CN103272572A - Preparation method capable of absorbing Ca<2+> material from magnesium sulfate waste water - Google Patents
Preparation method capable of absorbing Ca<2+> material from magnesium sulfate waste water Download PDFInfo
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- CN103272572A CN103272572A CN2013102713884A CN201310271388A CN103272572A CN 103272572 A CN103272572 A CN 103272572A CN 2013102713884 A CN2013102713884 A CN 2013102713884A CN 201310271388 A CN201310271388 A CN 201310271388A CN 103272572 A CN103272572 A CN 103272572A
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Abstract
The invention relates to a preparation method capable of absorbing a Ca<2+> material from magnesium sulfate waste water. According to the method, a reusable absorptive powder material with high selectively to calcium ions can be obtained by taking cheap attapulgite clay as a carrier material and adopting a Ca<2+> mark template reaction technology, and processes such as Ca<2+> mark template polymerization modification and molecular cross linkage. The method is mainly used for separating the calcium ions and magnesium ions from calcium-magnesium mixed liquid, and for a decalcification procedure of the waste water of the nickel laterite ore metallurgical industry.
Description
Technical field
The invention belongs to the engineering of water treatment field, relate to a class calcium ion is had preparation method than the strong selectivity sorbing material.
Background technology
Contain a large amount of magnesium sulfate, its Mg in the waste liquid after the lateritic nickel ore employing hydrometallurgy
2+Content usually greater than 50 g/L, have higher recovery value.Since in this waste liquid simultaneously and deposit Ca
2+, generally being about 360～600 mg/L, it can form cocrystallization with magnesium sulfate in removal process, thereby purity and the quality of product are reclaimed in influence.In addition, the Ca in the recovery liquid
2+Easily at the surface scale of evaporating heat exchanger and pipeline, influence heat exchange efficiency, increase production cost, therefore, production technology generally requires the Ca in the water
2+Concentration must be lower than 200 mg/L.
The difficult point of removing calcium ion from Adlerika is the proximity of calcium ions and magnesium ions chemical property.If adopt common water demineralization method, chemical precipitation method, hyperfiltration, electroosmose process etc. all are difficult to the two is separated, and at present commercially available cation exchange resin product lacks selectively the absorption of calcium ion, therefore development and application possesses the adsorption stuffing of high selectivity to calcium ion, should be a kind of simple and efficient ways of removing calcium ion impurities to the production of above-mentioned enterprise.
Summary of the invention
Purpose of the present invention: prepare and a kind of calcium ion is possessed the sorbing material of high selectivity, being used for the separation of calcium magnesium mixed liquor calcium ions and magnesium ions, and metallurgical waste water decalcification processing procedure.
Know-why of the present invention and advantage are that selected carrier material is cheap, and the attapulgite clay that absorption property is high, the inner surface of carrier micropore have adhered to one deck and adopted Ca
2+The polymer that the imprinted templates reaction technology prepares, it has very strong suction-operated to calcium ion, and very poor to the absorption affinity of magnesium ion, so calcium ion is had the adsorptive selectivity of height.This material can reuse through wash-out and drying as if after being adsorbed by saturated with calcium.
The preparation method of calcium ion selective sorbing material of the present invention is as follows:
1) activation of attapulgite clay
In 200～600 ℃ of roasting 1～6 h, the ammonium chloride solution immersion 2-40 h with 0.1 mol/L is washed till neutrality with distilled water, drying, grinding, sieving for standby with attapulgite clay;
2) preparation of sorbing material
To activate attapulgite clay and add appropriate amount of deionized water, making beating, (1%～5%) adding concentration is the acid of 0.5～4 mol/L by volume.Add the initator of aniline and trace then successively, wherein, initator is ammonium persulfate, potassium bichromate, potassium metaperiodate, potassium permanganate etc., and aniline is (0.1～1) with the mass ratio of activation attapulgite clay: 1.At normal temperatures behind stirring reaction 2～8 h, suction filtration, washing, drying, grind, sieve.Be the Ca of 50～800 mg/L with the above-mentioned sorbing material that makes and concentration
2+Solution mixes, and with pH value=6 of NaAC-HAC cushioning liquid regulation system, uses the deionized water cyclic washing to detecting less than Ca behind reaction 0.5～4 h down in steady temperature (40～80 ℃)
2+, dry, be ground into powder standby.
With above-mentioned powder after the aniline polymerization modification respectively with the sodium hydroxide solution of epoxychloropropane, 0.1 mol/L, and three kinds of medicaments such as silane coupler are by mass ratio 1:(0.1～1): (0.5～2): (0.03～0.5) joins successively and mixes in the reactor that fills absolute ethyl alcohol (accounting for cumulative volume 20～50%), and wherein silane coupler is KH-550, KH-560, KH-570 etc.Liquid mixture prepared is carried out cross-linking reaction under room temperature and stirring condition, the time is 2～8 h.
In washing container, the gained cross-linking products is used 0.1～2 mol/L hydrochloric acid solution respectively, 0.05～1 mol/L sodium hydroxide solution, and deionized water washs successively, filters, and detects less than Ca in filtrate
2+Till.To take off the washing vacuum drying at last, and grind, sieving namely obtains Ca
2+Powdery product with high selectivity absorption.
The specific embodiment
The present invention is further illustrated below by example, but the scope that the present invention requires is not limited to the scope that following embodiment is represented.
The preparation of embodiment 1 calcium ion selective sorbing material
Take by weighing the attapulgite clay of 100g, in 300 ℃ of roasting 4 h, soak 6 h with the ammonium chloride solution of 0.1 mol/L, be washed till neutrality with distilled water, dry, grind, cross 200 mesh sieves.
Attapulgite clay after the activation is added in the reaction vessel, add 1 L deionized water, making beating, adding concentration then successively is hydrochloric acid 20 mL of 1 mol/L, 40 g second distillation aniline, 3 g ammonium persulfates at room temperature constantly stir, after reacting 6 h, suction filtration, washing, drying, grinding, mistake 150 mesh sieves.
Take by weighing 50 g above-mentioned materials and 150 mL concentration are the Ca of 300 mg/L
2+Solution mixes, and with pH value=6 of NaAC-HAC cushioning liquid regulation system, reacts 40 min down at 50 ℃, uses the deionized water cyclic washing then, filters, until detecting less than Ca
2+Drying is standby with the grinding back again to leach thing.
Get above-mentioned Ca
2+Chelating modified powder 50 grams, place the 50ml absolute ethyl alcohol, the KH-570 that adds 15mL epoxychloropropane, 50mL sodium hydroxide solution and 2mL, stirring reaction 2 h under the room temperature, polymerisation is the hydrochloric acid of 0.5mol/L with concentration successively after finishing, 0.1mol/L sodium hydroxide solution and deionized water washing, filter, until detecting less than Ca
2+Till.With its vacuum drying, grind at last, sieving namely gets product.
The decalcification of embodiment 2 lateritic nickel ore hydrometallurgy waste water is handled
The calcium ion absorption powder that takes by weighing the preparation of 50g is added in the beaker of 2000 mL, adds then in the 1000 mL lateritic nickel ore hydrometallurgy magnesium sulfate waste water, and wherein the concentration of the calcium ion in the waste water and magnesium ion is respectively 360 mg/L and 58.34 g/L.At room temperature under 300 rad/min, stir 30 min and finish sand filtration.Measurement result to filtrate confirms that the residual calcium ion concentration after selective absorbent is handled is 100 mg/L, and except ca efficiency is 72%, the residual magnesium ion concentration is 57.26 g/L, and demagging efficient only is 1.85%.Magnesium sulfate after the deliming in the water can reclaim.
Claims (5)
1. one kind can adsorb Ca from magnesium sulfate waste water
2+Preparation methods is characterized in that carrying out as follows:
1) get attapulgite clay in 200～600 ℃ of roasting 1～6 h, soak 2～40 h with the ammonium chloride solution of 0.1～1 mol/L, be washed till neutrality with distilled water, dry, grind, sieve;
2) will activate attapulgite clay and add appropriate amount of deionized water, making beating, (1%～5%) adding concentration is the acid of 0.5～4 mol/L by volume; The initator that adds aniline and trace then successively, wherein aniline is (0.1～1) with the mass ratio of activation attapulgite clay: 1; Under the normal temperature behind stirring reaction 2～8 h, suction filtration, washing, drying, grind, sieve; Be the Ca of 50～800 mg/L with the above-mentioned sorbing material that makes and concentration
2+Solution mixes, and with pH value=6 of NaAC-HAC cushioning liquid regulation system, uses the deionized water cyclic washing behind reaction 0.5～4 h down in steady temperature (40～80 ℃), filters, until detecting less than Ca
2+Drying and grinding back are powdered;
With above-mentioned powder after the aniline polymerization modification respectively with the sodium hydroxide solution of epoxychloropropane, 0.1 mol/L, and three kinds of medicaments such as silane coupler are by mass ratio 1:(0.1～1): (0.5～2): (0.03～0.5) joins successively and mixes in the reactor that fills absolute ethyl alcohol (accounting for cumulative volume 20～50%), liquid mixture prepared is carried out cross-linking reaction under room temperature and stirring condition, the time is 2～8 h;
Products therefrom is used 0.1～2 mol/L hydrochloric acid solution respectively in washing container, 0.05～1 mol/L sodium hydroxide solution, and deionized water washs successively, filters, until detecting less than Ca
2+Till; To take off the washing vacuum drying at last, and grind, sieving namely obtains Ca
2+Powdery product with selective absorption function.
2. a kind of can absorption from magnesium sulfate waste water according to claim 1 removed Ca
2+Preparation methods is characterized in that used acid is: sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid etc.
3. a kind of can absorption from magnesium sulfate waste water according to claim 1 removed Ca
2+Preparation methods is characterized in that used initator is: ammonium persulfate, potassium bichromate, potassium metaperiodate, potassium permanganate etc.
4. a kind of can absorption from magnesium sulfate waste water according to claim 1 removed Ca
2+Preparation methods is characterized in that used silane coupler is: KH-550, KH-560, KH-570 etc.
5. a kind of can absorption from magnesium sulfate waste water according to claim 1 removed Ca
2+Preparation methods is characterized in that it is a kind of crystalloid hydrous magnesium aluminosilicate clays mineral of key component that used attapulgite clay refers to the attapulgite, has unique layer chain structure feature, and its desirable chemical molecular formula is: Mg
5Si
8O
2(OH)
2(OH
2)
44H
2O.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613720A (en) * | 2013-11-20 | 2014-03-05 | 东南大学 | Method for preparing silane coupling agent modified attapulgite surface molecular imprinting material aiming at bisphenol A |
| CN104226285A (en) * | 2014-09-22 | 2014-12-24 | 中国石油天然气集团公司 | Regeneration method of calcium ion sorbent |
| CN105170107A (en) * | 2015-10-16 | 2015-12-23 | 西安科技大学 | Preparation method for green heavy metal capturing agent |
| CN107098366A (en) * | 2017-04-25 | 2017-08-29 | 中国恩菲工程技术有限公司 | The method for handling magnesium-containing waste solution |
| CN110357198A (en) * | 2019-06-11 | 2019-10-22 | 武汉兴天宇环境股份有限公司 | A kind of adsorbent material and preparation method thereof for Low Concentration Ammonia Containing Wastewater processing |
| CN110616066A (en) * | 2019-10-14 | 2019-12-27 | 大庆市唯品科技开发有限公司 | Modified acrylamide microsphere gel plugging agent |
| CN113502251A (en) * | 2021-08-11 | 2021-10-15 | 湖北三雄科技发展有限公司 | Preparation method of anti-corrosion wax-control compound microbial agent for oil well exploitation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003033575A1 (en) * | 2001-10-16 | 2003-04-24 | The Johns Hopkins University | Polymer based permeable membrane for removal of ions |
| CN101024675A (en) * | 2006-02-16 | 2007-08-29 | 成均馆大学校产学协力团 | Selective separation of heavy metal ion using metal ion imprinted polymer |
-
2013
- 2013-06-27 CN CN2013102713884A patent/CN103272572A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003033575A1 (en) * | 2001-10-16 | 2003-04-24 | The Johns Hopkins University | Polymer based permeable membrane for removal of ions |
| CN101024675A (en) * | 2006-02-16 | 2007-08-29 | 成均馆大学校产学协力团 | Selective separation of heavy metal ion using metal ion imprinted polymer |
Non-Patent Citations (3)
| Title |
|---|
| HUI XU，ET AL: "Synthesis and Characterization of an Ion-Imprinted Polymer for Selective Adsorption of Copper Ions in Aqueous Solution", 《ADSORPTION SCIENCE & TECHNOLOGY》 * |
| THOMAS ROSATZIM，ET AL: "Preparation of Ca2+ Selective Sorbents by Molecular Imprinting using Polymerisable lonophores", 《JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 2》 * |
| 王丽，等: "改性凹凸棒土对钾、钙、镁离子交换作用的研究", 《中国矿业》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613720A (en) * | 2013-11-20 | 2014-03-05 | 东南大学 | Method for preparing silane coupling agent modified attapulgite surface molecular imprinting material aiming at bisphenol A |
| CN104226285A (en) * | 2014-09-22 | 2014-12-24 | 中国石油天然气集团公司 | Regeneration method of calcium ion sorbent |
| CN105170107A (en) * | 2015-10-16 | 2015-12-23 | 西安科技大学 | Preparation method for green heavy metal capturing agent |
| CN105170107B (en) * | 2015-10-16 | 2017-11-07 | 西安科技大学 | A kind of preparation method of green heavy metal chelating agent |
| CN107098366A (en) * | 2017-04-25 | 2017-08-29 | 中国恩菲工程技术有限公司 | The method for handling magnesium-containing waste solution |
| CN107098366B (en) * | 2017-04-25 | 2018-12-04 | 中国恩菲工程技术有限公司 | The method for handling magnesium-containing waste solution |
| CN110357198A (en) * | 2019-06-11 | 2019-10-22 | 武汉兴天宇环境股份有限公司 | A kind of adsorbent material and preparation method thereof for Low Concentration Ammonia Containing Wastewater processing |
| CN110616066A (en) * | 2019-10-14 | 2019-12-27 | 大庆市唯品科技开发有限公司 | Modified acrylamide microsphere gel plugging agent |
| CN113502251A (en) * | 2021-08-11 | 2021-10-15 | 湖北三雄科技发展有限公司 | Preparation method of anti-corrosion wax-control compound microbial agent for oil well exploitation |
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Application publication date: 20130904 |