CN101381148B - Method for removal of arsenic from water - Google Patents
Method for removal of arsenic from water Download PDFInfo
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- CN101381148B CN101381148B CN2008101688687A CN200810168868A CN101381148B CN 101381148 B CN101381148 B CN 101381148B CN 2008101688687 A CN2008101688687 A CN 2008101688687A CN 200810168868 A CN200810168868 A CN 200810168868A CN 101381148 B CN101381148 B CN 101381148B
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- resin
- water
- gram
- arsenic
- methyl
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
Abstract
A method for removing arsenic from water by contacting water with a strong base anion exchange resin comprising at least one metal ion or metal-containing ion whose arsenate salt has a Ksp no greater than 10<-5>, provided that the metal is not zirconium.
Description
The application's application number that to be the applicant submit on February 24th, 2005 for " 200510050959.7 ", denomination of invention divides an application for the application for a patent for invention of " from water, removing the method for arsenic ".
Technical field
The present invention relates to from the water that contains arsenic, remove the method for arsenic, and relate to the method for the resin that is combined with arsenic being carried out aftertreatment.
Background technology
Arsenic mainly is present in the water with the form of arsenate or arsenite, and the toxicity of arsenate or arsenite is all very big.Existing a large amount of report relates to and is used for treating water to remove the various resins that contain arsonium ion.For example, people such as M.J.DeMarco has reported at " wate research (Water Research) " the 37th volume 164-176 page or leaf (2003) and has adopted the Zeo-karb that is loaded with Fe (III) to remove to contain arsonium ion.Yet, this reference and the unexposed content relevant with other type ion exchange resin.
The problem that the present invention proposes is that the other method that adopts resin material from water, to remove arsenic need be provided.
Summary of the invention
The present invention relates to a kind of method of from water, removing arsenic, contact with strong basic type anion-exchange resin through making water, this strong basic type anion-exchange resin comprises at least a metals ion or metallic ion, the K of its arsenate
SpBe not more than 10
-5, as long as this metal is not a zirconium.
The invention further relates to a kind of method of from water, removing arsenic, contact with having at least one substituent ion exchange resin through making water, this substituting group is selected from hydroxyl, ether, amine, quaternary amine, divalent sulfur substituting group, amine oxide and oxyamine.
The invention further relates to a kind of method of from water, removing arsenic; Through water is contacted with Zeo-karb; This Zeo-karb comprises at least a metals ion or metallic ion, and this ion contains the metal that is selected from aluminium, lanthanum, calcium, magnesium, titanium, zinc, nickel, cobalt, manganese, lithium and tin.
The invention further relates to a kind of method of from water, removing arsenic, contact with absorbent resin through making water, this absorbent resin contains at least a metals ion or metallic ion, the K of its arsenate
SpBe not more than 10
-5, as long as this metal is not a zirconium.
Detailed Description Of The Invention
If there are not other indications, percentage ratio is meant weight percentage.Term used herein " (methyl) vinylformic acid " means acrylic or methacrylic acid.Term " vinyl monomer " means the monomer that is suitable for addition polymerization and comprises single polymerisable carbon-to-carbon double bond.Term " styrene polymer " is meant by vinyl monomer or comprises styrene monomer and/or multipolymer that the polymerization of mixtures of the vinyl monomer of at least a linking agent obtains that wherein the weight of vinylbenzene and linking agent addition is the 50wt% of total monomer weight at least.Linking agent is the monomer that contains at least two polymerisable carbon-to-carbon double bonds, and it for example comprises divinyl aromatic compound, two-and three-(methyl) acryliccompound and divinyl ether compound.Preferred linking agent is divinyl aromatics linking agent, for example Vinylstyrene.In a specific embodiments; Styrene polymer is processed by monomer mixture; This monomer mixture is at least 75% vinylbenzene and divinyl aromatics linking agent; More preferably at least 90% vinylbenzene and divinyl aromatics linking agent, most preferably styrene polymer is processed with the monomer mixture that is made up of vinylbenzene and at least a divinyl aromatics linking agent basically.In another embodiment, styrene polymer is processed with the monomer mixture that is made up of at least a divinyl aromatics linking agent basically.Term " XPA " is meant the multipolymer that the mixture by vinyl monomer that comprises at least one (methyl) vinylformic acid or ester and at least a linking agent forms, and wherein the weight of (methyl) vinylformic acid or ester and linking agent addition is the 50wt% of total monomer weight at least; Preferably being 75wt% at least, more preferably is 90wt% at least, and most preferably this multipolymer is with being processed by the monomer mixture of at least a (methyl) vinylformic acid or ester and at least a linking agent formation basically.Term " resol " is meant the cross-linking copolymer that is formed by formaldehyde (or aliphatics aldehydes or ketones) and phenol (or substituted phenol or other aromatic substance), and wherein the monomeric weight of phenol or substituted phenol is 10% of total monomer weight at least, preferably is 50% at least.
Term " polyamines condensation resins " is the cross-linking copolymer that is formed by polyamines and epoxy compounds (for example epoxy chloropropane), and wherein the weight of epoxy compounds is 10% of total monomer weight at least, preferably is 50% at least.
The cross-linking copolymer that term " polyvinyl alcohol resin " expression is formed by crosslinked vinyl acetate; Thereby deacetylate forms corresponding polyalcohols structure then; The weight of the wherein remaining monomeric unit that contains acetic ester is 10% of total polymer weight at least, preferably at least 50%.
" oxyamine " is any substituting group that has at least one hydroxy functional group and at least one amine functional group.Preferably, oxyamine is the aliphatics substituting group that has a more than hydroxyl, and wherein each hydroxyl is connected to different carbon atoms." divalent sulfur substituting group " is the substituting group that has at least one sulphur atom; This sulphur atom is connected to other atoms via two singly-bounds; For example comprise mercaptan, thiocarbamate, dithiocarbamate, sulfide, thiocarbonic ester, dithiocarbonates, trithiocarbonate, thioesters and xanthate substituting group.Quaterisation is a kind of like this reaction, wherein makes the tertiary amine substituting group change quaternary amine into through the addition alkyl group.It then is such reaction that ammonia is separated, thereby the functional group reactions wherein in amine and the polymkeric substance forms the stable compound such as acid amides or alkylamine.Functional group on the polymkeric substance comprises, the ester functional group of methyl (vinylformic acid) monomeric unit for example, and benzylic ether in the PS or chloro-methyl group.Chlormethylation is on aromatic ring, to settle the alkylated reaction of chloro-methyl group.
Term " gel " or " gel " resin relate to that extremely low (0 to 0.1cm by porosity
3/ g), mean pore size is little by (0 to 17
) and the B.E.T. surface-area little (0 to 10m
2/ g) multipolymer synthetic resin.Term " netted greatly " (or MR) resin is used for representing by have more senior middle school's macroporous copolymer synthetic resin of high surface area than gel resin.The overall porosity of MR resin is 0.1 to 0.7cm
3/ g, mean pore size be 17 to
And the B.E.T surface-area is 10 to 200m
2/ g.Term sorbent is used for representing the resin that can functionalised or can not functionalised, and it has high surface-area and porosity.The surface-area of these sorbent materials is 200 to 1300m
2/ g, mean pore size be 17 to
, overall porosity is 0.7 to 200cm
3/ g.Term " Zeo-karb " be meant can with the resin of environment exchange zone positive charge material.They comprise and are connected to cationic electronegative material that said positively charged ion is Na for example
+, K
+, Ca
++, Mg
++, Fe
+++Or H
+The most frequently used electronegative material is carboxylic acid, sulfonic acid and phosphonyl group.Term " anionite-exchange resin " then refer to can with the resin of environment exchange zone negative charge material.Term " strong basic type anion-exchange resin " means and comprises positively charged material and be connected to such as Cl
-, Br
-, F
-And OH
-And so on anionic anionite-exchange resin.The most frequently used positively charged material is quaternary amine and protonated secondary amine.
Term " hydrous oxide " the expression utmost point is insoluble in the compound of water, and the increase metallic cation along with pH in starting soln deposition takes place and forms this compound.Hydrous oxide can be in fact the oxide compound of single metal or the oxide compound or the oxyhydroxide of oxyhydroxide or two or more metal mixtures.Electric charge on the hydrous oxide depends on the acidity of oxide compound and medium to a great extent.They can be used as electronegative material, be electroneutral material or positively charged material and exist.The change of deposition condition causes generating various structure for metals ion, and these structures can have higher or lower reactivity to the arsonium ion in the water.Usually, precipitated metal is that the preferred pH scope of hydrous oxide is 2 to 8, most preferably 3.5 to 6.5.The structure of hydrous metal oxides can be amorphous or crystal.
Metal hydroxides is that Fe under the envrionment temperature (III) can be dissolved in the water when hanging down pH (being lower than 1.5) fully at an instance of the behavior under the different pH values.Can obtain another solvability structure under high pH and the high caustic sodium concentration, also be Fe (OH)
4Fe when pH is 2-3 (III) begins deposition, and this depends on the existence and the experiment condition of sequestrant.Fe (III) L
xThe stability of (L is a part) title complex may influence deposition pH value.In deposition pH scope, Fe (III) forms Fe (O)
x(OH)
y(oxo oxyhydroxide) and/or Fe (OH)
3(oxyhydroxide).The structure that wherein precipitates compound possibly be: Goethite (pyrrhosiderite), Akaganeite (akaganeite), Lepidocrocite (lepidocrokile) or Schwertmannite.Another example is an aluminium; At pH<it was with Al in 2 o'clock
3+There is (being dissolved in the water fully) in form, when pH is 7-9 with sedimentary Al (OH)
3Form exists, and is higher than at 12 o'clock then with AlO at pH
2-There is (being dissolved in the water fully) in form.
The method that the present invention is used for metal is written into resin is described below:
Metal loads on negatively charged ion or Zeo-karb
Metal can be trapped in the resin by physics; Perhaps for Zeo-karb; The solution metal positively charged ion can produce with the polymer materials that has negative charge and interact, and the anionic metals ion in the solution can influence each other with positively charged anionite-exchange resin generation.The pH of resin will determine sedimentary condition, thereby in resin structure, obtain hydrous oxide.Another possibility approach that metal loads be under low pH, to make the metallic cation solution equilibria with anionite-exchange resin.If pH changes sharp, the deposition of metal will take place.Usually, deposition condition comprises high pH, and this makes that dissolving metal is a metallic negatively charged ion in the resin.By this way, metal will uniform distribution, then can with positively charged functional group reactions on the anionite-exchange resin.Through after this stage, pH then can descend gradually, and precipitated metal is hydrous oxide or oxide compound simultaneously with it.Adopt high pH containing metal solution and Zeo-karb, make corresponding pH and change, can implement similar process equally.
Metal loads on uncharged polymer materials (sorbent material):
The another kind of method of precipitated metal in uncharged polymer materials that make described here.Use metal concentration to make the polymer materials balance as the metal salt solution of 5-60% weight/volume.Used concentration receives the influence that in polymer materials, precipitates required metal consumption, and receives the influence of the solubleness of used metal.In case metals ion within polymer architecture, is just discharged excessive water, stays the polymer materials that there is metal inside.Can swash the acute pH of change then or apply drying conditions, be hydrous oxide or oxide compound so that make precipitated metal.
Temperature of precipitation takes place can influence the microtexture that is obtained when precipitating equally.Preferably under condition, precipitate just about 20 ℃ to 35 ℃ near envrionment temperature.In a specific embodiments of the present invention, the content of contained metallic compound in the resin (based on the dried resin meter) is 2% at least, more preferably 2%-20%, most preferably 8%-20%.The content of metallic compound is measured through ICP.
In strong basic type anion-exchange resin, preferred metal is iron, calcium, magnesium, aluminium, lanthanum, titanium, zinc, nickel, cobalt, manganese, lithium and tin.In Zeo-karb, preferred metal is calcium, magnesium, aluminium, lanthanum, titanium, zinc, nickel, cobalt, manganese, lithium and tin.In sorbent material, preferred metal is iron, calcium, magnesium, aluminium, lanthanum, titanium, zinc, nickel, cobalt, manganese, lithium and tin.
In a specific embodiments of the present invention, resin is used for after water is removed arsenic, resin is carried out aftertreatment, so that arsenic is sweetened off by water not too easily.Usually, when the arsenic content of resin during, before process resin, earlier it is carried out aftertreatment near its ultimate load or near its ideal carrying capacity.Preferred post-treatment reagents is enough to and can arsenic be fixed in the resin; So that through EPA toxic characteristic leaching step (TCLP) test (ToxicityCharacteristic Leaching Procedure test); Method 113; It is consistent that this method is commonly used to prove that restrictive clause (LDR) is disposed on arsenic and ground, perhaps through specified other leaching tests of authoritative management mechanism.Usually resin has absorbed 10mg As/ (g dried resin) at least from water.Sometimes, resin has absorbed 80mg As/ (g dried resin) at least.Preferred post-treatment reagents is the salt or the metallic ionic salt of metals ion, and it is strapped in arsenic in the resin, most preferably can be in the aqueous solution arsenic precipitation hydrochlorate ionic metals ion, the just K of its arsenate
SpBe not more than 10
-5Metal.The preferred addition (based on dried resin meter) of post-treatment reagents in resin is at least 2%, more preferably at least 5%, more preferably at least 10%, most preferably at least 15%.The addition of preferred post-treatment reagents is no more than 35%, more preferably no more than 30%, more preferably no more than 25%, is most preferably not exceeding 20%.The preferable alloy that is used for aftertreatment comprises, for example the ion of iron, aluminium, lanthanum, titanium, zinc, nickel, cobalt, manganese, lithium and tin.More preferably, the ion of metals ion chosen from Fe, aluminium, lanthanum, titanium, manganese and zinc.Most preferably, metals ion is the ion of chosen from Fe, manganese, aluminium and titanium.
In a specific embodiments of the present invention, contact and from water, remove arsenic with having at least one substituent ion exchange resin through making water, this substituting group is selected from hydroxyl, ether, amine, quaternary amine, divalent sulfur substituting group, amine oxide and oxyamine; Preferred this resin has the substituting group that at least one is selected from thiocarbamate, dithiocarbamate, sulfide, thiocarbonic ester, dithiocarbonates, trithiocarbonate, thioesters, xanthate, amine oxide, phosphonic acids, iminodicarboxylic acid and oxyamine.In this embodiment, preferably this resin is substantially free of other metal except that sodium to remove before the arsenic using it for treating water, that is to say that based on the dry weight basis of resin, it contains these metals that are lower than 300ppm.
In a specific embodiments of the present invention; This resin is to have the substituent metal-resin of chelating, and this chelating substituting group is selected from phosphonic acids, sulfonic acid, dithiocarbamate, polymine, polyamines, oxyamine, carboxylic acid, aminocarboxylic acid and aminoalkyl group phosphonic acid ester.Preferred aminocarboxylic acid substituting group comprises; For example derived from NTA, YD 30 (EDTA), diethylene triaminepentaacetic acid(DTPA), three (ethyloic) amine, iminodiethanoic acid, N-(carbamoyl methyl) iminodiethanoic acid, N, the substituting group of two (ethyloic)-Beta-alanines of N-and N-((phosphonomethyl)) iminodiethanoic acid.In another specific embodiments of the present invention, the content of contained metallic compound is 2% based on the dry weight basis of resin at least in the resin, more preferably is 5% at least, more preferably is 10% at least, most preferably is 15% at least.The content of preferable alloy compound is no more than 35%, more preferably no more than 25%, is most preferably not exceeding 20%.In a specific embodiments of the present invention, resin is big netted or macroporous ion-exchange resin.
In another specific embodiments of the present invention, resin is the porous absorbability copolymer, and the salt that wherein is combined with the metallic compound of arsenic precipitates or has been absorbed.The content of contained metallic compound is 5% based on the dry weight basis of resin at least in the preferred resin, more preferably is 10% at least, most preferably is 15% at least.The content of preferable alloy compound is no more than 35%, more preferably no more than 30%, is most preferably not exceeding 25%.Multipolymer is porous adsorbent preferably.Be combined with the preferably such metals ion of metal of arsenic, at pH be 2-11, it can be at the surperficial or inner arsenate that generates utmost point indissoluble of multipolymer when preferred pH scope was 4-9.
In a specific embodiments of the present invention, the water that handle is surface water or underground water, and it contains the sulfate ion of 10ppm and the arsenic compound of 10ppb to 10ppm at least, more preferably 10ppb to 800ppb and most preferably 10 to 400ppb arsenic compound.The pH of water is preferably 4 to 10, for underground water more preferably 6 to 9, for surface water more preferably 5 to 9.In another specific embodiments of the present invention, the amount of the arsenic that the water that will handle is contained as stated, but sulphate content is lower.This water or come from natural protosulfate content water source, or came from before contacting with the used arsenic-selective resin of the present invention through pre-treatment to reduce the water of sulphate content.The vitriol of low levels can think 0 to 250ppm, and moderate content can think 250 to 1000ppm, and high-content can think to be higher than 1000ppm.
The preferred used resin of the present invention is styrene polymer, acrylic polymers or resol.Resin is that functionalized resin makes via the chloromethylation verivate of resin usually in the specific embodiments of the present invention of crosslinked gathering (aromatic vinyl) multipolymer therein.The chloromethylation that gathers (aromatic vinyl) multipolymer is well-known, for example referring to U.S. Patent application No.2003/0018091A1 and United States Patent(USP) No. 4900796.Resin is in the specific embodiments of the present invention of crosslinked acrylic copolymer therein, functionalized resin generally through with acrylic polymers on hydroxy-acid group form acid amides or the ester class makes.In another specific embodiments of the present invention, thereby make the amine groups generation oxidation on the resin obtain the amine oxide substituting group.
Specific embodiments of the present invention is the selectivity that improves arsenic compound, changes the resin that has the quaternary ammonium functionality through making the resin that has primary amine, secondary amine or tertiary amine functional group into via the alkylating of amine functional group.
In a specific embodiments of the present invention, resin is monodispersed resin, also is that uniformity coefficient is a kind of resin of 1.0 to 1.3, more preferably 1.0 to 1.05.Uniformity coefficient is that the size of mesh that about 40% resin can be retained on the sieve can be retained in the size of mesh on the sieve divided by about 90% resin.In a specific embodiments, monodispersed resin is ejection-type resin (jetted resin), for example referring to United States Patent(USP) No. 3922255.
In a specific embodiments of the present invention, resin is seed-expanded polystyrene veneer resin (seed-expandedresin), for example referring to United States Patent(USP) No. 5147937.
The resin that in following method, can be used for removing arsenic comprises the following Rohm andHaas company resin that is commercially available:
Amberlite
TMIRA-958S is the MR type acrylic acid or the like strongly basic anion exchange resin of chloride form.Functionality is the propyl group trialkyl ammonium group that is connected to propenoic acid main chain via amido linkage.It carries out crosslinked with Vinylstyrene and Diethylene Glycol divinyl ether;
Amberlite
TMIRC-50 is a slightly acidic macroporous type acrylic acid or the like ion exchange resin.It is the multipolymer of methylacrylic acid and Vinylstyrene.
DUOLITE A7 is the crosslinked P-F polycondensate that contains weakly-basic anion exchange functional group.
Amberlite
TMIRA-67 is a gel-type acrylic acid or the like weakly basic anion exchange resin.Functional group is the dimethylaminopropyl group (DMAPA) that is connected to propenoic acid main chain via amido linkage;
Amberlite
TMIRA-96 is big netted vinylbenzene/Vinylstyrene (DVB, 6%) resin of chloromethylation, makes it amination with dimethyl amine, makes it to take place oxidation with hydrogen peroxide then.
Amberlite
TMIRC747 is the big netted vinylbenzene/Vinylstyrene (DVB, 6%) that comprises the alkylamino phosphonyl group.
Amberlite
TMIRC743 is based on the polyvalent alcohol macroreticular-type resin of vinylbenzene/divinyl benzene copolymer, makes this multipolymer amination with the N-NMG.
Amberlite
TMIRC748 makes it functionalized porousness cross-linked styrene resin with the iminodicarboxylic acid group.
Amberlite
TMSR1LNa is crosslinked DVB-vinylbenzene gel resin, the sulfonated cation type resin.
Amberlite
TM200CNa is crosslinked DVB-vinylbenzene macroreticular-type resin, is the sulfonation cation type resin of Na form.
Amberlyst
TM121 resins are lightly crosslinked DVB-vinylbenzene gel resins, make it sulfonation with sulfuric acid.
Amberlyst
TM15 resins are highly cross-linked big netted sulfonation cation type resins of DVB-vinylbenzene.
Amberlite
TMIRA-400 is crosslinked vinylbenzene gel resin, makes it chloromethylation and functionalized with Trimethylamine.
Amberlite
TMIRA-900 is crosslinked vinylbenzene macroreticular-type resin, makes it chloromethylation and functionalized with Trimethylamine.
Amberlite
TMIRA-410 is crosslinked vinylbenzene gel resin, makes it chloromethylation and functionalized with dimethylethanolamine.
Amberlite
TMIRA-910 is crosslinked vinylbenzene macroreticular-type resin, makes it chloromethylation and functionalized with dimethylethanolamine.
DuoliteGT-73 is the cross-linked styrene resin that contains mercapto groups.
Amberlite
TMXAD-4 is the ethyl styrene-DVB macroreticular-type resin of high surface area.
The present invention comprises also and a kind ofly can be used for from water, removing arsenic and contain at least two substituent resins that this substituting group is selected from hydroxyl, thiocarbamate, dithiocarbamate, sulfide, thiocarbonic ester, dithiocarbonates, trithiocarbonate, thioesters, xanthate, amine oxide, phosphonic acids, iminodicarboxylic acid and oxyamine.
Should believe; Except from water, removing arsenical ion (for example arsenate) and arsenate; Resin of the present invention can also be removed other conventional impurity that pollutes from water, for example contain ion and phosphoric acid salt, perchlorate and the borate of Cd, Zn, Cu, Cr, Hg, Pb, Ni, Co, Mo, W, V, F, Sb and Se.
Embodiment
Abbreviation:
P (St-DVB) styrene diethylene benzene copoly mer
CME chloromethyl methyl ether
The CSA chlorsulfonic acid
HCHO formaldehyde
MeOH methyl alcohol
Meq/ml milli-equivalent/milliliter
Meq/g milli-equivalent/gram (doing)
The complete flawless bead of %PB % (intact and leakless)
MR is netted greatly
As/g dried resin milligram arsenic/gram dried resin of mg
m
2/ g SU: meters squared per gram resin
MHC moisture recoverable amount
The DVB Vinylstyrene
The ironic hydroxide that GFH grinds
The FeOOH hydrous iron oxide
BV bead capacity; # liquid volume/post intermediate ion exchange tree
Fat or sorbent material volume
The quaterisation product of Q tertiary amine and methyl chloride
Solute weight in the every volume of liquid of w/v
Embodiment 1: be loaded with the preparation of the Zeo-karb of zirconium
The preparation that is loaded with the vinylbenzene/DVB Zeo-karb of zirconium can be referring to United States Patent(USP) No. 2003/0139629A1.
Embodiment 2: the chloromethylation process of gel-type vinylbenzene-DVB multipolymer
Here described is to adopt the routine that does not reclaim with the recycling reaction soln to stir (stirring) quenching program.In 4 hour time, restrained the midbody that CSA make chloromethylation through in the reactor drum that stirs, adding 244; The ferric chloride in aqueous solution (40%) that comprises p (St-DVB) that 106 grams contain 4.3%DVB, 136 gram formalins (55% formaldehyde, 35%MeOH), the 40 gram HCl aqueous solution (35%), 32 gram MeOH and q.s (generally being about 15 grams) in the reactor drum of this stirring is so that iron(ic)chloride is 0.04/1 to the mol ratio of p (St-DVB).The temperature of reaction mixture remains on below 40 ℃ or 40 ℃ during the interpolation CSA.After the CSA interpolation finishes, reaction mixture was kept 2.5 hours under 38-40 ℃.Reaction mixture is cooled to 25-30 ℃, and when stirring, in the midbody of chloromethylation, adds quench solution in (330 gram water).After treating reaction mixture 10-30 minute of quenching, discharge mother liquor, mother liquor is collected in the receiving flask, collected 380 gram (%H until from reactor bottom
2SO
4=28%, calculated value).Use the midbody of other water washing chloromethylation then as stated.
Embodiment 3: the amination of halomethylation gel vinylbenzene-DVB multipolymer
Term " amine " is used for describing specific amine used among the embodiment, and it is the aqueous solution of 40% Trimethylamine.
The chloromethylation midbody what pulp that embodiment 2 is obtained with 200-400 gram water through washing, and use the 50%NaOH aqueous solution to be neutralized to pH to be 8-10; Then add 176 the gram have cooling effect amine so that temperature maintenance at 20-25 ℃.In 3 hours, the temperature of reaction mixture is increased to 50 ℃ and under 50 ℃, kept 2 hours again then.Add the NaOH aqueous solution of 8 grams 50% this moment in reaction mixture, be recovered to excessive Trimethylamine through distillation.Discharge residual liquid from the anion exchange resin beads (SBA) of gained, wash to remove residual iron and amine impurity with hot water and HCl dilute aqueous soln.Gained SBA is generally with 99% PB and have the anion exchange capacity of 1.3meq/ml (4.1meq/g).
Embodiment 4: big netted the gathering of chloromethylation (vinylbenzene-DVB) the preparation of multipolymer
Make the midbody of chloromethylation through in stirred mixture, adding 178 gram CSA gradually, this stirred mixture comprises macroporous type p (St-DVB), 134 gram formalins (55% formaldehyde, 35%MeOH), the sulfuric acid of 216 grams 96%, the 91 gram HCl aqueous solution (35%), 14 gram MeOH and the ferric chloride Solution(38s that 100 grams contain 6%DVB.Iron(ic)chloride uses with the form of 40% aqueous solution, and its amount makes that iron(ic)chloride is 0.04/1 to the mol ratio of p (St-DVB).The temperature of reaction mixture remains on below 45 ℃ and 45 ℃ during the interpolation CSA.After the CSA interpolation finishes, under stirring action, make reaction mixture under 40-50 ℃, keep 6 hour time.
Then reaction mixture is cooled to 25-30 ℃, stops to stir and making mixture leave standstill at least 5 minutes to reaching 1 hour.Discharge a part of original liquid and get into receiving flask from the bottom of bead bed (bead bed).Slowly add quench solution (240 gram water) to the top of pearl bed then, meanwhile discharge other liquid and be collected in the same receiving flask, up in the bead bed, discharging all liquid from the bottom of reactor drum; Collect 550 gram mother liquor (%H by this way
2SO
4=56%).Add the midbody that other water washs chloromethylation, expel liquid simultaneously through top afterwards from the bottom to the pearl bed.
Embodiment 5: the amination of the big netted vinylbenzene-DVB multipolymer of chloromethylation
Term amine is used for describing specific amine used among the embodiment here.Used amine is the aqueous solution of 40% dimethyl amine among this embodiment.
Make chloromethylation midbody what pulp with 200-400 gram water, and use the 50%NaOH aqueous solution to be neutralized to pH to be 8-10 through washing.Then add the 535 gram 24%NaOH aqueous solution and 190 and restrain the amine that cooling effect is arranged, so that temperature maintenance is at 20-25 ℃.Then the temperature of reaction mixture is increased to 74 ℃ and in 74 ℃ and pressure (0.7-1.4x10 from 25 ℃
2KPa or 10-20 pound/square inch) under kept again 2 hours, then residual amine is removed in distillation.Discharge residual liquid from the anion exchange resin beads (WBA) of gained, wash to remove residual iron and amine impurity with hot water and HCl dilute aqueous soln.Gained WBA is with 100% PB and have the anion exchange capacity of 1.4meq/ml (5.0meq/g).
Embodiment 6: the preparation of big netted strong base acrylics
The multipolymer that is used to make this resin is with Vinylstyrene (5%w/w) and crosslinked macroreticular (MR) the type methyl acrylate polymer of Diethylene Glycol divinyl ether (2.0%w/w).The resin that following step obtains is the MR strong base acrylic acid or the like anionite-exchange resin of chloride form.Functional group is the propyl group trialkyl ammonium group that is connected to propenoic acid main chain via amide group.The conversion process that multipolymer changes the anionic resin into was undertaken by two steps; Separate with dimethylamino propylamine (DMAPA) ammonia, then carry out ammonia and separate with quaternized.
Ammonia is separated:
The 2960 gram dimethylamino propylamines (DMAPA) and 791 of in reactor drum, packing into restrain acrylic copolymers.This process was carried out 8-9 hour under the nitrogen pressure of high temperature (170-189 ℃) and 35-50psig.When reaction is accomplished with nitrogen purge line and after its cools down the emptying reactor drum.With reactor cooling to 20-40 ℃.From batch of material, give off mother liquor.Add methyl alcohol and surpass resin bed up to consumption.Continue discharging and add more fresh methanol, operated 3 hours.Begin to add entry to the top of bed, discharging is higher than resin bed to keep water level.Water thoroughly washed 2 hours.Drain reactor drum and the final gained resin of manual screening.
Quaternized:
This batch of material (lot) water (2 liters) of last step is transferred to reactor drum.Add 460 gram methyl chlorides.The temperature of reaction must be controlled at 25 ℃ and pressure is lower than 5psig.Temperature was kept 2-9 hour at 30-40 ℃.The emptying reactor drum drains this batch of material and with a large amount of (15 times of reactor capacity) water washing 7 hours (discharge continuously and replenish).Drain product then and it is wired up.
The preparation of embodiment 7 ejection-type resins
Uniformity coefficient is that the preparation of ejection-type vinylbenzene/DVB multipolymer of 1.0-1.3 can be referring to United States Patent(USP) No. 3922255A embodiment 1.0.
Embodiment 8: the multipolymer for preparing uniform particle size through the seed expanding method
Adopt the seed expanding method to prepare controlled, the uniform multipolymer of size, this process prescription is in USP 5147937A embodiment 1.0.
The preparation of the basic anion exchange resin of embodiment 9:MR vinylbenzene/Vinylstyrene (DVB, 6%) amine oxide-functionalized
The method that is used for big netted macroporous type styrene copolymer according to embodiment 4 is carried out the chloromethylation step.
Amination:
According to embodiment 4 said methods, adopt the aqueous solution of 40% dimethyl amine to carry out amination as amine.
Oxidation step:
Oxidation step can guarantee that tertiary amine changes the structure of amine oxide into.Initial multipolymer is 6.0 to the ratio of hydrogen peroxide.For following embodiment, use 20 gram aqueous hydrogen peroxide solutions (35%w/w).Under 3 crust, stirred 2 hours.With a large amount of water washings, drain this batch of material and it is wired up.
Embodiment 10: prepare strong-weakly basic anion exchange resin with oxyamine and/or imine
The method that is used for gel vinylbenzene-DVB multipolymer according to embodiment 2 is carried out the chloromethylation step.
Use following amine in this method:
| Amine: | Initialism | The gained resin | Volume capacity meq/ml | Weight capacity meq/g |
| 2-methylamino ethanol | MAE | SBA | 0.62 | 1.30 |
| Diethylolamine | DEA | WBA | 1.19 | 2.72 |
| HSDB 338 | DIPA | WBA | 1.06 | 2.48 |
| N, N-dimethyl-diisopropylidene triamine | DMDIPTA | SBA-WBA | 1.50 | 4.25 |
| The trolamine of ethoxylation | TEAE | SBA | 1.38 | 3.45 |
| NSC 446 | DETA | WBA | 0.86 | 1.63 |
| Penten | PEHA | WBA | 1.07 | 2.24 |
| Polymine | PEI | WBA | 1.52 | 3.21 |
| Two-the hexa-methylene triamine | HMTA | SBA-WBA | 0.98 | 2.30 |
| TBuA 1.59 | TBA | SBA | 0.72 | 1.59 |
(SBA=strong base negatively charged ion, WBA=weak base type negatively charged ion, the combination of strong base and weak base type in the SBA-WBA=resin)
Amination
Then in the chloromethylation midbody of washing, adding 220 gram water and 165-200 gram isopropylcarbinol.Stir this mixture also with 50%NaOH aqueous solution neutralization this mixture (pH is 11-13).In reactor drum, add excessive amine (being derived from aforementioned table) at least 100% stoichiometry in this mixture.Then through 48 hours with mixture heating up to 77-89 ℃.With excessive methyl alcohol and this batch of material of water washing.Discharge residual liquid from gained anion exchange resin beads (SBA), with hot water and the washing of HCl dilute aqueous soln, so that remove residual impurity.Drain resin afterwards and it is wired up.
Embodiment 11: prepare strong-weakly basic anion exchange resin with oxyamine functional group
The method that is used for gel vinylbenzene-DVB multipolymer according to embodiment 2 is carried out the chloromethylation step.
Then in the chloromethylation midbody of washing, adding 350 gram water.Stir this mixture also with 50%NaOH aqueous solution neutralization this mixture (pH is 11-13).In this mixture, add 200-300 gram dimethylethanolamine (DMEA) (95%), the temperature of reaction mixture was kept 8-72 hour down at 75-90 ℃.With excessive methyl alcohol and this batch of material of water washing.Discharge residual liquid from gained anion exchange resin beads (SBA), wash so that remove residual iron and amine impurity with hot water and HCl dilute aqueous soln.The anion exchange capacity of gained SBA is 0.5-2.1meq/ml.
Embodiment 12: the preparation of amine-functionalized resin
The method that is used for big netted macroporous type vinylbenzene-DVB multipolymer according to embodiment 4 is carried out the chloromethylation step.
Amination:
Make chloromethylation midbody what pulp with 200-400 gram water, and use the 50%NaOH aqueous solution to be neutralized to pH to be 8-10 through washing.100 ml waters, 25 of before adding 100 milliliters of chloromethylated copolymers, in reactor drum, packing into earlier restrain sodium-chlor and 4 gram boric acid., after material and the stirring it is cooled in case reactor drum is packed into 25 ℃, the 150 gram NSC 446 (DETA) of in 60 minutes, packing into then, < 25 ℃ of maintenance batch temperatures.In the clock time whole materials were heated to 70 ℃ at 130 minutes afterwards.Temperature was kept 360 minutes down at 70 ℃.To container in add 150 ml waters thereafter.Siphon goes out aqueous mixture and adds more water once more.Continue this process up to the liquid clarification that becomes.The hydrochloric acid (35%) that adds 100 milliliters of hot water (50 ℃) and 200 milliliters of 0.1N then.Stirred 10 minutes.Be adjusted to pH with acid>1.0.Water washes bead and it is all wired up.
Embodiment 13: the preparation of strong base P-F condensation resin
Suitable polymeric phenol-formaldehyde resin the sample that is purchased is DUOLITE A7, and it makes it quaternized by the Rohm and Haas manufactured in U.S. Philadelphia through following method.
Quaternized:
Accomplish quaternized according to the following step.The 80-120 that in reactor drum, packs into restrains DUOLITEA7, and the 200-300 ml methanol of packing into.Add 100-150 gram methyl chloride.The temperature of reaction must be controlled at 10-25 ℃ and pressure is lower than 5psig.Temperature was being kept 24 hours below 30 ℃.Drain this batch of material and wash 7 hours (discharge continuously and replenish) with a large amount of water (reactor volume 15 times).Drain product then and it is wired up.
Embodiment 14: have the preparation of the resin of thiol functionalities
MR type vinylbenzene/DVB (6%DVB) multipolymer makes it functionalized with thiol functionalities.
The 250-320 that in reactor drum, packs into restrains ethylene dichloride (EDC).Add 50-100 gram multipolymer, 100-200 gram sulfur monochloride then and temperature is adjusted into 20-30 ℃.In 5.0 hours, add 15-32 gram chlorsulfonic acid (CSA).The temperature that does not make reactor drum is above 45 ℃.Reactor heating is to 82-90 ℃, and under this temperature, keeps 6.0-10 hour.At 6-9 hour internal cooling to < 50 ℃ and add entry.Reactor heating distills out ethylene dichloride.With reactor cooling to 25-30 ℃.With this batch of material of excessive water washing, a large amount of water washings is used in siphon water outlet in the reactor drum again.PH is 10-13 with soda lye (50%) adjustment, drains this batch of material.In reactor drum, add 290-350 gram sodium hydroxide solution (32%) and 115-140 gram particle material and 150-200 gram water.Stir and make the pellet dissolving.Add resin and be heated to 100-135 ℃, under this temperature, kept 48-72 hour.Be cooled to < 60 ℃ and add entry.Discharge mother liquor fully.5 adding 200-400 gram hot water (60 ℃) also stirred 2-5 hour.Drain this batch of material fully, the re-heat water wash step of laying equal stress on 4 times.Thoroughly drain batch of material and add entry.The 270-350 that packs into restrains hydrochloric acid.Add more water (3-4 liter) and at last pH is verified as 5-6.This batch of material is all wired up.
Embodiment 15: the preparation of resin
The preparation of gel alkylamino phosphonic acids resin can be referring to the embodiment 1.0 of United States Patent(USP) No. 4002564.
Embodiment 16: the preparation of big mesh structural porous type resin
The preparation method of macroporous type alkylamino phosphonic acids resin is described among the embodiment 1 and 2 of United States Patent(USP) No. 5804606.
Embodiment 17: the preparation of difunctionality strong base resin
According to United States Patent(USP) No. 5804606 the big network copolymer of 100 grams is reacted.The resin that obtains thus can make it quaternized with methyl chloride, thereby obtains near phosphonic acid functional groups, to contain the difunctionality ion exchange resin in strong basicity site.
Quaternized:
The 80-120 that in reactor drum, packs into gram macroporous type alkylamino phosphonic acids resin, and add the 200-300 ml methanol.Add 100-150 gram methyl chloride.The temperature of reaction must be controlled at 10-25 ℃ and pressure is lower than 5psig.Temperature was being kept 5.0-9.0 hour below 30 ℃.Reactor drum is heated to 38-48 ℃, and makes it to keep 1.0-4.0 hour down at 38-48 ℃.Drain this batch of material and wash 7 hours (discharge continuously and replenish) with a large amount of water (reactor volume 15 times).Drain product then and it is wired up.Thereby obtained having the resin of highly basic characteristic.
Embodiment 18: the preparation of iminodicarboxylic acid functionalized resins
The preparation of iminodicarboxylic acid functionalized resins is referring to United States Patent(USP) No. 5804606 embodiment 3.0.
The preparation of embodiment 19:N-NMG functionalized resins
Make the resin of chloromethylation by the crosslinked big reticular polystyrene/DVB material of 100 gram 6.0%DVB.
Through with 250 gram formalins (55% formaldehyde, 35%MeOH), 53 gram methyl alcohol, 75 gram water and 490 gram CSA generate title complexs and make the midbody of chloromethylation.The 100 gram multipolymers and wait for 1 hour of in reactor drum, packing into.Temperature must be controlled at below 25 ℃ then.In 1 hour, add 15 gram FeCl afterwards
3Solution (40%w/w) and do not make temperature be higher than 40 ℃.Through 2 hours reactor drum is heated to 40 ℃.Make reactor cooling to 30 ℃, with excessive DI water washing product.This batch of material neutralizes.Add 500 gram methyl alcohol, 200 gram N-NMGs and 40 gram yellow soda ash again.Be heated to 80 ℃ and reaction was kept 24 hours.Thereafter with water washing and with in the caustic soda and resin.
Embodiment 20: make the diethylolamine resin (DEA) of N-NMG (Q-resin) or embodiment 10 of embodiment 19 quaternized
The weakly-basic anion strongly basic anion
Quaternized:
Functionalized big netted resin or the DEA gelatinous resin of the 80-120 that in reactor drum, packs into gram glycosamine, and add the 200-300 ml methanol.Add 120-180 gram methyl chloride.The temperature of reaction must be controlled at 10-25 ℃ and pressure is lower than 5psig.Temperature was being kept 5.0-9.0 hour below 30 ℃.Drain this batch of material and wash 7 hours (discharge continuously and replenish) with a large amount of water (reactor volume 15 times).Drain product then and it is wired up.Q-IRA743: gross weight capacity 1.91:1.42 highly basic capacity and weak base capacity 0.49Q-DEA: gross weight capacity 2.67:0.95 highly basic capacity and weak base capacity 1.72.
Embodiment 21: the preparation of polyamines condenses anionite-exchange resin
The 1500-1871 that packs into gram orthodichlorobenzene (DCB), 300-470 restrain Epicholorohydrin (EPI).Stirring also is heated to 35-50 ℃.In reactor drum, add the mixture that Triethylenetetramine (TETA) (TETA) forms in 500-600 gram water.The mol ratio of Epicholorohydrin/TETA is 2.1 to 3.8.Cooling reactor, keeping temperature is 35-55 ℃.Amine feeds in raw material when finishing, and 100-700 is restrained DCB join in the reaction mixture.Novar400 (all 0.015-0.050% of DCB) packs into.Heat suspensoid then so that distill out DCB.Temperature had reached 125-135 ℃ when distillation finished.Make this batch of material keep after 2-6 hour reaction mixture being cooled to 70-95 ℃.Steamed distillates DCB then, does not have the smell of solvent up to bead.This batch of material is cooled to 25-40 ℃, washs with 50% soda lye.Resin capacity is the 9-13.0meq/g dried resin.In further reacting, of previous embodiment, make the weak base type resin that makes thus quaternized with methyl chloride.
Embodiment 22: the preparation of acrylic acid or the like weakly alkaline gel-type ion-exchange resin
Used multipolymer is with Vinylstyrene (4%) and the crosslinked gel-type methyl acrylate polymer of Diethylene Glycol divinyl ether (1%).Ion exchange resin obtained by this method is gel-type acrylic acid or the like weakly basic anion exchange resin.Functional group is the dimethylaminopropyl group (DMAPA) that is connected to propenoic acid main chain via amide group.
Ammonia is separated:
The 400-600 that in reactor drum, packs into gram DMAPA and 100-150 gram acrylic copolymer.This process was carried out 8-24 hour under the nitrogen pressure of high temperature (170-189 ℃) and 35-60psig.With reactor cooling to 20-40 ℃.From batch of material, give off mother liquor.Add methyl alcohol and surpass resin bed up to consumption.Continue discharging and add more fresh methanol, operated 3 hours.Begin to add entry to the top of bed, discharging is higher than resin bed to keep water level.Water thoroughly washed 2 hours.Drain reactor drum and the final gained resin of manual screening.
Embodiment 23: the preparation of big netted weak base type acrylic acid or the like anionite-exchange resin
The multipolymer that is used to make this resin is with Vinylstyrene (5%w/w) and crosslinked macroreticular (MR) the type methyl acrylate polymer of Diethylene Glycol divinyl ether (2.0%w/w).The resin that following step obtains is the MR strong base acrylic acid or the like anionite-exchange resin of chloride form.Functional group is the propyl group dialkyl ammonium weakly alkaline group that is connected to propenoic acid main chain via amido linkage.The conversion process that multipolymer changes the anionic resin into adopts dimethylamino propylamine (DMAPA) to carry out.
Ammonia is separated:
The 400-600 that in reactor drum, packs into gram DMAPA and 100-150 gram acrylic copolymer.This process was carried out 8-24 hour under the nitrogen pressure of high temperature (170-189 ℃) and 35-60psig.With reactor cooling to 20-40 ℃.From batch of material, give off mother liquor.Add methyl alcohol and surpass resin bed up to consumption.Continue discharging and add more fresh methanol, operated 3 hours.Begin to add entry to the top of bed, discharging is higher than resin bed to keep water level.Water thoroughly washed 2 hours.Reactor drum and the final gained resin of manual screening drain off.
Embodiment 24: the preparation of big netted strong base acrylic acid or the like anionite-exchange resin
The conversion process that changes the anionic resin with the MR type methyl acrylate polymer of Vinylstyrene (5%w/w), Diethylene Glycol divinyl ether (2.0%w/w) crosslinking copolymers into was undertaken by two steps; Separate with dimethylamino propylamine (DMAPA) ammonia, then carry out quaternized.
Quaternized:
The big netted acrylics of weakly alkaline that the 150 gram embodiment 23 that pack into make.Add 300 ml methanol then and add 75 gram methyl chlorides.The temperature of reaction must be controlled at 10-25 ℃ and pressure is lower than 5psig.Temperature was being kept 4.0-9.0 hour below 30 ℃.Reactor drum is heated to 38-48 ℃, and makes it to keep 1-5 hour down at 38-48 ℃.Drain this batch of material and wash 7 hours (discharge continuously and replenish) with a large amount of water (reactor volume 15 times).Drain product then and it is wired up.
Embodiment 25: the multipolymer preparation of adsorbent
The compound method of polymer absorbant is described among the US6387974.
Embodiment 26: the multipolymer preparation of adsorbent
The preparation method of the macroporous type multipolymer that the typical case is crosslinked; For example; Can comprise that preparation contains the continuous aqueous phase solution of suspension aids (such as dispersion agent, protective colloid and buffer reagent); Then mix with monomer mixture, this monomer mixture comprises polyvinyl aromatic monomer, radical initiator and the general 0.2-5 of each part monomer, preferred 0.3-3 and the more preferably porogen of 0.4-1 part (for example toluene, YLENE, (C
4-C
10)-alkanol, (C
6-C
12)-stable hydrocarbon or polyalkylene glycol).Make the mixture polymerization at elevated temperatures of monomer and porogen then, from the polymer beads of gained, remove porogen through various means subsequently; For example, toluene, YLENE and (C
4-C
10) alcohol can remove through distillation or solvent wash, polyalkylene glycol is then removed through washing.Isolate the macroporous type multipolymer of gained then by conventional means, for example drying is then carried out in dehydration.
Embodiment 27: be used for the balancing test of resin arsenic: the arsenite in the water, arsenate, vitriol and silicate
Used medium (resin or GFH) is dry through Buchner, then 0.05 gram (butt) resin or GFH is incorporated with in the bottle of 17 ml solns.The concentration of starting soln is listed in the table.With their vibrations 48 hours, adopt IC (ion chromatography) commercial measurement strength of solution.Unreacted anion concentration is commonly used to the negatively charged ion that has reacted is calculated as medium (GFH, anionic, cationic or sorbent material) in the liquid.Outcome record is the arsenic that has reacted in final unreacted As (ppm) in the liquor, vitriol (ppm) and the resin of expressing with mg As/g dried resin.
Embodiment 28: be used for the balancing test of resin arsenic: arsenate and vitriol are as negatively charged ion.The needed time of balance.
Make an experiment according to embodiment 27c, adopt IRA410 (the strong base resin anion(R.A) of chloride form).
| Sample # | Sample time (fate) | As(ppm) | SO 4 -2(ppm) |
| Initially | 0 | 200 | 200 |
| 39a | 1 | 121 | 52 |
| 39b | 4 | 123 | 54 |
| 39c | 7 | 122 | 51 |
Embodiment 29: be loaded with the preparation of the strong basic type anion-exchange resin of iron (II)
The resin of embodiment 11 preparations is used for the process method to the resin structure metal-loaded.
Add 200 milliliters of 40%FeCl in the 30 gram resins in reactor drum
2The aqueous solution, and mixed 4 hours.Solution siphon in the reactor drum is come out.Then resin beads is put into 200 milliliters of 4%w/wNaHCO
3In the solution.Make air bubbling 40 minutes in system when stirring.Through after this step with excessive water washing resin, to remove residue and to clean resin.Final pH is 5.2.Obtain being loaded with the anionic resin of iron then.
Embodiment 30: be loaded with the preparation of the absorbent resin of metal
Macroporous type sorbent material described in the US patent No.6387974 can use with the melts combine such as iron, titanium, zirconium, iron, manganese, to be used to remove the application of arsenic.The available metal-salt includes but not limited to: FeCl
3Or AlCl
3Or ZrOCl
2Or TiCl
3Or MnCl
2Or its combination.They are used for the aqueous solution with lower pH.
With 10 gram multipolymer sorbent material and 50 milliliters of 40%w/v FeCl
3Acidic aqueous solution mix.PH is lower than 2.0.Resin was softly stirred 96 hours.From excessive liquid solution, discharge bead.The sodium hydroxide that in reactor drum, adds 100 milliliter 4%, contact 60 minutes with caustic solution after, begin stirring.Continue to stir 15 minutes, and then the emptying reactor drum.With excessive water washing resin to neutral pH.Drain this batch of material then and it is wired up.
Embodiment 31: the macroporous type that is loaded with metal gathers the preparation of (vinyl alcohol) resin
Obtain the multi-hole type polyvinyl alcohol resin by following method:
Gathering the synthetic of (vinyl alcohol) crosslinked macroporous ion-exchange resin carries out in the method described in Polymer the 45th volume 71-77 page or leaf (2004) " preparation of high capacity multi-hole type cross-linked (vinyl alcohol) resin and sign (Preparation and characterization of high loading porouscrosslinked poly (vinyl alcohol) the resins) " literary composition according to people such as Ying W..
Adopt following steps to make to gather (vinyl alcohol) macroporous ion-exchange resin and be loaded with metal:
The aforesaid multi-hole type polyvinyl alcohol resin of 30 grams is packed in the post.Be ready to 1000 milliliters of 4%w/v FeCl in addition
3The aqueous solution.The pH < 2.0 of solution.In 60 minutes, make ferrous solution this post of flowing through.With continuous mode and to add 4000 milliliters of pH with the flow velocity of 2BVh be 7.5 5% sodium carbonate solution.With excessive DI water washing resin, making it final pH is 5.5.Drain this batch of material then and it is wired up.
Embodiment 32: the method for cation type resin metal-loaded in post
Make following resin: Amberlyst
TM36WET, Amberlyst
TM15Wet, Amberlyst
TM16Wet, Amberlyst
TM39Wet, 200CNa, SR1LNa, quaternised IRC743 metal-loaded salt brine solution.Used salt is: AlCl
3, FeCl
3, MnCl
2, ZrOCl
2And TiCl
3
The metallic solution of cation type resin with low pH (being lower than 3) contacted.20 gram samples are packed in the post.Make zirconyl chloride, zirconium sulfate, aluminum chloride, Manganous chloride tetrahydrate, iron(ic)chloride or the ferrum sulfuricum oxydatum solutum of one liter of 4%w/v this post of flowing through 40 fens clock times.Use excessive water washing resin then.The final pH of effusive elute is 5.5 from post.Then resin is drained and wires up.
Embodiment 33: the method for resin cation(R.C.) metal-loaded
Make Amberlyst according to following steps
TM36Wet, Amberlyst
TM15Wet, Amberlyst
TM16Wet, Amberlyst
TM39Wet, Amberlite
TM200CNa, Amberlite
TMThe SR1LNa metal-loaded, used metal is: AlCl
3, FeCl
3, MnCl
2, ZrOCl
2And TiCl
3
20 gram Buchner dry samples are packed in the post.The metal salt solution of 60 milliliters of 40%w/v is added this post.In case pack in the post then make its air mixed 60 minutes.Next step is thoroughly to discharge excessive ferrous solution.The DI water that adds 2BV is emptied completely then.Add the DI water of 40BV according to the mode of continuous interpolation with 2BV/h, be higher than 5.2 up to the final pH of elute.Make resin carry out the Buchner drying then, in order to the need of application test.
Embodiment 34: positively charged ion gel-type, MR, gather sulfonation and low DVB resin load iron in post method-low pH precipitator method
Make following resin: Amberlite according to step described herein
TMSR1L Na (gel), Amberlite
TM200CNa (MR), Amberlite121 (low DVB content), Amberlite36Wet (gathering sulfonation), IRC743 load Fe (III).
20 gram Buchner dry samples are packed in the post.FeCl with 60 milliliters of 40%w/v
3Solution adds in this post.In case pack in the post then make its air mixed 60 minutes.Next step is thoroughly to discharge excessive ferrous solution.The DI water that adds 2BV is emptied completely then.Add the DI water of 40BV according to the mode of continuous interpolation with 2BV/h, be higher than 5.2 up to the final pH of elute.Make resin carry out the Buchner drying then, in order to the need of application test.
Embodiment 35: positively charged ion gel-type, MR, gather sulfonation and low DVB resin load iron in post method-high pH precipitator method
Make following cation type resin: Amberlite according to step described herein
TMSR1LNa (gel), Amberlite
TM200CNa (MR), Amberlite121 (low DVB content), Amberlite 36 Wet (gathering sulfonation) load Fe (III).
20 gram Buchner dry samples are packed in the post.FeCl with 60 milliliters of 40%w/v
3Solution adds in this post.In case pack in the post then make its air mixed 60 minutes.Next step is thoroughly to drain excessive ferrous solution.The DI water that adds 2BV is emptied completely then.The caustic solution that in resin, adds 60 milliliters of 25%w.PH is higher than 10.Adding the DI water of 40BV according to the mode of continuous interpolation with 2BV/h, is 6-7 (chemically neutral) up to the final pH of elute.Make resin carry out the Buchner drying then, in order to the need of application test.
Embodiment 36: the method for strong base styrenic resin anion(R.A) metal-loaded
The metal loading method:
With the 20 gram anionite-exchange resin reactor drums of packing into.Enriching soln (the 40%w/v ZrOCl that adds 100 milliliters of aqueous metal salts
2).Reactor drum was stirred 4 hours.Then liquid siphon from reactor drum is come out.In reactor drum, slowly add soda lye (25%) and be higher than 12, and have the liquid of 2BV in the reactor drum at least up to pH.Before liquid siphon in the reactor drum is come out, this batch of material was stirred 15 minutes gently.The DI water that in reactor drum, adds 2BV.Begin then to stir.The beginning consecutive washing step.Water is added in the reactor drum, meanwhile its siphon is come out, so that the maintenance of the water column in the reactor drum is constant.It is neutral that final pH in the reactor drum is, and come the clarification that becomes of the liquid of autoreactor.This batch of material is transferred in the post, so that particulate and unconjugated iron back scrubbing are to bead.Then resin is drained away the water, be ready for use on the operation of removing arsenic.
Embodiment 37: the method for strong base styrenic resin anion(R.A) metal-loaded
The metal loading method:
With the 20 gram anionite-exchange resin reactor drums of packing into.Add 100 milliliters of metal salt solution (40%w/v FeCl
3).Reactor drum was stirred 4 hours.Then liquid siphon from reactor drum is come out.In reactor drum, slowly add soda lye (25%) and be higher than 12, and have the liquid of 2BV in the reactor drum at least up to pH.Before liquid siphon in the reactor drum is come out, this batch of material was stirred 15 minutes gently.The DI water that in reactor drum, adds 2BV.Begin then to stir.The beginning consecutive washing step.Water is added in the reactor drum, meanwhile its siphon is come out, so that the maintenance of the water column in the reactor drum is constant.It is neutral that final pH in the reactor drum is, and come the clarification that becomes of the liquid of autoreactor.This batch of material is transferred in the post, so that particulate and unconjugated iron back scrubbing are to bead.Then resin is drained away the water, be ready for use on the operation of removing arsenic.
Embodiment 38:Amberlite IRA410 gel type resin-loading iron
With the 20 gram AmberliteI RA410 reactor drum of packing into.In reactor drum, add Fe
2(SO
4)
36.5H
2O (Aldrich) (100 gram ferric sulfate in the 150 gram water) solution.Then reactor drum was stirred 3 hours.Liquid siphon is come out after the period through this section, the resin in the reactor drum was mixed 15 minutes with 25% soda lye (100 milliliters).Liquid siphon is come out.Wash the resin in the reactor drum with 20 liters of DI water with the plug flow mode then.Final pH is 5-7.The back scrubbing resin and is wrapped resin removing particulate and iron precipitate in post then.Before using it for the arsenic-selective test, make resin carry out the Buchner drying.
The column test of embodiment 39:GFH, the cation type resin that is loaded with iron or anionic resin relatively
Used column diameter is 10 millimeters in the experiment, and is high 250 millimeters.Used resin volume is 8.0 milliliters in the post, compares with GFH (grinding ironic hydroxide).Used resin is synthetic according to embodiment 36.The concentration of used solution is: a) 50ppm or b) arsenic (V) of 200ppm and a) 200ppm or b) sulfate anion of 2000ppm.Temperature is a room temperature, and flow velocity is 3.0 ml/min, and volumetric flow rate is 22.6BV/ hour.Elute is collected in the groove during all operations.Make column operation 24 hours, and adopted IC to measure the total concn of arsenic.Adopt 50ppm As (V), 200ppm SO
4 -2Come during the measuring operation leachability of iron in the post as influent.Used ICP working curve is 50ppb for the detection lower limit of iron.
Embodiment 40: in the de-ionized system, use arsenic-selective resin
In a kind of mapping mode, resin of the present invention is used for from traditional arsenic removal system of systems provider purchase, for example U.S.Filter, Layne Christensen, Severn Trent and Basin Waters.As more instance, senior de-ionized system (ADI) is commercially available from Rohm andHaas company, and uses with resin of the present invention.This system description is in the U.S. patented claim No.10/315773 of Miers etc.; And use fractal liquid distributor (fractal liquid distributor) as basic module, just rely on the roughly the same flowing-path of the hydraulic pressure device of uniform distribution liquid basically.This type systematic is disclosed in, for example among the U.S. patent Nos.4999102 and 5354460; And at M.Kearney " Controlof Fluid Dynamics with Engineered Fractals ", among Chem.Eng.Commun. the 173rd volume 43-52 (1999).Used cylindrical vessel is a pressurized vessel in preferred this system, and is established as vertical configuration.Container is fixed, and also promptly when system's entry into service, container is fixed on the appropriate location, but container can be removed when being in off line state.Container and relevant with it pipeline and valve adopt the water material compatible with regeneration soln any and that will handle to form.Preferable material comprises, for example, and butyl rubber lined steel and stainless steel.When medium by water-soluble when bloated the preferably treatment medium filled up internal tank basically.Container has flat-top and flat, for having the Qu Ding and the container at the bent end, has reduced the height of container.The preferred container internal diameter is 0.6 meter to 1.5 meters.The preferred container internal diameter is 0.75 meter at least, more preferably at least 0.9 meter.Preferred internal diameter is no more than 1.25 meters.In a preferred specific embodiments, inside diameter of vessel is 1.1 meters to 1.25 meters.Container height preferably is 0.6 meter at least, more preferably at least 0.9 meter, and most preferably at least 1.1 meters.Preferably, container height is no more than 1.3 meters.
Use has the container of flat-top and fractal liquid distributor, through between process stream and regeneration, regeneration and flushing logistics and flushing logistics and process stream, forming pointed " corrugated ", the amount of waste is minimized.In conventional container, sizable mixing is arranged between the logistics, thereby some process stream or flushing logistics and regeneration mix, and have to fall as waste disposal, make the total quantitative change of waste big thus.On container, use flat-top to eliminate and generally occur in the mixing between the logistics in the dome conventional container inner top space.Fractal liquid distributor uniform distribution and collection process streams and regeneration form approximate plug flow thus in container, make and obviously separate between the logistics.
In preferred specific embodiments, water treatment system comprises two to five containers that contain anionite-exchange resin.Usually, the pair of parallel container is used for treating water, one or more container is used for regeneration simultaneously.The preferably water system for handling comprises three or four containers.In a preferred specific embodiments, the IX system comprises three containers; In this embodiment, two parallel containers are used for treating water and the 3rd container is used for regeneration.In preferred specific embodiments, the IX system comprises three containers and relevant with it pipeline, all is built on the frame support (" slide block "), only is that the 2.30 meters wide high x6.08 rice of x2.37 rice are long.These sizes make each part in the standard ocean transport container, can both match.Preferred each container has two manifolds (" collector "), is made up of to distribute or collect liquid flowing pipeline, perhaps is made up of container, and is connected to each end, has inside and outside the flowing of two valve control containers.
In preferred embodiments, bead is to be commercially available and even-grained resin, and its harmonic mean is of a size of 400 microns to 700 microns, more preferably 500 microns to 650 microns, and most preferably 600 microns to 650 microns.Preferred at least 95% bead mean sizes is in 50 microns.Most preferably at least 95% bead size is 580 microns to 680 microns.The resin of uniform particle size is known and can be by prepared in various methods that these methods comprise sieve method, plavini and gunite.
Flow be evenly distributed with resin beads in preferred size range, make it possible to use higher flow velocity.Preferred each container comes treating water with 10 cubic metres/hour to 60 cubic metres/hour flow velocity; More preferably each container is with at least 20 cubic metres/hours flow velocity, more preferably each container with at least 30 cubic metres/hours and most preferably each container with at least 40 cubic metres/hours flow velocity treating water.In a preferred embodiment, each container comes treating water with 40 cubic metres/hour to 60 cubic metres/hour flow velocity.In another embodiment preferred, each container comes treating water with 30 cubic metres/hour to 40 cubic metres/hour flow velocity.In another preferred embodiment, each container comes treating water with 20 cubic metres/hour to 30 cubic metres/hour flow velocity.Preferably, lower flow range is corresponding to said smaller container size.This system can make up and can obtain good performance and efficient simultaneously with the intensive IX system of high flow rate through less resin bed (also being high linear space speed).Preferred ADI system was with at least 35 hours
-1, most preferably at least 40 hours
-1Linear space speed operate.Following table has compared this system and conventional ion switching architecture:
| Parameter | Traditional method | ADI |
| Vessel top | Dome | Flat-top |
| The flow sparger | Nozzle plate | Fractal manifold |
| Resin size | 550+/-50 micron | 550+/-50 micron |
| De-gassing vessel | Plenum | Film |
| Inside diameter of vessel | 1.384 rice (positively charged ion) 1.784 meters (negatively charged ion) | 1.19 rice (the two) |
| Resin capacity | 2.5 cubic meter | 1.4 cubic meter |
| The flow velocity that uses | 50 cubic metres/hour | 60 cubic metres/hour |
| Linear space speed (flow velocity/resin capacity of use) | 20 hours -1 | 43 hours -1 |
| The conductivity of product | <0.5μS/cm | <0.5μS/cm |
| Silicon-dioxide | <10ppb | <10ppb |
| Recovery time | 3-3.25 hour | 1 hour |
| The water aspect (bed volume, BV) | 5.1-6.8BV | 2BV |
Data show that than traditional system, the ADI system can turn round with much higher linear space speed, operates with respect to the tolerance mode of container dimensional with volumetric flow rate.And, having significantly reduced the recovery time, this has reduced the time that container is not produced deionized water, and water is also quite few aspect bed volume.Therefore, with respect to conventional container, this system can adopt less container to come treating water and have similar performance with high volumetric flow rate.This discovery makes it possible to be manufactured in the standard container transportation easily and also has more high efficiency intensive ion exchange system according to waste material and off line time.
Another system that can use arsenic-selective resin is the AMBERPACK system that buys from Rohm and Haas company, and wherein plate and nozzle arrangements are packed and used to resin container fully, and this can set up unified front portion when loading arsenic-containing water.
Resin can also be used to adopt the conventional ion exchange structure of post and traditional system of distribution and have excellent effect.
Form:
Table 1: undressed production piece
| Resin | Type | Negatively charged ion in the used water-based | ICP％-Fe | ppm?As | Ppm vitriol | Mg As/g dried resin |
| AmberliteSR1LNa | SAC | Vitriol-arsenate (embodiment 27d) | 0 | 200 | 200 | 0 |
| AmberliteIRA-410 | SBA | Vitriol-arsenate (embodiment 27d) | 0 | 117 | 56 | 58 |
| AmberliteIRA-410 | SBA | Arsenate (embodiment 27a) | 0 | 42 | 0 | 102 |
Anionic concentration when the balancing test that table 1 is illustrated in embodiment 27c and 27a finishes.Note: operation does not have vitriol under the 27a condition.
Table 2 sorbent material-iron (III)
The balancing test of embodiment 27d and 27c.
Table 3 is loaded with the cationic of metal and anionic resin.Different metal.
Table semi-finals alkali type resin anion(R.A)-technical grade
Table 5 strong basic type anion-exchange resin
Table 6 weak base type resin and strong base resin: IRA743 (the N-NMG functional group in the resin)
The balancing test of embodiment 27d and 27a.
Table 7 is loaded with the resin of metal
The balancing test of embodiment 27d.
Table 8 adopts the balancing test of silicon-dioxide, vitriol and arsenate
PH is 4.0-7.0 in this test.
Table 9 adopts the arsenite result of the resin that is loaded with metal
Table 10 inflow is 50ppm As (V) and the 200ppm SO that adopts the IC commercial measurement
4 -2From embodiment 41.
Each post does not all obtain important breakthrough under two kinds of situation.
The used comparison that is loaded with anionic resin, cation type resin and the GFH medium of iron in table 11 post.From embodiment 41.
| Material in the post | ICP | |||
| Embodiment | Inflow | Sample | In the resin-the Fe% dry basis | Mg As/g resin |
| 39 | 20000ppm?SO 4，200ppm?As | IRA410 | 0 | 0 |
| IRA-410 | 5.8 | 31 | ||
| GFH | Na | 26 | ||
| 39 | 2000ppm?SO 4，200ppm?As | 200CNa | 9.2 | 31 |
| GFH | Na | 20 | ||
| IRA410 | 5.8 | 30 |
The present invention's one specific embodiments is used the basic resin of acrylic acid or the like gel as metal-loaded, and this acrylic acid or the like gel is by making with 2-5%DVB and forming with the methyl acrylate/DVB multipolymer of 0-1.0% Diethylene Glycol divinyl ether as linking agent.Preferred embodiment will have the DVB of 3-4% and the Diethylene Glycol divinyl ether of 0.45-0.55%, and most preferred embodiment is about 3.6% DVB and about 0.49% Diethylene Glycol divinyl ether.Make this multipolymer functionalized with following functional group:
RR
1N{(CH
2)
xN(R
2)}
z(CH
2)
yNR
3R
4
Wherein R represents resin, and the amine nitrogen atom on the far-end left side is via the amido linkage that is bonded to the vinylformic acid carbonyl group or via the CH that is bonded on the acrylics
2The C-N key of group and be connected to resin; R
1And R
2=H, Me or Et; X and y=1-4, z=0-2 and R
3And R
4=Me, Et, Pr or Bu.Preferredly functionalizedly will have the R that connects via amido linkage; R
1=H or Me; Z=0; Y=1-4 and R
3And R
4=Me or Et.Most preferred embodiment will be R
1=H; Y=3 and R
3And R
4=Me.
Another specific embodiments of the present invention will be used the basic resin of macroreticular-type resin as metal-loaded, and this macroreticular-type resin is by making with 6-9%DVB and forming with the methyl acrylate/DVB multipolymer of 1.1-3.0% Diethylene Glycol divinyl ether as linking agent.Preferred embodiment will have the DVB of 7-8% and the Diethylene Glycol divinyl ether of 1.5-2.5%, and most preferred embodiment is about 7.6% DVB and about 2.0% Diethylene Glycol divinyl ether.Make multipolymer functionalized with above-mentioned group, above-mentioned group is via the amido linkage that is bonded to the vinylformic acid carbonyl group or via the CH that is bonded on the acrylics
2The C-N key of group and be connected to resin; R
1And R
2=H, Me or Et; X and y=1-4, z=0-2 and R
3And R
4=Me, Et, Pr or Bu.Preferredly functionalizedly will have the R that connects via amido linkage; R
1=H or Me; Z=0; Y=1-4 and R
3And R
4=Me or Et.Most preferred embodiment will be R
1=H; Z=0; Y=3 and R
3And R
4=Me.
Embodiment 41: gel-type or MR vinylformic acid/DVB or vinylbenzene/DVB weakly-basic anion type resin-loading iron
The FeCl of 30 gram resins and 50 milliliters of 40%w/v packs in post
3Solution.This post air mixed 3 hours is emptied completely then.In post, pack into the afterwards DI water of 0.5BV.The DI water that makes 1.5BV is with 4.5BV/ hour flow velocity this post of flowing through.This post of emptying then.50 milliliter of 12% soda lye added this post.Make this post air mixed 2 hours, use the DI water back scrubbing of 10BV then.Use 5% H then
2SO
4Solution obtains neutral pH.Before using it for the arsenic-selective test, make resin carry out the Buchner drying.
Embodiment 42: gel-type or MR vinylformic acid/DVB or vinylbenzene/DVB weakly-basic anion type resin-loading iron
The FeCl of 30 gram resins and 50 milliliters of 40%w/v packs in post
3Solution.This post air mixed 3 hours is emptied completely then.In post, pack into the afterwards DI water of 0.5BV.The DI water that makes 1.5BV is with 4.5BV/ hour flow velocity this post of flowing through.With 4%DI water NaHCO
3The solution washing resin also increases pH.This solution is flow through with 3BV/ hour flow velocity, is 7.0 up to the pH of this effluent.PH in the measurement column is stabilized in 6.5 through pH after one hour air mixed.It is dry and wire up then this batch of material to be carried out Buchner.
Embodiment 43: the preparation of gel type strong base property acrylic acid or the like anionite-exchange resin
The conversion process that changes the anionic resin with the MR type methyl acrylate polymer of Vinylstyrene (3.6%w/w), Diethylene Glycol divinyl ether (0.49%w/w) crosslinking copolymers into was undertaken by two steps; Separate with dimethylamino propylamine (DMAPA) ammonia, then carry out quaternized.
Quaternized:
The big netted acrylics of weakly alkaline that the 150 gram embodiment 23 that pack into make.Add 300 ml methanol then and add 75 gram methyl chlorides.The temperature of reaction must be controlled at 10-25 ℃ and pressure is lower than 5psig.Temperature was being kept 4.0-9.0 hour below 30 ℃.Reactor drum is heated to 38-48 ℃, and makes it to keep 1-5 hour down at 38-48 ℃.Drain this batch of material and wash 7 hours (discharge continuously and replenish) with a large amount of water (reactor volume 15 times).Drain product then and it is wired up.
Table 12 weak base type acrylics, strong base acrylics and be loaded with the resin of iron.
Note: Amberlite
TMThe IRA-35 resin is the MR acrylics according to embodiment 43 preparations.
Table 13 inflow is 50ppm As (V) and the 200ppm SO that adopts the IC commercial measurement
4 -2From embodiment 39.
Each post does not all obtain important breakthrough under two kinds of situation.For all samples in 1,4 and 24 hour Fe content < 0.050ppm in the elute.
Claims (3)
1. a method of from water, removing arsenic is connected resin with the contact of acrylic acid or the like gel to obtain arsenic through making water, and described acrylic acid or the like gel comprises the amine substituting group of formula:
R
1N{(CH
2)
xN(R
2)}
z(CH
2)
yNR
3R
4
Wherein, have substituent R
1Amine nitrogen be connected on the vinylformic acid carbonyl group via amido linkage, or be connected to the CH on the acrylic acid or the like gel via the C-N key
2Group; R
1And R
2=H, methyl or ethyl; X and y=1-4, z=0-2, R
3And R
4=methyl, ethyl, propyl group or butyl;
Wherein, iron is the hydrous oxide form, be captured in the acrylic acid or the like gel,
Wherein, described acrylic acid or the like gel is by making with the 2-5% Vinylstyrene, and forms with 0-1.0% di-alcohol divinyl ether methyl acrylate/divinyl benzene copolymer as linking agent.
2. the process of claim 1 wherein and have substituent R
1Amine nitrogen be connected with the vinylformic acid carbonyl group through amido linkage; R
1=H or methyl; Z=0; R
3And R
4=methyl or ethyl.
3. the method for claim 2, wherein R
1=H; Y=3; R
3And R
4=methyl.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US54731004P | 2004-02-24 | 2004-02-24 | |
| US60/547,310 | 2004-02-24 | ||
| US62719604P | 2004-11-12 | 2004-11-12 | |
| US60/627,196 | 2004-11-12 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005100509597A Division CN1660703A (en) | 2004-02-24 | 2005-02-24 | Method for removal of arsenic from water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101381148A CN101381148A (en) | 2009-03-11 |
| CN101381148B true CN101381148B (en) | 2012-01-11 |
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|---|---|---|---|
| CN2008101688687A Expired - Fee Related CN101381148B (en) | 2004-02-24 | 2005-02-24 | Method for removal of arsenic from water |
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| MX (1) | MXPA04012075A (en) |
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| CN102641730B (en) * | 2012-04-16 | 2014-10-15 | 申鸿志 | Synthetic method for fluorinion adsorption resin |
| CN102633930B (en) * | 2012-04-16 | 2013-11-13 | 白银恒鼎科技有限责任公司 | Synthesis and preparation method of dearsenifying resin |
| CN103232091A (en) * | 2013-04-25 | 2013-08-07 | 滨州学院 | Method for removing arsenium from water body by macroporous resin adsorption process |
| EP3308857B1 (en) * | 2016-10-11 | 2020-07-08 | LANXESS Deutschland GmbH | Strong basic polyacrylate anion exchangers |
| CN108295804A (en) * | 2018-02-24 | 2018-07-20 | 北京师范大学 | A kind of preparation method and application of the Fe-Cu binary oxide adsorbents of removal antimony |
| CN113272058A (en) * | 2018-11-27 | 2021-08-17 | Ddp特种电子材料美国第5有限公司 | Method for producing resin for semiconductor production |
| CN112079414A (en) * | 2020-09-15 | 2020-12-15 | 昆明理工大学 | Method for treating arsenic in arsenic-containing solution by using strong base anion resin loaded with cobalt |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4284726A (en) * | 1978-05-13 | 1981-08-18 | Yasumasa Shigetomi | Composite anion adsorbent and method for making same |
-
2004
- 2004-12-02 MX MXPA04012075 patent/MXPA04012075A/en not_active Application Discontinuation
-
2005
- 2005-02-24 CN CN2008101688687A patent/CN101381148B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4284726A (en) * | 1978-05-13 | 1981-08-18 | Yasumasa Shigetomi | Composite anion adsorbent and method for making same |
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|---|---|
| MXPA04012075A (en) | 2005-08-16 |
| CN101381148A (en) | 2009-03-11 |
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