CN111153539A - Salt separation crystallization system and process for high-salinity wastewater containing organic matters - Google Patents
Salt separation crystallization system and process for high-salinity wastewater containing organic matters Download PDFInfo
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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
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- C02F1/02—Treatment of water, waste water, or sewage by heating
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention discloses a salt separation crystallization system for high-salinity wastewater containing organic matters, which comprises a sodium sulfate evaporation crystallization unit, a freezing crystallization unit, an organic concentration unit, a sodium chloride evaporation crystallization unit, a concentrated solution collecting tank and a miscellaneous salt drying crystallizer; the invention also discloses a salt separation and crystallization system of the high-salinity wastewater containing the organic matters, which comprises the following working procedures: evaporating and crystallizing sodium sulfate in the step (1), freezing and crystallizing in the step (2), organically concentrating in the step (3), crystallizing sodium chloride in the step (4), and drying mixed salt in the step (5). The system and the process can be used for pertinently treating the high-salinity wastewater containing the organic matters and having relatively high sulfate radical concentration, the treatment process is short, the treatment period is short, and the economic benefit of an enterprise can be ensured; in addition, the invention not only can realize the recovery of salt resources, but also can effectively ensure the purity of the recovered salt.
Description
The technical field is as follows:
the invention relates to a salt separation crystallization system and a salt separation crystallization process, in particular to a salt separation crystallization system and a salt separation crystallization process for high-salinity wastewater containing organic matters.
Background art:
the chemical industry needs to generate a large amount of high-salinity wastewater, and if the high-salinity wastewater is directly discharged without being treated, serious water resource waste and environmental pollution are caused; the chemical high-salinity wastewater not only has high salinity, but also contains a certain amount of organic matters; at present, the treatment methods of high-salt water are various, the treatment modes are different according to specific water quality differences, and evaporation and salt separation treatment are mainly carried out in an evaporation pond. The problems that exist are mainly: 1. the evaporation pond evaporates water by utilizing the evaporation capacity of the evaporation pond, has an unsatisfactory natural evaporation effect, cannot recover salt in waste water, causes resource waste, and reduces the economic benefit of enterprises. 2. The salt separating treatment system adopted at present is generally suitable for industrial wastewater with high hardness and high COD, the salt separating treatment can be carried out after organic concentration treatment is carried out to remove COD and reduce the hardness in water, the treatment process is prolonged, the treatment period is long, and the economic benefit of an enterprise is seriously influenced. 3. For SO4 2-High content of Cl-The disposal of high salt water with less COD content does not have a complete and effective set of salt resourcesSource rate processing scheme.
The invention content is as follows:
the first purpose of the invention is to provide a salt separation and crystallization system of high-salinity wastewater containing organic matters.
The first purpose of the invention is implemented by the following technical scheme: a salt separation crystallization system of high-salinity wastewater containing organic matters comprises a sodium sulfate evaporation crystallization unit, a freezing crystallization unit, an organic concentration unit, a sodium chloride evaporation crystallization unit, a concentrated solution collecting tank and a miscellaneous salt drying crystallizer; a water outlet of a sodium sulfate evaporative crystallizer of the sodium sulfate evaporative crystallization unit is communicated with a feed inlet of a freezing crystallizer of the freezing crystallization unit, and a water outlet of the freezing crystallizer is communicated with a feed inlet of the organic concentration unit; the water production port of the organic concentration unit is communicated with the feed inlet of a sodium chloride evaporative crystallizer of the sodium chloride evaporative crystallization unit; a concentrated water port of the organic concentration unit and a mother liquor outlet of the sodium chloride evaporation crystallizer are both communicated with a feed inlet of the concentrated solution collecting tank, and a discharge outlet of the concentrated solution collecting tank is communicated with a feed inlet of the miscellaneous salt drying crystallizer;
and a discharge hole of a centrifugal dehydrator of the freezing crystallization unit is communicated with a feed inlet of the sodium sulfate evaporative crystallizer.
Furthermore, the sodium sulfate evaporative crystallization unit comprises a sodium sulfate evaporative crystallizer, a sodium sulfate thickener and a sodium sulfate centrifugal dryer, wherein a discharge port of the sodium sulfate evaporative crystallizer is communicated with a feed port of the sodium sulfate thickener, and a discharge port of the sodium sulfate thickener is communicated with a feed port of the sodium sulfate centrifugal dryer.
Furthermore, the freezing and crystallizing unit comprises a freezing crystallizer and a centrifugal dehydrator, and a discharge hole of the freezing crystallizer is communicated with a feed inlet of the centrifugal dehydrator.
Further, the organic concentration unit is an organic membrane concentration device.
Furthermore, the sodium chloride evaporative crystallization unit comprises a sodium chloride evaporative crystallizer, a sodium chloride thickener and a sodium chloride centrifugal dryer, wherein a discharge port of the sodium chloride evaporative crystallizer is communicated with a feed port of the sodium chloride thickener, and a discharge port of the sodium chloride thickener is communicated with a feed port of the sodium chloride centrifugal dryer.
Further, the sodium sulfate evaporation crystallizer is a multi-effect evaporation crystallizer.
The second purpose of the invention is to provide a salt separation crystallization process of high-salinity wastewater containing organic matters.
The second purpose of the invention is implemented by the following technical scheme: a salt separation crystallization process of high-salinity wastewater containing organic matters comprises the following working procedures: evaporating and crystallizing sodium sulfate, freezing and crystallizing in the step (2), organically concentrating in the step (3), crystallizing sodium chloride in the step (4), and drying mixed salt in the step (5); wherein
The step (1) is evaporation crystallization of sodium sulfate: the COD is 150-600mg/L, TDS ≥ 40000mg/L, SO4 2-≥23500mg/L、Cl-High-salinity wastewater with the concentration of not more than 9300mg/L, the total hardness (calculated by calcium carbonate) of not more than 10mg/L and the total silicon of not more than 10mg/L, SS of not more than 1mg/L is sent into a sodium sulfate evaporative crystallizer for heating crystallization to obtain sodium sulfate crystals and Cl-Evaporating and crystallizing mother liquor by using sodium sulfate with the concentration of other impurities being lower than the respective crystallization value and less than or equal to 180000mg/L, sequentially feeding the sodium sulfate crystals into a sodium sulfate thickener and a sodium sulfate centrifugal drier, and thickening and drying to obtain a product sodium sulfate;
the step (2) is freezing crystallization: the sodium sulfate evaporation crystallization mother liquor enters a freezing crystallizer, the temperature is controlled to be-5-0 ℃, freezing crystals and the freezing crystallization mother liquor are obtained through crystallization, and the freezing crystals are sent into a centrifugal dehydrator to be centrifugally dehydrated and then return to the step (1) of sodium sulfate evaporation crystallization treatment;
the step (3) is an organic concentration step: feeding the frozen crystallization mother liquor into an organic membrane concentration device, and controlling the water inlet pressure to be 1-3MPa and the water inlet temperature to be 15-25 ℃ to obtain concentrated product water and concentrated water; (COD is intercepted by a membrane, so that the removal rate of COD in the concentrated produced water reaches 40%; the process is simple and easy to operate)
The step (4) is a step of crystallizing sodium chloride: feeding the concentrated produced water into a sodium chloride evaporation crystallizer, heating for crystallization to obtain sodium chloride crystals and SO4 2-46000-48000mg/L sodium chloride evaporative crystallization mother liquor, sequentially sending the sodium chloride crystals into a sodium chloride thickener and a sodium chloride centrifugal dryer, and thickening and drying to obtain a product sodium chloride;
and (5) drying the mixed salt: and collecting the concentrated water and the mother liquor of sodium chloride evaporative crystallization into a concentrated solution collecting tank, and then sending the concentrated solution and the mother liquor into a mixed salt drying crystallizer for evaporative crystallization to obtain mixed salt.
Further, in the step (1) of sodium sulfate evaporative crystallization, the high-salinity wastewater is sequentially sent into a first-effect evaporator, a second-effect evaporator and a third-effect evaporator, the first-effect evaporation is carried out at 86-88 ℃, the second-effect evaporation is carried out at 68-70 ℃, and the third-effect evaporation is carried out at 46-48 ℃ to obtain sodium sulfate crystals and sodium sulfate evaporative crystallization mother liquor.
The invention has the advantages that: the invention discloses a salt separation and crystallization system for high-salinity wastewater containing organic matters, which can be used for pertinently treating the high-salinity wastewater containing the organic matters and having relatively high sulfate radical concentration, has the advantages of simple system and low cost, can realize the recovery of salt resources after treatment, can ensure the purity of recovered salt, and is suitable for wastewater treatment of enterprises.
The invention also discloses a salt separation crystallization process of the high-salinity wastewater containing the organic matters, which can be used for pertinently treating the high-salinity wastewater containing the organic matters with relatively high sulfate radical concentration by sodium sulfate evaporative crystallization, frozen crystallization, organic concentration, sodium chloride crystallization and miscellaneous salt drying treatment, has short treatment process and short treatment period, and can ensure the economic benefit of enterprises; in addition, the process can realize the recovery of salt resources, the recovered sodium sulfate crystal salt meets the II-class salt qualified standard in GB/T6009-2014 Industrial anhydrous sodium sulfate standard, and the sodium chloride crystal salt meets the secondary standard of refined industrial dry salt in GB/T5462-2015 Industrial salt standard and can be packaged and sold outside.
Description of the drawings:
in order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic system diagram of example 1.
FIG. 2 is a process flow diagram of examples 2-4.
In the figure: the system comprises a sodium sulfate evaporative crystallization unit 1, a single-effect evaporative crystallizer 1.1, a sodium sulfate double-effect evaporative crystallizer 1.2, a sodium sulfate triple-effect evaporative crystallizer 1.3, a sodium sulfate thickener 1.4, a sodium sulfate centrifugal dryer 1.5, a freezing crystallization unit 2, a freezing crystallizer 2.1, a centrifugal dehydrator 2.2, an organic membrane concentration device 3, a sodium chloride evaporative crystallization unit 4, a sodium chloride evaporative crystallizer 4.1, a sodium chloride thickener 4.2, a sodium chloride centrifugal dryer 4.3, a concentrated solution collecting tank 5 and a miscellaneous salt drying crystallizer 6.
The specific implementation mode is as follows:
the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1:
a salt separation crystallization system of high-salinity wastewater containing organic matters comprises a sodium sulfate evaporation crystallization unit 1, a freezing crystallization unit 2, an organic membrane concentration device 3, a sodium chloride evaporation crystallization unit 4, a concentrated solution collecting tank 5 and a miscellaneous salt drying crystallizer 6;
the sodium sulfate evaporative crystallization unit 1 comprises a sodium sulfate single-effect evaporative crystallizer 1.1, a sodium sulfate double-effect evaporative crystallizer 1.2, a sodium sulfate triple-effect evaporative crystallizer 1.3, a sodium sulfate thickener 1.4 and a sodium sulfate centrifugal dryer 1.5, wherein a discharge port of the sodium sulfate single-effect evaporative crystallizer 1.1 is communicated with a feed port of the sodium sulfate double-effect evaporative crystallizer 1.2, a discharge port of the sodium sulfate double-effect evaporative crystallizer 1.2 is communicated with a feed port of the sodium sulfate triple-effect evaporative crystallizer 1.3, a discharge port of the sodium sulfate triple-effect evaporative crystallizer 1.3 is communicated with a feed port of the sodium sulfate thickener 1.4, and a discharge port of the sodium sulfate thickener 1.4 is communicated with a feed port of the sodium sulfate centrifugal dryer 1.5;
the freezing and crystallizing unit 2 comprises a freezing crystallizer 2.1 and a centrifugal dehydrator 2.2, wherein a discharge hole of the freezing crystallizer 2.1 is communicated with a feed inlet of the centrifugal dehydrator 2.2;
the sodium chloride evaporative crystallization unit 4 comprises a sodium chloride evaporative crystallizer 4.1, a sodium chloride thickener 4.2 and a sodium chloride centrifugal dryer 4.3, wherein a discharge port of the sodium chloride evaporative crystallizer 4.1 is communicated with a feed port of the sodium chloride thickener 4.2, and a discharge port of the sodium chloride thickener 4.2 is communicated with a feed port of the sodium chloride centrifugal dryer 4.3;
the water outlet of the sodium sulfate triple-effect evaporative crystallizer 1.3 is communicated with the feed inlet of the freezing crystallizer 2.1, and the water outlet of the freezing crystallizer 2.1 is communicated with the feed inlet of the organic membrane concentration device 3; a water producing port of the organic film concentrating device 3 is communicated with a feed inlet of a sodium chloride evaporative crystallizer 4.1; a concentrated water port of the organic membrane concentration device 3 and a mother liquor outlet of the sodium chloride evaporative crystallizer 4.1 are communicated with a feed inlet of a concentrated solution collecting tank 5, and a discharge outlet of the concentrated solution collecting tank 5 is communicated with a feed inlet of a miscellaneous salt drying crystallizer 6; the discharge hole of the centrifugal dehydrator 2.2 is communicated with the feed inlet of the sodium sulfate triple-effect evaporative crystallizer 1.3.
Example 2:
the process for salt separation crystallization using the system of example 1 comprises the following steps: evaporating and crystallizing sodium sulfate, freezing and crystallizing in the step (2), organically concentrating in the step (3), crystallizing sodium chloride in the step (4), and drying mixed salt in the step (5); wherein
Step (1) evaporative crystallization of sodium sulfate: the COD is 200mg/L, TDS is 50400mg/L, SO4 2-＝24000mg/L、Cl-9000mg/L of high-salinity wastewater with total hardness (calculated as calcium carbonate) of 10mg/L and total silicon of 10mg/L, SS of 0.9mg/L are fed into a sodium sulfate single-effect evaporation crystallizer 1.1, a sodium sulfate double-effect evaporation crystallizer 1.2 and a sodium sulfate triple-effect evaporation crystallizer 1.3 in sequence, single-effect evaporation is carried out at 110 ℃, double-effect evaporation is carried out at 90 ℃, triple-effect evaporation is carried out at 70 ℃, and sodium sulfate crystals and COD 3900mg/L, TDS of 360000mg/L, SO are obtained4 2-＝48000mg/L、Cl-175000mg/L of sodium sulfate evaporation crystallization mother liquor, 195mg/L of total hard (calculated by calcium carbonate) and 5mg/L of total silicon (calculated by calcium carbonate), sequentially feeding sodium sulfate crystals into a sodium sulfate thickener 1.4 and a sodium sulfate centrifugal drier 1.5, and thickening and drying to obtain a product sodium sulfate;
step (2) freezing crystallization: mother liquor of sodium sulfate evaporation crystallization enters a freezing crystallizer 2.1, the temperature is controlled to be minus 1 ℃, and the freezing crystallization product and COD which is 3900mg/L, TDS mg/330000 mg/L, SO are obtained by crystallization4 2-＝25100mg/L、Cl-176000mg/L total hard (calculated as calcium carbonate) 195mg/L total silicon 196mg/L, SS mg/5 mg/L mother liquid for freezing crystallization, the frozen crystal is sent into a centrifugal dehydrator 2.2 for centrifugal dehydration, and then the mother liquid returns to the step (1) of sodium sulfate evaporation crystallization treatment;
step (3) organic concentration: filtering the mother liquid to remove SS, concentrating with organic membrane at 15-25 deg.C under 1-3MPa to obtain COD 2300mg/L, TDS 324000mg/L, SO4 2-＝23000mg/L、Cl-176000mg/L, 185mg/L total hard (calcium carbonate), 196mg/L, SS mg/0.6 mg/L total silicon and 53000mg/L, TDS mg/405000 mg/L, SO4 2-＝77000mg/L、Cl-176000mg/L, 450mg/L total hard (calculated by calcium carbonate), 196mg/L, SS mg/L total silicon and 0.7mg/L concentrated water;
step (4) sodium chloride crystallization: feeding the concentrated water into sodium chloride evaporator crystallizer 4.1, heating to crystallize to obtain sodium chloride crystal and COD 5522mg/L, TDS 367000mg/L, SO4 2-＝47500mg/L、Cl-180000mg/L of sodium chloride, 380mg/L of total hard (calculated by calcium carbonate) and 3.5mg/L of total silicon (410 mg/L, SS), evaporating and crystallizing mother liquor, sequentially feeding sodium chloride crystals into a sodium chloride thickener 4.2 and a sodium chloride centrifugal drier 4.3, thickening and drying to obtain a product sodium chloride;
step (5) drying the miscellaneous salt: and (3) collecting concentrated water and sodium chloride evaporative crystallization mother liquor into a concentrated liquor collecting tank 5, and then sending the concentrated water and the sodium chloride evaporative crystallization mother liquor into a mixed salt drying crystallizer 6 for evaporative crystallization to obtain mixed salt.
Example 3:
the process for salt separation crystallization using the system of example 1 comprises the following steps: evaporating and crystallizing sodium sulfate, freezing and crystallizing in the step (2), organically concentrating in the step (3), crystallizing sodium chloride in the step (4), and drying mixed salt in the step (5); wherein
Step (1) evaporative crystallization of sodium sulfate: the COD is 150mg/L, TDS is 52500mg/L, SO4 2-＝26000mg/L、Cl-8500mg/L of high-salinity wastewater, 7.5mg/L of total hard (calculated by calcium carbonate), 0.8mg/L of total silicon, 1.1 of sodium sulfate first-effect evaporation crystallizer, 1.2 of sodium sulfate second-effect evaporation crystallizer and 1.3 of sodium sulfate third-effect evaporation crystallizer are sequentially fed into the high-salinity wastewater, the first-effect evaporation is carried out at 110 ℃, the second-effect evaporation is carried out at 90 ℃, the third-effect evaporation is carried out at 70 ℃, and sodium sulfate crystals and COD 3106mg/L, TDS 361000mg/L, SO are obtained4 2-＝48000mg/L、Cl-176000mg/L, 146mg/L total hard (calculated by calcium carbonate) and 4.5mg/L total silicon 166mg/L, SS sodium sulfate evaporation crystallization mother liquor, sequentially sending sodium sulfate crystals into a sodium sulfate thickener 1.4 and a sodium sulfate centrifugal drier 1.5, thickening and drying to obtain a product sodium sulfate;
step (2) freezing crystallization: mother liquor of sodium sulfate evaporation crystallization is fed into a freezing crystallizer 2.1, the temperature is controlled to be-2 ℃, and the freezing crystallization product and COD which is 3130mg/L, TDS mg/L, SO are obtained by crystallization4 2-＝25100mg/L、Cl-177000mg/L total hard (calculated as calcium carbonate) 150mg/L total silicon 167mg/L, SS mg/4.5 mg/L mother liquid of frozen crystallization, the frozen crystallization is sent into a centrifugal dehydrator 2.2 to be centrifugally dehydrated and then returned to the step (1) of sodium sulfate evaporation crystallization treatment;
step (3) organic concentration: filtering the mother liquid to remove SS, concentrating with organic membrane at 15-25 deg.C under 1-3MPa to obtain mother liquid with COD 1370mg/L, TDS 326000mg/L, SO4 2-＝22800mg/L、Cl-177000mg/L, 138mg/L total hard (calcium carbonate), 167mg/L, SS mg/0.5 mg/L total silicon and 406000mg/L, SO mg/L, TDS COD4 2-＝77000mg/L、Cl-177000mg/L, 335mg/L total hard (calcium carbonate), 167mg/L, SS mg/L total silicon and 0.6mg/L concentrated water;
step (4) sodium chloride crystallization: feeding the concentrated water into sodium chloride evaporator crystallizer 4.1, heating for crystallization to obtain sodium chloride crystal and COD 2900mg/L, TDS-367000 mg/L, SO4 2-＝47600mg/L、Cl-180000mg/L of sodium chloride, 290mg/L of total hard (calcium carbonate) and 4mg/L of total silicon (350 mg/L, SS), sequentially feeding sodium chloride crystals into a sodium chloride thickener 4.2 and a sodium chloride centrifugal drier 4.3, thickening and drying to obtain a sodium chloride product;
step (5) drying the miscellaneous salt: and (3) collecting concentrated water and sodium chloride evaporative crystallization mother liquor into a concentrated liquor collecting tank 5, and then sending the concentrated water and the sodium chloride evaporative crystallization mother liquor into a mixed salt drying crystallizer 6 for evaporative crystallization to obtain mixed salt.
Example 4:
the process for salt separation crystallization using the system of example 1 comprises the following steps: evaporating and crystallizing sodium sulfate, freezing and crystallizing in the step (2), organically concentrating in the step (3), crystallizing sodium chloride in the step (4), and drying mixed salt in the step (5); wherein
Step (1) evaporative crystallization of sodium sulfate: the COD is 300mg/L, TDS is 56000mg/L, SO4 2-＝30000mg/L、Cl-7000mg/L of high-salinity wastewater, 5mg/L of total hardness (calculated as calcium carbonate) and 0.6mg/L of total silicon (calculated as total silicon carbonate) are fed into a sodium sulfate single-effect evaporation crystallizer 1.1, a sodium sulfate double-effect evaporation crystallizer 1.2 and a sodium sulfate triple-effect evaporation crystallizer 1.3 in sequence, single-effect evaporation is carried out at 110 ℃, double-effect evaporation is carried out at 90 ℃, triple-effect evaporation is carried out at 70 ℃, and then sodium sulfate crystals and COD 7400mg/L, TDS 356000mg/L, SO are obtained4 2-＝48000mg/L、Cl-173000mg/L of sodium sulfate, 100mg/L of total hard (calculated as calcium carbonate) and 4.7mg/L of total silicon (148 mg/L, SS), evaporating and crystallizing mother liquor, sequentially feeding sodium sulfate crystals into a sodium sulfate thickener 1.4 and a sodium sulfate centrifugal dryer 1.5, thickening and drying to obtain a product sodium sulfate;
step (2) freezing crystallization: mother liquor of sodium sulfate evaporation crystallization enters coldFreezing in a crystallizer 2.1 at-3 deg.C to obtain frozen crystal and COD 7470mg/L, TDS 324000mg/L, SO4 2-＝25100mg/L、Cl-174000mg/L total hard (calculated as calcium carbonate) 100mg/L total silicon 150mg/L, SS mg/4.7 mg/L mother liquid for freezing crystallization, the freezing crystallization is sent into a centrifugal dehydrator 2.2 for centrifugal dehydration, and then the mother liquid returns to the step (1) for sodium sulfate evaporation crystallization treatment;
step (3) organic concentration: filtering the mother liquid to remove SS, feeding into organic membrane concentration device 3, controlling water inlet pressure at 1-3MPa and water inlet temperature at 15-25 deg.C to obtain COD 4200mg/L, TDS 321000mg/L, SO4 2-＝22800mg/L、Cl-174000mg/L, 92mg/L total hard (calcium carbonate), 150mg/L, SS mg/0.7 mg/L total silicon, 75000mg/L, TDS mg/401000 mg/L, SO4 2-＝77100mg/L、Cl-174000mg/L, 225mg/L total hard (calculated by calcium carbonate), 150mg/L, SS mg/0.8 mg/L total silicon;
step (4) sodium chloride crystallization: feeding the concentrated water into sodium chloride evaporator crystallizer 4.1, heating to crystallize to obtain sodium chloride crystal and COD 10500mg/L, TDS 367000mg/L, SO4 2-＝47300mg/L、Cl-180000mg/L of sodium chloride, 193mg/L of total hard (calculated as calcium carbonate) and 5.5mg/L of total silicon (312 mg/L, SS), evaporating and crystallizing mother liquor, sequentially feeding sodium chloride crystals into a sodium chloride thickener 4.2 and a sodium chloride centrifugal drier 4.3, thickening and drying to obtain a product sodium chloride;
step (5) drying the miscellaneous salt: and (3) collecting concentrated water and sodium chloride evaporative crystallization mother liquor into a concentrated liquor collecting tank 5, and then sending the concentrated water and the sodium chloride evaporative crystallization mother liquor into a mixed salt drying crystallizer 6 for evaporative crystallization to obtain mixed salt.
The sodium sulfate obtained in the examples 2-4 is detected by the method of GB/T6009-2014 Industrial anhydrous sodium sulfate, and the sodium chloride is detected by the method of GB/T5462-2015 Industrial salt, and the detection results are respectively listed in Table 1 and Table 2.
As can be seen from Table 1, the sodium sulfates obtained in examples 2-4 all meet the standard of II-class salt qualified products in the GB/T6009-2014 Industrial anhydrous sodium sulfate standard; as can be seen from Table 2, the sodium chlorides obtained in examples 2-4 all meet the secondary standard of refined industrial salt industrial dry salt in GB/T5462-2015 Industrial salt Standard.
TABLE 1 table of sodium sulfate test results obtained in examples 2 to 4
TABLE 2 table of the results of detection of sodium chloride obtained in examples 2 to 4
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A salt separation crystallization system of high-salinity wastewater containing organic matters is characterized by comprising a sodium sulfate evaporation crystallization unit, a freezing crystallization unit, an organic concentration unit, a sodium chloride evaporation crystallization unit, a concentrated solution collecting tank and a miscellaneous salt drying crystallizer; a water outlet of a sodium sulfate evaporative crystallizer of the sodium sulfate evaporative crystallization unit is communicated with a feed inlet of a freezing crystallizer of the freezing crystallization unit, and a water outlet of the freezing crystallizer is communicated with a feed inlet of the organic concentration unit; the water production port of the organic concentration unit is communicated with the feed inlet of a sodium chloride evaporative crystallizer of the sodium chloride evaporative crystallization unit; a concentrated water port of the organic concentration unit and a mother liquor outlet of the sodium chloride evaporation crystallizer are both communicated with a feed inlet of the concentrated solution collecting tank, and a discharge outlet of the concentrated solution collecting tank is communicated with a feed inlet of the miscellaneous salt drying crystallizer;
and a discharge hole of a centrifugal dehydrator of the freezing crystallization unit is communicated with a feed inlet of the sodium sulfate evaporative crystallizer.
2. The salt separation and crystallization system of high-salinity wastewater containing organic matters according to claim 1, characterized in that the sodium sulfate evaporative crystallization unit comprises a sodium sulfate evaporative crystallizer, a sodium sulfate thickener and a sodium sulfate centrifugal dryer, wherein the discharge port of the sodium sulfate evaporative crystallizer is communicated with the feed port of the sodium sulfate thickener, and the discharge port of the sodium sulfate thickener is communicated with the feed port of the sodium sulfate centrifugal dryer.
3. The salt separating and crystallizing system of high-salinity wastewater containing organic matters according to claim 1, characterized in that the freezing and crystallizing unit comprises a freezing crystallizer and a centrifugal dehydrator, and the discharge port of the freezing crystallizer is communicated with the feed port of the centrifugal dehydrator.
4. The salt separating and crystallizing system of high-salinity wastewater containing organic matters according to claim 1, characterized in that the organic concentration unit is an organic membrane concentration device.
5. The salt separation and crystallization system of high-salinity wastewater containing organic matters according to claim 1, characterized in that the sodium chloride evaporative crystallization unit comprises a sodium chloride evaporative crystallizer, a sodium chloride thickener and a sodium chloride centrifugal dryer, wherein a discharge port of the sodium chloride evaporative crystallizer is communicated with a feed port of the sodium chloride thickener, and a discharge port of the sodium chloride thickener is communicated with a feed port of the sodium chloride centrifugal dryer.
6. The salt separating and crystallizing system of high-salinity wastewater containing organic matters according to claim 2, characterized in that the sodium sulfate evaporator crystallizer is a multi-effect evaporator crystallizer.
7. The process for performing the salt separation crystallization on the high-salinity wastewater containing the organic matters by using the salt separation crystallization system for the high-salinity wastewater containing the organic matters, which is disclosed by any one of claims 1 to 6, is characterized by comprising the following steps of: evaporating and crystallizing sodium sulfate, freezing and crystallizing in the step (2), organically concentrating in the step (3), crystallizing sodium chloride in the step (4), and drying mixed salt in the step (5); wherein
The step (1) is evaporation crystallization of sodium sulfate: the COD is 150-600mg/L, TDS ≥ 40000mg/L, SO4 2-≥23500mg/L、Cl-High-salinity wastewater with the concentration of not more than 9300mg/L, the total hardness (calculated by calcium carbonate) of not more than 10mg/L and the total silicon of not more than 10mg/L, SS of not more than 1mg/L is sent into a sodium sulfate evaporative crystallizer for heating crystallization to obtain sodium sulfate crystals and Cl-Evaporating and crystallizing mother liquor by using sodium sulfate with the concentration of other impurities being lower than the respective crystallization value and less than or equal to 180000mg/L, sequentially feeding the sodium sulfate crystals into a sodium sulfate thickener and a sodium sulfate centrifugal drier, and thickening and drying to obtain a product sodium sulfate;
the step (2) is freezing crystallization: the sodium sulfate evaporation crystallization mother liquor enters a freezing crystallizer, the temperature is controlled to be-5-0 ℃, freezing crystals and the freezing crystallization mother liquor are obtained through crystallization, and the freezing crystals are sent into a centrifugal dehydrator to be centrifugally dehydrated and then return to the step (1) of sodium sulfate evaporation crystallization treatment;
the step (3) is an organic concentration step: feeding the frozen crystallization mother liquor into an organic membrane concentration device, and controlling the water inlet pressure to be 1-3MPa and the water inlet temperature to be 15-25 ℃ to obtain concentrated product water and concentrated water; (COD is intercepted by a membrane, so that the removal rate of COD in the concentrated produced water reaches 40%; the process is simple and easy to operate)
The step (4) is a step of crystallizing sodium chloride: feeding the concentrated produced water into a sodium chloride evaporation crystallizer, heating for crystallization to obtain sodium chloride crystals and SO4 2-46000-48000mg/L sodium chloride evaporative crystallization mother liquor, sequentially sending the sodium chloride crystals into a sodium chloride thickener and a sodium chloride centrifugal dryer, and thickening and drying to obtain a product sodium chloride;
and (5) drying the mixed salt: and collecting the concentrated water and the mother liquor of sodium chloride evaporative crystallization into a concentrated solution collecting tank, and then sending the concentrated solution and the mother liquor into a mixed salt drying crystallizer for evaporative crystallization to obtain mixed salt.
8. The salt separation crystallization process of high-salinity wastewater containing organic matters as claimed in claim 7, wherein in the step (1) of sodium sulfate evaporation crystallization, the high-salinity wastewater is sequentially sent into a one-effect evaporator, a two-effect evaporator and a three-effect evaporator, the one-effect evaporation is performed at 100-120 ℃, the two-effect evaporation is performed at 80-100 ℃, and after the three-effect evaporation is performed at 60-80 ℃, sodium sulfate crystals and sodium sulfate evaporation crystallization mother liquor are obtained.
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