CN110818164A - Membrane integrated treatment method for high-salt high-COD wastewater - Google Patents
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5281—Installations for water purification using chemical agents
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- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
Abstract
The invention discloses a membrane method integrated treatment method of high-salt high-COD wastewater, which comprises the steps of pretreating the high-salt high-COD wastewater, sending the high-salt high-COD wastewater into a membrane separation system with preferential organic matter permeation, taking a membrane with preferential organic matter permeation as a separation carrier, taking pressure difference between the upstream side and the downstream side of the membrane as a driving force, and utilizing that the speed of organic components permeating the membrane is faster than that of water molecules, so that the high-COD wastewater without salt is obtained by enrichment at the membrane permeation side, and the COD value of the wastewater at the membrane permeation side is reduced; the membrane component is backwashed by industrial circulating water, salt crystallized on the surface of the membrane is removed, and the backwashed water and the wastewater on the retentate side of the membrane enter a reverse osmosis system to obtain reverse osmosis fresh water and reverse osmosis concentrated water; the reverse osmosis concentrated water can be directly sent into an evaporation system to obtain solid salt and evaporated clear solution. The technology of the invention can achieve the aim of efficiently treating the high-salt high-COD wastewater; on the other hand, the aim of minimizing investment and operation cost can be achieved.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a membrane method integrated treatment method of high-salt high-COD wastewater, and particularly relates to a treatment method of wastewater generated by various high-pollution product production lines such as medical intermediates, dye intermediates and the like and popularization and application thereof.
Background
The high-salt high-COD wastewater mainly comes from high-pollution product production lines such as various medical intermediates, dye intermediates and the like, and is characterized in that: the method has the advantages of huge water amount, multiple pollutant types, high salt content, high COD value and poor biodegradability, and belongs to industrial wastewater with great treatment difficulty. Biochemical method, physicochemical method, advanced oxidation, reverse osmosis membrane separation, multiple-effect evaporation method and the like are the commonly adopted technologies for wastewater treatment. However, for high-salt and high-COD wastewater, the technologies have obvious application bottlenecks at present. This is because the tolerance of microorganisms to high-concentration salts is poor, resulting in poor biochemical treatment effect, and in addition, the high-concentration wastewater generated in the pharmaceutical industry often has residual drug components, which have toxic effects on microorganisms. The traditional process for treating wastewater basically belongs to a destruction method, and when the wastewater contains a solvent with a high added value, the destruction method causes a great deal of resource waste; although the advanced oxidation technology can effectively reduce the COD value of the wastewater by generating hydroxyl free radicals to perform strong oxidation reaction with organic components of the wastewater, the advanced oxidation degradation of the high-COD wastewater requires a large amount of oxidant, the economy becomes the most main bottleneck of the engineering application, and when the types of pollutants in the wastewater are numerous, the combination of various biochemical treatment technologies is required, and the operation and management are difficult; the reverse osmosis membrane and the multi-effect evaporation coupling technology are high-efficiency processes for treating salt-containing wastewater at present, but the reverse osmosis membrane has strict requirements on the quality of inlet water, particularly the concentration of organic matters. To switch in a reverse osmosis system, the COD value in the wastewater must be reduced. The prior art does not overcome the problems of high efficiency, low cost and treatment of high-salt high-COD waste water.
Disclosure of Invention
The invention aims to provide a membrane integrated treatment method for high-salt high-COD wastewater. The membrane method integrated treatment method can be applied to the wastewater generated by production lines of various medical intermediates, dye intermediates and other high-pollution products, and realizes the high-efficiency and low-cost treatment of the high-salt high-COD wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme: a membrane method integrated treatment method for high-salt high-COD wastewater comprises the following steps:
(1) pretreatment: pretreating high-salt high-COD wastewater to remove part of COD and suspended matters in the original wastewater, wherein the pretreatment system comprises one or a combination of ultrafiltration membrane filtration, air flotation treatment and precipitation treatment;
(2) and (3) preferential organic membrane permeation separation: the pretreated filtrate enters a membrane separation system with preferential organic matter permeation, the downstream side of the membrane is connected with a vacuum system, the salt content of the wastewater at the permeation side of the membrane is removed under the pushing of the pressure difference between the upstream side and the downstream side of the membrane, and the COD value of the wastewater at the residual side of the membrane is obviously reduced;
(3) reverse osmosis: the membrane component is backwashed by using industrial circulating water to remove salt crystallized on the surface of the membrane, and wastewater and backwashed water on the retentate side of the membrane enter a reverse osmosis system to obtain reverse osmosis fresh water and reverse osmosis concentrated water, wherein the reverse osmosis membrane material is a polyamide membrane or an acetate fiber membrane;
(4) evaporation and crystallization: the reverse osmosis concentrated water is evaporated and crystallized by an evaporator to obtain solid salt and evaporated clear liquid, the evaporator is a natural circulation type evaporator or a forced circulation type evaporator, wherein the natural circulation type evaporator is a central circulation tube type evaporator, a suspension frame type evaporator, an external heating type evaporator or a Lengwen evaporator, and the forced circulation type evaporator is a rising film type evaporator, a falling film type evaporator or a scraper type evaporator.
Furthermore, the organic matters in the high-salt and high-COD wastewater in the step (1) are one or a combination of more of aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons, ketones, aldehydes, esters, nitriles, phenols, alcohols, amines, acids and chlorofluorocarbons.
Furthermore, the salt concentration range of the wastewater in the step (1) is 5000-20000 mg/L, and the COD concentration range is 5 multiplied by 104mg/L～3×105mg/L。
Further, the COD concentration of the retentate side in the step (2) can be reduced to be below 50mg/L, the water quality requirement of reverse osmosis treatment is met, and the penetrating fluid on the permeate side can be recovered and treated through one or more of rectification, absorption, adsorption and condensation. The membrane component has a back washing function so as to prevent salt substances from crystallizing on the surface of the membrane to influence the performance of the membrane. The working temperature of the membrane assembly is 30-60 ℃; the vacuum degree of the vacuum pump is 5-20 KPa.
Furthermore, the membrane used by the membrane separation system with preferential organic matter permeation is a membrane with preferential organic matter permeation, the membrane material is formed by compounding one or more of polydimethylsiloxane, polymethyl octyl siloxane, perfluoroacrylate polymer, polyether block amide, hydrophobic nano white carbon black or inorganic ceramic, and the membrane component is one or more of a roll membrane, a plate-frame membrane and a tubular membrane component.
Further, the reverse osmosis fresh water COD in the step (3) is lower than 50mg/L, the salt concentration is lower than 200mg/L, and the water quality requirement of industrial circulating water is met.
Furthermore, the reverse osmosis system in the step (3) comprises 2-4 sections of reverse osmosis.
Further, the evaporation process in the step (4) is further 1-8-effect evaporation; the steam temperature is 120-180 ℃; the pressure is 0.2-0.4 MPa.
Furthermore, the COD of the evaporated clear liquid generated in the step (4) is lower than 50mg/L, the salt concentration is lower than 30mg/L, the water quality requirement of industrial circulating water is met, and the generated salt mud can be deeply processed to be used as a desulfurization absorbent.
The invention can adjust part of the process in the integrated process according to the fluctuation of the raw water COD value. When the COD value in the raw water is too high, in order to reduce the using number of the membrane modules which are permeable to organic matters preferentially, an advanced oxidation process can be added between the membrane separation system which is permeable to organic matters preferentially and the reverse osmosis system so as to optimize the investment cost.
Drawings
FIG. 1 is an overall flow chart of a membrane process integration method of high-salt high-COD wastewater.
Detailed Description
Example 1
A membrane method integrated treatment method for high-salt high-COD wastewater comprises the following specific steps:
step (1): the main components are methanol, sodium acetate, telmisartan and the like, and the COD value is 1.152 multiplied by 105Filtering the medical wastewater with the salinity of 5000mg/L and the suspended matter of 50mg/L by an ultrafiltration membrane to remove part of COD and suspended matter in the original wastewater, wherein the COD is 1.14 multiplied by 105mg/L, salinity of 5000mg/L and suspended matters of 2.5 mg/L;
step (2): the pretreated wastewater enters a membrane separation system which is permeable to organic matters preferentially, a plate-and-frame membrane component is adopted, and a membrane is compounded by adopting polydimethylsiloxane-perfluoroacrylate polymer. The working temperature is 30 ℃, the vacuum degree is 12KPa, after separation, the salinity of the permeation side is 1mg/L, and the COD is 4.0 multiplied by 105mg/L, suspended matter is 0, and penetrating fluid at the penetration side can be recycled after absorption, rectification and condensation;
and (3): backwashing the membrane component by using industrial circulating water to remove salt crystallized on the surface of the membrane; COD on the retentate side is 20mg/L, salinity is 4800mg/L, suspended matters are 2.5mg/L, waste water on the retentate side and backwashing water enter a reverse osmosis system together, the reverse osmosis membrane adopts a polyamide membrane, reverse osmosis concentrated water and reverse osmosis fresh water are obtained through reverse osmosis, the reverse osmosis system adopts two-stage reverse osmosis, salinity of the reverse osmosis fresh water is 150mg/L, COD is 20mg/L, and the suspended matters are basically 0, so that the water quality requirement of industrial circulating water is met, and the reverse osmosis fresh water enters an industrial circulating water supply system;
and (4): the reverse osmosis concentrated water enters an evaporation crystallization system, the selected evaporator is a scraper evaporator of a forced circulation evaporator, 2-effect evaporation is carried out, the steam is 135 ℃ saturated steam, the steam pressure is 0.31 MPa, solid salt and evaporated clear liquid are obtained, the salinity of the evaporated clear liquid is 10mg/L, the COD is 20mg/L, suspended matters are basically 0, the water quality requirement of industrial circulating water is met, and the industrial circulating water enters an industrial circulating water supply system, and the solid salt is transported away.
Example 2
A membrane method integrated treatment method for high-salt high-COD wastewater comprises the following specific steps:
step (1): the main components are isobutanol and inorganic salt, and the COD is 5 multiplied by 104The industrial wastewater with the salinity of 10000 mg/L and the suspended matter of 100 mg/L is subjected to air floatation treatment to remove partial COD and most suspended matters, and the COD value is 4.99 multiplied by 104mg/L, the salinity is 10000 mg/L, and the suspended matter is 3 mg/L;
step (2): removing part of COD in the original wastewater and enabling the wastewater to enter a membrane separation system which is permeable to organic matters preferentially, wherein a tubular membrane component is adopted, and the membrane is formed by compounding polymethyl octyl siloxane-perfluoroacrylate polymer-inorganic alumina ceramic-hydrophobic nano white carbon black. The working temperature is 60 ℃, the vacuum degree is 20KPa, after separation, the permeation side is isobutanol solution with the concentration of more than 60 percent, the salinity is 0, the suspended matters are 0, and part of isobutanol can be recycled after rectification;
and (3): backwashing the membrane component by using industrial circulating water to remove salt crystallized on the surface of the membrane; COD on the retentate side is 30mg/L, salinity is 9800 mg/L, suspended matters are 3mg/L, waste water on the retentate side and backwashing water enter a reverse osmosis system together, the reverse osmosis membrane adopts an acetate fiber membrane, concentrated saline water and reverse osmosis fresh water are obtained after reverse osmosis, the reverse osmosis system adopts three-section reverse osmosis, the COD on the reverse osmosis fresh water is 30mg/L, the salinity is 180mg/L, and the suspended matters are 3mg/L and are used as industrial circulating water to enter a water supply system;
and (4): the reverse osmosis concentrated water enters an evaporation crystallization system, the selected evaporator is a falling film evaporator of a forced circulation evaporator, 8-effect evaporation is carried out, the steam is 120 ℃ saturated steam, the steam pressure is 0.2MPa, solid salt and evaporation clear liquid are obtained, the COD of the evaporation clear liquid is 30mg/L, the salinity is 10mg/L, the evaporation clear liquid is used as industrial circulating water and enters a water supply system, and the solid salt is transported and dragged away to be used as a sulfur removal agent after being processed.
Example 3
A membrane method integrated treatment method for high-salt high-COD wastewater comprises the following specific steps:
step (1): adding various organic solvents such as methanol, ethanol, acetone, ethyl acetate, toluene, acetic acid, etc., inorganic salt and organic salt, wherein COD is 3 × 105The waste water at the tail end of a certain pharmaceutical company with the salinity of 20000mg/L and the suspended matters of 200mg/L is subjected to air floatation to remove part of COD and most of suspended matters, and the COD value is 2.99 multiplied by 10 at the moment5mg/L, the salinity is 20000mg/L, and the suspended substance is 10 mg/L;
step (2): removing part of COD and wastewater in the original wastewater, introducing the wastewater into a membrane separation system with preferential permeability to organic matters, adopting a frame-type membrane assembly, compounding a polydimethylsiloxane-perfluoroacrylate polymer-polyether block amide membrane, performing separation at a working temperature of 45 ℃ and a vacuum degree of 5KPa, wherein the salinity of a permeation side is 5mg/L, and the COD value is 1.2 multiplied by 106mg/L, suspended matter is 0, and the part of wastewater is absorbed, rectified and condensed and then is recycled;
and (3): performing back flushing on the membrane component by using industrial circulating water to remove salt crystallized on the surface of the membrane, wherein COD (chemical oxygen demand) on the retentate side is 30mg/L, salinity is 18800 mg/L, suspended matters are 10mg/L, the wastewater on the retentate side and the back flushing water are treated by using an acetate fiber reverse osmosis membrane together, and after reverse osmosis, concentrated saline water and reverse osmosis fresh water are obtained, wherein a reverse osmosis system adopts two-stage reverse osmosis, the COD of the reverse osmosis fresh water is 30mg/L, the salinity is 130mg/L, and the suspended matters are 10mg/L, and the reverse osmosis fresh water is used as industrial circulating water and;
and (4): the reverse osmosis concentrated water enters an evaporation crystallization system, the selected evaporator is a central circulating tubular evaporator of a natural circulation type evaporator, single-effect evaporation is carried out, the steam is saturated steam at 180 ℃, the steam pressure is 0.4MPa, solid salt and evaporation clear liquid are obtained, the COD of the evaporation clear liquid is 30mg/L, the salinity is 30mg/L, the suspended matters are 5mg/L, the evaporation clear liquid is used as industrial circulating water and enters a water supply system, and the solid salt is transported out to be processed.
Example 4
A membrane method integrated treatment method for high-salt high-COD wastewater comprises the following specific steps:
step (1): the main components comprise ethyl acetate, methyl acetate, methanol, inorganic salt and organic salt, and COD is 1.31 × 105The industrial wastewater with the salinity of 8000mg/L and the suspended matters of 120mg/L is filtered by an ultrafiltration membrane and pretreated by air floatation to remove part of COD and most of suspended matters, and the COD value is at the moment1.3×105mg/L, the salinity is 8000mg/L, and the suspended matters are 10 mg/L;
step (2): removing part of COD and wastewater in the original wastewater, introducing the wastewater into a membrane separation system with preferential permeability to organic matters, adopting a spiral-wound membrane module, adopting a polymethyl octyl siloxane-polyether block amide composite membrane as the membrane, operating at 40 ℃ and vacuum degree of 10KPa, and separating to obtain a permeate side salinity of 10mg/L, COD value of 4.8 multiplied by 105mg/L and suspended matter 0, and the wastewater is recycled by rectification, absorption, adsorption and condensation;
and (3): backwashing the membrane component by using industrial circulating water to remove salt crystallized on the surface of the membrane; the COD of the retentate side is 28mg/L, the salinity is 7800mg/L, the suspended matters are 10mg/L, the waste water and the backwashing water on the retentate side are treated by a polyamide reverse osmosis membrane together, and are subjected to reverse osmosis to obtain concentrated saline water and reverse osmosis fresh water, a reverse osmosis system adopts four stages of reverse osmosis, the COD of the reverse osmosis fresh water is 28mg/L, the salinity is 120mg/L, and the suspended matters are 10mg/L, and the reverse osmosis fresh water is used as industrial circulating water and enters a water supply system;
and (4): the reverse osmosis concentrated water enters an evaporation crystallization system, the selected evaporator is a central circulating tubular evaporator of a natural circulation type evaporator, single-effect evaporation is carried out, the steam is saturated steam at 180 ℃, the steam pressure is 0.4MPa, solid salt and evaporation clear liquid are obtained, the COD of the evaporation clear liquid is 28mg/L, the salinity is 15mg/L, the evaporation clear liquid is used as industrial circulating water and enters a water supply system, and the solid salt is transported out for processing.
Claims (8)
1. A membrane method integrated treatment method for high-salt high-COD wastewater is characterized by comprising the following steps:
step (1): pretreating high-salt high-COD wastewater to remove part of COD and suspended matters in the original wastewater, wherein the pretreatment adopts one or a combination of ultrafiltration membrane filtration, air flotation treatment and precipitation treatment;
step (2): the pretreated filtrate enters a membrane separation system with preferential organic matter permeation, the downstream side of the membrane is connected with a vacuum system, under the pushing of the pressure difference between the upstream and downstream of the membrane, the salt in the wastewater at the permeation side of the membrane is removed, and the COD value of the wastewater at the residual side of the membrane is reduced;
and (3): performing back flushing on the membrane component by using industrial circulating water to remove salt crystallized on the surface of the membrane, and enabling the back flushing water and wastewater on the retentate side of the membrane to enter a reverse osmosis system to obtain reverse osmosis fresh water and reverse osmosis concentrated water, wherein the reverse osmosis membrane material is a polyamide membrane or an acetate fiber membrane;
and (4): the reverse osmosis concentrated water is evaporated and crystallized by an evaporator to obtain solid salt and evaporated clear liquid, the evaporator is a natural circulation type evaporator or a forced circulation type evaporator, wherein the natural circulation type evaporator is a central circulation tube type evaporator, a suspension frame type evaporator, an external heating type evaporator or a Lengwen evaporator, and the forced circulation type evaporator is a rising film type evaporator, a falling film type evaporator or a scraper type evaporator.
2. The membrane-method integrated treatment method for high-salt high-COD wastewater according to claim 1, wherein the organic substances in the high-salt high-COD wastewater of step (1) are one or more of aliphatic and aromatic hydrocarbons, chlorohydrocarbons, ketones, aldehydes, esters, nitriles, phenols, alcohols, amines, acids, chlorofluorocarbons.
3. The membrane-method integrated treatment method for high-salinity high-COD wastewater according to claim 1 or 2, characterized in that the wastewater in the step (1) has a salt concentration range of 5000-20000 mg/L and a COD concentration range of 5 x 104mg/L～3×105mg/L。
4. The membrane-method integrated treatment method for high-salinity high-COD wastewater according to claim 1, wherein the membrane used in the membrane separation system with preferential permeability to organic matters in step (2) is a membrane with preferential permeability to organic matters, the membrane material is one or more of polydimethylsiloxane, polymethyloctylsiloxane, perfluoroacrylate polymer, polyether block amide, hydrophobic nano white carbon black or inorganic ceramic, and the membrane module is one or more of a roll-type membrane, a plate-and-frame type membrane and a tubular membrane module.
5. The membrane-method integrated treatment method for high-salt high-COD wastewater according to claim 1, characterized in that the permeate at the membrane permeation side in the step (2) can be recovered and treated by one or more of rectification, absorption, adsorption and condensation.
6. The membrane-method integrated treatment method for high-salt high-COD wastewater according to claim 1, characterized in that the working temperature in the step (3) is 30-60 ℃ and the vacuum degree is 5-20 KPa.
7. The membrane-method integrated treatment method for high-salinity high-COD wastewater according to claim 6, characterized in that the reverse osmosis system in the step (3) comprises 2-4 stages of reverse osmosis.
8. The membrane-method integrated treatment method for high-salt high-COD wastewater according to claim 7, characterized in that the evaporation process in the step (4) is 1-8-effect evaporation, the steam temperature is 120-180 ℃, and the pressure is 0.2-0.4 MPa.
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|---|---|---|---|---|
| DE4130661C1 (en) * | 1991-09-14 | 1993-05-19 | Dornier Gmbh, 7990 Friedrichshafen, De | |
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- 2019-11-28 CN CN201911187816.9A patent/CN110818164A/en active Pending
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|---|---|---|---|---|
| DE4130661C1 (en) * | 1991-09-14 | 1993-05-19 | Dornier Gmbh, 7990 Friedrichshafen, De | |
| CN103342431A (en) * | 2013-07-23 | 2013-10-09 | 南京工业大学 | Process for reusing tail water in papermaking and pulping |
| CN108046482A (en) * | 2018-01-29 | 2018-05-18 | 广州华浩能源环保集团股份有限公司 | A kind of organic concentration wastewater treatment method of high salinity high rigidity difficult degradation and system |
| CN208378605U (en) * | 2018-05-11 | 2019-01-15 | 上海晶宇环境工程股份有限公司 | The special equipment of the separating technology of organic matter and salt in strong brine |
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