CN100532282C - Silicon dioxide adulterated composite material of humic acid and calcium, preparation method and application - Google Patents
Silicon dioxide adulterated composite material of humic acid and calcium, preparation method and application Download PDFInfo
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- CN100532282C CN100532282C CNB2007100989343A CN200710098934A CN100532282C CN 100532282 C CN100532282 C CN 100532282C CN B2007100989343 A CNB2007100989343 A CN B2007100989343A CN 200710098934 A CN200710098934 A CN 200710098934A CN 100532282 C CN100532282 C CN 100532282C
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Abstract
This invention relates to a method for preparing SiO2-doped calcium humate composite with 20-90 wt. % of calcium humate. The method comprises: (1) purifying industrial grade sodium humate; (2) uniformly mixing industrial grade sodium humate, Si source compound and water at a weight ratio of (0.1-7.5):1:10, heating to 80-90 deg.C, dropping acid at a rate of 1-10 mL/min until the pH value is 4-6, and reacting for 2 h to obtain composite precursor; (3) adding saturated CaCl2 solution into the composite precursor, reacting at 80-90 deg.C for 1 h for co-precipitation, centrifuging the reaction solution, taking out the lower layer black gel solid, and drying to obtain SiO2-doped calcium humate composite. The Si source compound is R2O.nSiO2 water glass, wherein, R is alkali metal, and n is 1-4.
Description
Technical field
The present invention relates to a kind of calcium humate matrix material and preparation method and the purposes in treating water body weight contaminant metal ions of doping silicon dioxide.
Background technology
China is a country that drought and water shortage is serious.-Freshwater resources total amount is 28000 billion cubic meters, account for 6% of water globe resource, be only second to Brazil, Russia and Canadian, occupy the 4th in the world, but have only 2300 cubic metres per capita, only be world average level 1/4th, the U.S. 1/5th, rank 121 in the world, be the whole world one of 13 countries that water resources is the poorest per capita.The per capita Freshwater resources of China do not enrich, and unbalanced because of spatial and temporal distributions, and quite a few geographic water resources extremely lacks.Along with the development of economic construction, town and country construction and the increase of population, the water consumption sustainable growth, the imbalance between supply and demand of water will become increasingly conspicuous.Simultaneously, because a large amount of trade effluent and sanitary sewages enters water body, further aggravated the imbalance between supply and demand of water.
The rivers and lakes of the whole nation more than 70% suffer to pollute in various degree at present, and water pollutes the not only shortage of exacerbate water resource, and the people's physical and mental health in the deterioration serious threat of water quality.At present, the heavy metal of polluted-water has mercury, cadmium, lead, chromium, vanadium, cobalt, barium etc.The toxicity maximum of mercury wherein, cadmium, lead, chromium also have bigger harm, and arsenic often is listed in heavy metal because toxicity is similar to heavy metal.Heavy metal is discharged with waste water in factory, mine production process, can not be degraded by microorganisms after entering water body, through the inrichment of food chain, can be step by step in the higher organisms body hundreds and thousands of times of ground increase content, finally enter human body.
Humic acids generally is meant what occurring in nature existed, the organic substance that forms through microbiological degradation and a series of chemical process by the remains of biological (mainly being plant), its main component is a carbon, oxygen, hydrogen, nitrogen and sulphur, this macromolecular organic compound is randomly distributed on the hydrophobic organic backbone by multiple hydrophilic radical and forms, its basic molecular structure is the aromatic ring of band side chain, condensed ring, cycloaliphatic ring and heterocyclic condensation system, active formyloxy is distributing on nuclear and side chain, methoxyl group, carbonyl, also may contain aerobic in the ring, atoms such as nitrogen, thereby metal ion had stronger sequestering action.And the derivative of humic acids---Sodium salts humic acids has stronger ion-exchange capacity, with the contacting of pollutent in can remove deleterious heavy metal ion.In addition because that humic acids and derivative thereof are is nontoxic, do not have the material of smelling, thereby is widely used in water treatment field, the sequestering power that utilizes humic acids with and spongy short texture, realize absorption to heavy metal ion.One of organic main component is exactly a humic acid substance in the natural water body, accounts for the 50-90% of total organic matter in the water.The content of the humic acids in most of fresh water is 1-12mg/L.In addition, liquid contains a certain amount of humic acids in industrial papermaking wastewater, the alcohol slops.
But because humic acids is water-soluble, it is met water meeting hydration swelling and produces the excessive phenomenon of water resistance, again because humic acids as a kind of fertilizer, water-soluble back shows black, humic acids content is excessive in the adding water body, can increase water body chroma, can cause body eutrophication simultaneously, so humic acids must could use through fixing earlier.As at document 1:Journal of Fuel Chemistry and Technology 18, disclose among the 149-157 (1990) a kind of be main raw material with the weathered coal humic acid, be used for the humic acids resin of Adsorption of Heavy Metal Ions.At document 2:Materials Protection 35, disclose among the 54-56 (2002) a kind of utilize calcium alginate for stablizer, utilize peat to go out the humic acids resin for feedstock production.But the preparation technology of these humic acids resins is all complicated, and brings excessive water resistance in order to prevent that ion hydration from expanding, and sorbent material must pass through granulating and forming, and this has all brought certain difficulty to suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of calcium humate matrix material of doping silicon dioxide, can make things convenient for, treating water body weight contaminant metal ions effectively.
Another object of the present invention is to provide the method for the calcium humate matrix material that a kind of technology simply prepares doping silicon dioxide.
A further object of the present invention is the purposes of calcium humate matrix material in treating water body weight contaminant metal ions of above-mentioned doping silicon dioxide.
The objective of the invention is to realize by the following technical solutions:
2, the calcium humate matrix material of doping silicon dioxide provided by the invention, it is characterized in that, this matrix material is the calcium humate matrix material of the doping silicon dioxide that evenly is doped with silicon-dioxide forms in calcium humate, wherein the weight of calcium humate account for this doping silicon dioxide calcium humate matrix material weight 20%～90%.
The preparation method of the calcium humate matrix material of doping silicon dioxide provided by the invention comprises the steps:
1) purifying industrial grade Sodium salts humic acids
With purity is that the Sodium salts humic acids and the water of technical grade is that 1:5 to 1:15 mixes centrifugation according to the weight part ratio scope; Isolate supernatant liquid; Abandon the lower black precipitation, add concentrated hydrochloric acid in supernatant liquid, the pH value that makes this supernatant liquid forms the Sodium salts humic acids suspension liquid of black below 1; This suspension liquid recentrifuge is separated, abandon supernatant liquid, in lower floor's black precipitate, add concentrated NaOH solution, dissolve this black precipitate, form dark solution, regulate the pH value scope 5～8 of this dark solution; Heating and oven dry obtain the Powdered or massive industrial level Sodium salts humic acids through purifying;
2) presoma of preparation matrix material
Powdered or massive industrial level Sodium salts humic acids, silicon source compound and water that step 1) is obtained through purifying with mass parts than the ratio uniform mixing that is X:1:10, wherein X gets 0.1-7.5, when being heated to 80-90 ℃, in the rate of addition scope of 1mL～10mL/min, drip acid to the pH value scope of reaction solution 4～6, reacted 2 hours, generation contains the presoma of the hydridization colloid of Sodium salts humic acids and silicon-dioxide hydrate as matrix material;
Described silicon source compound is that chemical formula is R
2OnSiO
2, wherein, R is a basic metal, n is a modulus, n=SiO
2Molecule number and R
2The ratio of O molecule number=1～4;
3) the calcium humate matrix material of preparation doping silicon dioxide
Saturated calcium chloride solution is added step 2) in the presoma of the matrix material that makes, 80-90 ℃ of reaction 1 hour; Sodium salts humic acids and calcium chloride generation coprecipitation reaction with the reaction solution centrifugation, are told the lower black gelatinous solid, dry, and obtain the calcium humate matrix material of doping silicon dioxide;
The weight part proportioning of contained Sodium salts humic acids is that the ratio of 1:3～1:10 is mixed in the presoma of saturated calcium chloride solution and matrix material.
The used water of described step 1) is deionized water.
The technical grade Sodium salts humic acids that described step 1) is used is from the technical grade Sodium salts humic acids in the weathered coal.
The technical grade Sodium salts humic acids that described step 1) is used from peat, brown coal or/and the technical grade Sodium salts humic acids in the weathered coal.
Described step 2) n=3 in.
Described step 2) acid described in is hydrochloric acid, nitric acid, sulfuric acid or its mixture.
Described step 2) water in is deionized water.
The calcium humate matrix material of the doping silicon dioxide of method preparation of the present invention can directly use; Also can further grind and sieve, make varigrained dusty material and use.
The calcium humate matrix material of doping silicon dioxide of the present invention can be used for heavy-metal pollution thing in the treating water.Sewage and this matrix material that will contain the heavy-metal pollution thing mix stirring, this matrix material and the sewage that contains the heavy-metal pollution thing are fully reacted, the heavy-metal pollution thing is adsorbed by matrix material in the water body, sewage after will handling then is by filtering, leach the matrix material that this has adsorbed heavy metal ion, the water body of discharge is purified.Separate the heavy metal ion of adsorbing on the adsorption desorption matrix material with acid then, regenerate with calcium acetate solution or calcium chloride liming mixed solution, this matrix material can use repeatedly.
Matrix material of the present invention can be handled the pollutent that comprises heavy metal ion such as mercury, cadmium, lead, chromium and metalloid arsenic, zinc, copper, cobalt, nickel, tin, vanadium, titanium, manganese, iron, rubidium, strontium, zirconium, niobium, molybdenum, silver, antimony, hafnium, tantalum, tungsten, bismuth.
The calcium humate matrix material of doping silicon dioxide of the present invention, compared with prior art, its advantage is as follows:
1) hardness of this matrix material is higher, can not produce the excessive phenomenon of bringing owing to the humic acids hydration swelling of water resistance, still can show the good adsorption ability to heavy metal ion under low pH value;
2) have the comprehensive treating process function, can remove contents of many kinds of heavy metal ion in the water body convenient, effectively;
3) can remove contents of many kinds of heavy metal ion in the water body simultaneously, effect is obvious, can not cause secondary pollution, is suitable for the particular requirement of industrial circle such as Electroplate Factory, chemical plant, Metallurgical Factory, printing house and waterworks etc., and particular design is installed;
4) this matrix material has improved the specific surface of material on the one hand owing to the vesicular structure of silicon-dioxide, has strengthened its adsorptive power; On the other hand, also improved the passage of transmission lead ion for material.
Embodiment
Embodiment 1
With purity is that the weathered coal humic acid sodium of technical grade and deionized water are that 1:5 mixes according to the weight part proportioning, centrifugation, isolate supernatant liquid, abandon the lower black precipitation, in supernatant liquid, add concentrated hydrochloric acid, until the pH of this supernatant liquid value is 0.5, this moment, this supernatant liquid became the suspension liquid of black, and this suspension liquid recentrifuge is separated, and abandoned supernatant liquid, in lower floor's dark solution, dropwise add concentrated NaOH solution, dissolve this black precipitate, form dark solution, and the pH value of controlling this dark solution is 5, after the moisture evaporation in this dark solution, the Sodium salts humic acids after obtaining purifying;
(the use modulus is 1 water glass Na to elder generation's prepare silicon acid sodium solution
2SiO
3With deionized water by weight ratio 1:10 mix, solid is dissolved fully, standby), Sodium salts humic acids after purifying and the sodium silicate solution for preparing are the mixed of 1:100 (Sodium salts humic acids at this moment: water glass: the proportioning of water=0.1:1:10) by weight ratio, be heated to 80 ℃ and fully stirring, speed with 1mL/min drips dilute hydrochloric acid in above-mentioned reaction system, make its pH value reduce to 4, continue reaction 2 hours, and then in reaction system, add saturated calcium chloride solution (the weight part proportioning of Sodium salts humic acids is 3:1 in saturated calcium chloride solution that is added and the reaction system), continue reaction 1 hour, the merit precipitin reaction takes place;
The suspension liquid centrifugation that reaction is obtained, abandon supernatant liquid, keep lower floor's black precipitate, dry this black precipitate, obtain the calcium humate matrix material of the doping silicon dioxide described in the present invention, in the calcium humate matrix material of the doping silicon dioxide that present embodiment is prepared, the weight part proportioning of calcium humate and silicon-dioxide is 1:4 (is the weight of calcium humate account for matrix material weight 20%).
With condition be: at room temperature, plumbum ion concentration is 30mg/L in the water body, and matrix material and staying water mass ratio are 1:200, and the pH value of regulating water body is about 7, and this matrix material and water body are mixed stirring 2 hours; After the reaction, plumbum ion concentration is less than 1mg/L in the water body, and matrix material, reaches more than 98% clearance plumbous in the water body greater than 200mg/g the saturated extent of adsorption of lead ion.
Embodiment 2
With purity is that the humic acid in peat sodium of technical grade and deionized water are that 1:10 mixes according to the weight part proportioning, centrifugation, isolate supernatant liquid, abandon the lower black precipitation, in supernatant liquid, add the vitriol oil, until the pH of this supernatant liquid value is 0.8, this moment, this supernatant liquid became the suspension liquid of black, and this suspension liquid recentrifuge is separated, and abandoned supernatant liquid, in lower floor's dark solution, dropwise add concentrated NaOH solution, dissolve this black precipitate, form dark solution, and the pH value of controlling this dark solution is 6, after the moisture evaporation in this dark solution, the Sodium salts humic acids after obtaining purifying;
(the use modulus is 2 water glass Na to the prepare silicon acid sodium solution
2O2SiO
2With deionized water by weight ratio 1:10 mix, solid is dissolved fully, standby), the mixed that Sodium salts humic acids after purifying and foregoing sodium silicate solution be 1:25 by weight ratio (Sodium salts humic acids at this moment: water glass: the proportioning of water=0.4:1:10), be heated to 85 ℃ and fully stirring, speed with 3mL/min drips dilute sulphuric acid in above-mentioned reaction system, make its pH value reduce to 5, continue reaction 2 hours, and then in reaction system, add saturated calcium chloride solution (the weight part proportioning of Sodium salts humic acids is 4:1 in saturated calcium chloride solution that is added and the reaction system), continue reaction 1 hour;
The suspension liquid centrifugation that reaction is obtained, abandon supernatant liquid, keep lower floor's black precipitate, dry this black precipitate, obtain the calcium humate matrix material of the doping silicon dioxide described in the present invention, in the calcium humate matrix material of the doping silicon dioxide that present embodiment is prepared, the weight part proportioning of calcium humate and silicon-dioxide is 2:3 (is the weight of calcium humate account for matrix material weight 40%).
The matrix material of present embodiment ground to sieve make powder, be used for handling the lead ion of water body, working conditions is: at room temperature, plumbum ion concentration is 30mg/L in the water body, matrix material and staying water mass ratio are 1:200, the pH value of regulating water body is about 9, and this matrix material and water body are mixed stirring 2 hours; After the reaction, plumbum ion concentration is less than 1mg/L in the water body, and matrix material, reaches more than 95% clearance plumbous in the water body greater than 200mg/g the saturated extent of adsorption of lead ion.
Embodiment 3
With purity is the weathered coal humic acid sodium of technical grade, humic acid in peat sodium and tap water are that 1:1:30 mixes according to the weight part proportioning, centrifugation, isolate supernatant liquid, abandon the lower black precipitation, in supernatant liquid, add Glacial acetic acid, until the pH of this supernatant liquid value is 1, this moment, this supernatant liquid became the suspension liquid of black, and this suspension liquid recentrifuge is separated, and abandoned supernatant liquid, in lower floor's dark solution, dropwise add concentrated NaOH solution, dissolve this black precipitate, form dark solution, and the pH value of controlling this dark solution is 7, after the moisture evaporation in this dark solution, the Sodium salts humic acids after obtaining purifying;
(the use modulus is 3 water glass Na to the prepare silicon acid sodium solution
2O3SiO
2With deionized water by weight ratio 1:10 mix, solid is dissolved fully, standby), the mixed that Sodium salts humic acids after purifying and foregoing sodium silicate solution be 1:7 by weight ratio (Sodium salts humic acids at this moment: water glass: the proportioning of water=1.5:1:10), be heated to 90 ℃ and fully stirring, speed with 5mL/min drips rare nitric acid in above-mentioned reaction system, make its pH value reduce to 5, continue reaction 2 hours, and then in reaction system, add saturated calcium chloride solution (the weight part proportioning of Sodium salts humic acids is 6:1 in saturated calcium chloride solution that is added and the reaction system), continue reaction 1 hour;
The suspension liquid centrifugation that reaction is obtained, abandon supernatant liquid, keep lower floor's black precipitate, dry this black precipitate, obtain the calcium humate matrix material of the doping silicon dioxide described in the present invention, in the calcium humate matrix material of the doping silicon dioxide that present embodiment is prepared, the weight part proportioning of calcium humate and silicon-dioxide is 7:3 (is the weight of calcium humate account for matrix material weight 70%).
The matrix material of present embodiment ground to sieve make powder, be used for handling the chromium ion of water body, working conditions is: at room temperature, chromium ion concentration is 30mg/L in the water body, matrix material and staying water mass ratio are 1:200, the pH value of regulating water body is about 7, and this matrix material and water body are mixed stirring 2 hours; After the reaction, chromium ion concentration is less than 1mg/L in the water body, and matrix material, reaches more than 98% the clearance of chromium in the water body greater than 200mg/g the saturated extent of adsorption of chromium ion.
Embodiment 4
With purity is the weathered coal humic acid sodium of technical grade, humic acid in peat sodium and tap water are that 2:1:30 mixes according to the weight part proportioning, centrifugation, isolate supernatant liquid, abandon the lower black precipitation, in supernatant liquid, add the mixture of Glacial acetic acid and concentrated hydrochloric acid (in this mixture, the weight part proportioning of Glacial acetic acid and concentrated hydrochloric acid is 1:1), until the pH of this supernatant liquid value is 1, this moment, this supernatant liquid became the suspension liquid of black, this suspension liquid recentrifuge is separated, abandon supernatant liquid, in lower floor's dark solution, dropwise add concentrated NaOH solution, dissolve this black precipitate, form dark solution, and the pH value of controlling this dark solution is 8, after the moisture evaporation in this dark solution, and the Sodium salts humic acids after obtaining purifying;
(the use modulus is 3 potash water glass K to the preparation potassium silicate solution
2O3SiO
2With deionized water by weight ratio 1:10 mix, solid is dissolved fully, standby), the mixed that Sodium salts humic acids after purifying and foregoing potassium silicate solution be 1:2 by weight ratio (Sodium salts humic acids at this moment: potassium silicate: the proportioning of water=5.5:1:10), be heated to 90 ℃ and fully stirring, in above-mentioned reaction system, drip the mixture of dilute hydrochloric acid and dilute sulphuric acid with the speed of 10mL/min, the weight part proportioning of dilute hydrochloric acid and dilute sulphuric acid is 1:1 in the mixture, make its pH value reduce to 6, continue reaction 2 hours, and then in reaction system, add saturated calcium chloride solution (the weight part proportioning of Sodium salts humic acids is 10:1 in saturated calcium chloride solution that is added and the reaction system), continue reaction 1 hour;
The suspension liquid centrifugation that reaction is obtained, abandon supernatant liquid, keep lower floor's black precipitate, dry this black precipitate, obtain the calcium humate matrix material of the doping silicon dioxide described in the present invention, in the calcium humate matrix material of the doping silicon dioxide that present embodiment is prepared, the weight part proportioning of calcium humate and silicon-dioxide is 9:1 (is the weight of calcium humate account for matrix material weight 90%).
The matrix material of present embodiment ground to sieve make powder, be used for handling the cupric ion of water body, working conditions is: at room temperature, copper ion concentration is 30mg/L in the water body, matrix material and staying water mass ratio are 1:200, the pH value of regulating water body is about 7, and this matrix material and water body are mixed stirring 2 hours; After the reaction, copper ion concentration is less than 2mg/L in the water body, and matrix material, reaches more than 90% the clearance of copper in the water body greater than 100mg/g the saturated extent of adsorption of cupric ion.
Embodiment 5
With purity is the weathered coal humic acid sodium of technical grade, humic acid in peat sodium and tap water are that 3:1:60 mixes according to the weight part proportioning, centrifugation, isolate supernatant liquid, abandon the lower black precipitation, in supernatant liquid, add Glacial acetic acid, until the pH of this supernatant liquid value is 1, this moment, this supernatant liquid became the suspension liquid of black, and this suspension liquid recentrifuge is separated, and abandoned supernatant liquid, in lower floor's dark solution, dropwise add concentrated NaOH solution, dissolve this black precipitate, form dark solution, and the pH value of controlling this dark solution is 7, after the moisture evaporation in this dark solution, the Sodium salts humic acids after obtaining purifying;
(the use modulus is 4 water glass Na to the prepare silicon acid sodium solution
2O4SiO
2With deionized water by weight ratio 1:10 mix, solid is dissolved fully, standby), the mixed that Sodium salts humic acids after purifying and foregoing sodium silicate solution be 2:3 by weight ratio (Sodium salts humic acids at this moment: water glass: the proportioning of water=7.5:1:10), be heated to 90 ℃ and fully stirring, speed with 5mL/min drips rare nitric acid in above-mentioned reaction system, make its pH value reduce to 5, continue reaction 2 hours, and then in reaction system, add saturated calcium chloride solution (the weight part proportioning of Sodium salts humic acids is 6:1 in saturated calcium chloride solution that is added and the reaction system), continue reaction 1 hour;
The suspension liquid centrifugation that reaction is obtained, abandon supernatant liquid, keep lower floor's black precipitate, dry this black precipitate, obtain the calcium humate matrix material of the doping silicon dioxide described in the present invention, in the calcium humate matrix material of the doping silicon dioxide that present embodiment is prepared, the weight part proportioning of calcium humate and silicon-dioxide is 9:1 (is the weight of calcium humate account for matrix material weight 90%).
The matrix material of present embodiment ground to sieve make powder, be used for handling the zine ion of water body, working conditions is: at room temperature, zinc ion concentration is 30mg/L in the water body, matrix material and staying water mass ratio are 1:200, the pH value of regulating water body is about 7, and this matrix material and water body are mixed stirring 2 hours; After the reaction, zinc ion concentration is less than 5mg/L in the water body, and matrix material, reaches more than 80% the clearance of zinc in the water body greater than 100mg/g the saturated extent of adsorption of zine ion.
Composite material powder of the present invention can also pass through regeneration back recycle: at room temperature, the heavy metal ion of being adsorbed by humic acids in the matrix material, usable acid is separated adsorption desorption, matrix material and dilute hydrochloric acid body are mixed 2 hours after-filtration of stirring, resulting process is separated the matrix material of adsorption desorption, recycle after available calcium acetate solution or calcium chloride liming mixed solution are regenerated.
Claims (7)
1, a kind of calcium humate matrix material of doping silicon dioxide, it is characterized in that, this matrix material is the calcium humate matrix material of the doping silicon dioxide that evenly is doped with silicon-dioxide forms in calcium humate, wherein the weight of calcium humate account for this doping silicon dioxide calcium humate matrix material weight 20%～90%.
2, the preparation method of the calcium humate matrix material of the described doping silicon dioxide of a kind of claim 1 comprises the steps:
1) purifying industrial grade Sodium salts humic acids
With purity is that the Sodium salts humic acids and the water of technical grade is that 1:5 to 1:15 mixes centrifugation according to the weight part ratio scope; Isolate supernatant liquid; Abandon the lower black precipitation, add concentrated hydrochloric acid in supernatant liquid, the pH value that makes this supernatant liquid forms the Sodium salts humic acids suspension liquid of black below 1; This suspension liquid recentrifuge is separated, abandon supernatant liquid, in lower floor's black precipitate, add concentrated NaOH solution, dissolve this black precipitate, form dark solution, regulate the pH value scope 5～8 of this dark solution; Heating and oven dry obtain the Powdered or massive industrial level Sodium salts humic acids through purifying;
2) presoma of preparation matrix material
Powdered or massive industrial level Sodium salts humic acids, silicon source compound and water that step 1) is obtained through purifying with mass parts than the ratio uniform mixing that is X:1:10, wherein X gets 0.1-7.5, when being heated to 80-90 ℃, in the rate of addition scope of 1mL～10mL/min, drip acid to the pH value scope of reaction solution 4～6, reacted 2 hours, generation contains the presoma of the hydridization colloid of Sodium salts humic acids and silicon-dioxide hydrate as matrix material;
Described silicon source compound is that chemical formula is R
2OnSiO
2, wherein, R is a basic metal, n is a modulus, n=SiO
2Molecule number and R
2The ratio of O molecule number=1～4;
3) the calcium humate matrix material of preparation doping silicon dioxide
Saturated calcium chloride solution is added step 2) in the presoma of the matrix material that makes, 80-90 ℃ of reaction 1 hour; Sodium salts humic acids and calcium chloride generation coprecipitation reaction with the reaction solution centrifugation, are told the lower black gelatinous solid, dry, and obtain the calcium humate matrix material of doping silicon dioxide;
The weight part proportioning of contained Sodium salts humic acids is that the ratio of 1:3～1:10 is mixed in the presoma of saturated calcium chloride solution and matrix material.
3, press the preparation method of the calcium humate matrix material of the described doping silicon dioxide of claim 2, it is characterized in that the used water of described step 1) is deionized water.
4, press the preparation method of the calcium humate matrix material of the described doping silicon dioxide of claim 2, it is characterized in that, the technical grade Sodium salts humic acids that described step 1) is used is from the technical grade Sodium salts humic acids in the weathered coal.
5, by the preparation method of the calcium humate matrix material of the described doping silicon dioxide of claim 2, it is characterized in that described step 2) in n=3.
6, by the preparation method of the calcium humate matrix material of the described doping silicon dioxide of claim 2, it is characterized in that described step 2) described in acid be hydrochloric acid, nitric acid, sulfuric acid or its mixture.
7, by the preparation method of the calcium humate matrix material of the described doping silicon dioxide of claim 2, it is characterized in that described step 2) in water be deionized water.
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| CN104355382B (en) * | 2014-11-04 | 2016-08-24 | 太原市润民环保节能有限公司 | Medicament for removing heavy metal ions in water and preparation method thereof |
| CN104624165B (en) * | 2015-02-06 | 2017-03-15 | 四川师范大学 | A kind of adsorbing material of adsorbent organic chlorine pollutant and preparation method thereof |
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| 腐植酸树脂的合成及吸附性能的研究. 张书圣等.荷泽师专学报，第20卷第2期. 1998 * |
| 腐植酸类制品及泥炭褐煤用于废水处理概况. 朱之培.环境科学，第1期. 1979 * |
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