CN109437243B - High-salt COD wastewater recovery process - Google Patents
High-salt COD wastewater recovery process Download PDFInfo
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- CN109437243B CN109437243B CN201811249104.0A CN201811249104A CN109437243B CN 109437243 B CN109437243 B CN 109437243B CN 201811249104 A CN201811249104 A CN 201811249104A CN 109437243 B CN109437243 B CN 109437243B
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- 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
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- 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
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- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
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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
- 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
- C02F5/06—Softening water by precipitation of the hardness using calcium compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/46—Solid fuels essentially based on materials of non-mineral origin on sewage, house, or town refuse
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
A high salt COD waste water recovery process, regard waste water containing sodium chloride, sulfate and calcium ion, magnesium ion, nitrate radical, COD plasma as raw materials, evaporate and concentrate this waste water under the condition of controlling its concentration with the antiscaling agent to get fresh water and nearly saturated solution; the nearly saturated solution is clarified and subjected to solid-liquid separation to obtain calcium sulfate precipitate and sulfate brine clarified liquid; separating the brine clarified liquid by salt and sulfate separation process to obtain sodium chloride, sulfate, fresh water and salt-making mother liquor with high COD content; spraying the salt-making mother liquor at high temperature to evaporate to obtain mixed salt containing COD, sodium chloride, sulfate, nitrate and the like; separating COD in the mixed miscellaneous salt from inorganic salts such as sodium chloride, sulfate, nitrate and the like by using a vertical classifier by adopting circulating filtrate of the near salt-making mother liquor component; the inorganic salts such as sodium chloride, sulfate, nitrate and the like obtained at the bottom are dissolved by fresh water and then are comprehensively utilized, the COD filtering cake in the overflow liquid is used as fuel, and the filtrate is recycled.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a high-salt COD (chemical oxygen demand) wastewater recovery process.
Background
COD is the chemical oxygen demand, which is the amount of oxidant consumed when a water sample is treated with a certain strong oxidant under a certain condition, and is an index representing the amount of reducing substances in the water. The reducing substances in the water include various organic substances, nitrites, sulfides, ferrous salts and the like. Therefore, the Chemical Oxygen Demand (COD) is often used as an index for measuring the content of the reducing substances in the water. Known processes for producing inorganic salt from high-salt COD wastewater include: 1) after complex pretreatment, the wastewater is concentrated by a membrane method (reverse osmosis, electrodialysis and other modes), and inorganic salt is separated by evaporation and crystallization, but the salt preparation mother liquor has high COD and large amount of miscellaneous salt; 2) after complex pretreatment, the wastewater is concentrated by an evaporation method (distillation, flash evaporation and other modes), and inorganic salt is separated by evaporation and crystallization, but the salt preparation mother liquor has high COD and large amount of miscellaneous salt. The processes all have the problems of large pretreatment water amount, high treatment requirement, large device, high COD content of salt making mother liquor, large salt impurity, difficult utilization, higher production cost, longer process flow and the like.
Disclosure of Invention
The invention aims to provide a high-salinity COD wastewater recovery process which has the advantages of strong raw material adaptability, no pretreatment process of wastewater, less salt impurity amount, recyclability, separable utilization of reductive substances corresponding to COD, lower production cost, shorter process flow, zero discharge of wastewater and waste impurities, and environmental protection and greenness of the process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-salt COD wastewater recovery process comprises the following steps:
A. taking waste water containing sodium chloride, calcium sulfate, magnesium sulfate, sodium nitrate and COD corresponding to reducing substances as raw materials, and evaporating and concentrating the waste water by using sand or indissolvable calcium sulfate as an antiscaling agent to obtain fresh water and a nearly saturated solution; clarifying the near-saturated solution, carrying out solid-liquid separation to obtain a calcium sulfate precipitate and a brine clarified solution;
B. evaporating and crystallizing the brine clarified liquid to obtain sodium chloride, fresh water and a first salt-making mother liquid;
C. carrying out spray high-temperature evaporation on the first salt making mother liquor to obtain mixed salt containing the reducing substances corresponding to COD, sodium chloride, magnesium sulfate and sodium nitrate;
D. separating the reducing substances corresponding to COD in the mixed miscellaneous salt from sodium chloride, sodium sulfate and sodium nitrate by using a vertical classifier by adopting a circulating filtrate close to the components of the first salt making mother liquor; the sodium chloride, sodium sulfate and sodium nitrate obtained at the bottom are dissolved by fresh water and then are comprehensively utilized, the filter cake of COD in the overflow liquid corresponding to the reducing substances is used as fuel, and the filtrate is recycled.
Further, in the step B, the first salt making mother liquor is frozen at a low temperature and subjected to solid-liquid separation to obtain magnesium sulfate heptahydrate and magnesium making mother liquor; carrying out evaporative crystallization and solid-liquid separation on the magnesium preparation mother liquor to obtain sodium chloride, fresh water and a second salt preparation mother liquor; and carrying out spray high-temperature evaporation on the second salt preparation mother liquor to obtain the mixed salt containing the reducing substance corresponding to COD, sodium chloride, magnesium sulfate and sodium nitrate.
Furthermore, the NaCl content in the raw material is 1-320g/l, and the sulfate content is 0.01-320 g/l; the NaCl content in the nearly saturated solution is 320-50g/l, and the sulfate content is 50-320 g/l; the NaCl content in the brine clarified liquid is 320-50g/l, and the sulfate content is 50-320 g/l; the NaCl content of the second salt-making mother liquor is 295-285g/l, and the sulfate content is 60-70 g/l; the NaCl content in the circulating filtrate is 295-285g/l, and the sulfate content is 60-70 g/l.
Further, the content of NaCl in the mixed miscellaneous salt is as follows: the sulfate content was 4.5: 1.
A high-salt COD wastewater recovery process comprises the following steps:
A. taking waste water containing reducing substances corresponding to sodium chloride, sodium sulfate, calcium sulfate, magnesium sulfate, sodium nitrate and COD as raw materials, and evaporating and concentrating the waste water by using sand or indissolvable calcium sulfate as an antiscaling agent to obtain fresh water and a nearly saturated solution; clarifying the near-saturated solution, carrying out solid-liquid separation to obtain a calcium sulfate precipitate and a brine clarified solution;
B. evaporating and crystallizing the brine clarified liquid to obtain sodium sulfate, fresh water and a nitrate preparation mother liquid; freezing the mother liquor for preparing the sodium sulfate at low temperature, and carrying out solid-liquid separation to obtain sodium sulfate decahydrate and frozen mother liquor; evaporating, crystallizing and carrying out solid-liquid separation on the frozen mother liquor to obtain sodium chloride, fresh water and salt making mother liquor;
C. spraying and evaporating the salt making mother liquor at high temperature to obtain mixed salt containing reducing substances corresponding to COD, sodium chloride, sodium sulfate and sodium nitrate;
D. separating the reducing substances corresponding to COD in the mixed miscellaneous salt from sodium chloride, sodium sulfate and sodium nitrate by using a vertical classifier by adopting a circulating filtrate which is close to the components of the salt making mother liquor; the sodium chloride, sodium sulfate and sodium nitrate obtained at the bottom are dissolved by fresh water and then are comprehensively utilized, the filter cake of COD in the overflow liquid corresponding to the reducing substances is used as fuel, and the filtrate is recycled.
Further, in the step B, directly evaporating, crystallizing and performing solid-liquid separation on the saltpeter making mother liquor to obtain sodium chloride, fresh water and saltpeter making mother liquor, circulating a part of the saltpeter making mother liquor to be mixed with the brine clear liquor, and performing the step C on the rest saltpeter making mother liquor.
Furthermore, the NaCl content in the raw material is 1-320g/l, and the sulfate content is 0.01-320 g/l; the NaCl content in the nearly saturated solution is 320-50g/l, and the sulfate content is 50-320 g/l; the NaCl content in the brine clarified liquid is 320-50g/l, and the sulfate content is 50-320 g/l; the NaCl content in the circulating filtrate is 295-285g/l, and the sulfate content in the circulating filtrate is 60-70 g/l; the NaCl content in the mixed miscellaneous salt is as follows: the sulfate content was 4.5: 1.
A high-salt COD wastewater recovery process comprises the following steps:
A. taking waste water containing reducing substances corresponding to sodium chloride, sodium sulfate, calcium sulfate, magnesium sulfate, sodium nitrate and COD as raw materials, and evaporating and concentrating the waste water by using sand or indissolvable calcium sulfate as an antiscaling agent to obtain fresh water and a nearly saturated solution; clarifying the near-saturated solution, carrying out solid-liquid separation to obtain a calcium sulfate precipitate and a brine clarified solution;
B. evaporating and crystallizing the brine clarified liquid to obtain sodium chloride, fresh water and a first salt-making mother liquid; freezing the first salt preparation mother liquor at low temperature for solid-liquid separation to obtain sodium sulfate decahydrate and frozen mother liquor; carrying out evaporative crystallization and solid-liquid separation on the frozen mother liquor to obtain sodium chloride, fresh water and a second salt manufacturing mother liquor;
C. spraying and high-temperature evaporating the second salt making mother liquor to obtain mixed salt containing the reducing substances corresponding to COD, sodium chloride, sodium sulfate and sodium nitrate;
D. separating the reducing substances corresponding to COD in the mixed miscellaneous salt from sodium chloride, sodium sulfate and sodium nitrate by using a vertical classifier by adopting the circulating filtrate close to the components of the second salt-making mother liquor; the sodium chloride, sodium sulfate and sodium nitrate obtained at the bottom are dissolved by fresh water and then are comprehensively utilized, the filter cake of COD in the overflow liquid corresponding to the reducing substances is used as fuel, and the filtrate is recycled.
Further, in the step B, a part of the first salt making mother liquor is subjected to evaporation crystallization and solid-liquid separation to obtain sodium sulfate, 2.41 tons of fresh water and a nitrate making mother liquor, and the nitrate making mother liquor is circulated to be mixed with the brine clear liquor; and carrying out spray high-temperature evaporation on the residual first salt preparation mother liquor to obtain the mixed miscellaneous salt containing the reducing substance corresponding to COD, sodium chloride, sodium sulfate and sodium nitrate.
Furthermore, the NaCl content in the raw material is 1-320g/l, and the sulfate content is 0.01-320 g/l; the NaCl content in the nearly saturated solution is 320-50g/l, and the sulfate content is 50-320 g/l; the NaCl content in the brine clarified liquid is 320-50g/l, and the sulfate content is 50-320 g/l; the NaCl content in the circulating filtrate is 295-285g/l, and the sulfate content in the circulating filtrate is 60-70 g/l; the NaCl content in the mixed miscellaneous salt is as follows: the sulfate content was 4.5: 1.
The invention has the beneficial effects that: the high-salt COD wastewater recovery process has the advantages of strong raw material adaptability, no pretreatment process of wastewater, less salt impurity, recyclability, separable utilization of reductive substances corresponding to COD, lower production cost, shorter process flow, zero discharge of wastewater and waste impurities, and environmental protection and greenness.
Drawings
FIG. 1 is a schematic process flow diagram of the high salt COD wastewater recovery process of the present invention.
Detailed Description
The present invention is illustrated in detail below by means of a number of specific examples, which, however, are not intended to limit the invention.
As shown in figure 1, the invention provides a high-salt COD wastewater recovery process, which takes wastewater containing sodium chloride, sulfate, calcium ions, magnesium ions, nitrate radicals, COD ions and the like as raw materials, and the wastewater is evaporated and concentrated under the condition that an insoluble substance is used as an antiscaling agent to control the concentration of the antiscaling agent to obtain fresh water and a nearly saturated solution (calcium sulfate supersaturated educt); the nearly saturated solution is clarified and subjected to solid-liquid separation to obtain calcium sulfate precipitate and sulfate brine clarified liquid; separating the brine clarified liquid by salt and sulfate separation process to obtain sodium chloride, sulfate, fresh water and salt-making mother liquor with high COD content; spraying the salt-making mother liquor at high temperature to evaporate to obtain mixed salt containing COD, sodium chloride, sulfate, nitrate and the like; separating COD in the mixed miscellaneous salt from inorganic salts such as sodium chloride, sulfate, nitrate and the like by using a vertical classifier by adopting circulating filtrate of the near salt-making mother liquor component; the inorganic salts such as sodium chloride, sulfate, nitrate and the like obtained at the bottom are dissolved by fresh water and then are comprehensively utilized, the COD filtering cake in the overflow liquid is used as fuel, and the filtrate is recycled.
Example 1 (cold high magnesium calcium brine):
get 1000m3Waste water (NaCl 3.4g/l, MgSO)4 0.1g/l、CaSO40.05g/l, 0.03g/l of reducing substance corresponding to COD, NaNO30.03g/l) as raw material, and evaporating and concentrating the wastewater under the condition of controlling the concentration by using sand as an antiscaling agent (the evaporation temperature is 40-140 ℃) to obtain 990 tons of fresh water and 10m3Nearly saturated solution (calcium sulfate supersaturated eluate) (NaCl 340g/l, MgSO)4 10g/l、CaSO43.0g/l, 3g/l of reduced matter corresponding to COD, NaNO3 3g/l)；10m3The nearly saturated solution is subjected to solid-liquid separation to obtain 20kg of calcium sulfate precipitate and 10m3Brine clear solution (NaCl 340gl、MgSO4 10g/l、CaSO43.0g/l, 3g/l of reduced matter corresponding to COD, NaNO3 3g/l)；10m3Evaporating and crystallizing (evaporation temperature 50 deg.C) to obtain 2.99 ton sodium chloride, 8.5 ton fresh water and 1.43m3First salt mother liquor (NaCl 285g/l, MgSO)470g/l、CaSO40.80g/l, 23g/l of reduced matter corresponding to COD, NaNO3 23g/l)；1.43m3Freezing the first salt-making mother liquor at low temperature (freezing temperature-5 ℃) to separate solid and liquid to obtain 0.183 ton of magnesium sulfate heptahydrate and 1.33m3Magnesium preparation mother liquor (NaCl 310g/l, MgSO)4 10g/l、CaSO40.86g/l, COD corresponding to reduced matter 24.8g/l, NaNO3 24.8g/l)；1.33m3The magnesium-making mother liquor is subjected to evaporation crystallization (evaporation temperature is 50 ℃) and solid-liquid separation to obtain 0.22 ton of sodium chloride (NaCl), 0.75 ton of fresh water and 0.58m3The second salt mother liquor (NaCl 332g/l, MgSO)4 23g/l、CaSO41.97g/l, 60g/l of reduced matter corresponding to COD, NaNO3 60g/l)；0.50m3Spraying and high-temperature evaporating the second salt-making mother liquor (evaporation temperature is 150 ℃) to obtain 0.277 ton mixed salt containing the reducing substance corresponding to COD, sodium chloride, magnesium sulfate and sodium nitrate; using 0.85m3Separating 0.035 tons of COD corresponding reducing substances in 0.238 tons of mixed miscellaneous salt from 0.242 tons of inorganic salts such as sodium chloride, sodium sulfate, sodium nitrate and the like by utilizing a vertical classifier for the circulating filtrate close to the components of the second salt-making mother liquor; 0.242 ton of inorganic salts such as sodium chloride, sodium sulfate, sodium nitrate and the like obtained at the bottom are dissolved by fresh water and then are comprehensively utilized, and the thickness of the inorganic salts is 0.85m30.035 ton COD in the overflow liquor is corresponding to the reducing substance and filtered cake is used as fuel, and the filtrate is recycled.
Example 2 (cold nitrate co-production):
get 1000m3Waste water (NaCl 3.4g/l, Na)2SO4 3.4g/l、MgSO4 0.01g/l、CaSO40.05g/l, 0.03g/l of reducing substance corresponding to COD, NaNO30.03g/l) as raw material, and evaporating and concentrating the wastewater under the condition of controlling the concentration by using sand as an antiscaling agent (the evaporation temperature is 40-140 ℃) to obtain 980 tons of fresh water and 20m3Nearly saturated solution (calcium sulfate supersaturated eluate) (NaCl 170g/l, Na)2SO4 170g/l、MgSO4 0.50g/l、CaSO41.0g/l, 1.5g/l of reduced matter corresponding to COD, NaNO3 1.5g/l)；20m3The nearly saturated solution is subjected to solid-liquid separation to obtain 30kg of calcium sulfate precipitate and 20m3Brine clear solution (NaCl 170g/l, Na)2SO4 170g/l、MgSO4 0.50g/l、CaSO41.0g/l, 1.5g/l of reduced matter corresponding to COD, NaNO3 1.5g/l)；20m3Evaporating and crystallizing the clear brine solution (evaporation temperature is 100 ℃) to separate solid and liquid to obtain 2.57 tons of sodium sulfate, 7.19 tons of fresh water and 11.85m3Mother liquor for preparing nitre (NaCl 285g/l, Na)2SO4 70g/l、CaSO40.80g/l, 2.53g/l of reduced matter corresponding to COD, NaNO3 2.53g/l)；11.85m3Freezing the mother liquor at low temperature (freezing temperature-5 deg.C) and separating solid and liquid to obtain 1.61 ton sodium sulfate decahydrate and 10.68m3Freezing mother liquor (NaCl 318g/l, Na)2SO4 10g/l、CaSO40.89g/l, 2.81g/l of reduced matter corresponding to COD, NaNO3 2.81g/l)；10.68m3The frozen mother liquor is subjected to evaporative crystallization (the evaporation temperature is 50 ℃) and solid-liquid separation to obtain 3.09 tons of sodium chloride, 8.19 tons of fresh water and 1.068m3Salt manufacturing mother liquor (NaCl 285g/l, Na)2SO470g/l、CaSO40.80g/l, 28.1g/l of reduced matter corresponding to COD, NaNO3 28.1g/l)；1.068m3Spraying the salt-making mother liquor at high temperature for evaporation (evaporation temperature 150 ℃) to obtain 0.442 ton of mixed miscellaneous salt containing the reduced substance corresponding to COD, sodium chloride, sodium sulfate, sodium nitrate and the like; using 1.36m3Separating 0.06 ton of COD corresponding reducing substances in 0.442 ton of mixed miscellaneous salt from 0.382 ton of inorganic salts such as sodium chloride, sodium sulfate, sodium nitrate and the like by utilizing a vertical classifier for the circulating filtrate close to the components of the salt making mother liquor; 0.382 ton of inorganic salts such as sodium chloride, sodium sulfate and sodium nitrate are obtained at the bottom, and the inorganic salts are dissolved by fresh water and are comprehensively utilized, namely 1.36m30.06 ton COD in the overflow liquid is corresponding to the filter cake of the reducing substances and is used as fuel, and the filtrate is recycled.
Example 3 (cold co-production of salt and nitrate):
get 1000m3Waste water (NaCl 6.0g/l, Na)2SO4 0.80g/l、MgSO4 0.01g/l、CaSO40.05g/l, 0.03g/l of reducing substance corresponding to COD, NaNO30.03g/l) as raw material, and evaporating and concentrating the wastewater under the condition of controlling the concentration by using sand as an antiscaling agent (the evaporation temperature is 40-140 ℃) to obtain 980 tons of fresh water and 20m3Near saturated solution (NaCl 300g/l, Na)2SO440g/l、MgSO4 0.50g/l、CaSO41.0g/l, 1.5g/l of reduced matter corresponding to COD, NaNO3 1.5g/l)；20m3The nearly saturated solution is subjected to solid-liquid separation to obtain 30kg of calcium sulfate precipitate and 20m3Brine clear solution (NaCl 300g/l, Na)2SO4 40g/l、MgSO4 0.50g/l、CaSO41.0g/l, 1.5g/l of reduced matter corresponding to COD, NaNO3 1.5g/l)；20m3Evaporating and crystallizing the clear brine solution (evaporation temperature is 100 ℃) to separate solid and liquid to obtain 2.72 tons of sodium chloride, 10.17 tons of fresh water and 11.43m3First salt mother liquor (NaCl 285g/l, Na)2SO4 70g/l、CaSO40.80g/l, 2.62g/l of reduced matter corresponding to COD, NaNO3 2.62g/l)；11.43m3Freezing the first salt-making mother liquor at low temperature (freezing temperature-5 ℃) to separate solid and liquid to obtain 1.56 tons of sodium sulfate decahydrate and 10.30m3Freezing mother liquor (NaCl 318g/l, Na)2SO4 10g/l、CaSO40.89g/l, 2.91g/l of reduced matter corresponding to COD, NaNO3 2.91g/l)；10.30m3The frozen mother liquor is subjected to evaporative crystallization (the evaporation temperature is 50 ℃) and solid-liquid separation to obtain 2.53 tons of sodium chloride, 7.66 tons of fresh water and 1.47m3Second salt mother liquor (NaCl 285g/l, Na)2SO4 70g/l、CaSO40.80g/l, 20.37g/l of reduced matter corresponding to COD, NaNO3 20.37g/l)；1.47m3Spraying and high-temperature evaporating the second salt-making mother liquor (evaporation temperature is 150 ℃) to obtain 0.586 ton of mixed salt containing the reducing substances corresponding to COD, sodium chloride, sodium sulfate, sodium nitrate and the like; using a 1.80m3Separating 0.06 ton of COD corresponding reducing substances in 0.586 ton of mixed miscellaneous salt from 0.526 ton of inorganic salts such as sodium chloride, sodium sulfate, sodium nitrate and the like by utilizing a vertical classifier for the circulating filtrate close to the components of the second salt-making mother liquor; 0.526 ton of inorganic salts such as sodium chloride, sodium sulfate and sodium nitrate obtained at the bottom are dissolved by fresh water and then are comprehensively utilized，1.80m30.06 ton COD in the overflow liquid is corresponding to the filter cake of the reducing substances and is used as fuel, and the filtrate is recycled.
Example 4 (hot calcium brine):
get 1000m3Waste water (NaCl 3.4g/l, MgSO)4 0.01g/l、CaSO40.05g/l, 0.03g/l of reducing substance corresponding to COD, NaNO30.03g/l) as raw material, and evaporating and concentrating the wastewater under the condition of controlling the concentration by using sand as an antiscaling agent (the evaporation temperature is 40-140 ℃) to obtain 990 tons of fresh water and 10m3Nearly saturated solution (calcium sulfate supersaturated eluate) (NaCl 340g/l, MgSO)4 1.0g/l、CaSO43.0g/l, 3g/l of reduced matter corresponding to COD, NaNO3 3g/l)；10m3The nearly saturated solution is subjected to solid-liquid separation to obtain 20kg of calcium sulfate precipitate and 10m3Brine clear solution (NaCl 340g/l, MgSO)4 1.0g/l、CaSO43.0g/l, 3g/l of reduced matter corresponding to COD, NaNO3 3g/l)；10m3Evaporating and crystallizing (evaporation temperature 50 deg.C) to obtain 3.23 ton sodium chloride (NaCl), 8.00 ton fresh water and 0.5m brine3Salt mother liquor (NaCl 340g/l, MgSO)420g/l、CaSO40.80g/l, 60g/l of reduced matter corresponding to COD, NaNO3 60g/l)；0.5m3Spraying the salt-making mother liquor at high temperature for evaporation (evaporation temperature 150 ℃) to obtain 0.240 ton of mixed salt containing the reducing substances corresponding to COD, sodium chloride, magnesium sulfate, sodium nitrate and the like; using 0.74m3Separating 0.06 ton of COD corresponding reducing substances in 0.240 ton of mixed miscellaneous salt from 0.180 ton of inorganic salts such as sodium chloride, sodium sulfate, sodium nitrate and the like by utilizing a vertical classifier to obtain circulating filtrate which is close to the components of the salt making mother liquor; 0.180 ton of inorganic salts such as sodium chloride, sodium sulfate and sodium nitrate obtained at the bottom are dissolved by fresh water and then are comprehensively utilized, and the concentration is 0.74m30.035 ton COD in the overflow liquor is corresponding to the reducing substance and filtered cake is used as fuel, and the filtrate is recycled.
Example 5 (thermal nitrate co-production):
get 1000m3Waste water (NaCl 0.2g/l, Na)2SO4 3.4g/l、MgSO4 0.01g/l、CaSO40.05g/l, 0.03g/l of reducing substance corresponding to COD, NaNO30.03g/l) as raw material, and evaporating and concentrating the wastewater under the condition of controlling the concentration by using sand as an antiscaling agent (the evaporation temperature is 40-140 ℃) to obtain 990 tons of fresh water and 10m3Nearly saturated solution (calcium sulfate supersaturated eluate) (NaCl 20g/l, Na)2SO4 340g/l、MgSO4 1.0g/l、CaSO41.0g/l, 3g/l of reduced matter corresponding to COD, NaNO3 3g/l)；10m3The nearly saturated solution is subjected to solid-liquid separation to obtain 40kg of calcium sulfate precipitate and 10m3Brine clear solution (NaCl 20g/l, Na)2SO4 340g/l、MgSO4 1.0g/l、CaSO41.0g/l, 3g/l of reduced matter corresponding to COD, NaNO3 3g/l)；10m3Brine clear liquor and circulating 2.11m3Salt manufacturing mother liquor (NaCl 285g/l, Na)2SO4 70g/l、CaSO40.80g/l, 60g/l of reduced matter corresponding to COD, NaNO360g/l) are mixed and subjected to solid-liquid separation by evaporation crystallization (evaporation temperature is 120 ℃) to obtain 3.365 tons of sodium sulfate, 7.81 tons of fresh water and 3.04m3Mother liquor for preparing nitre (NaCl 305g/l, Na)2SO4 55g/l、CaSO40.20g/l, 64.21g/l of reduced matter corresponding to COD, NaNO3 64.21g/l)；3.04m3The mother liquor for preparing the nitre is subjected to solid-liquid separation by evaporation crystallization (the evaporation temperature is 100-50 ℃) to obtain 0.0575 ton of sodium chloride, 0.40 ton of fresh water and 2.61m3Salt manufacturing mother liquor (NaCl 285g/l, Na)2SO4 70g/l、CaSO40.80g/l, 60g/l of reduced matter corresponding to COD, NaNO360 g/l); wherein 2.11m3The mother liquor is circulated to be mixed with the brine clear liquor, and the other part is 0.5m3Spraying the salt-making mother liquor at high temperature for evaporation (evaporation temperature is 150 ℃) to obtain 0.475 ton of mixed miscellaneous salt containing the reducing substances corresponding to COD, sodium chloride, sodium sulfate, sodium nitrate and the like; using a 1.46m3Separating 0.06 ton of COD corresponding reducing substances in 0.475 ton of mixed miscellaneous salt from 0.415 ton of inorganic salts such as sodium chloride, sulfate, nitrate and the like by utilizing a vertical classifier for the circulating filtrate close to the components of the salt-making mother liquor; 0.415 ton of inorganic salts such as sodium chloride, sodium sulfate and nitrate obtained at the bottom are dissolved by fresh water and then are comprehensively utilized, 1.46m3Filtering filter cake of 0.06 ton COD corresponding to reducing substance in overflow liquid as fuel, and circulating filtrateAnd (4) utilizing.
Example 6 (thermal co-production of saltpeter):
get 1000m3Waste water (NaCl 6.0g/l, Na)2SO4 0.80g/l、MgSO4 0.01g/l、CaSO40.05g/l, 0.03g/l of reducing substance corresponding to COD, NaNO30.03g/l) as raw material, and evaporating and concentrating the wastewater under the condition of controlling the concentration by using sand as an antiscaling agent (the evaporation temperature is 40-140 ℃) to obtain 980 tons of fresh water and 20m3Near saturated solution (NaCl 300g/l, Na)2SO440g/l、MgSO4 0.50g/l、CaSO41.0g/l, 1.5g/l of reduced matter corresponding to COD, NaNO3 1.5g/l)；20m3The nearly saturated solution is subjected to solid-liquid separation to obtain 30kg of calcium sulfate precipitate and 20m3Brine clear solution (NaCl 300g/l, Na)2SO4 40g/l、MgSO4 0.50g/l、CaSO41.0g/l, 1.5g/l of reduced matter corresponding to COD, NaNO3 1.5g/l)；20m3Brine clarified liquid and circulating 38.43m3Mother liquor for preparing nitre (NaCl 305g/l, Na)2SO4 55g/l、CaSO40.20g/l, 64.21g/l of reduced matter corresponding to COD, NaNO364.21g/l) are mixed and subjected to evaporative crystallization (the evaporation temperature is 140-50 ℃) and solid-liquid separation to obtain 5.86 tons of sodium chloride (NaCl), 14.59 tons of fresh water and 41.63m3Salt manufacturing mother liquor (NaCl 285g/l, Na)2SO4 70g/l、CaSO40.80g/l, 29.7g/l of reduced matter corresponding to COD, NaNO329.7 g/l); wherein 0.5m3The salt-making mother liquor is removed from a spray evaporation system, and the other 41.13m3Salt manufacturing mother liquor (NaCl 285g/l, Na)2SO4 70g/l、CaSO40.80g/l, 60g/l of reduced matter corresponding to COD, NaNO360g/l) is subjected to solid-liquid separation through evaporation crystallization (evaporation temperature is 100 ℃) to obtain 0.765 ton of sodium sulfate, 2.41 ton of fresh water and 38.43m3Mother liquor for preparing nitre (NaCl 305g/l, Na)2SO4 55g/l、CaSO40.20g/l, 64.21g/l of reduced matter corresponding to COD, NaNO3 64.21g/l)；0.5m3Salt manufacturing mother liquor (NaCl 285g/l, Na)2SO4 70g/l、CaSO40.80g/l, 60g/l of reduced matter corresponding to COD, NaNO360g/l) spray high temperatureEvaporating (evaporation temperature 150 ℃) to obtain 0.475 ton of mixed miscellaneous salt containing the reducing substance corresponding to COD, sodium chloride, sodium sulfate, sodium nitrate and the like; using a 1.46m3Separating 0.06 ton of COD corresponding reducing substances in 0.475 ton of mixed miscellaneous salt from 0.415 ton of inorganic salts such as sodium chloride, sodium sulfate, sodium nitrate and the like by utilizing a vertical classifier for the circulating filtrate close to the components of the salt making mother liquor; 0.415 ton of inorganic salt such as sodium chloride, sodium sulfate and sodium nitrate obtained at the bottom is dissolved by fresh water and then comprehensively utilized, 1.46m30.06 ton COD in the overflow liquid is corresponding to the filter cake of the reducing substances and is used as fuel, and the filtrate is recycled.
The high-salt COD wastewater recovery process has the characteristics of strong raw material adaptability, no pretreatment process, less salt impurity, recyclability, separable utilization of COD, lower production cost, shorter process flow, zero discharge of wastewater and waste impurities, environment-friendly process and the like.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the structure of the present invention in any way. Any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention still fall within the scope of the technical solution of the present invention.
Claims (6)
1. The high-salt COD wastewater recovery process is characterized by comprising the following steps of:
A. taking waste water containing sodium chloride, calcium sulfate, magnesium sulfate, sodium nitrate and COD corresponding to reducing substances as raw materials, and evaporating and concentrating the waste water by using sand or indissolvable calcium sulfate as an antiscaling agent to obtain fresh water and a nearly saturated solution; clarifying the near-saturated solution, carrying out solid-liquid separation to obtain a calcium sulfate precipitate and a brine clarified solution;
B. evaporating and crystallizing the brine clarified liquid to obtain sodium chloride, fresh water and a first salt-making mother liquid; in the step B, performing low-temperature freezing and solid-liquid separation on the first salt preparation mother liquor to obtain magnesium sulfate heptahydrate and magnesium preparation mother liquor; carrying out evaporative crystallization and solid-liquid separation on the magnesium preparation mother liquor to obtain sodium chloride, fresh water and a second salt preparation mother liquor;
C. spraying and evaporating the second salt-making mother liquor at high temperature to obtain mixed salt containing the reducing substances corresponding to COD, sodium chloride, magnesium sulfate and sodium nitrate;
D. separating the reducing substances corresponding to COD in the mixed miscellaneous salt from sodium chloride, sodium sulfate and sodium nitrate by using a vertical classifier by adopting the circulating filtrate close to the components of the second salt-making mother liquor; the sodium chloride, sodium sulfate and sodium nitrate obtained at the bottom are dissolved by fresh water and then are comprehensively utilized, the filter cake of COD in the overflow liquid corresponding to the reducing substances is used as fuel, and the filtrate is recycled.
2. The high salt COD wastewater recovery process of claim 1, wherein: the NaCl content in the raw material is 1-320g/l, and the sulfate content is 0.01-320 g/l; the NaCl content in the nearly saturated solution is 320-50g/l, and the sulfate content is 50-320 g/l; the NaCl content in the brine clarified liquid is 320-50g/l, and the sulfate content is 50-320 g/l; the NaCl content of the second salt-making mother liquor is 295-285g/l, and the sulfate content is 60-70 g/l; the NaCl content in the circulating filtrate is 295-285g/l, and the sulfate content is 60-70 g/l.
3. The high salt COD wastewater recovery process according to claim 1 or 2, characterized in that: the NaCl content in the mixed miscellaneous salt is as follows: the sulfate content was 4.5: 1.
4. The high-salt COD wastewater recovery process is characterized by comprising the following steps of:
A. taking waste water containing reducing substances corresponding to sodium chloride, sodium sulfate, calcium sulfate, magnesium sulfate, sodium nitrate and COD as raw materials, and evaporating and concentrating the waste water by using sand or indissolvable calcium sulfate as an antiscaling agent to obtain fresh water and a nearly saturated solution; clarifying the near-saturated solution, carrying out solid-liquid separation to obtain a calcium sulfate precipitate and a brine clarified solution;
B. evaporating and crystallizing the brine clarified liquid to obtain sodium sulfate, fresh water and a nitrate preparation mother liquid;
freezing the mother liquor for preparing the sodium sulfate at low temperature, and carrying out solid-liquid separation to obtain sodium sulfate decahydrate and frozen mother liquor; carrying out evaporative crystallization and solid-liquid separation on the frozen mother liquor to obtain sodium chloride, fresh water and salt making mother liquor, and carrying out step C on the salt making mother liquor;
or directly evaporating, crystallizing and carrying out solid-liquid separation on the saltpeter making mother liquor to obtain sodium chloride, fresh water and saltpeter making mother liquor, circulating a part of the saltpeter making mother liquor to be mixed with the brine clear liquor, and carrying out the step C on the rest saltpeter making mother liquor;
C. spraying and evaporating the salt making mother liquor at high temperature to obtain mixed salt containing reducing substances corresponding to COD, sodium chloride, sodium sulfate and sodium nitrate;
D. separating the reducing substances corresponding to COD in the mixed miscellaneous salt from sodium chloride, sodium sulfate and sodium nitrate by using a vertical classifier by adopting a circulating filtrate which is close to the components of the salt making mother liquor; the sodium chloride, sodium sulfate and sodium nitrate obtained at the bottom are dissolved by fresh water and then are comprehensively utilized, the filter cake of COD in the overflow liquid corresponding to the reducing substances is used as fuel, and the filtrate is recycled.
5. The high salt COD wastewater recovery process of claim 4, characterized in that: the NaCl content in the raw material is 1-320g/l, and the sulfate content is 0.01-320 g/l; the NaCl content in the nearly saturated solution is 320-50g/l, and the sulfate content is 50-320 g/l; the NaCl content in the brine clarified liquid is 320-50g/l, and the sulfate content is 50-320 g/l; the NaCl content in the circulating filtrate is 295-285g/l, and the sulfate content in the circulating filtrate is 60-70 g/l; the NaCl content in the mixed miscellaneous salt is as follows: the sulfate content was 4.5: 1.
6. The high-salt COD wastewater recovery process is characterized by comprising the following steps of:
A. taking waste water containing reducing substances corresponding to sodium chloride, sodium sulfate, calcium sulfate, magnesium sulfate, sodium nitrate and COD as raw materials, and evaporating and concentrating the waste water by using sand or indissolvable calcium sulfate as an antiscaling agent to obtain fresh water and a nearly saturated solution; clarifying the near-saturated solution, carrying out solid-liquid separation to obtain a calcium sulfate precipitate and a brine clarified solution;
B. evaporating and crystallizing the brine clarified liquid to obtain sodium chloride, fresh water and a first salt-making mother liquid; freezing the first salt preparation mother liquor at low temperature for solid-liquid separation to obtain sodium sulfate decahydrate and frozen mother liquor; carrying out evaporative crystallization and solid-liquid separation on the frozen mother liquor to obtain sodium chloride, fresh water and a second salt manufacturing mother liquor;
C. spraying and high-temperature evaporating the second salt making mother liquor to obtain mixed salt containing the reducing substances corresponding to COD, sodium chloride, sodium sulfate and sodium nitrate;
D. separating the reducing substances corresponding to COD in the mixed miscellaneous salt from sodium chloride, sodium sulfate and sodium nitrate by using a vertical classifier by adopting the circulating filtrate close to the components of the second salt-making mother liquor; dissolving sodium chloride, sodium sulfate and sodium nitrate obtained at the bottom by fresh water and then comprehensively utilizing the dissolved sodium chloride, sodium sulfate and sodium nitrate, filtering filter cakes of COD (chemical oxygen demand) corresponding to reducing substances in overflow liquid to be used as fuel, and recycling filtrate;
the NaCl content in the raw material is 1-320g/l, and the sulfate content is 0.01-320 g/l; the NaCl content in the nearly saturated solution is 320-50g/l, and the sulfate content is 50-320 g/l; the NaCl content in the brine clarified liquid is 320-50g/l, and the sulfate content is 50-320 g/l; the NaCl content in the circulating filtrate is 295-285g/l, and the sulfate content in the circulating filtrate is 60-70 g/l; the NaCl content in the mixed miscellaneous salt is as follows: the sulfate content was 4.5: 1.
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