CN105858954B - A kind of processing method of high concentrated organic wastewater - Google Patents
A kind of processing method of high concentrated organic wastewater Download PDFInfo
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- CN105858954B CN105858954B CN201610265933.2A CN201610265933A CN105858954B CN 105858954 B CN105858954 B CN 105858954B CN 201610265933 A CN201610265933 A CN 201610265933A CN 105858954 B CN105858954 B CN 105858954B
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- organic wastewater
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention discloses a kind of processing methods of high concentrated organic wastewater: high concentrated organic wastewater passes through catalytic wet oxidation first, most of oxidation operation is decomposed, remain acetate in obtained treatment fluid 1, further acetate is removed by the film process that deaerates again, waste water after film process obtains treatment fluid 2 through flocculation filtration and resin adsorption, and treatment fluid 2 softens removing calcium and magnesium through resin again and obtains soft water solution.
Description
Technical field
The present invention relates to waste water reclaiming recycling fields, and in particular to a kind of processing side of high concentrated organic wastewater
Method.
Background technique
The COD that high concentrated organic wastewater generally refers to be discharged by industries such as papermaking, leather, printing and dyeing and food is in 2000mg/L
Above waste water.Containing organic matters such as a large amount of carbohydrate, fat, protein, celluloses in these waste water, if directly
Discharge, will cause serious pollution.
Currently, the processing method of organic wastewater with high concentration mainly has absorption, coagulation, extraction, Fenton oxidation, light electrolysis, electricity
The processing methods such as oxidation, but effect is all not satisfactory.Absorption method is to use the solid absorbent with very strong adsorption capacity, makes waste water
One of or the several components method that is enriched in the surface of solids.The common active charcoal of adsorbent and resin, regenerating active carbon
It is difficult with elution；Resin adsorption is not influenced by inorganic salts in waste water, and adsorption effect is good, and elution and regeneration are easy, and performance is stablized,
But it is with high costs.Oxidation-adsorption method is to carry out preliminary coagulation, adsorption treatment with coal dust after diluting high-concentration waste water, is then used
Fenton reagent catalysis oxidation and acid cohesion, then with coal dust coagulation, adsorb.This method equally exist processing cost it is high lack
Point.
The Chinese patent of Publication No. CN 105271597A reports a kind of organic wastewater with high concentration processing method, by micro-
The kinds of processes such as electrolysis, deep oxidation, flocculation sedimentation, absorption retardance, UF membrane carry out specific aim to waste water by specific combination
Online processing.Although the processing method effect is preferable, processing step is more many and diverse, seriously increases cost for wastewater treatment.
Summary of the invention
In order to overcome the above-mentioned defects in the prior art, the present invention provides a kind of processing sides of high concentrated organic wastewater
Method does not remove only the organic matter in waste water, and the acid in waste water is utilized in resource utilization.
A kind of processing method of high concentrated organic wastewater, which comprises the following steps:
(1) catalytic wet oxidation: waste water is under the conditions of 200~300 DEG C, 2~10Mpa, using air or oxygen as oxidant,
Catalyst is added and carries out wet oxidation reaction, obtains treatment fluid 1；
(2) deaerate film process: treatment fluid 1 adjusts pH to 1~3 after cooling down, using the alkaline solution of pH10~13 as absorption
Liquid carries out film and takes off acetic acid processing；
(3) recycle catalyst: the waste water after degassed film process is adjusted to alkalinity, is stirred to react until no longer generating and sinks
Until shallow lake, filtrate 2 is obtained by filtration；Filtrate 2 enters the progress resin suction of HYC-100 type ion exchange resin after passing through accurate filter
Attached processing；
(4) resin sofening treatment: by resin adsorption treated waste water dynamically carries out with contacts ionic exchange resin from
Son exchange, obtains saline solns.
The waste water handled in the present invention is high concentrated organic wastewater.High concentrated organic wastewater passes through catalytic wet oxygen first
Change, most of oxidation operation is decomposed, acetate is remained in obtained treatment fluid 1, then is further by degassing film process
Acetate is removed, the waste water after film process obtains treatment fluid 2 through flocculation filtration and resin adsorption, and treatment fluid 2 is soft through resin again
It eliminates calcium and magnesium and obtains soft water solution.
Further, high concentrated organic wastewater can be generates the useless of volatile low order fatty acid after wet oxidation is handled
Water.
Step (1) catalyst be one or more of cupric, manganese, nickel, ruthenium, rhodium, palladium soluble catalyst or
Loaded catalyst.It is calculated with the effective component of catalyst, catalyst amounts are the 0.001%~5% of wastewater quality, preferably
Ground, catalyst amounts are the 0.05~1% of wastewater quality.
The temperature of step (1) catalytic wet oxidation is 230~260 DEG C, pressure is 4~8Mpa.
Feed liquid temperature into degassing film device is higher, and the saturated vapour pressure of acetic acid is bigger, and the removal effect of acetic acid is better,
But film highest tolerable temperature be 50 DEG C, and temperature be lower than 40 DEG C when acetic acid removal efficiency be remarkably decreased, therefore, in step (2)
1 temperature for the treatment of fluid enters film device and carries out the de- acetic acid processing of film after being down to 40~50 DEG C.
Film in step (2) uses hydrophobic polypropylene (PP) film, polytetrafluoroethylene (PTFE) (PTFE) film, Kynoar
(PVDF) one of film.
Film in step (2) is deamination film, and membrane module uses hollow fiber form or tubular membrane component.
Preferably, absorbing liquid described in step (2) is one or more of sodium hydroxide, potassium hydroxide, keep
Temperature is 40~50 DEG C.
Preferably, adjusting solution using one or more of vulcanized sodium, sodium hydroxide, potassium hydroxide in step (3)
To alkalinity, it is stirred to react until being generated without precipitating, pH is 8~10.
Step (4) ion exchange resin is preferably highly acid hydrogen type cation exchange resin.Ion exchange resin can chelate
HYC-100 type or HYC-106 type ion exchange resin may be selected in one or more of copper, manganese, nickel, ruthenium, rhodium, palladium ion.
Compared with the existing technology, the present invention has following remarkable advantage:
(1) concise in technology of the present invention, short flow, it is easy to operate；
(2) wet oxidation water outlet post-processing reaction condition of the present invention is mild, and equipment takes up an area less, is stable.
(3) processing method processing of the present invention is thorough, without secondary pollution, useful resources can be recycled and be easy to industry
Change.
Detailed description of the invention
Fig. 1 is the processing technological flow figure of high concentrated organic wastewater of the present invention.
Specific embodiment
Embodiment 1
One epoxychloropropane produces waste water, its TOC is about 10010mg/L after measured, and pH is about 10,
(1) wet oxidation: epoxychloropropane waste water is handled through wet oxidation, after measured TOC178mg/L, acetate concentration
For 435.6mg/L.Wet oxidation reaction condition: being added Cu-contained catalyst 1.5%, and gas is air, and 260 DEG C of reaction temperature, instead
Answer pressure 2MPa, reaction time 2h；
(2) deaerate film process: after the waste water that step 1 obtains is cooled to 40 DEG C, pH to 1.5 is adjusted, is 40 DEG C with temperature, pH
1.5h is absorbed for 12 sodium hydroxide solution, treatment fluid acetate concentration is down to 53mg/L, TOC20mg/L；
(3) resin adsorption recycles catalyst: the hydrogen-oxygen that mass concentration is 10% is added after the treatment fluid cooling that step 2 obtains
Change sodium water solution, it is stirring while adding, until no longer generate precipitate until (pH about 8~9), filtrate 2 is obtained by filtration, measures filtrate 2
Copper content be 221mg/L, filtrate 2 is by accurate filter (Q grade accurate filters) afterwards into HYC-100 type amberlite
Rouge absorption, the copper content for measuring out column liquid is 0.25mg/L.
(4) resin sofening treatment: the treatment fluid that step 3 obtains reaches chlor-alkali industry to salt water after ion exchange resin
Requirement, can sell.
Embodiment 2
In addition to " degassing film process: the waste water that step 1 obtains is cooled to 20 DEG C, is 20 DEG C with temperature, and pH is in step (2)
12 sodium hydroxide solution absorbs other than 1.5h ", remaining is same as Example 1.
Embodiment 3
In addition to " degassing film process: the waste water that step 1 obtains is cooled to 10 DEG C, is 10 DEG C with temperature, and pH is in step (2)
12 sodium hydroxide solution absorbs other than 1.5h ", remaining is same as Example 1.
Embodiment 4
One epoxychloropropane produces waste water, its TOC is about 10010mg/L after measured.
(1) wet oxidation: epoxychloropropane waste water is handled through wet oxidation, after measured TOC185mg/L, acetate concentration
For 445.6mg/L.Wet oxidation reaction condition: being added rhodium-containing catalyst 0.1%, and gas is air, and 260 DEG C of reaction temperature, instead
Answer pressure 2MPa, reaction time 2h；
(2) deaerate film process: after the waste water that step 1 obtains is cooled to 50 DEG C, pH to 1.5 is adjusted, is 50 DEG C with temperature, pH
1.5h is absorbed for 12 sodium hydroxide solution, treatment fluid acetate concentration is down to 45.6mg/L, TOC18.5mg/L；
(3) resin adsorption recycles catalyst: the hydrogen-oxygen that mass concentration is 10% is added after the treatment fluid cooling that step 2 obtains
Change sodium water solution, it is stirring while adding, until no longer generate precipitate until (pH about 8~9), filtrate 2 is obtained by filtration, measures filtrate 2
Copper content be 221mg/L, filtrate 2 is by accurate filter (Q grade accurate filters) afterwards into HYC-100 type amberlite
Rouge absorption, the copper content for measuring out column liquid is 0.25mg/L.
(4) resin sofening treatment: the treatment fluid that step 3 obtains reaches chlor-alkali industry to salt water after ion exchange resin
It is required that can sell.
Embodiment 5
One epoxychloropropane produces waste water, its TOC is about 10010mg/L after measured.
(1) wet oxidation: epoxychloropropane waste water is handled through wet oxidation, after measured TOC311mg/L, acetate concentration
For 455.1mg/L.Wet oxidation reaction condition: being added Cu-contained catalyst 1.0%, and gas is air, and 260 DEG C of reaction temperature, instead
Answer pressure 2MPa, reaction time 2h；
(2) deaerate film process: after the waste water that step 1 obtains is cooled to 40 DEG C, pH to 1.5 is adjusted, is 40 DEG C with temperature, pH
1.5h is absorbed for 12 sodium hydroxide solution, treatment fluid acetate concentration is down to 77.6mg/L, TOC33mg/L；
(3) resin adsorption recycles catalyst: the hydrogen-oxygen that mass concentration is 10% is added after the treatment fluid cooling that step 2 obtains
Change sodium water solution, it is stirring while adding, until no longer generate precipitate until (pH about 8~9), filtrate 2 is obtained by filtration, measures filtrate 2
Copper content be 221mg/L, filtrate 2 is by accurate filter (Q grade accurate filters) afterwards into HYC-100 type amberlite
Rouge absorption, the copper content for measuring out column liquid is 0.25mg/L.
(4) resin sofening treatment: the treatment fluid that step 3 obtains reaches chlor-alkali industry to salt water after ion exchange resin
It is required that can sell.
Under the conditions of embodiment 1-5, after treatment, obtained effluent quality is as follows: organic wastewater
From above data it is found that handling organic wastewater by processing method of the invention, not only can remove organic in waste water
Object, and the acid in waste water can be utilized with resource utilization.
Claims (9)
1. a kind of processing method of high concentrated organic wastewater, which comprises the following steps:
(1) catalytic wet oxidation: waste water is under the conditions of 200~300 DEG C, 2~10Mpa, using air or oxygen as oxidant, is added
Catalyst carries out wet oxidation reaction, obtains treatment fluid 1, and the high concentrated organic wastewater is to generate easily after wet oxidation is handled
The waste water of volatilization low order fatty acid；
(2) deaerate film process: treatment fluid 1 cool down after adjust pH to 1~3, using the alkaline solution of pH10~14 as absorbing liquid into
Row film takes off acetic acid processing；
(3) it recycles catalyst: alkaline solution is added in the waste water after degassed film process, be stirred to react until no longer generating and sink
Until shallow lake, filtrate 2 is obtained by filtration；Filtrate 2 enters ion exchange resin progress resin adsorption processing after passing through accurate filter；
(4) resin adsorption treated waste water dynamically resin sofening treatment: is subjected to ion friendship with contacts ionic exchange resin
It changes, obtains saline solns.
2. the processing method of high concentrated organic wastewater according to claim 1, which is characterized in that step (1) described catalysis
Agent is the soluble catalyst or loaded catalyst of one or more of cupric, manganese, nickel, ruthenium, rhodium, palladium, and catalyst adds
Amount is the 0.001%~5% of wastewater quality.
3. the processing method of high concentrated organic wastewater according to claim 1, which is characterized in that step (1) catalytic wet
The temperature of oxidation is 230~260 DEG C, pressure is 4~8Mpa, and the dosage of catalyst is the 0.05%~1% of wastewater quality.
4. the processing method of high concentrated organic wastewater according to claim 1, which is characterized in that the processing in step (2)
1 temperature of liquid enters film device and carries out the de- acetic acid processing of film after being down to 40~50 DEG C.
5. the processing method of high concentrated organic wastewater according to claim 1, which is characterized in that the film in step (2) is
Film is distilled, material is polypropylene screen, polytetrafluoroethylene film or polyvinylidene fluoride film.
6. the processing method of high concentrated organic wastewater according to claim 1, which is characterized in that the film in step (2) is
Deamination film, membrane module are doughnut or tubular type.
7. the processing method of high concentrated organic wastewater according to claim 1, which is characterized in that step (4) ion exchange
Resin is highly acid hydrogen type cation exchange resin.
8. the processing method of high concentrated organic wastewater according to claim 1, which is characterized in that step (4) ion exchange
One or more of resin chelated copper, manganese, nickel, ruthenium, rhodium, palladium ion.
9. the processing method of high concentrated organic wastewater according to claim 1, which is characterized in that step (4) ion exchange
Resin is HYC-100 type or HYC-106 type ion exchange resin.
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| CN106396135A (en) * | 2016-09-26 | 2017-02-15 | 汪传发 | Water softening apparatus and water softening method |
| CN107459164A (en) * | 2017-07-31 | 2017-12-12 | 浙江奇彩环境科技股份有限公司 | The recovery method of catalyst in a kind of CWO waste water |
| CN108911289B (en) * | 2018-07-27 | 2021-06-01 | 南京大学盐城环保技术与工程研究院 | Recovery processing device and method for methanol-containing alkaline resin desorption liquid |
| CN112441689B (en) * | 2020-09-29 | 2022-12-13 | 武汉天源环保股份有限公司 | Membrane concentrate harmless treatment system and method |
| CN112978997A (en) * | 2021-02-26 | 2021-06-18 | 浙江德强科技有限公司 | Treatment method and treatment device for landfill leachate wastewater |
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| CN102050535A (en) * | 2010-11-10 | 2011-05-11 | 浙江大学 | Processing method for resource recovery of acidic dye waste water |
| CN105236665A (en) * | 2014-05-28 | 2016-01-13 | 宝山钢铁股份有限公司 | Coking wastewater strong brine recycling method |
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| CN102050535A (en) * | 2010-11-10 | 2011-05-11 | 浙江大学 | Processing method for resource recovery of acidic dye waste water |
| CN105236665A (en) * | 2014-05-28 | 2016-01-13 | 宝山钢铁股份有限公司 | Coking wastewater strong brine recycling method |
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