CN111875125A - Wastewater treatment method combining membrane separation and electrodialysis - Google Patents
Wastewater treatment method combining membrane separation and electrodialysis Download PDFInfo
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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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
- C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/06—Pressure conditions
- C02F2301/063—Underpressure, vacuum
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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
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a wastewater treatment method combining membrane separation and electrodialysis, which comprises the following steps: (a) primarily filtering the wastewater stock solution to intercept large solid particle impurities to obtain primary filtrate, and introducing the primary filtrate into a membrane clarification unit to intercept solid suspended matters and macromolecular impurities to obtain membrane clarified liquid; (b) membrane separation is carried out on the membrane clarified liquid to remove part of divalent inorganic salt to obtain membrane separation clear liquid, the clear liquid obtained by membrane separation and filtration is sequentially subjected to membrane separation and interception on a small part of inorganic salt by a fine filtration unit of a membrane concentration unit under the low-pressure operation of the pressure less than 2.5MPa, clear liquid is output, concentrated liquid obtained by membrane separation of the fine filtration unit is treated by an electrodialysis concentration unit to obtain electrodialysis concentrated clear liquid, the electrodialysis concentrated clear liquid is returned to the fine filtration unit again to carry out membrane separation on the output clear liquid, and the concentrated solution obtained by the electrodialysis concentration unit is discharged out of the system. Therefore, the clear liquid side effluent is discharged or recycled after reaching the standard; reduce the one-time investment and the operation wastewater of electrodialysis.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a wastewater treatment method combining membrane separation and electrodialysis.
Background
The waste water mainly comprises the following types: the wastewater related to physical metallurgy is mainly generated in the mineral dressing and production processes, and the wastewater is characterized by simple components and low salt concentration. The wastewater in the chemical production field comprises wastewater generated in the processes in petrochemical industry, coal chemical industry, chemical synthesis, fine chemical industry, catalyst production industry, electroplating industry, paper-making industry and the like. The waste water in the pharmaceutical and health-care product production industry comprises raw material medicine extraction, pharmaceutical chemical synthesis, medical capsule production raw materials and other gelatin waste water. The environmental protection treatment engineering comprises saline water with high difficulty, secondary waste water generated in the treatment process and the like which cannot be treated in the environmental protection treatment process or can be treated by a technology with complex working conditions. In addition, various domestic wastes in daily life are collected in a landfill site, and salt-containing wastewater is leaked out after the wastes contain water and are leached by rainwater, and the salt-containing wastewater is called landfill leachate. And the waste water after the kitchen waste treatment in life, the waste water after the biochemical treatment of a farm and the like.
In the process of treating wastewater by adopting a membrane separation technology in the prior art, when a concentrated solution reaches a certain value, the operation pressure of equipment is very high, and when the operation pressure reaches the highest bearing pressure of a membrane, the concentration of the membrane is difficult to continuously increase, namely the concentration reaches a limit value. And the long-term high-pressure operation of the membrane can severely affect the service life of the membrane. The technical difficulty of operating the membrane equipment at high pressure is very high, and the one-time investment and the operation cost are high. The high-pressure operation membrane equipment has a very limited application range. In addition, the concentration of the membrane surface of the high-pressure operation membrane equipment is high, and the salt content of clear liquid effluent is difficult to reach the national discharge standard. In the prior art, in the process of treating wastewater by adopting an electrodialysis technology, clear water discharged from a system has high salt content; the single use of the composition can hardly meet the requirements of environmental protection or technology.
Disclosure of Invention
The invention mainly aims to provide a wastewater treatment method combining membrane separation and electrodialysis technologies, so as to solve the problem that the salt content of clean water of an outlet system is high in the prior art.
In order to achieve the above objects, a wastewater treatment system combining membrane separation and electrodialysis according to one aspect of the present invention includes a membrane clarification unit, an organic separation treatment unit, a membrane separation unit, a membrane concentration unit, which are connected in sequence;
the membrane concentration unit comprises a fine filtration unit for intercepting a small part of inorganic salt and an electrodialysis concentration unit, wherein a clear liquid outlet of the membrane separation unit is connected with a liquid inlet of the fine filtration unit, and a concentrated liquid outlet of the fine filtration unit is connected with a liquid inlet of the electrodialysis concentration unit.
Further, be equipped with the flocculation basin before the primary filter equipment be equipped with the circulation jar between primary filter equipment and the membrane clarification unit, the flocculation basin even has first pH monitor, the circulation jar even has the second pH monitor, still be equipped with organic separating element between membrane clarification unit and the membrane concentration unit, organic separation processing unit is including the separator of the separation macromolecule organic matter that connects gradually, the intercepting device of further interception organic matter.
Furthermore, a first intermediate tank is arranged between the separation device and the interception device, and a concentrated liquid outlet of the membrane separation unit is connected with the first intermediate tank;
in the step (b), the membrane clarified liquid is firstly introduced into an organic separation treatment unit, most of macromolecular organic matters are firstly removed through a separation device, and then the organic matters in the device are further intercepted through an interception device, so that clear liquid is obtained.
Furthermore, a first intermediate tank is arranged between the separation device and the interception device, and a concentrated liquid outlet of the membrane separation unit is connected with the first intermediate tank;
a second intermediate tank is arranged between the membrane separation unit and the fine filtration unit, a concentrated solution outlet of the fine filtration unit is connected with an inlet of the electrodialysis concentration unit, and a clear solution port of the electrodialysis concentration unit is connected with the second intermediate tank;
a third intermediate tank is arranged between the fine filtering unit and the electrodialysis concentration unit;
and a fourth intermediate tank is arranged between the interception device and the membrane separation unit.
Further, the membrane clarification unit is one of an inorganic membrane filtration device, an organic membrane filtration device, a spiral membrane filtration device, a butterfly membrane filtration device, a plate membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the molecular weight cutoff is 5000 Da; 8000D; a10000 Da; 30000 Da; 50000Da, 80000Da, 100000Da, 150000Da, 200000Da and 250000 Da.
Further, the liquid inlet of the membrane clarification unit is also provided with a primary filtering unit, the primary filtering unit comprises a cloth bag/plate frame filtering device, and a circulating tank is arranged between the primary filtering unit and the membrane clarification unit.
Further, the filtration precision of the cloth bag/plate frame filter device is 5 μm.
Further, the organic separation treatment unit comprises a first scroll type ultrafiltration membrane organic separation device and a second scroll type ultrafiltration or nanofiltration membrane organic separation device.
Further, the molecular weight cut-off of the first roll type ultrafiltration membrane organic separation device is one of 10000Da, 8000Da, 5000Da, 3000Da, 2500Da and 1000Da, and the molecular weight cut-off of the second roll type ultrafiltration membrane organic separation device is one of 2500Da, 1000Da,800Da, 600Da, 500Da,300Da and 150 Da.
Further, the membrane separation unit comprises a roll-up membrane nanofiltration device.
Further, the fine filtering unit is one of an organic membrane, an inorganic membrane, a spiral membrane, a plate-type membrane, a butterfly membrane, a tubular membrane, a central control fiber membrane, a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane; the molecular weight cut-off is 1000Da,800Da,500Da,300Da,150Da, 100Da, 50Da, 40Da, 30Da,20Da, 10 Da.
Further, the electrodialysis concentration unit is one of various devices with salt removal function in different combinations, which are the same as the electrodialysis principle and perform the dialysis under the action of an electric field, such as inorganic ion exchange membrane electrodialysis, organic polymer ion exchange membrane electrodialysis, homogeneous ion exchange membrane electrodialysis, semi-homogeneous ion exchange membrane electrodialysis, heterogeneous ion exchange membrane electrodialysis, gel ion exchange membrane electrodialysis, porous ion exchange membrane electrodialysis, macroporous ion exchange membrane electrodialysis, cation exchange membrane electrodialysis, anion exchange membrane electrodialysis, special function ion exchange membrane electrodialysis, general water treatment ion exchange membrane electrodialysis, special purpose ion exchange membrane electrodialysis, omeless electrodialysis, omentum electrodialysis, substrate membrane electrodialysis.
In order to achieve the above object, according to another aspect of the present invention, there is also provided a wastewater treatment method combining membrane separation and electrodialysis, comprising the steps of:
(a) primarily filtering the wastewater stock solution to intercept large solid particle impurities to obtain primary filtrate, and introducing the primary filtrate into a membrane clarification unit to intercept solid suspended matters and macromolecular impurities to obtain membrane clarified liquid;
(b) membrane separation is carried out on the membrane clarified liquid to remove part of divalent inorganic salt to obtain membrane separation clear liquid, the clear liquid obtained by membrane separation and filtration is sequentially subjected to membrane separation and interception on a small part of inorganic salt by a fine filtration unit of a membrane concentration unit under the low-pressure operation of the pressure less than 2.5MPa, clear liquid is output, concentrated liquid obtained by membrane separation of the fine filtration unit is treated by an electrodialysis concentration unit to obtain electrodialysis concentrated clear liquid, the electrodialysis concentrated clear liquid is returned to the fine filtration unit again to carry out membrane separation on the output clear liquid, and the concentrated solution obtained by the electrodialysis concentration unit is discharged out of the system.
Further, the method comprises the following steps:
when the wastewater stock solution is a high-salt protein solution;
adjusting the pH value of the wastewater stock solution before the primary filtration in the step (a), and monitoring the pH value of the wastewater stock solution to ensure that the protein in the wastewater stock solution entering the primary filtration is zero;
in the step (b), the membrane clarified liquid is firstly introduced into an organic separation treatment unit, most of macromolecular organic matters are firstly removed through a separation device, and then the organic matters in the device are further intercepted through an interception device, so that the membrane clarified liquid is obtained.
Furthermore, a first intermediate tank is arranged between the separation device and the interception device, and a concentrated liquid outlet of the membrane separation unit is connected with the first intermediate tank;
a second intermediate tank is arranged between the membrane separation unit and the fine filtration unit, a concentrated solution outlet of the fine filtration unit is connected with an inlet of the electrodialysis concentration unit, and a clear solution port of the electrodialysis concentration unit is connected with the second intermediate tank;
a third intermediate tank is arranged between the fine filtering unit and the electrodialysis concentration unit;
and a fourth intermediate tank is arranged between the interception device and the membrane separation unit.
Further, the membrane clarification unit is one of an inorganic membrane filtration device, an organic membrane filtration device, a spiral membrane filtration device, a butterfly membrane filtration device, a plate membrane filtration device, a hollow fiber membrane filtration device and a tubular membrane filtration device, and the molecular weight cutoff is 5000 Da; 8000D; a10000 Da; 30000 Da; 50000Da, 80000Da, 100000Da, 150000Da, 200000Da and 250000 Da.
Further, the liquid inlet of the membrane clarification unit is also provided with a primary filtering unit, the primary filtering unit comprises a cloth bag/plate frame filtering device, and a circulating tank is arranged between the primary filtering unit and the membrane clarification unit.
Further, the filtration precision of the cloth bag/plate frame filter device is 5 μm.
Further, the organic separation treatment unit comprises a first scroll type ultrafiltration membrane organic separation device and a second scroll type ultrafiltration or nanofiltration membrane organic separation device.
Further, the molecular weight cut-off of the first roll type ultrafiltration membrane organic separation device is one of 10000Da, 8000Da, 5000Da, 3000Da, 2500Da and 1000Da, and the molecular weight cut-off of the second roll type ultrafiltration membrane organic separation device is one of 2500Da, 1000Da,800Da, 600Da, 500Da,300Da and 150 Da.
Further, the membrane separation unit comprises a roll-up membrane nanofiltration device.
Further, the fine filtering unit is one of an organic membrane, an inorganic membrane, a spiral membrane, a plate-type membrane, a butterfly membrane, a tubular membrane, a central control fiber membrane, a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane; the molecular weight cut-off is 1000Da,800Da,500Da,300Da,150Da, 100Da, 50Da, 40Da, 30Da,20Da, 10 Da.
Further, the electrodialysis concentration unit is one of various devices with salt removal function in different combinations, which are the same as the electrodialysis principle and perform the dialysis under the action of an electric field, such as inorganic ion exchange membrane electrodialysis, organic polymer ion exchange membrane electrodialysis, homogeneous ion exchange membrane electrodialysis, semi-homogeneous ion exchange membrane electrodialysis, heterogeneous ion exchange membrane electrodialysis, gel ion exchange membrane electrodialysis, porous ion exchange membrane electrodialysis, macroporous ion exchange membrane electrodialysis, cation exchange membrane electrodialysis, anion exchange membrane electrodialysis, special function ion exchange membrane electrodialysis, general water treatment ion exchange membrane electrodialysis, special purpose ion exchange membrane electrodialysis, omeless electrodialysis, omentum electrodialysis, substrate membrane electrodialysis.
Therefore, the invention adopts the low-pressure operation membrane separation equipment and the electrodialysis combined middle fine filtering device to play a role, and has the following advantages:
(1) low-pressure operation membrane separation equipment and electrodialysis combined medium-low pressure membrane separation equipment
1) The low-pressure membrane separation equipment is responsible for discharging or recycling the side effluent of the clear liquid after reaching the standard by utilizing the operation characteristic that the salt content of the clear liquid effluent of the low-pressure membrane separation equipment is very low;
2) the salt content in the raw water solution can be effectively intercepted by utilizing the low-pressure operation membrane separation, the salt content of the raw water entering the electrodialysis is improved, the concentration difference between the concentrated solution side and the feed raw solution side of the electrodialysis is reduced, and the reverse migration volume of ions is reduced as much as possible, so that the one-time investment of the electrodialysis and the operation wastewater are reduced
(2) Low pressure operation of membrane separation device and electrodialysis in combination
1) The electrodialysis is operated at normal pressure and can adapt to the technical characteristics of strong acid and strong alkali, so that the one-time investment of equipment and the operation wastewater are greatly reduced;
2) the electrodialysis is easy to improve the concentration of the concentrated effluent, the concentration of the electrodialysis concentrated effluent is greatly improved, and the wastewater treatment and process material treatment range is greatly expanded.
The invention is further described with reference to the following figures and detailed description. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to assist in understanding the invention, and are included to explain the invention and their equivalents and not limit it unduly. In the drawings:
FIG. 1 is a schematic diagram of the apparatus flow of a wastewater treatment system combining membrane separation and electrodialysis techniques according to the present invention.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings. Those skilled in the art will be able to implement the invention based on these teachings. Before the present invention is described in detail with reference to the accompanying drawings, it is to be noted that:
the technical solutions and features provided in the present invention in the respective sections including the following description may be combined with each other without conflict.
Moreover, the embodiments of the present invention described in the following description are generally only examples of a part of the present invention, and not all examples. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
With respect to terms and units in the present invention. The terms "comprising," "having," and any variations thereof in the description and claims of this invention and the related sections are intended to cover non-exclusive inclusions.
The invention relates to a wastewater treatment system combining membrane separation and electrodialysis, which comprises a membrane clarification unit 12, an organic separation treatment unit 2, a membrane separation unit 3 and a membrane concentration unit which are sequentially connected;
the membrane concentration unit comprises a fine filtering unit 41 for intercepting a small part of inorganic salt and an electrodialysis concentration unit 42, a clear liquid outlet of the membrane separation unit 3 is connected with a liquid inlet of the fine filtering unit 41, and a concentrated liquid outlet of the fine filtering unit 41 is connected with a liquid inlet of the electrodialysis concentration unit 42.
Be equipped with before primary filter device 11 flocculation basin 13 be equipped with between primary filter device 11 and the membrane clarification unit 12 circulation jar 8, flocculation basin 13 even has first pH monitor 131, circulation jar 8 even has second pH monitor 81, still be equipped with organic separation unit 2 between membrane clarification unit 12 and the membrane concentration unit, organic separation processing unit 2 is including the separator 21 of the separation macromolecule organic matter that connects gradually, further interception intercepting organic matter intercepting device 22.
A first intermediate tank 5 is arranged between the separation device 21 and the interception device 22, and a concentrated solution outlet of the membrane separation unit 3 is connected with the first intermediate tank 5;
a second intermediate tank 6 is arranged between the membrane separation unit 3 and the fine filtration unit 41, a concentrated solution outlet of the fine filtration unit 41 is connected with an inlet of the electrodialysis concentration unit 42, and a clear solution outlet of the electrodialysis concentration unit 42 is connected with the second intermediate tank 6;
a third intermediate tank 7 is arranged between the fine filtering unit 41 and the electrodialysis concentration unit 42;
a fourth intermediate tank 9 is provided between the intercepting means 22 and the membrane separation unit 3.
The membrane clarification unit 12 comprises a hollow fiber membrane filtration unit.
The liquid inlet of the membrane clarification unit 12 is also provided with a primary filtering unit 11, the primary filtering unit 11 comprises a cloth bag/plate frame filtering device, and a circulating tank 8 is arranged between the primary filtering unit 11 and the membrane clarification unit 12.
The filtration precision of the cloth bag/plate frame filter device is 5 mu m.
The organic separation processing unit 2 comprises a first roll type ultrafiltration membrane organic separation device and a second roll type ultrafiltration or nanofiltration membrane organic separation device.
The molecular weight cut-off of the first roll type ultrafiltration membrane organic separation device is one of 10000Da, 8000Da, 5000Da, 3000Da, 2500Da and 1000Da, and the molecular weight cut-off of the second roll type ultrafiltration membrane organic separation device is one of 2500Da, 1000Da,800Da, 600Da, 500Da,300Da and 150 Da.
The membrane separation unit 3 comprises a spiral wound membrane nanofiltration device.
The fine filtering unit is one of an organic membrane, an inorganic membrane, a spiral membrane, a plate-type membrane, a butterfly-type membrane, a tubular membrane, a central control fiber membrane, a micro-filtration membrane, an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane; the molecular weight cut-off is 1000Da,800Da,500Da,300Da,150Da, 100Da, 50Da, 40Da, 30Da,20Da, 10 Da.
The electrodialysis concentration unit is one of various devices with salt removal function in different combinations, wherein the electrodialysis concentration unit is inorganic ion exchange membrane electrodialysis, organic polymer ion exchange membrane electrodialysis, homogeneous ion exchange membrane electrodialysis, semi-homogeneous ion exchange membrane electrodialysis, heterogeneous ion exchange membrane electrodialysis, gel ion exchange membrane electrodialysis, porous ion exchange membrane electrodialysis, macroporous ion exchange membrane electrodialysis, cation exchange membrane electrodialysis, anion exchange membrane electrodialysis, special functional ion exchange membrane electrodialysis, general water treatment ion exchange membrane electrodialysis, special purpose ion exchange membrane electrodialysis, omeless electrodialysis, omentum electrodialysis, substrate membrane electrodialysis, and different combinations of electrodialysis principles and electrodialysis under the action of an electric field.
The invention relates to a wastewater treatment method combining membrane separation and electrodialysis, which comprises the following steps:
a, primarily filtering a wastewater stock solution to intercept large solid particle impurities to obtain primary filtrate, and then introducing the primary filtrate into a membrane clarification unit 12 to intercept solid suspended matters and macromolecular impurities to obtain membrane clarified liquid;
b, removing part of divalent inorganic salt from the membrane clarified liquid through membrane separation to obtain membrane separation clear liquid, sequentially carrying out membrane separation on the clear liquid obtained through the membrane separation and filtration through a fine filtration unit 41 of a membrane concentration unit under the low-pressure operation condition that the pressure is less than 2.5MPa to intercept a small part of inorganic salt, outputting the clear liquid, treating the concentrated liquid obtained through the membrane separation of the fine filtration unit 41 through an electrodialysis concentration unit 42 to obtain electrodialysis concentrated clear liquid, returning the electrodialysis concentrated clear liquid to the fine filtration unit 41 again to carry out the membrane separation to output the clear liquid, and discharging the concentrated solution obtained through the electrodialysis concentration unit 42 out of the system.
When the wastewater stock solution is a high-salt protein solution;
b, before the preliminary filtration in the step a, firstly adjusting the pH value of the wastewater stock solution, and monitoring the pH value of the wastewater stock solution to ensure that the protein in the wastewater stock solution entering the preliminary filtration is zero;
in the step b, the membrane clarified liquid is firstly introduced into the organic separation treatment unit 2, most of macromolecular organic matters are firstly removed through the separation device 2, and then the organic matters in the device are further intercepted through the interception device 22, so that the membrane clarified liquid is obtained.
A first intermediate tank 5 is arranged between the separation device 21 and the interception device 22, and a concentrated solution outlet of the membrane separation unit 3 is connected with the first intermediate tank 5;
a second intermediate tank 6 is arranged between the membrane separation unit 3 and the fine filtration unit 41, a concentrated solution outlet of the fine filtration unit 41 is connected with an inlet of the electrodialysis concentration unit 42, and a clear solution outlet of the electrodialysis concentration unit 42 is connected with the second intermediate tank 6;
a third intermediate tank 7 is arranged between the fine filtering unit 41 and the electrodialysis concentration unit 42;
a fourth intermediate tank 9 is provided between the intercepting means 22 and the membrane separation unit 3.
The membrane clarification unit 12 comprises a hollow fiber membrane filtration unit.
The liquid inlet of the membrane clarification unit 12 is also provided with a primary filtering unit 11, the primary filtering unit 11 comprises a cloth bag/plate frame filtering device, and a circulating tank 8 is arranged between the primary filtering unit 11 and the membrane clarification unit 12.
The filtration precision of the cloth bag/plate frame filter device is 5 mu m.
The organic separation processing unit 2 comprises a first roll type ultrafiltration membrane organic separation device and a second roll type ultrafiltration membrane organic separation device.
The molecular weight cut-off of the first roll type ultrafiltration membrane organic separation device is one of 10000Da, 8000Da, 5000Da, 3000Da, 2500Da and 1000Da, and the molecular weight cut-off of the second roll type ultrafiltration membrane organic separation device is one of 2500Da, 1000Da,800Da and 600 Da.
The membrane separation unit 3 comprises a spiral wound membrane nanofiltration device.
The fine filtering unit is one of an organic membrane, an inorganic membrane, a spiral membrane, a plate-type membrane, a butterfly-type membrane, a tubular membrane, a central control fiber membrane, a micro-filtration membrane, an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane; the molecular weight cut-off is 1000Da,800Da,500Da,300Da,150Da, 100Da, 50Da, 40Da, 30Da,20Da, 10 Da.
The electrodialysis concentration unit is one of various devices with salt removal function in different combinations, wherein the electrodialysis concentration unit is inorganic ion exchange membrane electrodialysis, organic polymer ion exchange membrane electrodialysis, homogeneous ion exchange membrane electrodialysis, semi-homogeneous ion exchange membrane electrodialysis, heterogeneous ion exchange membrane electrodialysis, gel ion exchange membrane electrodialysis, porous ion exchange membrane electrodialysis, macroporous ion exchange membrane electrodialysis, cation exchange membrane electrodialysis, anion exchange membrane electrodialysis, special functional ion exchange membrane electrodialysis, general water treatment ion exchange membrane electrodialysis, special purpose ion exchange membrane electrodialysis, omeless electrodialysis, omentum electrodialysis, substrate membrane electrodialysis, and different combinations of electrodialysis principles and electrodialysis under the action of an electric field.
Pretreatment of wastewater
And (4) intercepting most of large particles, solidified grease and strip-shaped impurities from the wastewater at each process point through a fence, and then feeding the wastewater into a wastewater collection tank. The wastewater of each process point is uniformly mixed in a wastewater collection tank and then enters a pH adjusting tank, the pH value of the mixed wastewater is about 8.5 and then enters an air floatation machine treatment process, the floating slag floating on the water surface is separated by a slag skimming barrel of the air floatation machine and then enters a precise filtration process, fine particles in the solution are filtered by a precise filter and then enter a flocculation process, and the flocculation process is subjected to flocculation treatment and the supernatant is settled and enters a membrane clarification process. Solid matters generated at the lower part of the sedimentation tank enter other working procedures for treatment.
Membrane clarification
The mixed wastewater after the precise filtration enters a membrane clarification process: a membrane clarification system is used for filtering and intercepting a small amount of grease, fine suspended solid and part of macromolecular impurities which cannot be pretreated in feed liquid at high precision, and clear liquid is formed and enters an organic separation process. The intercepted small amount of grease, fine solid suspended matters and part of macromolecular impurities form concentrated solution due to the reduction of volume, and the concentrated solution is conveyed to a flocculation process. The macromolecular impurities are aggregated, settled and layered by adding a flocculating agent. And the supernatant enters a membrane clarification process and enters a membrane clarification system after being subjected to security filtration. And the clear liquid enters an organic separation process to remove macromolecular protein organic matters. The concentrated solution enters a flocculation process, and clear solution after flocculation layering returns to membrane clarification treatment; the lower sediment of the flocculation is combined with other impurities for treatment.
The membrane clarification process has the functions of removing fine suspended solids and macromolecular impurities: on one hand, the feeding condition of the organic separation membrane is achieved; on the other hand, after part of macromolecular impurities are removed, the burden of subsequent procedures is lightened, and the method has the advantages that compared with flocculation after pretreatment of the traditional process and then membrane clarification: a. the volume of the wastewater to be flocculated is less than 10 percent of the original volume, the addition amount of the flocculating agent is greatly reduced, and the economy is good; b. the additive is greatly reduced, the subsequent environment-friendly treatment pressure is reduced, the pollution and blockage of a subsequent organic film are reduced, the running cost is low, and the process is stable; c. the concentrated solution after the membrane clarification has high impurity content, is more beneficial to the flocculation and sedimentation reaction process, and has more scientific and reasonable process design; d. the membrane clarification process belongs to precision control, and overcomes the process problem of effluent quality stability caused by flocculation sedimentation due to fluctuation of raw water quality and process conditions.
Membrane elements used in the membrane clarification device are classified according to materials: inorganic films and organic films; the method is divided into the following steps according to the filtering precision: microfiltration (MF), Ultrafiltration (UF), Nanofiltration (NF), and Reverse Osmosis (RO); the method is divided into the following steps according to different structural forms of the membrane: plate, roll, disk, tubular and hollow fiber membranes.
The organic separation performance index is as follows:
organic separation step
The process comprises the following steps:
after a small amount of grease, fine suspended solid and part of macromolecular impurities are intercepted by a membrane clarification process, the quality of the mixed wastewater reaches the feeding requirement of an organic separation membrane; meanwhile, after the organic macromolecules are clarified and blocked by the membrane, the load of the subsequent process is reduced. The mixed wastewater enters an organic separation process, and a 2500Da filter precision membrane is adopted to cut most of macromolecular organic impurities (organic separation section): conveying the concentrated solution to other processes; the clear solution permeating the membrane still contains a large amount of organic matters, so that the filtration is carried out again by adopting a membrane with the filtration precision of 1000 Da: organic matters penetrating through the 2500Da filtering precision membrane in the organic separation clear liquid are intercepted to form concentrated liquid, and the concentrated liquid returns to the 2500Da filtering precision membrane inlet to be mixed with feed liquid clarified by the membrane and then enters the 2500Da filtering precision membrane; the pure liquid passing through the membrane with the filtration precision of 1000Da is taken as clear liquid and enters a concentration procedure for further treatment.
The organic separation process has the functions of: the subsequent concentration process is acted by removing organic macromolecular impurities to reduce the load.
Its advantage compared with prior art lies in: compared with the separation of organic matters by a single filtration precision membrane: firstly, flux attenuation of a single filtration precision membrane concentrated material is fast, the membrane flux can be maintained only by simply increasing pressure, energy consumption is high, and the membrane pollution condition is serious; secondly, the concentration of the membrane surface of the single-filtration-precision membrane concentrated material is high, the content of organic matters in the clear solution permeating the membrane is high, and great filtration pressure is caused to the subsequent concentration process or the technical standard is difficult to achieve; and thirdly, the membranes with two filtering precisions of a separation section and an interception section are used together, so that the membrane load distribution is uniform, the membrane flux is stable, and the low-pressure operation is economic and reasonable. And fourthly, the membranes with two filtering precisions of the separation section and the interception section are used together, so that the high content of the concentrated solution is ensured, the clear solution is ensured to reach the technical standard, and the process design is scientific and reasonable. e. The membrane with two filtering precisions of the separation section and the interception section is used together, the membrane load is distributed evenly, the membrane surface concentration is low, the membrane pollution degree is small, and the service life of the membrane is greatly prolonged.
Membrane elements used in the organic separation process: the method is divided into the following steps according to materials: inorganic films and organic films; the method is divided into the following steps according to the filtering precision: microfiltration (MF), Ultrafiltration (UF), Nanofiltration (NF), and Reverse Osmosis (RO); the method is divided into the following steps according to different structural forms of the membrane: plate type, roll type, disc type, tubular membrane and hollow fiber membrane. According to different membrane operating pressures, the method can be divided into the following steps: low pressure film (less than 2.5MPa) and high pressure film (more than or equal to 2.5 MPa).
The operation index is as follows:
concentration stage
Clear liquid after tiny molecules are intercepted by the organic separation intercepting section, the content of organic matters is greatly reduced, and most of the residual components in the wastewater are inorganic salts. The clear liquid enters a pre-filtering section of a concentration procedure to remove small molecular organic matters and partial divalent salt: intercepting micromolecular organic matters and divalent inorganic salts to form concentrated solution, returning the concentrated solution to the organic separation interception segment, mixing the concentrated solution with clear liquid from the organic separation segment, and entering an organic separation interception segment membrane separation system; and enabling the mixed wastewater intercepted with the micromolecular organic matters and the divalent inorganic matters to penetrate through a pre-filtering membrane to form clear liquid, and enabling the clear liquid to enter a concentration process for fine filtering.
Because the concentration of the membrane surface of the fine filtration is very low, the clear liquid discharged from the system can reach the expected technical standard and be reused for production, and the purposes of energy conservation and consumption reduction are achieved: after fine filtration, intercepting a small part of inorganic salt to form a concentrated solution, sending the concentrated solution to an electrodialysis concentration section for further concentration, and then evaporating and concentrating or drying concentrated water to obtain inorganic salt solid; the electrodialysis clear liquid returns to the fine filtration and concentration section, and the pre-filtered clear liquid enters the fine filtration and concentration section; the mixed wastewater is intercepted for a small part of inorganic salt and then permeates through the membrane to form clear liquid to reach the preset technical standard for discharge.
The effect of the concentration stage process is as follows: the normal pressure electrodialysis is adopted to replace the high pressure membrane concentration with higher technical difficulty, so that the concentration of inorganic salt in the concentrated water of the whole system is higher.
Compared with the prior art, the concentration stage process has the advantages that: a. the content of inorganic salt in the concentrated solution discharged from the system is improved by about 50 percent, and the one-time investment and the total operating cost of subsequent evaporation drying equipment are greatly reduced; b. the normal pressure electrodialysis is difficult to implement than the high pressure membrane concentration technology, and the safety performance is high; c. the concentration of the electrodialysis clear liquid is lower than that of the fine filtration feeding, the operation concentration of the membrane surface is lower, and the technical index of the clear liquid discharged from the system is better; d. the concentration of the electrodialysis clear solution is lower than that of the fine filtration feeding, the operation concentration of the membrane surface is lower, the membrane pollution degree is small, and the service life of the membrane is greatly prolonged.
Membrane elements used in the concentration stage: the molecular weight cut-off is 1000Da,800Da,500Da,300Da,150Da, 100Da, 50Da, 40Da, 30Da,20Da, 10 Da. The selection is carried out according to different systems of the wastewater.
Membrane elements are classified according to the material: inorganic films and organic films; the method is divided into the following steps according to the filtering precision: microfiltration (MF), Ultrafiltration (UF), Nanofiltration (NF), and Reverse Osmosis (RO); the method is divided into the following steps according to different structural forms of the membrane: plate type, roll type, disc type, tubular membrane and hollow fiber membrane. According to different membrane operating pressures, the method can be divided into the following steps: low pressure film (less than 2.5MPa) and high pressure film (more than or equal to 2.5 MPa).
Types of electrodialysis devices that can be used:
the electrodialysis membranes are of various types and can be classified according to the base material, structure, function, use, composition, and production method.
1) According to the base material for forming the membrane, the membrane can be divided into an inorganic ion exchange membrane and an organic polymer ion exchange membrane;
2) according to the macro structure of the membrane body, the ion exchange membrane can be divided into a homogeneous phase ion exchange membrane, a semi-homogeneous phase ion exchange membrane and an heterogeneous phase ion exchange membrane;
3) ion exchange membranes can be classified into gel ion exchange membranes, porous ion exchange membranes, and macroporous ion exchange membranes according to the microstructure of the membrane.
4) Film-based materials can be classified by film-based materials, i.e., by the permselectivity of the film. Can be divided into cation exchange membranes, anion exchange membranes and special function ion exchange membranes;
5) the ion exchange membranes can be divided into general water treatment ion exchange membranes and special purpose ion exchange membranes according to different purposes;
6) ion exchange membranes can be classified into omeless membranes, omentum membranes, and substrate membranes by membrane composition.
Index of organic separation operation
Fine filtration:
an electrodialysis concentration section:
examples
The following is an example of the application of the invention in the comprehensive treatment of gelatin production wastewater, and in addition, the invention is also suitable for the comprehensive treatment process of beryllium and beryllium oxide production wastewater.
The high-salt protein liquid stock solution enters a wastewater treatment system according to the following process parameters. The interface material is only sampled and detected, and the statistical average data is as follows:
processing the request
The quality of the clear water after the wastewater is treated is required to reach GB/T19923-2005 quality of industrial water for urban sewage recycling. Table 1 "process and product water" standard.
TABLE 1
Description of the Process
The pretreatment part in the process adopts an ultrafiltration membrane which has high strength, good pollution resistance, economy and easy obtainment, and the membrane is durable and is not easy to block. The membrane also has the defect that hard particles or large solid particles in stock solution enter the ultrafiltration membrane at a high speed under the conveying of a pump, the membrane is easily scratched, and thus membrane elements are damaged, so that the stock solution is primarily filtered by a cloth bag or a plate frame with the thickness of 5 mu m before entering ultrafiltration pretreatment, and the ultrafiltration membrane is protected from being damaged.
Membrane clarification system
The clarifying system is in the most heavy-load and most polluted environment in the whole process, so that the specific structure is selected to improve the anti-pollution performance of the membrane, and the specific design on the operation process is also needed. In view of the working condition of the clarifying membrane, an open type operation process is preferably adopted. The greatest disadvantage of the open process is that it can only be operated batchwise.Thus, for 1300m3The throughput of the reaction is 80m3The circulating tank can meet the process requirement, and two circulating tanks which are connected in parallel and are 20m in length can be adopted for convenient cleaning and maintenance3And 60m3One for each recycle tank.
Organic separation processing unit
The organic separation system integrates the separation section and the interception section of the organic separation into a skid-mounted base. The material membrane used in the organic separation section can exert the best advantage of difficult blockage of cross flow filtration only under a certain membrane surface flow rate. Therefore, it is desirable to use a semi-open and semi-closed process to reduce the operating cost of the organic separation system. The organic separation system consists of a separation section and an interception section, and two intermediate tanks are required to be configured at the same time. The organic separation system is configured to be 10m due to the adoption of a semi-open and semi-close operation process and the consideration of the cleaning and maintenance requirements of the membrane equipment3And 15m3One for each tundish.
In addition, if the concentrated solution is discharged in a sectional manner, the total amount of the concentrated solution cannot be controlled within a specified range, so that the concentrated solution flows back to the inlet of the separation section through the interception section, and is then discharged out of the system after being concentrated by the separation section.
Nanofiltration system
The nanofiltration system functions relatively independently. The nanofiltration has certain interception efficiency on salt, so that the load of the subsequent process can be reduced, and the continuous and stable operation of the subsequent process is ensured. The nanofiltration system has higher operating pressure, is suitable for adopting a half-open and half-close process, and adopts two 15m nanofiltration systems in production due to the huge nanofiltration system and the complicated pipelines3The intermediate tank is used for containing liquid and cleaning and maintaining.
In addition, in order to reduce the discharge amount of the concentrated liquid of the whole system, the nanofiltration concentrated liquid is not suitable to be discharged independently. The nanofiltration concentrated solution is reasonably returned to the inlet of the interception section from the technology (the effluent of the separation section is not diluted) and the economy.
Because the concentration of the membrane surface of the fine filtration is very low, the clear liquid discharged from the system can reach the expected technical standard and be reused for production, and the purposes of energy conservation and consumption reduction are achieved: after fine filtration, intercepting a small part of inorganic salt to form a concentrated solution, sending the concentrated solution to an electrodialysis concentration section for further concentration, and then evaporating and concentrating or drying concentrated water to obtain inorganic salt solid; the electrodialysis clear liquid returns to the fine filtration and concentration section, and the pre-filtered clear liquid enters the fine filtration and concentration section; the mixed wastewater is intercepted for a small part of inorganic salt and then permeates through the membrane to form clear liquid to reach the preset technical standard for discharge.
Besides the high-salt protein liquid, the invention is also suitable for treating gelatin wastewater and beryllium-containing wastewater.
The contents of the present invention have been explained above. Those skilled in the art will be able to implement the invention based on these teachings. All other embodiments, which can be derived by a person skilled in the art from the above description without inventive step, shall fall within the scope of protection of the present invention.
Claims (10)
1. A wastewater treatment method combining membrane separation and electrodialysis is characterized by comprising the following steps:
(a) the method comprises the steps of firstly, preliminarily filtering a wastewater stock solution to intercept large solid particle impurities to obtain a preliminary filtrate, and then introducing the preliminary filtrate into a membrane clarification unit (12) to intercept solid suspended matters and macromolecular impurities to obtain membrane clarified liquid;
(b) membrane separation is carried out on the membrane clarified liquid to remove part of divalent inorganic salt to obtain membrane separation clear liquid, the clear liquid obtained by the membrane separation filtration is sequentially subjected to membrane separation and interception on a small part of inorganic salt by a fine filtration unit (41) of a membrane concentration unit under the low-pressure operation of which the pressure is less than 2.5MPa, clear liquid is output, concentrated liquid obtained by the membrane separation of the fine filtration unit (41) is treated by an electrodialysis concentration unit (42) to obtain electrodialysis concentrated clear liquid, the electrodialysis concentrated clear liquid is returned to the fine filtration unit (41) again to carry out the membrane separation to output the clear liquid, and the concentrated solution obtained by the electrodialysis concentration unit (42) is discharged out of the system.
2. A method of treating wastewater by combining membrane separation and electrodialysis according to claim 1, comprising the steps of:
when the wastewater stock solution is a high-salt protein solution;
adjusting the pH value of the wastewater stock solution before the primary filtration in the step (a), and monitoring the pH value of the wastewater stock solution to ensure that the protein in the wastewater stock solution entering the primary filtration is zero;
in the step (b), the membrane clarified liquid is firstly introduced into an organic separation treatment unit (2), most of macromolecular organic matters are firstly removed through a separation device (2), and then the organic matters in the device are further intercepted through an interception device (22) to obtain the membrane clarified liquid.
3. A method for treating waste water by combined membrane separation and electrodialysis according to claim 2, characterized in that a first intermediate tank (5) is provided between the separation device (21) and the interception device (22), and the concentrate outlet of the membrane separation unit (3) is connected to the first intermediate tank (5);
a second intermediate tank (6) is arranged between the membrane separation unit (3) and the fine filtration unit (41), a concentrated solution outlet of the fine filtration unit (41) is connected with an inlet of the electrodialysis concentration unit (42), and a clear solution port connected with the electrodialysis concentration unit (42) is connected with the second intermediate tank (6);
a third intermediate tank (7) is arranged between the fine filtering unit (41) and the electrodialysis concentration unit (42);
a fourth intermediate tank (9) is arranged between the interception device (22) and the membrane separation unit (3).
4. The wastewater treatment method combining membrane separation and electrodialysis according to claim 1, wherein the membrane clarification unit (12) is one of an inorganic membrane filtration device, an organic membrane filtration device, a roll-up membrane filtration device, a butterfly membrane filtration device, a plate membrane filtration device, a hollow fiber membrane filtration device, and a tubular membrane filtration device, and has a molecular weight cutoff of 5000 Da; 8000D; a10000 Da; 30000 Da; 50000Da, 80000Da, 100000Da, 150000Da, 200000Da and 250000 Da.
5. A method for treating waste water by combining membrane separation and electrodialysis according to claim 1, wherein the liquid inlet of the membrane clarifying unit (12) is further provided with a primary filtering unit (11), and a circulation tank (8) is arranged between the primary filtering unit (11) and the membrane clarifying unit (12).
6. The wastewater treatment method combining membrane separation and electrodialysis according to claim 1, wherein the organic separation treatment unit (2) comprises a first roll type ultrafiltration membrane organic separation device and a second roll type ultrafiltration membrane organic separation device.
7. The wastewater treatment method combining membrane separation and electrodialysis according to claim 6, wherein the first roll-up ultrafiltration membrane organic separation device has a molecular weight cut-off of one of 10000Da, 8000Da, 5000Da, 3000Da, 2500Da, 1000Da, and the second roll-up ultrafiltration membrane organic separation device has a molecular weight cut-off of one of 2500Da, 1000Da,800Da, 600 Da.
8. The combined membrane separation and electrodialysis wastewater treatment method according to claim 1, wherein the membrane separation unit (3) comprises a roll-up membrane nanofiltration device.
9. The wastewater treatment method combining membrane separation and electrodialysis as claimed in claim 1, wherein the fine filtration unit (41) is one of an organic membrane, an inorganic membrane, a spiral membrane, a plate-type membrane, a butterfly membrane, a tubular membrane, a middle control fiber membrane, a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, and a reverse osmosis membrane; the molecular weight cut-off is one of 1000Da,800Da,500Da,300Da,150Da, 100Da and 50 Da.
10. The method for treating wastewater by combining membrane separation and electrodialysis according to claim 1, the electrodialysis concentration unit (42) is one of various devices with salt removal function in different combinations, wherein the devices have the same principle as inorganic ion exchange membrane electrodialysis, organic polymer ion exchange membrane electrodialysis, homogeneous ion exchange membrane electrodialysis, semi-homogeneous ion exchange membrane electrodialysis, heterogeneous ion exchange membrane electrodialysis, gel ion exchange membrane electrodialysis, porous ion exchange membrane electrodialysis, macroporous ion exchange membrane electrodialysis, cation exchange membrane electrodialysis, anion exchange membrane electrodialysis, special function ion exchange membrane electrodialysis, general water treatment ion exchange membrane electrodialysis, special purpose ion exchange membrane electrodialysis, omeless electrodialysis, omentum electrodialysis, substrate membrane electrodialysis and different combinations of electrodialysis under the action of an electric field.
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