CN102114401A

CN102114401A - Arsenic removal adsorbent and preparation method thereof

Info

Publication number: CN102114401A
Application number: CN2009102443304A
Authority: CN
Inventors: 张昱; 赵蓓; 豆小敏; 杨敏; 高迎新; 于建伟
Original assignee: Research Center for Eco Environmental Sciences of CAS
Current assignee: Research Center for Eco Environmental Sciences of CAS
Priority date: 2009-12-31
Filing date: 2009-12-31
Publication date: 2011-07-06
Anticipated expiration: 2029-12-31
Also published as: CN102114401B

Abstract

The invention provides an arsenic removal adsorbent and a preparation method thereof. The adsorbent contains sulfate akaganeite and high-molecular material agglomerant. In the invention, the particles of the arsenic removal adsorbent have high adsorption property to have high adsorption selectivity to arsenic in drinking water, the adsorption capacity is high, the adsorbed particles have large strength under a drying state or a moisture state, the particle crushing rate is low during use, no adsorbent is dissolved out, and the arsenic removal adsorbent is suitable for being used for a long time and under the condition of larger water flow pressure change.

Description

A kind of arsenic-removing adsorption agent and preparation method thereof

Technical field

The invention belongs to the sorbing material technical field, particularly a kind of preparation method who is used for the Removal of Arsenic in Drinking Water absorbent particles.

Background technology

For a long time, drink arsenic-containing water to the harm of health also always by focus that people paid close attention to.The water that studies show that in recent years, long-term drinking contain low concentration arsenic also can cause the generation of a lot of diseases.Regulation in the drinking water sanitary standard (GB5479-2006) of new promulgation in 2006, the limit value of arsenic concentration is 0.01mg/L in the Drinking Water, the limit value of arsenic concentration is 0.05mg/L in small-sized centralized water supply and the water dispersion type water quality index.

The removal method of arsenic comprises absorption method, molysite coagulant sedimentation, electrocoagulation and counter-infiltration etc. in the water.Wherein, adsorption technology is considered to be suitable for small community and the most cost-effective treatment technology of remote suburb central water supply.The arsenic removal material of domestic present use mainly is an activated alumina, bone black and active carbon etc., but activated alumina is as arsenic-removing adsorption agent, and its optimal adsorption pH value is 5, and adsorption capacity is on the low side, causes the stripping of aluminium easily; There are the low defective of adsorption capacity in bone black and active carbon equally as arsenic-removing adsorption agent.

At present, Study on Removal of Arsenic more is that emphasis development screening effect of removing arsenic is good except conventional materials such as activated alumina, bone black are improved the research, the arsenic removal material of applied range and stable performance.Studies show that in recent years, synthetic ferriferous oxide some natural generations or artificial has stronger adsorption capacity to harmful anion in the water.

Notification number is that the patent of invention of CN100386141C discloses a kind of composite adsorbing material of removing arsenic in the water and preparation method thereof, and this arsenic-removing adsorption agent is composited by active carbon and iron oxide, and the active carbon after will washing earlier is incubated 24 hours down at 90 ℃, drying.Add then in the nitric acid, stir, place after 4 hours, washing, and stand-by at 95～100 ℃ times dry 24 hours.With FeSO ₄7H ₂O and FeCl ₃6H ₂After O is dissolved in water, add among the NaOH of 5mol/l, stir, generate iron oxide precipitation, be titrated to pH value of solution=9～10 with NaOH at 70 ℃; Wash with water, add laurate again, drip NaOH simultaneously, stirred 10 minutes, be heated to 90 ℃, constant temperature 30 minutes.Adjust pH=4～5.But this arsenic removal composite adsorbing material need use under the slant acidity condition, and its specific area is little, and adsorption capacity is low.

Granted publication number be CN100352541C patent disclosure a kind of preparation method of iron carrying active carbon dearsenic adsorber, by Datong District's raw coal: iron oxide: binding agent=12～9: 3～1: 1～0.4 part of quality is measured.Then raw coal is worn into powder, sneak into iron oxide, add binding agent again, the back that is shaped is 300～500 ℃ of charings in the anoxic temperature, is to activate under 850～950 ℃ in temperature then, makes the active carbon arsenic-removing adsorption agent of iron oxide bearing.But need high-temperature roasting in the preparation process of this arsenic-removing adsorption agent, energy consumption is big, the technology more complicated.In addition, along with the prolongation of adsorption time, there is the phenomenon of decay in the iron oxide of above-mentioned two kinds of adsorbent surfaces, limits its use and long-play.

Publication number is that the application for a patent for invention of CN 101073762A discloses a kind of arsenic-removing adsorbent containing lanthanum mesic-porous molecular sieve and preparation method thereof, this adsorbent is made up of mesopore silicon oxide MCM-48 and load lanthanum thereon with the mutual disjunct three-dimensional open-framework of two covers, the weight content of lanthanum is 1.17-9.80%, and surface area is 202-732m ²/ g, average pore size is 2.7-3.2nm, pore volume is 0.2-0.7ml/g.But this arsenic-removing adsorption agent cost of material height, and need high-temperature roasting in the preparation process, energy consumption is big, the technology more complicated.

In recent years the exploitation by aluminium, magnesium, iron, the compound adsorbent that polyvalent metal such as zirconium and rare earth (hydration) oxide is made, because of its unique surface nature and design feature, more traditional sorbing material of its adsorption capacity such as activated alumina to arsenic, the characteristic that bone black is contour, for example: Granted publication changes compound water treatment adsorbent by divalent number for the patent of invention of CN 1094070C has proposed a kind of iron-rare earth element compound water treatment adsorbent and preparation method thereof, 3 valency molysite are (as frerrous chloride, iron chloride or ferrous sulfate/ferric sulfate etc.) and the rare earth element salt (as cerium salt, lanthanum salt etc.) reaction is synthetic under alkali condition.And for example, publication number be CN 101485970A disclosure of the Invention a kind of preparation method of high-efficient arsenic-removing sorbent of Fe-Zr composite oxides, with ZrOCl ₂.8H ₂O, FeCl ₃.6H ₂O and CO (NH ₂) ₂Be mixed with certain density mixed solution by a certain percentage, wherein FeCl ₃6H ₂O and ZrOCl ₂8H ₂The mass ratio of O is 16: 8-14; FeCl ₃.6H ₂O and ZrOCl ₂.8H ₂The total concentration of O is 0.05-0.3mol/L; CO (NH ₂) ₂With (FeCl ₃.6H ₂O+ZrOCl ₂.8H ₂O) mass ratio is 4: 12-17; The baking oven of then mixed liquor being put into 80-200 ℃ is incubated 3-10 hour, and reaction generates brown precipitate, with the precipitate with deionized water washing, then at 30-70 ℃ dry 48h, makes Fe-Zr composite oxides arsenic-removing adsorption agent.But above-mentioned two kinds of adsorbents are powdered form, need special arrangement to carry out Separation of Solid and Liquid during use, not only easily cause adsorbent to run off, but also easy occluding device, impregnate layer comes off influences effluent quality.

Granted publication number discloses a kind of cubic sulfate lepidocrocite preparation of adsorbent method that is used for arsenic removal for the Chinese invention patent application of 100460056C, this method is 3-4 with molysite and sulfate in the mol ratio of contained iron ion and sulfate ion: 1 ratio is dissolved in the aqueous solution, the concentration of molysite is greater than 0.3M, adding aqueous slkali earlier is 4.0 until pH value of solution, after continuing to stir, slowly add aqueous slkali again to pH7.5-9.5, left standstill 24 hours; Centrifugation spends the deionised water solid, is drying to obtain.Compare with adding the terres rares adsorbent, above-mentioned adsorbent cost of material is low, and the preparation method is simple, the adsorbance height.But the particle diameter of this absorbent powder is a nanoscale, directly drops into the loss that not only easily causes adsorbent in the water, and needs special arrangement to carry out Separation of Solid and Liquid, and is difficult for regenerating and reuse after reclaiming.Also have different problems and use powder or powder simply to be immersed in some carriers (as haydite) filling fixed bed, big as: the loss of flood peak, easily stop up, impregnate layer comes off influences effluent quality.

Summary of the invention

The objective of the invention is provides a kind of arsenic-removing adsorption agent particle that is used for drinking water and preparation method thereof at the problem that above-mentioned prior art exists, the intensity height of the arsenic-removing adsorption agent particle of the inventive method preparation, long-term use is not broken, mass loss is little, no stripping, the non-secondary pollution problem, safe and reliable, be suitable for long-term and under water flow pressure changes big situation, use.

For realizing purpose of the present invention, one aspect of the present invention provides a kind of Removal of Arsenic in Drinking Water adsorbent that is used for to comprise cubic sulfate lepidocrocite and binding agent.

Wherein, the weight portion proportioning of cubic sulfate lepidocrocite and binding agent is 1: 0.5-1.5 is preferably 1: 0.7-1.2.

Particularly, described binding agent is selected one or more in polyacrylate dispersion, JSF liquid, polyvinyl alcohol ester glue, Kynoar glue, inorganic silicon colloidal sol, the organic silica gel.

Wherein, the solid content of described polyacrylate dispersion 〉=52%; Dioxide-containing silica in the described Ludox 〉=25%; Described organic silica gel comprises silicon rubber and silicones, and room temperature curing type does not add metal salt of organic carboxylic acid and makes curing catalysts; Described Kynoar glue is that Kynoar is dissolved in N, the dinethylformamide (DMF) and forms.

Particularly, described polyacrylate dispersion mass percent concentration is 4-25%, viscosity 500-1000mPas, pH value 5.0-7.5; Dioxide-containing silica is preferably 25-40% in the described Ludox; Described silicon rubber is selected room temperature vulcanized silicone rubber, viscosity 200-1000mPas; The mass percent concentration of described Kynoar glue is 3-18%.

Especially, described Ludox pH value 6-8, viscosity 5-35mPas, average grain diameter 5-30nm, stabilizing agent Na ₂O content≤0.40%.

Particularly, described JSF liquid forms for Pioloform, polyvinyl acetal is dissolved in ethanol, and its mass percent concentration is 1-25%;

Especially, the molecular weight of described Pioloform, polyvinyl acetal is 90-200k.

Especially, described Pioloform, polyvinyl acetal is polyvinyl formal, polyvinyl butyral resin, polyvinyl acetal, polyvinyl alcohol glutaraldehyde, polyvinyl alcohol contract in the methacrylaldehyde one or more of crotonaldehyde, polyvinyl alcohol that contract that contract.

Particularly, to be dissolved in the mass percent concentration of the formaldehyde polyvinyl acetal liquid that ethanol forms be 2-20% to described polyvinyl formal; The mass percent concentration that described polyvinyl butyral resin is dissolved in the butvar adhesive liquid of ethanol formation is 1-25%; The described polyvinyl alcohol glutaraldehyde that contracts is dissolved in ethanol to form the contract mass percent concentration of glutaraldehyde glue of polyvinyl alcohol is 2-25%; The mass percent concentration that described polyethylene acetal is dissolved in the polyethylene acetal glue of ethanol formation is 2-25%; Described polyethylene contracts, and to be dissolved in the contract mass percent concentration of methacrylaldehyde glue of polyethylene that ethanol forms be 3-25% to methacrylaldehyde; Described polyethylene contracts, and to be dissolved in the contract mass percent concentration of butylene glue of polyethylene that ethanol forms be 2-25% to crotonaldehyde;

Wherein, described polyvinyl alcohol ester glue makes for polyvinyl alcohol and little carboxylic acids are carried out esterification, and wherein, polyvinyl alcohol is 100 with the ratio of the weight of little carboxylic acids: 2-25.

Particularly, the temperature of esterification is 40-100 ℃, and the reaction time is 30-300min;

Particularly, also comprise at first with polyvinyl alcohol water-soluble after, carry out described esterification with little carboxylic acids again, wherein, polyvinyl alcohol is 2-25 with the ratio of the weight of water: 100.

Wherein, described polyvinyl alcohol selective polymerization degree is 1700-2600, alcoholysis degree＞95%; Described little carboxylic acids is selected citric acid, maleic acid, succinic acid, malonic acid, ethanedioic acid or acrylic acid.

Wherein, described cubic sulfate lepidocrocite is made up of molysite and sulfate, and wherein the mol ratio of contained iron ion and sulfate ion is 3-4 in molysite and the sulfate: 1.

Particularly, described molysite is ferric trichloride or ferric nitrate; Described sulfate is sodium sulphate or potassium sulfate.

Wherein, described cubic sulfate lepidocrocite is made according to following steps:

1), be 3-4 with molysite and sulfate in the mol ratio of contained iron ion and sulfate ion while stirring at 10-50 ℃: 1 ratio, generation mixed liquor soluble in water, wherein the concentration of iron ion is 0.31-0.55M in the mixed liquor;

2) adding aqueous slkali while stirring in mixed liquor, is 4.0 until the pH of solution, continue to stir 1-12h, then add then aqueous slkali to the pH of solution be 7.5-9.5, stop to stir, leave standstill 24h;

3) with step 2) solution centrifugal that makes separates, and spends the deionised water solid, is neutral until cleaning solution pH, and chromatography of ions can't check sulfate ion, and the product after the washing is drying to obtain.

Particularly, it is NaOH, potassium hydroxide, sodium carbonate or the sodium bicarbonate aqueous solution of 2-6M that the aqueous slkali step 2) is selected concentration; Described aqueous slkali is that concentration is the ammoniacal liquor of 6M.

Particularly, the drying described in the step 3) is for to dry or freeze drying under 40 ℃.

The present invention provides a kind of Removal of Arsenic in Drinking Water preparation of adsorbent method that is used on the other hand, comprise and carry out pelletization treatment and dry the processing successively after evenly with cubic sulfate lepidocrocite and binding agent are mixed, wherein, the weight portion proportioning of described cubic sulfate lepidocrocite and binding agent is 1: 0.5-1.5.

Wherein, the weight portion proportion optimization of described cubic sulfate lepidocrocite and binding agent is 1: 0.7-1.2.

Wherein, the solid content of described polyacrylate dispersion 〉=52%; Dioxide-containing silica in the described Ludox 〉=25%; Described organic silica gel is selected room temperature curing type, is not added silicon rubber or silicones that metal salt of organic carboxylic acid is made curing catalysts; Described Kynoar glue is that Kynoar is dissolved in N, dinethylformamide

(DMF) glue that forms in.

Especially, the pH value 6-8 of described Ludox, viscosity 5-35mPas, average grain diameter 5-30nm, stabilizing agent Na ₂O content≤0.40%.

Wherein, described JSF liquid is that Pioloform, polyvinyl acetal is dissolved in ethanol to form mass percent concentration be the glue of 1-25%;

Particularly, described Pioloform, polyvinyl acetal is selected polyvinyl formal, polyvinyl butyral resin, polyvinyl acetal, polyvinyl alcohol glutaraldehyde, polyvinyl alcohol contract in the methacrylaldehyde one or more of crotonaldehyde, polyvinyl alcohol that contract that contract.

Especially, it is 1-25% formaldehyde polyvinyl acetal liquid that described polyvinyl formal is dissolved in ethanol formation mass percent concentration, and wherein concentration is preferably 2-25%, further preferred 2-10%; The molecular weight of polyvinyl formal is 100-150k; It is the butvar adhesive liquid of 1-25% that described polyvinyl butyral resin is dissolved in ethanol formation mass percent concentration, and wherein concentration is preferably 5-15%; The molecular weight of polyvinyl butyral resin is 130-175k; The described polyvinyl alcohol glutaraldehyde that contracts is dissolved in ethanol to form mass percent concentration is the polyvinyl alcohol of the 1-25% glutaraldehyde glue that contracts, and wherein, concentration is preferably 2-25%; The contract molecular weight of glutaraldehyde of polyvinyl alcohol is 130-200k; It is the polyethylene acetal glue of 1-25% that described polyethylene acetal is dissolved in ethanol formation mass percent concentration, and wherein, concentration is preferably 2-25%; The molecular weight of polyvinyl acetal is 110-160k; The described polyethylene methacrylaldehyde that contracts is dissolved in ethanol to form mass percent concentration is the polyethylene of the 1-25% methacrylaldehyde glue that contracts, and wherein, concentration is preferably 3-25%; The contract molecular weight of methacrylaldehyde of polyvinyl alcohol is 130-170k; The described polyethylene crotonaldehyde that contracts is dissolved in ethanol to form mass percent concentration is the polyethylene of the 1-25% crotonaldehyde glue that contracts, and wherein, concentration is preferably 2-25%; The contract molecular weight of crotonaldehyde of polyvinyl alcohol is 130-170k;

Wherein, described polyvinyl alcohol ester glue is that polyvinyl alcohol and little carboxylic acids esterification form, and wherein, polyvinyl alcohol is 100 with the ratio of the weight of little carboxylic acids: 2-25.

Wherein, described polyvinyl alcohol selective polymerization degree is 1700-2600, alcoholysis degree＞95%; Described little carboxylic acids is selected citric acid, maleic acid, succinic acid, malonic acid, ethanedioic acid or acrylic acid; The temperature of described esterification is 40-100 ℃, and the time is 30-300min.

Wherein, described pelletization treatment is carried out according to following steps:

A) cubic sulfate lepidocrocite and binding agent are mixed make mixed material;

B) mixed material through comminutor extrude, segment, make the material grain.

Particularly, the mixing steps A) is to place mixer to carry out described the mixing cubic sulfate lepidocrocite and binding agent; Step B) relative pressure in the extrusion of comminutor described in is 0.5-15MPa.

Especially, step B) also comprise mixed material mediated 2-15 minute in kneader after, send into again and carry out the described processing of extruding, cut off in the comminutor.

Wherein, the described dry temperature of handling is 40-130 ℃, is preferably 65-120 ℃.

Wherein, described arsenic-removing adsorption agent particle is cylindrical or spherical.

Particularly, the diameter of described cylindrical particle is 0.5-3.0mm, is preferably 0.9-2.5mm; Long for 2-15mm, be preferably 3-10mm.

Particularly, described spheric granules is that described cylindrical particle forms through extruding the spheronizator processing.

Especially, the diameter of described spheric granules is 0.5-4.0mm.

Wherein, described molysite is ferric trichloride or ferric nitrate; Described sulfate is sodium sulphate or potassium sulfate.

Wherein, it is NaOH, potassium hydroxide, sodium carbonate or the sodium bicarbonate aqueous solution of 2-6M that the aqueous slkali step 2) is selected concentration; Described aqueous slkali is that concentration is the ammoniacal liquor of 6M.

Wherein, the drying described in the step 3) is for to dry or freeze drying under 40 ℃.

The absorbent particles of the present invention's preparation has following advantage:

1, the ion selectivity of adsorbent of the present invention is good, at its object removal ion (arsenic ion) higher selectivity is arranged, and other common anion all do not have obviously influence in the water in the drinking water scope;

2, the adsorption capacity height of adsorbent of the present invention, under nearly neutrallty condition, arsenic removal adsorption particle saturated adsorption capacity reaches 16-27mg/g, especially for high-arsenic underground water as drinking water, though its arsenic concentration exceeds drinking water standard, be not more suitable under the very high situation, and conventional relatively activated alumina adsorbents, do not need to regulate pH, and higher adsorption capacity is arranged;

3, the specific area of adsorbent of the present invention is big, and average specific surface area reaches 10-30m ²/ g, the pore volume height, average pore volume reaches 0.020-0.050mL/g, and specific area is big, surface and internal capillary and mesoporous abundant, the adsorption capacity of raising adsorbent;

4, adsorbent of the present invention is done, better intensity is all arranged under the wet condition, the breaking strength height, and the dry state compressive strength reaches more than the 25N, and loss late is less than 2%, uses not brokenly for a long time, is suitable for long-term and uses under water flow pressure changes big situation;

5, mass loss is little in the adsorbent use of the present invention, no stripping, and the non-secondary pollution problem, safe and reliable, reuse.

6, preparation of adsorbent method of the present invention is simple, and low production cost is easy to use, compares with external commodity adsorbent, and its manufacturing cost and use cost significantly reduces, and its cost only is READ-

1/6 of adsorbent, and adsorbance is identical under nearly neutrallty condition.

The specific embodiment

Cubic sulfate lepidocrocite arsenic-removing adsorption agent of the present invention is cubic sulfate lepidocrocite powder for the method that provides according to Chinese patent ZL200610078899.4 prepares.

Embodiment 1

1, the cubic sulfate lepidocrocite powder of preparation

With ferric trichloride, sodium sulphate is Fe in molar ratio ³⁺: SO4 ^2-=4: 1 ratio is dissolved in the aqueous solution, at 20 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.4M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 2M sodium hydroxide solution fast, be 4.0 until the pH of solution value; Slowly drip the 2M sodium hydroxide solution again to pH9.5 after stirring 6h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is dried to moisture content less than 1% at 40 ℃, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation absorbent particles

Cubic sulfate lepidocrocite powder and binding agent polyacrylate dispersion are added mixing in the colter mixer, absorbent powder is all soaked into by emulsion, make mixed material, wherein, the polyacrylate dispersion mass percent concentration is 15%, and solid content is 55%, viscosity 800mPas, pH value 6.0, the mass ratio of powder and emulsion are 1: 0.7.

The polyacrylate dispersion that the present invention uses is not limited to above-mentioned emulsion, solid content 〉=52%, and concentration is 4-25%, viscosity 500-1000mPa.s, the polyacrylate dispersion of pH value 5.0-7.5 all is applicable to the present invention.

With the wet stock that mixes through pressure-type kneading machine (dragon Xinghua, Shandong construction machinery group; the NH-10 type) mediates after 5 minutes; send into the double-screw extruding pelletizing machine; be after extruding under the pressure of 4MPa at relative pressure; cut off, granulate; then make sphere under spheronizator (Yingge Granulating Covering Technology Co., Ltd., Chongqing) effect, obtaining moisture content 45 ℃ of oven dry then is 2% arsenic-removing adsorption agent finished granule, and the capability and performance index testing result of finished product sees Table 1.

Adopt granule strength analyzer (hemisphere (China), model: KC-2) measure arsenic removal finished granule dry state compressive strength; Adopt ASAP Micromeritics (Macross, USA) specific surface analyzer mensuration absorbent particles specific area, pore volume;

Measure the mass loss rate of arsenic removal particle as follows:

An amount of arsenic removal particle is placed the conical flask that the 100mL deionized water is housed, behind 150rpm vibration 8h on the shaking table, adsorbent is taken out, use the accurate test sieve of 60 targets to filter and washing arsenic removal particle, then in baking oven, dry 12h down in 65 ℃, granular mass after weighing is dried then, the difference of the quality before and after the test is a mass loss rate with the ratio of the quality of the preceding particle of test;

Make particle and be used to handle the water that contains arsenic, the arsenic initial concentration is 0.5mg/L in the water, particle throwing amount is 2g/L, and pH=7.0 ± 0.1 condition following time, recording its adsorbance to arsenic is 0.25mg/g (being the arsenic of this composite metal oxidate arsenic removal adsorbents adsorb of every gram 0.25mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the arsenic initial concentration respectively is that this particle is to the adsorbance of arsenic in the 1-50mg/L scope, and obtaining its saturated extent of adsorption to arsenic through the mathematics The Fitting Calculation is 19mg/g.

Embodiment 2

1, the cubic sulfate lepidocrocite powder of preparation

With ferric sulfate, potassium sulfate is Fe in molar ratio ³⁺: SO4 ^2-=4: 1 ratio is dissolved in the aqueous solution, at 40 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.4M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 4M sodium hydroxide solution fast, be 4.0 until the pH of solution value; Slowly drip the 4M sodium hydroxide solution again to pH8.5 after stirring 6h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is dried to moisture content less than 1% at 40 ℃, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation high polymer binder

In obturator, be under the condition of 150rpm in stir speed (S.S.), with the polyvinyl formal powder dissolution in ethanol, leave standstill bubble, make mass percent concentration and be 10% formaldehyde polyvinyl acetal liquid, wherein, the molecular weight of polyvinyl formal is 100-150K.

The concentration of formaldehyde polyvinyl acetal liquid is not limited to 10%, and the formaldehyde polyvinyl acetal liquid of concentration in the 1-25% scope all is applicable to the present invention.

3, preparation absorbent particles

Under normal temperature (25 ℃), cubic sulfate lepidocrocite powder and formaldehyde polyvinyl acetal liquid joined in the colter mixer mix, powder is all soaked into by glue, make mixed material, wherein the mass ratio of absorbent powder and formaldehyde polyvinyl acetal liquid is 1: 1.2.

With the wet stock of mixing after kneading machine is mediated 3 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure effect of 8MPa at relative pressure; cut off, granulate; then under the effect of spheronizator, make sphere; then 65 ℃ dry 4 hours down, obtaining moisture content through 80 ℃ of oven dry again is 2% arsenic-removing adsorption agent finished granule, the capability and performance index testing result of finished product sees Table 1.

Make particle and be used to handle the water that contains arsenic, the arsenic initial concentration is 0.5mg/L in the water, particle throwing amount is 1g/L, and pH=7.0 ± 0.1 condition following time, recording its adsorbance to arsenic is 0.25mg/g (being the arsenic of this composite metal oxidate arsenic removal adsorbents adsorb of every gram 0.25mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the arsenic initial concentration respectively is that this particle is to the adsorbance of arsenic in the 1-50mg/L scope, and obtaining its saturated extent of adsorption to arsenic through the mathematics The Fitting Calculation is 21mg/g.

Embodiment 3

1, the cubic sulfate lepidocrocite powder of preparation

With ferric trichloride, potassium sulfate is Fe in molar ratio ³⁺: SO4 ^2-=3: 1 ratio is dissolved in the aqueous solution, at 50 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.33M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 3M sodium hydroxide solution fast, be 4.0 until the pH of solution value; Slowly drip the 3M sodium hydroxide solution again to pH7.5 after stirring 1h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is dried to moisture content for less than 1% at 40 ℃, grinds and makes cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation high polymer binder

Under 95 ℃ of conditions with polyvinyl alcohol (2499) water-soluble after, adding little carboxylic acids citric acid stirs, carry out esterification, make polyvinyl alcohol citrate glue, wherein, esterification reaction temperature is 70 ℃, and the reaction time is 120min, polyvinyl alcohol (2499) is 5: 100 with the ratio of the weight of water, and polyvinyl alcohol (2499) is 100: 10 with the ratio of the weight of citric acid.

Polyvinyl alcohol is not limited to polyvinyl alcohol (2499), and other degree of polymerization are 1700-2600, and the polyvinyl alcohol of alcoholysis degree＞95% all is applicable to the present invention; Little carboxylic acids is not limited to citric acid, and other all are applicable to the present invention as maleic acid, succinic acid, malonic acid, ethanedioic acid, acrylic acid; Esterification reaction temperature is not limited to 70 ℃, reaction time and is not limited to 120min, and reaction temperature is at 40-100 ℃, and the time all is applicable to the present invention at 30-300min.

Polyvinyl alcohol was not limited to 5: 100 with the ratio of the weight of water, polyvinyl alcohol was not limited to 100: 10 with the ratio of the weight of citric acid, polyvinyl alcohol is 2-25 with the ratio of the weight of water: 100, and polyvinyl alcohol is 100 with the ratio of the weight of little carboxylic acids: 2-25 all is applicable to the present invention.

3, preparation absorbent particles

Cubic sulfate lepidocrocite powder and binding agent polyvinyl alcohol citrate glue joined in the colter mixer mix, make all bonded dose of infiltrations of powder, make mixed material, wherein the mass ratio of powder and polyvinyl alcohol citrate glue is 1: 0.8;

With the wet stock that mixes after kneading machine is mediated 5 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure of 10MPa at relative pressure; cut off, granulate; then under the effect of spheronizator, make sphere; obtaining moisture content 65 ℃ of oven dry then is 2% arsenic-removing adsorption agent finished granule, and the capability and performance index testing result of finished product sees Table 1.

Make particle and be used to handle the water that contains arsenic, the arsenic initial concentration is 0.5mg/L in the water, particle throwing amount is 1g/L, and pH=7.0 ± 0.1 condition following time, recording its adsorbance to arsenic is 0.25mg/g (being the arsenic of this composite metal oxidate arsenic removal adsorbents adsorb of every gram 0.25mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the arsenic initial concentration respectively is that this particle is to the adsorbance of arsenic in the 1-50mg/L scope, and obtaining its saturated extent of adsorption to arsenic through the mathematics The Fitting Calculation is 23mg/g.

Embodiment 4

1, the cubic sulfate lepidocrocite powder of preparation

With ferric trichloride, potassium sulfate is Fe in molar ratio ³⁺: SO4 ^2-=4: 1 ratio is dissolved in the aqueous solution, at 40 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.55M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 4M sodium hydroxide solution fast, be 4.0 until the pH of solution value; Slowly drip the 4M sodium hydroxide solution again to pH7.5 after stirring 4h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is less than 1% at 40 ℃ of freeze dryings to moisture content, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation absorbent particles

Arsenic-removing adsorption agent powder and binding agent inorganic silicon colloidal sol joined in the colter mixer mix, absorbent powder is all soaked into by glue, make mixed material, wherein, dioxide-containing silica is 25% in the inorganic silicon colloidal sol, pH value 6, viscosity 20mPa.s, average grain diameter 10-20nm, stabilizing agent Na ₂O content 0.05%, the mass ratio of absorbent powder and inorganic silicon colloidal sol is 1: 1.1;

Dioxide-containing silica is not limited to 25% in the Ludox, and dioxide-containing silica is 25-40%, pH value 6-8, viscosity 5-35mPa.s, average grain diameter 5-30nm, stabilizing agent Na ₂The Ludox of O content≤0.40% all is applicable to the present invention.

With the wet stock of mixing after kneading machine is mediated 15 minutes; send in the double-screw extruding pelletizing machine; be to extrude under the pressure effect of 8MPa at relative pressure; cut off, granulate; then under the effect of spheronizator, make sphere; 80 ℃ of down oven dry, obtain moisture content and be 2% arsenic-removing adsorption agent finished granule, the capability and performance index testing result of finished product sees Table 1.

Make particle and be used to handle the water that contains arsenic, the arsenic initial concentration is 0.5mg/L in the water, particle throwing amount is 2g/L, and pH=7.0 ± 0.1 condition following time, recording its adsorbance to arsenic is 0.24mg/g (being the arsenic of this composite metal oxidate arsenic removal adsorbents adsorb of every gram 0.24mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the arsenic initial concentration respectively is that this particle is to the adsorbance of arsenic in the 1-50mg/L scope, and obtaining its saturated extent of adsorption to arsenic through the mathematics The Fitting Calculation is 18mg/g.

Embodiment 5

1, the cubic sulfate lepidocrocite powder of preparation

With ferric sulfate, potassium sulfate is Fe in molar ratio ³⁺: SO4 ^2-=4: 1 ratio is dissolved in the aqueous solution, at 30 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.4M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 2M sodium hydroxide solution fast, be 4.0 until the pH of solution value; Slowly drip the 2M sodium hydroxide solution again to pH9.5 after stirring 4h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is less than 1% at 40 ℃ of freeze dryings to moisture content, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation absorbent particles

High polymer binder is for being organic silica gel (1750), and room temperature curing type does not add metal salt of organic carboxylic acid and makes curing catalysts.

Organic silica gel is not limited to organic silica gel (1750), other room temperature vulcanized silicone rubbers, and viscosity is that the organic silica gel of 200-1000mPas all is applicable to the present invention.

3, preparation absorbent particles

Arsenic-removing adsorption agent powder and binding agent organic silica gel (1750) joined in the colter mixer mix, make all bonded dose of infiltrations of powder, make mixed material, wherein the mass ratio of absorbent powder and binding agent is 1: 1;

With the wet stock that mixes after kneading machine is mediated 10 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure effect of 8MPa at relative pressure; cut off, granulate; then under the effect of spheronizator, make sphere; at 65 ℃ of oven dry 10h, obtaining moisture content through 80 ℃ of oven dry again is 3% arsenic-removing adsorption agent finished granule then, and the capability and performance index testing result of finished product sees Table 1.

Make particle and be used to handle the water that contains arsenic, the arsenic initial concentration is 0.5mg/L in the water, particle throwing amount is 2g/L, and pH=7.0 ± 0.1 condition following time, recording its adsorbance to arsenic is 0.24mg/g (being the arsenic of this composite metal oxidate arsenic removal adsorbents adsorb of every gram 0.24mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the arsenic initial concentration respectively is that this particle is to the adsorbance of arsenic in the 1-50mg/L scope, and obtaining its saturated extent of adsorption to arsenic through the mathematics The Fitting Calculation is 19mg/g.

Embodiment 6

1, the cubic sulfate lepidocrocite powder of preparation

With ferric trichloride, potassium sulfate is Fe in molar ratio ³⁺: SO4 ^2-=3: 1 ratio is dissolved in the aqueous solution, at 10 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.4M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 2M sodium carbonate liquor fast, be 4.0 until the pH of solution value; Slowly drip the 2M sodium carbonate liquor again to pH8.5 after stirring 12h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is less than 1% at 40 ℃ of freeze dryings to moisture content, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation high polymer binder

In obturator, be under the 200rpm in stir speed (S.S.), Kynoar is dissolved among the DMF, leave standstill and remove bubble, make mass percent concentration and be 16% Kynoar glue, the molecular weight of Kynoar is 130-170k.

The mass percent concentration of Kynoar glue is not limited to 16%, and concentration is that the Kynoar glue of 3-18% all is applicable to the present invention.

3, preparation absorbent particles

Arsenic-removing adsorption agent powder and binding agent Kynoar glue joined in the colter mixer mix, absorbent powder is all soaked into by glue, make mixed material, wherein the mass ratio of absorbent powder and glue is 1: 0.9;

With the wet stock that mixes after kneading machine is mediated 15 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure effect of 6MPa at relative pressure; cut off, granulate; then under the effect of spheronizator, make sphere; at 65 ℃ of oven dry 4h, obtaining moisture content through 80 ℃ of oven dry again is 3% arsenic-removing adsorption agent finished granule then, and the capability and performance index testing result of finished product sees Table 1.

Embodiment 7

1, the cubic sulfate lepidocrocite powder of preparation

With ferric nitrate, potassium sulfate is Fe in molar ratio ³⁺: SO4 ^2-=4: 1 ratio is dissolved in the aqueous solution, at 30 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.31M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 6M sodium hydroxide solution fast, be 4.0 until the pH of solution value; Slowly drip the 6M sodium hydroxide solution again to pH8.0 after stirring 10h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is less than 1% at 40 ℃ of freeze dryings to moisture content, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation high polymer binder

In obturator, be under the 150rpm in stir speed (S.S.), the polyvinyl butyral powder end is dissolved in the ethanol, leave standstill and remove bubble, make mass percent concentration and be 15% butvar adhesive liquid, wherein, the molecular weight of polyvinyl butyral resin is 130-175k.

The mass percent concentration of butvar adhesive liquid is not limited to 15%, and concentration is that the butvar adhesive liquid of 1-25% all is applicable to the present invention.

3, preparation absorbent particles

Arsenic-removing adsorption agent powder and binding agent butvar adhesive liquid joined in the colter mixer mix, absorbent powder is all soaked into by glue, make mixed material, wherein the mass ratio of absorbent powder and butvar adhesive liquid is 1: 0.8;

With the wet stock that mixes after kneading machine is mediated 3 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure of 10MPa at relative pressure; cut off, granulate; then at 65 ℃ of oven dry 4h; obtaining moisture content through 80 ℃ of oven dry again is 2% arsenic-removing adsorption agent finished granule, and the length of finished product is 3-5mm, and capability and performance index testing result sees Table 1.

Make particle and be used to handle the water that contains arsenic, the arsenic initial concentration is 0.5mg/L in the water, particle throwing amount is 2g/L, and pH=7.0 ± 0.1 condition following time, recording its adsorbance to arsenic is 0.24mg/g (being the arsenic of this composite metal oxidate arsenic removal adsorbents adsorb of every gram 0.24mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the arsenic initial concentration respectively is that this particle is to the adsorbance of arsenic in the 1-50mg/L scope, and obtaining its saturated extent of adsorption to arsenic through the mathematics The Fitting Calculation is 23mg/g.

Embodiment 8

1, the cubic sulfate lepidocrocite powder of preparation

With ferric nitrate, potassium sulfate is Fe in molar ratio ³⁺: SO4 ^2-=4: 1 ratio is dissolved in the aqueous solution, at 20 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.4M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 2M sodium bicarbonate solution fast, be 4.0 until the pH of solution value; Slowly drip the 2M sodium bicarbonate solution again to pH8.0 after stirring 12h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is less than 1% at 40 ℃ of freeze dryings to moisture content, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation high polymer binder

In obturator, be under the condition of 140rpm in stir speed (S.S.), the polyvinyl butyral powder end is dissolved in the ethanol, leave standstill bubble, make mass percent concentration and be 5% butvar adhesive liquid, wherein, the molecular weight of polyvinyl butyral resin is 130-175k.

The mass percent concentration of polyvinyl butyral resin is not limited to 5%, and concentration is that the butvar adhesive liquid of 1-25% all is applicable to the present invention.

3, preparation absorbent particles

With the wet stock that mixes after kneading machine is mediated 3 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure of 8MPa at relative pressure; cut off, granulate; obtaining moisture content 80 ℃ of oven dry then is 2% arsenic-removing adsorption agent finished granule; the length of finished product is 5-7mm, and capability and performance index testing result sees Table 1.

Make particle and be used to handle the water that contains arsenic, the arsenic initial concentration is 0.5mg/L in the water, particle throwing amount is 1g/L, and pH=7.0 ± 0.1 condition following time, recording its adsorbance to arsenic is 0.24mg/g (being the arsenic of this composite metal oxidate arsenic removal adsorbents adsorb of every gram 0.24mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the arsenic initial concentration respectively is that this particle is to the adsorbance of arsenic in the 1-50mg/L scope, and obtaining its saturated extent of adsorption to arsenic through the mathematics The Fitting Calculation is 24mg/g.

Embodiment 9

1, the cubic sulfate lepidocrocite powder of preparation

With ferric trichloride, sodium sulphate is Fe in molar ratio ³⁺: SO4 ^2-=3.5: 1 ratio is dissolved in the aqueous solution, at 20 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.35M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 6M ammonia spirit fast, be 4.0 until the pH of solution value; Slowly drip the 6M ammonia spirit again to pH8.0 after stirring 12h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is less than 1% at 40 ℃ of freeze dryings to moisture content, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation high polymer binder

In obturator, be under the condition of 160rpm in stir speed (S.S.), Kynoar is dissolved among the DMF, leave standstill bubble, make mass percent concentration and be 5% Kynoar glue, the molecular weight of Kynoar is 130-170k.

The mass percent concentration of Kynoar glue is not limited to 5%, and concentration is that the Kynoar glue of 3-18% all is applicable to the present invention.

3, preparation absorbent particles

Arsenic-removing adsorption agent powder and binding agent Kynoar glue joined in the colter mixer mix, absorbent powder is all soaked into by glue, make mixed material, wherein, the mass ratio of absorbent powder and Kynoar glue is 1: 0.9;

With the wet stock that mixes after kneading machine is mediated 3 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure effect of 6MPa at relative pressure; cut off, granulate; then under the effect of spheronizator, make sphere; at 65 ℃ of oven dry 4h, obtaining moisture content through 80 ℃ of oven dry again is 2% arsenic-removing adsorption agent finished granule then, and the capability and performance index testing result of finished product sees Table 1.

Make particle and be used to handle the water that contains arsenic, the arsenic initial concentration is 0.5mg/L in the water, particle throwing amount is 1g/L, and pH=7.0 ± 0.1 condition following time, recording its adsorbance to arsenic is 0.24mg/g (being the arsenic of this composite metal oxidate arsenic removal adsorbents adsorb of every gram 0.24mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the arsenic initial concentration respectively is that this particle is to the adsorbance of arsenic in the 1-50mg/L scope, and obtaining its saturated extent of adsorption to arsenic through the mathematics The Fitting Calculation is 20mg/g.

Embodiment 10

1, the cubic sulfate lepidocrocite powder of preparation

With ferric nitrate, sodium sulphate is Fe in molar ratio ³⁺: SO4 ^2-=3.5: 1 ratio is dissolved in the aqueous solution, at 20 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.55M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 6M ammonia spirit fast, be 4.0 until the pH of solution value; Slowly drip the 6M ammonia spirit again to pH8.0 after stirring 12h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is less than 1% at 40 ℃ of freeze dryings to moisture content, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation high polymer binder

In closed container, be under the condition of 150rpm in stir speed (S.S.), the polyvinyl formal powder is dissolved in the ethanol, leave standstill bubble, make mass percent concentration and be 2% formaldehyde polyvinyl acetal liquid, wherein, the molecular weight of polyvinyl formal is 100-150k.

Formaldehyde polyvinyl acetal liquid mass percent concentration is not limited to 2%, and concentration is that the formaldehyde polyvinyl acetal liquid of 1-25% all is applicable to the present invention.

3, preparation absorbent particles

Sulfate lepidocrocite arsenic-removing adsorption agent powder and binding agent formaldehyde polyvinyl acetal liquid joined in the colter mixer mix, absorbent powder is all soaked into by glue, make mixed material, wherein absorbent powder is 1: 1.5 with the ratio of the quality of binding agent

With the wet stock that mixes after kneading machine is mediated 5 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure effect of 10MPa at relative pressure; cut off, granulate; obtaining moisture content 80 ℃ of oven dry then is 2% arsenic-removing adsorption agent finished granule; the length of finished product is 3-5mm, and capability and performance index testing result sees Table 1.

Embodiment 11

1, the cubic sulfate lepidocrocite powder of preparation

With ferric nitrate, potassium sulfate is Fe in molar ratio ³⁺: SO4 ^2-=4: 1 ratio is dissolved in the aqueous solution, at 20 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.45M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 6M sodium hydroxide solution fast, be 4.0 until the pH of solution value; Slowly drip the 6M sodium hydroxide solution again to pH9.0 after stirring 12h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is less than 1% at 40 ℃ of freeze dryings to moisture content, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation high polymer binder

Under 95 ℃, with polyvinyl alcohol (1799) water-soluble after, adding little carboxylic acids acrylic acid stirs, carry out esterification, make the polyvinyl alcohol acrylate adhesives, wherein, esterification reaction temperature is 100 ℃, reaction time is 60min, and polyvinyl alcohol (1799) is 25: 100 with the ratio of the weight of water, and polyvinyl alcohol (1799) is 100: 25 with the ratio of acrylic acid weight.

Polyvinyl alcohol is not limited to polyvinyl alcohol (1799), and other degree of polymerization are 1700-2600, and the polyvinyl alcohol of alcoholysis degree＞95% all is applicable to the present invention; Little carboxylic acids is not limited to acrylic acid, and other all are applicable to the present invention as maleic acid, succinic acid, malonic acid, ethanedioic acid, citric acid; The temperature of esterification is not limited to 100 ℃, and the reaction time is not limited to 60min, and reaction temperature is at 40-100 ℃, and the reaction time all is applicable to the present invention at 30-300min.

Polyvinyl alcohol was not limited to 25: 100 with the ratio of the weight of water, polyvinyl alcohol was not limited to 100: 25 with the ratio of acrylic acid weight, polyvinyl alcohol is 2-25 with the ratio of the weight of water: 100, and polyvinyl alcohol is 100 with the ratio of the weight of little carboxylic acids: 2-25 all is applicable to the present invention.

3, preparation absorbent particles

Cubic sulfate lepidocrocite powder and polyvinyl alcohol acrylate adhesives joined in the colter mixer mix, make all bonded dose of infiltrations of absorbent powder, make mixed material, wherein absorbent powder is 1: 0.5 with the ratio of the quality of polyvinyl alcohol acrylate adhesives;

With the wet stock that mixes after kneading machine is mediated 3 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure effect of 15MPa at relative pressure; cut off, granulate; obtaining moisture content 80 ℃ of oven dry then is 3% arsenic-removing adsorption agent finished granule, and the capability and performance index testing result of finished product sees Table 1.

Make particle and be used to handle the water that contains arsenic, the arsenic initial concentration is 0.5mg/L in the water, particle throwing amount is 1g/L, and pH=7.0 ± 0.1 condition following time, recording its adsorbance to arsenic is that 0.25mg/g (is this composite metal oxidate arsenic removal adsorbents adsorb of every gram 0.25mg (arsenic).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the arsenic initial concentration respectively is that this particle is to the adsorbance of arsenic in the 1-50mg/L scope, and obtaining its saturated extent of adsorption to arsenic through the mathematics The Fitting Calculation is 24mg/g.

Embodiment 12

1, the cubic sulfate lepidocrocite powder of preparation

With chlorination three-iron, potassium sulfate is Fe in molar ratio ³⁺: SO4 ^2-=3: 1 ratio is dissolved in the aqueous solution, at 25 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.40M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 2M potassium hydroxide solution fast, be 4.0 until the pH of solution value; Slowly drip the 2M potassium hydroxide solution again to pH9.0 after stirring 12h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is less than 1% at 40 ℃ of freeze dryings to moisture content, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation high polymer binder

Under 95 ℃ with polyvinyl alcohol (2499) water-soluble after, adding little carboxylic acids ethanedioic acid stirs, carry out esterification, make polyvinyl alcohol ethanedioic acid ester binding agent, wherein, esterification reaction temperature is 40 ℃, and the reaction time is 30min, polyvinyl alcohol (2499) is 15: 100 with the ratio of the weight of water, and polyvinyl alcohol (2499) is 100: 2 with the ratio of the weight of ethanedioic acid.

Polyvinyl alcohol is not limited to polyvinyl alcohol (2499), and other degree of polymerization are 1700-2600, and the polyvinyl alcohol of alcoholysis degree＞95% all is applicable to the present invention; Little carboxylic acids is not limited to ethanedioic acid, and other all are applicable to the present invention as maleic acid, succinic acid, malonic acid, citric acid, acrylic acid; The temperature of esterification is not limited to 40 ℃, and the reaction time is not limited to 30min, and reaction temperature is at 40-100 ℃, and the reaction time all is applicable to the present invention at 30-300min.

Polyvinyl alcohol was not limited to 15: 100 with the ratio of the weight of water, polyvinyl alcohol was not limited to 100: 2 with the ratio of acrylic acid weight, polyvinyl alcohol is 2-25 with the ratio of the weight of water: 100, and polyvinyl alcohol is 100 with the ratio of the weight of little carboxylic acids: 2-25 all is applicable to the present invention.

3, preparation absorbent particles

Cubic sulfate lepidocrocite powder and polyvinyl alcohol ethanedioic acid ester binding agent joined in the colter mixer mix, make all bonded dose of infiltrations of absorbent powder, make mixed material, wherein absorbent powder is 1: 1.5 with the ratio of the quality of polyvinyl alcohol ethanedioic acid ester binding agent.

With the wet stock that mixes after kneading machine is mediated 2 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure of 15MPa at relative pressure; cut off, granulate; obtaining moisture content 65 ℃ of oven dry then is 3% arsenic-removing adsorption agent finished granule, and the capability and performance index testing result of finished product sees Table 1.

Make particle and be used to handle the water that contains arsenic, the arsenic initial concentration is 0.5mg/L in the water, particle throwing amount is 1g/L, and pH=7.0 ± 0.1 condition following time, recording its adsorbance to arsenic is 0.23mg/g (being the arsenic of this composite metal oxidate arsenic removal adsorbents adsorb of every gram 0.23mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the arsenic initial concentration respectively is that this particle is to the adsorbance of arsenic in the 1-50mg/L scope, and obtaining its saturated extent of adsorption to arsenic through the mathematics The Fitting Calculation is 18mg/g.

Embodiment 13

1, the cubic sulfate lepidocrocite powder of preparation

With chlorination three-iron, sodium sulphate is Fe in molar ratio ³⁺: SO4 ^2-=3.5: 1 ratio is dissolved in the aqueous solution, at 25 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.31M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 2M potassium hydroxide solution fast, be 4.0 until the pH of solution value; Slowly drip the 2M potassium hydroxide solution again to pH9.0 after stirring 12h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is less than 1% at 40 ℃ of freeze dryings to moisture content, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation high polymer binder

In closed container, in stir speed (S.S.) is under the condition of 150rpm, and polyvinyl alcohol is contracted the glutaraldehyde powder dissolution in ethanol, leaves standstill bubble, make mass percent concentration and be 25% the polyvinyl alcohol glutaraldehyde glue that contracts, the molecular weight of polyvinyl alcohol glutaraldehyde is 130-200k.

The contract mass percent concentration of glutaraldehyde glue of polyvinyl alcohol is not limited to 25%, and concentration is that the polyvinyl alcohol of the 1-25% glutaraldehyde glue that contracts all is applicable to the present invention.

3, preparation absorbent particles

Cubic sulfate lepidocrocite arsenic-removing adsorption agent powder and the binding agent polyvinyl alcohol glutaraldehyde glue that contracts is joined in the colter mixer and mixes, absorbent powder is all soaked into by glue, make mixed material, wherein absorbent powder is 1: 0.7 with the ratio of the quality of binding agent

With the wet stock that mixes after kneading machine is mediated 3 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure effect of 10MPa at relative pressure; cut off, granulate; obtaining moisture content 80 ℃ of oven dry then is 2% arsenic-removing adsorption agent finished granule, and the capability and performance index testing result of finished product sees Table 1.

Make particle and be used to handle the water that contains arsenic, the arsenic initial concentration is 0.5mg/L in the water, particle throwing amount is 1g/L, and pH=7.0 ± 0.1 condition following time, recording its adsorbance to arsenic is 0.25mg/g (being the arsenic of this composite metal oxidate arsenic removal adsorbents adsorb of every gram 0.25mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the arsenic initial concentration respectively is that this particle is to the adsorbance of arsenic in the 1-50mg/L scope, and obtaining its saturated extent of adsorption to arsenic through the mathematics The Fitting Calculation is 24mg/g.

Embodiment 14

1, the cubic sulfate lepidocrocite powder of preparation

With chlorination three-iron, sodium sulphate is Fe in molar ratio ³⁺: SO4 ^2-=3.0: 1 ratio is dissolved in the aqueous solution, at 25 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.4M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 2M potassium hydroxide solution fast, be 4.0 until the pH of solution value; Slowly drip the 2M potassium hydroxide solution again to pH9.0 after stirring 12h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is less than 1% at 40 ℃ of freeze dryings to moisture content, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation high polymer binder

High polymer binder is organic silica gel (1750), the room temperature curing type sulphurated siliastic, and viscosity 600mPas does not add metal salt of organic carboxylic acid and makes curing catalysts.

3, preparation absorbent particles

Composite metal oxide powder and binding agent organic silica gel (1750) joined in the colter mixer mix, make all bonded dose of infiltrations of absorbent powder, make mixed material, wherein absorbent powder is 1: 1.5 with the ratio of the quality of binding agent;

With the wet stock that mixes after kneading machine is mediated 5 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure of 15MPa at relative pressure; cut off, granulate; then at 65 ℃ of oven dry 10h; again through 80 ℃ of oven dry, obtain moisture content and be 2% arsenic-removing adsorption agent finished granule, end product quality performance indications testing result sees Table 1.

Make particle and be used to handle the water that contains arsenic, the arsenic initial concentration is 0.5mg/L in the water, particle throwing amount is 1g/L, and pH=7.0 ± 0.1 condition following time, recording its adsorbance to arsenic is 0.22mg/g (being the arsenic of this composite metal oxidate arsenic removal adsorbents adsorb of every gram 0.22mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the arsenic initial concentration respectively is that this particle is to the adsorbance of arsenic in the 1-50mg/L scope, and obtaining its saturated extent of adsorption to arsenic through the mathematics The Fitting Calculation is 16mg/g.

Embodiment 15

1, the cubic sulfate lepidocrocite powder of preparation

With ferric nitrate, sodium sulphate is Fe in molar ratio ³⁺: SO4 ^2-=3.0: 1 ratio is dissolved in the aqueous solution, at 25 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.5M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 2M potassium hydroxide solution fast, be 4.0 until the pH of solution value; Slowly drip the 2M potassium hydroxide solution again to pH9.5 after stirring 12h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is less than 1% at 40 ℃ of freeze dryings to moisture content, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation absorbent particles

Composition metal lead oxide powder and adhesive silicon sol joined be mixed to absorbent powder in the colter mixer and all soaked into, make mixed material, wherein by glue, dioxide-containing silica is 40% in the Ludox, pH value 7, viscosity 30mPas, average grain diameter 10-20nm, stabilizing agent Na ₂The mass ratio of O content 0.10% absorbent powder and inorganic silicon colloidal sol is 1: 1.2.

Dioxide-containing silica is not limited to 40% in the Ludox, and dioxide-containing silica is 25-40%, pH value 6-8, viscosity 5-35mPa.s, average grain diameter 5-30nm, stabilizing agent Na ₂The Ludox of O content≤0.40% all is applicable to the present invention.

With the wet stock that mixes after kneading machine is mediated 5 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure effect of 8MPa at relative pressure; cut off, granulate; then under the effect of spheronizator, make spheric granules; then 100 ℃ of oven dry, obtain moisture content and be 2% arsenic-removing adsorption agent finished granule, the capability and performance index testing result of finished product sees Table 1.

Make particle and be used to handle the water that contains arsenic, the arsenic initial concentration is 0.5mg/L in the water, particle throwing amount is 1g/L, and pH=7.0 ± 0.1 condition following time, recording its adsorbance to arsenic is 0.20mg/g (being the arsenic of this composite metal oxidate arsenic removal adsorbents adsorb of every gram 0.20mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the arsenic initial concentration respectively is that this particle is to the adsorbance of arsenic in the 1-50mg/L scope, and obtaining its saturated extent of adsorption to arsenic through the mathematics The Fitting Calculation is 18mg/g.

Embodiment 16

1, the cubic sulfate lepidocrocite powder of preparation

With ferric nitrate, sodium sulphate is Fe in molar ratio ³⁺: SO4 ^2-=4.0: 1 ratio is dissolved in the aqueous solution, at 25 ℃, and stirring and evenly mixing, wherein, iron concentration is 0.5M in the mixed liquor; Under condition of stirring, in above-mentioned mixed liquor, drip the 6M potassium hydroxide solution fast, be 4.0 until the pH of solution value; Slowly drip the 6M potassium hydroxide solution again to pH9.5 after stirring 12h, stop then stirring, leave standstill 24h; Solution centrifugal after leaving standstill is separated, spends the solid of deionised water after centrifugal then, until water outlet pH near neutral, and the SO in the water outlet ₄ ^2-Can not detect with chromatography of ions; Product after the washing is less than 1% at 40 ℃ of freeze dryings to moisture content, grinds to make cubic sulfate lepidocrocite arsenic-removing adsorption agent powder.

2, preparation absorbent particles

To mix in arsenic-removing adsorption agent powder and the binding agent polyacrylate dispersion adding colter mixer, make mixed material, wherein, the solid content of polyacrylate dispersion is 52%, mass percent concentration is 15%, viscosity 600mPas, pH value 6.5, the mass ratio of absorbent powder and emulsion is 1: 1.4.

Polyacrylate dispersion is not limited to above-mentioned emulsion, other solid contents 〉=52%, and concentration is 4-25%, viscosity 500-1000mPa.s, the polyacrylate dispersion of pH value 5.0-7.5 all is applicable to the present invention.

With the wet stock that mixes after the pressure-type kneading machine is mediated 3 minutes; send into the double-screw extruding pelletizing machine; be after extruding under the pressure effect of 2MPa at relative pressure; cut off, granulate; then under the effect of spheronizator, make sphere; obtaining moisture content 65 ℃ of oven dry then is 2% arsenic-removing adsorption agent finished granule, and the capability and performance index testing result of finished product sees Table 1.

Make particle and be used to handle the water that contains arsenic, the arsenic initial concentration is 0.5mg/L in the water, particle throwing amount is 1g/L, and pH=7.0 ± 0.1 condition following time, recording its adsorbance to arsenic is 0.22mg/g (being the arsenic of this composite metal oxidate arsenic removal adsorbents adsorb of every gram 0.22mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the arsenic initial concentration respectively is that this particle is to the adsorbance of arsenic in the 1-50mg/L scope, and obtaining its saturated extent of adsorption to arsenic through the mathematics The Fitting Calculation is 18mg/g.

Table 1 arsenic removal particle performance test results

	Moisture content (%)	Diameter (mm)	Dry state compressive strength (N)	Loss late (%)	Specific area (m ²/g)	Pore volume (mL/g)
							Embodiment 1	2	1.5	32	＜1	24	0.040
Embodiment 2	2	2.0	30	＜1	13	0.025
							Embodiment 3	2	2.0	33	＜1	22	0.040
Embodiment 4	2	1.8	28	＜2	13	0.020
							Embodiment 5	3	1.8	35	＜2	22	0.036
Embodiment 6	3	1.5	25	＜1	20	0.037
							Embodiment 7	2	1.6	27	＜1	23	0.040
Embodiment 8	2	0.7	30	＜1	20	0.040
							Embodiment 9	2	1.6	33	＜1	20	0.040
Embodiment 10	2	1.8	30	＜1	13	0.025
							Embodiment 11	3	1.8	29	＜1	25	0.045
Embodiment 12	3	1.5	33	＜1	22	0.040
							Embodiment 13	2	1.6	30	＜1	15	0.030
Embodiment 14	2	0.7	36	＜2	20	0.031
							Embodiment 15	2	1.8	25	＜2	16	0.027
Embodiment 16	2	1.6	36	＜1	22	0.035

Claims

1. an arsenic-removing adsorption agent is characterized in that containing cubic sulfate lepidocrocite and binding agent.

2. adsorbent as claimed in claim 1 is characterized in that the weight portion proportioning of described cubic sulfate lepidocrocite and binding agent is 1: 0.5-1.5.

3. adsorbent as claimed in claim 1 or 2 is characterized in that described binding agent selects one or more in polyacrylate dispersion, JSF liquid, polyvinyl alcohol ester glue, Kynoar glue, inorganic silicon colloidal sol, the organic silica gel.

4. adsorbent as claimed in claim 3 is characterized in that described JSF liquid is that Pioloform, polyvinyl acetal is dissolved in ethanol and forms.

5. adsorbent as claimed in claim 3 is characterized in that described polyvinyl alcohol ester glue is that polyvinyl alcohol and little carboxylic acids are carried out esterification and formed.

6. adsorbent as claimed in claim 1 or 2 is characterized in that described cubic sulfate lepidocrocite makes according to following steps:

1), under stirring condition, be 3-4 in the mol ratio of contained iron ion and sulfate ion with molysite and sulfate at 10-50 ℃: 1 ratio, generation mixed liquor soluble in water, wherein the concentration of iron ion is 0.31-0.55M in the mixed liquor;

3) with step 2) solution centrifugal that makes separates, and spends the deionised water solid, is neutrality and chromatography of ions detects the sulfate radical-free ion until cleaning solution pH, and the product after the washing is drying to obtain.

7. the preparation method of an arsenic-removing adsorption agent comprises and carries out pelletization treatment and dry the processing successively after evenly with cubic sulfate lepidocrocite and binding agent are mixed that wherein, the weight portion proportioning of described cubic sulfate lepidocrocite and binding agent is 1: 0.5-1.5.

8. preparation method as claimed in claim 7 is characterized in that described binding agent selects one or more in polyacrylate dispersion, JSF liquid, polyvinyl alcohol ester glue, Kynoar glue, inorganic silicon colloidal sol, the organic silica gel.

9. as claim 7 or 8 described preparation methods, it is characterized in that described pelletization treatment carries out according to following steps:

A) cubic sulfate lepidocrocite and binding agent are mixed mixed material;

B) mixed material through comminutor extrude, segment, make particle.

10. as claim 7 or 8 described preparation methods, it is characterized in that described cubic sulfate lepidocrocite makes according to following steps:

1) at 10-50 ℃, stir on the limit, and the limit is 3-4 with molysite and sulfate in the mol ratio of contained iron ion and sulfate ion: 1 ratio, and generation mixed liquor soluble in water, wherein the concentration of iron ion is 0.31-0.55M in the mixed liquor;