CN102276081A - Process for treating industrial organic waste water by serial catalytic oxidization - Google Patents
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Abstract
The invention relates to a process for treating industrial organic waste water by serial catalytic oxidization and belongs to the technical field of environment protection. The process for treating industrial organic waste water by serial catalytic oxidization realizes the quick treatment of complex organic pollutants in pretreated industrial waste water by coordination between oxidizers in a mode of serially connecting and coordinating catalytic oxidization by ozone and catalytic oxidization by hydrogen peroxide. In the first catalytic oxidization process, a large amount of free radicals are formed by catalytic oxidization by ozone, so that organic matters in waste water are oxidized and decomposed; and the rest ozone and organic pollutants enter the second hydrogen peroxide catalytic decomposition process, so that the organic matters are decomposed, the degradation action and coordinated reaction of the hydrogen peroxide and ozone are activated and the organic pollutants are degraded quickly. The process for treating industrial organic waste water by serial catalytic oxidization not only improves the processing capacity of nondegradable organic pollutants, but also improves the utilization rate of oxidizers and effectively reduces operation cost.
Description
Technical field
The present invention relates to a kind of series connection catalytic oxidation treatment industrial organic waste water technology, belong to environmental protection technical field.
Background technology
The waste water of industrial park is more unmanageable waste water, its complicated component of originating, and organic pollutant wherein is a refractory organic often, intractability is big.The COD of this part has benzene ring structure often greater than 2000mg/L, and the organic pollutant of stable in properties occupies large percentage, has therefore increased the difficulty of handling.At present, industrial park waste water adopts single-oxidizer treatment process: H
2O
2Catalytic oxidation or O
3Catalytic oxidation is decomposed into small organic molecule or CO with the oxidation operation in the waste water
2And H
2O, thereby the organic pollutant in the removal waste water.Traditional chemical oxidization method only depends on the oxidation capacity of oxygenant often can not reach the ideal oxidation effectiveness, so use some supplementary meanss to improve oxidation efficiency.UV/O has appearred
3, UV/H
2O
2, catalytic oxidation such as Fenton, improved the processing efficiency of chemical oxidization method.Methods such as other treating method such as catalytic wet oxidation have also appearred simultaneously, wet oxidation technology (WAO) as F.J.Zimmermann proposition in 1958 is to make oxygenant with air or pure oxygen, at high temperature (150t～350 ℃), high pressure (under the condition of 0.5MPa～28MPa), is small organic molecule or CO with the hardly degraded organic substance oxygenolysis in the waste water
2And H
2O.Owing in the WAO technology, used higher temperature and pressure, all brought sizable difficulty therefore for manufacturing, the operation of equipment.The operational conditions of High Temperature High Pressure is the major cause that this technology can not be promoted always.Fenton in 1894 finds can produce hydroxyl radical free radical (OH) after ferrous iron and hydrogen peroxide mix,-OH has high oxidizing potential (2.8V) because of it, its oxidation capacity is extremely strong, with most organic pollutants chain reaction fast can take place, and non-selectivity objectionable impurities is oxidized to CO
2, H
2O or mineral salt, non-secondary pollution.Fenton reagent has solved the problem that the catalyzed oxidation technology is used at normal temperatures and pressures, significantly improves processing efficiency.After the eighties in 20th century, the application of catalysis water technology in trade effluent of ozone and hydrogen peroxide becomes trade effluent gradually and improves biodegradability, effectively reduces the main method of pollution concentration.In the process of using, oxygenant has also appearred in the method for the organic pollutant of this simple application single catalyst catalytic oxidation treatment complexity to the active different phenomenon of the processing of different organic pollutants, problems such as treatment types is limited, industrial organic waste water, the organic waste water of industrial park particularly, its complicated component of originating, organic pollutant wherein often is a refractory organic, intractability is big, is organic wastewater with difficult degradation thereby.The COD of this part has benzene ring structure often greater than 2000mg/L, and the organic pollutant of stable in properties occupies large percentage, has therefore increased the difficulty of handling.So the method that multiple method for oxidation coupling is handled has obtained application gradually in industrial practical application, as add FeSO4 in early stage, the degraded precipitation, and then the technology of carrying out the oxygenant oxidation, but for the synergy of considering between the different oxygenants, improve the oxygenant utilization ratio, improve the technology of treatment effect, also have not seen reported.
Summary of the invention
At above-mentioned existing problems, the object of the present invention is to provide a kind of series connection catalytic oxidation treatment industrial organic waste water technology to achieve these goals, technical solution of the present invention is as follows:
A kind of series connection catalytic oxidation treatment industrial organic waste water technology, the catalytic oxidation treatment mode that the organic waste water behind preprocessing process is adopted is one-level catalyzed oxidation and secondary concerted catalysis oxidation.Described one-level catalyzed oxidation refers to that industrial organic waste water enters first step catalyzed oxidation pond body, Chi Tizhong by quality than water: one-level catalyzer=1000: 1 is placed catalyzer, after finishing, water inlet adds ozone, the ozone add-on is 100～800g/Th, reaction times is 30 minutes, and waste water carries out first step catalyzed oxidation internal recycle in the pond, and working cycle continues 40 minutes, make waste water and the abundant contact reacts of one-level catalyzer, first step catalytic oxidation finishes.
Described secondary concerted catalysis oxidation is meant that the industrial organic waste water after the one-level catalyzed reaction drains into second stage reaction tank from first step reaction tank, Chi Tizhong by quality than water: second catalyst=1100: 1 is placed catalyzer, and unreacted ozone in the one-level catalytic oxidation process is collected into second stage reaction tank, aeration is gone into catalyzed oxidation pond, second stage body, pumping into concentration is 20% hydrogen peroxide, 100～700g/Th, stop and handled 30 minutes, carry out internal recycle during this time, working cycle continues 30 minutes, and second stage catalytic oxidation finishes.
Described one-level catalyzer is for being carrier with the gac, and surface recombination contains the manganese metal ion, and compounding quantity is 3g/kg.
Described second catalyst is for being carrier with the gac, surface recombination ferrous metal ion, and compounding quantity is 5g/kg.
Owing to adopt above technical scheme, series connection catalytic oxidation treatment industrial organic waste water technology of the present invention, adopt the series connection and collaborative mode of catalytic ozonation and catalysis dioxygen aquation, with multiple oxidizer catalytic method series connection, realized collaborative between oxygenant and to the fast processing of complicated organic pollutant, described series connection catalyzed oxidation technology is at normal temperature, under the condition of normal pressure, fix first catalyzer in first catalytic oxidation process, be the catalytic ozonation process: use immobilized catalyst catalytic decomposition ozone, generate great amount of hydroxy group free radical (.OH), utilize .OH redox potential and Electron Affinities to interrupt chromophore in the organic pollutant molecule structure, organic pollutant in the water is degraded fast, and make a position C-H key of polymeric oxide in the waste water, β-C key, γ-C key, C-C is broken into low molecular compound, thereby the organism in the waste water is carried out oxygenolysis, fast degradation of organic substances COD; Remaining ozone and remaining organic pollutant enter second catalytic decomposition process, in this process, adopt second catalyst to decompose hydrogen peroxide, produce OH free radical cracking oxidation residue organic dirt, and, ozone and hydrogen peroxide generation chain reaction in this process entered, produce the more freedom base, activated the Degradation of hydrogen peroxide and ozone, concerted reaction reaches the purpose of quick degradable organic pollutant.
Series connection catalytic oxidation treatment industrial organic waste water technology of the present invention has not only improved and has handled the processing efficiency ability of Persistent organic pollutants, and has improved the utilising efficiency of oxygenant; Can effectively reduce running cost, the Application Areas of expansion technology.It has changed the catalytic oxidation treatment method of single employing hydrogen peroxide of existing industrial organic waste water or ozone, and it is handled, and kind of waste water is limited, running cost is high, operation operation complicated problems.The present invention is applied under the equal operational conditions, can increase substantially the industrial organic waste water processing efficiency, can reduce equipment investment cost and running cost, make it to be applicable to industrial organic waste water widely, as the processing of kinds such as paper waste, textile printing and dyeing wastewater or agricultural chemicals waste water.
Description of drawings
Accompanying drawing is a kind of series connection catalytic oxidation treatment industrial organic waste water process flow sheet of the present invention.
Embodiment
Below in conjunction with drawings and the specific embodiments the present invention is done to describe in further detail, see accompanying drawing.
A kind of series connection catalytic oxidation treatment industrial organic waste water technology, its technical process is: industrial organic waste water → all and aeration → in and coagulating sedimentation → intermediate pool → one-level catalyzed oxidation → secondary concerted catalysis oxidation → water outlet
Described organic waste water pre-treatment comprise to waste water all with the aeration flow process and in and the coagulating sedimentation flow process, all and aeration flow process employing is equal and the aeration tank, all with aeration tank control air aeration intensity 1～7m
3/ m
2.h, so that all types of industries organic waste water fully all with; In and the coagulating sedimentation flow process adopt in and coagulative precipitation tank, adopt trip valve to add white lime or salt acid for adjusting pH value at neutral zone, control pH value 6～9, back thread adds 0.5% coagulant aids PAC, controls dosage 1～10mg/L; By most suspended substances and the oil content in the pretreatment technology removal waste water.
The catalytic oxidation treatment mode that organic waste water behind preprocessing process is adopted is one-level catalyzed oxidation and secondary concerted catalysis oxidation, described one-level catalyzed oxidation refers to that industrial organic waste water enters first step catalyzed oxidation pond body through intermediate pool, Chi Tizhong by quality than water: one-level catalyzer=1000: 1 is placed the one-level catalyzer, described one-level catalyzer is for being carrier with the gac, surface recombination contains the manganese metal ion, compounding quantity is 3g/kg, after finishing, water inlet adds ozone, the ozone add-on is 100～800g/Th, reaction times is 30 minutes, waste water carries out internal recycle in first step catalyzed oxidation pond in the pond, working cycle continues 40 minutes, make waste water and catalysis advance abundant contact reacts, first step catalytic oxidation finishes.
Described secondary concerted catalysis oxidation is meant that the industrial organic waste water after the one-level catalyzed reaction drains into catalyzed oxidation pond, the second stage from first step reaction tank, Chi Tizhong by quality than water: second catalyst=1100: 1 is placed second catalyst, described second catalyst is for being carrier with the gac, surface recombination ferrous metal ion, compounding quantity is 5g/kg, and unreacted ozone in the one-level catalytic oxidation process is collected into second stage reaction tank, aeration is gone into catalyzed oxidation pond, second stage body, pumping into concentration is 20% hydrogen peroxide, 100～700g/Th, stop and handled 30 minutes, carry out internal recycle during this time, working cycle continues 30 minutes, and second stage catalytic oxidation finishes.
Described series connection catalyzed oxidation technology is at normal temperature, under the condition of normal pressure, stagnant catalyst is in first catalytic oxidation process, be the catalytic ozonation process: use immobilized catalyst catalytic decomposition ozone, generate great amount of hydroxy group free radical (.OH), utilize .OH redox potential and Electron Affinities to interrupt chromophore in the organic pollutant molecule structure, organic pollutant in the water is degraded fast, and make a position C-H key of polymeric oxide in the waste water, β-C key, γ-C key, C-C is broken into low molecular compound, thereby the organism in the waste water is carried out oxygenolysis, fast degradation of organic substances COD; Remaining ozone and remaining organic pollutant enter second catalytic decomposition process, in this process, adopt not outer a kind of catalyst to decompose hydrogen peroxide, produce OH free radical cracking oxidation residue organic dirt, and, ozone and hydrogen peroxide generation chain reaction in this process entered, produce the more freedom base, activated the Degradation of hydrogen peroxide and ozone, concerted reaction reaches the purpose of quick degradable organic pollutant.
Described series connection catalyzed oxidation process using bi-level treatment technology is made up of water inlet-reaction, circulation-drainage flow path, continuously operation; Industrial organic waste water enters first step catalyzed oxidation pond body, after finishing, water inlet adds ozone, add-on is according to the concentration of entry COD, add 100～800g/Th, air inlet 30 minutes, waste water first step catalyzed oxidation internal recycle in the pond, working cycle continues 40 minutes, make the abundant contact reacts of waste water and filler, first step catalytic oxidation finishes; Waste water drains into second stage circulatory pool from first step reaction tank, and with unreacted ozone collection, aeration is gone into catalyzed oxidation pond, second stage body, pumping into concentration is 20% hydrogen peroxide, 100～700g/Th, stop and handle after 30 minutes, waste water begins second stage catalyzed oxidation internal recycle in the pond, and working cycle continues 20 minutes, second stage catalytic oxidation finishes, and cuts off the electricity supply; Through the two-stage catalytic oxidation, finish a useless series connection catalytic oxidation treatment industrial organic waste water technology according to claim 1, it is characterized in that, describedly all preferably control aeration intensity 1～7m with the aeration tank
3/ m
2.H.
Specific embodiment:
Embodiment one: press above-mentioned technical process:
Described organic waste water is pharmacy waste water, and index is: treatment capacity 1T, and concentration is COD:2000mg/L; Its organic waste water pre-treatment comprise to waste water all with the aeration flow process and in and the coagulating sedimentation flow process, all and aeration flow process employing is equal and the aeration tank, all with aeration tank control air aeration intensity 7m
3/ m
2.h, fully all with; In and the coagulating sedimentation flow process adopt in and coagulative precipitation tank, adopt trip valve to add white lime or hydrochloric acid or salt acid for adjusting pH value at neutral zone, control pH value 6～9, the follow-up 0.5% coagulant aids PAC that adds controls dosage 8mg/L; By most suspended substances and the oil content in the pretreatment technology removal waste water.
Organic waste water behind preprocessing process is entered first step catalyzed oxidation pond body through intermediate pool, and it is the compound activated-carbon catalyst that contains the manganese metal ion of 3g/kg that Chi Tizhong places the 1000g charge capacity.Add ozone after water inlet is finished, the ozone add-on is 700g/Th, and the reaction times is 30 minutes, waste water first step catalyzed oxidation internal recycle in the pond, and working cycle continues 40 minutes, makes waste water and catalysis advance abundant contact reacts, and first step catalytic oxidation finishes.
Industrial organic waste water after the one-level catalyzed reaction drains into second stage reaction tank from first step reaction tank, and it is the compound ferrous metal ionic of 5g/kg activated-carbon catalyst that Chi Tizhong places the 910g charge capacity.And unreacted ozone collected, aeration is gone into catalyzed oxidation pond, second stage body, pumps into concentration and be 20% hydrogen peroxide 800g/Th, stop and handled 30 minutes, during carry out internal recycle, working cycle continues 30 minutes, second stage catalytic oxidation finishes.Water treatment process finishes; Effluent index is: treatment capacity 1T, concentration is COD:800mg/L.
Embodiment two: press above-mentioned technical process:
Described organic waste water is pharmacy waste water, index is: treatment capacity 1T, concentration is COD:2000mg/L, its organic waste water pre-treatment comprise to waste water all with the aeration flow process and in and the coagulating sedimentation flow process, all adopt all and the aeration tank, all with aeration tank control air aeration intensity 6m with the aeration flow process
3/ m
2.h, fully all with; In and the coagulating sedimentation flow process adopt in and coagulative precipitation tank, adopt trip valve to add white lime or salt acid for adjusting pH value at neutral zone, control pH value 6～9, the follow-up 0.5% coagulant aids PAC that adds controls dosage 5mg/L; By most suspended substances and the oil content in the pretreatment technology removal waste water.
Organic waste water behind preprocessing process is entered first step catalyzed oxidation pond body through intermediate pool, and it is the compound activated-carbon catalyst that contains the manganese metal ion of 3g/kg that Chi Tizhong places the 1000g charge capacity.Add ozone after water inlet is finished, the ozone add-on is 400g/Th, and the reaction times is 30 minutes, waste water first step catalyzed oxidation internal recycle in the pond, and working cycle continues 40 minutes, makes waste water and catalysis advance abundant contact reacts, and first step catalytic oxidation finishes;
Industrial organic waste water after the one-level catalyzed reaction drains into second stage reaction tank from first step reaction tank, and it is the compound ferrous metal ionic of 5g/kg activated-carbon catalyst that Chi Tizhong places the 910g charge capacity.And unreacted ozone collected, aeration is gone into catalyzed oxidation pond, second stage body, pumps into concentration and be 20% hydrogen peroxide 500g/Th, stop and handled 30 minutes, during carry out internal recycle, working cycle continues 30 minutes, second stage catalytic oxidation finishes.Water treatment process finishes; Effluent index is: treatment capacity 1T, concentration is COD:1000mg/L
Embodiment three: press above-mentioned technical process:
Described organic waste water is pharmacy waste water, index is: treatment capacity 1T, concentration is COD:2000mg/L, its organic waste water pre-treatment comprise to waste water all with the aeration flow process and in and the coagulating sedimentation flow process, all adopt all and the aeration tank, all with aeration tank control air aeration intensity 1m with the aeration flow process
3/ m
2.h, fully all with; In and the coagulating sedimentation flow process adopt in and coagulative precipitation tank, adopt trip valve to add white lime or salt acid for adjusting pH value at neutral zone, control pH value 6～9, the follow-up 0.5% coagulant aids PAC that adds controls dosage 1mg/L; By most suspended substances and the oil content in the pretreatment technology removal waste water.
Organic waste water behind preprocessing process is entered first step catalyzed oxidation pond body through intermediate pool, and it is the compound activated-carbon catalyst that contains the manganese metal ion of 3g/kg that Chi Tizhong places the 1000g charge capacity.Add ozone after water inlet is finished, the ozone add-on is 100g/Th, and the reaction times is 30 minutes, waste water first step catalyzed oxidation internal recycle in the pond, and working cycle continues 40 minutes, makes waste water and catalysis advance abundant contact reacts, and first step catalytic oxidation finishes;
Industrial organic waste water after the one-level catalyzed reaction drains into second stage reaction tank from first step reaction tank, and it is the compound ferrous metal ionic of 5g/kg activated-carbon catalyst that Chi Tizhong places the 910g charge capacity.And unreacted ozone collected, aeration is gone into catalyzed oxidation pond, second stage body, pumps into concentration and be 20% hydrogen peroxide 100g/Th, stop and handled 30 minutes, during carry out internal recycle, working cycle continues 30 minutes, second stage catalytic oxidation finishes.Water treatment process finishes; Effluent index is: treatment capacity 1T, concentration is COD:1800mg/L
Embodiment four: press above-mentioned technical process:
Described organic waste water is dyeing waste water, index is: treatment capacity 1T, concentration is COD:2000mg/L, its organic waste water pre-treatment comprise to waste water all with the aeration flow process and in and the coagulating sedimentation flow process, all adopt all and the aeration tank, all with aeration tank control air aeration intensity 4m with the aeration flow process
3/ m
2.h, fully all with; In and the coagulating sedimentation flow process adopt in and coagulative precipitation tank, adopt trip valve to add white lime or salt acid for adjusting pH value at neutral zone, control pH value 6～9, the follow-up 0.5% coagulant aids PAC that adds controls dosage 8mg/L; By most suspended substances and the oil content in the pretreatment technology removal waste water.
Organic waste water behind preprocessing process is entered first step catalyzed oxidation pond body through intermediate pool, and it is the compound activated-carbon catalyst that contains the manganese metal ion of 3g/kg that Chi Tizhong places the 1000g charge capacity.Add ozone after water inlet is finished, the ozone add-on is 800g/Th, and the reaction times is 30 minutes, waste water first step catalyzed oxidation internal recycle in the pond, and working cycle continues 40 minutes, makes waste water and catalysis advance abundant contact reacts, and first step catalytic oxidation finishes;
Industrial organic waste water after the one-level catalyzed reaction drains into second stage reaction tank from first step reaction tank, and it is the compound ferrous metal ionic of 5g/kg activated-carbon catalyst that Chi Tizhong places the 910g charge capacity.And unreacted ozone collected, aeration is gone into catalyzed oxidation pond, second stage body, pumps into concentration and be 20% hydrogen peroxide 800g/Th, stop and handled 30 minutes, during carry out internal recycle, working cycle continues 30 minutes, second stage catalytic oxidation finishes.Water treatment process finishes; Effluent index is: treatment capacity 1T, concentration is COD:800mg/L
Embodiment five: press above-mentioned technical process:
Described organic waste water is paper waste, index is: treatment capacity 1T, concentration is COD:2000mg/L, its organic waste water pre-treatment comprise to waste water all with the aeration flow process and in and the coagulating sedimentation flow process, all adopt all and the aeration tank, all with aeration tank control air aeration intensity 7m with the aeration flow process
3/ m
2.h, fully all with; In and the coagulating sedimentation flow process adopt in and coagulative precipitation tank, adopt trip valve to add white lime or salt acid for adjusting pH value at neutral zone, control pH value 6～9, the follow-up 0.5% coagulant aids PAC that adds controls dosage 2mg/L; By most suspended substances and the oil content in the pretreatment technology removal waste water.
Organic waste water behind preprocessing process is entered first step catalyzed oxidation pond body through intermediate pool, and it is the compound activated-carbon catalyst that contains the manganese metal ion of 3g/kg that Chi Tizhong places the 1000g charge capacity.Add ozone after water inlet is finished, the ozone add-on is 800g/Th, and the reaction times is 30 minutes, waste water first step catalyzed oxidation internal recycle in the pond, and working cycle continues 40 minutes, makes waste water and catalysis advance abundant contact reacts, and first step catalytic oxidation finishes;
Industrial organic waste water after the one-level catalyzed reaction drains into second stage reaction tank from first step reaction tank, and it is the compound ferrous metal ionic of 5g/kg activated-carbon catalyst that Chi Tizhong places the 910g charge capacity.And unreacted ozone collected, aeration is gone into catalyzed oxidation pond, second stage body, pumps into concentration and be 20% hydrogen peroxide 600g/Th, stop and handled 30 minutes, during carry out internal recycle, working cycle continues 30 minutes, second stage catalytic oxidation finishes.Water treatment process finishes; Effluent index is: treatment capacity 1T, concentration is COD:800mg/L
Claims (3)
1. series connection catalytic oxidation treatment industrial organic waste water technology, it comprises carries out pre-treatment and catalytic oxidation treatment to industrial organic waste water, it is characterized in that: the mode of the catalytic oxidation treatment that the organic waste water behind preprocessing process is adopted is one-level catalyzed oxidation and secondary concerted catalysis oxidation, described one-level catalyzed oxidation refers to that industrial organic waste water enters first step catalyzed oxidation pond body, Chi Tizhong by quality than water: one-level catalyzer=1000: 1 is placed catalyzer, after finishing, water inlet adds ozone, the ozone add-on is 100～800g/Th, reaction times is 30 minutes, waste water carries out first step catalyzed oxidation internal recycle in the pond, working cycle continues 40 minutes, make waste water and the abundant contact reacts of one-level catalyzer, first step catalytic oxidation finishes, described secondary concerted catalysis oxidation is meant that the industrial organic waste water after the one-level catalyzed reaction drains into second stage reaction tank from first step reaction tank, Chi Tizhong by quality than water: second catalyst=1100: 1 is placed second catalyst, and with unreacted ozone collection second stage reaction tank in the one-level catalytic oxidation process, aeration is gone into catalyzed oxidation pond, second stage body, pumping into concentration is 20% hydrogen peroxide, 100～700g/Th, stop and handled 30 minutes, carry out internal recycle during this time, working cycle continues 30 minutes, and second stage catalytic oxidation finishes.
2. series connection catalytic oxidation treatment industrial organic waste water technology according to claim 1 is characterized in that: described one-level catalyzer is for being carrier with the gac, and surface recombination contains the manganese metal ion, and compounding quantity is 3g/kg.
3. series connection catalytic oxidation treatment industrial organic waste water technology according to claim 1 is characterized in that: described second catalyst is for being carrier with the gac, surface recombination ferrous metal ion, and compounding quantity is 5g/kg.
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