CN104250044B - A kind of sea water advanced processing method of gas hydrate and device - Google Patents
A kind of sea water advanced processing method of gas hydrate and device Download PDFInfo
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- CN104250044B CN104250044B CN201410516256.8A CN201410516256A CN104250044B CN 104250044 B CN104250044 B CN 104250044B CN 201410516256 A CN201410516256 A CN 201410516256A CN 104250044 B CN104250044 B CN 104250044B
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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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Abstract
The invention belongs to reverse osmosis water desalination technology field. Be specifically related to the sea water advanced processing method of a kind of gas hydrate and device. The method comprises the step of seawater being carried out to desalination by reverse osmosis process, then the seawater utilization chlorine hydrate after desalination by reverse osmosis process is again desalinated, is disinfected. The present invention carries out continuously the generation of chlorine hydrate, separation and decomposable process through the seawater of first desalination in definitely airtight chlorine gas-circulating system, in comparatively loose temperature, under the lower pressure condition that the seawater of operation processing before carries, realize when the desalination of seawater boron removal secondary is processed, disinfected and carrying out. In improving Seawater Treatment efficiency, reduce industrial cost.
Description
Technical field
The invention belongs to reverse osmosis water desalination technology field. Being specifically related to one utilizes gas hydrate to carry out desalinization to disappear except boronThe method and apparatus of poison.
Background technology
Water is the tellurian requisite important substance of depending on for existence, is that the mankind carry out daily life, and carrying out industrial production can notAlternative natural resources. But freshwater resources only account for whole water resources 2%, wherein 87% freshwater resources again by freeze-up at the two poles of the earth and heightIn the ice sheet and glacier on mountain, be difficult to develop. Along with the high speed development of industrial economy and the problem of environmental pollution increasingly sharpening,Freshwater resources scarcity has become a worldwide problem. According to statistics, China per capita water resource not as good as the world per capita freshwater resources 1/4,Have at present 300,000,000 populations need to lean on the reprocessing of seawater or salt ground water to obtain domestic water, the shortage of China's freshwater resourcesBecome the bottleneck of restriction economic growth and social progress. Success finds the effective way meaning of a sustainable use water resourceGreat. Desalination technology solves as a kind of the effective means that freshwater resources are in short supply, is more and more subject to the wide of coastal local governmentGeneral concern.
Counter-infiltration, as the mainstream technology of desalinization, is to plant under pressure-driven, will by means of the selective retention effect of pellicleThe method that salt ion in seawater separates with water, can effectively remove the most ions in seawater, but due to boron molecule notHave electrically and the radius of boron molecule is less than reverse osmosis membrane aperture, thus very low to the clearance of boron, its boron content that produces water higher thanDrinking Water in China standard. Boron excessive concentration can produce totally unfavorable impact to human body and crops, has hindered greatly seawater lightThe development of chemical industry. Therefore hyperfiltration desalinization need to combine and reach drinking water standard with additive method. Hydrate seawater is lightChange method is a kind of novel desalination technology, be utilize hydrating agents at certain pressure and temperature with seawater in water moleculesGenerate hydrate, and molecules of salt in seawater is stayed in liquid phase, isolated hydrate and it is dissolved at normal temperatures and pressures and get final productTo realize the object of desalinization, and boron ion being had to obvious removal effect to fresh water, is 80% to the removal efficiency of boron ionLeft and right. Gas hydrate agent should meet lower hydrate and generate force value, higher hydrates generation temperature value, chemically stable, easily cheapMust wait condition, thereby make hydrate desalination technology meet the targets such as high yield, low energy consumption, economic environmental protection. Forefathers proposeUse CO2Hydrate generates to desalinize seawater, but CO2The seawater of hydrate sea water desalination method processing also needs further sterilization to removeOrganic matter in water, this has just increased the cost of desalinization processing.
Summary of the invention
For the deficiency of above-mentioned existence, the present invention still needs sterilization after efficiently solving conventional hyperfiltration desalinization, removes boron processingProblem, make full use of the high pressure of output water in reverse osmosis process and chlorine reaction and form hydrate, realize sea water advanced processing,Reach national drinking water standard. The present invention utilizes the high pressure of reverse osmosis water outlet and the lower natural temperature of seawater, and collection is except boron mistakeJourney, disinfecting process are integrated, and simplified technological process, have greatly reduced desalinization cost.
Gas hydrate of the present invention sea water advanced processing method, comprises seawater is carried out to desalination by reverse osmosis processStep, then again desalinates the seawater utilization chlorine hydrate after desalination by reverse osmosis process, disinfects.
The described chlorine hydrate that utilizes is again desalinated, is disinfected, and refers to that hydrone in reverse osmosis produced water is in hydrationIn thing reaction tower with after hydrating agents gas (chlorine) water generation reaction compound, deliver to and in hydrate separator, make hydrate crystal slurrySeparate with concentrated seawater, the hydrate crystal slurry after separation is sent in decomposition of hydrate device and decomposes, carry out simultaneously water body disinfection withAnd the chlorine being dissolved in the water removes.
Concrete implementation step, as Fig. 1,2: seawater a enters seawater desalination system under the effect of water pump 1, by machineryBefore filter 2, add flocculant e in pipeline, make impurity and colloid condense in seawater, then mechanical filter 2 is removed seawaterIn colloidal impurity, make SDI≤5, meet pretreated requirement. Pretreated seawater adds antisludging agent f, in anti-sealing moreRO membrane stack 6 is stopped up in little impurity fouling. The minimum filtering accuracy of cartridge filter 3 is 2 μ m, is that seawater enters RO membrane stack 6Last procedure. High-pressure pump 4 reaches required high pressure to be squeezed into seawater in RO membrane stack 6, and the salt ion in seawater separates with water,Water and minor radius ion, through reverse osmosis membrane, obtain reverse osmosis produced water b. Reverse osmosis produced water b itself is required with subsequent handlingReaction pressure. Reverse osmosis produced water b is undertaken after precooling by two heat exchangers under the effect of pump, then reaches through auxiliary cooler 13Arrive required temperature lower than 12 DEG C. If seawater natural temperature is lower than 12 DEG C, heat exchanger can not start. Cooled counter-infiltrationProduct water enters in reaction tower 15 and generates hydrate with chlorine contact, and the salt solution slurry that contains crystal of hydrate is centrifuged pump sucking-off defeatedDeliver in hydrate separator 16, thereby hydrate crystal is separated with concentrated seawater. Hydrate slurry is delivered to hydration by pumpIn thing decomposer 17, concentrated seawater c enters in heat exchanger 10 and heats up and discharge under Action of Gravity Field. Hydrate is at decomposer 17Under middle normal temperature and pressure, be decomposed into fresh water and chlorine, fresh water d enters and produces pond 8 by heating up in Action of Gravity Field inflow heat exchanger 9,The chlorine decomposing enters in gas tank 18 by disconnecting check-valves, enters in reaction tower 15 and repeat under the effect of compressor 20Utilize, gas recycle process the 15 → 16 → 17 → 18 → 20 → 15th, a complete totally enclosed system, in the time that air pressure is not enough, chlorine gasTank 19 can be supplied with chlorine. Pressure in 5 moment of Pressure gauge observation system changes, the temperature in 14 moment of thermometer observation systemDegree.
The present invention also provides the device for said method: the heat exchanger 9,10 that it comprises two series connection, stops by cutoutReturn valve 11 and centrifugal pump 12 and be connected with cooler 13, thermometer is equipped with in cooler 13 outlets; Cooler 13 is by cutout non-returnValve is connected with reaction tower 15, and reaction tower 15 is provided with thermometer and Pressure gauge; Reaction tower lower end is by centrifugal pump and stop check valveBe connected with hydrate separator 16; Hydrate separator 16 tops are by stop check valve and centrifugal pump and decomposition of hydrate device 17Be connected; Hydrate separator 16 bottoms are connected with heat exchanger 10 by stop check valve; Decomposition of hydrate device 17 is provided with Pressure gauge,Top is connected and is connected with gas tank 18 by valve; Decomposition of hydrate device 17 bottoms are connected with heat exchanger 9 by stop check valve; StorageGas tank 18 is connected with chlorine gas tank 19 by valve; Gas tank 18 is connected with compressor 20, and compressor 20 leads to reaction tower 15 phasesConnect. Because the corrosivity of seawater is very large, therefore adopt two-way stainless steel material.
Be applied to after the elementary desalinization operation of hyperfiltration a kind of chlorine hydrate seawater second level treating apparatus, i.e. reverse osmosisThoroughly, after the first desalination of method, utilize chlorine hydrate again to desalinate and disinfect. Device is as Fig. 2. Comprise pending reverse osmosisThoroughly produce water supply system, water treatment system, gas-circulating system. Pending reverse osmosis produced water supply system by heat exchanger 9, changeHot device 10, stop check valve 11, centrifugal pump 12, cooler 13 form. This system provides through reverse osmosis membrane continuously for installingThe reverse osmosis produced water b of first desalination. In isolated concentrated seawater c and decomposition of hydrate process in hydrate build environmentThe temperature of the more pending reverse osmosis produced water b of fresh water d generating is on the low side. For realizing energy-conservation object, dense by above-mentioned lower temperatureSeawater and fresh water before discharge respectively through over-heat-exchanger 9 and heat exchanger 10. Two heat exchangers 9 and 10 heat in seriesExchange system, pending reverse osmosis produced water b successively by heat exchanger 9 and heat exchanger 10 respectively with low temperature concentrated seawater c andLow temperature fresh water d carries out heat exchange, realizes precooling. Wherein, seawater, concentrated seawater, fresh water are all not mixed flows of independent tubes. CoolingDevice 13, according to the reaction temperature of the reverse osmosis produced water b temperature of precooling and generation hydrate, can be adjusted the temperature of water bath with thermostatic control at any time,The reverse osmosis produced water b that the cold energy that guarantee provides can make to deliver in reaction tower is down to reaction temperature. Due to reaction temperature only need 12 DEG C withUnder, if the temperature of reverse osmosis produced water b, lower than 12 DEG C, can not start cooler 13. Water treatment system comprises hydrate reaction tower15, hydrate separator 16, decomposition of hydrate device 17. Hydrone in reverse osmosis produced water b in hydrate reaction tower 15 withAfter hydrating agents gas reaction generation hydrate, deliver in hydrate separator 16 and separate with concentrated seawater c, pure hydrate crystalSlurry decomposes in decomposition of hydrate device 16, and carries out water body disinfection and the chlorine that is dissolved in the water removes simultaneously. Gas circulationSystem comprise hydrate reaction tower 15, hydrate separator 16, decomposition of hydrate device 17, gas tank 18, chlorine gas tank 19,Compressor 20 forms, and this system is definitely airtight system of requirement, can not have gas leakage. Gas is in the effect of compressor 20Under the pipeline that is full of hydrate reaction tower 15, separator 16, decomposer 17 and connects, the gas of decomposition of hydrate and not anti-The gas of answering reclaims and enters gas tank 18, recycling. Because the gas meeting oligodynamical as hydrating agents is in water body, dischargeSystem, therefore if the air pressure that in water body processing procedure, gas tank shows is when not enough, chlorine gas tank 19 is in time to gas injection in gas tank 18For hydrate generates and seawater sterilization provides recyclegas. Being dissolved in chlorine in fresh water can be by being exposed to the sun water body or in water bodyThrow in biology is almost discharged without modes such as the antichlors of adverse effect.
Device also comprises stop check valve, centrifugal pump, compressor etc. except above system. Due to the present invention's chlorine water usedCompound density is about 1.24g/ml, is greater than the 1.025g/ml of seawater, and the hydrate crystal of generation can accumulate in reactor bottom,Therefore centrifugal pump is placed in to reaction tower bottom.
The hydrating agents that the present invention adopts chlorine gas to generate as hydrate, has not only utilized the chlorine gas can be at relatively low pressureRelatively under high-temperature, form hydrate and remove the object of boron ion to reach seawater secondary desalination, and can utilize chlorine gas withWater reaction generates hypochlorous acid and reaches the object of disinfecting of carrying out seawater. The reverse osmosis seawater desalting method of main flow needs to utilize at presentSeawater is squeezed into putamina by high-pressure pump, by reverse osmosis membrane, penetrates first desalination water, therefore have through the seawater of reverse osmosis membraneThe pressure of 6-8MPa, before therefore can utilizing completely as the hydrate of subsequent handling, the pressure of hyperfiltration operation, has realizedThe recycling of energy, has saved industrial cost, has greatly improved economy.
Compared with carbon dioxide hydrate method, chlorine desalination of sea water by hydrate method device has following difference:
1, carbon dioxide hydrate averag density is less than seawater averag density, therefore the hydration that utilizes carbon dioxide to generate as hydrating agentsThing slurry floats on seawater, and centrifugal pump need be placed in reaction tower top. Pressure in seawater surface is little, and hydrate is unstable mayDecompose to some extent. If ensure, hydrate does not decompose, and needs the pressure in augmenting response tower, is unfavorable for energy-conserving and environment-protective. And chlorine waterCompound averag density is greater than seawater averag density, therefore chlorine hydrate slurry is by Action of Gravity Field, is gathered in reactor bottom, bottomPressure is large, and hydrate crystal is difficult for decomposing, and centrifugal pump is placed in reactor bottom. Reaction tower top feed liquor body, the hydration of generationThing is because Action of Gravity Field sinks, and reaction tower bottom goes out hydrate slurry. Be beneficial to constantly carrying out of hydrate formation.
2, carbon dioxide hydrate sea water desalinating unit need to add fresh water chlorination equipment, because chlorine itself has the characteristic of sterilization,Therefore without adding fresh water chlorination equipment. Simplify operation, saved industrial funds.
Beneficial effect of the present invention:
1, chlorine hydrate chemical formula is Cl2·nH2O, n > 8, belong to high WGR hydrate and the heat of transformation low, Seawater Treatment effectRate is high.
2, can under relatively gentle temperature, pressure, generate hydrate. Under 6-8 not atmospheric condition, temperature reaches 12 DEG CWhen following, can generate in a large number chlorine hydrate.
3, the product water itself that passes through reverse osmosis membrane is with elevated pressures, and chlorine hydrate seawater after-treatment system is as counter-infiltration seaThe subsequent handling of water desalination, the industrial condition of its required temperature, pressure can utilize heat transmission and the counter-infiltration operation institute of low temperature seawaterThe pressure providing, the recycling of the energy. And hydrate seawater after-treatment system can also be removed reverse osmosis seawater desalting institute notThe boron ion that can remove, is up to state standards the product water of desalinization. In sum, there is very strong environmental protection and energy saving.
4, chlorine is cheap and easy to get, and cost is low. Chlorine hydrate sea water desalination method has the effect of sterilization in desalinization,Equipment is simple, compactness, and cost is low, and technological process is simple, has good economic benefit.
5, the present invention proposes to utilize chlorine generation hydrate to process seawater, and its advantage mainly contains two: the first, chlorineHydrate can carry out disinfection to water, does not need to establish sterilization process again, cost-saving. The disinfection principle of chlorine is that it reacts raw with waterBecome hypochlorous acid, hypochlorous strong oxidizing property can be killed most germs and the microorganism in water, and Disinfection Effect is fine; ItsThe 2nd,, chlorine hydrate production cost is low comparatively speaking, and can effectively deviate from boron ion.
To sum up, the present invention carries out continuously chlorine hydration through the seawater of first desalination in definitely airtight chlorine gas-circulating systemThing generation, separation and decomposable process, in comparatively loose temperature, the lower pressure condition that the seawater of operation processing before carriesLower realization when the desalination of seawater boron removal secondary is processed, disinfected carried out. In improving Seawater Treatment efficiency, reduce workIndustry cost.
Brief description of the drawings
Fig. 1 is for being seawater desalination system;
Fig. 2 is hydrate seawater second level treating apparatus.
Description of reference numerals:
1, water pump; 2, mechanical filter; 3, cartridge filter; 4, high-pressure pump; 5, Pressure gauge; 6, RO membrane stack; 7,Hydrate seawater after-treatment system; 8, produce pond; 9-heat exchanger 1; 10-heat exchanger 2; 11-stop check valve; 12-Centrifugal pump; 13-cooler; 14-thermometer; 15-reaction tower; 16-hydrate separator; 17-decomposition of hydrate device; 18-Gas tank; 19-chlorine gas tank; 20-compressor; A-seawater; B-reverse osmosis produced water; C-concentrated seawater; D-fresh water; E-flocculant;F-antisludging agent.
Detailed description of the invention
Below in conjunction with accompanying drawing, enforcement of the present invention is further illustrated.
Shown in Fig. 2, apparatus of the present invention by 9, heat exchanger 10, heat exchanger 11, stop check valve 12, centrifugal pump13, cooler 14, thermometer 15, reaction tower 16, hydrate separator 17, decomposition of hydrate device 18, gas tank 19,Chlorine gas tank 20, compressor form.
As Fig. 1, seawater a enters seawater desalination system under the effect of water pump 1, by before mechanical filter 2, at pipelineIn add flocculant e, make impurity and colloid condense in seawater, then mechanical filter 2 is removed the colloidal impurity in seawater, makesSDI≤5, meet pretreated requirement. Pretreated seawater adds antisludging agent f, and impurity fouling less in anti-sealing is stopped upRO membrane stack 6. The minimum filtering accuracy of cartridge filter 3 is 2 μ m, is last procedure that seawater enters RO membrane stack 6. HighPress pump 4 reaches required high pressure to be squeezed into seawater in RO membrane stack 6, and the salt ion in seawater separates with water, water and minor radius ionThrough reverse osmosis membrane, obtain reverse osmosis produced water b. Reverse osmosis produced water b itself is with the required reaction pressure of subsequent handling.
Reverse osmosis produced water b is undertaken after precooling by two heat exchangers under the effect of pump, then reaches required through auxiliary cooler 13Temperature lower than 12 DEG C. If seawater natural temperature is lower than 12 DEG C, heat exchanger can not start. Cooled reverse osmosis produced water entersEnter in reaction tower 15 and generate hydrate with chlorine contact, the salt solution slurry that contains crystal of hydrate is centrifuged pump sucking-off and is delivered to waterIn compound separator 16, thereby hydrate crystal is separated with concentrated seawater. Hydrate slurry is delivered to decomposition of hydrate by pumpIn device 17, concentrated seawater c enters in heat exchanger 10 and heats up and discharge under Action of Gravity Field. Hydrate is normal temperature in decomposer 17Under normal pressure, be decomposed into fresh water and chlorine, fresh water d enters and produces pond 8, decomposition by heating up in Action of Gravity Field inflow heat exchanger 9Chlorine enters in gas tank 18 by disconnecting check-valves, enters recycling in reaction tower 15 under the effect of compressor 20,Gas recycle process the 15 → 16 → 17 → 18 → 20 → 15th, a complete totally enclosed system, in the time that air pressure is not enough, chlorine gas tank 19Can supply with chlorine. Pressure in 5 moment of Pressure gauge observation system changes, the temperature in 14 moment of thermometer observation system.
Claims (2)
1. the sea water advanced processing method of gas hydrate, is characterized in that, seawater enters seawater under the effect of water pump (1)Desalination system front by mechanical filter (2), adds flocculant in pipeline, makes impurity and colloid condense in seawater, soRear mechanical filter (2) is removed the colloidal impurity in seawater, makes SDI≤5, meets pretreated requirement; Pretreated seawaterAdd antisludging agent, RO membrane stack (6) is stopped up in impurity fouling less in anti-sealing; The minimum filtering accuracy of cartridge filter (3) is2 μ m are last procedures that seawater enters RO membrane stack (6); High-pressure pump (4) reaches required high pressure seawater is squeezed intoIn RO membrane stack (6), the salt ion in seawater separates with water, and water and minor radius ion, through reverse osmosis membrane, obtain reverse osmosis producedWater; Reverse osmosis produced water itself is with the required reaction pressure of subsequent handling; Reverse osmosis produced water is handed over by two heat under the effect of pumpParallel operation carries out after precooling, then reaches required temperature lower than 12 DEG C through auxiliary cooler (13); If seawater natural temperature lower than12 DEG C, heat exchanger can not start; Cooled reverse osmosis produced water enters in reaction tower (15) and generates hydrate with chlorine contact,The salt solution slurry that contains crystal of hydrate is centrifuged pump sucking-off and is delivered in hydrate separator (16), thereby hydrate crystalline substanceBody is separated with concentrated seawater; Hydrate slurry is delivered in decomposition of hydrate device 17 by pump, and concentrated seawater c is under Action of Gravity FieldEnter in heat exchanger (10) and heat up and discharge; Hydrate is decomposed into fresh water and chlorine under normal temperature and pressure in decomposer (17),Fresh water enters and produces pond (8) by heating up in Action of Gravity Field inflow heat exchanger (9), and the chlorine of decomposition enters by disconnecting check-valvesEnter in gas tank (18), under the effect of compressor (20), enter recycling in reaction tower (15), gas recycle processBe a complete totally enclosed system, in the time that air pressure is not enough, chlorine gas tank (19) can be supplied with chlorine; The observation of Pressure gauge (5) momentIntrasystem pressure changes, the temperature in thermometer (14) moment observation system.
2. for a device for method described in claim 1, it is characterized in that, this device comprise two series connection heat exchanger (9),(10), be connected with cooler (13) by stop check valve (11) and centrifugal pump (12), cooler (13) outlet is equipped withThermometer; Cooler (13) is connected with reaction tower (15) by stop check valve, and reaction tower (15) is provided with thermometer and pressurePower table; Reaction tower lower end is connected with hydrate separator (16) with stop check valve by centrifugal pump; Hydrate separator (16)Top is connected with decomposition of hydrate device (17) with centrifugal pump by stop check valve; Hydrate separator (16) bottom is by stoppingCheck-valves is connected with heat exchanger (10); Decomposition of hydrate device (17) is provided with Pressure gauge, and top is connected and gas tank (18) by valveBe connected; Decomposition of hydrate device (17) bottom is connected with heat exchanger (9) by stop check valve; Gas tank (18) is by valve and chlorineGas gas tank (19) is connected; Gas tank (18) is connected with compressor (20), and compressor (20) leads to reaction tower (15) phaseConnect.
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2014
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Effective date of registration: 20201110 Address after: 221300 Chahe Town New District, Pizhou City, Xuzhou City, Jiangsu Province Patentee after: Pizhou Borui Investment Management Co.,Ltd. Address before: 213164 Jiangsu Province, Changzhou city Wujin District Gehu Lake Road No. 1 Patentee before: CHANGZHOU University |
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