CN111484178A - Comprehensive treatment method for seawater or strong brine - Google Patents
Comprehensive treatment method for seawater or strong brine Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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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
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
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Abstract
The invention relates to a comprehensive treatment method of seawater or strong brine, which comprises the following steps: pretreatment, low-interception nanofiltration separation, low-interception nanofiltration permeate treatment, reverse osmosis concentrated water treatment, nanofiltration permeate treatment and nanofiltration concentrated water treatment. The method of the invention can completely recover fresh water, greatly reduce the yield of low-value magnesium chloride and calcium sulfate (gypsum) by-products, avoid the generation of low-value sodium sulfate, magnesium bromide and the like, and obviously improve the yield of high-purity high-value products such as sodium chloride, calcium chloride, potassium sulfate, magnesium sulfate and the like.
Description
Technical Field
The invention belongs to the fields of seawater desalination, comprehensive utilization of seawater resources, comprehensive utilization of salt lake or underground bittern resources and the like, and particularly relates to a comprehensive treatment method of seawater or strong brine.
Background
China has abundant marine resources and bittern resources, according to relevant statistics, the coastal underground bittern resources of Bohai sea can reach 100 hundred million m3Left and right with abundant contentAnd cheap water resources and chemical element resources. At present, the development and utilization of ocean and bittern resources in China mainly take seawater desalination, salt production and salt chemical production of soda, chlor-alkali and the like as main materials, all industries are combined, the comprehensive utilization of seawater and strong brine resources is developed, and the development of circular economy and sustainable development is one of the inevitable trends of the development of related industries at present.
At present, the comprehensive utilization modes of marine resources and bittern resources at home and abroad mainly comprise the following modes:
(1) the membrane method (reverse osmosis) and the thermal method (multi-effect evaporation or multi-stage flash evaporation) are used as core technologies to desalt seawater and produce fresh water. Thermal processes require the consumption of large amounts of steam, usually built around power plants; the conventional seawater desalination treatment process has the fresh water yield of about 40-55%. The by-product strong brine from the sea water desalination cannot be directly processed and utilized in factories due to the scaling problem of calcium sulfate, and part of the by-product strong brine enters a solar salt plant for solar salt production and is usually directly discharged to the sea. Because the salinity of the concentrated seawater is high (close to twice of the salinity of the common seawater) and the concentrated seawater contains pretreatment agents, a large amount of seawater which is directly discharged from the sea can cause marine ecological pollution; fresh water resources and various salt resources in the concentrated seawater are wasted.
(2) The traditional combination of salt pan tedding and salt chemical engineering is the mainstream mode of comprehensive utilization of ocean and bittern resources at present, but has the defects of serious influence by seasons, large amount of salt pan dependence, low resource utilization rate and the like. In addition, in the traditional spreading and drying process of the salt pan, firstly precipitated salt is calcium sulfate and secondly sodium chloride, and in the subsequent advanced treatment process of bittern crystallization mother liquor, calcium ions are completely precipitated in the form of calcium sulfate, so that the production of other calcium salts such as high-value calcium chloride from seawater is impossible, and meanwhile, 30-40% of sulfate ions in the original seawater are consumed by calcium sulfate precipitation, so that the yield of other high-value sulfates (such as magnesium sulfate and potassium sulfate) is reduced. Therefore, in the comprehensive treatment of seawater and concentrated brine, a process and a method for limiting the production of low-value calcium sulfate and increasing the production of other calcium salts (such as calcium chloride) and other sulfate (such as magnesium sulfate, potassium sulfate, etc., which are both chlorine-free fertilizers and supplement sulfur elements required for the growth of crops) in seawater resources are actively sought.
(3) The comprehensive utilization technology of extracting calcium and magnesium first and then concentrating and crystallizing, i.e. firstly, chemical precipitation method (adding NaOH and Na)2CO3Chemical agents and the like), an ion exchange method or an electrochemical technology is adopted to remove calcium and magnesium in the concentrated seawater, and then various solid salt products are prepared by deep concentration crystallization processes such as multi-effect evaporation or vapor compression distillation concentration and the like. The technology effectively solves the problem of scaling of equipment in the process, has high resource utilization rate, but needs to consume a large amount of chemical agents or electric energy, and meanwhile, byproducts such as calcium carbonate and magnesium hydroxide have low equivalent values, so that the operation cost and the investment cost are high, and the economic efficiency of the whole process is to be improved.
(4) The comprehensive utilization technology takes a multi-effect evaporation or vapor compression distillation-seed crystal method (also called a crystal descaling method or an on-line crystallization process) as a core. For example, patent CN103253818A, etc. uses similar technology to realize comprehensive utilization and zero emission of seawater resources. The utilization rate of seawater resources by adopting the comprehensive utilization technology is far higher than that of the traditional process, but the process still produces a large amount of gypsum (calcium sulfate) as a byproduct, the added value is lower, the treatment of a large amount of low-value gypsum becomes a difficult problem, the power consumption in the process is very high, generally 8% of strong brine is concentrated to about 26%, the power consumption is about 35-40 degrees when 1 ton of fresh water is distilled out (meanwhile, the steam consumption is about 15 kg), and the economical efficiency of the process is to be further improved.
(5) The comprehensive utilization technology using electrodialysis concentration to prepare salt is described in patent CN100999364B, etc. the technology mainly uses electrodialysis technology to concentrate concentrated seawater to replace salt pan brine preparation (the salt concentration is concentrated to more than 200 g/L), and then prepares raw salt through multi-effect evaporation or vapor compression evaporation crystallization.
(6) The combination of ordinary nanofiltration and concentrated crystal phase, for example, CN 102849887B, CN102272053A, adopts ordinary nanofiltration membrane (for SO)4 2-The retention rate is more than or equal to 90 percent, and the Mg content is reduced2+The retention rate is more than or equal to 77 percent, and the Ca content is relatively high2+The retention rate is more than or equal to 70 percent and the retention rate to NaCl<30%) of the seawater, and obtaining the nanofiltration penetrating fluid which is high-purity monovalent salt solution, and then obtaining the high-purity NaCl through concentration and crystallization. Because the interception rate of the common nanofiltration membrane to all divalent ions is higher, sulfate ions and calcium ions which are easy to scale are mainly intercepted to the nanofiltration concentrated water side, the use of the common nanofiltration membrane in the patent can effectively reduce the risk of scaling of subsequent concentration equipment of nanofiltration penetrating fluid, improve the purity of solid salt and the like, but when the method is used for treating feed liquid with higher content of calcium ions and sulfate ions (such as concentrated seawater of a seawater desalination plant, underground bittern and the like), the yield of nanofiltration penetrating fluid is very limited, because the common nanofiltration membrane does not have the capability of fundamentally and selectively splitting the sulfate ions and the calcium ions in the feed liquid, if the concentration multiple is increased, the scaling of calcium sulfate salts on the concentrated water side of the common nanofiltration membrane can be possibly caused, and therefore, the economic maximization of the comprehensive seawater treatment process can not be realized. Meanwhile, a large amount of divalent ions, particularly sulfate ions and calcium ions which are easy to scale are enriched in the common nanofiltration concentrated water obtained by the process route of the patent, and even if the nanofiltration concentrated water is subjected to multi-effect evaporation or vapor compression distillation-seed crystal method for concentration and crystallization, the calcium ions (namely more than 68 percent of calcium ions in the raw material liquid) and most of sulfate radicals in the concentrated water still use almost worthless calcium sulfate (instead of CaCl with higher value)2、MgSO4Etc.) and the equipment has the risk of scaling, so the waste is only piled as waste (partially used as building materials or used for sea reclamation), and the resource waste is serious. Therefore, the common nanofiltration process is introduced in the membrane process or the hot process seawater desalination process, the problem of scaling of calcium sulfate during deep concentration of nanofiltration permeate can be solved, pure strong brine with higher concentration can be obtained, the recovery rate of fresh water is not increased on the whole, sulfate ions and most calcium ions in seawater are still lost in comprehensive utilization, and the product with low market acceptance is still mainly used for producing magnesium chloride, but is not mainly used for producing magnesium sulfate (chlorine-free fertilizer). In addition, for concentrated seawater or underground bittern and other concentrated strong brine with high concentration(the concentration of the salt water is more than or equal to 8 percent), the common nanofiltration can not be directly used, and the method is only suitable for the condition of low salt concentration.
In conclusion, the conventional treatment process of seawater and strong brine can not avoid the scaling problem of calcium sulfate, the problem of a large amount of byproduct low-value calcium sulfate and the problem of incapability of obtaining a high value-added product, namely potassium sulfate and magnesium sulfate; the technology for extracting salt resources in seawater and strong brine with high added value is yet to be further developed. The defects of traditional ocean and bittern resource comprehensive utilization equipment and process routes are overcome by adopting technical innovation, the economic competitive advantage is improved, and the method has important technical, economic and environmental protection significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and the method and provide the comprehensive treatment method of the seawater or the strong brine, which has the advantages of high efficiency, energy conservation, low operation risk, high product income and environmental friendliness.
The method can completely extract and fully utilize fresh water and various salt resources in the seawater, produce high value-added products different from the traditional salt farm on the basis of greatly improving the yield of the fresh water, completely avoid the back drainage of the concentrated seawater, and realize that the traditional low-yield salt farm which is spread out on the plane eating in the heaven is replaced by the high-yield three-dimensional compact modern salt factory.
In order to achieve the purpose, the comprehensive treatment method of the seawater or the strong brine comprises the following steps:
1) pretreatment: the seawater or strong brine to be treated is treated by adopting microfiltration and ultrafiltration processes with low molecular weight cut-off, and bacteria, algae, silt, suspended matters, organic matters and the like are removed to obtain pretreated feed liquid;
2) low interception nanofiltration separation: the pretreated feed liquid is separated by adopting a low-interception nanofiltration membrane device with high interception rates of magnesium sulfate, sodium sulfate and magnesium chloride and low interception rate of calcium chloride to respectively obtain the feed liquid rich in SO4 2-、Mg2+And Na-containing nanofiltration concentrate, and+、Cl-、Br-、NO3 -、K+、Ca2+the nanofiltration permeate;
3) and (3) treating the low-interception nanofiltration permeating liquid: the nanofiltration permeate liquid obtained in the step 2) is subjected to a reverse osmosis process to produce fresh water, the yield of the fresh water is 60-80%, and meanwhile reverse osmosis concentrated water with the Be degree of 8-15 degrees can be obtained;
4) reverse osmosis concentrated water treatment: carrying out nanofiltration treatment on the concentrated water obtained in the step 3) to obtain nanofiltration concentrated water rich in divalent and high-valence ions and nanofiltration permeate rich in monovalent ions of 7-14 DEG Be;
5) and (3) nanofiltration permeating liquid treatment: concentrating and crystallizing the nanofiltration permeate liquid in the step 4) to obtain refined NaCl, then removing silicon, and sequentially and respectively extracting bromine, magnesium (magnesium chloride), potassium, calcium (calcium chloride) and lithium; the fresh water produced in the process is directly used or used after low-pressure reverse osmosis and other post-treatments;
6) and (3) nanofiltration concentrated water treatment: mixing nanofiltration concentrated water obtained in the step 2) with the nanofiltration concentrated water obtained in the step 4), evaporating and crystallizing to obtain calcium sulfate, strontium sulfate, sodium chloride and the like in sequence, and then removing silicon, extracting bromine, extracting magnesium (a large amount of magnesium sulfate and a small amount of magnesium chloride) and extracting lithium in sequence; the fresh water produced in the process can be directly used or used after low-pressure reverse osmosis and other post-treatments.
Furthermore, the strong brine can be the concentrated water by-product in the seawater desalination process by the reverse osmosis method, the concentrated water by-product in the seawater desalination process by the multi-effect evaporation method or the multi-stage flash evaporation method, the concentrated water by-product in the seawater desalination process by the air compression distillation method, the concentrated water by-product in the seawater desalination process by the membrane distillation method, the concentrated seawater produced by the seawater through electrodialysis, the concentrated water by-product in any industrialized seawater or brackish water desalination process, the concentrated seawater produced by tedding part of a salt pan, the waste water produced by the external drainage of a seawater medium circulation cooling system of a thermal power plant, the waste water produced by the flue gas desulfurization by the seawater method of the thermal power plant, the brine in a salt lake or.
Further, the microfiltration and low cut-off molecular weight ultrafiltration process is adopted in the step 1) to replace the traditional processes of medicament sterilization, algae removal, flocculation sedimentation and the like, so that bacteria, algae, silt, suspended matters, organic matters and the like in the feed liquid are removed; meanwhile, the organic matter concentrated water generated in the ultrafiltration process with low molecular weight cut-off is subjected to biochemical treatment by halotolerant bacteria, and the generated biological sludge and the micro-filtration cut-off substances are subjected to resource recovery treatment.
Further, the nanofiltration membrane with low interception in the step 2) can be used for treating SO4 2-Has better retention property on Ca2+Has good permeability, and is preferably to divalent anion (such as SO)4 2-、HPO4 2-、CO3 2-Etc.) with high rejection rates for monovalent anions, monovalent cations and certain divalent cations (especially Ca)2+、Sr2+、Ba2+) Nanofiltration membranes with very low rejection rates; preference for low-rejection nanofiltration membrane to SO4 2-The retention rate is more than or equal to 95 percent (more preferably more than 98 percent) and the Mg content2+The retention rate is more than or equal to 75 percent, and the Ca content is relatively high2+Retention rate<35% (more preferably)<20%) and rejection rate of monovalent ions<20% (more preferably)<5％)。
Further, the low-interception nanofiltration process of the step 2) has the following characteristics: realizing divalent anion SO under high yield water recovery rate and high membrane flux4 2-With divalent cations Ca2+And Sr2+To make SO in the feed liquid4 2-The ions are concentrated.
Further, the low-interception nanofiltration membrane in the step 2) is suitable for the operation conditions: the operation pressure is 0.5-4.1 MPa, the operation temperature is 5-45 ℃, and the pH value is 3-12.
Further, the reverse osmosis in the step 3) adopts coupling of one or more processes such as low-pressure reverse osmosis, medium-pressure reverse osmosis, high-pressure reverse osmosis and the like.
Further, the common nanofiltration of the step 4) is performed on SO4 2-、Ca2+、Mg2+And Sr2+The divalent ions or the high-valent ions have higher retention rate and Na resistance+、Cl-、Br-The rejection rate of the plasma monovalent ions is low.
Further, the concentration-crystallization process of the steps 5) and 6) is one of simple evaporation-crystallization, multi-effect evaporation-crystallization, membrane distillation-crystallization, vapor compression distillation-crystallization and the like.
Further, the silicon removal process of the steps 5) and 6) is as follows: and (3) regulating the pH value of the feed liquid to 3-4 by using hydrochloric acid, and separating out silicon in the feed liquid in a solid silicon dioxide form.
Further, the bromine extraction process of the steps 5) and 6) is as follows: and (3) introducing chlorine into the desilicated acidic feed liquid, and extracting bromine by using a traditional stripping, rectifying or gaseous membrane method.
Further, the magnesium extraction process of the steps 5) and 6): and (3) adjusting the pH value of the feed liquid after bromine extraction to 7.0-8.5 by using sodium hydroxide, and evaporating and crystallizing to separate out magnesium salt. Wherein the magnesium chloride and the carnallite are obtained in the step 5); the product obtained in step 6) is a large amount of magnesium sulfate and a small amount of magnesium chloride.
Further, the potassium extraction process in the step 5) comprises the following steps: recovering potassium salt by using carnallite as a raw material, and producing potassium sulfate by using the carnallite and the magnesium sulfate produced in the step 6).
Further, the calcium extraction process in the step 5) comprises the following steps: the calcium salt is recovered as calcium chloride.
Further, the lithium extraction process of the steps 5) and 6) is as follows: the potassium salt was recovered as lithium chloride and lithium sulfate.
Furthermore, the invention greatly avoids mass production of low-value by-product gypsum, and the high-value products such as high-purity sodium chloride, calcium chloride, potassium sulfate, magnesium sulfate, bromine and the like have remarkably increased yield, so that the low-value sodium sulfate product is completely avoided; and no sewage or wastewater is discharged.
Compared with the traditional comprehensive utilization process of seawater, concentrated seawater, salt lake water or underground bittern and the like, the invention has the following positive effects and advantages:
1) permeate liquid in the low-interception nanofiltration process mainly comprises monovalent ions, partial calcium ions and a small amount of magnesium ions, can be deeply concentrated through the reverse osmosis process, the fresh water yield reaches 60-80%, and the fresh water yield is improved by 30-80% compared with that of the conventional membrane method seawater desalination industry;
2) for special solution systems such as seawater and concentrated seawater, the low-interception nanofiltration process objectively treats SO in seawater or concentrated brine4 2-、Ca2+Effectively disassembled and combined with reverse osmosis and common nanofiltration processes, thereby not only greatly reducing the generation of low-value products such as calcium sulfate and the like, but also obviously improving the yield of the low-value productsThe yields of high-value products such as calcium chloride, magnesium sulfate, potassium sulfate, refined sodium chloride and the like are reduced, and the scaling risk of subsequent concentration equipment is reduced;
3) the seawater or strong brine containing biomass generated by pretreatment can be subjected to biochemical treatment by halotolerant bacteria, a small amount of biological sludge formed after treatment can be further subjected to resource treatment, and no wastewater, sewage or concentrated water is discharged outside, so that no secondary pollution is caused;
4) the process adopts a reverse osmosis technology with low investment and low operation cost which is coupled with a low interception nanofiltration technology compared with compressed air distillation, and greatly reduces the equipment investment and energy consumption in the processes of seawater desalination and deep concentration, thereby obviously reducing the investment, operation risk and operation cost of the whole process;
5) the invention can completely extract and fully utilize fresh water and various salt resources in the seawater, produces high value-added products different from the traditional salt field on the basis of completely recovering the fresh water, completely avoids seawater back drainage, has high resource utilization rate, low operation risk and no secondary pollution, and can realize that the traditional plane spread type low-yield salt field eating by a high-yield three-dimensional compact modern salt factory is replaced by the traditional plane spread type low-yield salt field eating on the sky.
Drawings
FIG. 1 is a schematic view of the process flow of the comprehensive treatment method of seawater or concentrated brine.
Detailed Description
The invention is further described with reference to the accompanying drawings and the embodiments. Elements and features depicted in one drawing or one embodiment of the invention may be combined with elements and features shown in one or more other drawings or embodiments. It should be noted that the figures and description omit representation and description of components or processes that are not relevant to the present invention and that are known to those of ordinary skill in the art for the sake of clarity.
The components used in the examples were all commercially available.
As shown in fig. 1, the present invention is mainly directed to the comprehensive treatment and utilization of resources by using seawater, concentrated seawater (including but not limited to the concentrated water by-product of the reverse osmosis seawater desalination process, the concentrated water by-product of the multiple-effect evaporation or multistage flash evaporation seawater desalination process, the concentrated water by-product of the air compression distillation seawater desalination process, the concentrated water by membrane distillation seawater desalination process, the concentrated seawater produced by seawater electrodialysis, the concentrated water by any industrialized seawater or brackish water desalination process, the concentrated seawater produced by tedding in the salt pan, the water discharged from the seawater medium circulation cooling system of the thermal power plant), the wastewater produced by the flue gas desulfurization in the seawater process of the thermal power plant, salt lake water, underground bittern, etc. as raw materials.
The method comprises the following specific steps:
1) pretreatment of
Firstly, the feed liquid of seawater, concentrated seawater, salt lake water or underground bittern is treated by conventional sand filtration, microfiltration and ultrafiltration with low molecular weight cut-off, so as to remove bacteria, colloid, algae, silt and organic pollutants with molecular weight more than 1000Da, even more than 400 Da. The organic matter concentrated water generated by the ultrafiltration with low molecular weight cut-off can be biochemically treated by halotolerant bacteria, and the generated biological sludge and the micro-filtration cut-off substances are recycled.
2) Low retention nanofiltration separation
The pretreated seawater, concentrated seawater, salt lake water or underground brine is treated by a high-flux and high-selectivity low-interception nanofiltration membrane. The separation and interception performances of the nanofiltration membrane adopted by the invention are shown in table 1:
TABLE 1 rejection performance of low rejection nanofiltration membranes
The pretreated feed liquid is subjected to low-interception nanofiltration process, and the permeation liquid contains Na+、Cl-、NO3 -、Br-、K+Plasma monovalent ion and part of Ca2+Small amount of Mg2+Trace amount of SO4 2-(ii) a The concentrated water is rich in SO4 2-、Mg2+And a certain amount of Ca2+And the recovery rate of the permeation liquid in other monovalent ion low-interception nanofiltration processes can reach 75-85%.
3) And (3) treating the low-interception nanofiltration permeate: reverse osmosis, common nanofiltration
And (3) the low-interception nanofiltration permeate is subjected to a concentration process coupling one or more processes of low-pressure reverse osmosis, medium-pressure reverse osmosis, high-pressure reverse osmosis and the like to produce fresh water, and meanwhile, concentrated water with the Be of about 8-15 degrees can be obtained.
The concentrated water in the reverse osmosis process enters the common nanofiltration process, and the condition that the main ions in the feed liquid are intercepted is shown in table 2; obtaining nanofiltration concentrated water rich in divalent and high-valence ions and nanofiltration permeating liquid rich in monovalent ions and having a temperature of 7-14 DEG Be.
TABLE 2 Primary ion rejection in common nanofiltration Process
The ratio of total amount of ions in the concentrated water to total amount of ions in the permeate and the concentrated water
4) Treatment of common nanofiltration permeate
Concentrating and crystallizing common nanofiltration permeate to obtain refined NaCl and calcium sulfate in turn, adjusting the pH value of the feed liquid to 3-4 by hydrochloric acid to remove silicon in the feed liquid after most of sodium chloride in the feed liquid is separated out, introducing chlorine, and extracting bromine by using a traditional stripping, rectifying or gaseous membrane method. Thereby avoiding the mixed crystallization of magnesium bromide and magnesium chloride.
Adjusting the pH value of the feed liquid to 7.0-8.5 by using sodium hydroxide after bromine extraction, evaporating and crystallizing to separate out magnesium salt (mainly in a magnesium chloride form), extracting potassium (mainly in a carnallite form), extracting calcium (in a calcium chloride form, a high-efficiency snow melting agent) and extracting lithium.
The fresh water produced in the process can be directly used or used after low-pressure reverse osmosis and other post-treatments.
5) Treatment of nanofiltration concentrate
Mixing the concentrated water in the common nanofiltration process with the concentrated water in the low-interception nanofiltration process, adjusting the pH value of the feed liquid by hydrochloric acid, and concentrating the feed liquid by adopting a concentration evaporation-online crystallization technology to obtain calcium sulfate, strontium sulfate, sodium chloride and the like.
After most of sodium chloride in the feed liquid is crystallized, adding hydrochloric acid, adjusting the pH value of the feed liquid to 3-4 to remove silicon in the feed liquid, introducing chlorine, and extracting bromine by using a traditional stripping, rectifying or gaseous membrane method.
Then sodium hydroxide is used for regulating the pH value back to 7.0-8.5, and concentration and crystallization are continued to obtain magnesium sulfate and a small amount of magnesium chloride; the mother liquor is used for extracting potassium and lithium.
The fresh water produced in the process can be directly used or used after low-pressure reverse osmosis and other post-treatments.
Or adding the carnallite obtained in the step 4) into the nanofiltration concentrated water after bromine extraction, re-dissolving magnesium chloride and potassium chloride, and further evaporating and concentrating to obtain kainite (magnesium sulfate and potassium sulfate). Further evaporation and crystallization are carried out to obtain magnesium chloride, and the remaining mother liquor is used for extracting lithium salt.
The invention is further illustrated by the following specific examples.
Example 1
Feed liquid: seawater at 3.4 ° be, pH 8.1, and composition as shown in table 3 below:
TABLE 3
Pretreatment: the polypropylene spray-melt filter with the precision of 5 mu m and the ultrafiltration membranes with the molecular weight cut-off of 6000 and 2000 are used for treatment, and the integral operating pressure of the microfiltration process and the ultrafiltration process is 0.25 MPa. The microfiltration and ultrafiltration concentrated water enters a sludge resource recovery device for treatment, and the generated clear liquid returns to the pretreatment stage.
And (3) low-interception nanofiltration process:
the pretreated feed liquid enters a low interception nanofiltration device (the core membrane element is an NF8040 roll type membrane, the performance is shown in table 1, and the effective area is 30.7m2) The operating pressure was 1.45MPa, the temperature was 35 ℃ and the pH was 8.1. The volume ratio of the nanofiltration penetrating liquid 1 obtained after treatment to the nanofiltration concentrated water 1 is about 4:1, and the specific composition is as follows in table 4:
TABLE 4
Comprehensive utilization of nanofiltration permeate:
concentrating the nanofiltration permeate 1 to about 9 degrees Be by using a reverse osmosis membrane of SUPER RO, wherein the yield of fresh water in the reverse osmosis process is about 73 percent, and recycling; the reverse osmosis concentrated water is subjected to secondary treatment by using a nanofiltration membrane of the model NF270, the operating pressure is 3.5MPa, and the temperature is 35 ℃. The volume ratio of the nanofiltration penetrating liquid 2 obtained after treatment to the nanofiltration concentrated water 2 is about 0.85:0.15, and the specific composition is as follows in the following table 5:
TABLE 5
The pH of the nanofiltration permeate 2 is adjusted to about 6.0 by using hydrochloric acid, then the nanofiltration permeate is concentrated to about 25 degrees Be by compression distillation, brine with the temperature of about 25 degrees Be is prepared into sodium chloride crystals by using a two-effect evaporation-crystallization device, the purity of the sodium chloride product can reach more than 99 percent after the crystals are dried, and the total content of calcium and magnesium ions carried out in the crystallization process is only about 150 ppm. And (3) acidifying and oxidizing the obtained crystallization mother liquor, and extracting bromine in the crystallization mother liquor by using a blow-off method or a gaseous membrane method, wherein the pH value is adjusted to be about 3.5 by using hydrochloric acid in the acidification process, and at the moment, silicon element in the mother liquor is also precipitated and separated out in the form of silicon dioxide solid so as to be removed. Adjusting the pH of the feed liquid after bromine extraction to 8.5 by using NaOH, and sequentially and respectively obtaining products such as magnesium chloride, carnallite, calcium chloride and the like by continuously adopting an evaporation concentration-crystallization mode; after the mother liquor is further concentrated, tributyl phosphate is used as an extracting agent, and a solvent extraction method is adopted to extract lithium chloride from the mother liquor. After carnallite is hydrolyzed by water to be crystallized and demagging, water is added for washing to directly obtain a potassium chloride crystal product.
Comprehensive utilization of nanofiltration concentrated water:
mixing the nanofiltration concentrated water 1 and 2 obtained in the steps, adjusting the pH of the mixed solution to about 6 by using hydrochloric acid, then feeding the mixed solution into a vapor compression distillation-calcium sulfate on-line crystallization device, and concentrating the mixed solution to 24 degrees BAbout re, separating precipitated calcium sulfate, strontium sulfate and the like by a hydraulic separator; the feed liquid with 24 degrees Be is simply evaporated and crystallized to obtain a sodium chloride product (containing a small amount of calcium magnesium sulfate radical); the bromine in the crystallization mother liquor is extracted by a blow-off method or a gaseous membrane method after the crystallization mother liquor is acidified and oxidized, the acidification process is to use hydrochloric acid to adjust the pH value to about 3.5, and at the moment, silicon element in the mother liquor is also precipitated in the form of silicon dioxide and removed. Adjusting the pH of the feed liquid after bromine extraction to 8.5 by using NaOH, and sequentially and respectively obtaining products such as magnesium sulfate, potassium-magnesium alum, magnesium chloride and the like by continuously adopting an evaporation concentration-crystallization mode; adding Na into the residual mother liquor2CO3The precipitant is lithium carbonate.
Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, devices, means, methods, or steps.
Claims (15)
1. A comprehensive treatment method of seawater or strong brine is characterized by comprising the following steps:
1) pretreatment: the seawater or strong brine to be treated is treated by adopting microfiltration and ultrafiltration processes with low molecular weight cut-off, and bacteria, algae, silt, suspended matters and organic matters are removed to obtain pretreated feed liquid;
2) low interception nanofiltration separation: the pretreated feed liquid is separated by adopting a low-interception nanofiltration membrane device with high interception rates of magnesium sulfate, sodium sulfate and magnesium chloride and low interception rate of calcium chloride to respectively obtain the feed liquid rich in SO4 2-、Mg2+And Na-containing nanofiltration concentrate, and+、Cl-、Br-、NO3 -、K+、Ca2+the nanofiltration permeate;
3) and (3) treating the low-interception nanofiltration permeating liquid: the nanofiltration permeate liquid obtained in the step 2) is subjected to a reverse osmosis process to produce fresh water, the yield of the fresh water is 60-80%, and meanwhile reverse osmosis concentrated water with the Be degree of 8-15 degrees can be obtained;
4) reverse osmosis concentrated water treatment: performing nanofiltration treatment on the reverse osmosis concentrated water obtained in the step 3) to obtain nanofiltration concentrated water rich in divalent and high-valence ions and 7-14 DEG Be nanofiltration permeate rich in monovalent ions;
5) and (3) nanofiltration permeating liquid treatment: concentrating and crystallizing the nanofiltration permeate liquid obtained in the step 4) to obtain refined NaCl, then removing silicon, and sequentially and respectively extracting bromine, magnesium, potassium, calcium and lithium;
6) and (3) nanofiltration concentrated water treatment: and (3) mixing the nanofiltration concentrated water obtained in the step (2) with the nanofiltration concentrated water obtained in the step (4), evaporating and crystallizing to obtain calcium sulfate, strontium sulfate and sodium chloride in sequence, and then removing silicon, extracting bromine, extracting magnesium and extracting lithium in sequence.
2. The method according to claim 1, wherein the brine is the concentrated water produced by the reverse osmosis seawater desalination process, the concentrated water produced by the multiple-effect evaporation or multi-stage flash evaporation seawater desalination process, the concentrated water produced by the compressed air distillation seawater desalination process, the concentrated water produced by the membrane distillation seawater desalination process, the concentrated seawater produced by the seawater electrodialysis treatment, the concentrated water produced by any industrialized seawater or brackish water desalination process, the concentrated seawater produced by tedding in a salt pan, the effluent discharged from a seawater medium circulation cooling system of a thermal power plant, the wastewater produced by flue gas desulfurization in the seawater process of the thermal power plant, the salt lake water or underground salt brine.
3. The comprehensive treatment method of seawater or concentrated brine according to claim 1, wherein the organic matter concentrated water generated in the low cut-off molecular weight ultrafiltration process in step 1) is subjected to biochemical treatment by halotolerant bacteria, and the generated biological sludge and micro-filtration trapped substances are subjected to resource recovery treatment.
4. The comprehensive treatment method of seawater or concentrated brine as claimed in claim 1, wherein the low-cut-off nanofiltration membrane device in step 2) adopts a low-cut-off nanofiltration membrane for SO4 2-Has good retention property on Ca2+The nanofiltration membrane has good permeability, and preferably has high rejection rate on divalent anions and low rejection rate on monovalent anions, monovalent cations and some divalent cations; preferred low-rejection nanofiltration membrane to SO4 2-The retention rate is more than or equal to 95 percent, more preferably more than 98 percent, for Mg2+The retention rate is more than or equal to 75 percent, and for Ca2+Retention rate<35%, more preferably<20% rejection rate for monovalent ion<20%, more preferably<5％。
5. The comprehensive treatment method of seawater or concentrated brine according to claim 4, wherein the operating pressure of the low interception nanofiltration membrane is 0.5-4.1 MPa, the operating temperature is 5-45 ℃, and the pH is 3-12.
6. The method of claim 1, wherein the reverse osmosis in step 3) is one or more of low pressure reverse osmosis, medium pressure reverse osmosis and high pressure reverse osmosis.
7. The integrated seawater or brine treatment process of claim 1, wherein the nanofiltration treatment in step 4) is performed on SO4 2-、Ca2+、Mg2+Higher retention of divalent or higher valent ions and Na+、Cl-、Br-The rejection of monovalent ions is low.
8. The integrated seawater or brine treatment process as claimed in claim 1, wherein the concentration crystallization of step 5) is one of simple evaporation-crystallization, multiple effect evaporation-crystallization, membrane distillation-crystallization, and vapor compression distillation-crystallization.
9. The comprehensive treatment method of seawater or concentrated brine as claimed in claim 1, wherein the pH value of the feed liquid is adjusted to 3-4 by hydrochloric acid in the silicon removal in the steps 5) and 6), and silicon in the feed liquid is precipitated in the form of solid silicon dioxide.
10. The comprehensive treatment method of seawater or concentrated brine according to claim 1, wherein the bromine extraction in the steps 5) and 6) is carried out by introducing chlorine into the acidic feed liquid after silicon removal and extracting bromine by using a traditional stripping, rectification or gaseous membrane method.
11. The comprehensive treatment method of seawater or concentrated brine according to claim 1, wherein the magnesium extraction in the steps 5) and 6) adopts bromine extraction feed liquid, sodium hydroxide is used for adjusting the pH value of the feed liquid to 7.0-8.5, and magnesium salt is separated out through evaporation and crystallization.
12. The integrated process for the treatment of seawater or brine according to claim 1 or 11, wherein the magnesium extraction step 5) results in magnesium chloride, carnallite; the product obtained in step 6) is a large amount of magnesium sulfate and a small amount of magnesium chloride.
13. The integrated process of claim 1, wherein the potassium extraction in step 5) is performed by recovering potassium salt from carnallite used as raw material and further producing potassium sulfate.
14. The integrated seawater or brine treatment process of claim 1 wherein the calcium extraction of step 5) recovers calcium salts as calcium chloride.
15. The integrated process for the treatment of seawater or concentrated brine as claimed in claim 1, wherein the lithium extraction in steps 5) and 6) is carried out to recover lithium salts in the form of lithium chloride and lithium sulfate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112607942A (en) * | 2020-12-14 | 2021-04-06 | 烟台金正环保科技有限公司 | Seawater recycling treatment system and process |
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Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999364A (en) * | 2006-05-16 | 2007-07-18 | 葛文宇 | Comprehensive utilization high advantage zero discharge seawater desalination production technology |
| CN101234767A (en) * | 2008-02-29 | 2008-08-06 | 天津长芦海晶集团有限公司 | Thick seawater comprehensive utilization technique after seawater desalination |
| US20090050565A1 (en) * | 2005-04-05 | 2009-02-26 | Muralidhara Harapanahalli S | System and Method for Removing Contaminants From Wastewater |
| US20100163471A1 (en) * | 2008-12-30 | 2010-07-01 | Irving Elyanow | Water desalination plant and system for the production of pure water and salt |
| ES2377067A1 (en) * | 2008-12-18 | 2012-03-22 | Desalación Integral Systems, S.L. | Improvements in the purpose of the patent n¿ p200600257 and in the patent of addition n¿ p200802271 by: desalination plant-water tanker salt and industrial waste with zero liquid discharge. (Machine-translation by Google Translate, not legally binding) |
| US20120267308A1 (en) * | 2011-04-25 | 2012-10-25 | Trevi Systems Inc. | Recovery of retrograde soluble solute for forward osmosis water treatment |
| CN102849887A (en) * | 2012-10-07 | 2013-01-02 | 中国海洋大学 | Seawater desalting method |
| CN103114211A (en) * | 2013-02-19 | 2013-05-22 | 宁波莲华环保科技股份有限公司 | Method for extracting lithium from primary lithium extraction solution of lithium ore |
| CN103253818A (en) * | 2013-04-19 | 2013-08-21 | 金逹行有限公司 | Seawater desalination, resource comprehensive utilization and zero discharge processing system |
| CN103407965A (en) * | 2013-08-22 | 2013-11-27 | 洁海瑞泉膜技术（北京）有限公司 | Method for preparing/gathering bromine from bromine-containing feed liquid or waste water |
| CN104261443A (en) * | 2014-09-25 | 2015-01-07 | 池州西恩新材料科技有限公司 | Process for calcium-method production of magnesium hydrate by using nanofiltration membrane |
| CN104556302A (en) * | 2014-12-09 | 2015-04-29 | 上海力脉环保设备有限公司 | Concentration and separation process utilizing combination of reverse osmosis membrane and nanofiltration membrane |
| CN106396234A (en) * | 2016-11-25 | 2017-02-15 | 洁海瑞泉膜技术（天津）有限公司 | Zero-discharge treatment method for reverse osmosis concentrated water |
| KR20170089230A (en) * | 2016-01-26 | 2017-08-03 | 고려대학교 산학협력단 | Desalination method of sea water using hybrid process of nanofiltration and draw solution assisted reverse osmosis |
| CN107089753A (en) * | 2017-05-05 | 2017-08-25 | 浙江大维高新技术股份有限公司 | The processing method of power plant desulfurization wastewater |
| CN108178408A (en) * | 2017-12-26 | 2018-06-19 | 杭州水处理技术研究开发中心有限公司 | A kind of device and method of desulfurization wastewater processing |
| CN108314064A (en) * | 2018-02-09 | 2018-07-24 | 陕西省膜分离技术研究院有限公司 | The full membrane separating method of production lithium liquor is concentrated by salt lake bittern Multistage Membranes |
| CN108658101A (en) * | 2017-08-10 | 2018-10-16 | 青海盐湖工业股份有限公司 | A kind of new process of salt lake bittern production high-purity lithium chloride |
-
2019
- 2019-01-29 CN CN201910085351.XA patent/CN111484178B/en active Active
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090050565A1 (en) * | 2005-04-05 | 2009-02-26 | Muralidhara Harapanahalli S | System and Method for Removing Contaminants From Wastewater |
| CN100999364A (en) * | 2006-05-16 | 2007-07-18 | 葛文宇 | Comprehensive utilization high advantage zero discharge seawater desalination production technology |
| CN101234767A (en) * | 2008-02-29 | 2008-08-06 | 天津长芦海晶集团有限公司 | Thick seawater comprehensive utilization technique after seawater desalination |
| ES2377067A1 (en) * | 2008-12-18 | 2012-03-22 | Desalación Integral Systems, S.L. | Improvements in the purpose of the patent n¿ p200600257 and in the patent of addition n¿ p200802271 by: desalination plant-water tanker salt and industrial waste with zero liquid discharge. (Machine-translation by Google Translate, not legally binding) |
| US20100163471A1 (en) * | 2008-12-30 | 2010-07-01 | Irving Elyanow | Water desalination plant and system for the production of pure water and salt |
| CN102272053A (en) * | 2008-12-30 | 2011-12-07 | 通用电气公司 | Water desalination plant and system for the production of pure water and salt |
| US20120267308A1 (en) * | 2011-04-25 | 2012-10-25 | Trevi Systems Inc. | Recovery of retrograde soluble solute for forward osmosis water treatment |
| CN102849887A (en) * | 2012-10-07 | 2013-01-02 | 中国海洋大学 | Seawater desalting method |
| CN103114211A (en) * | 2013-02-19 | 2013-05-22 | 宁波莲华环保科技股份有限公司 | Method for extracting lithium from primary lithium extraction solution of lithium ore |
| CN103253818A (en) * | 2013-04-19 | 2013-08-21 | 金逹行有限公司 | Seawater desalination, resource comprehensive utilization and zero discharge processing system |
| CN103407965A (en) * | 2013-08-22 | 2013-11-27 | 洁海瑞泉膜技术（北京）有限公司 | Method for preparing/gathering bromine from bromine-containing feed liquid or waste water |
| CN104261443A (en) * | 2014-09-25 | 2015-01-07 | 池州西恩新材料科技有限公司 | Process for calcium-method production of magnesium hydrate by using nanofiltration membrane |
| CN104556302A (en) * | 2014-12-09 | 2015-04-29 | 上海力脉环保设备有限公司 | Concentration and separation process utilizing combination of reverse osmosis membrane and nanofiltration membrane |
| KR20170089230A (en) * | 2016-01-26 | 2017-08-03 | 고려대학교 산학협력단 | Desalination method of sea water using hybrid process of nanofiltration and draw solution assisted reverse osmosis |
| CN106396234A (en) * | 2016-11-25 | 2017-02-15 | 洁海瑞泉膜技术（天津）有限公司 | Zero-discharge treatment method for reverse osmosis concentrated water |
| CN107089753A (en) * | 2017-05-05 | 2017-08-25 | 浙江大维高新技术股份有限公司 | The processing method of power plant desulfurization wastewater |
| CN108658101A (en) * | 2017-08-10 | 2018-10-16 | 青海盐湖工业股份有限公司 | A kind of new process of salt lake bittern production high-purity lithium chloride |
| CN108178408A (en) * | 2017-12-26 | 2018-06-19 | 杭州水处理技术研究开发中心有限公司 | A kind of device and method of desulfurization wastewater processing |
| CN108314064A (en) * | 2018-02-09 | 2018-07-24 | 陕西省膜分离技术研究院有限公司 | The full membrane separating method of production lithium liquor is concentrated by salt lake bittern Multistage Membranes |
Non-Patent Citations (6)
| Title |
|---|
| AL-JLIL, SAAD: ""PERFORMANCE OF NANO-FILTRATION AND REVERSE OSMOSIS PROCESSES FOR WASTEWATER TREATMENT"", 《MATERIALI IN TEHNOLOGIJE》 * |
| HILAL, N等: "Nanofiltration of magnesium chloride, sodium carbonate, and calcium sulphate in salt solutions", 《SEPARATION SCIENCE AND TECHNOLOGY》 * |
| 吕福喜等: ""聚四氟乙烯气态膜法浓海水提溴实验研究"", 《盐科学与化工》 * |
| 国家海洋局海洋科技情报研究所《中国海洋年鉴》编辑部: "《中国海洋年鉴》", 31 October 1988, 海洋出版社 * |
| 毕飞等: "纳滤膜系统优化设计模式探讨", 《膜科学与技术》 * |
| 王奔等: ""多效膜蒸馏过程用于海水和浓海水的深度浓缩"", 《化工进展》 * |
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