CN110655258A - Novel integrated treatment system and process for zero discharge of high-salinity wastewater in coal chemical industry - Google Patents
Novel integrated treatment system and process for zero discharge of high-salinity wastewater in coal chemical industry Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 88
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- 239000012528 membrane Substances 0.000 claims abstract description 50
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- 238000000926 separation method Methods 0.000 claims abstract description 40
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- 230000003197 catalytic effect Effects 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
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- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims description 5
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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
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/60—Silicon compounds
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- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C02F2101/30—Organic compounds
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
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Abstract
The invention discloses a novel integrated treatment system and a novel integrated treatment process for zero discharge of high-salinity wastewater in coal chemical industry. The novel integrated treatment system and the novel integrated treatment process for zero discharge of the high-salinity wastewater in the coal chemical industry greatly improve the stability, economy and rationality of the operation of the system, the high-salinity wastewater at the tail end of the coal chemical industry treated by the integrated treatment process is finally and completely reused in a circulating water system, the reuse rate reaches more than 95%, and sodium sulfate and sodium chloride meeting the industrial standards are obtained by adopting a coupled salt separation process of membrane salt separation-thermal salt separation, so that the yield of miscellaneous salts in the system is below 15% of the total salt content, the external discharge of inorganic salts is reduced, the environment is protected, the technical application and popularization prospect is wide, and the social and economic benefits are very remarkable.
Description
Technical Field
The invention relates to the technical field of high-salinity wastewater treatment in the coal chemical industry, in particular to a novel integrated treatment system and process for zero discharge of high-salinity wastewater in the coal chemical industry.
Background
The basic situation of resources in China is 'oil shortage, gas shortage and relative coal enrichment', so that coal becomes one of the most important energy and chemical raw materials in China, coal is used as a raw material, the implementation of clean and efficient utilization of the coal resources has great significance for maintaining the rapid growth of economy in China and guaranteeing the energy safety of China, large-scale engineering demonstration taking coal liquefaction, coal gas production, coal olefin production, coal-based poly-generation, comprehensive utilization of coal oil and gas resources and the like as main directions is actively promoted on the basis of the existing deep coal processing project, meanwhile, specific requirements for ecological environment protection are also put forward in planning, the matched environment-friendly industry is required to be developed sufficiently, the water resource quantity of the coal chemical industry is large, the waste water production quantity is also large, according to the current level, the oil consumption of natural gas per cubic meter coal is 9.5 tons, the water production of coal is 10 tons per ton, and the waste water of the coal chemical industry has the advantages of high operation cost, high cost and the coal chemical industry is capable of ensuring the comprehensive, The invention provides a technology reliable, economical and stable coal chemical industry high-salt wastewater treatment process for treating high-salt wastewater by effectively combining various treatment units, so that all high-salt wastewater is completely recycled, sodium sulfate and sodium chloride in water are subjected to quality-grading crystallization to obtain salt meeting the industrial standard, and finally the salt content of the system is controlled below 20 percent, the treatment cost of the miscellaneous salt is reduced.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a novel integrated treatment system and a novel integrated treatment process for zero discharge of high-salinity wastewater in coal chemical industry, which can recycle all the produced water of the wastewater after treatment for a circulating cooling water system, and sodium chloride and sodium sulfate obtained by quality-based crystallization respectively meet the industrial recycling requirements, and the miscellaneous salt rate of the system is controlled below 15% of the total salt content, so that the influence of the high-salinity wastewater at the tail end of the coal chemical industry on the external environment is reduced.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: the utility model provides a novel integrated processing system of high salt waste water zero release of coal industry, includes that the desiliconization unit that removes, compound organic matter desorption unit, remove turbid and degree of depth softening unit, membrane decrement and concentration unit, salt nitre separation unit and evaporation crystallization unit.
Preferably, the hardness removing and silicon removing unit adopts a composite silicon removing and hardness removing medicament and is matched with a flocculating agent and a coagulant aid to carry out hardness removing and silicon removing treatment on the wastewater, the hardness can be effectively controlled below 150mg/L, the silicon content is controlled below 5mg/L, inhibitor ions of high-grade oxidation such as H +, HCO 3-and the like are eliminated after the treatment section, and the alkaline environment of unit effluent also provides an optimal operating environment for high-grade oxidation.
Preferably, the composite organic matter removal unit is used for removing organic matters in wastewater by combining a UV photolysis technology and an ozone catalytic oxidation technology in the same reactor, and because the high-salt wastewater has high content of anions such as chloride ions and sulfate ions which have inhibition effect on ozone catalytic oxidation, a NCUO technology which is coupled by the UV photolysis technology and the ozone catalytic oxidation technology is adopted to generate a large amount of HO- (hydroxyl free radicals), H + and eaq- (hydrated electrons), O in water under the irradiation of ultraviolet rays and the dual action of an ozone-catalyst3And the active intermediates and the organic matters in the water undergo nucleophilic, electrophilic and electron transfer reactions to cause the degradation and mineralization of the organic matters in the water and reduce the TOC concentration of the organic matters, thereby finally achieving the effect of degrading the TOC in the water.
Preferably, the turbidity removal and deep softening unit is used for filtering the wastewater by mechanical filtration in a slightly alkaline environment with the pH value of 7.5-8.3 and the concentration of 0.8-1.5mol/L sodium hydroxide, and then performing ion softening treatment, wherein most of calcium and magnesium ions and silicon in the wastewater after the silicon is removed by chemical precipitation are precipitated in a precipitate manner, and part of fine particles cannot be removed by gravity precipitation, so that the wastewater is filtered by the mechanical filtration in a slightly alkaline environment, and the pollution and blockage of suspended matters, calcium and magnesium ions and the like to the membrane reduction unit are further reduced.
Preferably, the membrane reduction and concentration unit is a membrane reduction unit which is arranged for reducing the investment of a subsequent salt and nitrate separation treatment unit after pretreatment, and a wastewater physicochemical concentration device at a monovalent side and a thermal wastewater concentration device at a divalent side after salt and nitrate separation, respectively, because the investment of a common reverse osmosis membrane is much lower than that of a salt separation nanofiltration membrane, the pretreated wastewater is firstly subjected to primary reduction treatment by adopting a reverse osmosis membrane, and the recovery rate is determined according to the TDS of the incoming water; the hardness, organic matters and the like of wastewater on the monovalent side are little after salt separation by salt and nitrate, so that concentration treatment is carried out by adopting an electrodialysis or high-pressure reverse osmosis membrane, the water salt content of an evaporative crystallization system is ensured to be more than 100000mg/L, and the investment and operation cost of the evaporative crystallization system are reduced; the salt content of the waste water on the divalent side after salt separation by salt and nitrate is generally controlled to be more than 50000mg/L, if the waste water directly enters a subsequent freezing and crystallizing unit, the yield of sodium sulfate is lower, and the concentration cannot be concentrated by adopting a conventional physical and chemical method because the concentration is higher, so that the integrated process adopts a thermal method concentration device, and the concentration multiple is controlled according to the saturated concentration of a water-sodium chloride-sodium sulfate three-phase system.
Preferably, the salt and nitrate separation unit is a reverse osmosis membrane with high divalent ion rejection rate and low monovalent ion rejection rate, the primary separation of sodium sulfate and sodium chloride is carried out by utilizing different rejection rates of monovalent ions and divalent ions through a membrane, and the core process of the integrated process is a coupling salt separation process of membrane salt separation and thermal salt separation.
Preferably, the evaporative crystallization unit is provided with three sets of evaporative crystallization devices, namely a sodium chloride evaporative crystallization device, a sodium sulfate freezing, crystallizing, evaporative and dehydrating device and a sodium sulfate crystallization mother liquor evaporative crystallization unit, and because the nanofiltration monovalent side wastewater has good water quality and basically does not contain pollutants such as COD (chemical oxygen demand), the purity of sodium chloride obtained by subjecting part of wastewater to evaporative crystallization treatment is high and can reach more than 99.5%; freezing and crystallizing the waste water at the divalent side (-5-0 ℃) to obtain mirabilite, and adding water into dilute salt to evaporate and dehydrate to obtain anhydrous sodium sulfate with the concentration of more than 99 percent; because the freezing crystallization mother liquor contains a certain amount of organic matters and the like, an evaporation crystallization unit is independently arranged to obtain sodium chloride with the purity of more than 98.5 percent, and finally the centrifugal mother liquor is dried by a drying device to obtain miscellaneous salt; and meanwhile, the sodium chloride centrifugal mother liquor is refluxed to a freezing and crystallizing device, so that the concentration of the sodium sulfate on the divalent side is increased, the salt yield of the sodium sulfate is improved, and the yield of miscellaneous salts is reduced.
The invention also discloses a novel integrated treatment process for zero discharge of the high-salinity wastewater in the coal chemical industry, which specifically comprises the following steps:
s1, after the water quality and the water quantity of the wastewater are adjusted by a homogenizing adjusting tank, the wastewater is lifted by a pump to enter a high-efficiency flocculation sedimentation tank, calcium, magnesium ions, silicon dioxide and the like in the wastewater are changed into calcium carbonate, magnesium hydroxide, silicon dioxide colloid and other substances by adding a silicon removal agent, a fluorine removal agent, alkali and sodium carbonate, and the precipitates are removed by adding a flocculating agent and a coagulant aid, so that the scaling and fouling of a subsequent treatment unit are reduced, the fluorine content in the water is reduced, the corrosion to equipment is reduced, and the pH values controlled by the silicon removal and the hardness removal are different;
s2, because the COD content of the incoming water is high, the degradation of organic matters in the incoming water is carried out to avoid the pollution and blockage of the COD to a membrane system and the purity of the obtained salt, the salt content of the waste water is high, and the removal rate of the organic matters is greatly reduced because a single conventional oxidation technology is influenced by chloride ions, sulfate ions and the like in the water. The unit adopts UV photolysis technology of a composite organic matter removing unit and ozoneThe NCUO technology coupled with catalytic oxidation technology generates a large amount of HO- (hydroxyl radical), H + and eaq- (hydrated electron) and O in water under the irradiation of ultraviolet rays and the action of an ozone-catalyst3The active intermediates and the organic matters in the water generate nucleophilic, electrophilic and electron transfer reactions to cause the degradation and mineralization of the organic matters in the water and reduce the TOC concentration of the organic matters, and finally the effect of degrading the TOC in the water is achieved;
s3, treating the water after silicon removal and softening and organic matter degradation by adopting a combined process of mechanical filtration and ion softening, so that the water can meet the water inlet requirement of a membrane concentration system, and the stable operation of the system is ensured. In order to reduce the investment cost of a system, pretreated high-salt water is subjected to primary concentration treatment by reverse osmosis, then salt separation is carried out by a salt-nitrate separation membrane to obtain two kinds of wastewater mainly containing sodium chloride and sodium sulfate, the obtained wastewater mainly containing sodium chloride is subjected to membrane separation, the obtained wastewater mainly containing sodium chloride is subjected to secondary concentration by high-pressure reverse osmosis, the salt content is concentrated to 96500mg/L, then evaporation treatment is carried out by MED triple effect evaporation to obtain sodium chloride with purity of more than 99.5%, the third effect evaporation temperature is controlled to be 60-70 ℃, the concentration of sodium sulfate in centrifugal mother liquor is controlled to be 4.5%, and then the sodium chloride is discharged into a freezing and crystallizing unit;
s4, obtaining wastewater mainly containing sodium sulfate through a salt-nitrate separation membrane, wherein the salt content of the wastewater is 74000mg/L, if the sodium sulfate concentration is low, the yield of the sodium sulfate is too low, therefore, the second concentration treatment is considered, but the conventional membrane cannot be concentrated, so that the concentration is carried out by a thermal method, then according to a curve diagram of three systems of sodium chloride, sodium sulfate and water at a certain temperature, the concentration multiple is controlled to be 3-3.2 times, the sodium sulfate enters a freezing and crystallizing device, the crystallization temperature is controlled to be 0-2 ℃, the obtained sodium sulfate decahydrate is evaporated and dehydrated to obtain anhydrous sodium sulfate with the purity of more than 99%, the centrifugal mother liquor enters a triple-effect evaporator to obtain sodium chloride with the purity of more than 98.5%, and finally the centrifugal mother liquor is dried by adopting spray drying, so that the salt content of the system is controlled to be less than 15% of the salt content of the total system.
(III) advantageous effects
The invention provides a novel integrated treatment system and a novel integrated treatment process for zero discharge of high-salinity wastewater in coal chemical industry. Compared with the prior art, the method has the following beneficial effects:
(1) the novel integrated treatment system and the novel integrated treatment process for zero discharge of the high-salinity wastewater in the coal chemical industry greatly improve the stability, economy and rationality of the operation of the system through effective combination and improvement optimization of various treatment processes, well achieve the aim of green energy conservation, finally and completely recycle the high-salinity wastewater at the tail end of the coal chemical industry after treatment by the integrated treatment process to a circulating water system, wherein the recycling rate is over 95 percent, and sodium sulfate and sodium chloride meeting the industrial standards are obtained by adopting a coupling salt separation process of 'membrane salt separation-thermal salt separation', so that the impurity salt yield of the system is below 15 percent of the total salt content, the external discharge of inorganic salt is reduced, the environment is protected, the technical application and popularization prospect is wide, and the social and economic benefits are very obvious.
(2) The novel integrated treatment system and the novel integrated treatment process for zero discharge of the high-salinity wastewater in the coal chemical industry can reuse more than 95% of wastewater as fresh water for a production system after treatment by the integrated treatment process, reduce the consumption of fresh water by enterprises, and save water resources.
(3) The novel integrated treatment system and the novel integrated treatment process for zero discharge of the high-salinity wastewater in the coal chemical industry are obtained according to the type and the purity of salt after treatment by the integrated treatment process, and the resource utilization of sodium sulfate with the concentration of more than 99%, sodium chloride with the concentration of more than 99.5% and sodium chloride with the concentration of more than 98.5% is realized according to the purity classification of the salt, so that the final miscellaneous salt yield of the system is controlled to be less than 15% of the total salt content, and the treatment cost of the miscellaneous salt as hazardous waste is reduced.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a flow chart of the processing procedure used in the application case engineering of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-2, the embodiment of the present invention provides three technical solutions: the utility model provides a novel integrated processing system of high salt waste water zero release of coal industry, is including removing hard desiliconization unit, compound organic matter desorption unit, remove turbid and degree of depth softening unit, membrane decrement and concentration unit, salt nitre separating element and evaporation crystallization unit, adopts compound desiliconization to remove hard medicament and cooperation use flocculating agent and coagulant aid and carry out the processing of removing hard desiliconization of waste water in removing hard desiliconization unit, can effectually control the hardness below 150mg/L, and the silicon content control is below 5 mg/L. Simultaneously, after the treatment process, inhibitor ions of H +, HCO 3-and other advanced oxidation are eliminated, the alkaline environment of unit effluent also provides the best operating environment for advanced oxidation, a composite organic matter removing unit combines a UV photolysis technology and an ozone catalytic oxidation technology in the same reactor for removing organic matters in wastewater, a turbidity removing and deep softening unit filters the wastewater by mechanical filtration under the pH of 7.6 slightly alkaline environment with the concentration of 1mol/L sodium hydroxide and then carries out ion softening treatment, a membrane reduction and concentration unit is respectively a membrane reduction unit which is arranged for reducing the investment of a subsequent salt and nitrate separation treatment unit after pretreatment, a wastewater physicochemical concentration device on a monovalent side and a wastewater thermal concentration device on the divalent side after salt and nitrate separation, a salt and nitrate separation unit adopts a reverse osmosis membrane with high divalent ion rate and low monovalent ion rate, the membrane is utilized to carry out primary separation of sodium sulfate and sodium chloride on univalent ions and bivalent ions with different retention rates, and the evaporative crystallization unit is provided with three sets of evaporative crystallization devices which are respectively a sodium chloride evaporative crystallization device, a sodium sulfate freezing crystallization evaporative dehydration device and a sodium sulfate crystallization mother liquor evaporative crystallization unit.
The invention also discloses a novel integrated treatment process for zero discharge of the high-salinity wastewater in the coal chemical industry, which specifically comprises the following embodiments:
example 1
S1, after the water quality and the water quantity of the wastewater are adjusted by a homogenizing adjusting tank, the wastewater is lifted by a pump to enter a high-efficiency flocculation sedimentation tank, calcium, magnesium ions, silicon dioxide and the like in the wastewater are changed into calcium carbonate, magnesium hydroxide, silicon dioxide colloid and other substances by adding a silicon removal agent, a fluorine removal agent, alkali and sodium carbonate, and the precipitates are removed by adding a flocculating agent and a coagulant aid, so that the scaling and fouling of a subsequent treatment unit are reduced, the fluorine content in the water is reduced, the corrosion to equipment is reduced, and the pH values controlled by the silicon removal and the hardness removal are different;
s2, because the COD content of the incoming water is high, the degradation of organic matters in the incoming water is carried out to avoid the pollution and blockage of the COD to a membrane system and the purity of the obtained salt, the salt content of the waste water is high, and the removal rate of the organic matters is greatly reduced because a single conventional oxidation technology is influenced by chloride ions, sulfate ions and the like in the water. The unit adopts the NCUO technology that the UV photolysis technology of the composite organic matter removing unit is coupled with the ozone catalytic oxidation technology, and generates a large amount of HO- (hydroxyl free radical), H + and eaq- (hydrated electron) and O in water under the irradiation of ultraviolet rays and the action of an ozone-catalyst3The active intermediates and the organic matters in the water generate nucleophilic, electrophilic and electron transfer reactions to cause the degradation and mineralization of the organic matters in the water and reduce the TOC concentration of the organic matters, and finally the effect of degrading the TOC in the water is achieved;
s3, treating water subjected to silicon removal softening and organic matter degradation by adopting a combined process of mechanical filtration and ion softening to enable the water to meet the requirement of water inlet of a membrane concentration system and ensure stable operation of the system, in order to reduce investment cost of the system, carrying out primary concentration treatment on pretreated high-salt water by utilizing reverse osmosis, then carrying out membrane separation on salt by utilizing a salt-nitrate separation membrane to obtain two types of wastewater mainly comprising sodium chloride and sodium sulfate, concentrating the salt content to 96500mg/L by adopting MED triple effect evaporation to carry out evaporation treatment to obtain 99.5% purity sodium chloride, controlling the triple effect evaporation temperature to 65 ℃, controlling the concentration of sodium sulfate in centrifugal mother liquor to 4.5%, and then discharging the sodium chloride into a freezing and crystallizing unit;
s4, the salt content of wastewater mainly containing sodium sulfate obtained by a salt-nitrate separation membrane is 74000mg/L, if the wastewater directly enters a freezing crystallization unit, because the concentration of the sodium sulfate is low and the yield of the sodium sulfate is too low, secondary concentration treatment is considered, but the conventional membrane cannot be concentrated, thermal concentration is adopted, then the concentration multiple is controlled to be 3.1 times according to a curve diagram of three systems of sodium chloride, sodium sulfate and water at a certain temperature, then the wastewater enters a freezing crystallization device, the crystallization temperature is controlled to be 1 ℃, the obtained sodium sulfate decahydrate is evaporated and dehydrated to obtain anhydrous sodium sulfate with the purity of 99.6%, the centrifugal mother liquor enters a triple-effect evaporator to obtain sodium chloride with the purity of 98.5%, and finally the centrifugal mother liquor is dried by spray drying, so that the salt content of the system is controlled to be 13% of the salt content of the total system.
Example 2
S1, after the water quality and the water quantity of the wastewater are adjusted by a homogenizing adjusting tank, the wastewater is lifted by a pump to enter a high-efficiency flocculation sedimentation tank, calcium, magnesium ions, silicon dioxide and the like in the wastewater are changed into calcium carbonate, magnesium hydroxide, silicon dioxide colloid and other substances by adding a silicon removal agent, a fluorine removal agent, alkali and sodium carbonate, and the precipitates are removed by adding a flocculating agent and a coagulant aid, so that the scaling and fouling of a subsequent treatment unit are reduced, the fluorine content in the water is reduced, the corrosion to equipment is reduced, and the pH values controlled by the silicon removal and the hardness removal are different;
s2, because the COD content of the incoming water is high, the degradation of organic matters in the incoming water is carried out to avoid the pollution and blockage of the COD to a membrane system and the purity of the obtained salt, the salt content of the waste water is high, and the removal rate of the organic matters is greatly reduced because a single conventional oxidation technology is influenced by chloride ions, sulfate ions and the like in the water. The unit adopts the NCUO technology that the UV photolysis technology of the composite organic matter removing unit is coupled with the ozone catalytic oxidation technology, and generates a large amount of HO- (hydroxyl free radical), H + and eaq- (hydrated electron) and O in water under the irradiation of ultraviolet rays and the action of an ozone-catalyst3Active body, these active intermediates and organic matter in water produce nucleophilic, electrophilic and electron transfer reaction to degrade and mineralize organic matter in waterAnd the TOC concentration is reduced, and finally the effect of degrading TOC in water is achieved;
s3, treating water subjected to silicon removal softening and organic matter degradation by adopting a combined process of mechanical filtration and ion softening to enable the water to meet the requirement of water inlet of a membrane concentration system and ensure stable operation of the system, in order to reduce investment cost of the system, carrying out primary concentration treatment on pretreated high-salt water by utilizing reverse osmosis, then carrying out membrane separation on salt by utilizing a salt-nitrate separation membrane to obtain two types of wastewater mainly comprising sodium chloride and sodium sulfate, concentrating the salt content to 96500mg/L by adopting MED triple effect evaporation to carry out evaporation treatment to obtain 99.6% purity sodium chloride, controlling the triple effect evaporation temperature to be 60 ℃, controlling the concentration of sodium sulfate in centrifugal mother liquor to be 4.5%, and then discharging the sodium chloride into a freezing and crystallizing unit;
s4, the salt content of wastewater mainly containing sodium sulfate obtained by a salt-nitrate separation membrane is 74000mg/L, if the wastewater directly enters a freezing crystallization unit, the concentration multiple is controlled at 3 times according to a curve diagram of three systems of sodium chloride, sodium sulfate and water at a certain temperature, then the wastewater enters a freezing crystallization device, the crystallization temperature is controlled at 0 ℃, the obtained sodium sulfate decahydrate is evaporated and dehydrated to obtain anhydrous sodium sulfate with the purity of 99.3%, the centrifugal mother liquor enters a triple-effect evaporator to obtain sodium chloride with the purity of 98.6%, and finally the centrifugal mother liquor is dried by spray drying, so that the salt content of the system is controlled at 15% of the salt content of the total system.
Example 3
S1, after the water quality and the water quantity of the wastewater are adjusted by a homogenizing adjusting tank, the wastewater is lifted by a pump to enter a high-efficiency flocculation sedimentation tank, calcium, magnesium ions, silicon dioxide and the like in the wastewater are changed into calcium carbonate, magnesium hydroxide, silicon dioxide colloid and other substances by adding a silicon removal agent, a fluorine removal agent, alkali and sodium carbonate, and the precipitates are removed by adding a flocculating agent and a coagulant aid, so that the scaling and fouling of a subsequent treatment unit are reduced, the fluorine content in the water is reduced, the corrosion to equipment is reduced, and the pH values controlled by the silicon removal and the hardness removal are different;
s2, because the COD content of the incoming water is high, the degradation of organic matters in the incoming water is carried out to avoid the pollution and blockage of the COD to a membrane system and the purity of the obtained salt, the salt content of the waste water is high, and the removal rate of the organic matters is greatly reduced because a single conventional oxidation technology is influenced by chloride ions, sulfate ions and the like in the water. The unit adopts the NCUO technology that the UV photolysis technology of the composite organic matter removing unit is coupled with the ozone catalytic oxidation technology, and generates a large amount of HO- (hydroxyl free radical), H + and eaq- (hydrated electron) and O in water under the irradiation of ultraviolet rays and the action of an ozone-catalyst3The active intermediates and the organic matters in the water generate nucleophilic, electrophilic and electron transfer reactions to cause the degradation and mineralization of the organic matters in the water and reduce the TOC concentration of the organic matters, and finally the effect of degrading the TOC in the water is achieved;
s3, treating water subjected to silicon removal softening and organic matter degradation by adopting a combined process of mechanical filtration and ion softening to enable the water to meet the requirement of water inlet of a membrane concentration system and ensure stable operation of the system, in order to reduce investment cost of the system, carrying out primary concentration treatment on pretreated high-salt water by utilizing reverse osmosis, then carrying out membrane separation on salt by utilizing a salt-nitrate separation membrane to obtain two types of wastewater mainly comprising sodium chloride and sodium sulfate, concentrating the salt content to 96500mg/L by adopting MED triple effect evaporation to carry out evaporation treatment to obtain 99.7% purity sodium chloride, controlling the triple effect evaporation temperature to be 70 ℃, controlling the concentration of sodium sulfate in centrifugal mother liquor to be 4.5%, and then discharging the sodium chloride into a freezing and crystallizing unit;
s4, the salt content of wastewater mainly containing sodium sulfate obtained by a salt-nitrate separation membrane is 74000mg/L, if the wastewater directly enters a freezing crystallization unit, because the concentration of the sodium sulfate is low and the yield of the sodium sulfate is too low, secondary concentration treatment is considered, but the conventional membrane cannot be concentrated, thermal concentration is adopted, then the concentration multiple is controlled to be 3.2 times according to a curve diagram of three systems of sodium chloride, sodium sulfate and water at a certain temperature, then the wastewater enters a freezing crystallization device, the crystallization temperature is controlled to be 2 ℃, the obtained sodium sulfate decahydrate is evaporated and dehydrated to obtain anhydrous sodium sulfate with the purity of 99.8%, the centrifugal mother liquor enters a triple-effect evaporator to obtain sodium chloride with the purity of 98.7%, and finally the centrifugal mother liquor is dried by spray drying, so that the yield of miscellaneous salts in the system is controlled to be 12% of the salt content in the total system.
Application case
The integrated process uses coal to produce gas of 100m3The application test is carried out by taking/h high-salinity wastewater as an example.
TABLE 1 water quality of engineering
| Detecting items | Unit of | Quality of system inlet water |
| pH value | — | 6～9 |
| COD | mg/L | ≤150 |
| TDS | mg/L | ≤16000 |
| Bicarbonate radical | mg/L | ≤1100 |
| Calcium ion | mg/L | ≤2500 |
| Magnesium ion | mg/L | ≤500 |
| Chloride ion | mg/L | ≤6500 |
| Sulfate ion | mg/L | ≤3000 |
| Silicon dioxide | mg/L | ≤20 |
As shown in table 1, by adopting the integrated process of embodiments 1 to 3 of the present invention, the effluent can completely meet the water quality requirement of the circulating water replenishing, the water recovery rate of the system can reach more than 95%, the produced salt meets the new standards of coal chemical industry byproduct industrial sodium sulfate (T/CCT001-2019) and coal chemical industry byproduct industrial sodium chloride (T/CCT002-2019), the final mixed salt yield of the system is controlled below 15% of the total salt content, and the operation of the device is completely stable, so the integrated process is feasible.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The utility model provides a novel integrated processing system of high salt waste water zero release of coal industry which characterized in that: comprises a hard-removing and silicon-removing unit, a composite organic matter removing unit, a turbidity-removing and deep-softening unit, a membrane reduction and concentration unit, a salt-nitrate separation unit and an evaporation crystallization unit.
2. The novel integrated treatment system for zero discharge of high-salinity wastewater in coal chemical industry according to claim 1, characterized in that: in the hardness and silicon removal unit, a composite silicon and silicon removal agent is adopted and matched with a flocculating agent and a coagulant aid to carry out hardness and silicon removal treatment on the wastewater.
3. The novel integrated treatment system for zero discharge of high-salinity wastewater in coal chemical industry according to claim 1, characterized in that: the composite organic matter removing unit is used for removing organic matters in wastewater by combining a UV photolysis technology and an ozone catalytic oxidation technology in the same reactor.
4. The novel integrated treatment system for zero discharge of high-salinity wastewater in coal chemical industry according to claim 1, characterized in that: the turbidity removal and deep softening unit is used for filtering the wastewater by mechanical filtration in a slightly alkaline environment with the concentration of 0.8-1.5mol/L sodium hydroxide and the pH value of 7.5-8.3, and then performing ion softening treatment.
5. The novel integrated treatment system for zero discharge of high-salinity wastewater in coal chemical industry according to claim 1, characterized in that: the membrane reduction and concentration unit is a membrane reduction unit which is arranged for reducing the investment of a subsequent salt-nitrate separation treatment unit after pretreatment, and a wastewater physicochemical concentration device at a monovalent side and a wastewater thermal concentration device at a divalent side after salt-nitrate separation.
6. The novel integrated treatment system for zero discharge of high-salinity wastewater in coal chemical industry according to claim 1, characterized in that: the salt and nitrate separation unit adopts a reverse osmosis membrane with high divalent ion rejection rate and low monovalent ion rejection rate, and utilizes the membrane to carry out primary separation of sodium sulfate and sodium chloride on monovalent ions and divalent ions with different rejection rates.
7. The novel integrated treatment system for zero discharge of high-salinity wastewater in coal chemical industry according to claim 1, characterized in that: the evaporative crystallization unit is provided with three sets of evaporative crystallization devices, namely a sodium chloride evaporative crystallization device, a sodium sulfate freezing crystallization evaporative dehydration device and a sodium sulfate crystallization mother liquor evaporative crystallization unit.
8. The novel integrated treatment process of the high-salinity wastewater in the coal chemical industry based on the claim 1 is characterized in that: the method specifically comprises the following steps:
s1, after the water quality and the water quantity of the wastewater are adjusted by a homogenizing adjusting tank, the wastewater is lifted by a pump to enter a high-efficiency flocculation sedimentation tank, calcium, magnesium ions, silicon dioxide and the like in the wastewater are changed into calcium carbonate, magnesium hydroxide and silicon dioxide colloidal substances by adding a silicon removal agent, a fluorine removal agent, alkali and sodium carbonate, and the precipitates are removed by adding a flocculating agent and a coagulant aid;
s2, adopting the NCUO technology coupling the UV photolysis technology of the composite organic matter removing unit and the ozone catalytic oxidation technology, generating a large amount of HO-, H + and eaq-and O in water under the irradiation of ultraviolet rays and the action of an ozone-catalyst3Active body, these active intermediates and organic matter in water produce nucleophilic, electrophilic and electron transfer reaction to produce degradation of organic matter in waterAnd mineralization and reduction of its TOC concentration;
s3, treating water subjected to silicon removal softening and organic matter degradation by adopting a combined process of mechanical filtration and ion softening to enable the water to meet the requirement of water inlet of a membrane concentration system, carrying out primary concentration treatment on pretreated high-salt water by utilizing reverse osmosis, carrying out membrane separation on salt by utilizing a salt-nitrate separation membrane to obtain two kinds of wastewater mainly comprising sodium chloride and sodium sulfate, concentrating the wastewater mainly comprising sodium chloride by adopting high-pressure reverse osmosis for the next time because the TDS of the wastewater mainly comprising sodium chloride is 26000mg/L, concentrating the salt content to 96500mg/L, carrying out evaporation treatment by utilizing MED triple effect evaporation to obtain sodium chloride with the purity of more than 99.5%, controlling the triple effect evaporation temperature to be 60-70 ℃, controlling the concentration of sodium sulfate in centrifugal mother liquor to be 4.5%, and then discharging the sodium chloride into a freezing and crystallizing unit;
s4, controlling the salt content of wastewater mainly containing sodium sulfate obtained by a salt-nitrate separation membrane to be 74000mg/L, controlling the concentration multiple to be 3-3.2 times according to a curve diagram of three systems of sodium chloride, sodium sulfate and water at a certain temperature, then entering a freezing and crystallizing device, controlling the crystallization temperature to be 0-2 ℃, evaporating and dehydrating the obtained sodium sulfate decahydrate to obtain anhydrous sodium sulfate with the purity of more than 99%, entering a centrifugal mother liquor into a triple-effect evaporator to obtain sodium chloride with the purity of more than 98.5%, and finally drying the centrifugal mother liquor by spray drying to control the salt content of the system to be less than 15% of the salt content of the total system.
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| WO2023173927A1 (en) * | 2022-03-14 | 2023-09-21 | 天津正达科技有限责任公司 | Circulating cooling water zero pollution discharge treatment system and method |
| CN115504615A (en) * | 2022-10-20 | 2022-12-23 | 倍杰特集团股份有限公司 | Zero-discharge system for salt conversion of high-salt-content wastewater |
| CN115504615B (en) * | 2022-10-20 | 2023-06-27 | 倍杰特集团股份有限公司 | Salt conversion zero-emission system for high-salt-content wastewater |
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Application publication date: 20200107 |