CN102936067A - Method for selectively removing calcium ions from concentrated water byproduct of sea water desalination process and other high-calcium-magnesium-content concentrated brines - Google Patents
Method for selectively removing calcium ions from concentrated water byproduct of sea water desalination process and other high-calcium-magnesium-content concentrated brines Download PDFInfo
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- CN102936067A CN102936067A CN2012104799283A CN201210479928A CN102936067A CN 102936067 A CN102936067 A CN 102936067A CN 2012104799283 A CN2012104799283 A CN 2012104799283A CN 201210479928 A CN201210479928 A CN 201210479928A CN 102936067 A CN102936067 A CN 102936067A
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- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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Abstract
The invention relates to a method for selectively removing calcium ions from a concentrated water byproduct of a sea water desalination process and other high-calcium-magnesium-content concentrated brines, which comprises the following steps: regulating the pH value of the concentrated water to 7.0-8.5, and then heating to a certain temperature; introducing the concentrated water into a heat-insulating apparatus capable of realizing sealed stirring, adding a sodium sulfite or sodium carbonate solution having a certain concentration while stirring, reacting for 1-40 minutes while sufficiently stirring, standing for 5-10 minutes, and then filtering to remove calcium sulfite or calcium carbonate precipitate; and adding hydrochloric acid into the filtrate to regulate the pH value back to 6. According to the invention, the problems of low calcium removal rate, high magnesium loss rate, long stirring time and the like during the concentrated water treatment based on the traditional normal-temperature sodium carbonate precipitation method are overcome, the operation is convenient, the investment is low, and the operation cost is low; and the concentrated water liquid subjected to decalcification treatment can be further deeply concentrated through a membrane method or hot method, thereby improving the fresh water recovery rate and realizing the reutilization and zero discharge of the resources. The method provided by the invention is suitable for selectively removing calcium ions from sea water, sea water or brackish water subjected to other treatment processes such as reverse osmosis or multiple-effect evaporation and concentration, underground salt brines and concentrated water of industrial waste water subjected to reverse osmosis treatment.
Description
Technical field
The invention belongs to chemical industry feed liquid or Wastewater Pretreatment technical field, relate to dense water decalcification, especially a kind of from the dense water of desalting process by-product or other high contents of calcium and magnesium strong brines the method for selectively removing calcium ion.
Background technology
China's Freshwater resources are deficient, and time and areal distribution inequality.In recent years, because the aggravation of polluting, so that the imbalance between supply and demand of fresh water is more aobvious outstanding, Freshwater resources lack the restraining factors that become economic and social sustainable development.The advanced treatment and reclamation of the trade effluents such as desalimtor, refinery, Steel Plant and power plant has become an effective means that solves China's water shortage problem.Yet, all can produce the dense water of high-concentration Ca magnesium in the advanced treatment and reclamation process of sea water desaltination and a lot of trade effluents, process 1 ton of seawater such as present method for desalting seawater (embrane method and Re Fa), the dense water of by-product 0.45-0.60 ton, and two embrane method (ultrafiltration+reverse osmosis) processing one ton of refinery, steel plant wastewater also can produce the dense water of 0.25-0.30 ton high contents of calcium and magnesium.Except containing a large amount of calcium ions and magnesium ions, usually also contain sulfate ion in these dense water, will produce CaSO when being concentrated to a certain degree (when reaching 13 ° of B é left and right sides such as concentration of seawater)
4Precipitate (hard scale), and then affect efficient and the operation of desalting plant.
At present, people are different for the treatment process of the dense water of sea water desaltination by-product or the dense water of other high contents of calcium and magnesium.The dense water of desalimtor's by-product normally is sent to the saltern and evaporates brine except directly flowing back to the sea.In process was evaporated brine in classification, calcium sulfate is saturated precipitation gradually, and before sodium-chlor reached capacity in dense water, calcium sulfate almost all was precipitated out.If but adopt the strong brine of the modern industry means concentrating low-concentrations such as multiple-effect evaporation, membrane distillation and produce fresh water, then must remove in advance calcium ion.Do not process if do not carry out decalcification, products obtained therefrom then contains calcium sulfate impurity.If strong brine is directly used in the raw material of soda ash or chlorine industry, then require used strong brine must remove first wherein calcium even magnesium addition.The treatment process of refinery, waste water of steel plants dense water after reverse-osmosis treated has deep-well injection, sprinkling irrigation, evaporation concentration, recycling etc. usually, but deep-well injection, sprinkling irrigation etc. are in fact pollution transportation and the waste that has caused water resources, and evaporation concentration and recycling then need be removed first the fouling salinities such as calcium magnesium.
At present, the method for deliming mainly contains chemical precipitation method, absorption method, ion exchange method, coagulation, extraction process etc., and wherein chemical precipitation method is because technique is simple, facility investment is supported, production cost is low, easy to operate the most commonly used.Na
2CO
3It then is the chemical precipitation agent that people commonly use.But there is experiment to find, when normal temperature is processed the concentrated seawater of high contents of calcium and magnesium concentration, if use Na
2CO
3Do precipitation agent, the decreasing ratio of calcium ion is lower, and the reaction times long (4-5 hour).Use yellow soda ash to process 20-25 ℃ concentrated seawater (about 13 ° of B é) such as article " concentrated seawater is proposed yellow soda ash deliming research in the magnesium process ", the add-on of yellow soda ash is 1.3 times of theoretical amount, reaction times 4h, but the decreasing ratio of calcium only has 61.34%.Possible reason is Mg in the concentrated seawater
2+Affect removing of calcium, add Na
2CO
3After, Mg
2+Easily form magnesium hydroxide and magnesiumcarbonate precipitation, Mg
2+Thereby the magnesium precipitate of competition, formation in fact reduced low decreasing ratio and the magnesium ion loss that dense water pH value and carbonate concentration cause calcium by various factorss such as precipitation of calcium carbonate institute's embedding or absorption.
By retrieval, find one piece in relevant publication document: a kind of seawater by single-decalcification method (publication number CN1778718A), its with the insoluble calcium salt (such as CaCO
3, CaSO
3, CaF
2, CaC
2O
4, Ca
3(PO
4)
2Deng) for inducing crystal seed, and take the sodium salt of correspondence as precipitation agent, induced crystallization under normal temperature or the condition of heating can be with the Ca in the seawater
2+Take off to 40mg/L.
For the disclosure patent documentation, applicant's suggestion is:
Use the method to process seawater, calcium salt (CaCO
3, CaSO
3, CaF
2, CaC
2O
4, Ca
3(PO
4)
2Deng) in seawater, be in state of saturation, as long as concentrated a little, will produce precipitation in the seawater, this class decalcification is processed and has in fact been increased the weight of continuation degree of depth concentration process calcium scale problems.
Use Na
2SO
3When processing seawater or the low dense calcium magnesium aqueous solution, CaSO
3Exist mainly with hypersaturated state, and a part of calcium magnesium exists with the double salt form, the decreasing ratio of calcium is extremely low.And use Na
2SO
3Process concentrated seawater or the dense water of high contents of calcium and magnesium and then there is no relevant report.And use NaF, Na
2C
2O
4, Na
3PO
4Be same as Na as the precipitation agent effect
2CO
3, the decreasing ratio of calcium is low, the rate of loss of magnesium high, running cost is high, is unsuitable for processing for the selectivity decalcification of the dense water of high contents of calcium and magnesium.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of from the dense water of sea water desaltination by-product or the dense water of other high contents of calcium and magnesium the method for selectively removing calcium ion, the method not only has higher decreasing ratio, and easy and simple to handle, investment is supported, and running cost is low, and the feed liquid after decalcification is processed can use embrane method or hot method further concentrated, improve fresh-water recovery rate, realize recycling and the zero release of resource.
The present invention realizes that the concrete technical scheme of purpose is:
A kind of from the dense water of desalting process by-product or other high contents of calcium and magnesium strong brines the method for selectively removing calcium ion, step is:
⑴ at first introduce dense water in the pH regulator tank, by adding alkali lye with the pH regulator to 7.0 of dense water ~ 8.5;
⑵ the dense water that will mix up pH is heated to 80 ~ 90 ℃ by interchanger, then the dense water after the heat exchange is incorporated in the heat insulation stirred pot of sealing, adds except calcon in dense water while stirring, fully stirring reaction 1 ~ 40min;
⑶ then it is introduced in continuous precipitation pond with the dense water of abundant stirring reaction, leaves standstill or stop 5 ~ 10min;
⑷ the dense water after will precipitate is removed wherein residual calcium sulfite or precipitation of calcium carbonate by filtering unit, then filtrate is incorporated in the storage tank, by in storage tank, adding hydrochloric acid readjustment pH to 6, make calcium sulfite saturated in the filtrate or calcium carbonate change calcium bisulfite or the calcium chloride of high-dissolvability into; Or pass into air aeration, calcium sulfite oxidation is become the calcium sulfate of high-dissolvability.
And, described dense water is the dense water of reverse osmosis method desalting process by-product, multiple-effect evaporation or the dense water of multistage flash evaporation method desalting process by-product, membrane distillation or the dense water of multiple-effect membrane distillation method desalting process by-product, seawater de-salted water that electrodialysis is produced, or the dense water after the seawater nanofiltration, power plant's Seawater recirculated cooling water, in the power plant and water, dense water after the oil refinery effluent reverse-osmosis treated, dense water after the waste water of steel plants reverse-osmosis treated, the earth's surface of inland or coastland or underground brackish water, underground bittern or well lake salt halogen, this dense water concentration is higher than 5 ° of B é, calcium magnesium mol ratio≤1:1.
And, described except calcon be Na
2SO
3Or Na
2CO
3, this Na
2SO
3Or Na
2CO
3Technical grade product, or the sodium sulfite aqueous solution of sodium method flue gas desulfurization generation or the sodium carbonate solution that contains sodium-chlor of soda factory by-product.
And, described except calcon be solution, its weight percent concentration is 10 ~ 20%, add-on doubly is advisable with the 0.7-1.2 of stoichiometric ratio.
And that described filtering unit comprises is centrifugal, one or more the combination in the coarse filtration, micro-filtration, ultrafiltration makes precipitation separate with clear liquid.
With traditional use Na
2CO
3Do precipitation agent and compare, beneficial effect of the present invention and advantage are:
1, the present invention processes the dense water of sea water desaltination by-product or the dense water of other high contents of calcium and magnesium, and the decreasing ratio of calcium can reach more than 90%, and Mg
2+Rate of loss but less than 5%, be applicable to the selectivity decalcification process of the low dense water of calcium of high degree Beaume seawater or other high contents of calcium and magnesium concentration salt solution, high magnesium, the concentration of dense water (degree Beaume) is higher, the decreasing ratio of calcium is higher.
2, the present invention only need stir 1 ~ 30min and can react completely, and speed of response is fast, and the reaction times is short, greatly reduces running cost and initial outlay; And use Na in document and the patent
2CO
3Do precipitation agent, churning time and digestion time are up to 4 ~ 5h.
3, the CaSO among the present invention
3The larger CaSO of oxidable one-tenth solubleness
4, the dense water after the processing can be by modes such as oxidation, aerations to reduce its saturation ratio, and oxidising process can realize naturally in some occasion, need not deliberately to implement.
The problems such as the decreasing ratio of calcium rate of loss low, magnesium was high when 4, the present invention had overcome traditional normal temperature yellow soda ash precipitator method and processes dense water, churning time is long, easy and simple to handle, investment is supported, running cost is low, dense water feed liquid after decalcification is processed can use embrane method or the further degree of depth of hot method to concentrate, improve fresh-water recovery rate, realize recycling and the zero release of resource.
5, the present invention is applicable to from seawater, for example the seawater that concentrated of reverse osmosis or multiple-effect evaporation or brackish water, underground bittern, trade effluent optionally remove calcium ion through the dense water that reverse-osmosis treated is crossed through other processes.
Description of drawings
Fig. 1 is process flow diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are described further; Following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
A kind of from the dense water of desalting process by-product or other high contents of calcium and magnesium strong brines the method for selectively removing calcium ion, step is:
⑴ at first introduce dense water 1 in the pH regulator tank 3, by adding alkali lye 2 pH regulator to 7.0 with dense water ~ 8.5;
⑵ the dense water 4 that will mix up pH is heated to 80 ~ 90 ℃ by interchanger 5, then the dense water 6 after the heat exchange is incorporated in the heat insulation stirred pot 7 of sealing, adds except calcon 8 in dense water while stirring, fully stirring reaction 1 ~ 40min;
⑶ then it is introduced in continuous precipitation ponds 10 with the dense water 9 of abundant stirring reaction, leaves standstill or stop 5 ~ 10min;
⑷ the dense water 11 after will precipitate is removed wherein residual calcium sulfite or precipitation of calcium carbonate by filtering unit 12, then filtrate 13 is incorporated in the storage tank 14, by in storage tank, adding about hydrochloric acid 15 readjustment pH to 6, make calcium sulfite saturated in the filtrate or calcium carbonate change calcium bisulfite or the calcium chloride of high-dissolvability into; Or pass into air aeration, calcium sulfite oxidation is become the calcium sulfate of high-dissolvability.
Described dense water is the dense water of reverse osmosis method desalting process by-product, multiple-effect evaporation or the dense water of multistage flash evaporation method desalting process by-product, membrane distillation or the dense water of multiple-effect membrane distillation method desalting process by-product, seawater de-salted water that electrodialysis is produced, or the dense water after the seawater nanofiltration, power plant's Seawater recirculated cooling water, in the power plant and water, dense water after the oil refinery effluent reverse-osmosis treated, dense water after the waste water of steel plants reverse-osmosis treated, the earth's surface of inland or coastland or underground brackish water, underground bittern or well lake salt halogen, this dense water concentration is higher than 5 ° of B é, calcium magnesium mol ratio≤1:1.
Described except calcon be Na
2SO
3Or Na
2CO
3, this Na
2SO
3Or Na
2CO
3Technical grade product, or the sodium sulfite aqueous solution of sodium method flue gas desulfurization generation or the sodium carbonate solution that contains sodium-chlor of soda factory by-product.Used Na
2SO
3Can be solid, also can use by wiring solution-forming, preferably use Na
2SO
3Solution, Na
2SO
3Strength of solution is advisable with 10 ~ 20%(wt).H
2SO
3PKa
2=7.2, so use Na
2SO
3When processing dense water, dense water pH need be adjusted to more than 7, preferably regulates pH to 7 ~ 8.5(pH＞8.5, Mg
2+Begin precipitation; As a comparison, H
2CO
3PKa
2=10.2, so use Na
2CO
3When processing dense water, dense water pH need be adjusted to more than 10, and a large amount of magnesium ion precipitations run off).Na
2SO
3Add-on doubly be advisable with the 0.7-1.2 of stoichiometric ratio.
CaSO
3Solubility with temperature in water raises and reduces, for example CaSO 90 ℃ the time
3Solubleness CaSO when only being 20 ℃
31/3rd of solubleness, for guaranteeing high calcium decreasing ratio and minimizing reaction times, handled dense water need be heated to certain temperature, and preferred temperature is higher than 80 ℃.Na
2SO
3Easily be oxidized to Na
2SO
4Thereby, affect Ca
2+Remove, so the deliming process should be carried out in the airtight container that stirs, the liquid level in the container also should not be excessively low.
The viscosity with temperature of dense water raises and reduces, and the spread coefficient of each component in the dense water raises with temperature and increases, and this helps the formation of calcium sulfite crystallization.
The dense water of precipitation after fully should be removed precipitation by methods such as filtrations, method can for leave standstill, the optimum combination of the methods such as centrifugal, coarse filtration, micro-filtration and ultrafiltration.Because CaSO in the gained filtrate
3Still be in state of saturation, continuation is concentrated still can to produce precipitation, so will add about hydrochloric acid readjustment pH to 6, calcium sulfite is changed into the calcium bisulfite of high-dissolvability, or pass into air aeration make calcium sulfite saturated in the filtrate change into undersaturated calcium sulfate (under the uniform temp, CaSO
4Solubleness is about CaSO
380 times).Dense water after the processing can use embrane method or hot method further concentrated, with the rate of recovery or the utilization salinity wherein that improves fresh water.That described filtering unit comprises is centrifugal, one or more the combination in the coarse filtration, micro-filtration, ultrafiltration makes precipitation separate with clear liquid.
The present invention utilizes the greatest differences of the oxidation-reduction quality of acidity, sulfuric acid and the sulfurous acid of solubleness, sulfuric acid and the sulfurous acid of calcium sulfite and calcium sulfate solubleness, calcium sulfite and the magnesium sulfite in water in water to realize.For example, under 25 ℃, CaSO
4Solubleness is about CaSO
380 times, MgSO
3Solubleness is about CaSO
3100 times.
Embodiment 1:
The dense water of certain multistage flash evaporation seawater desalting factory by-product, 5.4 ° of B é, pH=8.2, [Ca
2+]=650mg/L, [Mg
2+]=2000mg/L is heated to 85 ℃ in the container that airtight band stirs, then add theoretical equivalent (n
Ca2+: n
Na2SO3=1:1.2) 20%(wt) Na
2SO
3Solution stirs 40min, filters after leaving standstill 5min, according to [Ca in the filtrate
2+] calculate Ca
2+Decreasing ratio is 90.5%, Mg
2+Rate of loss be 0.45%;
The Comparative Examples 1 of embodiment 1:
Dense water water quality is with embodiment 1, and precipitation agent changes 20%(wt into) Na
2CO
3Solution, temperature are 25 ℃, and other operational conditions are processed rear Ca with embodiment 1
2+Decreasing ratio is 37%, Mg
2+Rate of loss be 13.5%.
The Comparative Examples 2 of embodiment:
Dense water water quality is with the lower 20%(wt that uses of 1,25 ℃ of embodiment) Na
2SO
3Solution-treated, other operational conditions are processed rear Ca with embodiment 1
2+Decreasing ratio be 72.5%.
In addition, the filtrate of embodiment 1 gained adds concentrated hydrochloric acid, regulates pH to 6.2, then uses evaporator evaporation concentrated, and concentration there is no precipitation and produces when being 25 ° of B é; Or the dense water aeration 30min after the decalcification, then use afterwards evaporator evaporation concentrated, concentration there is no precipitation and produces when being 25 ° of B é.
Embodiment 2:
The dense water of certain factory's reverse osmosis method sea water desaltination by-product, 6 ° of B é, pH=7.0, [Ca
2+]=871mg/L, [Mg
2+]=2680mg/L is heated to 85 ℃ in the container that airtight band stirs, then add theoretical equivalent (n
Ca2+: n
Na2SO3=1:1.2) 20%(wt) Na
2SO
3Solution stirs 40min, filters after leaving standstill 5min, records Ca
2+Decreasing ratio is 92.5%, Mg
2+Rate of loss be 0.40%.
The Comparative Examples of embodiment 2:
Dense water water quality and operational condition are with embodiment 2, and precipitation agent changes 20%(wt into) Na
2CO
3Solution, Ca after processing
2+Decreasing ratio be 81.5%, Mg
2+Rate of loss be 12.5%.
Embodiment 3:
Dense water among the concentrated embodiment 1 of multiple-effect membrane distillation method, when being concentrated into 15 ° of B é, pH=7.96, [Ca
2+]=2443mg/L, [Mg
2+]=7510mg/L is heated to 85 ℃ in the container that airtight band stirs, add the 20%(wt of theoretical equivalent) Na
2SO
3Solution stirs 40min, filters after leaving standstill 5min, records Ca
2+Decreasing ratio be 93.5%, Mg
2+Rate of loss be 1.94%.
Dense water water quality and operational condition are with embodiment 3, and precipitation agent changes 20%(wt into) Na
2CO
3Solution, Ca after processing
2+Decreasing ratio be 83.6%, Mg
2+Rate of loss be 15.1%.
Embodiment 4:
The dense water of multiple-effect membrane distillation method sea water desaltination by-product, 13.1 ° of B é, pH=8.0, [Ca
2+]=2051mg/L, [Mg
2+]=6360mg/L is heated to 85 ℃ in the container that airtight band stirs, add the 20%(wt of theoretical equivalent) Na
2SO
3Solution stirs 40min, filters after leaving standstill 5min, records Ca
2+Decreasing ratio be 90.3%, Mg
2+Rate of loss be 2.40%.
Embodiment 5:
Certain power plant's Seawater recirculated cooling water, 4.8 ° of B é, pH=8.0, [Ca
2+]=635mg/L, [Mg
2+]=1954mg/L, [SO
4 2-]=2150mg/L is heated to 85 ℃ in the container that airtight band stirs, then add the 20%(wt of 1.2 times of theoretical equivalents) Na
2SO
3Solution stirs 40min, filters after leaving standstill 5min, records liquor C a
2+Decreasing ratio be 90.2%, Mg
2+Rate of loss be 0.31%.
Embodiment 6:
Certain power plant's Seawater recirculated cooling water, 4.8 ° of B é, pH=8.0, [Ca
2+]=635mg/L, [Mg
2+]=1954mg/L, [SO
4 2-]=2150mg/L.Precipitation agent is for adopting the byproduct of desulfurization in the sodium carbonate method stack gas, and the byproduct solution composition after flue gas desulfurization (FGD) is: Na
2SO
3Molten content is 75%, and sodium bicarbonate content is 20%, and carbonate content is 5%; Be heated to 85 ℃ in the container that airtight band stirs, then add the 20%(wt of 1.2 times of theoretical equivalents) this mixed precipitant, stir 40min, filter after leaving standstill 5min, record liquor C a
2+Decreasing ratio be 90.2%, Mg
2+Rate of loss be 0.31%.
Embodiment 7:
Certain oil refinery effluent biochemical treatment water outlet is the dense water after ultrafiltration and reverse-osmosis treated again, pH=7, [Ca
2+]=594mg/L, [Mg
2+]=305mg/L, [SO
4 2-]=954mg/L, [Cl
-]=446mg/L is heated to 85 ℃ in the container that airtight band stirs, then add the 20%(wt of 1.2 times of theoretical equivalents) Na
2SO
3Solution stirs 40min, filters after leaving standstill 5min, records Ca
2+Decreasing ratio is 90%, Mg
2+Rate of loss be 0.40%.
Embodiment 8
The dense water of certain waste water of steel plants after reverse-osmosis treated, pH=8.2, [Ca
2+]=1039mg/L, [Mg
2+]=80mg/L, basicity 480mg/L is heated to 85 ℃ in the container that airtight band stirs, then add the 20%(wt of theoretical equivalent) Na
2SO
3Solution stirs 40min, filters after leaving standstill 5min, records Ca
2+Decreasing ratio be 93.7%.
Embodiment 9:
In certain power plant and water, pH=2.4, [Ca
2+]=846.2mg/L, [Mg
2+]=296.4mg/L, [SO
4 2-]=793.9mg/L at first regulates about pH to 8.2 with NaOH, then is heated to 85 ℃ in the container that airtight band stirs, and then adds the 20%(wt of 1.2 times of theoretical equivalents) Na
2SO
3Solution stirs 40min, filters after leaving standstill 5min, records Ca
2+Decreasing ratio be 91%, Mg
2+Rate of loss be 0.39%.
Embodiment 10:
Somewhere bittern, 16.7 ° of B é, pH=7.0, [Ca
2+]=2490mg/L, [Mg
2+]=7160mg/L, [SO
4 2-]=3873mg/L, [HCO
3 -]=620mg/L is heated to 85 ℃ in the container that airtight band stirs, then add the 20%(wt of theoretical equivalent) Na
2SO
3Solution stirs 40min, filters after leaving standstill 5min, records Ca
2+Decreasing ratio be 93.2%, Mg
2+Rate of loss be 0.26%.
Embodiment 11:
Electroosmose process is processed the light salt brine that former seawater is produced, [Ca
2+]=220mg/L, [Mg
2+]=1100mg/L, [SO
4 2-]=4013mg/L is heated to 85 ℃ in the container that airtight band stirs, then add the 20%(wt of 1.2 times of theoretical equivalents) Na
2SO
3Solution stirs 40min, filters after leaving standstill 5min, records Ca
2+Decreasing ratio be 90%, Mg
2+Rate of loss be 0.61%.
Embodiment 12:
Dense water after the seawater nanofiltration, 6.4 ° of B é, pH=7.46, [Ca
2+]=730mg/L, [Mg
2+]=2200mg/L, [SO
4 2-]=4950mg/L is heated to 85 ℃ in the container that airtight band stirs, then add the 20%(wt of 1.2 times of theoretical equivalents) Na
2SO
3Solution stirs 40min, filters after leaving standstill 5min, records Ca
2+Decreasing ratio be 92.4%, and Mg
2+Rate of loss be 0.40%.
Claims (5)
1. the method for a selectively removing calcium ion from the dense water of desalting process by-product or other high contents of calcium and magnesium strong brines, it is characterized in that: step is:
⑴ at first introduce dense water in the pH regulator tank, by adding alkali lye with the pH regulator to 7.0 of dense water ~ 8.5;
⑵ the dense water that will mix up pH is heated to 80 ~ 90 ℃ by interchanger, then the dense water after the heat exchange is incorporated in the heat insulation stirred pot of sealing, adds except calcon in dense water while stirring, fully stirring reaction 1 ~ 40min;
⑶ then it is introduced in continuous precipitation pond with the dense water of abundant stirring reaction, leaves standstill or stop 5 ~ 10min;
⑷ the dense water after will precipitate is removed wherein residual calcium sulfite or precipitation of calcium carbonate by filtering unit, then filtrate is incorporated in the storage tank, by in storage tank, adding hydrochloric acid readjustment pH to 6, make calcium sulfite saturated in the filtrate or calcium carbonate change calcium bisulfite or the calcium chloride of high-dissolvability into; Or pass into air aeration, calcium sulfite oxidation is become the calcium sulfate of high-dissolvability.
According to claim 1 from the dense water of desalting process by-product or other high contents of calcium and magnesium strong brines the method for selectively removing calcium ion, it is characterized in that: described dense water is the dense water of reverse osmosis method desalting process by-product, multiple-effect evaporation or the dense water of multistage flash evaporation method desalting process by-product, membrane distillation or the dense water of multiple-effect membrane distillation method desalting process by-product, seawater de-salted water that electrodialysis is produced, or the dense water after the seawater nanofiltration, power plant's Seawater recirculated cooling water, in the power plant and water, dense water after the oil refinery effluent reverse-osmosis treated, dense water after the waste water of steel plants reverse-osmosis treated, the earth's surface of inland or coastland or underground brackish water, underground bittern or well lake salt halogen, this dense water concentration is higher than 5 ° of B é, calcium magnesium mol ratio≤1:1.
According to claimed in claim 1 from the dense water of desalting process by-product or other high contents of calcium and magnesium strong brines the method for selectively removing calcium ion, it is characterized in that: described except calcon be Na
2SO
3Or Na
2CO
3, this Na
2SO
3Or Na
2CO
3Technical grade product, or the sodium sulfite aqueous solution of sodium method flue gas desulfurization generation or the sodium carbonate solution that contains sodium-chlor of soda factory by-product.
According to claim 1 or 3 described from the dense water of desalting process by-product or other high contents of calcium and magnesium strong brines the method for selectively removing calcium ion, it is characterized in that: described except calcon be solution, its weight percent concentration is 10 ~ 20%, and add-on doubly is advisable with the 0.7-1.2 of stoichiometric ratio.
According to claimed in claim 1 from the dense water of desalting process by-product or other high contents of calcium and magnesium strong brines the method for selectively removing calcium ion, it is characterized in that: described filtering unit comprises that one or more the combination in centrifugal, coarse filtration, micro-filtration, the ultrafiltration makes precipitation separate with clear liquid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104799283A CN102936067A (en) | 2012-11-23 | 2012-11-23 | Method for selectively removing calcium ions from concentrated water byproduct of sea water desalination process and other high-calcium-magnesium-content concentrated brines |
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|---|---|---|---|
| CN2012104799283A CN102936067A (en) | 2012-11-23 | 2012-11-23 | Method for selectively removing calcium ions from concentrated water byproduct of sea water desalination process and other high-calcium-magnesium-content concentrated brines |
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| CN103193342A (en) * | 2013-05-05 | 2013-07-10 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Treatment process for preventing nonferrous smelting wastewater salt steaming crystallizing device from scaling |
| CN104030485A (en) * | 2014-05-29 | 2014-09-10 | 新疆中泰化学股份有限公司 | Device for carrying out impurity removal treatment on crude brine for electrolysis and treatment method using same |
| CN104762073A (en) * | 2015-03-09 | 2015-07-08 | 中国石油集团渤海钻探工程有限公司 | A base liquid for preparing a workover liquid and a preparing method thereof |
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| CN104030485B (en) * | 2014-05-29 | 2016-04-13 | 新疆中泰化学股份有限公司 | Electrolysis crude brine removal of impurities treatment unit and treatment process thereof |
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| US9915136B2 (en) | 2016-05-26 | 2018-03-13 | X Development Llc | Hydrocarbon extraction through carbon dioxide production and injection into a hydrocarbon well |
| US9914683B2 (en) | 2016-05-26 | 2018-03-13 | X Development Llc | Fuel synthesis from an aqueous solution |
| CN106396234B (en) * | 2016-11-25 | 2019-06-04 | 洁海瑞泉膜技术（天津）有限公司 | A kind of Zero discharge treatment method of reverse osmosis concentrated water |
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| CN108887163A (en) * | 2018-07-05 | 2018-11-27 | 中山大学 | A method of utilizing seawater planting vegetables |
| CN109006283A (en) * | 2018-08-15 | 2018-12-18 | 绩溪袁稻农业产业科技有限公司 | The implantation methods of kermes rice |
| CN109006283B (en) * | 2018-08-15 | 2021-02-19 | 绩溪袁稻农业产业科技有限公司 | Method for planting Dactylicapnos asiaticus |
| CN110563166A (en) * | 2019-09-23 | 2019-12-13 | 厦门嘉戎技术股份有限公司 | Method and device for softening and removing calcium from desulfurization wastewater |
| CN110697935A (en) * | 2019-10-17 | 2020-01-17 | 青海盐湖工业股份有限公司 | Refining system and refining method for byproduct brine |
| CN110983365A (en) * | 2019-11-22 | 2020-04-10 | 首钢京唐钢铁联合有限责任公司 | System and method for preparing chlorine by electrolyzing seawater |
| CN111099709A (en) * | 2019-12-24 | 2020-05-05 | 珠海广睿汇利发展有限公司 | Seawater potassium removal method |
| CN112679021A (en) * | 2020-12-25 | 2021-04-20 | 儋州市中等职业技术学校 | Method for preparing salt from seawater |
| CN112679021B (en) * | 2020-12-25 | 2023-04-25 | 儋州市中等职业技术学校 | Salt-making method by using seawater |
| CN113401929A (en) * | 2021-06-23 | 2021-09-17 | 湖北富邦科技股份有限公司 | Method for preparing nano calcium carbonate magnesium material by using nanofiltration seawater to trap carbon dioxide |
| CN113830953A (en) * | 2021-10-13 | 2021-12-24 | 烟台金正环保科技有限公司 | Comprehensive utilization system and method for seawater desalination concentrated water |
| CN115806350A (en) * | 2022-12-07 | 2023-03-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Deep calcium removal method for high-magnesium sodium chloride brine |
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