CN101538105B - Physicochemistry-biochemistry combined technology for optical brightener wastewater treatment - Google Patents
Physicochemistry-biochemistry combined technology for optical brightener wastewater treatment Download PDFInfo
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- CN101538105B CN101538105B CN2009100979139A CN200910097913A CN101538105B CN 101538105 B CN101538105 B CN 101538105B CN 2009100979139 A CN2009100979139 A CN 2009100979139A CN 200910097913 A CN200910097913 A CN 200910097913A CN 101538105 B CN101538105 B CN 101538105B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a combined technology for optical brightener wastewater treatment, belonging to the technical field of wastewater treatment. The invention mainly adopts the combination of multi-level physicochemical pretreatment and biofilm process, and is realized by the method that the optical brightener wastewater is subjected to the multi-level physicochemical pretreatment of an Fe-C-Cu system, including catalytic reduction and dehalogenation, coagulative precipitation and wet-type catalytic oxidation, and then enters the biofilm treatment process, pollutants are removed by immobilized microorganisms, and the biochemical treatment process is the biological filter process adopting polyurethane as a carrier and having the combination of the anaerobic process and the aerobic process. The combined technology can economically and effectively degrade the pollutants which are hard to be degraded, such as aromatic hydrocarbon chloride and nitrogen-bearing heterocycle-type compounds and the like in the optical brightener wastewater, and the process route has strong pertinence, thorough degradation to the pollutants, and reasonable cost for wastewater treatment.
Description
Technical field
The present invention relates to the Industrial Wastewater Treatment field, relate in particular to a kind of materialization-biochemistry combination process of white dyes wastewater treatment.
Background technology
White dyes is a kind ofly can absorb UV-light and inspire blueness or the organic compound of bluish voilet fluorescence, white dyes excites the yellow complementary color each other of the script of the blue-fluorescence of generation and object, can eliminate the color of object yellowing originally, make object pure whiter bright.White dyes is mainly used in fields such as textile printing and dyeing, papermaking, synthetic detergent and plastics additive, its main products kind has: CPA (double styrene type derivative), OB-1 (diphenylethyllene dibenzoxazine type), APB-L, APC (toluylene pyrrolotriazine derivatives), the white dyes raw materials for production mainly contain cyano group benzyl chloride, tricresyl phosphite second fat, terephthalaldehyde, oxazole, DMF, methyl alcohol, cyanuric chloride, DSD acid, morpholine, aniline, thanomin etc.Its factory effluent is as the representative of high density, difficult degradation wastewater from chemical industry, its saltiness height, NH3-N concentration height, the organic pollutants that mainly contains in the waste water has cyano group benzyl chloride, terephthalaldehyde, oxazole, DMF, cyanuric chloride, DSD acid, morpholine, aniline, thanomin, tricresyl phosphite second fat, methyl alcohol, and residual a small amount of white dyes etc.
Wherein to cyano group benzyl chloride, o-cyanobenzyl chloride, a cyano group benzyl chloride, 4-(benzoxazole-2-yl) benzyl chloride, 4-(5-Jia base benzoxazole-2-yl) benzyl chloride and cyanuric chloride be the hydrochloric ether that contains phenyl ring, its chemical property is stable, belong to typical carcinogenic substance, toxicity is stronger, endangers bigger.DMF, DSD acid, oxazole, morpholine, aniline and thanomin mostly are nitrogenous heterocyclic compound greatly, and enrichment in the organism has carcinogenic and mutagenic effect easily.
Because most of pollutents are that macromolecular substance, bio-toxicity are big in the white dyes waste water, be difficult for biochemical treatment, less about white dyes waste water research report both at home and abroad, its Study on Processing Methods concentrates on chemical oxidation treatment mostly, conventional Fenton oxidation style, ozone oxidation method, catalytic wet oxidation method, photodegradation method all exist the consumption of energy consumption height, oxygenant big, problems such as shortage is stable, reliable plant-scale reaction unit.Cause waste water persistent organism (POPs) residual quantity height in discharge process, have a strong impact on discharging waters water quality safety.
The present invention mainly pollutes white dyes waste water and is divided into aromatic hydrocarbon chloride and nitrogenous heterocyclic compound, at aromatic hydrocarbon chloride chemical stability height, be easy to the reductive characteristics, adopts the catalytic reduction dehalogenation to reduce the bio-toxicity of waste water.The catalytic wet oxidation method that then adopts nitrogenous heterocyclic compound improves the biodegradability of waste water, is beneficial to the thorough degrade residual pollutent of rear end biochemical process, guarantees standard wastewater discharge.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of materialization-biochemistry combination process of white dyes wastewater treatment is provided.
The materialization-biochemistry combination process that is used for the white dyes wastewater treatment is: white dyes waste water at first enters the catalytic reduction unit, through catalytic reduction 1-2 hour of Fe-C-Cu system, the water outlet of catalytic reduction unit enters coagulative precipitation tank, add coagulated agent and coagulant aids, the coagulation time is 15～20 minutes, and coagulating sedimentation is removed part non-solubility Persistent organic pollutants; The coagulative precipitation tank water outlet enters the catalytic wet oxidation unit, and oxidizing reaction is 0.5～1 hour under the multicomponent catalyst effect, and temperature of reaction is 110～120 ℃, and reaction pressure is 0.8～1.0MPa; The water outlet of catalytic wet oxidation unit enters the microbiological deterioration organic pollutant that the microbial film processing unit utilizes urethane filling surface and the inner apposition growth of hole, the microbial film processing unit is divided into hold concurrently oxygen section and aerobic section, the hydraulic detention time of the oxygen section of holding concurrently is 24～36 hours, the pH value is 6.2～7.5, and dissolved oxygen is 0.1～0.5mg/L; The hydraulic detention time of aerobic section is 18～24 hours, and the pH value is 7.5～8.4, and dissolved oxygen is 2～4mg/L, and the water outlet of aerobic section enters settling tank, and sedimentation time is 1.5～2 hours, and surface load is 0.8～1.2m
3/ m
2.h, the water outlet qualified discharge of settling tank.
Fe in the reductive dehalogenation agent of described Fe-C-Cu three-element catalytic reduction system: the mass ratio of C: Cu is 1: 1: 0.1, the reductive dehalogenation agent dosage be 5-10g/L.The carrier of multicomponent catalyst is cocos active carbon or activated alumina, and active ingredient is Cu and Mn, and its Cu-Mn mol ratio is 1: 1, and helping active ingredient is CeO
2Coagulated agent is polymerize aluminum chloride or bodied ferric sulfate, and the dosage of coagulated agent is 200～500mg/L.Coagulant aids is a polyacrylamide, and the dosage of coagulant aids is 0.5～1mg/L.Filtrate is a snappiness cellular polyurethane filler, its component is: polyester polyol or polyether glycol 50～100 weight parts, polymer polyatomic alcohol 0.1～60 weight part, isocyanic ester 80～100 weight parts, water 1～10 weight part, catalyzer 0.1～1.0 weight part, whipping agent 0.1～40 weight part, suds-stabilizing agent 0.1～6 weight part.Catalyzer is stannous octoate, dicaprylate dibutyl tin, dibutyltin diacetate, triethylene diamine, trolamine, thanomin, dimethylcyclohexylamine or dimethyl benzylamine.Whipping agent is water and fluoro trichloromethane, methyl chlorofluoride or methylene dichloride.Suds-stabilizing agent is silicone based suds-stabilizing agent.
The present invention can degrade cost-effectively aromatic hydrocarbon chloride and nitrogenous difficult degradation pollutents such as heterocyclic compound in the white dyes waste water, its operational path is with strong points, thorough to contaminant degradation, and cost for wastewater treatment is reasonable.
Description of drawings
Accompanying drawing is the materialization-biochemistry combination process schema of white dyes wastewater treatment.
Embodiment
Embodiment 1:
COD is 10280mg/L, Cl
-Be 8134mg/L, BOD is 3524mg/L, NH
3-N is 18mg/L, TN is that the white dyes waste water of 3804mg/L at first enters the catalytic reduction unit, the catalytic reduction of process Fe-C-Cu system 2 hours, the reductive dehalogenation agent dosage of Fe-C-Cu three-element catalytic reduction system is 10g/L, the mass ratio of Fe in the reductive dehalogenation agent: C: Cu is 1: 1: 0.1, the water outlet of catalytic reduction unit enters coagulative precipitation tank, add coagulated agent and coagulant aids, the dosage of coagulated agent polymerize aluminum chloride is 400mg/L, the dosage of coagulant aids polyacrylamide is 0.8mg/L, the coagulation time is 15 minutes, and coagulating sedimentation is removed part non-solubility Persistent organic pollutants; The coagulative precipitation tank water outlet enters the catalytic wet oxidation unit, and oxidizing reaction is 0.8 hour under the multicomponent catalyst effect, and temperature of reaction is 110 ℃, and reaction pressure is 0.8MPa; Wherein the multiple catalyzing agent carrier is a cocos active carbon, and active ingredient is Cu and Mn, and its Cu-Mn mol ratio is 1: 1, and helping active ingredient is CeO
2The water outlet of catalytic wet oxidation unit enters the microbiological deterioration organic pollutant that the microbial film processing unit utilizes filter material surface and the inner apposition growth of hole, filtrate is a snappiness cellular polyurethane filler, its component is: polyester polyol 80 weight parts, polymer polyatomic alcohol 10 weight parts, isocyanic ester 82 weight parts, water 3 weight parts, catalyzer 0.3 weight part, whipping agent 5 weight parts, suds-stabilizing agent 2 weight parts.Catalyzer is stannous octoate and dimethyl benzylamine, and whipping agent is water and fluoro trichloromethane, and suds-stabilizing agent is a silicone oil 580.The microbial film processing unit is divided into hold concurrently oxygen section and aerobic section, and the hydraulic detention time of the oxygen section of holding concurrently is 30 hours, and the pH value is 6.3, and dissolved oxygen is 0.1mg/L; The hydraulic detention time of aerobic section is 20 hours, and the pH value is 7.2, and dissolved oxygen is 2mg/L, and the water outlet of aerobic section enters settling tank, and sedimentation time is 1.5 hours, and surface load is 0.8m
3/ m
2.h, the water outlet qualified discharge of settling tank.Coagulating sedimentation mud and settling tank mud enter sludge thickener and concentrate, the outer sludge ultimate disposal ground that is transported to after the mechanism filter-pressing.
Embodiment 2:
COD is 6526mg/L, and Cl-is 11360mg/L, and BOD is 2107mg/L, NH
3-N is 53mg/L, TN is that the white dyes waste water of 2872mg/L at first enters the catalytic reduction unit, the catalytic reduction of process Fe-C-Cu system 1 hour, the reductive dehalogenation agent dosage of Fe-C-Cu three-element catalytic reduction system is 7g/L, the mass ratio of Fe in the reductive dehalogenation agent: C: Cu is 1: 1: 0.1, the water outlet of catalytic reduction unit enters coagulative precipitation tank, add coagulated agent and coagulant aids, the dosage of coagulated agent polymerize aluminum chloride is 250mg/L, the dosage of coagulant aids polyacrylamide is 0.6mg/L, the coagulation time is 15 minutes, and coagulating sedimentation is removed part non-solubility Persistent organic pollutants; The coagulative precipitation tank water outlet enters the catalytic wet oxidation unit, and oxidizing reaction is 0.5 hour under the multicomponent catalyst effect, and temperature of reaction is 115 ℃, and reaction pressure is 0.9MPa; Wherein the multiple catalyzing agent carrier is a cocos active carbon, and active ingredient is Cu and Mn, and its Cu-Mn mol ratio is 1: 1, and helping active ingredient is CeO
2The water outlet of catalytic wet oxidation unit enters the microbiological deterioration organic pollutant that the microbial film processing unit utilizes filter material surface and the inner apposition growth of hole, filtrate is a snappiness cellular polyurethane filler, its component is: polyester polyol 80 weight parts, polymer polyatomic alcohol 10 weight parts, isocyanic ester 82 weight parts, water 3 weight parts, catalyzer 0.3 weight part, whipping agent 5 weight parts, suds-stabilizing agent 2 weight parts.Catalyzer is stannous octoate and dimethyl benzylamine, and whipping agent is water and fluoro trichloromethane, and suds-stabilizing agent is a silicone oil 580.The microbial film processing unit is divided into hold concurrently oxygen section and aerobic section, and the hydraulic detention time of the oxygen section of holding concurrently is 25 hours, and the pH value is 6.4, and dissolved oxygen is 0.1mg/L; The hydraulic detention time of aerobic section is 18 hours, and the pH value is 7.2, and dissolved oxygen is 2mg/L, and the water outlet of aerobic section enters settling tank, and sedimentation time is 1.5 hours, and surface load is 0.8m
3/ m
2.h, the water outlet qualified discharge of settling tank.Coagulating sedimentation mud and settling tank mud enter sludge thickener and concentrate, the outer sludge ultimate disposal ground that is transported to after the mechanism filter-pressing.
Embodiment 3:
COD is 8574mg/L, and Cl-is 12120mg/L, and BOD is 1807mg/L, NH
3-N is 63mg/L, TN is that the white dyes waste water of 3172mg/L at first enters the catalytic reduction unit, the catalytic reduction of process Fe-C-Cu system 1.4 hours, the reductive dehalogenation agent dosage of Fe-C-Cu three-element catalytic reduction system is 8g/L, the mass ratio of Fe in the reductive dehalogenation agent: C: Cu is 1: 1: 0.1, the water outlet of catalytic reduction unit enters coagulative precipitation tank, add coagulated agent and coagulant aids, the dosage of coagulated agent polymerize aluminum chloride is 287mg/L, the dosage of coagulant aids polyacrylamide is 0.6mg/L, the coagulation time is 15 minutes, and coagulating sedimentation is removed part non-solubility Persistent organic pollutants; The coagulative precipitation tank water outlet enters the catalytic wet oxidation unit, and oxidizing reaction is 0.6 hour under the multicomponent catalyst effect, and temperature of reaction is 115 ℃, and reaction pressure is 1.0MPa; Wherein the multiple catalyzing agent carrier is a cocos active carbon, and active ingredient is Cu and Mn, and its Cu-Mn mol ratio is 1: 1, and helping active ingredient is CeO
2The water outlet of catalytic wet oxidation unit enters the microbiological deterioration organic pollutant that the microbial film processing unit utilizes filter material surface and the inner apposition growth of hole, filtrate is a snappiness cellular polyurethane filler, its component is: polyester polyol 80 weight parts, polymer polyatomic alcohol 10 weight parts, isocyanic ester 82 weight parts, water 3 weight parts, catalyzer 0.3 weight part, whipping agent 5 weight parts, suds-stabilizing agent 2 weight parts.Catalyzer is stannous octoate and dimethyl benzylamine, and whipping agent is water and fluoro trichloromethane, and suds-stabilizing agent is a silicone oil 580.The microbial film processing unit is divided into hold concurrently oxygen section and aerobic section, and the hydraulic detention time of the oxygen section of holding concurrently is 28 hours, and the pH value is 6.4, and dissolved oxygen is 0.1mg/L; The hydraulic detention time of aerobic section is 20 hours, and the pH value is 7.2, and dissolved oxygen is 2mg/L, and the water outlet of aerobic section enters settling tank, and sedimentation time is 1.5 hours, and surface load is 0.8m
3/ m
2.h, the water outlet qualified discharge of settling tank.Coagulating sedimentation mud and settling tank mud enter sludge thickener and concentrate, the outer sludge ultimate disposal ground that is transported to after the mechanism filter-pressing.
Embodiment 4:
COD is 9753mg/L, and Cl-is 9360mg/L, and BOD is 1707mg/L, NH
3-N is 65mg/L, TN is that the white dyes waste water of 3214mg/L at first enters the catalytic reduction unit, the catalytic reduction of process Fe-C-Cu system 1.6 hours, the reductive dehalogenation agent dosage of Fe-C-Cu three-element catalytic reduction system is 8.3g/L, the mass ratio of Fe in the reductive dehalogenation agent: C: Cu is 1: 1: 0.1, the water outlet of catalytic reduction unit enters coagulative precipitation tank, add coagulated agent and coagulant aids, the dosage of coagulated agent polymerize aluminum chloride is 300mg/L, the dosage of coagulant aids polyacrylamide is 0.7mg/L, the coagulation time is 15 minutes, and coagulating sedimentation is removed part non-solubility Persistent organic pollutants; The coagulative precipitation tank water outlet enters the catalytic wet oxidation unit, and oxidizing reaction is 0.7 hour under the multicomponent catalyst effect, and temperature of reaction is 110 ℃, and reaction pressure is 0.9MPa; Wherein the multiple catalyzing agent carrier is a cocos active carbon, and active ingredient is Cu and Mn, and its Cu-Mn mol ratio is 1: 1, and helping active ingredient is CeO
2The water outlet of catalytic wet oxidation unit enters the microbiological deterioration organic pollutant that the microbial film processing unit utilizes filter material surface and the inner apposition growth of hole, filtrate is a snappiness cellular polyurethane filler, its component is: polyester polyol 80 weight parts, polymer polyatomic alcohol 10 weight parts, isocyanic ester 82 weight parts, water 3 weight parts, catalyzer 0.3 weight part, whipping agent 5 weight parts, suds-stabilizing agent 2 weight parts.Catalyzer is stannous octoate and dimethyl benzylamine, and whipping agent is water and fluoro trichloromethane, and suds-stabilizing agent is a silicone oil 580.The microbial film processing unit is divided into hold concurrently oxygen section and aerobic section, and the hydraulic detention time of the oxygen section of holding concurrently is 27 hours, and the pH value is 6.4, and dissolved oxygen is 0.1mg/L; The hydraulic detention time of aerobic section is 19 hours, and the pH value is 7.0, and dissolved oxygen is 2mg/L, and the water outlet of aerobic section enters settling tank, and sedimentation time is 1.5 hours, and surface load is 0.8m
3/ m
2.h, the water outlet qualified discharge of settling tank.Coagulating sedimentation mud and settling tank mud enter sludge thickener and concentrate, the outer sludge ultimate disposal ground that is transported to after the mechanism filter-pressing.
Claims (3)
1. materialization-biochemistry combination process that is used for the white dyes wastewater treatment, it is characterized in that, white dyes waste water at first enters the catalytic reduction unit, through catalytic reduction 1-2 hour of Fe-C-Cu system, the water outlet of catalytic reduction unit enters coagulative precipitation tank, add coagulated agent and coagulant aids, the coagulation time is 15～20 minutes, and coagulating sedimentation is removed part non-solubility Persistent organic pollutants; The coagulative precipitation tank water outlet enters the catalytic wet oxidation unit, and oxidizing reaction is 0.5～1 hour under the multicomponent catalyst effect, and temperature of reaction is 110～120 ℃, and reaction pressure is 0.8～1.0MPa; The water outlet of catalytic wet oxidation unit enters the microbiological deterioration organic pollutant that the microbial film processing unit utilizes filter material surface and the inner apposition growth of hole, the microbial film processing unit is divided into hold concurrently oxygen section and aerobic section, the hydraulic detention time of the oxygen section of holding concurrently is 24～36 hours, the pH value is 6.2～7.5, and dissolved oxygen is 0.1～0.5mg/L; The hydraulic detention time of aerobic section is 18～24 hours, and the pH value is 7.5～8.4, and dissolved oxygen is 2～4mg/L, and the water outlet of aerobic section enters settling tank, and sedimentation time is 1.5～2 hours, and surface load is 0.8～1.2m
3/ m
2.h, the water outlet qualified discharge of settling tank; Fe in the reductive dehalogenation agent of described Fe-C-Cu three-element catalytic reduction system: the mass ratio of C: Cu is 1: 1: 0.1, and the dosage of reductive dehalogenation agent is 5-10g/L; The carrier of described multicomponent catalyst is cocos active carbon or activated alumina, and active ingredient is Cu and Mn, and its Cu-Mn mol ratio is 1: 1, and helping active ingredient is CeO
2Described coagulated agent is polymerize aluminum chloride or bodied ferric sulfate, and the dosage of coagulated agent is 200～500mg/L; Described coagulant aids is a polyacrylamide, and the dosage of coagulant aids is 0.5～1mg/L; Described filtrate is a snappiness cellular polyurethane filler, its component is: polyester polyol or polyether glycol 50～100 weight parts, polymer polyatomic alcohol 0.1～60 weight part, isocyanic ester 80～100 weight parts, water 1～10 weight part, catalyzer 0.1～1.0 weight part, whipping agent 0.1～40 weight part, suds-stabilizing agent 0.1～6 weight part; Described catalyzer is stannous octoate, dicaprylate dibutyl tin, dibutyltin diacetate, triethylene diamine, trolamine, thanomin, dimethylcyclohexylamine or dimethyl benzylamine.
2. the materialization-biochemistry combination process of a kind of white dyes wastewater treatment according to claim 1 is characterized in that, described whipping agent is water and fluoro trichloromethane.
3. the materialization-biochemistry combination process of a kind of white dyes wastewater treatment according to claim 1 is characterized in that, described suds-stabilizing agent is silicone based suds-stabilizing agent.
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| CN101830601B (en) * | 2010-04-30 | 2012-05-09 | 浙江大学 | Biological treatment system and method thereof specific to industrial wastewater of fluorescent brightener |
| CN102951693B (en) * | 2012-11-21 | 2013-10-02 | 山西青山化工有限公司 | Method for processing and recycling production wastewater of fluorescent brightener CBS |
| CN105859062B (en) * | 2016-06-25 | 2019-02-22 | 山东文远环保科技股份有限公司 | Family sewage treatment recirculating fluidized bed |
| CN110423236B (en) * | 2019-08-22 | 2020-12-18 | 江苏格罗瑞化学有限公司 | Preparation method of fluorescent whitening agent for whitening textiles |
| CN113087192B (en) * | 2019-12-23 | 2022-04-01 | 南京延长反应技术研究院有限公司 | Treatment system and method for cephalosporin wastewater |
| CN112811562A (en) * | 2021-01-21 | 2021-05-18 | 江苏鼎弘环境科技有限公司 | Treatment equipment and treatment process for degradation-resistant wastewater |
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