CN117923704A - Resource utilization method of shale oil high-salinity wastewater - Google Patents
Resource utilization method of shale oil high-salinity wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000003079 shale oil Substances 0.000 title claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 120
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 92
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 85
- 238000001728 nano-filtration Methods 0.000 claims abstract description 63
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- 239000012528 membrane Substances 0.000 claims abstract description 24
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- 230000008014 freezing Effects 0.000 claims abstract description 14
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- 150000003839 salts Chemical class 0.000 claims description 20
- 238000004062 sedimentation Methods 0.000 claims description 20
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- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 14
- 229920002401 polyacrylamide Polymers 0.000 claims description 14
- 239000001488 sodium phosphate Substances 0.000 claims description 14
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 14
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 14
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
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Abstract
The application relates to the technical field of shale oil high-salt wastewater treatment, in particular to a resource utilization method of shale oil high-salt wastewater. Removing suspended matters in the wastewater by adopting an air floatation technology, performing oxidation treatment by adopting a high-grade oxidation technology, and concentrating by using a reverse osmosis membrane; separating with nanofiltration membrane to obtain nanofiltration concentrated water containing sodium sulfate and nanofiltration clear water containing sodium chloride; freezing and crystallizing the sodium sulfate nanofiltration concentrated water to obtain mirabilite, and then melting and crystallizing the mirabilite to obtain high-purity sodium sulfate; and (3) performing first concentration reduction treatment and first-stage evaporation on the nanofiltration water containing sodium chloride to obtain high-purity sodium chloride. The resource utilization method of the shale oil high-salt wastewater mainly solves the problem of high-efficiency removal of organic matters in the shale oil high-salt wastewater, obtains high-purity sodium chloride and sodium sulfate, realizes resource utilization of the shale oil high-salt wastewater, and reduces environmental pollution and resource waste.
Description
Technical Field
The application relates to the technical field of shale oil high-salt wastewater treatment, in particular to a resource utilization method of shale oil high-salt wastewater.
Background
Shale oil wastewater is mainly generated during hydraulic fracturing operations. The process consumes a large amount of water. Typically, each well requires about 19000m of water and about 1000 times of transportation by a water tank truck, and simultaneously, the produced fracturing flowback fluid accounting for 60% -80% of the water-injected fracturing fluid can return to the stratum. The main characteristics of these waste solutions are: ① four high: "high viscosity, high iron, high suspended solids, high salt". ② The components are complex: twenty or more chemical additives, including friction reducers, cross-linking agents, scale inhibitors, and the like, contain multiple mineral elements and reservoir solubles due to contact with formation water. ③ The water quality fluctuation is large: in the process of flowback of the fracturing fluid, the composition of the fracturing flowback fluid can be changed continuously. The initial flowback fluid component and the fracturing fluid component are basically the same, the ion concentration is in a trend of continuously rising in the middle and later stages of the flowback process, and certain differences exist in physical properties and chemical properties of different reservoirs. ④ The difference of the discharge amount of the flowback fluid is large: because of the different effects of the oil and gas reservoir well locations, the discharge amount of the flowback fluid can also be greatly different, and in some cases, no flowback fluid can even appear.
The shale oil wastewater can realize the treatment targets of reinjection, back-mixing, recycling or discharge of flowback fluid and the like through methods of oil removal, oxidation, flocculation air floatation, multi-medium filtration or membrane treatment and the like. However, in the past shale oil wastewater treatment process, a large amount of salt contained in the shale oil wastewater is generally treated by adopting a combined process of concentration and evaporation crystallization, the byproduct crystalline salt of the shale oil wastewater is in a mixed form, contains a plurality of ions, has low recycling degree, and the national hazardous waste directory in 2021 formally lists distillation and reaction residues, waste mother liquor, waste such as a reaction tank, container cleaning waste liquid and the like in a plurality of production processes into the hazardous waste directory. This results in a ton salt treatment cost of up to 3000 yuan or more. At present, waste salt is generally processed in a mode of centralized temporary storage in a warehouse, high storage and management cost is faced, enterprises are hard to bear, and the problem of 'neck clamping' which restricts the development of the enterprises is already caused. Meanwhile, industrial waste salt is also an important chemical raw material, if the industrial waste salt can be recycled as industrial raw material salt, not only can the pollution of the industrial raw material salt to the environment be eliminated, but also salt resources can be fully utilized, and the recycling and cyclic utilization of the byproduct salt can be realized.
Therefore, development of a resource utilization method of shale oil high-salt wastewater is needed to meet market demands.
Disclosure of Invention
In order to solve the technical problems in the prior art, the application provides a resource utilization method of shale oil high-salt wastewater.
A resource utilization method of shale oil high-salt wastewater adopts the following technical scheme:
a resource utilization method of shale oil high-salt wastewater comprises the following steps:
s11, removing suspended matters in the wastewater by adopting air floatation treatment;
S12, performing oxidation treatment on the wastewater by adopting an advanced oxidation technology;
s13, performing coagulating sedimentation on the advanced oxidation effluent, filtering to remove the generated sediment, and reducing the concentration of suspended matters in the coagulating effluent to below 100 mg/L;
S14, performing reverse osmosis membrane concentration on the overmixed condensate water to obtain reverse osmosis concentrated water and reverse osmosis clear water;
S15, separating the reverse osmosis concentrated water by using a nanofiltration membrane to obtain nanofiltration concentrated water containing sodium sulfate and nanofiltration clear water containing sodium chloride;
S16, freezing and crystallizing sodium sulfate nanofiltration concentrated water to obtain mirabilite, recycling water and a first crystallization mother solution, and then melting and crystallizing the mirabilite to obtain sodium sulfate;
S17, carrying out first concentration and reduction treatment on filtered water containing sodium chloride, and then carrying out first-stage evaporation on the obtained concentrated water to obtain sodium chloride, recovered water and second crystallization mother liquor;
S18, mixing the first crystallization mother liquor and the second crystallization mother liquor, performing second concentration and reduction treatment, and performing secondary evaporation on the obtained concentrated water to obtain recovered water and mixed salt.
By adopting the technical scheme, S11, suspended matters in the wastewater are removed by adopting air floatation treatment: suspended matters in the wastewater can be effectively removed by the air floatation technology, and the water quality of the wastewater is improved. S12, carrying out oxidation treatment on the wastewater by adopting an advanced oxidation technology: advanced oxidation technology can utilize strong oxidant such as ozone to decompose and oxidize organic matters in the wastewater, so as to reduce the concentration of the organic matters. S13, performing coagulating sedimentation on the advanced oxidation effluent, filtering to remove the generated sediment, and reducing the concentration of suspended matters in the coagulating effluent to below 100 mg/L: the turbidity particles in the wastewater can be aggregated to form precipitate through coagulation treatment, and the generated precipitate can be removed through filtration, so that the concentration of suspended substances is further reduced. S14, performing reverse osmosis membrane concentration on the overmixed condensate water to obtain reverse osmosis concentrated water and reverse osmosis clear water: and concentrating solutes in the wastewater through the separation of the reverse osmosis membrane to obtain concentrated water and clear water. S15, performing nanofiltration membrane separation on the reverse osmosis concentrated water to obtain nanofiltration concentrated water containing sodium sulfate and nanofiltration filtered water containing sodium chloride: the nanofiltration membrane can separate different solutes in the wastewater in a selective interception mode to obtain concentrated water rich in sodium sulfate and clear water rich in sodium chloride. S16, freezing and crystallizing sodium sulfate nanofiltration concentrated water to obtain mirabilite, recovering water and a first crystallization mother solution, and then melting and crystallizing the mirabilite to obtain sodium sulfate: the superfluous water in the sodium sulfate nanofiltration concentrated water can be frozen through freezing crystallization to obtain mirabilite and reclaimed water, and then the mirabilite can be refined into sodium sulfate crystals with higher purity through melting crystallization. S17, carrying out first concentration and reduction treatment on filtered water containing sodium chloride, and then carrying out first-stage evaporation on the obtained concentrated water to obtain sodium chloride, recovered water and second crystallization mother liquor: the solute of the nanofiltration clear water containing sodium chloride can be concentrated through concentration and reduction treatment, and then sodium chloride crystals, recovered water and second crystallization mother liquor can be obtained through evaporation. S18, mixing the first crystallization mother liquor and the second crystallization mother liquor, performing second concentration and reduction treatment, and performing secondary evaporation on the obtained concentrated water to obtain recovered water and mixed salt: the first crystallization mother liquor and the second crystallization mother liquor are mixed and then subjected to concentration and reduction treatment, and then the recovered water and the mixed salt can be obtained through secondary evaporation. Through the continuous implementation of the steps, organic matters can be efficiently removed from the shale oil high-salt wastewater, and meanwhile, high-purity sodium chloride and sodium sulfate can be obtained, and the products can be applied to a plurality of industries, such as chemical industry, building industry, municipal industry and the like.
Preferably, in step S11, the air-floating treatment is performed by a dissolved air-floating technique, and the suspended matter after the treatment is reduced to less than 2000 mg/L.
By adopting the technical scheme, in the step S11, the air floatation treatment adopts the dissolved air floatation technology to treat, and the effect of reducing the suspended matters to below 2000mg/L after the treatment is to remove the suspended matters in the wastewater, so that the water quality of the wastewater is improved. Air flotation is a common physical and chemical treatment method in which suspended matter is bubbled up to the liquid surface by injecting gas (usually air) into the wastewater, and then separated from the water by buoyancy. Compared with the traditional air floatation technology, the dissolved air floatation technology is more efficient, because tiny bubbles are generated when gas enters the wastewater, the surface area of the bubbles is increased, suspended matters are more easily adhered to the bubbles and float upwards, and therefore the suspended matters removal efficiency is improved. The suspended matters are reduced to below 2000mg/L, so that the wastewater is cleaner, and a better water quality foundation is provided for subsequent treatment.
Preferably, in the step S12, the advanced oxidation technology adopts ozone oxidation, the ozone oxidation device adopts a contact oxidation tank, the ozone oxidant is provided by an ozone generator, the adding amount of the ozone oxidant is 60-80mg/L of wastewater, and the residence time of the wastewater in the contact oxidation tank is 20-50min.
By adopting the above technical scheme, the advanced oxidation technology adopted in step S12 means that an ozone oxidation method is adopted to treat the wastewater. The ozone oxidation device adopts a contact oxidation pond, and the ozone oxidant is provided by an ozone generator. The adding amount of the ozone oxidant is 60-80mg/L of wastewater, and the residence time of the wastewater in the contact oxidation pond is 20-50min. These conditions are set in order to achieve several effects: the control of the addition amount and the residence time of the ozone oxidant can ensure enough ozone to contact the wastewater so as to promote the reaction and oxidation of organic matters and ozone. Ozone has strong oxidizing property, and can efficiently decompose and degrade organic matters, so that the organic matters in the wastewater are effectively removed. The contact oxidation pond is adopted as an ozone oxidation device, so that the contact area of oxygen, ozone and wastewater can be increased, and the reaction efficiency is improved. The design and operation of the contact oxidation pond can fully mix the wastewater with ozone to promote the reaction. In summary, in the present application, the advanced oxidation technology in step S12 adopts ozone oxidation, the ozone oxidation device adopts a contact oxidation tank, and the setting of the addition amount of the ozone oxidizing agent and the residence time of the wastewater in the contact oxidation tank can realize efficient removal of organic matters in the wastewater, thereby improving the treatment effect of the wastewater.
Preferably, in step S13, the coagulating sedimentation is performed by adding polyacrylamide, polymeric ferric sulfate, and trisodium phosphate to the wastewater; the adding amount of the polyacrylamide is 3-8mg/L; the adding amount of the polymeric ferric sulfate is 10-50mg/L; the adding amount of trisodium phosphate is 10-30mg/L.
By adopting the technical scheme, the coagulating sedimentation process in the step S13 refers to coagulating sedimentation treatment by adding the polyacrylamide, the polymeric ferric sulfate and the trisodium phosphate into the wastewater. The specific parameters are that the adding amount of polyacrylamide is 3-8mg/L, the adding amount of polymeric ferric sulfate is 10-50mg/L, and the adding amount of trisodium phosphate is 10-30mg/L. The action of the coagulating sedimentation process is as follows: the addition of polyacrylamide can increase the gelatinous substances in the wastewater, promote the mutual aggregation of suspended matters and gelatinous particles, and form larger precipitate. This can increase the sedimentation rate of the suspended matter and facilitate the effective removal of suspended matter from the water. The addition of polymeric ferric sulfate can produce iron ions and hydroxyl groups, and the substances can react with alkaline substances and gelling substances in the wastewater to form relatively stable gelling substances. Thus, the coagulating sedimentation speed can be increased, and the sedimentation and removal of suspended matters are promoted. The addition of trisodium phosphate provides phosphate ions which react chemically with iron ions and alkaline substances in the wastewater to form the desired gelled precipitate. This can increase the effect of coagulating sedimentation and further promote the removal of suspended matter. In summary, in the coagulating sedimentation process in step S13, the addition amount of the polyacrylamide, the polymeric ferric sulfate and the trisodium phosphate is controlled, so that the sedimentation and removal of suspended matters in the wastewater can be effectively promoted, the concentration of suspended matters in the coagulating effluent is reduced, and a good water treatment effect is provided for the subsequent treatment step.
Preferably, in step S14, the reverse osmosis membrane concentration is operated at a pressure of 8-10Mpa.
Preferably, in step S15, the operating pressure of the nanofiltration is 3.0-5.0Mpa, and the mass concentration of sodium sulfate in the concentrated water containing sodium sulfate nanofiltration is not less than 7%.
By adopting the technical scheme, the nanofiltration process in the step S15 refers to separating the reverse osmosis concentrated water through a nanofiltration membrane to obtain nanofiltration concentrated water containing sodium sulfate and nanofiltration clear water containing sodium chloride. The specific parameters are that the operation pressure of nanofiltration is 3.0-5.0Mpa, and the mass concentration of sodium sulfate in the sodium sulfate nanofiltration concentrated water is more than or equal to 7%. The nanofiltration process works as follows: the nanofiltration membrane has a high separation effect, and can separate low molecular weight solutes, dissolved ions and water in reverse osmosis concentrated water. And separating reverse osmosis concentrated water into nanofiltration concentrated water containing sodium sulfate and nanofiltration clear water containing sodium chloride through a nanofiltration process. The operating pressure in the nanofiltration process can control the rate of nanofiltration and the separation effect. The operation pressure of nanofiltration is 3.0-5.0Mpa, the nanofiltration speed can be adjusted, and a higher separation effect can be obtained. The mass concentration of sodium sulfate in the sodium sulfate nanofiltration concentrated water is controlled to be more than or equal to 7 percent, and a sodium sulfate solution with higher concentration can be obtained. So that the sodium sulfate is subjected to subsequent purification treatment.
Preferably, in step S16, the temperature of the freeze crystallization is-5 to 0 ℃; the purity of sodium sulfate obtained by melt crystallization of mirabilite is more than or equal to 99 percent.
By adopting the technical scheme, the step S16 involves the processes of freezing crystallization and mirabilite melting crystallization. The specific parameters are that the temperature of freezing crystallization is-5-0 ℃, and the purity of sodium sulfate obtained by melting crystallization of mirabilite is more than or equal to 99 percent. The function of this step is as follows: freezing and crystallizing: freezing and crystallizing nanofiltration concentrated water containing sodium sulfate, and controlling the temperature within the range of-5-0 ℃ to promote the sodium sulfate crystallization and separation. The process of freeze crystallization can increase the purity of sodium sulfate and produce mirabilite, recovered water, and a first crystallization mother liquor. Mirabilite is a hydrate of sodium sulfate, and can be further subjected to melt crystallization to obtain high-purity sodium sulfate. And (3) melting and crystallizing mirabilite: and (3) carrying out melt crystallization on mirabilite to obtain sodium sulfate with purity more than or equal to 99%. The mirabilite is melted at high temperature, and then impurities are removed through a crystallization process, so that high-purity sodium sulfate is obtained. The high-purity sodium sulfate can be applied to various fields of chemical industry, building industry, municipal industry and the like, and has higher economic value and market potential. In summary, the freezing crystallization and mirabilite melt crystallization process in step S16 can improve the purity of sodium sulfate, and finally obtain high-purity sodium sulfate. The high-purity sodium sulfate can be widely applied to different industries, and the resource utilization of the shale oil high-salt wastewater is realized.
Preferably, in step S17, the first concentration and reduction treatment is to concentrate the filtered water containing sodium chloride to a concentration of 100000-200000mg/L by using MVR falling film evaporation, DTRO or ED concentration device; the purity of the obtained sodium chloride is 98-99%.
Preferably, in step S17, the primary evaporation is vacuum crystallization in a crystallization device at a temperature of 25-50 ℃ and a reaction pressure of 0.01-0.04Mpa, and the sodium chloride product is obtained after centrifugal separation and drying.
By adopting the above technical scheme, the purpose of the first concentration reducing treatment in step S17 is to treat nanofiltration water containing sodium chloride by a concentration device so as to increase the concentration thereof to a higher level. The purpose of this is to further increase the purity of the sodium chloride and to collect more sodium chloride. The primary evaporation is realized by vacuum crystallization in a crystallization device with the temperature of 25-50 ℃ and the reaction pressure of 0.01-0.04 Mpa. In the process, the generated sodium chloride product is treated by centrifugal separation and drying operation to obtain high-purity sodium chloride, so that the recycling utilization of the shale oil high-salt wastewater is further realized.
Preferably, in step S18, the secondary evaporation is performed with vacuum crystallization in a crystallization device at a temperature of 40-60 ℃ and a reaction pressure of 0.03-0.06Mpa, and the mixed salt is obtained after centrifugal separation and drying.
In summary, the beneficial technical effects of the application are as follows:
The resource utilization method of the shale oil high-salt wastewater mainly solves the problem of high-efficiency removal of organic matters in the shale oil high-salt wastewater, and obtains high-purity sodium chloride and sodium sulfate, and the products can be widely applied to various fields of chemical industry, building industry, municipal industry and the like, realize resource utilization of the shale oil high-salt wastewater, and reduce environmental pollution and resource waste.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
A resource utilization method of shale oil high-salt wastewater comprises the following steps:
S11, removing suspended matters in the wastewater by adopting dissolved air flotation treatment, and reducing the suspended matters to 1850mg/L after treatment;
s12, carrying out oxidation treatment on the wastewater by adopting an ozone oxidation technology, wherein an ozone oxidation device adopts a contact oxidation tank, an ozone oxidant is provided by an ozone generator, the adding amount of the ozone oxidant is 60mg/L of wastewater, and the residence time of the wastewater in the contact oxidation tank is 50min;
S13, performing coagulating sedimentation on the advanced oxidation effluent, wherein the coagulating sedimentation is to throw polyacrylamide, polymeric ferric sulfate and trisodium phosphate into the wastewater; the adding amount of the polyacrylamide is 3mg/L; the adding amount of the polymeric ferric sulfate is 10mg/L; the adding amount of trisodium phosphate is 30mg/L, the generated precipitate is removed by filtration, and the concentration of suspended matters in the coagulating effluent is reduced to 95mg/L;
S14, performing reverse osmosis membrane concentration on the overmixed condensate water, wherein the operation pressure of the reverse osmosis membrane concentration is 8Mpa, and obtaining reverse osmosis concentrated water and reverse osmosis clear water;
s15, performing nanofiltration membrane separation on reverse osmosis concentrated water, wherein the nanofiltration operation pressure is 3.0Mpa, and obtaining nanofiltration concentrated water containing sodium sulfate and nanofiltration clear water containing sodium chloride, wherein the mass concentration of sodium sulfate in the nanofiltration concentrated water containing sodium sulfate is 7.5%;
s16, freezing and crystallizing sodium sulfate nanofiltration concentrated water at the temperature of-5 ℃, firstly obtaining mirabilite, reclaimed water and first crystallization mother liquor, and then melting and crystallizing the mirabilite to obtain sodium sulfate with the purity of 99.3%;
S17, concentrating sodium chloride-containing nanofiltration clear water in an MVR falling film evaporation device until the concentration of sodium chloride is 200000mg/L, and performing primary evaporation on the obtained concentrated water to obtain sodium chloride, recovered water and a second crystallization mother liquor; the primary evaporation is to perform vacuum crystallization in a crystallization device with the temperature of 25 ℃ and the reaction pressure of 0.01Mpa, and obtain sodium chloride with the purity of 98% through centrifugal separation and drying;
S18, mixing the first crystallization mother liquor and the second crystallization mother liquor, performing second concentration and reduction treatment, performing secondary evaporation on the obtained concentrated water, performing vacuum crystallization in a crystallization device with the temperature of 40 ℃ and the reaction pressure of 0.03Mpa, performing centrifugal separation, and drying to obtain the mixed salt.
Example 2
A resource utilization method of shale oil high-salt wastewater comprises the following steps:
s11, removing suspended matters in the wastewater by adopting dissolved air flotation treatment, and reducing the suspended matters to 1978mg/L after the treatment;
S12, carrying out oxidation treatment on the wastewater by adopting an ozone oxidation technology, wherein an ozone oxidation device adopts a contact oxidation tank, an ozone oxidant is provided by an ozone generator, the adding amount of the ozone oxidant is 80mg/L of wastewater, and the residence time of the wastewater in the contact oxidation tank is 20min;
S13, performing coagulating sedimentation on the advanced oxidation effluent, wherein the coagulating sedimentation is to throw polyacrylamide, polymeric ferric sulfate and trisodium phosphate into the wastewater; the adding amount of the polyacrylamide is 8mg/L; the adding amount of the polymeric ferric sulfate is 50mg/L; the adding amount of trisodium phosphate is 10mg/L, the generated precipitate is removed by filtration, and the concentration of suspended matters in the coagulating effluent is reduced to 70mg/L;
s14, performing reverse osmosis membrane concentration on the overmixed condensate water, wherein the operation pressure of the reverse osmosis membrane concentration is 10Mpa, and obtaining reverse osmosis concentrated water and reverse osmosis clear water;
S15, performing nanofiltration membrane separation on reverse osmosis concentrated water, wherein the nanofiltration operation pressure is 5.0Mpa, and obtaining nanofiltration concentrated water containing sodium sulfate and nanofiltration clear water containing sodium chloride, wherein the mass concentration of sodium sulfate in the nanofiltration concentrated water containing sodium sulfate is 10.5%;
S16, freezing and crystallizing sodium sulfate nanofiltration concentrated water at the temperature of 0 ℃ to obtain mirabilite, reclaimed water and first crystallization mother liquor, and then melting and crystallizing the mirabilite to obtain sodium sulfate with the purity of 99.5%;
S17, concentrating the nanofiltration clear water containing sodium chloride in a DTRO concentration device until the concentration of sodium chloride is 100000mg/L, and performing primary evaporation on the obtained concentrated water to obtain sodium chloride, recovered water and a second crystallization mother liquor; the primary evaporation is to perform vacuum crystallization in a crystallization device with the temperature of 50 ℃ and the reaction pressure of 0.04Mpa, and obtain sodium chloride with the purity of 99 percent through centrifugal separation and drying;
s18, mixing the first crystallization mother liquor and the second crystallization mother liquor, performing second concentration and reduction treatment, performing secondary evaporation on the obtained concentrated water, performing vacuum crystallization in a crystallization device with the temperature of 60 ℃ and the reaction pressure of 0.06Mpa, performing centrifugal separation, and drying to obtain the mixed salt.
Example 3
A resource utilization method of shale oil high-salt wastewater comprises the following steps:
S11, removing suspended matters in the wastewater by adopting dissolved air flotation treatment, and reducing the suspended matters to 1790mg/L after treatment;
S12, carrying out oxidation treatment on the wastewater by adopting an ozone oxidation technology, wherein an ozone oxidation device adopts a contact oxidation tank, an ozone oxidant is provided by an ozone generator, the adding amount of the ozone oxidant is 70mg/L of wastewater, and the residence time of the wastewater in the contact oxidation tank is 35min;
S13, performing coagulating sedimentation on the advanced oxidation effluent, wherein the coagulating sedimentation is to throw polyacrylamide, polymeric ferric sulfate and trisodium phosphate into the wastewater; the adding amount of the polyacrylamide is 5mg/L; the adding amount of the polymeric ferric sulfate is 30mg/L; the adding amount of trisodium phosphate is 18mg/L, the generated precipitate is removed by filtration, and the concentration of suspended matters in the coagulating effluent is reduced to 98mg/L;
s14, performing reverse osmosis membrane concentration on the overmixed condensate water, wherein the operation pressure of the reverse osmosis membrane concentration is 9Mpa, and obtaining reverse osmosis concentrated water and reverse osmosis clear water;
S15, performing nanofiltration membrane separation on reverse osmosis concentrated water, wherein the nanofiltration operation pressure is 4.0Mpa, and obtaining nanofiltration concentrated water containing sodium sulfate and nanofiltration clear water containing sodium chloride, wherein the mass concentration of sodium sulfate in the nanofiltration concentrated water containing sodium sulfate is 8.8%;
S16, freezing and crystallizing sodium sulfate nanofiltration concentrated water at the temperature of-2 ℃, firstly obtaining mirabilite, reclaimed water and first crystallization mother liquor, and then melting and crystallizing the mirabilite to obtain sodium sulfate with the purity of 99.0%;
s17, concentrating sodium chloride-containing nanofiltration clear water in an MVR falling film evaporation, DTRO or ED concentration device until the concentration of sodium chloride is 150000mg/L, and performing primary evaporation on the obtained concentrated water to obtain sodium chloride, recovered water and second crystallization mother liquor; the primary evaporation is to perform vacuum crystallization in a crystallization device with the temperature of 38 ℃ and the reaction pressure of 0.03Mpa, and obtain sodium chloride with the purity of 98.6% through centrifugal separation and drying;
S18, mixing the first crystallization mother liquor and the second crystallization mother liquor, performing second concentration and reduction treatment, performing secondary evaporation on the obtained concentrated water, performing vacuum crystallization in a crystallization device with the temperature of 50 ℃ and the reaction pressure of 0.04Mpa, performing centrifugal separation, and drying to obtain the mixed salt.
The above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the above embodiments specifically illustrate the present application, it should be understood by those skilled in the art that modifications and equivalents may be made to the specific embodiments of the present application without departing from the spirit and scope of the present application, and any modifications and equivalents are intended to be included in the scope of the present application.
Claims (10)
1. The resource utilization method of the shale oil high-salt wastewater is characterized by comprising the following steps of:
s11, removing suspended matters in the wastewater by adopting air floatation treatment;
S12, performing oxidation treatment on the wastewater by adopting an advanced oxidation technology;
s13, performing coagulating sedimentation on the advanced oxidation effluent, filtering to remove the generated sediment, and reducing the concentration of suspended matters in the coagulating effluent to below 100 mg/L;
S14, performing reverse osmosis membrane concentration on the overmixed condensate water to obtain reverse osmosis concentrated water and reverse osmosis clear water;
S15, separating the reverse osmosis concentrated water by using a nanofiltration membrane to obtain nanofiltration concentrated water containing sodium sulfate and nanofiltration clear water containing sodium chloride;
S16, freezing and crystallizing sodium sulfate nanofiltration concentrated water to obtain mirabilite, recycling water and a first crystallization mother solution, and then melting and crystallizing the mirabilite to obtain sodium sulfate;
S17, carrying out first concentration and reduction treatment on filtered water containing sodium chloride, and then carrying out first-stage evaporation on the obtained concentrated water to obtain sodium chloride, recovered water and second crystallization mother liquor;
S18, mixing the first crystallization mother liquor and the second crystallization mother liquor, performing second concentration and reduction treatment, and performing secondary evaporation on the obtained concentrated water to obtain recovered water and mixed salt.
2. The method for recycling shale oil high-salinity wastewater according to claim 1, wherein in the step S11, the air floatation treatment is carried out by adopting a dissolved air floatation technology, and suspended matters after the treatment are reduced to below 2000 mg/L.
3. The method for recycling shale oil high-salt wastewater according to claim 1, wherein in the step S12, the advanced oxidation technology adopts ozone oxidation, an ozone oxidation device adopts a contact oxidation tank, an ozone oxidant is provided by an ozone generator, the adding amount of the ozone oxidant is 60-80mg/L of wastewater, and the residence time of the wastewater in the contact oxidation tank is 20-50min.
4. The method for recycling shale oil high-salinity wastewater according to claim 1, wherein in the step S13, the coagulating sedimentation is to throw poly acrylamide, polymeric ferric sulfate and trisodium phosphate into the wastewater; the adding amount of the polyacrylamide is 3-8mg/L; the adding amount of the polymeric ferric sulfate is 10-50mg/L; the adding amount of trisodium phosphate is 10-30mg/L.
5. The method for recycling shale oil high-salinity wastewater according to claim 1, wherein in the step S14, the operation pressure of reverse osmosis membrane concentration is 8-10Mpa.
6. The method for recycling shale oil high-salt wastewater according to claim 1, wherein in the step S15, the operation pressure of the nanofiltration is 3.05.0mpa, and the mass concentration of sodium sulfate in the sodium sulfate-containing nanofiltration concentrated water is more than or equal to 7%.
7. The method for recycling shale oil high-salinity wastewater according to claim 1, wherein in the step S16, the temperature of the freezing crystallization is-5-0 ℃; the purity of sodium sulfate obtained by melt crystallization of mirabilite is more than or equal to 99 percent.
8. The method for recycling shale oil high-salinity wastewater according to claim 1, wherein in the step S17, the first concentration reduction treatment is to concentrate filtered water containing sodium chloride to a concentration of 100000-200000mg/L by adopting MVR falling film evaporation, DTRO or ED concentration device; the purity of the obtained sodium chloride is 98-99%.
9. The recycling method of shale oil high-salt wastewater according to claim 1, wherein in the step S17, the primary evaporation is to perform vacuum crystallization in a crystallization device with the temperature of 25-50 ℃ and the reaction pressure of 0.01-0.04Mpa, and the sodium chloride product is obtained after centrifugal separation and drying.
10. The recycling method of shale oil high-salt wastewater according to claim 1, wherein in the step S18, the secondary evaporation is performed with vacuum crystallization in a crystallization device with the temperature of 40-60 ℃ and the reaction pressure of 0.03-0.06Mpa, and the mixed salt is obtained after centrifugal separation and drying.
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| CN104909497A (en) * | 2015-06-07 | 2015-09-16 | 长春黄金研究院 | Method for treating acid waste water of nonferrous metal mine |
| CN212924707U (en) * | 2020-06-12 | 2021-04-09 | 杭州上拓环境科技股份有限公司 | Shale gas fracturing flowback liquid membrane type treatment recycling system |
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