CN102114402A - Defluorinating adsorbent and preparation method thereof - Google Patents
Defluorinating adsorbent and preparation method thereof Download PDFInfo
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- CN102114402A CN102114402A CN2009102443319A CN200910244331A CN102114402A CN 102114402 A CN102114402 A CN 102114402A CN 2009102443319 A CN2009102443319 A CN 2009102443319A CN 200910244331 A CN200910244331 A CN 200910244331A CN 102114402 A CN102114402 A CN 102114402A
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Abstract
The invention provides a defluorinating adsorbent for drinking water, which is a composite metal oxide defluorinating adsorbent and a high polymer material playing a role of adhering absorbent particles. Absorbent powder and a high polymer binder are mixed, extruded, cut and dried to prepare into particles. The defluorinating adsorbent has the characteristics of good ion selectivity, high adsorption capacity, better strength in both dry and wet states, and no crushing or dissolving after being used for a long time.
Description
Technical field
The present invention relates to a kind of preparation method of solid sorbent compositions, particularly a kind of preparation method who is used for the de-fluoridation adsorbent of drinking water metal oxide.
Background technology
Fluorine is one of trace element of needed by human, and an amount of fluorine (0.5-1.0mg/L) can strengthen the robustness of bone, and certain carious tooth effect of preventing and treating is arranged.The fluorine of taking in too much can damage health again, causes fluorine poisoning, causes fluorine dental plaque and fluorosis of bone; Serious caused human body pain in low back and legs, anchylosis, hunchback even paraplegia; Also can cause the thyroid function imbalance, renal dysfunction etc.
Fluorine poisoning is one of the endemic disease the most widely that distributes in the world, comprises that in the world all there is the sick existence of fluorine in a plurality of countries of China.The source of human body fluorine mainly obtains by drinking-water and food.Investigation statistics shows that the incidence of disease of fluorinated volume and fluorine disease is proportionate in the drinking-water.Therefore, always there is clear and definite standard in country to the limit value of the fluorine concentration in the drinking water, regulation in the drinking water sanitary standard (GB5479-2006) of new promulgation in 2006, the limit value of fluorine concentration is 1mg/L in the Drinking Water, and the limit value of fluorine concentration is 1.2mg/L in small-sized centralized water supply and the water dispersion type water quality index.
In China, it is one of major issue that influences drinking water of rural area safety that high fluorine, high arsenic etc. have a strong impact on healthy quality problem, and the Eleventh Five-Year Plan period, under the promotion energetically and financial support of government, China's drinking water of rural area safety engineering construction is carried out comprehensively.At present main method is still playing new well and water transfer modify-water, but is subjected to condition restriction such as water-bearing layer geological conditions and underground water storage level.
Therefore, some select to adopt the absorption method defluorination in the villages and small towns of central water supply on a small scale.The domestic de-fluoridation adsorbent that generally adopts has zeolite, activated alumina, bone black etc., and these adsorbents not only adsorption capacity are low, and life cycle is short, and regeneration is frequent, and also has other shortcoming, and is low as zeolite regeneration efficient; Activated alumina exists in when using under pH slant acidity (4.5-5.5) condition, and aluminium ion is easy to stripping, and granule strength is low, and long period of soaking is used shortcomings such as easy fragmentation.The commodity adsorbent READ-that abroad promotes the use of
At pH the good adsorption performance is arranged about 3, and repeated regeneration, but because of its narrow application range, need under low ph condition, use, causing complicated operation, cost is too high, is not suitable for using in the vast rural area of China.So, press for the high fluorine high-arsenic underground water of sorbent treatment that efficient, safety, cost are lower, can repeatedly regenerate, use for a long time, guarantee safe drinking water.
Aspect de-fluoridation adsorbent research, develop the compound adsorbent of making by polyvalent metal (hydration) oxides such as aluminium, magnesium, iron, zirconium and rare earths in recent years, because of its unique surface nature and design feature, it is big that the more traditional sorbing material of fluorine such as activated alumina, bone black etc. are had adsorption capacity, the adsorption efficiency advantages of higher.
For example, publication number is that the application for a patent for invention of CN101428208A discloses a kind of preparation method who removes the sorbing material of excessive fluoride in the drinking-water.This sorbing material is a raw material with natural seabed iron-manganese concretion, uses ferric trichloride modifiedly after the pulverizing again, makes ferric ion (Fe
3+) and hydroxide be adsorbed on the iron-manganese concretion promptly, this material is at 20 ℃, defluorination is more than 90% under the pH=5-7 condition.But this material belongs to the support type granule adsorbent, and material active component in use comes off easily, and stability of material is poor.
Publication number is that the application for a patent for invention of CN101507911A discloses a kind of defluorination absorbing material and preparation method based on aluminium base composite oxides, and this defluorination absorbing material comprises active component and porous load matrix two parts; Wherein active component is the aluminium base composite oxides that is prepared from through chemical reaction by aluminum salt solution and inorganic alkali solution, aluminium base composite oxides loads on porous load matrix surface by the method for original position load, and the mass ratio of aluminium base composite oxides and porous load matrix is 0.25～25: 100.The defluorination absorbing material of preparation can be used for fluorine contaminant in the water, the especially absorption of common fluorine in the underground drinking water source.Exist in when using under the slant acidity condition the easy stripping of aluminium ion, defective such as granule strength is low but contain aluminium oxide in this sorbing material.
And for example, the Chinese patent of Yang Min, Wu Xiaomei, Zhang Yu, the little quick application of beans " a kind of composite oxides de-fluoridation adsorbent " (patent No. ZL200510116751.0) discloses a kind of composite metal oxide de-fluoridation adsorbent and preparation side thereof, and this de-fluoridation adsorbent contains transition metal, Al and rare earth metal; The mol ratio of transition metal, Al and rare earth metal is 0.5-1.5: 2-6: 0.5-1.5; Transition metal is Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn; Rare earth metal is Ce or La; The preparation method comprises: will contain the compound of transition metal thing, aluminium and rare earth metal, and be dissolved into the aqueous solution by above-mentioned mol ratio; Dripping aqueous slkali in above-mentioned solution, to make pH value of solution be 9.0-9.5, leaves standstill; Separate with the deionized water centrifuge washing, be neutral to water outlet pH; The washing afterproduct is dried to constant weight, forms through roasting, grinding.This composite metal oxide de-fluoridation adsorbent under neutrallty condition to the saturated extent of adsorption of fluorine sorbing material up to 179mg/g.But this adsorbent is pulverous nanometer materials, directly drops into and not only easily causes loss in the water, 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, there is big, the susceptible to plugging problem of the loss of flood peak in the former, and the latter impregnate layer then can occur and come off, and influences effluent quality.
Summary of the invention
The objective of the invention is provides a kind of preparation method of the de-fluoridation adsorbent particle that is used for drinking water and by the de-fluoridation adsorbent particle of this method preparation at the problem that above-mentioned prior art exists, the intensity height of the de-fluoridation adsorbent 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 drinking water defluorination adsorbent that is used for to comprise composite metal oxide and binding agent.
Wherein, the weight portion proportioning of composite metal oxide and binding agent is 1: 0.5-2.5 is preferably 1: 1-2.
Particularly, described binding agent is selected one or more in polyacrylate dispersion, JSF liquid, polyvinyl alcohol ester glue, Kynoar glue, Ludox, 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 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 the glue that forms in N, the dinethylformamide (DMF).
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, the pH value 6-8 of described Ludox, 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 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.
Particularly, to be dissolved in the mass percent concentration of the glue that ethanol forms be 2-20% to described polyvinyl formal; The mass percent concentration that described polyvinyl butyral resin is dissolved in the glue of ethanol formation is 1-25%; Described polyvinyl alcohol contracts, and to be dissolved in the mass percent concentration that ethanol forms glue be 2-25% to glutaraldehyde; The mass percent concentration that described polyethylene acetal is dissolved in the glue of ethanol formation is 2-25%; The described polyethylene mass percent concentration that methacrylaldehyde is dissolved in the glue that ethanol forms that contracts is 3-25%; The described polyethylene mass percent concentration that crotonaldehyde is dissolved in the glue that ethanol forms that contracts is 2-25%;
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, composite metal oxide contains transition metal, Al and rare earth metal, the mol ratio of described transition metal, Al and rare earth metal is 0.5-1.5: 2-6: 0.5-1.5, and described transition metal is Ti, V, Mn, Fe, Co, Ni, Cu or Zn, and described rare earth metal is Ce or La.
The present invention provides a kind of drinking water defluorination 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 composite metal oxide and binding agent are mixed, wherein, the weight portion proportioning of described composite metal oxide and binding agent is 1: 0.5-2.5.
Wherein, the weight portion proportion optimization of described composite metal oxide and binding agent is 1: 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 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 the glue that forms in N, the dinethylformamide (DMF).
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, 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%;
Especially, the molecular weight of described Pioloform, polyvinyl acetal is 90-200k.
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, the mass percent concentration that described polyvinyl formal is dissolved in ethanol formation is a 1-25% formaldehyde polyvinyl acetal liquid, and wherein, concentration is preferably 2-25%, more preferably 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 130-170k; 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.
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; 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) composite metal oxide and binding agent are mixed make mixed material;
B) mixed material through comminutor extrude, segment handles, and makes the material grain.
Particularly, the mixing steps A) is to place mixer to carry out described the mixing composite metal oxide and binding agent; Step B) relative pressure that comminutor described in is extruded in the processing procedure 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 de-fluoridation adsorbent 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 composite metal oxide contains transition metal, Al and rare earth metal; The mol ratio of described transition metal, Al and rare earth metal is 0.5-1.5: 2-6: 0.5-1.5; Described transition metal is Ti, V, Mn, Fe, Co, Ni, Cu or Zn; Described rare earth metal is Ce or La.
Particularly, described composite metal oxide is prepared from according to following steps:
1) compound that will contain transition metal, aluminium and rare earth metal is that the ratio of 0.5-1.5: 2-6: 0.5-1.5 is soluble in water in the mol ratio of transition metal, aluminium and rare earth metal, form the aqueous solution, and stir, wherein, the compound of described transition metal is nitrate, chloride or the sulfate that contains transition metal, and described transition metal is Ti, V, Mn, Fe, Co, Ni, Cu or Zn; The described compound that contains aluminium is aluminum sulfate, aluminum nitrate or aluminium chloride; The described compound that contains rare earth metal is cerium chloride, cerous nitrate, cerous sulfate, lanthanum chloride, lanthanum nitrate or lanthanum sulfate;
2) under stirring state, in the aqueous solution, add aqueous slkali, be 9.0-9.5 until the pH of solution, leave standstill the back and separate with the deionized water centrifuge washing, be neutral until water outlet pH;
3) product after the washing is dried to constant weight under 90-120 ℃, grinds after 250-500 ℃ of following roasting, promptly again.
Wherein, said aqueous slkali is NaOH, ammonia, sodium carbonate or sodium bicarbonate solution step 2).
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 (fluorine 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, defluorination adsorption particle saturated adsorption capacity is 28-45mg/g, especially for high fluorine groundwater as drinking water, though its fluorine concentration exceeds drinking water standard, but be not under the very high situation, Chang Gui activated alumina adsorbents need not to regulate under the condition of pH relatively also higher adsorption capacity;
3, the specific area of adsorbent of the present invention is big, and average specific surface area reaches 10-41m
2/ g, the pore volume height, average pore volume reaches 0.021-0.050mL/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 28N, and the adsorbent 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.
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 11 times of the latter under nearly neutrallty condition.
Description of drawings
Fig. 1 is to be the absorption property contrast figure of de-fluoridation adsorbent particle of the present invention and commercially available activated alumina particle under 7 the condition at pH
The specific embodiment
The composite metal oxide adsorbent powder that composite metal oxide de-fluoridation adsorbent of the present invention provides for Chinese patent ZL200510116751.0.
Embodiment 1
1, preparation composite metal oxide powder
With manganese nitrate, aluminum nitrate, cerous nitrate is Mn: Al: Ce=1 in molar ratio: 4: 1 the ratio formation aqueous solution soluble in water;
Under stirring state, in the above-mentioned aqueous solution, drip ammonia solution, be 9.5 until the pH of solution; Left standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 100 ℃, 400 ℃ of following roastings 2 hours, grind and make the composite metal oxide de-fluoridation adsorbent powder.
2, preparation absorbent particles
With mixing in de-fluoridation adsorbent powder and the binding agent polyacrylate dispersion adding colter mixer, make mixed material, wherein, the solid content of polyacrylate dispersion is 53%, and concentration is 10%, viscosity 800mPas, pH value 6.0, the mass ratio of absorbent powder and emulsion are 1: 1.4.
The polyacrylate dispersion that the present invention uses is not limited to above-mentioned emulsion, solid content 〉=52%, and concentration is 4-25%, viscosity 500-1000mPas, 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 effect of 2MPa at relative pressure; cut off, granulate; then make sphere under the effect of spheronizator (Yingge Granulating Covering Technology Co., Ltd., Chongqing), obtaining moisture content 65 ℃ of oven dry then is 2% de-fluoridation adsorbent finished granule, and the capability and performance index testing result of finished product is as shown in table 1.
Adopt granule strength analyzer (hemisphere (China), model: KC-2) measure defluorination particle compression failure intensity; Adopt ASAP Micromeritics (Macross, USA) specific surface analyzer mensuration absorbent particles specific area, pore volume;
Measure the mass loss rate of defluorination particle as follows:
An amount of defluorination 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 defluorination 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 fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, recording its adsorbance to fluorine is 4.0mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 4.0mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 39mg/g.
Embodiment 2
1, preparation composite metal oxide powder
With iron chloride, aluminum sulfate, lanthanum nitrate is Fe: Al: La=1 in molar ratio: 4: 1 ratio dissolving forms the aqueous solution, at room temperature, and stirring and evenly mixing;
Under stirring state, in the above-mentioned aqueous solution, drip sodium carbonate liquor, be 9.0 until the pH of solution, left standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 90 ℃, 500 ℃ of following roastings 3 hours, grind and make the composite metal oxide de-fluoridation adsorbent powder.
2, preparation high polymer binder
In closed container, 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
Composite metal oxide de-fluoridation adsorbent 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: 1.8 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 15MPa 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% de-fluoridation adsorbent finished granule then, and the capability and performance index testing result of finished product is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, recording its adsorbance to fluorine is 4.2mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 4.2mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 39mg/g.
Embodiment 3
1, preparation composite metal oxide powder
With ferric nitrate, aluminium chloride, cerous sulfate is Fe: Al: Ce=1 in molar ratio: 6: 1 the ratio formation aqueous solution soluble in water;
Under stirring state, dropping sodium solution in the above-mentioned aqueous solution is 9.5 until the pH of solution, leaves standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 95 ℃, 450 ℃ of following roastings 1 hour, grind and make the composite metal oxide de-fluoridation adsorbent powder.
2, preparation high polymer binder
After under 95 ℃ of conditions polyvinyl alcohol (2499) being dissolved in the water, adding little carboxylic acids citric acid stirs, carry out esterification, make polyvinyl alcohol citrate binding agent, 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.
The polyvinyl alcohol that adopts in the esterification 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; The temperature of esterification is not limited to 70 ℃, and reaction temperature all is applicable to the present invention at 40-100 ℃; Reaction time is not limited to 120min, and the reaction 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
Composite metal oxide powder and polyvinyl alcohol citrate 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: 1.4 with the ratio of the quality of polyvinyl alcohol citrate binding agent
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 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% de-fluoridation adsorbent finished granule, and the capability and performance index testing result of finished product is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, recording its adsorbance to fluorine is 4.5mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 4.5mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 40mg/g.
Embodiment 4
1, preparation composite metal oxide powder
With nickelous sulfate, aluminum nitrate, cerous sulfate in molar ratio for Ni: Al: Ce=1: 4: 0.5 the ratio formation aqueous solution that is dissolved in the water;
Under stirring state, dropping sodium solution in the above-mentioned aqueous solution is 9.5 until the pH of the aqueous solution, leaves standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 120 ℃, 250 ℃ of following roastings 3 hours, grind and make the composite metal oxide de-fluoridation adsorbent powder.
2, preparation absorbent particles
Composition metal lead oxide powder and adhesive silicon 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 Ludox, pH value 6, viscosity 20mPas, 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.
Dioxide-containing silica in the adhesive silicon sol is not limited to 25%, 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 15 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 80 ℃ of oven dry, obtain moisture content and be 3% de-fluoridation adsorbent finished granule, the capability and performance index testing result of finished product is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, under pH=7.0 ± 0.1 condition, is 4.8mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 4.8mg) to the adsorbance of fluorine.In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 45mg/g.
Embodiment 5
1, preparation de-fluoridation adsorbent powder
With iron chloride, aluminum nitrate, cerous sulfate in molar ratio for Fe: Al: Ce=1: 4: 1.5 the ratio formation aqueous solution that is dissolved in the water;
Under stirring state, dropping sodium solution in the above-mentioned aqueous solution is 9.5 until the pH of the aqueous solution, leaves standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 110 ℃, 400 ℃ of following roastings 2.5 hours, grind and make the composite metal oxide de-fluoridation adsorbent powder.
2, preparation high polymer binder
High polymer binder is 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
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: 1.2 with the ratio of the quality of binding agent;
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 of 8MPa at relative pressure; cut off, granulate; then under the effect of spheronizator, make sphere, then at 65 ℃ of oven dry 10h, again through 80 ℃ of oven dry; obtaining moisture content is 3% de-fluoridation adsorbent finished granule, and the capability and performance index testing result of finished product is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, under pH=7.0 ± 0.1 condition, is 4.0mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 4.0mg) to the adsorbance of fluorine.In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 36mg/g.
Embodiment 6
1, preparation composite metal oxide powder
With zinc sulfate, aluminum nitrate, lanthanum chloride in molar ratio for Zn: Al: La=0.5: 4: 1 the ratio formation aqueous solution that is dissolved in the water;
Under stirring state, dropping sodium solution in the above-mentioned aqueous solution is 9.0 until the pH of the aqueous solution, leaves standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 120 ℃, 250 ℃ of following roastings 3 hours, grind and make the composite metal oxide de-fluoridation adsorbent powder.
2, preparation high polymer binder
In closed container, be under the condition of 200rpm in stir speed (S.S.), Kynoar is dissolved among the DMF, leave standstill 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 mass percent concentration is that the Kynoar glue of 3-18% all is applicable to the present invention.
3, preparation absorbent particles
De-fluoridation adsorbent 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 binding agent is 1: 1.3.
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; at 65 ℃ of oven dry 4h,, obtain moisture content and be 3% de-fluoridation adsorbent finished granule then again through 80 ℃ of oven dry; the length of finished product is 3-5mm, and capability and performance index testing result is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, under pH=7.0 ± 0.1 condition, is 4.3mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 4.3mg) to the adsorbance of fluorine.In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 38mg/g.
1, preparation composite metal oxide powder
With copper sulphate, aluminum nitrate, cerium chloride in molar ratio for Cu: Al: Ce=1: 2: 1 the ratio formation aqueous solution that is dissolved in the water;
Under stirring state, in the above-mentioned aqueous solution, drip sodium bicarbonate solution, be 9.5 until the pH of the aqueous solution, left standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 110 ℃, 300 ℃ of following roastings 1.5 hours, grind and make the composite metal oxide de-fluoridation adsorbent powder.
2, preparation high polymer binder
In obturator, be under the condition of 150rpm in stir speed (S.S.), the polyvinyl butyral powder end is dissolved in the ethanol, leave standstill 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 polyvinyl butyral resin 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
Composite metal oxide 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: 1.5.
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; at 65 ℃ of oven dry 4h,, obtain moisture content and be 2% de-fluoridation adsorbent finished granule then again through 80 ℃ of oven dry; the length of finished product is 5-9mm, and capability and performance index testing result is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, under pH=7.0 ± 0.1 condition, is 4.4mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 4.4mg) to the adsorbance of fluorine.In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 42mg/g.
Embodiment 8
1, preparation composite metal oxide powder
With manganese nitrate, aluminum nitrate, cerous nitrate is Mn: Al: Ce=1.5 in molar ratio: 4: 1 the ratio formation aqueous solution soluble in water;
Under stirring state, in the above-mentioned aqueous solution, drip ammonia solution, be 9.5 until the pH of solution; Left standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 100 ℃, 400 ℃ of following roastings 2 hours, grind and make the composite metal oxide de-fluoridation adsorbent 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% in the binding agent, and the butvar adhesive liquid of mass percent concentration in the 1-25% scope all is applicable to the present invention.
3, preparation absorbent particles
Compound de-fluoridation adsorbent 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: 1.5;
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; at 65 ℃ of oven dry 4h, again through 100 ℃ of oven dry, obtaining moisture content is 2% de-fluoridation adsorbent finished granule then; the length of finished product is 3-5mm, and capability and performance index testing result is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, under pH=7.0 ± 0.1 condition, is 4.8mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 4.8mg) to the adsorbance of fluorine.In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 45mg/g.
Embodiment 9
1, preparation composite metal oxide powder
With copper chloride, aluminum nitrate, lanthanum chloride in molar ratio for Cu: Al: La=1: 4: 1 the ratio formation aqueous solution that is dissolved in the water;
Under stirring state, dropping sodium solution in the above-mentioned aqueous solution is 9.5 until the pH of the aqueous solution, leaves standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 100 ℃, 300 ℃ of following roastings 2.5 hours, grind and make the composite metal oxide de-fluoridation adsorbent 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 3% Kynoar glue, the molecular weight of Kynoar is 130-170k.
The mass percent concentration of Kynoar glue is not limited to 3%, and concentration is that the Kynoar glue of 3-18% all is applicable to the present invention.
3, preparation absorbent particles
Composite metal oxide 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 binding agent is 1: 1.6;
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; then under the effect of spheronizator, make sphere, then at 60 ℃ of oven dry 4h, again through 80 ℃ of oven dry; obtaining moisture content is 2% de-fluoridation adsorbent finished granule, and the capability and performance index testing result of finished product is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, under pH=7.0 ± 0.1 condition, is 4.2mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 4.2mg) to the adsorbance of fluorine.In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 37mg/g.
Embodiment 10
1, preparation composite metal oxide powder
With iron chloride, aluminum sulfate, lanthanum nitrate is Fe: Al: La=1.5 in molar ratio: 4: 1 ratio dissolving forms the aqueous solution, at room temperature, and stirring and evenly mixing;
Under stirring state, dropping sodium solution in the above-mentioned aqueous solution is 9.0 until the pH of solution, leaves standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 90 ℃, 400 ℃ of following roastings 4 hours, grind and make the composite metal oxide de-fluoridation adsorbent powder.
2, preparation high polymer binder
In closed container, in stir speed (S.S.) is under the condition of 150rpm, and the polyvinyl formal powder dissolution in ethanol, is left standstill bubble, make mass percent concentration and be 2% formaldehyde polyvinyl acetal liquid wherein, the molecular weight of polyvinyl formal is 100-150k.
The mass percent concentration of polyvinyl formal is not limited to 2% in the binding agent, and the formaldehyde polyvinyl acetal liquid of mass percent concentration in the 1-25% scope all is applicable to the present invention.
3, preparation absorbent particles
Composite metal oxide de-fluoridation adsorbent 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: 2.5 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% de-fluoridation adsorbent finished granule, and the capability and performance index testing result of finished product is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, recording its adsorbance to fluorine is 4.3mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 4.3mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 39mg/g.
Embodiment 11
1, preparation composite oxide power
With ferric nitrate, aluminium chloride, cerous sulfate is Fe: Al: Ce=1 in molar ratio: 5: 1 the ratio formation aqueous solution soluble in water;
Under stirring state, dropping sodium solution in the above-mentioned aqueous solution is 9.5 until the pH of solution, leaves standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 95 ℃, 450 ℃ of following roastings 1 hour, grind and make the composite metal oxide de-fluoridation adsorbent 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; Esterification reaction temperature 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
Composite metal oxide 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 of 15MPa at relative pressure; cut off, granulate; then under the effect of spheronizator, make sphere; obtaining moisture content 65 ℃ of oven dry then is 3% de-fluoridation adsorbent finished granule, and the capability and performance index testing result of finished product is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, recording its adsorbance to fluorine is 4.8mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 4.8mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 42mg/g.
Embodiment 12
1, preparation composite oxide power
With ferric nitrate, aluminium chloride, lanthanum nitrate is Fe: Al: La=1 in molar ratio: 5: 1 the ratio formation aqueous solution soluble in water;
Under stirring state, dropping sodium solution in the above-mentioned aqueous solution is 9.5 until the pH of solution, leaves standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 95 ℃, 450 ℃ of following roastings 1 hour, grind and make the composite metal oxide de-fluoridation adsorbent 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.
The polyvinyl alcohol that adopts in the esterification 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
Composite metal oxide 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: 2 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 3 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure of 5MPa at relative pressure; cut off, granulate; then under the effect of spheronizator, make sphere; obtaining moisture content 65 ℃ of oven dry then is 3% de-fluoridation adsorbent finished granule, and the capability and performance index testing result of finished product is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, recording its adsorbance to fluorine is 3.8mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 3.8mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 30mg/g.
Embodiment 13
1, preparation composite metal oxide powder
With iron chloride, aluminum sulfate, lanthanum nitrate is Fe: Al: La=1.0 in molar ratio: 4: 1 ratio dissolving forms the aqueous solution, at room temperature, and stirring and evenly mixing;
Under stirring state, dropping sodium solution in the above-mentioned aqueous solution is 9.0 until the pH of solution, leaves standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 90 ℃, 500 ℃ of following roastings 4 hours, grind and make the composite metal oxide de-fluoridation adsorbent 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 130-170k.
The contract mass percent concentration of glutaraldehyde 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
Composite metal oxide de-fluoridation adsorbent 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: 1.5 with the ratio of the quality of binding agent
With the wet stock that mixes after kneading machine is mediated 4 minutes; send in the double-screw extruding pelletizing machine; be after extruding under the pressure effect of 10MPa 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% de-fluoridation adsorbent finished granule then, and the capability and performance index testing result of finished product is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, recording its adsorbance to fluorine is 3.5mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 3.5mg).In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 28mg/g.
Embodiment 14
1, preparation de-fluoridation adsorbent powder
With ferric nitrate, aluminum nitrate, cerous sulfate in molar ratio for Fe: Al: Ce=1: 4: 1.5 the ratio formation aqueous solution that is dissolved in the water;
Under stirring state, dropping sodium solution in the above-mentioned aqueous solution is 9.5 until the pH of the aqueous solution, leaves standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 110 ℃, 450 ℃ of following roastings 2.5 hours, grind and make the composite metal oxide de-fluoridation adsorbent 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.
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
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 10MPa at relative pressure; cut off, granulate; then under the effect of spheronizator, make sphere, then at 65 ℃ of oven dry 10h, again through 80 ℃ of oven dry; obtain moisture content and be 3% de-fluoridation adsorbent finished granule, the capability and performance index testing result of finished product is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, under pH=7.0 ± 0.1 condition, is 4.1mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 4.1mg) to the adsorbance of fluorine.In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 35mg/g.
Embodiment 15
1, preparation composite metal oxide powder
With nickelous sulfate, aluminum nitrate, lanthanum sulfate in molar ratio for Ni: Al: La=1: 4: 1 the ratio formation aqueous solution that is dissolved in the water;
Under stirring state, dropping sodium solution in the above-mentioned aqueous solution is 9.5 until the pH of the aqueous solution, leaves standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 120 ℃, 500 ℃ of following roastings 3 hours, grind and make the composite metal oxide de-fluoridation adsorbent 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 a 40%pH value 7 in the Ludox, viscosity 30mPa.s, average grain diameter 10-20nm, stabilizing agent Na
2O content 0.10%, the mass ratio of absorbent powder and inorganic silicon colloidal sol is 1: 1.2.
Dioxide-containing silica in the Ludox is not limited to 40%, 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 8 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% de-fluoridation adsorbent finished granule, the capability and performance index testing result of finished product is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, under pH=7.0 ± 0.1 condition, is 4.0mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 4.0mg) to the adsorbance of fluorine.In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 38mg/g.
Embodiment 16
1, preparation composite metal oxide powder
With manganese nitrate, aluminum nitrate, lanthanum nitrate is Mn: Al: La=1.5 in molar ratio: 4: 1 the ratio formation aqueous solution soluble in water;
Under stirring state, in the above-mentioned aqueous solution, drip ammonia solution, be 9.5 until the pH of solution; Left standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight under 100 ℃, 250 ℃ of following roastings 4 hours, grind and make the composite metal oxide de-fluoridation adsorbent powder.
2, preparation absorbent particles
With mixing in de-fluoridation adsorbent powder and the binding agent polyacrylate dispersion adding colter mixer, make mixed material, wherein, the solid content of polyacrylate dispersion is 52%, and concentration is 15%, viscosity 600mPas, pH value 6.5, the mass ratio of absorbent powder and emulsion are 1: 1.4.
The polyacrylate dispersion that the present invention uses is not limited to above-mentioned emulsion, solid content 〉=52%, and concentration is 4-25%, viscosity 500-1000mPas, 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 5 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% de-fluoridation adsorbent finished granule, and the capability and performance index testing result of finished product is as shown in table 1.
Make particle and be used to handle fluorine-containing water, the fluorine initial concentration is 10mg/L in the water, and particle throwing amount is 2g/L, under pH=7.0 ± 0.1 condition, is 3.8mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 3.8mg) to the adsorbance of fluorine.In particle throwing amount is 2g/L, and under pH=7.0 ± 0.1 condition, measuring the fluorine initial concentration respectively is that this particle is to the adsorbance of fluorine in the 10-200mg/L scope, and obtaining its saturated extent of adsorption to fluorine through the mathematics The Fitting Calculation is 36mg/g.
Table 1 defluorination 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 | 40 | ＜1 | 28 | 0.045 |
| Embodiment 2 | 2 | 2.0 | 33 | ＜1 | 15 | 0.029 |
| Embodiment 3 | 2 | 1.8 | 32 | ＜1 | 25 | 0.044 |
| Embodiment 4 | 3 | 1.8 | 28 | ＜2 | 15 | 0.024 |
| Embodiment 5 | 3 | 1.8 | 35 | ＜2 | 25 | 0.040 |
| Embodiment 6 | 3 | 1.5 | 35 | ＜1 | 24 | 0.041 |
| |
2 | 1.6 | 30 | ＜1 | 25 | 0.045 |
| Embodiment 8 | 2 | 0.7 | 30 | ＜1 | 24 | 0.043 |
| Embodiment 9 | 2 | 1.6 | 33 | ＜1 | 24 | 0.045 |
| Embodiment 10 | 2 | 1.8 | 36 | ＜1 | 17 | 0.032 |
| Embodiment 11 | 3 | 1.5 | 29 | ＜2 | 29 | 0.048 |
| Embodiment 12 | 3 | 1.5 | 37 | ＜1 | 22 | 0.039 |
| Embodiment 13 | 2 | 2.0 | 33 | ＜1 | 23 | 0.040 |
| Embodiment 14 | 3 | 1.5 | 35 | ＜1 | 25 | 0.040 |
| Embodiment 15 | 2 | 1.5 | 28 | ＜1 | 15 | 0.026 |
| Embodiment 16 | 2 | 1.8 | 38 | ＜1 | 41 | 0.047 |
Claims (10)
1. a de-fluoridation adsorbent is characterized in that containing composite metal oxide and binding agent.
2. adsorbent as claimed in claim 1, the weight portion proportioning that it is characterized in that described composite metal oxide and binding agent is 1: 0.5-2.5.
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 composite metal oxide contains transition metal, Al and rare earth metal; The mol ratio of described transition metal, Al and rare earth metal is 0.5-1.5: 2-6: 0.5-1.5; Described transition metal is Ti, V, Mn, Fe, Co, Ni, Cu or Zn; Described rare earth metal is Ce or La.
7. the preparation method of a de-fluoridation adsorbent comprises and carries out pelletization treatment and dry the processing successively after evenly with composite metal oxide and binding agent are mixed that wherein, the weight portion proportioning of described composite metal oxide and binding agent is 1: 0.5-2.5.
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) composite metal oxide 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 composite metal oxide contains transition metal, Al and rare earth metal; The mol ratio of described transition metal, Al and rare earth metal is 0.5-1.5: 2-6: 0.5-1.5; Described transition metal is Ti, V, Mn, Fe, Co, Ni, Cu or Zn; Described rare earth metal is Ce or La.
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