CN114671554A - Zero-discharge sewage system containing guanidine salt and application method - Google Patents

Zero-discharge sewage system containing guanidine salt and application method Download PDF

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CN114671554A
CN114671554A CN202011556908.2A CN202011556908A CN114671554A CN 114671554 A CN114671554 A CN 114671554A CN 202011556908 A CN202011556908 A CN 202011556908A CN 114671554 A CN114671554 A CN 114671554A
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water
unit
desalting
concentrated water
water outlet
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韩国美
毛治强
孙杰
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Dalian Bomei Technology Co ltd
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Dalian Bomei Technology Co ltd
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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
    • 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
    • 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
    • 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
    • C02F1/22—Treatment of water, waste water, or sewage by freezing
    • 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
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • 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
    • 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
    • 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
    • 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
    • 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
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • 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
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage

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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)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The invention discloses a guanidine salt-containing sewage zero-discharge system and an application method thereof, belonging to the field of sewage treatment. The sewage is mainly from the sewage processed in an air bag primary explosive workshop and the production of medicines, pesticides, dyes and other organic compound intermediates. This system mainly includes sewage pretreatment unit, desalination unit, carries salt unit, retrieval and utilization unit and waste disposal unit, its characterized in that: the pretreatment unit comprises a precipitation unit I, a filter pressing unit and a microfiltration unit. The desalting unit can adopt an evaporation method for desalting and an electrochemical method for desalting. The salt extraction unit comprises a precipitation unit II, a filtration unit I, a freezing unit, a centrifugation unit and a centrifugate processing unit. The recycling unit comprises an RO unit, an ion exchange unit, an ECR unit, a filtering II unit and a COD treatment system. The waste disposal unit comprises an incinerator. Also discloses a processing method of the processing system.

Description

Zero-discharge sewage system containing guanidine salt and application method
Technical Field
The invention relates to a sewage treatment system and a sewage treatment method, in particular to a sewage zero-discharge system containing guanidine salt and an application method.
Background
At present, sewage from processing in an air bag primary explosive workshop mainly contains pollutants such as guanidine nitrate, basic copper nitrate, glass fiber, silicon dioxide and the like. In addition, guanidine salt sewage is also mostly produced in the production of medicines, pesticides, dyes and other organic compound intermediates, and how to treat sewage efficiently and energy-efficiently and meet the requirement of zero emission after treatment becomes a problem to be solved urgently at present.
Disclosure of Invention
Aiming at the technical problems, the invention provides a guanidine salt-containing sewage zero-discharge system and a treatment method.
A sewage zero discharge system containing guanidine salt is characterized in that sewage containing guanidine salt to be treated is connected to a raw water tank, the raw water tank is sequentially connected with a reaction tank I, a filter press, a special microfiltration membrane and a desalting device I through pipelines, the desalting device I is provided with a concentrated water port outlet and a desalted water outlet, the desalted water outlet of the desalting device I is connected with a reverse osmosis device, and the concentrated water port outlet of the desalting device I is connected with a concentrated water barrel b; the reverse osmosis device is provided with a concentrated water port outlet and a desalted water outlet, the desalted water outlet of the reverse osmosis device is sequentially connected with the reverse ion exchange device and the clean water tank, and the concentrated water port outlet of the reverse osmosis device is sequentially connected with the electrochemical reaction device for silicon removal, the filtering device II and the COD treatment system and is connected to a pipeline between the special microfiltration membrane and the desalting device I; the concentrated water barrel b is sequentially connected with the reaction tank II, the filtering device I, the crystallization kettle and the centrifuge through pipelines; the crystal that centrifuge separated gets into the crystallization collecting vessel, and the liquid that centrifuge separated gets into the centrifugate storage tank, and the centrifugate storage tank links to each other with demineralizer III, and demineralizer III has dense mouth of a river export and desalted water outlet, and demineralizer III's dense mouth of a river export links to each other with the pipeline between reaction tank II and the dense water bucket b, and demineralizer III's desalted water outlet links to each other with the pipeline between special type microfiltration membrane and the demineralizer I.
Further, in the above technical solution, the COD processing system comprises an advanced oxidation COD processing system or a biochemical COD processing system.
Furthermore, in the above technical scheme, a concentrated water barrel a and a desalination device II are sequentially connected to a pipeline between the desalination device I and the concentrated water barrel b from a concentrated water inlet outlet side of the desalination device I, the desalination device II is provided with a concentrated water inlet outlet and a desalted water outlet, the concentrated water inlet outlet of the desalination device II is connected with the concentrated water barrel b, and the desalted water outlet of the desalination device II is connected with a pipeline between the special microfiltration membrane and the desalination device I; and a desalted water outlet of the desalting device III is connected to a pipeline between the concentrated water bucket b and the reaction tank II, and a concentrated water bucket c is connected to the pipeline.
Further, in the above technical solution, the desalination apparatus includes one of an electrochemical desalination apparatus, an evaporation desalination apparatus, and a physical desalination apparatus.
The sewage flowing out of the desalting device I and entering the reverse osmosis device is desalted water, and the sewage entering the concentrated water barrel b is concentrated water; the sewage flowing out of the desalting device II and entering a special microfiltration membrane and a pipeline before the desalting device I is desalted water, and the sewage flowing into a concentrated water barrel b is concentrated water; the sewage flowing out of the desalting device III and entering the special micro-filtration membrane and the pipeline before the desalting device I is desalted water, and the sewage flowing into the concentrated water bucket c is concentrated water.
Furthermore, in the above technical solution, the conductivity of the desalted water flowing out of the desalted water outlet is below 1000 μ s/cm, and the conductivity of the concentrated water flowing out of the concentrated water outlet is 180000-.
Further, in the above technical scheme, the liquid separated by the centrifuge is also connected with the waste treatment unit through a pipeline.
Further, in the above technical solution, the waste treatment unit includes an incinerator.
When the desalting device is an electrochemical desalting device, an electrodialysis method is adopted for desalting, and the preferable device is a device with the following patent technical application numbers: 201620007937.6, named as EFD, the EFD device has desalting effect and has dense water outlet and desalted water outlet.
When the desalination device is an evaporation desalination device, the selected device can be an MVR device, and can also be a multi-effect evaporation device, a thin film evaporation device or other types of evaporation devices.
When the desalting device is a desalting device adopting other physical methods, the desalting device can be a desalting device which can play the same role of electro-adsorption, reverse osmosis and the like.
Regardless of the form of desalination employed, a portion of desalinated water and another portion of highly saline concentrated water are produced. The desalted water enters a recycling unit for continuous treatment and recycling, and the concentrated water is further extracted with guanidine salt.
An application method of a sewage zero discharge system comprises the following steps:
(1) the method comprises the following steps of (1) connecting sewage containing guanidine salt to be treated into a raw water tank, enabling the sewage to enter a reaction tank I, adding a precipitator into the reaction tank I until the pH value is 11-13, and removing copper ions in the sewage, and organic matters and copper ion derivatives which are hydrolyzed or form precipitates in an alkaline environment; continuously feeding the sewage into a filter press to remove precipitates; the outlet water of the filter press is communicated with a special microfiltration membrane, the special microfiltration membrane intercepts macromolecular organic matters in the sewage, and the sewage is added with a regulator until the pH value is 6-9 and then enters a desalting device I;
(2) after the sewage is treated by the desalting device I, desalted water flowing out of a desalted water outlet enters a reverse osmosis device, desalted water flowing out of a desalted water outlet of the reverse osmosis device enters a reverse ion exchange device to remove ammonia nitrogen in the water, enters a clean water tank to be recovered, concentrated water flowing out of a concentrated water outlet of the reverse osmosis device enters an electrochemical reaction device for silicon removal to remove silicon dioxide in the water, is further filtered by a filtering device II, is subjected to COD treatment by a COD treatment system to remove COD enriched in the concentrated water, and then flows into the desalting device I for repeated desalting; concentrated water flowing out of a concentrated water outlet of the desalting device I enters a concentrated water barrel b, and further salt extraction is continued;
(3) The concentrated water in the concentrated water barrel b flows into a reaction tank II, a precipitator is added into the reaction tank II to remove copper ions and organic matters and copper ion derivatives which are hydrolyzed or form precipitates under an alkaline environment, the generated precipitates are removed by a filtering device I and then enter a crystallization kettle, the crystallization kettle is frozen and crystallized at the temperature of 0 to minus 5 ℃, the mixed solution after the crystallization is separated by a centrifuge, the crystals are collected in a crystal collection barrel, the crystals collected in the crystal collection barrel are guanidine salt, and the centrifugate enters a centrifugate storage tank after the pH value is adjusted to be neutral by adding a regulator;
(4) the liquid in the centrifugate storage tank further flows into a desalting device III, after the liquid is treated by the desalting device, the effluent desalted water flows into a pipeline between a special micro-filtration membrane and the desalting device I for repeated desalting, and the effluent concentrated water after the liquid is treated by the desalting device III flows into a pipeline between a concentrated water bucket b and a reaction tank II for repeated salt extraction;
(5) after the centrifugate flowing out of the centrifuge is repeatedly concentrated and crystallized for 2-3 times in the system, the centrifugate is treated by a waste treatment unit, the centrifugate is evaporated to be crystallized by the generated waste heat, and the crystal enters the waste treatment unit for treatment and recycling.
Further, in the above technical scheme, the precipitant is an alkaline substance, including sodium hydroxide, potassium hydroxide, calcium oxide, and the like; the regulator is an acidic substance, and comprises hydrochloric acid, sulfuric acid, nitric acid and the like.
Further, in the above technical scheme, the macromolecular organic substance includes fatty acid ester.
Further, among the above-mentioned technical scheme, the crystallization that the crystallization collecting vessel was collected mainly becomes guanidine nitrate and potassium perchlorate, and the crystallization can be retrieved as raw materials for production, perhaps gets into the incinerator and burns, and the waste heat or the flue gas that produce after burning can be used to concentrated water evaporation to crystallization.
Further, in the above technical scheme, the concentrated water flowing out of the desalting unit in the step (2) enters a concentrated water barrel b, and enters a desalting device II for primary desalting treatment before further salt extraction.
The waste water containing guanidine salt mainly contains pollutants such as guanidine nitrate, basic copper nitrate, glass fiber, silicon dioxide and the like.
The conductivity of the fresh water generated by the desalting unit is less than 1000 mu s/cm, and the fresh water can be reused as the production water after entering the reuse unit for reprocessing. And simultaneously, the conductivity of the generated high-salt-content concentrated water reaches 180000-200000 mu s/cm, the guanidine salt in the wastewater is extracted by a freezing and centrifuging technology, and the centrifugate can be subjected to concentration and freezing for many times and then discharged to a waste treatment unit when other ions in the water are in a near-saturation state.
The reverse osmosis device removes pollutant substances exceeding the standard in water in order to further treat desalted water generated by the desalting device, and the reverse osmosis effluent enters an ion exchange reactor to remove ammonia nitrogen in the water, so that the conductivity of the effluent is ensured to reach the standard of domestic miscellaneous water. The reverse osmosis concentrated water is prepared by the following application numbers: 201821179928.0, entitled electrochemical reaction device for removing silicon, which removes silicon dioxide in water, and the effluent water passes through a filter to remove suspended matters in the water and then returns to a desalting device for circular treatment.
The water outlet of the reverse osmosis device is communicated with the ion exchange device, the water outlet of the ion exchange device is communicated with the clean water tank for storage, and the water in the clean water tank can be reused in production and can also be used for flushing toilets and cleaning equipment. The concentrated water outlet of the reverse osmosis device is communicated to the electrochemical reaction device for silicon removal to remove silicon and colloidal COD in the water, the water outlet of the electrochemical reaction device for silicon removal is communicated to the filtering device II, the water outlet of the filtering device II is communicated to the COD treatment system to remove COD in the water, and the water outlet of the COD treatment system is communicated to the water inlet of the desalination device.
This system is zero discharge system, and the back product water of handling can reach the domestic miscellaneous water standard and use as the process water retrieval and utilization, can draw the guanidine salt in the waste water out simultaneously and use as raw materials for production, and a small amount of dense water that produces in the system passes through to burn burning furnace and handles, and entire system does not have outer waste discharge.
Furthermore, substances contained in the mother liquor of the frozen and crystallized concentrated solution of the system are not guanidine salt, other ions in water cannot be crystallized and separated out in the freezing process, and other ions in water can be separated out after long-term circulation when the other ions reach a saturation value and are concentrated again, so that the frozen mother liquor is independently circulated, concentrated and crystallized for 2-3 times and then is discharged out of the system as wastewater, and finally the amount of the discharged wastewater is less than 2%. And this portion of the waste water can be treated entirely by the incinerator.
Drawings
FIG. 1 is a schematic diagram of zero discharge of wastewater treatment according to the present invention.
FIG. 2 is a schematic diagram of one of the treatment modalities of zero-emission treatment of wastewater according to the invention.
In the figure: 1-raw water tank, 2-reaction tank I, 3-filter press, 4-special microfiltration membrane, 5-desalination device I, 6-reverse osmosis device, 7-counter ion exchange device, 8-clear water tank, 9-electrochemical reaction device for silicon removal, 10-filtration device II, 11-concentrated water barrel B, 12-reaction tank II, 13-filtration device I, 14-crystallization kettle, 15-centrifuge, 16-crystallization collection barrel, 17-waste treatment unit, 18-waste heat, 19-centrifugate storage tank, 20-desalination device II, 21-concentrated water barrel a, 22-desalination device III, 23-concentrated water barrel c, 24-COD treatment system, A-precipitant and B-regulator.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
The method comprises the following steps that waste water containing guanidine salt in a raw water tank 1 is connected to a water inlet of a reaction tank I2 through a water pump, and meanwhile, a precipitator is added to a pipeline connected with the raw water tank 1 and the reaction tank 2 through a metering pump; the outlet of the reaction tank I2 is communicated to the feed inlet of the filter press 3 through a water pump, the water outlet of the filter press 3 is communicated to the water inlet of the special microfiltration membrane 4, the water outlet of the special microfiltration membrane 4 is communicated to the water inlet of the desalting device I5, and meanwhile, a regulator is added to a pipeline communicated with the special microfiltration membrane 4 and the desalting device I5 through a metering pump. A desalination water port of the desalination device I5 is communicated with a water inlet of the reverse osmosis device 6, a desalination water port of the reverse osmosis device 6 is communicated with a water inlet of the ion exchange device 7, and water produced by the ion exchange device 7 enters a clean water tank 8; the concentrated water port of the reverse osmosis device 6 is communicated with the water inlet of the electrochemical reaction device 9 for silicon removal, the water outlet of the electrochemical reaction device 9 for silicon removal is communicated with the water inlet of the filtering device II 10, the water outlet of the filtering device II 10 is communicated with the water inlet of the COD treatment system 24, and the water outlet of the COD treatment unit is communicated with the water inlet of the desalination device I5.
A concentrated water outlet of the desalting device I5 is communicated to a water inlet of a concentrated water barrel b 11, a water outlet of the concentrated water barrel b 11 is communicated to a water inlet of a reaction tank II 12, and meanwhile, a precipitator is added to a pipeline for connecting the concentrated water barrel b 11 and the reaction tank II 12 through a metering pump. The water outlet of the reaction tank II 12 is communicated with the water inlet of a filtering device I13, the water outlet of a filtering device I13 is communicated with the water inlet of a crystallization kettle 14, the material outlet of the crystallization kettle 14 is communicated with the material inlet of a centrifugal machine 15, crystals separated by the centrifugal machine 15 enter a crystallization collecting barrel 16 for storage, the centrifugate water outlet of the centrifugal machine 15 is communicated with the water inlet of a centrifugate storage tank 19, meanwhile, a regulator is added to a pipeline connected with the centrifugal machine 15 and the centrifugate storage tank 19 through a metering pump, the water outlet of the centrifugate storage tank 19 is communicated with the water inlet of a desalting device III 20, the desalting water inlet of the desalting device III 20 is communicated with a pipeline between a desalting device I5 and a special microfiltration membrane 4, and concentrated water of the desalting device III 20 is communicated with a pipeline between the reaction tank II 12 and a concentrated water barrel b 11. When the times of repeatedly concentrating and crystallizing the centrifugate in the system reach 2-3, evaporating the part of centrifugate to be crystallized by using the waste heat 18 generated by the incinerator 17, and then burning the crystals in the incinerator 17.
Example 1
As shown in fig. 1-2, in the guanidine salt-containing sewage zero discharge system, guanidine salt-containing sewage to be treated is connected to a raw water tank 1, the raw water tank 1 is sequentially connected to a reaction tank I2, a filter press 3, a special microfiltration membrane 4 and a desalination device I5 through pipelines, the desalination device I5 is provided with a concentrated water outlet and a desalted water outlet, the desalted water outlet of the desalination device I5 is connected to a reverse osmosis device 6, and the concentrated water outlet of the desalination device I5 is connected to a concentrated water barrel b 11; the reverse osmosis device 6 is provided with a concentrated water port outlet and a desalted water outlet, the desalted water outlet of the reverse osmosis device 6 is sequentially connected with a reverse ion exchange device 7 and a clean water tank 8, and the concentrated water port outlet of the reverse osmosis device 6 is sequentially connected with an electrochemical reaction device 9 for desiliconization, a filtering device II 10 and a COD treatment system 24 and is connected to a pipeline between the special microfiltration membrane 4 and the desalting device I5; the concentrated water barrel b 11 is sequentially connected with the reaction tank II 12, the filtering device I13, the crystallization kettle 14 and the centrifuge 15 through pipelines; the crystal separated by the centrifuge 15 enters a crystallization collecting barrel 16, the liquid separated by the centrifuge enters a centrifugate storage tank 19, the centrifugate storage tank 19 is connected with a desalting device III 20, the desalting device III 20 is provided with a concentrated water port outlet and a desalted water outlet, the concentrated water port outlet of the desalting device III 20 is connected with a pipeline between a reaction tank II 12 and a concentrated water barrel b 11, and the desalted water outlet of the desalting device III 20 is connected with a pipeline between a special microfiltration membrane 4 and a desalting device I5.
A concentrated water barrel a 21 and a desalination device II 22 are sequentially connected to a pipeline between the desalination device I5 and the concentrated water barrel b 11 from the outlet side of a concentrated water port of the desalination device I5, the desalination device II 22 is provided with a concentrated water port outlet and a desalted water outlet, the concentrated water port outlet of the desalination device II 22 is connected with the concentrated water barrel b 11, and the desalted water outlet of the desalination device II 22 is connected with a pipeline between the special microfiltration membrane 4 and the desalination device I5; a thick water bucket c 23 is connected to a pipeline of the desalting device III 20 connected to a pipeline between the thick water bucket b 11 and the reaction tank II 12. The desalination device comprises one of an electrochemical desalination device, an evaporation desalination device and a physical desalination device. The conductivity of desalted water flowing out of the desalted water outlet is below 1000 mu s/cm, and the conductivity of concentrated water flowing out of the concentrated water outlet is 180000-200000 mu s/cm. The liquid separated by the centrifuge is also connected with an incinerator through a pipeline.
Example 2
The main components of sewage processed in an initiating explosive workshop of an automobile safety air bag comprise pollutants such as guanidine nitrate, basic copper nitrate, glass fiber, silicon dioxide and the like. The desalting device adopts an electrochemical desalting method, and the selected devices are the following devices in the patent technical application number of the company: 201620007937.6, named as "electrically driven membrane desalter set", the EFD is short for the device manufactured by the technology.
The apparatus for treating the centrate also employs electrochemical desalting.
The wastewater conductivity is 10000 mus/cm, the wastewater is stored in a raw water tank 1, the wastewater in the raw water tank 1 is conveyed to a water inlet of a reaction tank I2 through a water pump, a precipitator adopts sodium hydroxide and is added to a water inlet pipeline of the reaction tank I2 through a metering pump, an online pH meter is arranged at the rear end of a medicament adding port, the medicament adding amount of the precipitator is controlled through the pH value, and the end point pH value is set to be 12. Waste water stops 1h in reaction tank I2, the play water passes through the water pump and carries to pressure filter 3 feed inlet, get rid of the sediment that the previous step generated through pressure filter 3, pressure filter 3 delivery port communicates to special microfiltration membrane 4 water inlet, get rid of macromolecule organic matters such as fatty acid fat in the waste water, special microfiltration membrane 4 delivery port communicates to demineralizer I5 water inlet, the demineralizer adopts the electrochemistry method desalination, the demineralizer of adoption is the EFD device, regulator hydrochloric acid adds to the demineralizer I5 water inlet pipeline through the measuring pump on, regulator adds the medicine mouth rear end simultaneously and is equipped with online pH meter, add the dose through pH control regulator, it is 7 to set up terminal pH. Desalting by adopting a desalting device I5, transferring salt in the wastewater to the concentrated water side of the desalting device I5, and communicating a concentrated water outlet of the desalting device I5 to a concentrated water bucket a 21. The water outlet (namely a desalted water outlet) of the desalter I5 is communicated with the water inlet of a reverse osmosis device 6 of the reuse unit. More than 90% of pollutants in the wastewater are removed by the reverse osmosis device 6, a water outlet of the reverse osmosis device 6 is communicated to a water inlet of the ion exchange device 7, the ion exchange device 7 is used as a safety measure to remove redundant ammonia nitrogen in the water, a water outlet of the ion exchange device 7 is communicated to a water inlet of the clean water tank 8, finally generated reuse water is stored, the conductivity of the outlet water is less than 100 mu s/cm, the ammonia nitrogen is less than 0.5mg/L, the ammonia nitrogen is less than 15mg/L, the standard of domestic miscellaneous water is met, and the reuse water is used as workshop flushing equipment and production water for reuse. The concentrated water outlet of the reverse osmosis device 6 is communicated to the water inlet of the electrochemical reaction device 9 for silicon removal, the silicon dioxide contained in the water is removed by the electrochemical reaction device 9 for silicon removal, the water outlet of the electrochemical reaction device 9 for silicon removal is communicated to the water inlet of the filtering device II 10, and the floc generated by the electrochemical reaction device 9 for silicon removal is intercepted. The water outlet of the filter device II 10 is communicated with the water inlet of the COD treatment system 24 to remove most COD in the water to ensure that the outlet water is close to or reaches the inlet water quality, and the water outlet of the COD treatment system 24 is communicated with the water inlet of the desalter I5E to be circularly treated. The conductivity of the concentrated water in the concentrated water barrel a 21 is 70000-. A water outlet of the concentrated water barrel b 11 is conveyed to a water inlet of the reaction tank II 12 through a water pump, a precipitator is sodium hydroxide and is added to a water inlet pipeline of the reaction tank II 12 through a metering pump, an online pH meter is arranged at the rear end of a precipitator adding opening, the adding amount of the precipitator is controlled through pH, and the end point pH is set to be 12. The wastewater stays in the reaction tank II 12 for 1 hour, the effluent is conveyed to a water inlet of a filter device I13 through a water pump, the precipitate generated in the previous step is removed through a filter device I13, a water outlet of the filter device I13 is communicated to a water inlet of a crystallization kettle 14, and the wastewater is frozen and crystallized for 1 hour at the temperature of minus 5 ℃. A discharge port of the crystallization kettle 14 is communicated to a feed port of a centrifuge 15, crystals and water generated in the previous step are separated, and the crystals enter a crystal collecting barrel 16 for storage and are used as production raw materials or enter an incinerator 17 of a waste treatment unit for incineration treatment. A centrifugate outlet of the centrifuge 15 is communicated to a water inlet of a centrifugate liquid storage tank 19, a regulator hydrochloric acid is added into a water inlet pipeline of the centrifugate liquid storage tank 19 through a metering pump, an online pH meter is arranged at the rear end of a regulator adding port, the adding amount of the regulator is controlled through pH, and the final pH is set to be 7. The conductivity of the centrifugate in the centrifugate storage tank 19 is 8000-13000 mu s/cm, the water outlet of the centrifugate storage tank 21 is communicated to the water inlet of the desalting device III 20, the centrifugal mother liquor is concentrated again through the desalting device III 20, the water outlet of the desalting device III 20 (namely a desalted water outlet) is communicated to the water inlet of the desalting device I5, and the treatment is circulated. A concentrated water outlet of the desalting device III 20 is communicated to a water inlet of the reaction tank II 12. Adding medicine again to precipitate and then crystallizing. Because the waste water does not contain one guanidine salt, the concentration of other ions in the concentrated water reaches a saturation value after multiple times of concentration, the crystallization yield is reduced, and the conductivity of the centrifugate is increased. Therefore, after the centrifugate is repeatedly concentrated for 2 times, the centrifugate is discharged to a waste treatment unit, the centrifugate generated after multiple centrifugations is evaporated to crystals by adopting the waste heat or the flue gas 18 generated by the incinerator 17, and the crystals are sent to the incinerator 17 for incineration. The final discharge to the incinerator 17 is less than 2% of the total treatment amount of the centrifugal liquid.
Example 3
The main components of sewage processed in an initiating explosive workshop of an automobile safety air bag comprise guanidine nitrate, basic copper nitrate, glass fiber and silicon dioxide pollutants.
The desalination method adopted by the desalination device I, the desalination device II and the desalination device III is an evaporation method, and the selected device is an MVR evaporation device.
The wastewater conductivity is 10000 mus/cm, the wastewater is stored in a raw water tank 1, the wastewater in the raw water tank 1 is conveyed to a water inlet of a reaction tank I2 through a water pump, a precipitator adopts sodium hydroxide and is added to a water inlet pipeline of the reaction tank I2 through a metering pump, an online pH meter is arranged at the rear end of a medicament adding port, the medicament adding amount of the precipitator is controlled through the pH value, and the end point pH value is set to be 12. Waste water stops for 1h in reaction tank I2, the effluent is conveyed to a feed inlet of a filter press 3 through a water pump, the precipitate generated in the previous step is removed through the filter press 3, a water outlet of the filter press 3 is communicated to a water inlet of a special microfiltration membrane 4, macromolecular organic matters such as fatty acid ester and the like in the waste water are removed, a water outlet of the special microfiltration membrane 4 is communicated to a water inlet of a desalting device I5, the desalting device I5 adopts an evaporation method for desalting, the adopted desalting device is an MVR evaporation device, regulator hydrochloric acid is added to a water inlet pipeline of the desalting device I5 MVR evaporation device through a metering pump, meanwhile, an online pH meter is arranged at the rear end of a regulator dosing port, the dosage of the regulator is controlled through pH, and the end point pH is set to be 7. Desalting by adopting a desalting device I5 MVR evaporation device, and concentrating salt in the wastewater into a concentrated water barrel b 11. The distilled water outlet of the I5 MVR evaporation device of the desalting device is communicated to the water inlet of a reverse osmosis device 6 of the reuse unit. More than 90% of pollutants in the wastewater are removed by the reverse osmosis device 6, a water outlet of the reverse osmosis device 6 is communicated to a water inlet of the ion exchange device 7, the ion exchange device 7 is used as a safety measure to remove redundant ammonia nitrogen in the water, a water outlet of the ion exchange device 7 is communicated to a water inlet of the clean water tank 8, finally generated reuse water is stored, the conductivity of the outlet water is less than 100 mu s/cm, the ammonia nitrogen is less than 0.5mg/L, the ammonia nitrogen is less than 15mg/L, the standard of domestic miscellaneous water is met, and the reuse water is used as workshop flushing equipment and production water for reuse. The concentrated water outlet of the reverse osmosis device 6 is communicated to the water inlet of the ECR device 9, the silicon dioxide contained in the water is removed by the electrochemical reaction device 9 for silicon removal, the water outlet of the electrochemical reaction device 9 for silicon removal is communicated to the water inlet of the filtering device II 10, and the flocs generated by the electrochemical reaction device 9 for silicon removal are intercepted. The water outlet of the filter device II 10 is communicated to the water inlet of the COD treatment system 24 to remove most COD in the water to enable the outlet water to approach or reach the inlet water quality, and the water outlet of the COD treatment system 24 is communicated to the water inlet of the desalination device I5 MVR evaporation device for circular treatment. The desalination device I5 MVR evaporation device finally concentrates the concentrated water to 180000-. A water outlet of the concentrated water barrel b 11 is conveyed to a water inlet of the reaction tank II 12 through a water pump, a precipitator is sodium hydroxide and is added to a water inlet pipeline of the reaction tank II 12 through a metering pump, an online pH meter is arranged at the rear end of a precipitator adding opening, the adding amount of the precipitator is controlled through pH, and the end point pH is set to be 12. The wastewater stays in the reaction tank II 12 for 1 hour, the effluent is conveyed to a water inlet of a filter device I13 through a water pump, the precipitate generated in the previous step is removed through a filter device I13, a water outlet of the filter device I13 is communicated to a water inlet of a crystallization kettle 14, and the wastewater is frozen and crystallized for 1 hour at the temperature of minus 5 ℃. A discharge port of the crystallization kettle 14 is communicated to a feed port of a centrifuge 15, crystals and water generated in the previous step are separated, and the crystals enter a crystal collecting barrel 16 for storage and are used as production raw materials or enter an incinerator 17 of a waste treatment unit for incineration treatment. A centrifugate outlet of the centrifuge 15 is communicated to a water inlet of a centrifugate liquid storage tank 19, a regulator hydrochloric acid is added into a water inlet pipeline of the centrifugate liquid storage tank 19 through a metering pump, an online pH meter is arranged at the rear end of a regulator adding port, the adding amount of the regulator is controlled through pH, and the final pH is set to be 7. The conductivity of the centrifugate in the centrifugate storage tank 19 is 8000-13000 mu s/cm, the water outlet of the centrifugate storage tank 21 is communicated to the water inlet of the desalting device III 20MVR evaporation device, the centrifugate is concentrated again by the desalting device III 20MVR evaporation device, the water outlet of the desalting device III 20MVR evaporation device is communicated to the water inlet of the desalting device I5 MVR evaporation device, and the circulation treatment is carried out. A concentrated water outlet of the desalting device III 20MVR evaporation device is communicated to a water inlet of the reaction tank II 12. Adding medicine again for precipitation and then crystallizing. Because the waste water does not contain one guanidine salt, the concentration of other ions in the concentrated water reaches a saturation value after multiple times of concentration, the crystallization yield is reduced, and the conductivity of the centrifugate is increased. Therefore, after the centrifugate is repeatedly concentrated for 2 times, the centrifugate is discharged to a waste treatment unit, the centrifugate generated after multiple centrifugations is evaporated to crystals by adopting the waste heat or the flue gas 18 generated by the incinerator 17, and the crystals are sent to the incinerator 17 for incineration. The final discharge to the incinerator 17 is less than 2% of the total treatment amount of the centrifugal liquid.

Claims (10)

1. The sewage zero discharge system containing guanidine salt is characterized in that sewage containing guanidine salt to be treated is connected into a raw water tank (1), the raw water tank (1) is sequentially connected with a reaction tank I (2), a filter press (3), a special microfiltration membrane (4) and a desalting device I (5) through pipelines, the desalting device I (5) is provided with a concentrated water outlet and a desalted water outlet, the desalted water outlet of the desalting device I (5) is connected with a reverse osmosis device (6), and the concentrated water outlet of the desalting device I (5) is connected with a concentrated water barrel b (11); the reverse osmosis device (6) is provided with a concentrated water outlet and a desalted water outlet, the desalted water outlet of the reverse osmosis device (6) is sequentially connected with the reverse ion exchange device (7) and the clean water tank (8), and the concentrated water outlet of the reverse osmosis device (6) is sequentially connected with the electrochemical reaction device (9) for desilicification, the filtering device II (10) and the COD treatment system (24) and is connected to a pipeline between the special microfiltration membrane (4) and the desalting device I (5); the concentrated water barrel b (11) is sequentially connected with the reaction tank II (12), the filtering device I (13), the crystallization kettle (14) and the centrifuge (15) through pipelines; the crystal that centrifuge (15) separated gets into crystallization collecting vessel (16), the liquid that centrifuge separated gets into centrifugate storage tank (19), centrifugate storage tank (19) link to each other with demineralizer III (20), demineralizer III (20) have dense mouth of a river export and desalination water outlet, the pipeline between dense mouth of a river export and reaction tank II (12) and dense bucket b (11) of demineralizer III (20) links to each other, the desalination water outlet of demineralizer III (20) links to each other with the pipeline between special type micro-filtration membrane (4) and demineralizer I (5).
2. The system for zero discharge of sewage containing guanidine salt according to claim 1, wherein a concentrate tank a (21) and a desalination device II (22) are connected in sequence from the concentrate outlet side of the concentrate port of the desalination device I (5) to a pipeline between the desalination device I (5) and the concentrate tank b (11), the desalination device II (22) is provided with a concentrate port outlet and a desalted water outlet, the concentrate port outlet of the desalination device II (22) is connected with the concentrate tank b (11), and the desalted water outlet of the desalination device II (22) is connected with a pipeline between the special microfiltration membrane (4) and the desalination device I (5); and a concentrated water barrel c (23) is connected to a pipeline of the desalting device III (20) connected to a pipeline between the concentrated water barrel b (11) and the reaction tank II (12).
3. The system of claim 1, wherein the desalination device comprises one of an electrochemical desalination device, an evaporative desalination device, and a physical desalination device; the COD treatment system comprises an advanced oxidation COD treatment system or a biochemical COD treatment system.
4. The system of claim 1, wherein the conductivity of the desalted water from the desalted water outlet is 1000 μ s/cm or less, and the conductivity of the concentrated water from the concentrated water outlet is 180000-200000 μ s/cm.
5. The system for zero discharge of waste water containing guanidine salts as claimed in claim 1, wherein the liquid separated by the centrifuge is further connected to a waste disposal unit (17) through a pipeline.
6. The system for zero discharge of waste water containing guanidine salts as claimed in claim 5, wherein the waste disposal unit (17) comprises an incinerator.
7. The method of applying the sewage zero discharge system of any one of claims 1 to 6, characterized by comprising the steps of:
(1) the method comprises the steps of (1) connecting the sewage containing guanidine salt to be treated into a raw water tank (1), enabling the sewage to enter a reaction tank I (2), adding a precipitator into the reaction tank I (2) until the pH value is 11-13, and removing copper ions in the sewage, and organic matters and copper ion derivatives which are hydrolyzed or form precipitates in an alkaline environment; the sewage continuously enters a filter press (3) to remove the sediment; the outlet water of the filter press is communicated with a special microfiltration membrane, the special microfiltration membrane intercepts macromolecular organic matters in the sewage, and the sewage enters a desalting device I (5) after being added with a regulator until the pH value is 6-9;
(2) after sewage is treated by a desalting device I (5), desalted water flowing out of a desalted water outlet enters a reverse osmosis device (6), desalted water flowing out of a desalted water outlet of the reverse osmosis device (6) enters a reverse ion exchange device (7) to remove ammonia nitrogen in water, enters a clean water tank (8) to be recovered, concentrated water flowing out of a concentrated water outlet of the reverse osmosis device (6) enters an electrochemical reaction device (9) for desiliconization to remove silicon dioxide in water, is further filtered by a filtering device II (10), and flows into the desalting device I (5) for repeated desalting after COD enriched in the concentrated water is removed by a COD treatment system (24); concentrated water flowing out of a concentrated water outlet of the desalting device I (5) enters a concentrated water barrel b (11) to continuously further extract salt;
(3) Concentrated water in a concentrated water bucket b (11) flows into a reaction tank II (12), a precipitator is added into the reaction tank II (12) to remove copper ions and organic matters and copper ion derivatives which are hydrolyzed or form precipitates in an alkaline environment, the generated precipitates are removed by a filter device I (13) and then enter a crystallization kettle (14), the precipitates are frozen and crystallized at the temperature of 0 to-5 ℃, mixed liquid after crystallization is separated by a centrifugal machine (15), the crystals are collected into a crystal collection bucket (16), the crystals collected by the crystal collection bucket (16) are guanidine salt, and the centrifugate is added with a regulator to adjust the pH value to be neutral and then enters a centrifugate storage tank (19);
(4) the liquid in the centrifugate storage tank (19) further flows into a desalting device III (20), after the liquid is treated by the desalting device, the effluent desalted water flows into a pipeline between a special micro-filtration membrane (4) and a desalting device I (5) for repeated desalting, and the effluent concentrated water after the liquid is treated by the desalting device III (20) flows into a pipeline between a concentrated water bucket b (11) and a reaction tank II (12) for repeated salt extraction;
(5) after the centrifugate flowing out of the centrifuge (15) is repeatedly concentrated and crystallized for 2-3 times in the system, the centrifugate is treated by a waste treatment unit (17), the generated waste heat evaporates the centrifugate to be crystallized, and the crystals enter the waste treatment unit (17) for treatment.
8. The use of the method according to claim 7, wherein the precipitant is an alkaline substance including sodium hydroxide, potassium hydroxide, calcium oxide; the regulator is an acidic substance and comprises hydrochloric acid, sulfuric acid and nitric acid; the macromolecular organic matter comprises fatty acid ester.
9. The application method of the claim 7, characterized in that, the crystallization collected by the crystallization collecting barrel (16) is mainly guanidine nitrate and potassium perchlorate, the crystallization can be recovered as raw material for production, or enters into an incinerator for incineration, and the waste heat or smoke generated after incineration can be used for evaporating concentrated water to crystallization.
10. The use of the method according to claim 7, wherein the concentrated water from the desalination unit in step (2) is fed into a concentrated water tank b (11) and further desalted in a desalter II (22) before further salt extraction.
CN202011556908.2A 2020-12-24 2020-12-24 Zero-discharge sewage system containing guanidine salt and application method Pending CN114671554A (en)

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Application publication date: 20220628