CN105478073A - Preparation method of chalk-powder composite material for enriching rhodium ion in mine-tailing wastewater - Google Patents
Preparation method of chalk-powder composite material for enriching rhodium ion in mine-tailing wastewater Download PDFInfo
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- CN105478073A CN105478073A CN201510633037.2A CN201510633037A CN105478073A CN 105478073 A CN105478073 A CN 105478073A CN 201510633037 A CN201510633037 A CN 201510633037A CN 105478073 A CN105478073 A CN 105478073A
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- whiting
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- rape stalk
- rhodium
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Abstract
The invention belongs to the field of composite materials, and relates to a preparation method of a chalk-powder composite material for enriching rhodium ion in mine-tailing wastewater. The provided preparation method comprises filling holes of ammoniated brassica-campestris straws with modified chalk powder. The concrete technology comprises cleaning brassica-campestris straws, ammoniating, modifying chalk powder, and preparing the composite material. Compared with brassica-campestris straws, the composite material substantially improves in rhodium ion saturation enrichment amount, and overflow pollution of brassica-campestris straw organic carbon during water processing is avoided. The prepared composite material improves the rhodium ion enrichment amount to 111.7 mg/g, is applicable to process mine-tailing rhodium-containing wastewater, and is extensive in market prospect.
Description
Technical field
The invention belongs to technical field of composite materials, be specifically related to the preparation method of the whiting composite of rhodium ion in a kind of enrichment mine tailing wastewater.
Background technology
The chemical composition of the leachate of ion type rareearth ore is complicated, there is following characteristic: 1. concentration is very low, the rare earth concentration of leachate is generally 0.5 ~ 2g/L, for the leaching tail washings of Rare-earth Mine, concentration is lower, and precipitation cost is high thus do not recycle, and the concentration of carrying out extract and separate operation needs to reach 250g/L, bring problems to the recovery of follow-up rare earth, and be unfavorable for the rate of recovery improving rare earth; 2. the content of impurity aluminum, iron and silicon etc. is high, with oxalic acid precipitation, generates solvable complex Re [Al (C
2o
4)
3] etc., increase the consumption of oxalic acid, rare-earth yield reduces greatly, if use NH
4hCO
3precipitation, impurity can generate coprecipitated thing, affects the purity of rare-earth products; 3. day output is large, and the liquor capacity of leaching is very large, and usually all will build multiple sedimentation basin, carry out rare earth removal of impurities and precipitation, the load of post-treatment procedures is large; 4. composition fluctuation is large, and the different grade of Rare Earth Mine partition in different mining area is also different, and process conditions during leaching and operating environment have change, thus the rare earth feed liquid concentration leached is different, and chemical composition is also different, unfavorable to the recovery of rare earth.
Chalk is a kind of loose earthy calcite or lime stone, and main chemical compositions is CaCO
3, main mineral constituent is biological micrite calcite, the purer person of quality, and calcite content can reach more than 99%, normal containing impurity such as quartz, feldspar, clay mineral and glauconites.According to color and degree of consolidation, chalk can be divided into white chalk (CaCO
3content reaches 99), plaster chalk, like chalkstone limestone, glauconite chalk four kinds.
With sodium acetate substrate in contrast, under different Cu mass of ion concentration, sulfate reducing bacteria (sulfate-reducingbacteria, be called for short SRB) be matrix treatments acid mine drainage with rape stalk, show when initial copper ion mass concentration be respectively 0,6.4,12.8,32.0,48.0mg/l, time, pH value in each system of initial reaction stage is elevated to 7.0 ~ 7.5 rapidly from 5.0, in reactor, TOC mass concentration starts all first to rise in several days in experiment, and declines rapidly after reaching peak value; Research shows, the suction-operated of stalk reduces the toxic action of copper ion to SRB.Rape stalk not only can provide slow release carbon source for substrate, and can weaken the inhibitory action of heavy metal ion to SRB as adsorbent.
Creativeness of the present invention is: (1) whiting composite is a kind of advanced composite material (ACM), has a high potential as environment-friendly materials functional development; (2) be fixed in ammonification rape stalk by modification whiting with 3-aminopropyl triethoxysilane, the preparation technology preparing whiting composite has no bibliographical information; (3) compared with whiting, or rape stalk metal enrichment material is compared, and the performance such as physical aspect, the structure of matter, metal enrichment amount, recycling utilization of composite all possesses outstanding substantive distinguishing features and progress significantly.
Summary of the invention
The invention belongs to field of compound material, relate to the preparation method of the whiting composite of rhodium ion in a kind of enrichment mine tailing wastewater.Modification whiting is compound in the duct of ammonification rape stalk by the preparation method that the present invention proposes, and concrete technology comprises that rape stalk is cleaned, prepared by ammonification, whiting modification and composite.Whiting composite prepared by the present invention has the following advantages: whiting is fixed in rape stalk with 3-aminopropyl triethoxysilane by (1), the characteristic that rape stalk density is light, specific area is large can be played, the advantage that whiting heavy metal rhodium ion accumulation ability is strong can be make use of again; (2) compared with chalk powder, the problem that composite avoids chalk powder reuniting caking, rhodium ion enrichment power reduces, can avoid again the whiting of enrichment rhodium ion to be difficult to reclaim, cause the problem of secondary pollution; (3) compared with rape stalk, composite significantly improves the saturated enriching quantity of rhodium ion, and the spilling of rape stalk organic carbon in water treatment procedure can be avoided again to pollute.The enriching quantity of rhodium ion is promoted to 111.7mg/g by composite, and namely every gram of composite can enrichment 111.7mg rhodium ion.Rhodium ion enrichment material prepared by the present invention can be used for the wastewater treatment of mine tailing rhodium-containing, wide market.
The preparation method of the whiting composite that the present invention proposes, is characterized in that:
1) clean rape stalk: by rape stalk rinsing, oven dry;
2) rape stalk ammonification: the rape stalk after clean is placed in ammoniated solution, places 100 minutes in 60 DEG C, rinsing, oven dry; Wherein the formula of ammoniated solution is solvent is deionized water, and in solution, various solute concentration is respectively: concentration of hydrazine hydrate 3 ~ 6g/L, ammonia concn 3 ~ 6g/L, 1,3-propane diamine concentration 3 ~ 6g/L, ethylenediamine concentration 1 ~ 3g/L;
3) whiting modification: whiting is placed in acrylic acid/Macrogol 4000 mixed aqueous solution, stirs 1 hour, filters, and in 100 DEG C of dryings 3 ~ 12 hours, cooling, spent deionized water, dry, obtained the whiting of modification; Wherein material/the liquor ratio of whiting and acrylic acid/Macrogol 4000 mixed solution is 1/5 ~ 1/20g/mL; In wherein acrylic acid/Macrogol 4000 mixed aqueous solution, acrylic acid mass concentration is 20 ~ 30%, and the mass concentration of Macrogol 4000 is 0.1 ~ 0.3%;
4) composite preparation: 3-aminopropyl triethoxysilane is dissolved in ethanol, adds ammonification rape stalk and modification whiting successively, stir 1 ~ 4 hour, be placed in drying box, in 40 ~ 60 DEG C of dryings 12 hours, obtain whiting composite; Wherein the weight ratio of various material is: ammonification rape stalk/modification whiting/3-aminopropyl triethoxysilane/ethanol=2/1/2/5.
Whiting composite is placed in rhodium-containing mine tailing wastewater, and regulate solution ph to be 5 ~ 6, in 25 DEG C of enrichments 4 hours, in waste water, the concentration of rhodium ion was 50 ~ 500mg/L, and enrichment is complete, filtered, and detected the rhodium ion amount of enrichment in composite.
The composite of above-mentioned enrichment rhodium ion is placed in the disodium ethylene diamine tetra-acetic acid aqueous solution 1 hour that concentration is 0.2M, filters, clean, dry, complete solution process of enriching, obtain the whiting composite of regeneration; Again above-mentioned regenerated composite material is placed in rhodium-containing mine tailing wastewater, carries out rhodium ion enrichment.Multiple circulation like this, until the rhodium ion enriching quantity of composite is less than 85% of first enriching quantity.
Detailed description of the invention
The invention is further illustrated by the following examples
Embodiment 1
Rape stalk is gathered in, cleans with running water, dry.
Be dissolved in deionized water by hydrazine hydrate, ammoniacal liquor, 1,3-propane diamine, ethylenediamine, concentration of hydrazine hydrate is 3g/L, and ammonia concn is 3g/L, 1,3-propane diamine concentration is 6g/L, and ethylenediamine concentration is 1g/L, obtains ammoniated solution.
The rape stalk that 50g cleans is placed in 500mL ammoniated solution, and place 100 minutes in 60 DEG C, rinsing, oven dry, obtain the rape stalk of ammonification.
Be dissolved in deionized water by acrylic acid, Macrogol 4000, acrylic acid mass concentration is 20%, and the mass concentration of Macrogol 4000 is 0.3%, obtains acrylic acid/Macrogol 4000 mixed aqueous solution.
100g whiting is placed in 500mL acrylic acid/Macrogol 4000 mixed aqueous solution, stirs 1 hour, filter, in 100 DEG C of dryings 3 hours, cooling, spent deionized water, dry, obtained the whiting of modification.
20g3-aminopropyl triethoxysilane is dissolved in 50g ethanol, adds 20g ammonification rape stalk and 10g modification whiting successively, stir 1 hour, be placed in drying box, in 60 DEG C of dryings 12 hours, obtain whiting composite.
100g whiting composite is placed in 100L rhodium-containing mine tailing wastewater, and regulate solution ph to be 5 ~ 6, in 25 DEG C of enrichments 4 hours, in waste water, the concentration of rhodium ion was 50mg/L, and enrichment is complete, filtered, and the rhodium ion amount detecting composite enrichment is 41.1mg/g.
The composite of above-mentioned enrichment rhodium ion is placed in the disodium ethylene diamine tetra-acetic acid aqueous solution 1 hour that concentration is 0.2M, filters, clean, dry, complete solution process of enriching, obtain the whiting composite of regeneration; Again above-mentioned regenerated composite material is placed in rhodium-containing mine tailing wastewater, carries out rhodium ion enrichment.4 circulations like this, the rhodium ion enriching quantity of composite is less than 85% of first enriching quantity.
Embodiment 2
Rape stalk is gathered in, cleans with running water, dry.
Be dissolved in deionized water by hydrazine hydrate, ammoniacal liquor, 1,3-propane diamine, ethylenediamine, concentration of hydrazine hydrate is 6g/L, and ammonia concn is 6g/L, 1,3-propane diamine concentration is 3g/L, and ethylenediamine concentration is 3g/L, obtains ammoniated solution.
The rape stalk that 50g cleans is placed in 500mL ammoniated solution, and place 100 minutes in 60 DEG C, rinsing, oven dry, obtain the rape stalk of ammonification.
Be dissolved in deionized water by acrylic acid, Macrogol 4000, acrylic acid mass concentration is 30%, and the mass concentration of Macrogol 4000 is 0.1%, obtains acrylic acid/Macrogol 4000 mixed aqueous solution.
100g whiting is placed in 2000mL acrylic acid/Macrogol 4000 mixed aqueous solution, stirs 1 hour, filter, in 100 DEG C of dryings 12 hours, cooling, spent deionized water, dry, obtained the whiting of modification.
200g3-aminopropyl triethoxysilane is dissolved in 500g ethanol, adds 200g ammonification rape stalk and 100g modification whiting successively, stir 4 hours, be placed in drying box, in 40 DEG C of dryings 12 hours, obtain whiting composite.
10g whiting composite is placed in 100L rhodium-containing mine tailing wastewater, and regulate solution ph to be 5 ~ 6, in 25 DEG C of enrichments 4 hours, in waste water, the concentration of rhodium ion was 50mg/L, and enrichment is complete, filtered, and the rhodium ion amount detecting composite enrichment is 100.6mg/g.
The composite of above-mentioned enrichment rhodium ion is placed in the disodium ethylene diamine tetra-acetic acid aqueous solution 1 hour that concentration is 0.2M, filters, clean, dry, complete solution process of enriching, obtain the whiting composite of regeneration; Again above-mentioned regenerated composite material is placed in rhodium-containing mine tailing wastewater, carries out rhodium ion enrichment.6 circulations like this, the rhodium ion enriching quantity of composite is less than 85% of first enriching quantity.
Embodiment 3
Rape stalk is gathered in, cleans with running water, dry.
Be dissolved in deionized water by hydrazine hydrate, ammoniacal liquor, 1,3-propane diamine, ethylenediamine, concentration of hydrazine hydrate is 4g/L, and ammonia concn is 5g/L, 1,3-propane diamine concentration is 5g/L, and ethylenediamine concentration is 2g/L, obtains ammoniated solution.
The rape stalk that 100g cleans is placed in 500mL ammoniated solution, and place 100 minutes in 60 DEG C, rinsing, oven dry, obtain the rape stalk of ammonification.
Be dissolved in deionized water by acrylic acid, Macrogol 4000, acrylic acid mass concentration is 25%, and the mass concentration of Macrogol 4000 is 0.2%, obtains acrylic acid/Macrogol 4000 mixed aqueous solution.
100g whiting is placed in 1000mL acrylic acid/Macrogol 4000 mixed aqueous solution, stirs 1 hour, filter, in 100 DEG C of dryings 4 hours, cooling, spent deionized water, dry, obtained the whiting of modification.
100g3-aminopropyl triethoxysilane is dissolved in 250g ethanol, adds 100g ammonification rape stalk and 50g modification whiting successively, stir 3 hours, be placed in drying box, in 50 DEG C of dryings 12 hours, obtain whiting composite.
20g whiting composite is placed in 10L rhodium-containing mine tailing wastewater, and regulate solution ph to be 5 ~ 6, in 25 DEG C of enrichments 4 hours, in waste water, the concentration of rhodium ion was 500mg/L, and enrichment is complete, filtered, and the rhodium ion amount detecting composite enrichment is 94.1mg/g.
The composite of above-mentioned enrichment rhodium ion is placed in the disodium ethylene diamine tetra-acetic acid aqueous solution 1 hour that concentration is 0.2M, filters, clean, dry, complete solution process of enriching, obtain the whiting composite of regeneration; Again above-mentioned regenerated composite material is placed in rhodium-containing mine tailing wastewater, carries out rhodium ion enrichment.5 circulations like this, the rhodium ion enriching quantity of composite is less than 85% of first enriching quantity.
Embodiment 4
Rape stalk is gathered in, cleans with running water, dry.
Be dissolved in deionized water by hydrazine hydrate, ammoniacal liquor, 1,3-propane diamine, ethylenediamine, concentration of hydrazine hydrate is 5g/L, and ammonia concn is 4g/L, 1,3-propane diamine concentration is 4g/L, and ethylenediamine concentration is 3g/L, obtains ammoniated solution.
The rape stalk that 10g cleans is placed in 500mL ammoniated solution, and place 100 minutes in 60 DEG C, rinsing, oven dry, obtain the rape stalk of ammonification.
Be dissolved in deionized water by acrylic acid, Macrogol 4000, acrylic acid mass concentration is 28%, and the mass concentration of Macrogol 4000 is 0.3%, obtains acrylic acid/Macrogol 4000 mixed aqueous solution.
100g whiting is placed in 1500mL acrylic acid/Macrogol 4000 mixed aqueous solution, stirs 1 hour, filter, in 100 DEG C of dryings 5 hours, cooling, spent deionized water, dry, obtained the whiting of modification.
10g3-aminopropyl triethoxysilane is dissolved in 25g ethanol, adds 10g ammonification rape stalk and 5g modification whiting successively, stir 2 hours, be placed in drying box, in 40 DEG C of dryings 12 hours, obtain whiting composite.
20g whiting composite is placed in 50L rhodium-containing mine tailing wastewater, and regulate solution ph to be 5 ~ 6, in 25 DEG C of enrichments 4 hours, in waste water, the concentration of rhodium ion was 160mg/L, and enrichment is complete, filtered, and the rhodium ion amount detecting composite enrichment is 111.7mg/g.
The composite of above-mentioned enrichment rhodium ion is placed in the disodium ethylene diamine tetra-acetic acid aqueous solution 1 hour that concentration is 0.2M, filters, clean, dry, complete solution process of enriching, obtain the whiting composite of regeneration; Again above-mentioned regenerated composite material is placed in rhodium-containing mine tailing wastewater, carries out rhodium ion enrichment.7 circulations like this, the rhodium ion enriching quantity of composite is less than 85% of first enriching quantity.
Claims (1)
1. the preparation method of the whiting composite of rhodium ion in enrichment mine tailing wastewater, is characterized in that:
1) clean rape stalk: by rape stalk rinsing, oven dry;
2) rape stalk ammonification: the rape stalk after clean is placed in ammoniated solution, places 100 minutes in 60 DEG C, rinsing, oven dry; Wherein the formula of ammoniated solution is solvent is deionized water, and in solution, various solute concentration is respectively: concentration of hydrazine hydrate 3 ~ 6g/L, ammonia concn 3 ~ 6g/L, 1,3-propane diamine concentration 3 ~ 6g/L, ethylenediamine concentration 1 ~ 3g/L;
3) whiting modification: whiting is placed in acrylic acid/Macrogol 4000 mixed aqueous solution, stirs 1 hour, filters, and in 100 DEG C of dryings 3 ~ 12 hours, cooling, spent deionized water, dry, obtained the whiting of modification; Wherein material/the liquor ratio of whiting and acrylic acid/Macrogol 4000 mixed solution is 1/5 ~ 1/20g/mL; In wherein acrylic acid/Macrogol 4000 mixed aqueous solution, acrylic acid mass concentration is 20 ~ 30%, and the mass concentration of Macrogol 4000 is 0.1 ~ 0.3%;
4) composite preparation: be dissolved in ethanol by 3-aminopropyl triethoxysilane, add ammonification rape stalk and modification whiting successively, stir 1 ~ 4 hour, mixture is placed in drying box, in 40 ~ 60 DEG C of dryings 12 hours, obtains whiting composite; Wherein the weight ratio of various material is: ammonification rape stalk/modification whiting/3-aminopropyl triethoxysilane/ethanol=2/1/2/5.
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| CN201510633037.2A CN105478073B (en) | 2015-09-30 | 2015-09-30 | The preparation method of the chalk powder composite material of rhodium ion in a kind of enrichment mine tailing wastewater |
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| CN201510633037.2A CN105478073B (en) | 2015-09-30 | 2015-09-30 | The preparation method of the chalk powder composite material of rhodium ion in a kind of enrichment mine tailing wastewater |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030116504A1 (en) * | 2001-07-24 | 2003-06-26 | Vempati Rajan K. | Absorbent for arsenic species and method of treating arsenic-contaminated waters |
| CN103551121A (en) * | 2013-11-15 | 2014-02-05 | 南京大学 | Adsorbing material prepared from waste straws and capable of adsorbing trivalent arsenic from water as well as preparation method and application thereof |
| CN104383896A (en) * | 2014-10-31 | 2015-03-04 | 田琳琳 | Composite material for purifying industrial waste water |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030116504A1 (en) * | 2001-07-24 | 2003-06-26 | Vempati Rajan K. | Absorbent for arsenic species and method of treating arsenic-contaminated waters |
| CN103551121A (en) * | 2013-11-15 | 2014-02-05 | 南京大学 | Adsorbing material prepared from waste straws and capable of adsorbing trivalent arsenic from water as well as preparation method and application thereof |
| CN104383896A (en) * | 2014-10-31 | 2015-03-04 | 田琳琳 | Composite material for purifying industrial waste water |
Non-Patent Citations (2)
| Title |
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| 中国五金矿产进出口总公司编: "《金属及矿产品国际贸易指南》", 31 August 1989 * |
| 朱春山主编: "《汽车胶黏剂》", 31 March 2009 * |
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