CN115140881A - Organic wastewater treatment system and treatment process - Google Patents
Organic wastewater treatment system and treatment process Download PDFInfo
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- CN115140881A CN115140881A CN202210806920.7A CN202210806920A CN115140881A CN 115140881 A CN115140881 A CN 115140881A CN 202210806920 A CN202210806920 A CN 202210806920A CN 115140881 A CN115140881 A CN 115140881A
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 122
- 238000005373 pervaporation Methods 0.000 claims abstract description 101
- 239000002351 wastewater Substances 0.000 claims abstract description 63
- 239000013505 freshwater Substances 0.000 claims abstract description 60
- 239000012528 membrane Substances 0.000 claims abstract description 50
- 238000001704 evaporation Methods 0.000 claims abstract description 34
- 230000008020 evaporation Effects 0.000 claims abstract description 33
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 23
- 239000012141 concentrate Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000012452 mother liquor Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 238000002309 gasification Methods 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 11
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- 239000003507 refrigerant Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000010815 organic waste Substances 0.000 claims 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 238000005265 energy consumption Methods 0.000 description 14
- 239000003973 paint Substances 0.000 description 12
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000005416 organic matter Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
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- 238000009279 wet oxidation reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/366—Apparatus therefor
-
- 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
- C02F1/448—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by pervaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/14—Paint wastes
-
- C—CHEMISTRY; METALLURGY
- 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]
Abstract
The invention discloses a treatment system and a treatment process for organic wastewater. The organic wastewater treatment system comprises a low-temperature evaporation unit and a pervaporation unit; the low-temperature evaporation unit comprises a low-temperature evaporator; the pervaporation unit comprises a pervaporation device; a feed port of the pervaporation device is connected with a steam outlet of the low-temperature evaporator; the pervaporation device comprises a pervaporation membrane, the pervaporation membrane divides the pervaporation device into a concentrated water side and a fresh water side, the pervaporation membrane is a hydrophobic membrane, the low-temperature evaporation unit is provided with a water inlet, and the organic wastewater enters the low-temperature evaporator through the water inlet. The organic wastewater treatment system and the treatment process are suitable for concentrating low-concentration organic wastewater, and have the advantages of low equipment and site investment, low operation cost and loose requirements on operation environment.
Description
Technical Field
The invention particularly relates to a treatment system and a treatment process of organic wastewater.
Background
Part of organic wastewater, such as water paint wastewater, has high organic content, and the COD of the wastewater is easily increased rapidly when the wastewater is not treated in time, so that the one-time treatment cost is very high when the high-COD wastewater is sent to sewage treatment; and organic substances, such as water paint, cleaning agent and the like, have higher recycling value.
In the field of traditional organic matter separation, the common separation modes are rectification, distillation, extraction and filtration. For difficult-to-treat azeotropes, common separation methods are extraction, filtration or membrane separation. The pervaporation technology is one membrane separation process, and mainly utilizes the selective permeability of the pervaporation membrane material to realize the mass transfer driving force through the concentration difference or pressure difference between two sides of the membrane. Because the rear side of the membrane is at a low pressure, the components are vaporized to steam through the membrane thickness, and the steam is removed by a vacuum pump or by purging with an inert gas, so that the permeation process is continued. With appropriate membrane materials and manufacturing methods, membranes can be made that have a high permeation rate for one component and a relatively low, or even near zero, permeation rate for the other component, so that the pervaporation process can efficiently separate liquid mixtures.
Chinese patent document CN104959037a discloses a solvent dehydration apparatus, which mainly uses the water permeability principle of a pervaporation membrane to block permeation of organic substances. Chinese patent document CN107137958a discloses a pervaporation membrane organic solvent dehydration device, which also utilizes the water permeable function of the pervaporation membrane to perform evaporation in the form of a rectification column. In the prior art, rectification and pervaporation are coupled, after liquid is evaporated, moisture in the liquid permeates a permeable membrane through a pervaporation membrane, and separation of the liquid from organic matters is realized. The treatment system has high equipment investment cost, large occupied area and high site investment cost; the rectifying tower relates to high-temperature and high-pressure operation, the energy consumption investment is large, the system operation environment requirement is severe, and the safety and the fire and explosion protection level of a site are limited; in addition, the permeable gasification membranes in the prior art are all water permeable membranes, and are suitable for purifying high-concentration organic wastewater, for example, organic wastewater with water content of less than 10% is purified to water content of less than 1%; for the concentration of low concentration organic wastewater, for example, the concentration of organic wastewater with water content exceeding 40%, the operation cost is multiplied. For high-concentration organic wastewater, for example, organic wastewater with concentration more than 30% can also be treated by a method of hazardous waste incineration; for ultra-low concentration organic wastewater, for example, wastewater with concentration less than 1% can be treated by conventional water treatment processes such as biochemical, advanced oxidation or wet oxidation. At present, for organic wastewater with the concentration range of 1-30%, a treatment system and a treatment process which have low equipment and site cost investment, low energy consumption and loose requirements on the operating environment do not exist.
Disclosure of Invention
The invention aims to solve the technical problems of high equipment investment cost, large occupied area and high site investment cost of the existing organic wastewater treatment system; the energy consumption input is large, the requirement on the system operation environment is strict, and the operation cost is doubled when the system is used for concentrating low-concentration organic wastewater. The organic wastewater treatment system and the treatment process are suitable for concentrating organic wastewater with the concentration of 1-30%, and have the advantages of low equipment and site investment, low operation cost and loose requirements on operation environment.
The invention adopts the following technical scheme to solve the technical problems:
the invention provides a treatment system of organic wastewater, which comprises a low-temperature evaporation unit and a pervaporation unit; the low-temperature evaporation unit comprises a low-temperature evaporator; the pervaporation unit comprises a pervaporation device; the feed inlet of the pervaporation device is connected with the steam outlet of the low-temperature evaporator; the pervaporation device comprises a pervaporation membrane, the pervaporation membrane divides the pervaporation device into a concentrated water side and a fresh water side, and the pervaporation membrane is a hydrophobic membrane; the low-temperature evaporation unit is provided with a water inlet, and the organic wastewater enters the low-temperature evaporator through the water inlet.
In the present invention, it is preferable that the low temperature evaporator and the pervaporation device are independently provided with an abnormal condition discharge port.
In the present invention, the low temperature evaporator may be a reactor conventionally used in the art for generating steam by adding the evaporation waste liquid in a low temperature and low pressure state.
It is conventionally understood by those skilled in the art that when the evaporation system is an azeotropic system of an organic substance such as alcohol or ether and water, the vapor generated by the evaporation in the low-temperature evaporator is a mixture of the organic substance and water.
In the present invention, the material of the low temperature evaporator may be conventional in the art, and may be generally stainless steel, carbon steel or glass.
In the present invention, the shape of the low temperature evaporator may be conventional in the art, and may be generally cylindrical, rectangular or irregular.
In the present invention, the volume of the low temperature evaporator may be conventionally adjusted as needed.
In the present invention, it is conventionally understood by those skilled in the art that the low-temperature evaporator is generally provided with a discharge port for the evaporation mother liquor.
In the invention, the low-temperature evaporation unit preferably further comprises an evaporation mother liquor collecting box, and the evaporation mother liquor collecting box is connected with the evaporation mother liquor discharging port and is used for collecting the evaporated mother liquor.
In the present invention, it is conventionally understood by those skilled in the art that the hydrophobic membrane may be a membrane selectively permeable to organic substances, which is conventionally known in the art.
Due to the limitation of the formula of the hydrophobic membrane in the prior art, the hydrophobic membrane cannot realize complete interception of water when selectively permeating organic matters, or part of water can permeate the hydrophobic membrane to form a concentrated water side on the other side of the hydrophobic membrane.
In the present invention, the pervaporation device generally further comprises a pervaporation membrane backflow plate and a pervaporation pipe network.
In the present invention, it is conventionally understood by those skilled in the art that the pervaporation device is separated by the pervaporation membrane to form a concentrate side and a dilute side. The feed side of the permeation gasification device is low-concentration organic wastewater, namely a fresh water side; the organic matter selectively permeates the permeation gasification membrane, and a high-concentration organic matter solution is formed on the other side of the membrane, namely the concentrated water side.
In the present invention, as can be conventionally understood by those skilled in the art, the pervaporation device is generally further provided with a desalted liquid discharge port and a concentrated liquid discharge port, wherein the desalted liquid discharge port is arranged on the fresh water side, and the concentrated liquid discharge port is arranged on the concentrated water side.
In the invention, preferably, the pervaporation unit further comprises a concentrated water condensing tank and a fresh water condensing tank; the concentrated water condensing tank is connected with the concentrated solution discharge port; the fresh water condensing tank is connected with the desalted liquid discharge port.
In the invention, preferably, the infiltration gasification unit further comprises a concentrated water collecting box and a fresh water collecting box, wherein the concentrated water collecting box is connected with an outlet of the concentrated water condensing tank; the fresh water collecting box is connected with the outlet of the fresh water condensing tank.
In the present invention, the organic wastewater treatment system generally further comprises a vacuum circulation unit, wherein the vacuum circulation unit is connected to the concentrated water side of the pervaporation device, and is configured to form a high vacuum environment for the concentrated water side, so as to ensure a pressure difference driving force on two sides of the pervaporation membrane.
Preferably, the vacuum circulation unit is connected with the concentrated water condensing tank, and negative pressure is formed on the concentrated water side of the infiltration gasification device through negative pressure formed in the concentrated water condensing tank.
Wherein the vacuum circulation unit may be conventional in the art, generally comprising a vacuum ejector, a circulation pump and a collection water tank.
It is conventionally understood by those skilled in the art that the vacuum unit forms a circulation in the circulation pump by a liquid, and simultaneously, the liquid or gas in the condensed water tank is pumped out by the vacuum ejector by using the venturi principle, so that a negative pressure is formed in the condensed water tank.
The circulation pump is preferably a variable frequency pump. The variable frequency pump is typically connected to a central controller for controlling the frequency of the variable frequency pump.
The vacuum unit preferably further comprises a mechanical vacuum pump, and the mechanical vacuum pump is connected with the concentrated water side and is used for assisting the concentrated water side to form a high-vacuum negative-pressure environment.
Preferably, the mechanical vacuum pump is connected with the concentrated water condensing tank, and the high negative pressure is formed on the concentrated water side of the permeation gasification device through the high negative pressure of the concentrated water condensing tank.
In certain preferred embodiments of the present invention, the concentrate side of the pervaporation unit is connected to the inlet of the low temperature evaporator for reflux of the concentrate to further increase the concentration of the concentrate.
Wherein, preferably, the outlet of the concentrated water collecting box is connected with the inlet of the low-temperature evaporator.
In certain preferred embodiments of the present invention, the fresh water side of the pervaporation device is connected to the inlet of the cryogenic evaporator for returning fresh water to further reduce the concentration of fresh water.
As will be routinely understood by those skilled in the art, the higher the feed concentration to the pervaporation unit, the higher the concentration on the concentrate side; the lower the feed concentration to the pervaporation unit, the lower the concentration on the fresh water side. Thus, the return of the concentrate can be selected as desired to further increase the concentration of the concentrate or the return of the fresh water to further decrease the concentration of the fresh water.
Wherein, preferably, the outlet of the fresh water collecting box is connected with the inlet of the low-temperature evaporator.
In the present invention, the system for treating organic wastewater preferably further comprises a feeding unit connected to the inlet of the low-temperature evaporator.
Wherein the feed unit generally comprises a raw material tank, a feed pump and a vacuum maintaining valve connected in sequence, the vacuum maintaining valve being connected to the inlet of the cryogenic evaporator by a pipeline.
The vacuum pump and the vacuum maintaining valve are preferably connected to a central control system for real-time feedback and regulation of temperature, pressure, liquid level, etc. within the cryogenic evaporator.
In the present invention, the organic wastewater treatment system generally further includes a heat pump unit in which a refrigerant flows for heating or cooling the organic wastewater treatment system.
Wherein, the heat pump unit generally comprises a compressor, a heating coil, a condenser and a condensing coil which are sequentially communicated through a pipeline, and an outlet of the condensing coil is connected with an inlet of the compressor.
Wherein the refrigerant may be conventional in the art, and may typically be freon or cyclopentane.
As is conventionally understood by those skilled in the art, after the refrigerant passes through the compressor, the pressure and temperature are increased, and the material in the low-temperature evaporator is heated by the heating coil; the temperature of the refrigerant flowing out of the heating coil pipe is reduced, and the refrigerant enters the condensing coil pipe through pressure release and temperature reduction after the condenser and the expansion valve and is used for cooling the gas in the concentrated water condensing tank and the gas in the fresh water condensing tank.
The material of the pipeline can be a material suitable for heat exchange in the field, and generally can be a copper pipe or a stainless steel pipe.
Wherein the heating coil is generally custom sized according to the heat exchange area and the size of the cryogenic evaporator.
Wherein the size of the condensing coil is generally conventionally designed according to the required heat exchange area and the size of the concentrate or fresh water condensing tank.
The invention also provides a treatment process of the organic wastewater, which is carried out by utilizing the treatment system of the organic wastewater, wherein the feeding temperature of the permeation gasification device is 50-70 ℃, and the organic wastewater comprises organic matters which form azeotropy with water.
In the present invention, the concentration of the organic wastewater is preferably 1 to 30%, more preferably not higher than 15%, for example, 3 to 5%, and the concentration of the organic wastewater is the mass percentage of the organic matter in the organic wastewater.
In the present invention, the organic substance may be an organic substance that forms an azeotropic system with water as is conventional in the art, and may be generally an alcohol or ether organic substance, such as ethanol or ethylene glycol monobutyl ether.
It is conventionally understood by those skilled in the art that the organic wastewater is vaporized by the low-temperature vaporization unit, the azeotropic system enters the pervaporation unit in the form of steam, concentrated water is formed on the concentrated water side of the pervaporation device, and fresh water is formed on the fresh water side of the pervaporation device, so that all organic matters and the water are separated.
In the present invention, the concentration of the concentrated water can be conventionally set according to needs, and is generally not higher than 50%, preferably 20 to 40%, for example 30%, and the concentration of the concentrated water is the mass percentage of the organic matter in the concentrated water.
As will be conventionally understood by those skilled in the art, the concentration of the concentrate is highest when the pervaporation device starts feeding, and as pervaporation progresses, the concentration of the fresh water on the fresh water side gradually decreases, and the concentration of the concentrate on the concentrate side also gradually decreases, when the concentration of the concentrate or the concentration of the fresh water meets the requirement.
In the present invention, the feed temperature of the pervaporation unit is preferably 55 to 65 ℃, more preferably 55 to 62 ℃, for example 60 ℃.
In the present invention, the temperature difference Δ T between the temperature of the low temperature evaporator and the feed temperature of the pervaporation unit is preferably 5 to 15 ℃, for example 10 ℃ or 13 ℃.
As will be conventionally understood by those skilled in the art, the temperature of the low-temperature evaporator is the temperature of the liquid in the low-temperature evaporator and also the temperature of the outlet steam of the low-temperature evaporator, heat loss occurs during the process of conveying the outlet steam to the inlet of the pervaporation device through a pipeline, accordingly, the temperature is reduced, and the magnitude of the temperature reduction is the temperature difference Δ T. The higher the feed temperature of the pervaporation unit, the higher the temperature difference Δ T.
In the present invention, the feed temperature of the pervaporation unit is 55 to 65 ℃, and the temperature difference Δ T is preferably 8 to 13 ℃, more preferably 10 ℃.
In the present invention, the temperature of the low-temperature evaporator is preferably 60 to 85 ℃, more preferably 65 to 80 ℃, for example 70 ℃ or 78 ℃.
In the invention, the pressure of the low-temperature evaporator is the pressure of boiling gasification of the organic wastewater at the temperature of the low-temperature evaporator.
In certain preferred embodiments of the invention, the pressure of the low temperature vaporizer is in the range of-50 kPa to-80 kPa, such as-55 kPa, -75kPa, or-70 kPa.
In the invention, the feeding pressure of the pervaporation device is the saturated vapor pressure of the azeotropic system at the feeding temperature.
In certain preferred embodiments of the invention, the feed pressure to the pervaporation unit is between-50 and-80 kPa, such as-56 kPa, -72kPa, or-77 kPa.
In the present invention, it is conventionally understood by those skilled in the art that since the feed temperature of the pervaporation device is lower than the temperature of the low temperature evaporator and the pervaporation device is close to the vacuum circulation unit, the feed pressure of the pervaporation is generally slightly lower than the pressure of the low temperature evaporator.
In the present invention, the discharge pressure of the pervaporation device can be the maximum negative pressure which can be conventionally achieved in the field, and is preferably-50 to-99.9 KPa, and more preferably-90 to-99.9 kPa.
In the present invention, preferably, the pressure difference Δ P between the feed pressure of the pervaporation device and the discharge pressure of the pervaporation device is not less than 18kPa, and more preferably not less than 20kPa.
In the present invention, the discharge vacuum degree of the pervaporation device is preferably 1.5 times or more, more preferably 2 times or more, the feed vacuum degree of the pervaporation device.
In the invention, when the organic wastewater treatment system comprises the concentrated water condensing tank and the fresh water condensing tank, the temperature of the concentrated water condensing tank and the temperature of the fresh water condensing tank are respectively lower than the condensing point of the concentrated water and the condensing point of the fresh water.
In some preferred embodiments of the present invention, the temperature of the concentrated water condensing tank and the temperature of the fresh water condensing tank are independently 0 to 10 ℃, for example, 5 ℃.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: 1) The invention provides a treatment system and a treatment process of azeotropic organic wastewater with concentration of 1-30 wt% and low boiling point; the concentrated water can be used as an organic solvent for recycling, and the fresh water can also be used as circulating water for recycling.
2) The equipment and site investment of the low-temperature evaporation coupled permeation gasification system is greatly lower than that of rectification coupled permeation gasification in the prior art, the system operation does not involve high temperature and high pressure, and the environmental requirements are more relaxed.
3) The invention greatly reduces the energy consumption for treating low-concentration organic wastewater, and by taking the concentration of 5 percent of ethylene glycol monobutyl ether to 30 percent as an example, the operation energy consumption of the invention can be less than or equal to 203 yuan per ton of water, even as low as 168 yuan per ton of water, thereby greatly reducing the operation cost.
Drawings
FIG. 1 is a schematic view of a system for treating organic wastewater according to example 1.
1-a feed unit; 11-a raw material tank; 12-a feed pump; 13-vacuum maintenance valve; 2-a low temperature evaporation unit; 21-a low temperature evaporator; 22-evaporation mother liquor collection box; 23-a discharge pump; 3-a pervaporation unit; 31-a pervaporation unit; 32-concentrated water condensing tank; 33-fresh water condensation tank; 34-a concentrated water collecting box; 35-fresh water collecting box; 4-a vacuum circulation unit; 41-vacuum ejector; 42-a circulation pump; 43-an auxiliary vacuum pump; 5-a heat pump unit; 51-a compressor; 52-a heating coil; 53-a condenser; 54-a condenser coil; 55-auxiliary heating system; 56-auxiliary condensing system.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The hydrophobic films used in the following examples were manufactured by Shanghai electric group, inc. under the SEPV model; the water permeable membrane is MD-BX200-IDW type produced by Ningbo Xin far membrane separation Co.
Example 1
Referring to fig. 1, the system for treating organic wastewater of the present embodiment includes a feeding unit 1, a low-temperature evaporation unit 2, a pervaporation unit 3, a vacuum circulation unit 4, and a heat pump unit 5.
The feed unit 1 includes a raw material tank 11, a feed pump 12, and a vacuum maintenance valve 13, which are communicated by a pipe. The low-temperature evaporation unit 2 comprises a low-temperature evaporator 21 and an evaporation mother liquor collecting box 22, wherein the evaporation mother liquor collecting box 22 is connected with a bottom outlet of the low-temperature evaporator 21 through a discharge pump 23 and is used for discharging and collecting evaporated mother liquor. The inlet of the low temperature evaporator 21 is connected to the vacuum maintaining valve 13 through a pipe.
The pervaporation unit 3 includes a pervaporation device 31, a concentrated water condensation tank 32, a fresh water condensation tank 33, a concentrated water collection tank 34, and a fresh water collection tank 35. The feed inlet of the pervaporation unit 31 is connected to the vapor outlet of the low temperature evaporator 21. The pervaporation device 31 is a pervaporation membrane made of a hydrophobic membrane, and the pervaporation membrane divides the pervaporation device 31 into a concentrated water side and a fresh water side, where the feed side of the pervaporation device 31 is the fresh water side and the permeate side of the organic matter is the concentrated water side. The concentrated water side is provided with a concentrated water outlet, and the fresh water side is provided with a fresh water outlet; the concentrated water condensing tank 32 is connected with a concentrated water outlet for condensing the concentrated water, and the concentrated water collecting box 34 is connected with an outlet of the concentrated water condensing tank 32 for collecting, storing and transporting the concentrated water. The fresh water condensing tank 33 is connected with the fresh water outlet and is used for condensing fresh water; the fresh water collecting tank 35 is connected with the outlet of the fresh water condensing tank 33 and is used for collecting, storing and transporting fresh water. The concentrate side of the pervaporation unit 31 is connected to the inlet of the low temperature evaporator 21 for refluxing a part of the concentrate to further increase the concentration of the concentrate.
The vacuum circulation unit 4 is connected with a concentrated water condensing tank 32 of the pervaporation unit 3 and is used for providing a high vacuum environment for the concentrated water side of the pervaporation device 31 and ensuring the pressure difference driving force on two sides of the pervaporation membrane. The vacuum circulation unit 4 includes a vacuum ejector 41, a circulation pump 42, and an auxiliary vacuum pump 43. The vacuum unit forms a circulation in the circulation pump 42 by a liquid, and simultaneously pumps out the liquid or gas in the condensed water condensation tank 32 by the vacuum ejector 41 by using the venturi principle, so that a negative pressure is formed in the condensed water condensation tank 32. The circulating pump 42 is a variable frequency pump, and is connected to the central controller for controlling the frequency of the variable frequency pump. The auxiliary vacuum pump 43 is connected with the concentrated water condensing tank 32 and is used for assisting the concentrated water side to form a high vacuum negative pressure environment.
The heat pump unit 5 comprises a compressor 51, a heating coil 52, a condenser 53 and a condensing coil 54 which are sequentially communicated, wherein the outlet of the condensing coil 54 is connected with the inlet of the compressor 51; a heating coil 52 is provided inside the low temperature evaporator 21, a condensing coil 54 is provided inside the concentrated water condensing tank 32 and the fresh water condensing tank 33, and a refrigerant flows through the heat pump unit 5 to heat or cool the organic wastewater treatment system. After the refrigerant passes through the compressor 51, the pressure and the temperature are increased, the material in the low-temperature evaporator 21 is heated through the heating coil 52, and if the heating temperature is not enough, an auxiliary heating system 55 can be arranged in the low-temperature evaporator 21 for auxiliary heating; the refrigerant flowing out of the heating coil 52 is lowered in temperature, passes through the condenser 53 and the expansion valve, is released in pressure and lowered in temperature, and enters the condensing coil 54 to cool the materials in the concentrate condensing tank 32 and the fresh water condensing tank 33. If the temperature of the coolant passing through the condenser 53 is not low enough, the coolant may further be cooled by the auxiliary cooling system 55 and then sequentially enter the condensing coils 54 of the concentrated water condensing tank 32 and the fresh water condensing tank 33.
Examples 2 to 4
The aqueous paint cleaning wastewater was treated by the organic wastewater treatment system of example 1.
The water paint cleaning waste water is water paint cleaning liquid from a coating production workshop of an automobile factory, which contains water paint, cleaning agent and other substances, and the main components of chemical molecules of the water paint cleaning waste water are ethylene glycol monobutyl ether and diethylene glycol monobutyl ether and also comprise water-based chromogenic groups in colored paint. Removing solid-containing substances of the wastewater through coagulation pretreatment. Then the wastewater is put into the raw material box of the invention, the CODcr in the water is 125000mg/L, and the concentration of the ethylene glycol monobutyl ether is 7%. The process parameters of examples 2 to 4 are respectively shown in table 1, the concentration of ethylene glycol monobutyl ether on the side of the permeation and gasification concentrated water is controlled to be 30wt%, and the energy consumption calculation result for treating each ton of water-based paint cleaning wastewater is shown in table 1. 30wt% of ethylene glycol monobutyl ether can reach a purity of more than 98% after further concentration, and the secondary recycling of the ethylene glycol monobutyl ether as a workshop cleaning agent can be completely realized.
Table 1 table of process parameters and energy consumption results for examples 2-4
In table 1, "the temperature of the concentrated water/fresh water condensation tank" indicates that the temperatures of the concentrated water condensation tank and the fresh water condensation tank are the same and are the values in table 1.
Example 5
The ethanol wastewater was treated by using the organic wastewater treatment system of example 1.
The ethanol wastewater is discharged from a production workshop containing pollutants such as ethanol and salt, and contains substances such as ethanol. The ethanol wastewater is treated by coagulation pretreatment, solid-containing substances in waste solid suspended substances are removed, and the ethanol wastewater is put into a raw material box of the invention, wherein CODcr in the water is 50000-80000 mg/L, and the concentration of ethanol is 3-5wt%.
The CODcr of the concentrated water in the concentrated water collection box is increased to 200000-300000mg/L, the concentration of the ethanol reaches 45-55%, the CODcr of the fresh water in the fresh water collection box is reduced to 5000-10000mg/L, and the concentration of the ethanol is reduced to 0.5-1%. After the concentrated water is further concentrated, the concentration of the ethanol can reach more than 99 percent, and the aim of recycling the ethanol can be completely fulfilled.
Comparative example
The organic wastewater treated by the comparative example is the same as the organic wastewater treated by the examples 2 to 4, and is the water paint cleaning wastewater, wherein CODcr is 125000mg/L, and the concentration of ethylene glycol monobutyl ether is 7%. The concentration of the concentrated ethylene glycol monobutyl ether is also controlled to be 30wt%, and the energy consumption calculation results of the adopted treatment system and the corresponding treatment of each ton of water-based paint cleaning wastewater are shown in a table 2.
Wherein, in the comparative example 2, the vacuum rectification operation is adopted, the number of the tower plates of the rectification tower is 20, the height of the tower body is 8-10m, the operation pressure is 5kPa, the temperature at the top of the tower is 98-150 ℃, and the temperature at the bottom of the tower is 160-190 ℃.
Comparative example 3, a low-temperature evaporation operation was employed, the low-temperature evaporation control conditions were the same as in example 2, the pervaporation (permeable membrane) membrane area was 5 times that of the pervaporation permeable organic membrane, the temperature was controlled at 50 ℃, and the vacuum side negative pressure value was-99 KPa.
Comparative example 4, atmospheric distillation was used, the number of plates was 15, the operating pressure was 0.1MPa, the height of the column was 5-8 m, the temperature at the top of the column was 98 to 150 ℃ and the temperature at the bottom of the column was 160 to 190 ℃. After condensation and temperature reduction, further adopting pervaporation (permeable membrane) operation, wherein the operation conditions are consistent with those of the pervaporation in comparative example 3.
TABLE 2 comparative example wastewater treatment system and operation energy consumption meter
As can be seen from the energy consumption result data in tables 1 and 2, the energy consumption cost of the treatment system of the invention for treating low-concentration organic wastewater is lower than the operation energy consumption of rectification or low-temperature evaporation coupled pervaporation (permeable membrane) in the prior art, and is basically equivalent to the operation energy consumption of rectification coupled pervaporation (permeable membrane), but the treatment system of the invention has lower equipment construction cost and smaller occupied area than the treatment system of comparative example 4, the operation environment does not involve high temperature and high pressure, the treatment system is safer, and the requirement on the operation environment is wider.
For the treatment of the aqueous paint cleaning wastewater used in examples 2 to 4, the treatment process of example 2 was operated with lower energy consumption than those of examples 3 and 4.
Claims (10)
1. The organic wastewater treatment system is characterized by comprising a low-temperature evaporation unit and a pervaporation unit; the low-temperature evaporation unit comprises a low-temperature evaporator; the pervaporation unit comprises a pervaporation device; the feed inlet of the pervaporation device is connected with the steam outlet of the low-temperature evaporator; the pervaporation device comprises a pervaporation membrane, the pervaporation membrane divides the pervaporation device into a concentrated water side and a fresh water side, and the pervaporation membrane is a hydrophobic membrane; the low-temperature evaporation unit is provided with a water inlet, and the organic wastewater enters the low-temperature evaporator through the water inlet.
2. The organic wastewater treatment system according to claim 1, wherein the low-temperature evaporator is provided with an evaporation mother liquor discharge port for discharging the evaporation mother liquor; preferably, the low-temperature evaporation unit further comprises an evaporation mother liquor collection box, and the evaporation mother liquor collection box is connected with the evaporation mother liquor discharge port and is used for collecting the evaporated mother liquor;
and/or the permeation gasification device further comprises a concentrated liquid discharge port and a desalted liquid discharge port, wherein the concentrated liquid discharge port is arranged on the concentrated water side, and the desalted liquid discharge port is arranged on the fresh water side; preferably, the pervaporation unit further comprises a concentrated water condensing tank and a fresh water condensing tank, wherein the concentrated water condensing tank is connected with the concentrated liquid discharge port, and the fresh water condensing tank is connected with the desalted liquid discharge port; preferably, the infiltration gasification unit further comprises a concentrated water collection box and a fresh water collection box, the concentrated water collection box is connected with an outlet of the concentrated water condensation tank, and the fresh water collection box is connected with an outlet of the fresh water condensation tank.
3. The organic wastewater treatment system according to claim 1, further comprising a vacuum circulation unit connected to the concentrate side of the pervaporation device for creating a high vacuum environment for the concentrate side;
wherein the vacuum circulation unit preferably comprises a vacuum ejector, a circulation pump and a collection water tank; the circulating pump is preferably a variable frequency pump;
the vacuum circulation unit preferably further comprises a mechanical vacuum pump connected to the concentrated water side for assisting the concentrated water side in forming a high vacuum negative pressure environment.
4. The system for treating organic wastewater according to claim 1, further comprising a feed unit connected to an inlet of the cryogenic evaporator;
preferably, the feeding unit comprises a raw material tank, a feeding pump and a vacuum maintaining valve which are connected in sequence, and the vacuum maintaining valve is connected with an inlet of the low-temperature evaporator through a pipeline.
5. The organic wastewater treatment system of claim 2, further comprising a heat pump unit, wherein a refrigerant is circulated in the heat pump unit for heating or cooling the organic wastewater treatment system;
preferably, the heat pump unit comprises a compressor, a heating coil, a condenser and a condensing coil which are sequentially communicated through a pipeline, wherein an outlet of the condensing coil is connected with an inlet of the compressor;
preferably, the heating coil is arranged inside the low-temperature evaporator, and the condensing coil is arranged inside the concentrated water condensing tank and the fresh water condensing tank;
or the concentrated water side of the permeation gasification device is connected with the inlet of the low-temperature evaporator and is used for the reflux of the concentrated water so as to further improve the concentration of the concentrated water;
or the fresh water side of the pervaporation device is connected with the inlet of the low-temperature evaporator and used for returning the fresh water so as to further reduce the concentration of the fresh water.
6. A process for treating organic waste water, which is carried out in the system for treating organic waste water according to any one of claims 1 to 5, wherein the feed temperature of the pervaporation device is 50 to 70 ℃, and the organic waste water contains organic substances that form azeotropy with water.
7. The process for treating organic wastewater according to claim 6, wherein the concentration of the organic wastewater is 1 to 30%, preferably not higher than 15%, such as 3 to 5%, and the concentration of the organic wastewater is the mass percentage of the organic matters in the organic wastewater;
and/or the organic wastewater has CODcr of 10000-1000000 mg/L, preferably 30000-250000 mg/L, more preferably 50000-80000 mg/L or 100000-150000 mg/L, such as 125000mg/L;
and/or the concentration of the concentrated water on the concentrated water side is not higher than 50%, preferably 20-40%, for example 30%, and the concentration of the concentrated water is the mass percentage of the organic matters in the concentrated water.
8. A process for the treatment of organic waste water according to claim 6, wherein the feed temperature to the pervaporation unit is between 55 ℃ and 65 ℃, preferably between 55 ℃ and 62 ℃, for example 60 ℃;
and/or the temperature difference between the temperature of the low-temperature evaporator and the feeding temperature of the pervaporation device is 5-15 ℃, preferably 10 ℃ or 13 ℃;
and/or the temperature of the low-temperature evaporator is 60-85 ℃, preferably 65-80 ℃, more preferably 70 ℃ or 78 ℃.
9. The process for treating organic wastewater according to claim 6, wherein the pressure of the low-temperature evaporator is a pressure at which the organic wastewater boils and gasifies at the temperature of the low-temperature evaporator;
or the pressure of the low-temperature evaporator is-50 kPa to-80 kPa, preferably-55 kPa to-75 kPa or-70 kPa;
and/or the feed pressure of the pervaporation device is the saturated vapor pressure of the organic wastewater at the feed temperature;
alternatively, the feed pressure of the pervaporation device is between-50 and-80 kPa, preferably between-56 kPa and-72 kPa or between-77 kPa.
10. The process for treating organic wastewater according to claim 6, wherein the discharge pressure of the pervaporation device is from-50 to-99.9 KPa, preferably from-90 to-99.9 kPa, more preferably from-99 kPa;
alternatively, the pressure difference between the feed pressure of the pervaporation device and the discharge pressure of the pervaporation device is not less than 18kPa, preferably not less than 20kPa.
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