 2019-01-11 佛山科学技术学院 A kind of catalytic wet oxidation processing equipment of the industrial wastewater with multistage filtering
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CN109399846A (en) * 2017-08-18 2019-03-01 中国科学院大连化学物理研究所 A kind of method of catalytic wet oxidation processing high concentration cymoxanil waste water
CN108383231A (en) * 2018-03-09 2018-08-10 涂学炎 A method of based on MVR system two-phase catalytic treatments high concentrated organic wastewater with high salt
CN108383231B (en) * 2018-03-09 2021-01-12 涂学炎 Method for double-phase catalytic treatment of high-salt high-concentration organic wastewater based on MVR system
CN109293116A (en) * 2018-11-07 2019-02-01 苏州工业园区承叶环境科技有限公司 A kind for the treatment of process of high concentration cymoxanil waste water
CN109179791A (en) * 2018-11-16 2019-01-11 佛山科学技术学院 A kind of catalytic wet oxidation processing equipment of the industrial wastewater with multistage filtering
CN112456720A (en) * 2021-01-25 2021-03-09 华夏碧水环保科技有限公司北京分公司 CWO and MVR combined wastewater pretreatment system and pretreatment method

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