CN105478073B - The preparation method of the chalk powder composite material of rhodium ion in a kind of enrichment mine tailing wastewater - Google Patents
The preparation method of the chalk powder composite material of rhodium ion in a kind of enrichment mine tailing wastewater Download PDFInfo
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- CN105478073B CN105478073B CN201510633037.2A CN201510633037A CN105478073B CN 105478073 B CN105478073 B CN 105478073B CN 201510633037 A CN201510633037 A CN 201510633037A CN 105478073 B CN105478073 B CN 105478073B
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- whiting
- rape stalk
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Abstract
The invention belongs to field of compound material, is related to a kind of preparation method for being enriched with the chalk powder composite material of rhodium ion in mine tailing wastewater.Preparation method proposed by the present invention is that modified whiting is combined in the duct of ammonification rape stalk, and concrete technology includes clean rape stalk, ammonification, whiting modification and composite preparation etc..Compared with rape stalk, rhodium ion saturation enriching quantity is greatly improved in composite, and and can avoids the spilling of rape stalk organic carbon in water treatment procedure from polluting.The enriching quantity of rhodium ion is promoted to 111.7mg/g by composite prepared by the present invention, available for mine tailing rhodium-containing wastewater treatment, wide market.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of whiting for being enriched with rhodium ion in mine tailing wastewater is answered
The preparation method of condensation material.
Background technology
The chemical composition of the leachate of ion type rareearth ore is complicated, there is following characteristic：1. concentration is very low, leachate it is dilute
Native concentration is generally 0.5 ~ 2 g/L, and the leaching tail washings for Rare-earth Mine, concentration is lower, and precipitation cost is high so as to unrecovered profit
With, and the concentration for carrying out extract and separate operation needs to reach 250 g/L, the recovery to follow-up rare earth brings problems, and not
Beneficial to the rate of recovery for improving rare earth；2. the content of impurity aluminum, iron and silicon etc. is high, with oxalic acid precipitation, solvable complex Re is generated
[Al(C2O4)3] etc., increase the consumption of oxalic acid, rare-earth yield substantially reduces, if using NH4HCO3Precipitation, impurity can generate coprecipitated thing,
Influence the purity of rare-earth products；3. day output is big, the liquor capacity of leaching is very big, will generally build multiple sedimentation basins, carries out
Rare earth cleans and precipitation, the load of post-treatment procedures are big；4. composition fluctuation is big, the Rare Earth Mine partition difference grade in different mining areas
Difference, and leach when process conditions and operating environment have change, so as to leach rare earth feed liquid concentration difference, chemical group
Into also different, the recovery to rare earth is unfavorable.
Chalk is a kind of loose earthy calcite or lime stone, and main chemical compositions are CaCO3, main mineral constituent is
Biological micrite calcite, the purer person of quality, calcite content is up to more than 99%, often containing quartz, feldspar, clay mineral and sea green
The impurity such as stone.According to color and degree of consolidation, chalk can be divided into white chalk（CaCO3Content reaches 99）, plaster chalk, like white
Chalkstone limestone, four kinds of glauconite chalk.
Control substrate, under different Cu mass of ion concentration, sulfate reducing bacteria (sulfate- are used as using sodium acetate
Reducing bacteria, abbreviation SRB) using rape stalk as matrix treatments acid mine drainage, show to work as initial copper ion matter
It is respectively 0,6.4,12.8,32.0,48.0 mg/l to measure concentration, when, pH value in each system of initial reaction stage is from 5.0 rapid rises
To 7.0~7.5, TOC mass concentrations start first to rise in several days in experiment in reactor, and under rapid after reaching peak value
Drop；Research shows that the suction-operated of stalk reduces toxic action of the copper ion to SRB.Rape stalk is that substrate not only can be with
Slow release carbon source is provided, and inhibitory action of the heavy metal ion to SRB can be weakened as adsorbent.
The creativeness of the present invention is：（1）Chalk powder composite material is a kind of advanced composite material (ACM), as environment-friendly materials work(
Energy potentiality to be exploited is huge；（2）Modified whiting is fixed in ammonification rape stalk with 3- aminopropyl triethoxysilanes, prepared
The preparation technology of chalk powder composite material has no document report；（3）Compared with whiting, or rape stalk metal enrichment
Material is compared, and the performance such as the physical aspect of composite, the structure of matter, metal enrichment amount, recycling utilization is provided with protruding
Substantive distinguishing features and significant progressive.
The content of the invention
The invention belongs to field of compound material, is related to the chalk powder composite material of rhodium ion in a kind of enrichment mine tailing wastewater
Preparation method.Preparation method proposed by the present invention is that modified whiting is combined in the duct of ammonification rape stalk, specific work
Skill includes clean rape stalk, ammonification, whiting modification and composite preparation etc..Whiting composite wood prepared by the present invention
Material has advantages below：（1）Whiting is fixed in rape stalk with 3- aminopropyl triethoxysilanes, rape can be played
The characteristic that densified straw is light, specific surface area is big, the advantages of and can make use of whiting heavy metal rhodium ion accumulation ability strong；
（2）With whiting body phase ratio, composite avoids chalk powder reuniting caking, rhodium ion is enriched with the problem of power reduces, and can
Avoid be enriched with rhodium ion whiting be difficult to reclaim, trigger secondary pollution the problem of；（3）Compared with rape stalk, composite
Rhodium ion saturation enriching quantity is greatly improved, and can avoids the spilling of rape stalk organic carbon in water treatment procedure from polluting.
The enriching quantity of rhodium ion is promoted to 111.7mg/g by composite, i.e. every gram of composite can be enriched with 111.7 mg rhodium ions.This
Rhodium ion enrichment material prepared by invention can be used for mine tailing rhodium-containing wastewater treatment, wide market.
The preparation method of chalk powder composite material proposed by the present invention, it is characterised in that：
1）Clean rape stalk：Rape stalk is rinsed, dried；
2）Rape stalk ammonification：Rape stalk after cleaning is placed in ammoniated solution, placed 100 minutes in 60 DEG C, drift
Wash, dry；The formula of wherein ammoniated solution is that solvent is deionized water, and various solute concentrations are respectively in solution：Hydrazine hydrate is dense
Spend 3 ~ 6g/L, ammonia concn 3 ~ 6g/L, 1,3- propane diamine 3 ~ 6g/L of concentration, 1 ~ 3g/L of ethylenediamine concentration；
3）Whiting is modified：Whiting is placed in acrylic acid/Macrogol 4000 mixed aqueous solution, stirred 1 hour, mistake
Filter, dry 3 ~ 12 hours, cooling, be washed with deionized in 100 DEG C, dry, obtain modified whiting；Wherein whiting and third
Material/liquor ratio of olefin(e) acid/Macrogol 4000 mixed solution is 1/5 ~ 1/20 g/ mL；Wherein acrylic acid/Macrogol 4000 mixes
The mass concentration of acrylic acid is 20 ~ 30% in Heshui solution, and the mass concentration of Macrogol 4000 is 0.1 ~ 0.3%；
4）It is prepared by composite：3- aminopropyl triethoxysilanes are dissolved in ethanol, sequentially add ammonification rape stalk
And modified whiting, stir 1 ~ 4 hour, be placed in drying box, dried 12 hours in 40 ~ 60 DEG C, obtain chalk powder composite material；Its
In the weight ratios of various materials be：Ammonification rape stalk/modification whiting/3- aminopropyl triethoxysilanes/ethanol=2/1/2/
5。
Chalk powder composite material is placed in rhodium-containing mine tailing wastewater, regulation solution ph is 5 ~ 6, is enriched with 4 hours in 25 DEG C,
The concentration of rhodium ion is 50 ~ 500mg/L in waste water, and enrichment finishes, and filtering, detects the rhodium ion amount being enriched with composite.
It is small in 0.2M disodium ethylene diamine tetra-acetic acid aqueous solution 1 that the composite of above-mentioned enrichment rhodium ion is placed in concentration
When, filter, clean, drying, complete solution process of enriching, obtain the chalk powder composite material of regeneration；Again by above-mentioned regenerated composite material
It is placed in rhodium-containing mine tailing wastewater, carries out rhodium ion enrichment.Such multiple circulations, until the rhodium ion enriching quantity of composite is less than
The 85% of first enriching quantity.
Embodiment
The invention is further illustrated by the following examples
Embodiment 1
Rape stalk is gathered in, cleaned with running water, is dried.
Hydrazine hydrate, ammoniacal liquor, 1,3- propane diamine, ethylenediamine are dissolved in deionized water, concentration of hydrazine hydrate 3g/L, ammoniacal liquor is dense
It is 6g/L to spend for 3g/L, 1,3- propane diamine concentration, and ethylenediamine concentration is 1g/L, obtains ammoniated solution.
The 50g rape stalks cleaned are placed in 500mL ammoniated solutions, placed 100 minutes in 60 DEG C, rinsing, drying, are obtained
The rape stalk of ammonification.
Acrylic acid, Macrogol 4000 are dissolved in deionized water, the mass concentration of acrylic acid is 20%, polyethylene glycol
4000 mass concentration is 0.3%, obtains acrylic acid/Macrogol 4000 mixed aqueous solution.
100g whiting is placed in 500mL acrylic acid/Macrogol 4000 mixed aqueous solution, stirred 1 hour, filtering,
Dry 3 hours, cooling, be washed with deionized in 100 DEG C, dry, obtain modified whiting.
20g3- aminopropyl triethoxysilanes are dissolved in 50g ethanol, 20g ammonifications rape stalk is sequentially added and 10g changes
Property whiting, stir 1 hour, be placed in drying box, in 60 DEG C dry 12 hours, obtain chalk powder composite material.
100g chalk powder composite materials are placed in 100L rhodium-containing mine tailing wastewaters, regulation solution ph is 5 ~ 6, in 25 DEG C of richnesses
Collection 4 hours, the concentration of rhodium ion is 50mg/L in waste water, and enrichment finishes, filtering, and the rhodium ion amount of detection composite enrichment is
41.1mg/g。
It is small in 0.2M disodium ethylene diamine tetra-acetic acid aqueous solution 1 that the composite of above-mentioned enrichment rhodium ion is placed in concentration
When, filter, clean, drying, complete solution process of enriching, obtain the chalk powder composite material of regeneration；Again by above-mentioned regenerated composite material
It is placed in rhodium-containing mine tailing wastewater, carries out rhodium ion enrichment.Such 4 circulations, the rhodium ion enriching quantity of composite are less than for the first time
The 85% of enriching quantity.
Embodiment 2
Rape stalk is gathered in, cleaned with running water, is dried.
Hydrazine hydrate, ammoniacal liquor, 1,3- propane diamine, ethylenediamine are dissolved in deionized water, concentration of hydrazine hydrate 6g/L, ammoniacal liquor is dense
It is 3g/L to spend for 6g/L, 1,3- propane diamine concentration, and ethylenediamine concentration is 3g/L, obtains ammoniated solution.
The 50g rape stalks cleaned are placed in 500mL ammoniated solutions, placed 100 minutes in 60 DEG C, rinsing, drying, are obtained
The rape stalk of ammonification.
Acrylic acid, Macrogol 4000 are dissolved in deionized water, the mass concentration of acrylic acid is 30%, polyethylene glycol
4000 mass concentration is 0.1%, obtains acrylic acid/Macrogol 4000 mixed aqueous solution.
100g whiting is placed in 2000mL acrylic acid/Macrogol 4000 mixed aqueous solution, stirred 1 hour, filtering,
Dry 12 hours, cooling, be washed with deionized in 100 DEG C, dry, obtain modified whiting.
200g3- aminopropyl triethoxysilanes are dissolved in 500g ethanol, sequentially add 200g ammonifications rape stalk and
100g is modified whiting, stirs 4 hours, is placed in drying box, is dried 12 hours in 40 DEG C, obtains chalk powder composite material.
10g chalk powder composite materials are placed in 100L rhodium-containing mine tailing wastewaters, regulation solution ph is 5 ~ 6, in 25 DEG C of richnesses
Collection 4 hours, the concentration of rhodium ion is 50mg/L in waste water, and enrichment finishes, filtering, and the rhodium ion amount of detection composite enrichment is
100.6mg/g。
It is small in 0.2M disodium ethylene diamine tetra-acetic acid aqueous solution 1 that the composite of above-mentioned enrichment rhodium ion is placed in concentration
When, filter, clean, drying, complete solution process of enriching, obtain the chalk powder composite material of regeneration；Again by above-mentioned regenerated composite material
It is placed in rhodium-containing mine tailing wastewater, carries out rhodium ion enrichment.Such 6 circulations, the rhodium ion enriching quantity of composite are less than for the first time
The 85% of enriching quantity.
Embodiment 3
Rape stalk is gathered in, cleaned with running water, is dried.
Hydrazine hydrate, ammoniacal liquor, 1,3- propane diamine, ethylenediamine are dissolved in deionized water, concentration of hydrazine hydrate 4g/L, ammoniacal liquor is dense
It is 5g/L to spend for 5g/L, 1,3- propane diamine concentration, and ethylenediamine concentration is 2g/L, obtains ammoniated solution.
The 100g rape stalks cleaned are placed in 500mL ammoniated solutions, placed 100 minutes in 60 DEG C, rinsing, drying,
Obtain the rape stalk of ammonification.
Acrylic acid, Macrogol 4000 are dissolved in deionized water, the mass concentration of acrylic acid is 25%, polyethylene glycol
4000 mass concentration is 0.2%, obtains acrylic acid/Macrogol 4000 mixed aqueous solution.
100g whiting is placed in 1000mL acrylic acid/Macrogol 4000 mixed aqueous solution, stirred 1 hour, filtering,
Dry 4 hours, cooling, be washed with deionized in 100 DEG C, dry, obtain modified whiting.
100g3- aminopropyl triethoxysilanes are dissolved in 250g ethanol, sequentially add 100g ammonifications rape stalk and
50g is modified whiting, stirs 3 hours, is placed in drying box, is dried 12 hours in 50 DEG C, obtains chalk powder composite material.
20g chalk powder composite materials are placed in 10L rhodium-containing mine tailing wastewaters, regulation solution ph is 5 ~ 6, in 25 DEG C of enrichments
4 hours, the concentration of rhodium ion was 500mg/L in waste water, and enrichment finishes, filtering, and the rhodium ion amount of detection composite enrichment is
94.1mg/g。
It is small in 0.2M disodium ethylene diamine tetra-acetic acid aqueous solution 1 that the composite of above-mentioned enrichment rhodium ion is placed in concentration
When, filter, clean, drying, complete solution process of enriching, obtain the chalk powder composite material of regeneration；Again by above-mentioned regenerated composite material
It is placed in rhodium-containing mine tailing wastewater, carries out rhodium ion enrichment.Such 5 circulations, the rhodium ion enriching quantity of composite are less than for the first time
The 85% of enriching quantity.
Embodiment 4
Rape stalk is gathered in, cleaned with running water, is dried.
Hydrazine hydrate, ammoniacal liquor, 1,3- propane diamine, ethylenediamine are dissolved in deionized water, concentration of hydrazine hydrate 5g/L, ammoniacal liquor is dense
It is 4g/L to spend for 4g/L, 1,3- propane diamine concentration, and ethylenediamine concentration is 3g/L, obtains ammoniated solution.
The 10g rape stalks cleaned are placed in 500mL ammoniated solutions, placed 100 minutes in 60 DEG C, rinsing, drying, are obtained
The rape stalk of ammonification.
Acrylic acid, Macrogol 4000 are dissolved in deionized water, the mass concentration of acrylic acid is 28%, polyethylene glycol
4000 mass concentration is 0.3%, obtains acrylic acid/Macrogol 4000 mixed aqueous solution.
100g whiting is placed in 1500mL acrylic acid/Macrogol 4000 mixed aqueous solution, stirred 1 hour, filtering,
Dry 5 hours, cooling, be washed with deionized in 100 DEG C, dry, obtain modified whiting.
10g3- aminopropyl triethoxysilanes are dissolved in 25g ethanol, 10g ammonifications rape stalk is sequentially added and 5g changes
Property whiting, stir 2 hours, be placed in drying box, in 40 DEG C dry 12 hours, obtain chalk powder composite material.
20g chalk powder composite materials are placed in 50L rhodium-containing mine tailing wastewaters, regulation solution ph is 5 ~ 6, in 25 DEG C of enrichments
4 hours, the concentration of rhodium ion was 160mg/L in waste water, and enrichment finishes, filtering, and the rhodium ion amount of detection composite enrichment is
111.7mg/g。
It is small in 0.2M disodium ethylene diamine tetra-acetic acid aqueous solution 1 that the composite of above-mentioned enrichment rhodium ion is placed in concentration
When, filter, clean, drying, complete solution process of enriching, obtain the chalk powder composite material of regeneration；Again by above-mentioned regenerated composite material
It is placed in rhodium-containing mine tailing wastewater, carries out rhodium ion enrichment.Such 7 circulations, the rhodium ion enriching quantity of composite are less than for the first time
The 85% of enriching quantity.
Claims (1)
- A kind of 1. preparation method for being enriched with the chalk powder composite material of rhodium ion in mine tailing wastewater, it is characterised in that：1）Clean rape stalk：Rape stalk is rinsed, dried；2）Rape stalk ammonification：Rape stalk after cleaning is placed in ammoniated solution, placed 100 minutes in 60 DEG C, rinsing, is dried It is dry；The formula of wherein ammoniated solution is that solvent is deionized water, and various solute concentrations are respectively in solution：Concentration of hydrazine hydrate 3 ~ 6g/L, ammonia concn 3 ~ 6g/L, 1,3- propane diamine 3 ~ 6g/L of concentration, 1 ~ 3g/L of ethylenediamine concentration；3）Whiting is modified：Whiting is placed in acrylic acid/Macrogol 4000 mixed aqueous solution, stirred 1 hour, filtering, Dry 3 ~ 12 hours, cooling, be washed with deionized in 100 DEG C, dry, obtain modified whiting；Wherein whiting and propylene Material/liquor ratio of acid/Macrogol 4000 mixed solution is 1/5 ~ 1/20 g/ mL；Wherein acrylic acid/Macrogol 4000 mixing The mass concentration of acrylic acid is 20 ~ 30% in the aqueous solution, and the mass concentration of Macrogol 4000 is 0.1 ~ 0.3%；4）It is prepared by composite：3- aminopropyl triethoxysilanes are dissolved in ethanol, ammonification rape stalk is sequentially added and changes Property whiting, stir 1 ~ 4 hour, mixture is placed in drying box, in 40 ~ 60 DEG C dry 12 hours, obtain chalk powder composite material； The weight ratio of wherein various materials is：Ammonification rape stalk/modification whiting/3- aminopropyl triethoxysilanes/ethanol=2/1/ 2/5。
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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 |
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