CN102107972A - Seawater desalinization pretreatment method by using bipolar membrane through reverse osmosis process - Google Patents
Seawater desalinization pretreatment method by using bipolar membrane through reverse osmosis process Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 62
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- 238000001223 reverse osmosis Methods 0.000 title claims description 34
- 238000002203 pretreatment Methods 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 92
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
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- 230000005611 electricity Effects 0.000 claims description 7
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- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 5
- 238000009287 sand filtration Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052796 boron Inorganic materials 0.000 abstract description 25
- 238000011161 development Methods 0.000 abstract description 14
- 239000002384 drinking water standard Substances 0.000 abstract description 11
- 230000001105 regulatory effect Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000011780 sodium chloride Substances 0.000 abstract description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract 1
- 235000011152 sodium sulphate Nutrition 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000010612 desalination reaction Methods 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 4
- UCUJUFDOQOJLBE-UHFFFAOYSA-N [Cl].[Ca] Chemical compound [Cl].[Ca] UCUJUFDOQOJLBE-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000011033 desalting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002352 surface water Substances 0.000 description 3
- 238000005496 tempering Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 235000012206 bottled water Nutrition 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000006735 deficit Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 239000003651 drinking water Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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- 229910021538 borax Inorganic materials 0.000 description 1
- 125000000707 boryl group Chemical group B* 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
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- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a chemical treatment method, in particular to a seawater desalinization pretreatment method. The pretreatment method comprises the following steps of: placing seawater in a bipolar membrane device, wherein a bipolar membrane is a divalent separation membrane, and a polar liquid is a sodium chloride or sodium sulfate solution with mass concentration of 1-10 percent; mixing an alkali liquid in an alkali chamber of the bipolar membrane device with inlet water, filtering the alkalized inlet water by using a micro-filtering membrane of 0.1-0.5 micrometer, and regulating a pH value to be 8.2-8.8 by using an acid liquid in an acid chamber of the bipolar membrane device for seawater desalinization treatment. The pretreatment method has the advantages of less investment, low operating cost and simple operation. By the pretreatment method, boron content in yielding water accords with the drinking water standard, a yielding water quality regulating method and process of seawater desalinization by using the bipolar membrane applied in a large-scale project can be carried out, and the technical bottleneck of seawater desalinization development is overcome. Therefore, the pretreatment method can be widely applied in a seawater desalinization occasion.
Description
Technical field
The present invention relates to a kind of chemical treatment method, specifically be meant a kind of the preceding pretreatment process in the desalting process.
Technical background
Earth surface has approximately more than 70% and is covered by water, and also there is the existence of water on all the other land that account for earth surface 30%.Earth Total Water is 138.6 hundred million hundred million tons, and wherein the fresh water reserves are 3.5 hundred million hundred million tons, account for 2.53% of total reserves.Because the restriction of exploitation difficulty or Technological Economy, only account for 0.34% of fresh water total reserves than what be easier to develop, be 104.6 hundreds of millions tons, be less than ten thousand of water globe total reserves/.According to United Nations's analysis of giving information, the water resources in china total amount is 2.8 hundreds of millions tons, occupies the 6th in the world, and Chinese water resource of per capita is 2340 tons, and the whole world comes 109.To the middle of this century, Chinese population predicts at 1,600,000,000 o'clock, and water resources is 1600 tons per capita, becomes the country of serious water shortage.In 668 cities of China, about 400 of lack of water city, about 108 of the city of serious water shortage.These, water deficit was 1,600 ten thousand tons city day, and annual water deficit is 20,000,000,000 tons.The annual industry of China, sanitary sewage quantity discharged have reached about 60,000,000,000 tons, and 90% urban waters is subjected to pollution in various degree, and surface water is subjected to pollution in various degree owing to adopt surface water to do the water source in especially southern city.Therefore cause the water quality lack of water again.Water is the strategic resource of China's economy, social development.The Chinese government attaches great importance to exploitation, utilization, the protection of water resources.In order to ask for fresh water to the sea, last century early fifties, membrane technique has just preferentially been put forward, and has realized commercialization in the world to the seventies desalination technology, through product renewal, technological innovation, most economical sea water desaltination and high salinity brackish water desalting technology have been become at present.
At present, China has possessed the favourable condition of sea water desaltination industry development.The first, the understanding of sea water desaltination is obviously improved.Along with the measures of increasing income such as underground water intaking in coastland and trans-regional water transfer are subjected to increasing technical qualification restriction, seeking the new road of increasing income has become the task of top priority that solves coastal economy developed regions water shortage problem.This understanding of new water source that desalinizes seawater as economy development of coastal area and living needs obtains deepening gradually.The second, sea water desaltination key equipment and supporting technology further improve.Up till now till the position, no matter be equipment such as the reverse-osmosis membrane element that is used for the embrane method desalinating process, pressurized vessel, high-pressure pump, energy recycle device, still the heat pump, vacuum pump, vaporizer and other heat-transfer matcrial and the equipment that are used for hot method desalinating process, all have domestic independent development product and move on probationly on device, estimating all has the progressively possibility of substituting import one equipment in the future.The 3rd, sea water desaltination equipment manufacture blank basic building produces device fabrication enterprises such as a collection of distillation, reverse osmosis, ultrafiltration, and engineering corporation.The 4th, along with the industry science and technology progress, sea water desaltination investment and total cost decline to a great extent, and sea water desaltination price and municipal water supply gap reduce gradually.The 5th, government payes attention to.In recent years, water resources and Seawater Resource Exploitation and Utilization have obtained showing great attention to of party and state leaders and governments at all levels.Sea water desaltination is put into " National Program for Medium-to Long-term Scientific and Technological Development (2006-2020) " and first develops theme.
This shows that the basic condition of China's sea water desaltination industry development possesses, sea water desaltination will become emerging sunrise industry in this century, and the sea water desaltination industry of China also will enter a high-speed developing period.To the end of the year 2009, domestic sea water desalinating plant 62 covers that built up, about 500,000 tons/day of design desalination water ultimate production; Building device 6 covers, about 180,000 tons/day of design desalination water ultimate production.Built and in building sea water desalinating plant, reverse osmosis method accounts for 74% of total volume, low-temperature multiple-effect distillation accounts for 25%, and other method for desalting seawater account for 1%.2009, build up Qingdao 10,000 tons of/day reverse osmosis units of alkali industry first phase and be constructed and put into operation; 100,000 tons of/day reverse osmosis units of Tianjin Xin Quan company; Zhejiang 10,000 tons of/day reverse osmosis units of six horizontal first phases are finished debugging, enter trial run.The sea water desalinating plant ultimate production of building up in 2009 years increases about 40% than 2008 years.Desalinizing seawater and using maximum industries is electric power, petrochemical industry, iron and steel etc., and wherein electric power enterprise accounts for about 50% of national sea water desaltination total amount.
Though sea water desaltination growth momentum and prospect are all very good, also there are some problems.Handle later tap water through desalination by reverse osmosis and compare, have content of mineral substances problems such as particularly calcium-magnesium content is on the low side, the pH value is on the low side, boron content exceeds standard sometimes with other tap water.Reason is the characteristics of reverse osmosis technology own, requires the water inlet of sea water desaltination to carry out necessary pre-treatment, as add Scale inhibitors, carry out suitably softening, regulate pH value etc.And the used reverse osmosis membrane overwhelming majority of reverse osmosis method sea water desaltination is the high pressure reverse osmosis membrane of bear electricity, more than these reasons all can make it produce the pH value (pH is about 6.0) on the low side of water, this makes and produces the obvious slant acidity of water, currently used means generally are that the method by follow-up reinforcement adjusting PH with base makes and produces water pH value and transfer to weak base, but all also have pH value instability, problem such as content of mineral substances is on the low side.Because original tap water all is that hardness is higher basically, the long-time use can form one deck layer of scale at the municipal pipeline inwall, this moment, the desalination product water of slant acidity can produce corrosive nature to city planting ductwork through piping, and can make the dissolving again slowly of original layer of scale, make the user can go out yellow water when just use or inactive for some time have been reused at the beginning and influence use.
At present in the drinking water standard put into effect of country to the requirement of boron content than higher, concentration will be below 0.5mg/L.Owing to generally seawater is carried out pre-treatment with strong acid to seawater during the reverse osmosis method sea water desaltination, so boron is with boric acid substantially in seawater, the faintly acid form exists, the rule of holding back according to reverse osmosis as can be known, rejection to boric acid is not so good as mineral ion height such as chlorion and sodium ion, rejection is generally 70%～95%, can be with the temperature of seawater, the variation of pH and changing, the concentration of seawater boron is 0.5-9.5mg/L, about average out to 4.5mg/L, when the rejection of reverse osmosis is lower than 90%, can make the boron content that produces water might surpass 0.5mg/L, even can surpass 1.0mg/L, though the person is not had influence substantially, do not meet drinking water standard, the popularization that influences the reverse osmosis method sea water desaltination is with universal.
Comprehensive above factor, mostly there are problems such as hardness is not enough, the pH value is on the low side, pipeline goes out yellow water easily, boron content exceeds standard sometimes in the tap water that causes present reverse osmosis method sea water desaltination to prepare.Relatively earth surface water source utilizes shared ratio of sea water desaltination potable water and scale still very little, thus the problems referred to above performance neither be clearly.In case along with the ratio of tap water in whole public works and the rising of scale that sea water desaltination is produced, these problems can become increasingly conspicuous, particularly might people's psychology be caused the erroneous effects of " sea water desaltination is produced water and is unsuitable for drinking ".And then influence sea water desaltination popularize, hinder the process that solves coastland or island water shortage problem, so modified research that water is produced in sea water desaltination is a relatively urgent task.
This project is from drinking water standard, take into full account economic benefit, study a kind of less investment, running cost low, easy to operate, produce water meet drinking water standard, utilize the principle of cushioning balance make pH value can be steady in a long-term 7.0～8.2, mineral substance meets drinking water standard with boron content, can carry out sea water desaltination product water hardening and tempering method and technology that heavy construction is used, can be sea water desaltination Engineering Service on a large scale at last.Solve the technical bottleneck of sea water desaltination development, desalination technology can better be provided safeguard for the national economic development.
Over nearly more than 20 years, along with the improvement of preconditioning technique, the use of energy recycle device and the optimization of film properties etc., make the reverse osmosis method desalination technology increasingly mature, the scale of project is increasing, from ten tonnes of tons every days ten till now every day of the eighties, several thousand times of increase in sizes.The quantity and the scale that wherein are used for municipal domestic water are also growing, there are many islands and coastal cities all to have the sea water desaltination of utilizing to replenish the deficiency of municipal water use at present, in these projects, generally all directly utilize original municipal pipeline, and water terminal major part all is people's domestic water.Because problems such as the pH value of sea water desaltination product water is on the low side can go out yellow water in the time of can causing the terminal water to use at the beginning and then influence is used.General way is to carry out municipal pipeline to transform again, or further carry out modified to producing water, but because the pipeline modification that carries out entire city will be a huge engineering, even and carry out the municipal pipeline transformation but do not produce that water is modified can not to solve pH value meta-acid, instability, problems such as mineral concentration is on the low side relatively, boron content overproof.
Carry out suitably modifiedly if water is produced in sea water desaltination, can accomplish not transform city planting ductwork, and the stability and numerical value, mineral concentration and the boron content that produce the pH value of water reach drinking water standard.And can reuse original city planting ductwork, reduce the local resident to the misgivings of sea water desaltination potable water and increase supporting dynamics, for improving island and the coastal cities water shortage problem approach that facilitates, save substantial contribution and also obtain better social benefit.Owing to solved the technical bottleneck that water is produced in sea water desaltination, can make desalination technology get development at faster speed, be able to better application in every field, fully solve the problem of general lack of water, advance society, sustainable economic development.
At present the product water of the reverse osmosis method sea water desaltination of developed country all adopts modified technology basically, and the simple soda acid that passes through that begins most comes adjust pH, and developing into present is to adjust pH value by equilibrium system basically, adjusts the content of product water mineral simultaneously.Produce the content of the various compositions in the water and factors such as weather at that time by monitoring, adjust the addition and the addition manner of various adjusting materials according to the equilibrium kinetics model automatically.And domestic because starting than later, is produced water from the not modified sea water desaltination that begins most, to simply modified, but owing to lack technique means and method, modified effect is undesirable, as the pH instability, is up to standard in the time of modified, but departs from soon.Owing to do not have utilizable equilibrium kinetics Model Calculation, so the content and the addition manner of various adjusting materials undertaken by experience basically.So how to accomplish to stablize, accurately, the modified product water of automatization is the target of development after us.And aspect the control of boron content, generally have only two-pass reverse osmosis, reservoir water method such as blend to reduce the boron content of last product water, these methods all exist cost high or be subjected to shortcoming such as Freshwater resources restriction.Later developing direction generally is to change the decreasing ratio that raw water quality improves boron by certain pre-treatment, or improves the content that the boron performance reduces boron in the product water that takes off of reverse osmosis membrane, thereby guarantees that the boron content that produces water meets drinking water standard.
The present invention is from drinking water standard, take into full account economic benefit, study a kind of less investment, running cost boron content low, easy to operate, that produce water and meet drinking water standard, can carry out the Bipolar Membrane sea water desaltination that heavy construction uses and produce water hardening and tempering method and technology, solve the technical bottleneck of sea water desaltination development.
The present invention utilizes the Bipolar Membrane technology to produce acid solution and alkali lye, need not to add in addition reagent, solves some place to the inconvenient problem of hydrochloric acid transportation, also solves people need other reagent to sea water desaltination doubt.
Summary of the invention
The present invention is directed to deficiency of the prior art, proposed a kind of efficiently, treatment process easily.
The present invention is achieved by following technical proposals:
A kind of Bipolar Membrane is characterized in that comprising the steps: to reverse osmosis method sea water desaltination pretreatment process
(1) being the water inlet of Bipolar Membrane device through flocculation sediment, the filtering seawater of sand filtration, the negative electricity of Bipolar Membrane device very stainless steel or titanium is coated with ruthenium electrode, and anode is coated with ruthenium electrode or platinum electrode with titanium, and the Bipolar Membrane device is the assemblings of three compartments; Each three compartment unit is made up of Bipolar Membrane, anode membrane, cavity block, three Bipolar Membrane elastic baffles, anode membrane wherein is a divalence separatory membrane: to a divalent cation resolution more than 95%, membrane resistance is lower than 2 Europe/square centimeters, and thickness is less than 0.2 millimeter, and degree of crosslinking is more than 30%; The current density of Bipolar Membrane device operation is 100-2000A/m
2, the film surface velocity is 1-15cm/s, utmost point liquid is sodium-chlor or the metabisulfite solution of mass concentration 1-10%; The method that adopts local circulation or increase membrane area makes the mass concentration of the alkali lye of the acid solution of sour chamber or alkali chamber reach 0.5-15%; As preferably, make the mass concentration of the alkali lye of the acid solution of sour chamber or alkali chamber reach 9.5-10%.
(2) alkali lye in the Bipolar Membrane device alkali chamber is mixed with the water inlet of reverse osmosis unit, the blended ratio is: alkali lye 0.2-20mL is added in every liter of water inlet, and making into, the pH value of water is raised to 9.2-10.9;
(3) regulate pH the micro-filtrate membrane filtration of the water inlet after the above-mentioned alkalization, and then with the acid solution of bipolar acid chamber, regulate the pH value to 8.2-8.8 with the 0.1-0.5 micron.
As preferably, Bipolar Membrane running current density is 500-1000A/m in the above-mentioned process method step (1)
2, the film surface velocity is 5-8cm/s.
As preferably, above-mentioned process method step (2) makes into that the pH value of water is raised to 10.0-10.6.
As preferably, the water inlet after above-mentioned process method step (3) alkalization is with 0.45 micron micro-filtrate membrane filtration, then with acid solution adjusting pH value to 8.4-8.6.
Used Bipolar Membrane device of the present invention, being that the sodium chloride solution of 0.5-10% is charging through pretreated seawater such as flocculation sediment or concentration, under galvanic action, produce acid solution and alkali lye, the negative electricity of Bipolar Membrane device very stainless steel or titanium is coated with ruthenium electrode, anode is coated with ruthenium electrode or platinum electrode with titanium, adopts the assembling of three compartments.Bipolar Membrane running current density adopts 100-2000A/m
2, the film surface velocity is 1-15cm/s, and utmost point liquid adopts sodium-chlor or the metabisulfite solution of 1-10%, and the method that adopts local circulation or increase membrane area makes the concentration of the alkali lye of the acid solution of sour chamber or alkali chamber reach 0.5-15%.
The positive one pole film of the Bipolar Membrane device that the present invention is used adopts a divalence separate, dedicated film, as CSO film, CMO film, CSZX2 film etc., in order to separate sodium ion and calcium ions and magnesium ions, calcium ions and magnesium ions is gone out with concentrated water drainage, avoided magnesium hydroxide or calcium hydroxide at Bipolar Membrane or anode membrane surface scale.
The principal character of the divalence separate, dedicated anode membrane among the present invention is coated with the very thin positively charged coating of one deck again for the anode membrane surface at the negative exchange ion group of normal tape, increase and align the ionic repulsive force, because it is big that the charge ratio univalent electric charge of bivalent positive ion is wanted, so special-purpose anode membrane is bigger to the repulsive force of divalence, and to the smaller penetrated preferably anode membrane of the repulsive force of monovalence positive ion.
The present invention adopts and adds alkali removal carbonate earlier, and the method that adds acid for adjusting pH value is again carried out pre-treatment.
Former seawater after regulating the pH value can produce the carbonate in the precipitation of calcium carbonate removal seawater.Filter through accurate filter, pore size filter is the 0.1-0.5 micron.
Of the present invention when adding acid and regulate adopting the acid solution of sour chamber of Bipolar Membrane row regulate.Seawater after the filtration is regulated pH with the Bipolar Membrane acid solution again, makes that minute quantity dissolved lime carbonate is converted into chlorine calcium in the seawater, pH greater than 8 situation under, solve the problem of reverse osmosis membrane fouling.
And the pH value of seawater is greater than 8 after regulating, and this form with Sodium Tetraborate of the boryl in the seawater exists, and significantly improves the rejection of reverse osmosis membrane to boron, thereby makes the boron content in the product water of seawater after reverse-osmosis treated meet the tap water requirement.
The present invention is also at some occasion not high to the boron content requirement, need not heightening pH value and improve the decreasing ratio of reverse osmosis boron, can be directly add former seawater and carry out acidifying with the acid solution of Bipolar Membrane device acid chamber, the ratio of adding acid solution 0.02-2mL in every liter of seawater adds the acid solution of bipolar acid chamber in the former seawater with volume pump, make the pH value of seawater drop to 5.2-6.7, solve the problem of lime carbonate at the reverse osmosis surface scale.
Beneficial effect: less investment, running cost boron content low, easy to operate, that produce water meet drinking water standard, can carry out Bipolar Membrane sea water desaltination product water hardening and tempering method and technology that heavy construction is used, solve the technical bottleneck of sea water desaltination development.
Description of drawings
The reaction formula of the bipolar embrane method sea water desaltination of Fig. 1 preprocessing process
The schematic diagram of Fig. 2 Bipolar Membrane relieving haperacidity alkali
Fig. 3 Bipolar Membrane sea water desaltination height takes off boron pretreatment process figure
Fig. 4 Bipolar Membrane sea water desaltination acidifying pretreatment process figure
Embodiment
Knot enforcement of the present invention specifies below
Embodiment 1
With process flocculation sediment, the filtering seawater of sand filtration is water inlet, bipolar devices is the device of BMP2-500,40 of the Bipolar Membrane of employing 200*400, anode membrane adopts 40 of CSO one divalence separatory membranes, cavity block adopts the AMV film, the elastic baffle of 80 200*400, negative electricity very titanium are coated with ruthenium electrode, the anode platinum electrode.Current density adopts 1000A/m
2, the film surface velocity is 5cm/s, utmost point liquid adopts 3% metabisulfite solution, adopts the method for local circulation that the concentration of the alkali lye of the acid solution of sour chamber or alkali chamber is reached about 10%.The alkali lye of alkali chamber is added the alkali lye of Bipolar Membrane alkali chamber in the former seawater with volume pump in the ratio that every liter of seawater adds alkali lye 10mL with volume pump, make the pH value of seawater be raised to 10.4.PH is regulated with the Bipolar Membrane acid solution again with behind 0.45 micron the micro-filtrate membrane filtration in the back, and adjusting pH value to 8.4 makes that minute quantity dissolved lime carbonate is converted into chlorine calcium in the seawater.After this pretreated seawater advanced the seawater membrane reverse osmosis, the boron decreasing ratio that produces water reached more than 90%, there is no the film scale problems to occur.
To be water inlet through flocculation sediment, the filtering seawater of sand filtration, bipolar devices is the device of BMP2-2500,20 of the Bipolar Membrane of employing 400*800, cavity block and anode membrane adopt 20 pairs of divalence separatory membranes, the elastic baffle of 60 400*800, negative electricity very titanium are coated with ruthenium electrode, the anode platinum electrode.Current density adopts 500A/m
2, the film surface velocity is 6cm/s, utmost point liquid adopts 5% metabisulfite solution, adopts the method for local circulation that the concentration of the alkali lye of the acid solution of sour chamber or alkali chamber is reached about 5%.The alkali lye of alkali chamber is added the alkali lye of Bipolar Membrane alkali chamber in the former seawater with volume pump in the ratio that every liter of seawater adds alkali lye 15mL with volume pump, make the pH value of seawater be raised to 10.3.PH is regulated with the Bipolar Membrane acid solution again with behind 0.45 micron the micro-filtrate membrane filtration in the back, and adjusting pH value to 8.6 makes that minute quantity dissolved lime carbonate is converted into chlorine calcium in the seawater.After this pretreated seawater advanced the seawater membrane reverse osmosis, the boron decreasing ratio that produces water reached more than 95%, there is no the film scale problems to occur.
Embodiment 3
With process flocculation sediment, the filtering seawater of sand filtration is water inlet, bipolar devices is the device of BMP2-2500,20 of the Bipolar Membrane of employing 400*800, cavity block and anode membrane adopt 20 pairs of divalence separatory membrane CMO+AMV films, the elastic baffle of 60 400*800, negative electricity very titanium is coated with ruthenium electrode, the anode platinum electrode.Current density adopts 800A/m
2, the film surface velocity is 7cm/s, utmost point liquid adopts 6% metabisulfite solution, adopts the method for local circulation that the concentration of the alkali lye of the acid solution of sour chamber or alkali chamber is reached about 10%.Direct acid solution with Bipolar Membrane device acid chamber adds former seawater and carries out acidifying, the ratio of adding acid solution 0.05mL in every liter of seawater adds the acid solution of bipolar acid chamber in the former seawater with volume pump, make the pH value of seawater drop to 5.5-6.0 and carry out acidification, after this pretreated seawater advances the seawater membrane reverse osmosis, there is no and the film scale problems occurs.
Claims (6)
1. a Bipolar Membrane is characterized in that comprising the steps: to reverse osmosis method sea water desaltination pretreatment process
(1) being the water inlet of Bipolar Membrane device through flocculation sediment, the filtering seawater of sand filtration, the negative electricity of Bipolar Membrane device very stainless steel or titanium is coated with ruthenium electrode, and anode is coated with ruthenium electrode or platinum electrode with titanium, and the Bipolar Membrane device is the assemblings of three compartments; Each three compartment unit is made up of Bipolar Membrane, anode membrane, cavity block, three Bipolar Membrane elastic baffles, anode membrane wherein is a divalence separatory membrane: be more than 95% to a divalent cation resolution, membrane resistance is lower than 2 Europe/square centimeters, thickness is less than 0.2 millimeter, and degree of crosslinking is at the anode membrane more than 30%; The current density of Bipolar Membrane device operation is 100-2000A/m
2, the film surface velocity is 1-15cm/s, utmost point liquid is sodium-chlor or the metabisulfite solution of mass concentration 1-10%;
(2) alkali lye in the Bipolar Membrane device alkali chamber is mixed with the water inlet of reverse osmosis unit, the blended ratio is: alkali lye 0.2-20mL is added in every liter of water inlet, and making into, the pH value of water is raised to 9.2-10.9;
(3) regulate pH the micro-filtrate membrane filtration of the water inlet after the above-mentioned alkalization, and then with the acid solution of bipolar acid chamber, regulate the pH value to 8.2-8.8 with the 0.1-0.5 micron.
2. treatment process according to claim 1, it is characterized in that: sodium-chlor or the metabisulfite solution of 1-10% is utmost point liquid in the step (1), and the method that adopts local circulation or increase membrane area makes the mass concentration of the alkali lye of the acid solution of sour chamber or alkali chamber reach 0.5-15%.
3. treatment process according to claim 2, it is characterized in that: sodium-chlor or the metabisulfite solution of 1-10% is utmost point liquid in the step (1), and the method that adopts local circulation or increase membrane area makes the mass concentration of the alkali lye of the acid solution of sour chamber or alkali chamber reach 9.5-10%.
4. treatment process according to claim 1 is characterized in that: Bipolar Membrane running current density is 500-1000A/m in the step (1)
2, the film surface velocity is 5-8cm/s.
5. treatment process according to claim 1 is characterized in that: step (2) makes into that the pH value of water is raised to 10.0-10.6.
6. treatment process according to claim 1 is characterized in that: the water inlet after step (3) alkalization is with 0.45 micron micro-filtrate membrane filtration, then with acid solution adjusting pH value to 8.4-8.6.
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| CN110038440B (en) * | 2019-05-30 | 2021-07-27 | 河北工业大学 | Bipolar membrane electrodialysis device and method for seawater decalcification |
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