CN103787443B - Formula absorber is flow through in order to what remove total dissolved solid - Google Patents
Formula absorber is flow through in order to what remove total dissolved solid Download PDFInfo
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- CN103787443B CN103787443B CN201210419700.5A CN201210419700A CN103787443B CN 103787443 B CN103787443 B CN 103787443B CN 201210419700 A CN201210419700 A CN 201210419700A CN 103787443 B CN103787443 B CN 103787443B
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Abstract
The present invention discloses a kind ofly flows through formula absorber in order to what remove total dissolved solid.Containing a large amount of total dissolved solid (Total Dissolved Solids, TDS) seawater stoste flows through formula absorber (Flow Through Adsorber by an a kind of sorbing material of splendid attire, FTA), the TDS of seawater is just removed at once in a large number, and sorbing material need not be energized.Many materials can be used to make the sorbing material with Shuan Xing functional group that above-mentioned FTA uses.One of Shuan Xing functional group of sorbing material carrys out the atomic group of the Liquidity limit that autophosphorylation (phosphorylation) is given, the atomic group of the adsorpting anion that another functional group then produces from ammonium (amination).According to the needs of application, sorbing material can be made into the form through film or packed bed.When sorbing material is saturated, the liquid that TDS can be utilized lower than liquid to be treated is to carry out on-line regeneration.Except seawater, the present invention can also with other waste water perplexed for TDS of extremely low expense process.
Description
Technical field
The present invention has flows through formula absorber (Flow Through Adsorber, FTA) about one, with cold suction ion processes, removes the total dissolved solid (Total Dissolved Solids, TDS) in water.For seawater, its TDS contacts with the adsorbent one in FTA at seawater, just declines to a great extent at once.Especially, the adsorbent be transformed by agricultural waste or raw material, can the effective and TDS removed in water and in various liquid cheaply.
Background technology
TDS is the common contaminant of all waste water comprising seawater.Make desalinization be in the technique of drinking water, the removal of TDS is main target, is also the most unmanageable project.At present, counter-infiltration (ReverseOsmosis, RO) is two kinds of desalination technologies being the most often used to the TDS removing seawater with distillation.Many solids are soluble in water is decomposed into ion, attracting fast by positive charge and negative electrical charge, and ion is easily held the effect reaching desalination by electrostatic field.Capacitive deionization CDI (Capacitive Deionization) technology is the principle utilizing positive and negative charge attracting, carries out desalinization to flow through formula capacitor FTC (Flow Through Capacitor).The present inventor is devoted to more than ten years of exploitation of CDI technology, obtains several sections of United States Patent (USP)s, such as, and United States Patent (USP) the 6th, 462, No. 935 and the 6th, 795, No. 298.CDI can become RO and the effective substitute technology of distillation, has speciality such as " electric energy used when the rate of recovery without chemicals, water is high, it is low to consume energy and directly reclaim and store suction ion " because of CDI.But, CDI technology also containing some defects, comprising: use the titanium of high price as the ground of FTC electrode, carry out the automatic regeneration of FTC electrode with the Electronic Control of costliness, and the most serious " FTC electrode production capacity is low short with the life-span " problem.
Document there is the report of many " with inexpensive adsorbent under no power, reducing TDS and the chemical oxygen demand COD (Chemical Oxygen Demand) of water through absorbing process ".Such as, United States Patent (USP) the 4th, 877, No. 534 and the 7th, 727, No. 398 respectively with the organic pollution in the paddy of charing absorption water and stain.United States Patent (USP) the 6th, 579, No. 977 and the 7th, agricultural waste is converted into carbonaceous adsorbent by 098, No. 327, with the heavy metal removed in water.Yabusaki, at United States Patent (USP) the 7th, in 803, No. 937, discloses the technology of softening running water with cabamidated cotton.In addition, the people such as Lori are at " environmental science and technology bulletin " (Journal of Environmental Science and Technology), and the 1st (3) phase, in 124-134 page (2008 years) literary composition, disclose and make activated carbon, in order to absorb the stain in water with crops stalk.Shareef is at " world agriculture science bulletin " (World Journal ofAgricultural Science), 5th (S) phase, in 819-831 page (2009) literary composition, look back a series of raw material (biomass materials) with trade waste through carbonizing and activating the adsorbent formed, to remove the research of the various heavy in water.Above-mentioned United States Patent (USP) and journal article, all as reference data of the present invention.
Due to huge surface area, highdensity hole and various surface functional group, water treatment industry extensively using activated carbon as the filtering material except many pollutants in anhydrating, but does not comprise the removal of TDS.But upper joint discloses a lot of natural goods and manufactured products, by the technique more more economical than the industrial process of current activated carbon, carbonizing adsorbent can be made through low temperature and gentle medicine.Meanwhile, these adsorbents be made up of discarded object are better than activated carbon commodity in the application of many water treatments.The material of nearly all carbon elements all can be made into carbonizing adsorbent, such as: the shell of sewage sludge, cereal and drupe, wood fibre discarded object, Oil wastes and trade waste, as tire and rubber etc., all can be used as the raw material of carbonizing adsorbent.The people such as Shen are at " Chemical Engineering recent patent " (Recent Patents on ChemicalEngineering), and the 1st phase, 27-40 page, in (2008) literary composition, sums up eight kinds of techniques of the surfaction of above-mentioned discarded object and activated carbon.Through surfaction, original surface functional group of discarded object and activated carbon is changed, and becoming discarded object can except the atomic group of the middle specific pollutant that anhydrates, and activated carbon has new treatment function.In order to the example of water treatment and other activated carbon surface upgrading applied and design, be found in United States Patent (USP) the 3rd, 658,790,4,851,120,6,107,401,6,117,328,6,900,157 and 8,052,783 sections such as grade, other is not as good as repeating.
The present invention finds in all chemical reactions of surfaction, with phosphorylation (phosphorylation) and ammonium (amination) to except the TDS in anhydrating the most effective, the former can produce the atomic group of Liquidity limit, and latter provides the atomic group of adsorpting anion.To a kind of raw material first after-applied " cationization " and " anionization " of carbonaceous adsorbent, this raw material can be made to become " Shuan Xing functional group adsorbent ", and as United States Patent (USP) the 7th, 098, No. 327 disclosed.But, the 7th, 098, No. 327 with the document of other all adsorbed water process, there is no one for the waste water of high TDS level, as seawater, bittern, production line and saline groundwater, propose a large amount of solution reducing TDS.In addition, all old technologies do not propose on-line regeneration adsorbent yet, can the enforcement technology of continuous operations.The present invention propose with " Shuan Xing functional group activated carbon " through film or packed bed, or the packed bed of " Shuan Xing functional group charring rice husk " make flow through formula absorber FTA, can under adsorbent be energized, the seawater that desalination is a large amount of continuously, or softening a large amount of running water.When adsorbent is saturated, the seawater that its available running water, deionized water, surface water or TDS is low compared with processed water, fast with repeatedly on-line regeneration.
Summary of the invention
A project of the present invention be with minimum chemicals, minimum reaction temperature and the shortest reaction time, make " the Shuan Xing functional group activated carbon " that be used for desalinization.In order to remove cation in seawater and anion simultaneously, active carbon particle must possess Shuan Xing functional group.Therefore, selected powder or granular activated charcoal have to pass through the chemical treatment of phosphorylation (phosphorylation) and ammonium (amination), and phosphorylation is first implemented.In the phosphorylation of non-biochemistry, phosphoric acid (H
3pO
4) be host, but diammonium hydrogen phosphate [(NH
4)
2hPO
4] can be used as auxiliary agent with urea.The phosphorylation of activated carbon, generally in the mixture of activated carbon and above-mentioned medicament, can carry out 1 to 3 hours with 140 ° of C to 200 ° of C under air.On the other hand, the ammonium chemical drug agent of activated carbon is selected more, comprising: the basic species of ammonia, ammoniacal liquor, straight chain and aromatic amine, heterocyclic amine and ammonium and salt.The ammoniumization of activated carbon generally under 45 ° of C to 100 ° of C, can be carried out 6 to 12 hours.Because the reaction temperature of ammonium is lower, therefore implement after phosphorylation.Activated carbon after phosphorylation, must remake ammonium with clear water eccysis medicament.Shuan Xing functional group activated carbon after ammonium, must clean medicine again, last vacuum drying is for subsequent use to collect.
Though powder or granular activated carbon commodity are commonly used to water treatment, on the high side.Section 2 object of the present invention, for using various agricultural waste as the substitute of activated carbon, reduces the expense of water treatment.The present invention inspects some agricultural wastes of TaiWan, China local products, chooses the raw material of rice husk as the alternative adsorbent of activated carbon.Without under any processing, rice husk directly with the condition of the phosphorylation of activated carbon except temperature, carbonizes between 200-500 ° of C, makes the rice husk of brown color change black into.After rice hull carbon is cleaned, then with the ammonium condition process of activated carbon, and then become " Shuan Xing functional group rice hull carbon ".
Granular " Shuan Xing functional group activated carbon " and " Shuan Xing functional group rice hull carbon ", for the best implementation method of water treatment, becomes " packed bed " FTA for being installed in a container.But, " the Shuan Xing functional group activated carbon " of powdery if also make packed bed, water will be not easy to flow through.Therefore, Section 3 object of the present invention, for powdery " Shuan Xing functional group activated carbon " makes the optimal design of FTA.The present invention proposes the method for three kinds of fixing powderies " Shuan Xing functional group activated carbon ": (1) " Shuan Xing functional group activated carbon " powder and adhesive agent, solvent are mixed into slurry, then with spraying and dry and be fixed on a kind of netted plastic bottom material and become through net; (2) a certain amount of " Shuan Xing functional group activated carbon " powder is added to Homogeneous phase mixing in a kind of plastics of molten state, roll and formed through film; (3) the porous blanket made by activated carbon, through the chemical treatment of phosphorylation and ammonium, becomes Shuan Xing functional group through blanket.Due to through film be integrated through the activated carbon contained by blanket and plastic tie, activated carbon compared with through net surface attachment powder difficult drop-off.Simultaneously integrally formed product has three-dimensional structure, the ion remaval rate of the adsorbent of its Unit Weight, also than two dimension through net height.But, two dimension is through the production cost of net, lower than the product of three-dimensional.
Section 4 object of the present invention, for being settled in a vessel through film through net or activated carbon by activated carbon, forms FTA.After activated carbon is folded into the form of an accordion through net or activated carbon through film, then fill in the negotiable plastic containers of water, namely become independent and flow through formula absorber FTA card casket.The process water yield of a FTA card casket, is directly proportional to the activated carbon area be placed in FTA card casket, and the area of folded accordion is large not as the area of winding.Therefore, one block of rectangular activated carbon is through net, or one block of rectangular activated carbon is through film, and centered by a water inlet pipe, clockwise becomes a helical coil, just can provide maximum activated carbon area with minimum volume.The flowing of processed water in FTA card casket, with activated carbon through net or activated carbon vertical through the surface of film, pass through activated carbon net or active carbon film equably, then flow out FTA card casket.Processed water is when by helical coil, and contact with Shuan Xing functional group activated carbon one, the charge species in water is just adsorbed.When the adsorbent of FTA reaches saturated because of process seawater, flow through can make adsorbent reactivation immediately with the running water of a FTA card casket capacity.No matter FTA card casket uses packed bed, through net or through film, their ionic adsorption and the circulation of ion desorption are all fast and are reversible.
Can be further understood by the following detailed description and accompanying drawings about the advantages and spirit of the present invention.
Accompanying drawing explanation
Fig. 1 shows the preparation method flow process of Shuan Xing functional group activated carbon, and wherein activated carbon first accepts phosphorylation, makes the surface of activated carbon plant the atomic group of Liquidity limit.Then, activated carbon carries out ammonium again, makes the surface of activated carbon obtain the atomic group of adsorpting anion.
Fig. 2 shows the preparation method flow process of activated carbon through net, and wherein Shuan Xing functional group activated carbon is attached on a plastic wire by spraying becomes through net.After activated carbon is converted into the form of an accordion through net, fill in the negotiable plastic containers of water, what namely become removal TDS flows through formula absorber FTA unit.Arrow in figure represents the flowing of processed water in FTA unit, vertical through the surface of netting with activated carbon.
Fig. 3 shows activated carbon and forms the making of helical coil through net or activated carbon through film, and wherein one block of rectangular activated carbon is through net, or one block of rectangular activated carbon is through film, and centered by the water inlet pipe of a porous, winding forms helical coil.
Fig. 4 shows the feasibility desalinized seawater through net with Shuan Xing functional group activated carbon, and wherein ordinate is the TDS of seawater, and abscissa is the cycle-index of ionic adsorption and ion desorption.Along with the increase of cycle-index, the TDS of seawater reduces gradually.
Fig. 5 shows the feasibility desalinized seawater through film with Shuan Xing functional group activated carbon, and wherein ordinate is the TDS of seawater, and abscissa is the cycle-index of ionic adsorption and ion desorption.Fig. 5 through film, be dispersed in a kind of plastics of molten state with the Shuan Xing functional group activated carbon identical with Fig. 4 to roll formation.The speed desalinized seawater through film of Fig. 5 be better than Fig. 4 through net.
Fig. 6 shows Shuan Xing functional group rice hull carbon and is filled in plastic containers, forms fixed bed FTA unit.
Fig. 7 shows the TDS remover that four fixed bed FTA unit strings are unified into the one group high process water yield.
Wherein, description of reference numerals is as follows:
10: method flow 101 ~ 110: step
20: make and assembling flow path 220 ~ 280: step
30: helical coil 310: through net
330: center water inlet pipe 600:FTA unit
640: container 610,710: entrance
630,730: go out 660: propping bar
680: Liquid distribution grid 700: module
Detailed description of the invention
The invention provides and a kind ofly use economic adsorbent, in the mode of near-zero power consumption, effectively and remove the ion of seawater stoste rapidly, become a kind of desalinization adsorption technology of innovation.Severally reach Two decades years, the present inventor is devoted to the exploitation of capacitive deionization CDI technology, as the desalination technology of " without chemicals and low power consuming ", achievement sees United States Patent (USP) the 6th, 462, No. 935 and the 6th, 795, No. 298, and the patent that other various countries authorize.CDI relies on its center of desalting, and namely flows through electrostatic field that formula capacitor FTC sets up and removes ion in seawater.CDI is only applied on the active carbon electrode of FTC with 1-3 volt DC voltage, and in the electric energy applied, and at least 1/3 directly can to reclaim when FTC electrode regeneration, to store for future use, make the power consumption of CDI lower than the light method in RO sea.But the irreversibility of the ionic adsorption of activated carbon surface micropore, and the unavoidable water electrolysis that 1-3 volt operation voltage produces, make the method for desalting seawater that CDI technology cannot become commercial.Aforesaid irreversible ionic adsorption and water electrolysis, cause FTC electrode cannot holomorphosis, FTC electrode loses adsorption site, electric leakage and TDS rise.Therefore, CDI be only suitable for desalinate TDS 5, below 000ppm seawater and salt solution.If CDI is in order to desalinate the waste water of TDS higher than 5,000ppm, FTC electrode is incited somebody to action saturated rapidly and cannot regenerate, and makes CDI just like useless art.In practicality, CDI needs a kind of TDS load to alleviate device, to improve the problem of its low production capacity and difficult life.FTA provided by the invention, can meet the demand of CDI.
Many water purification process are reached by the particular functional group of various adsorbent and the suction-operated of water pollutant.Aforementioned particular functional group can design and build on: the surface of the thing such as cellulose, fluoropolymer resin, crops, earth, raw material, pottery, metal oxide and activated carbon.Can be comprised by the charged contaminants of Adsorption: single or hydrated ion, heavy metal, organic matter, inorganic matter, blood and protein.Generally speaking, remove the ionic contaminants in water with suction-operated, neither power consumption, does not need the equipment of complex and expensive yet.Meanwhile, if a kind of physical attraction of the combination between ion and adsorbent, made adsorbent can rapid regeneration by the ion that adsorbs by easily departing from.Table 1 lists the pairing of some adsorbent-absorbates, and to illustrate between particular functional group with water pollutant adsorbing associates.Table 1 focuses on specific adsorption functional group, and therefore in order to clear cause, the adsorbent that these functional groups lodge is not shown in table 1.
Table 1: the pairing of adsorbent-absorbate
The ionic adsorption functional group that table 1 lists, and in the ionic adsorption atomic group occurred in document, neither one was once disclosed " can carry out a large amount of desalinizations ".The reason of exploitation out in the cold of " adsorbing extra large light method ", may come from the waste water that seawater is a kind of complexity, average dissolution 35g salt in 1 liter of seawater, or TDS is 35,000ppm, and in addition, the organic pollution being difficult in addition in seawater remove hinders desalinating process.In typical seawater, front 5 cations that concentration is the highest, concentration is from high to low: Na
+, Mg
2+, Ca
2+, K
+and Sr
2+; Similarly, front 5 anion that concentration is the highest, concentration is from high to low: Cl
-, SO
4 2-, HCO
3 -, Br
-and H
2bO
3 -.To remove cation in seawater and anion with " absorption method " simultaneously, adsorbent used must have enough surface areas, and the adsorption site of Shuan Xing functional group.A series of material, comprise: activated carbon, CNT, metal oxide (such as magnesia, aluminium oxide, iron oxide, manganese oxide, zinc oxide, nickel oxide, cupric oxide, tin oxide), metal carbides (such as magnesium carbide and barium carbide), cellulose, cotton, fine hair, earth, silicate, pottery and raw material etc., all can be developed as the adsorbent for " adsorbing extra large light method ".The present invention is based on the following speciality of activated carbon, first select the raw material of activated carbon as Shuan Xing functional group adsorbent, then make and flow through formula absorber FTA unit.The speciality of activated carbon is as follows:
1. the raw material sources of activated carbon are very wide;
2. activated carbon has huge surface area;
3. activated carbon can resist the corrosion of seawater and the pollutant contained by it;
4. activated carbon is easily processed;
5. activated carbon is the material of environmental protection; And
6., relative to the raw material of CNT and some inorganic adsorbents, the price of activated carbon is low.
According to table 1, the present invention selects phosphate (PO
4 3-) as the cationic atomic group of adsorbing seawater, and ammonium/amino acid (NH
4 +/ NH
2) be the atomic group of the anion of adsorbing seawater.The present invention selects again a kind of inexpensive activated carbon commodity, as the carrier of adsorption functional group.In other words, after selected activated carbon accepts phosphorylation and ammonium, its surface just can obtain phosphate and ammonium, becomes Shuan Xing functional group activated carbon.The activated carbon commodity selected, from coconut husk, have 1,000m
2the specific area of/g, is used for filtering drinking water by Running-water Company usually, and is used for adsorb volatile organic compound by semiconductor company.But if the phosphorylation carried without the present invention and ammonium, this activated carbon or more expensive activated carbon cannot reduce the TDS of seawater at all.
Fig. 1 shows one of the present invention preferably specific embodiment, and it is changed through functional group by selected activated carbon, becomes the preparation method of Shuan Xing functional group activated carbon.In the method flow 10 of Fig. 1, the activated carbon selected of aequum is put in a reaction vessel in step 101, and the material of container can be pottery, glass or stainless steel.Then, in step 102, according to the weight of activated carbon, with special ratios, phosphorylation medicament is added in reaction vessel to carry out phosphorylation.In the phosphorylation of activated carbon, phosphoric acid (H
3pO
4) be host, account for maximum ratio, diammonium hydrogen phosphate [(NH
4)
2hPO
4] can be used as auxiliary agent with urea.Phosphorylation is the aqueous solution by activated carbon and above-mentioned medicine, carries out 1 to 3 hours under air and 140 ° of C to 200 ° of C.After phosphorylation, the activated carbon muddy water of generation filters in step 103, and removes the Residuals of phosphorylation with clear water.Phosphorylation Residuals must be removed completely, hinders ensuing ammonium to prevent them.PH and the TDS of the activated carbon cleaning fluid of phosphorylation, can be used as the basis for estimation of the cleannes of activated carbon, namely pH is between 6-8, and TDS should at below 300ppm.The selection of the ammonium pharmacy response of activated carbon is more, comprising: ammonia (NH
3), ammoniacal liquor (NH
4oH), three grades and quaternary ammonium compound, straight chain and aromatic amine, heterocyclic amine, and ammonium salt (comprise chlorine, bromine, nitric acid, cross the salts such as chloric acid).The present invention selects the same in aforesaid medicament, the ammoniumization reaction of the activated carbon after step 104 carries out phosphorylation with the time of the temperature range of 45 ° of C to 100 ° of C and 6 to 12 hours.After ammoniumization reaction, twice chemically treated activated carbon mud, filters in step 105 and cleans, and accept the vacuum and heating drying of ten a few hours in step 106.Last in step 110, dry Shuan Xing functional group activated carbon collection is for subsequent use.
During filtering material as water treatment, activated carbon generally becomes fixed bed use to fill filter.Because particle diameter is little, activated carbon powder and water form fine and close clod, water permeation is passed, but not flows fast through the FTA containing activated carbon powder clod.Therefore, Shuan Xing functional group activated carbon powder is fixed on a kind of netted ground by the present invention, makes water can flow fast through FTA containing this kind of activated carbon net.With resistance to water and cost consideration, polymerizable material is the best ground supporting Shuan Xing functional group activated carbon powder.Suitable polymeric substrate comprises: cellulose acetate, cellulose triacetate, polyamide, polypropylene, polysulfones, polycarbonate, polyvinyl chloride, polyester fiber and polytetrafluoroethylene (PTFE).Meanwhile, polymeric substrate must be network structure, makes it coat Shuan Xing functional group activated carbon powder last, water can freely be flowed fast through.Fig. 2 shows a kind of specific embodiment preferably fixing activated carbon powder of the present invention, and comprising the making of coating net, and coating net becomes the installation of the FTA unit removing TDS in a container.In the making and assembling flow path 20 of Fig. 2, one piece of plastic wire is ready in step 220 with required size, for Shuan Xing functional group activated carbon powder in step 240, adds solidification be positioned net to become one piece of coating net with spraying process.Coating net is then folded into the shape of accordion in step 260, then, several required accordion coating nets, in step 280, are filled in a water through plastic tube in two ends, namely forms an independent FTA unit.As Fig. 2 display: water is in the flowing of FTA unit, vertical with the surface of coating net, makes adsorbent obtain maximum utilization.Coating net relies on adhesive agent and is positioned on net by Shuan Xing functional group activated carbon powder, and therefore adsorbent is decided by the adhesion of adhesive agent through the life-span of netting.So coating net is when folding, or current constantly apply pressure to coating layer, and the loss of Shuan Xing functional group activated carbon powder is unavoidable.
In order to reduce the loss of activated carbon powder, and hide the interference of activated carbon powder to reduce adhesive agent, the present invention assesses the concrete enforcement technology of two kinds " Shuan Xing functional group activated carbon powder and plastic bottom material fuse into one ".A wherein technology, is dispersed in a kind of plastics of molten state with specified quantitative activated carbon powder, then in adhesive-bonded fabric mode, roll become porous adsorbent through film.Another kind of technology, be then use the blanket made without chemically treated activated carbon powder, be transformed into the adsorbent of Shuan Xing functional group through blanket with the preparation method of Fig. 1.No matter which kind of carbon dust activated carbon blanket uses, the method for Fig. 1 all can make it become Shuan Xing functional group activated carbon.Adsorbent all can pass through the assemble method of Fig. 2 through film and adsorbent through blanket, makes independent FTA unit.In appearance, adsorbent scrapes sponge, as 3M hundred profit through film and adsorbent through the similar kitchen tools of blanket; This scrapes washing is inorganic matter abrasive material and sponge are fused into one.Except adsorbent is through film and the adsorbent consumption adjustable through the carbon dust of blanket, the flow passage aperture in their three-dimensional structures also can be customized, to meet the demand of application.Similar packing carbon powder article, are also shown in No. the 6th, 117,328, N-95 mouth mask, airstrainer, bamboo charcoal cloth and United States Patent (USP).
Utilize " absorption sea light " technology of FTA, its production capacity depends on adsorbent in FTA through net, adsorbent through film or the adsorbent area through blanket.Identical logic also appears at the filter core of ultrafiltration and RO, and namely production capacity is directly proportional to the area of filter material.All over the world, filter core all makes the shape of helical coil.Reason is: helical coil with minimum volume, can provide maximum area.Fig. 3 shows the specific embodiment that a kind of preferably FTA of the present invention adsorbs helical coil.Fig. 3 helical coil 30, be with one piece through net, through film or through blanket 310, reel with one heart formation along a center water inlet pipe 330.Meanwhile, the top and bottom sealing of helical coil prevents from leaking.As shown in Figure 3: center water inlet pipe 330 has been cut a hole some holes, allow water flow into helical coil, and with the arrow shown in Fig. 3, vertically penetrate adsorbent layer by layer.When helical coil is flow through in water inlet, the ion in water and adsorbent contact are just held.When the adsorbent of helical coil is saturated, flow through helical coil with appropriate rinse water, just can make adsorbent reactivation.The adsorbent spiral core of Fig. 3, can adopt the technique identical with RO filter core with ultrafiltration and specification to produce, and makes ultrafiltration and the existing hardware of RO can be used for FTA product.FTA uses marketing for many years and control the ultrafiltration in water treatment market and the system of RO commodity, and people just can the FTA product of exploitation of innovation with its custom be familiar with and knowledge, will contribute to the popularization of FTA product in water treatment market.FTA product also can in the application of the removal TDS in water treatment market, contributes a kind of new method of pollution-free, low power consuming.
The production of activated carbon is the industry of a kind of high pollution, highly energy-consuming.The processing of activated carbon first makes the raw material of activated carbon carbonize with 400 ° of C, then activates with 800 ° of C, produces high surface area.Consume many energy in whole process, and produce the air pollution of a large amount of carbon dioxide, smog and ashes.But, the raw material of activated carbon with lower temperature and shorter time, can carbonize and become various Shuan Xing functional groups adsorbent.Although the material that low temperature process produces, be charcoal and carbon non-activated, Shuan Xing functional group adsorbent charcoal specific activity carbon is more suitable for carrying out " absorption sea is light " to manufacture fresh water.Be in the covering of chemicals due to low-temperature carbonization and carry out without under flame, therefore do not produce carbon dioxide and smog (only having aqueous vapor to produce).Produce many agricultural wastes and raw material all over the world, can be used as the raw material of the adsorbent removing TDS.Enumerate the raw material of some adsorbents below:
1) shell of following cereal or stalk: rice, wheat, barley, oat, rye, Chinese sorghum, corn, soybean and soya bean.
2) shell or sub real of following fruit: coconut, palm, durian, mango and honey peach.
3) pericarp of following fruit or slag: pineapple, oranges and tangerines, shaddock, jackfruit and sugarcane.
4) shell of following nut: peanut, English walnut, ginkgo nut (all kinds of fruits), cashew nut, almond, acorn nut and acorn-cup fruit.
5) cellulose in following substances and lignin: flax, wood fragments, sawdust, bamboo and fiber (cotton/silk floss/yarn/silk/suede).
After assessing above-mentioned raw material, the present invention selects the raw material of rice husk as the adsorbent of removal TDS, and assessment rice hull carbon is in the performance of the TDS of reduction seawater, waste water and running water.The rice husk in the TaiWan, China native country that the present invention buys is not reprocessed, and just directly carries out phosphorylation and ammonium with the technique of Fig. 1.The rockiness of rice husk is from two kinds of hard compositions: silica (SiO
2) and lignin [C
9h
10o
3(OCH
3)
0.9-1,7]
n.In the typical composition of rice husk, cellulose [(C
6h
10o
5)
x] at most, account for 44% to 60%, wherein comprise lignin and hemicellulose [(C
5h
8o
4)
m].All the other compositions of rice husk have: silica is main inorganic ash, with volatile materials as water/fat/proteins.Lignin is a kind of aromatic polymer of monokaryon, and as cellulosic cement, lignin is also combined into the guiding thing of the current in plant with hemicellulose.The phosphorylation of rice husk of the present invention, main purpose is the lignin of charring rice husk, the functional group of Liquidity limit is grown in carbochain simultaneously.For reaching the charing of rice husk, phosphorylation is carried out between 200 to 400 ° of C.Whether completely the degree that rice husk turns black, be the sign of phosphorylation, and be decided by three response parameters: the weight ratio of rice husk and phosphorylation medicament, reaction temperature and reaction time.Experiment is pointed out, the charing of rice husk is more complete, and its ionic adsorption rate is higher.But excessive charing can make rice hull carbon pulverize as particulate, causes a large amount of material damages.The ammonium of rice hull carbon, then use the reaction condition identical with activated carbon, finally make Shuan Xing functional group rice hull carbon adsorbent.
Being different from Shuan Xing functional group activated carbon and having multiple installation method in FTA unit, the installation that Shuan Xing functional group rice hull carbon is best in FTA unit, is the form of packed bed.The concrete enforcement that the Shuan Xing functional group rice hull carbon that Fig. 6 shows a kind of preference of the present invention is installed in FTA unit: in FTA unit 600, the particle of Shuan Xing functional group rice hull carbon, between two propping bars 660, fills up the inner space of container 640, becomes fixed bed FTA.According to internal diameter and the aspect ratio of container 640, or claim aspect ratio (aspect ratio), the centre of the packed bed of rice hull carbon, must one or more Liquid distribution grid 680 be placed, water can be uniformly distributed in fixed bed FTA card casket flow through, fully contact with rice hull carbon.Waste water enters fixed bed FTA unit 600 from entrance 610, then leans on the conveying of gravity or pump, flows out from the outlet 630 of FTA unit 600.In order to lifting waste water flows through result once, multiple fixed bed FTA unit of can connecting uses, module 700 as shown in Figure 7, wherein the FTA units in series of 4 Ge Zhuanliaoshuan functional group rice hull carbon packed beds.Waste water flows into from entrance 710, flows out from outlet 730, accepts the process of cascading formula.At least two flow through formula adsorber unit also can form parallel combination.By phosphorylation of the present invention and ammonium, above-mentioned agricultural waste as rice husk, can be converted into the adsorbent removing TDS with raw material.
No matter be that adsorbent through blanket or adsorbent packed beds, uses the FTA of adsorbent of the present invention through film, adsorbent through net, adsorbent, all can when waste water and adsorbent contact, the TDS in water just reduces fast significantly.Moreover disclosed phosphorylation and ammonium, can make powdery and granular activated carbon, agricultural waste and raw material, be converted into powerful effective adsorbent.The mechanism of ion removed by adsorbent, is not ion-exchange because make the TDS of the rinse water of adsorbent reactivation lower than processed waste water TDS(namely the former containing the ion of small amount).In the application of many FTA, rinse water only contains very small amount of ion, such as, and the deionized water that distilled water and RO produce.The rinse water of aforesaid low TDS, can make adsorbent surface very clean.Therefore " absorption sea light " of the present invention mechanism, should be adsorbent activated centre with by the interionic a kind of physical attraction inhaled, and this gravitation is by the ionic strength being about formed on water.Briefly, ionic strength be in water each ion concentration be multiplied by the valence mumber of this ion square summation.When the water of LIS contacts saturated adsorbent, namely being expelled by the ion adsorbed of high ionic strength water, makes the activated centre of adsorbent surface live again, and continues to play the function removing TDS.The present invention also comprises: one first electronic controller, in order to manage the removal of total dissolved solid; And one second electronic controller, in order to manage the regeneration that this flows through formula adsorber unit, wherein this first electronic controller comprises the online detector of electrical conductivity, acid-base value and total dissolved solid for detecting liquid, and this second electronic controller comprises the online detector of electrical conductivity, acid-base value and total dissolved solid for detecting liquid.Following four embodiments, the disclosed FTA that demonstrates, with different adsorbent, removes ability and the output of TDS to various water sample.But these embodiments are not limit range of application of the present invention.
Embodiment 1
Under not doing any process, a collection of seawater stoste taking from TaiWan, China straits, directly carries out through net process of desalting with the adsorbent containing Shuan Xing functional group activated carbon.This adsorbent is coated in a wide 100mm through net with the slurry of activated carbon powder, and long 1,000mm, thick 0.6mm, net hole is 1mm
2polypropylene net on formed.The dosage of the activated carbon of every bar adsorbent net is 60g/1m
2, six adsorbents contain 36g activated carbon altogether through net, after being respectively folded into the shape of accordion, fill in six in the plastic tube of a two ends water flowing through net, become and flow through formula absorber FTA.Then, the above-mentioned seawater of 5 liters is admitted in FTA pipe, flows through adsorbent through net to feeder, for TDS measurement.5 liters of seawater often flow through FTA manages once, immediately with six adsorbent nets in 2 liters of running water regeneration FTA pipes.Primary ions absorption adds primary ions desorption (i.e. adsorbent reactivation), forms a desalinization circulation.Desalinization circulation about needs 1 minute, and six adsorbent nets just can perform down extra large light circulation of taking second place.
Fig. 4 shows the TDS decline of seawater and associating of the light cycle-index in sea, and wherein the initial TDS of seawater is 26.8ppt(26.8/1000ths), the TDS value of seawater is just measured in the light circulation in every 5 continuous print sea.From the data of Fig. 4, following 3 inferences can be obtained:
1.1 light circulations in sea just make the TDS decline 300-500ppm (300 to hundred/1000000ths 500/10000ths) of 5 liters of seawater; But every 5 continuous extra large light circulations can make TDS decline 2200-2600ppm.
2., using running water as rinse water, the holomorphosis of adsorbent net can be made.
3., when the ion concentration of seawater reduces, the rate that desalts of each extra large light circulation and then declines.
In embodiment 1, adsorbent is not yet saturated, namely regenerates.The TDS of monitoring stream water outlet, can learn that whether adsorbent is saturated.When the TDS flowing out water presents the trend of rising, namely represent adsorbent and reached saturated.Therefore, online electrical conductivity/TDS monitor can judge the orthochronous of adsorbent reactivation.The absorption output of Shuan Xing functional group activated carbon can represent with every gram of milliequivalent (mEq/g), or to be represented by the weight ratio of absorption salt as sodium chloride (NaCl) and activated carbon adsorbent.Be different from ion exchange resin surface and can only have unisexuality (cation or the anion) functional group of fixed number, activated carbon surface Zhi Rushuan functional group, and can be made through net, through film, form through blanket or packed bed.When activated carbon blanket accepts phosphorylation and ammonium, not only activated carbon, plastic carrier also may give Shuan Xing functional group.
Embodiment 2
To be same as the Shuan Xing functional group activated carbon of embodiment 1 as filler, to add in the polypropylene of molten state and mix, making activated carbon concentration is 240g/m
2adsorbent through film.Get one section of wide 150mm, long 470mm, thick 3mm, the adsorbent about containing 17g activated carbon, through film, after being converted into the shape of accordion, carries out the light circulation in sea of the similar embodiment 1 of the seawater stoste of 1 liter.Fig. 5 shows the TDS decline of seawater and associating of the light cycle-index in sea, and wherein the TDS of seawater is down to 306ppm from 23,900ppm, close to the TDS level of drinking water.Desalinization in embodiment 2, only uses activated carbon adsorbent through film, other process any useless.
Use equivalent activated carbon under, Fig. 5 adsorbent through the rate that desalts of the light circulation in each sea of film, for Fig. 4 adsorbent through net 4 times.Adsorbent is through film and adsorbent through the maximum differential of netting, and for the former is three-dimensional structure and the latter is two-dimentional, therefore the utilization ratio of the former adsorbent is higher.The salt content that Fig. 5 still shows along with seawater reduces, and the removal amount of TDS follows downward trend.But, the rate that desalts of each extra large light circulation still maintains 25%.In other words, no matter the salt content of seawater, the saliferous of the seawater entered can be removed 25% through film by adsorbent.Compared to adsorbent through film, adsorbent is high through the activated carbon content of blanket, therefore high through film through the amount of the desalting ratio of blanket.
Embodiment 3
Except activated carbon content is 60g/m
2, the activated carbon adsorbent of embodiment 2 is used to a desalinization test in Bohai Sea Gulf, China's Mainland through film.This test uses 6 diameters 6 " (150mm internal diameter), 40 in length " (1 meter is long) plastic tube series connection, each pipe close 7.5m
2the adsorbent of accordion like through film, the area always through film is 45m
2.The TDS of a collection of locality be the seawater stoste of 24,000ppm just with the FTA module of aforesaid series connection, carry out the process of removing TDS.Table 2 lists one group of typical data in test, and water is flowed out in collection per minute a barrel, and with the flow velocity of 600 liters per hour, every barrel of water yield is 10 liters.After the TDS pH-value determination pH of every barrel of water, to be listed in table in the second hurdle.The on-the-spot test of table 2 only has the pump electricity consumption of conveying seawater, and the process of the removal TDS of adsorbent is then without electric treatment.
Table 2: be the on-the-spot test [water flow velocity: 0.6m that the seawater stoste in the Bohai Sea Gulf of 24,800ppm carries out " adsorbing seawater desalination " to TDS through the FTA of film to use activated carbon adsorbent
3/ hour (600 liters per hour)]
| Water outlet per minute | The TDS (ppm, mg/L) of water outlet |
| 0 | 240 |
| 1 | 410 |
| 2 | 550 |
| 3 | 990 |
| 4 | 1,500 |
| 5 | 2,400 |
| 6 | 4,320 |
| 7 | 8,700 |
| 8 | 10,450 |
| 9 | The adsorbent of regeneration FTA is through film |
" commercialization " feasibility of technology that table 2 clearly shows " adsorbing seawater desalination ", the release of " FTA seawater desalination system ", first must complete hardware and the control logic of following subsystem:
1. the TDS of online detecting water outlet, judges the recovery time of FTA unit.
The automatic switchover of the absorption and regeneration of 2.FTA unit.
The execution specification of 3.FTA regeneration unit: discharge of wastewater/rinse dosage and recovery/regeneration order.
The monitoring of the functional stabilization of 4.FTA unit and maintenance.
5. the recovery of the resource of tool economic worth in seawater.
6. the post processing of adsorption fouling thing.
The present invention proves: the adsorbent using Shuan Xing functional group activated carbon as " adsorbing seawater desalination " technology, can generally desalination technology as the pretreatment of " dosing → precipitation → float and remove → filtration " of distillation, RO, electrodialysis and ion-exchange, just can under no power, directly desalinize seawater stoste, simplify the technique of desalinization, and eliminate cost and the pollution of agent-feeding treatment.The intensity of Shuan Xing functional group activated carbon adsorbent, fast suction ion and rapid regeneration also obtain checking.
Embodiment 4
Through functional group conversions's method of Fig. 1, first the rice husk of the local output in a kind of Taiwan is carbonized, and then after ammonium, becomes Shuan Xing functional group rice hull carbon, as the adsorbent of " adsorbing seawater desalination " technology.With the series connection method of Fig. 7, the fixed bed FTA unit of 6 splendid attire rice hull carbon is linked to be one group of stepped TDS remover.Often prop up FTA unit and fill 80g rice hull carbon, 6 pipes altogether 480g adsorbent remove test for TDS.The internal capacity often propping up FTA unit is 500cc, after inserting 80g rice hull carbon, loses free space, but rice hull carbon can hold the water yield of 250 to 350cc.Table 3 sums up four kinds of water samples with the fixed bed FTA cell processing of the rice hull carbon of above-mentioned 6 series connection, and in the process reducing TDS, the TDS that suction ion and FTA regenerate changes, i.e. the front TDS of TDS – process after Δ TDS(Δ TDS=process):
Table 3 four kinds of water samples reduce the test of TDS with the fixed bed FTA of the rice hull carbon of 6 series connection
Table 3 shows: the Δ TDS value flowing out residual water (being adsorbed by rice hull carbon) in water and FTA unit differs greatly, and the former TDS fall exceeds much than the latter.This is because flow out water progressively inhale ion through the staged of 6 FTA unit, the amplitude that TDS declines is large, and the residual water level in FTA unit is after outflow water, and because adsorbent is saturated gradually, available adsorption site reduces, therefore the TDS of residual water is in high level.Therefore waste water flows through 1 FTA unit once, the TDS removal amount that FTA is maximum, depends on following three factors:
1. the volume that flows through of waste water.
2. the consumption (weight) of adsorbent.
3. the ability of adsorbent and capacity.
The Shuan Xing functional group rice hull carbon that the present invention discloses is not activated, and namely rice hull carbon does not accept the catalytic reaction under 800-900 ° of C and anaerobic state, the structure of formation porous surface.Therefore the surface area of Shuan Xing functional group of the present invention rice hull carbon, can not show a candle to commercial activated carbon big.But the ability that Shuan Xing functional group rice hull carbon desalinizes seawater is greater than Shuan Xing functional group activated carbon, rice hull carbon can soften running water (testing 1 see table 3), and upgrading activity carbon cannot soften running water in fact.Moreover the regeneration efficiency of rice hull carbon, is better than upgrading activity carbon.Activated carbon surface has nano level hole, and rice hull carbon surface is comparatively level and smooth, proves that the surface micropore of adsorbent is not " adsorbing seawater desalination " important document needed for technology.On the yield of functional group conversions's reaction, activated carbon is better than rice hull carbon, because the yield of activated carbon is close to 100%.Because rice husk contains volatile component, tar (tar), ashes and particulate, rice husk is when low-temperature carbonization, and by the weight of loss 20-30%, yield only has 70-80%.Agricultural waste is with raw material, and bagasse is higher than rice husk with the lignin contained by bamboo, and ashes composition is lower, therefore the raw material that bagasse and bamboo should be more suitable for as producing adsorbent charcoal than rice husk.But, consider from the rice farming area in the whole world, rice husk has the advantage of steady sources and handling ease.
" suction-operated " is applied to desalinization, more than 40 years.Unfortunately, exploitation center of gravity is but placed on the processor of capacitive deionization CDI, namely flows through on formula capacitor FTC.Activated carbon and gas glue carbon are the common materials of early development FTC electrode, and in recent years, someone studies CNT, Graphene and metal oxide etc., as the material of FTC electrode.CNT, Graphene or close carbon material, except expensive, the regeneration of their nano aperture impeded electrode.After ion enters nano aperture, be just difficult to expulsion, make FTC electrode lose adsorption area.The activated carbon that the present invention uses originally does not remove the ability of TDS, but the phosphorylation disclosed through the present invention and ammonium, become Shuan Xing functional group activated carbon, just can yield unusually brilliant results in " adsorbing seawater desalination ".The present invention also proves the rice husk of agricultural waste, can make adsorbent more more effective than Shuan Xing functional group activated carbon, have broader water treatment applications scope.Agricultural waste, with raw material, also has other raw material ratio rice husk to have more potentiality, waits for the adsorbent being developed to and removing TDS or other application.Because adsorbent must first make its surface adhere to without any ion, it could by the TDS of waste water rapidly and be down to low-level in large quantities, such as below 20ppm.Make adsorbent reach the situation of 20ppm, then must use the rinse water of lower TDS, such as TDS is the deionized water of 1ppm.Carrying out the cleaning of adsorbent with deionized water, is a process lacking economic benefit.At the category of low TDS as below 100ppm, absorption and the desorption of CDI because relying on electric field to carry out ion, when the electric field is off, ion is the automatic surface desorption from FTC electrode just, the rinse water consumption of FTC electrode is afterwards few in the cleaning of low TDS category compared with Shuan Xing functional group adsorbent.Therefore Shuan Xing functional group adsorbent can complement each other with CDI, the TDS as CDI all carries instrument, gives CDI by the water treatment work of ultralow TDS.Shuan Xing functional group adsorbent also can assist water treatment systems such as " distillation, RO, electrodialysis and ion-exchanges ", solves cost and the pollution problem of Chemical Pretreatment.
By the above detailed description of preferred embodiments, be that hope clearly can describe the feature of the present invention and spirit, and not with above-mentioned disclosed preferred embodiment, category of the present invention limited.On the contrary, its objective is wish to contain various change and tool equality be arranged in the present invention institute in the category of claims applied for.Therefore, the category of claims that the present invention applies for should do the broadest explanation, with the arrangement causing it to contain all possible change and tool equality according to above-mentioned explanation.
Claims (15)
1. flow through a formula absorber in order to what remove total dissolved solid, comprise:
At least onely flow through formula adsorber unit, comprise:
One container; And
A pair of functional group adsorbent, at least one method is placed in this container, and this Shuan Xing functional group adsorbent surface possesses the atomic group of the Liquidity limit coming from phosphorylation reaction and comes from the atomic group of the adsorpting anion that ammoniumization is reacted;
At least one entrance, is arranged at and this container enters this for a liquid flows through formula adsorber unit;
At least one outlet, is arranged at and this container leaves this for this liquid flows through formula adsorber unit;
At least one pump, flows through formula adsorber unit to carry out the removal of total dissolved solid in order to promote this liquid through this;
At least one cleaning fluid, flows through formula adsorber unit in order to regenerate this;
One first electronic controller, in order to manage the removal of total dissolved solid; And
One second electronic controller, in order to manage the regeneration that this flows through formula adsorber unit.
2. as claimed in claim 1 flow through formula absorber in order to what remove total dissolved solid, wherein the raw material of this Shuan Xing functional group adsorbent is selected from one group of material, comprising: activated carbon, CNT, magnesia, aluminium oxide, iron oxide, manganese oxide, zinc oxide, nickel oxide, cupric oxide, tin oxide, magnesium carbide, barium carbide, earth, silicate and pottery.
3. as claimed in claim 1 flow through formula absorber in order to what remove total dissolved solid, wherein the raw material of this Shuan Xing functional group adsorbent is selected from shell or the stalk of cereal, and described cereal comprises: rice, wheat, barley, oat, rye, Chinese sorghum, corn, soybean and soya bean.
4. as claimed in claim 1 flow through formula absorber in order to what remove total dissolved solid, wherein the raw material of this Shuan Xing functional group adsorbent be selected from the shell of fruit or son real, described fruit comprises: coconut, palm, durian, mango and honey peach.
5. as claimed in claim 1 flow through formula absorber in order to what remove total dissolved solid, wherein the raw material of this Shuan Xing functional group adsorbent is selected from pericarp or the slag of fruit, and described fruit comprises: pineapple, oranges and tangerines, shaddock, jackfruit and sugarcane.
6. as claimed in claim 1 flow through formula absorber in order to what remove total dissolved solid, wherein the raw material of this Shuan Xing functional group adsorbent is selected from the shell of nut, and described nut comprises: peanut, English walnut, ginkgo nut, cashew nut, almond, acorn nut and acorn-cup fruit.
7. as claimed in claim 1 flow through formula absorber in order to what remove total dissolved solid, wherein the raw material of this Shuan Xing functional group adsorbent is selected from cellulose from a material and lignin, and this material comprises: flax, wood fragments, sawdust, bamboo and fiber; Described fiber comprises cotton, silk floss, yarn, silk and suede further.
8. as claimed in claim 1 flow through formula absorber in order to what remove total dissolved solid, wherein phosphoric acid is the major pharmaceutical agent of phosphorylation reaction.
9. as claimed in claim 1 flow through formula absorber in order to what remove total dissolved solid, the medicament of wherein ammoniumization reaction is selected from one group of chemicals, comprising: ammonia, ammoniacal liquor, three grades and quaternary ammonium compound, straight chain and aromatic amine, heterocyclic amine, and ammonium salt; Described ammonium salt comprises ammonium chloride, ammonium bromide, ammonium nitrate and ammonium perchlorate further.
10. as claimed in claim 1 flow through formula absorber in order to what remove total dissolved solid, wherein this Shuan Xing functional group adsorbent is in the container flowing through formula adsorber unit, with through net, through film, install through the mode of blanket or packed bed.
11. as claimed in claim 1 flow through formula absorber in order to what remove total dissolved solid, and wherein this cleaning fluid is selected from one group of material, comprising: the seawater of running water, distilled water, deionized water, the surface water, underground water and low total dissolved solid.
12. as claimed in claim 1 flow through formula absorber in order to what remove total dissolved solid, wherein the first electronic controller of the removal of this management total dissolved solid, comprises the online detector of the electrical conductivity for detecting liquid, acid-base value and total dissolved solid.
13. as claimed in claim 1 flow through formula absorber in order to what remove total dissolved solid, wherein the second electronic controller of the regeneration of formula adsorber unit is flow through in this management, comprises the online detector of the electrical conductivity for detecting liquid, acid-base value and total dissolved solid.
14. as claimed in claim 1 flow through formula absorber in order to what remove total dissolved solid, comprise at least two further and flow through the parallel combination that formula adsorber unit formed.
15. as claimed in claim 1 flow through formula absorber in order to what remove total dissolved solid, comprise at least two further and flow through the tandem compound that formula adsorber unit formed.
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