CN104609526A - Heavy metal collector and preparation method thereof - Google Patents
Heavy metal collector and preparation method thereof Download PDFInfo
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- CN104609526A CN104609526A CN201410828302.8A CN201410828302A CN104609526A CN 104609526 A CN104609526 A CN 104609526A CN 201410828302 A CN201410828302 A CN 201410828302A CN 104609526 A CN104609526 A CN 104609526A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a DTC (dithiocarbamate) heavy metal collector synthesized by taking inorganic polymer as a parent and a preparation method of the heavy metal collector. The inorganic polymer parent used by the collector has porosity and has good absorption capacity; a grafted DTC functional group also has better chelation capability, so that a bifunctional collection active site is formed; the collector can rapidly chelate and absorb as well as precipitate and separate heavy metal ions such as Pb<2+>, Cd<2+>, Cu<2+>, Cr<3+> and Hg<2+> in water and remove heavy metals. Compared with the prior art, the collector has the following advantages: 1, an inorganic polymer material serves as the collector parent, so that the floc volume can be increased significantly, and precipitation and separation after collection are facilitated in comparison to the traditional small molecular DTC collector; 2, compared with the traditional polyethyleneimine parent, the inorganic polymer material serves as the collector parent, so that the cost is greatly lowered, and industrial mass production and application are facilitated; and 3, the inorganic polymer material as the collector parent is porous and has the good absorption capacity, and is combined with DTC with better chelation capability to allow the synthesized collector to form the chelation and absorption bifunctional collection active site, and the collection capability is improved.
Description
Technical field
The present invention relates to technical field of chemical products, be specially a kind of heavy metal chelating agent relevant with the silylation dithiocar-bamate of inorganic matrix grafting and preparation method thereof.
Background technology
Current, industrial development is rapid, but the environmental pollution brought also increasingly sharpens, and heavy-metal pollution is its importance.Because heavy metal ion source is numerous, complicated component, wastewater discharge standard improves gradually.Traditional moderate water-cut stage process heavy metal wastewater thereby technology has many defects, such as, the pH value that needs to keep under strict control, is easy to secondary pollution, needs fractional precipitation to cause complex process etc.; Silica gel, diatomite, wilkinite etc. is used comparatively to rely on porousness and the high-specific surface area of sorbent material as the absorption rule of sorbent material, and comparatively responsive to pH value.Given this, bring into use organic heavy metal trapping agent heavy-metal ion removal in the world, many is dithiocar-bamate (dithiocarbamate is called for short DTC), by means of the sequestering power that it is extremely strong, contents of many kinds of heavy metal ion can be removed efficiently.
Use organic polyamine molecule for parent can synthesized micromolecule DTC, although heavy metal ion chelating efficiency is high, the flco formed is little, and settling property is poor; Then apply limited because cost is high with the macromole DTC that polymer synthesizes for parent as polymine.Bibliographical information also obtains good heavy metals removal effect with the natural polymer such as starch, glucose product as the DTC that parent synthesizes, but its parent does not have porousness, and only play support and flco effect as section bar, function is comparatively single.
Summary of the invention
In order to overcome above-mentioned existing DTC trapping agent above shortcomings or defect, the invention provides a kind of DTC type heavy metal chelating agent synthesized as parent by inorganic polymer and preparation method thereof; The inorganic polymer parent that this trapping agent uses has porousness, inherently has good adsorptive power, and the DTC functional group of grafting also has stronger sequestering power, therefore forms difunctional trapping active sites; This trapping agent can with the Pb in water
2+, Cd
2+, Cu
2+, Cr
3+, Hg
2+etc. the rapid chelating of heavy metal ion and absorption, make it to precipitate and be separated, heavy metal being separated and removing.
Order of the present invention realizes in the following way:
A kind of structural formula of heavy metal chelating agent is:
Wherein R is CH
2cH
2cH
2, CH
2cH
2cH
2nHCH
2cH
2, CH
2cH
2cH
2nHCH
2cH
2nHCH
2cH
2in one, atom N wherein all can form N-CS by said structure
2me functional group; Me=Na or K; The structure wherein with chelating function is N-CS
2me functional group.
The preparation method of above-mentioned heavy metal chelating agent comprises the steps:
(1), by the inorganic polymer parent of drying be placed in solvent, add aminosilane, back flow reaction, be finally separated, wash, dry, obtain the inorganic matrix of aminosilane grafting;
(2), in the basic conditions, inorganic matrix and the dithiocarbonic anhydride of aminosilane grafting step (1) prepared react, the inorganic matrix of obtained DTC grafting, i.e. described heavy metal chelating agent.
Above-mentioned preparation method inorganic polymer parent used is the one in silica gel, wilkinite, diatomite or attapulgite.
Above-mentioned preparation method aminosilane used is the one in γ-aminopropyltriethoxy dimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane or γ-divinyl triammonium hydroxypropyl methyl dimethoxysilane.
Above-mentioned preparation method's solvent for use is the one in toluene, octane, hexanaphthene or sherwood oil.
Alkaline alkali used is kept to be one in sodium hydroxide or potassium hydroxide in above-mentioned preparation method.
Trapping agent prepared by above-mentioned preparation method is used for the removal of heavy metal ions in wastewater.
positive beneficial effect:1, use inorganic macromolecule material as trapping agent parent, comparing traditional small-molecular-weight DTC trapping agent can significantly increase flco volume, contributes to trapping posterior settlement and is separated;
2, use inorganic macromolecule material as trapping agent parent, compare traditional polymine parent Costco Wholesale and greatly reduce, contribute to industrial scale and produce and application;
3, use inorganic macromolecule material as trapping agent parent, itself porous, has good adsorptive power, and the sequestering power stronger with DTC is combined, and makes the trapping agent of synthesis form chelating and the difunctional trapping active sites of absorption, improves trapping ability.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
A kind of structural formula of heavy metal chelating agent is:
Wherein R is CH
2cH
2cH
2, CH
2cH
2cH
2nHCH
2cH
2, CH
2cH
2cH
2nHCH
2cH
2nHCH
2cH
2in one, atom N wherein all can form N-CS by said structure
2me functional group; Me=Na or K; The structure wherein with chelating function is N-CS
2me functional group.
The preparation method of above-mentioned heavy metal chelating agent comprises the steps:
(1), by the inorganic polymer parent of drying be placed in solvent, add aminosilane, back flow reaction, be finally separated, wash, dry, obtain the inorganic matrix of aminosilane grafting;
(2), in the basic conditions, inorganic matrix and the dithiocarbonic anhydride of aminosilane grafting step (1) prepared react, the inorganic matrix of obtained DTC grafting, i.e. described heavy metal chelating agent.
Above-mentioned preparation method inorganic polymer parent used is the one in silica gel, wilkinite, diatomite or attapulgite.
Above-mentioned preparation method aminosilane used is the one in γ-aminopropyltriethoxy dimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane or γ-divinyl triammonium hydroxypropyl methyl dimethoxysilane.
Above-mentioned preparation method's solvent for use is the one in toluene, octane, hexanaphthene or sherwood oil.
Alkaline alkali used is kept to be one in sodium hydroxide or potassium hydroxide in above-mentioned preparation method.
Trapping agent prepared by above-mentioned preparation method is used for the removal of heavy metal ions in wastewater.
embodiment 1
(1), in 250 mL there-necked flasks, add 100 mL dry toluenes and 2 g dry silica gels, stir and be warming up to boiling, instill 1 mL γ-divinyl triammonium hydroxypropyl methyl dimethoxysilane, continue boiling reflux, stir 4 h, filter, wash, obtain intermediate product divinyl triammonium base silica gel, be designated as a
1;
(2), in 50 mL there-necked flasks, 2 g intermediate product a are added
1, 0.5 g dithiocarbonic anhydride, 1 g sodium hydroxide and 20 mL water, stir 4 h under 20 oC, filter, washing, obtain product dithio divinyl triammonium base sodium formiate grafting silica gel, be designated as trapping agent 1.
embodiment 2
(1) in 250 mL there-necked flasks, add 100 mL dry toluenes and the dry diatomite of 2 g, stirring is warming up to boiling, instill 1 mL N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, continue boiling reflux, stir 4 h, filter, wash, obtain intermediate product aminoethylaminopropyl diatomite, be designated as a
2;
(2), in 50 mL there-necked flasks, 6 g product a are added
2, 1 g dithiocarbonic anhydride, 1 g potassium hydroxide and 20 mL water, stir 4 h under 20 oC, filter, washing, obtain product dithio ethylamino third potassium carbamate grafting diatomite, be designated as trapping agent 2.
embodiment 3
(1), in 250 mL there-necked flasks, add the anhydrous octane of 100 mL and the dry wilkinite of 2 g, stir and be warming up to boiling, instill 1 mL γ-aminopropyltriethoxy dimethoxysilane, continue boiling reflux, stir 4 h, filter, wash, obtain intermediate product aminopropyl wilkinite, be designated as a
3;
(2), in 50 mL there-necked flasks, 2 g product a are added
3, 1 g dithiocarbonic anhydride, 1 g sodium hydroxide and 20 mL water, stir 4 h under 20 oC, filter, washing, obtain product dithio third carboxylamine sodium graft bentonite, be designated as trapping agent 3.
embodiment 4
(1) in 250 mL there-necked flasks, add the anhydrous octane of 100 mL and the dry attapulgite of 2 g, stirring is warming up to boiling, instill 1 mL γ-divinyl triammonium hydroxypropyl methyl dimethoxysilane, continue boiling reflux, stir 4 h, filter, wash, obtain intermediate product divinyl triammonium based attapulgite, be designated as a
4;
(2), in 50 mL there-necked flasks, 2 g product a are added
4, 1 g dithiocarbonic anhydride, 1 g potassium hydroxide and 20 mL water, stir 4 h under 20 oC, filter, washing, obtain product dithio divinyl triammonium base potassium formiate grafting attapulgite, be designated as trapping agent 4.
embodiment 5
(1), in 250 mL there-necked flasks, 100 mL anhydrous cyclohexanes and 2 g dry silica gels are added, stirring is warming up to boiling, instill 1 mL N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, continue boiling reflux, stir 4 h, filter, wash, obtain intermediate product aminoethylaminopropyl silica gel, be designated as a
5;
(2), in 50 mL there-necked flasks, 2 g product a are added
5, 1 g dithiocarbonic anhydride, 1 g sodium hydroxide and 20 mL water, stir 4 h under 20 oC, filter, washing, obtain product dithio ethylamino third carboxylamine sodium grafting silica gel, be designated as trapping agent 5.
embodiment 6
(1), in 250 mL there-necked flasks, add 100 mL anhydrous cyclohexanes and the dry diatomite of 2 g, stir and be warming up to boiling, instill 1 mL γ-aminopropyltriethoxy dimethoxysilane, continue boiling reflux, stir 4 h, filter, wash, obtain intermediate product aminopropyl diatomite, be designated as a
6;
(2), in 50 mL there-necked flasks, 2 g product a are added
6, 1 g dithiocarbonic anhydride, 1 g potassium hydroxide and 20 mL water, stir 4 h under 20 oC, filter, washing, obtain product dithio third potassium carbamate grafting diatomite, be designated as trapping agent 6.
embodiment 7
(1) in 250 mL there-necked flasks, add 100 mL dry oil ethers and the dry wilkinite of 2 g, stirring is warming up to boiling, instill 1 mL γ-divinyl triammonium hydroxypropyl methyl dimethoxysilane, continue boiling reflux, stir 4 h, filter, wash, obtain intermediate product divinyl triammonium base bentonite, be designated as a
7;
(2), in 50 mL there-necked flasks, 2 g product a are added
7, 1 g dithiocarbonic anhydride, 1 g sodium hydroxide and 20 mL water, stir 4 h under 20 oC, filter, washing, obtain product dithio divinyl triammonium base sodium formiate graft bentonite, be designated as trapping agent 7.
embodiment 8
(1) in 250 mL there-necked flasks, add 100 mL dry oil ethers and the dry attapulgite of 2 g, stirring is warming up to boiling, instill 1 mL N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, continue boiling reflux, stir 4 h, filter, wash, obtain intermediate product aminoethylaminopropyl attapulgite, be designated as a
8;
(2), in 50 mL there-necked flasks, 2 g product a are added
8, 1 g dithiocarbonic anhydride, 1 g potassium hydroxide and 20 mL water, stir 4 h under 20 oC, filter, washing, obtain product dithio ethylamino third potassium carbamate grafting attapulgite, be designated as trapping agent 8.
Adopt the present invention and existing method heavy metal to trap effectiveness comparison to see the following form:
| Trapping agent | Q Pb(%) | Q Cd(%) | Q Cu(%) | Q Cr(%) | Q Hg(%) | Cost |
| 1 | 99.0 | 98.7 | 98.6 | 99.2 | 98.8 | 4.0 |
| 2 | 97.7 | 96.1 | 97.2 | 95.6 | 96.2 | 4.2 |
| 3 | 95.9 | 95.6 | 94.4 | 94.7 | 93.7 | 3.5 |
| 4 | 99.3 | 98.9 | 99.0 | 98.9 | 98.6 | 4.1 |
| 5 | 94.9 | 94.8 | 94.7 | 94.4 | 94.4 | 4.2 |
| 6 | 95.9 | 95.6 | 94.4 | 94.7 | 93.7 | 3.9 |
| 7 | 98.6 | 98.9 | 99.0 | 98.4 | 98.6 | 4.3 |
| 8 | 95.7 | 96.3 | 96.2 | 95.9 | 95.6 | 4.1 |
| Contrast sample 1 | 94.7 | 94.1 | 95.2 | 93.6 | 94.2 | 128 |
| Contrast sample 2 | 99.1 | 97.9 | 98.3 | 97.0 | 97.8 | 4.8 |
| Contrast sample 3 | 99.3 | 98.3 | 98.6 | 99.4 | 99.0 | 5.6 |
Annotation and supplementary notes:
1, in table
q pb(%)-Pb
2+trapping clearance, other metal method for expressing is identical;
Metal ion Pb
2+, Cd
2+, Cu
2+, Cr
3+, Hg
2+concentration is 1 mmol/L, and mass concentration is corresponding is respectively 207,112,64,52,201 mg/L;
Cost-process 1 ton of simulated wastewater (concentration of metal ions is 1 mmol/L) is spent fund, and unit is Renminbi/unit;
Contrast sample 1-Y zeolite;
Contrast sample 2-polymine nabam;
Contrast sample 3-dithio divinyl triammonium base sodium formiate;
2, heavy metals trapping experiment
Take trapping agent 0.1 gram, put in 250 mL flasks, add 100 mL, metal ion solution that concentration is 1 mmol/L, magnetic agitation 2 h, filters, and is solution after trapping.Concentration of metal ions before and after being trapped by atomic absorption spectroscopy determination, and then calculate heavy metal removing rate
q(%):
q(%)=(initial Nong Du – traps rear concentration)/starting point concentration × 100%
Result explanation
As can be seen from above-mentioned heavy metals trapping experimental result, the present invention has and traps effect preferably, but cost is lower, can use as efficient heavy metal chelating agent.
Compared with prior art, tool has the following advantages in the present invention: 1, use inorganic macromolecule material as trapping agent parent, comparing traditional small-molecular-weight DTC trapping agent can significantly increase flco volume, contributes to trapping posterior settlement and is separated;
2, use inorganic macromolecule material as trapping agent parent, compare traditional polymine parent Costco Wholesale and greatly reduce, contribute to industrial scale and produce and application;
3, use inorganic macromolecule material as trapping agent parent, itself porous, has good adsorptive power, and the sequestering power stronger with DTC is combined, and makes the trapping agent of synthesis form chelating and the difunctional trapping active sites of absorption, improves trapping ability.
Above case study on implementation is only for illustration of the preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; in the ken that described exercising ordinary skill possesses; the any amendment done within the spirit and principles in the present invention, equivalent to substitute and improvement etc., the protection domain of the application all should be considered as.
Claims (6)
1. a heavy metal capturing agent, is characterized in that, its structure is:
Wherein R is CH
2cH
2cH
2, CH
2cH
2cH
2nHCH
2cH
2, CH
2cH
2cH
2nHCH
2cH
2nHCH
2cH
2in one, atom N wherein all can form N-CS by said structure
2me functional group; Me=Na or K; The structure wherein with chelating function is N-CS
2me functional group.
2. the preparation method of heavy metal capturing agent as claimed in claim 1, is characterized in that, comprise the steps:
(1) the inorganic polymer parent of drying is placed in solvent, adds aminosilane, back flow reaction, be finally separated, washs, dry, obtain the inorganic matrix of aminosilane grafting;
(2) in the basic conditions, inorganic matrix and the dithiocarbonic anhydride of aminosilane grafting step (1) prepared react, the inorganic matrix of obtained DTC grafting, i.e. described heavy metal chelating agent.
3. the preparation method of heavy metal capturing agent according to claim 2, is characterized in that: inorganic polymer parent used is the one in silica gel, wilkinite, diatomite or attapulgite.
4. the preparation method of heavy metal capturing agent according to claim 2, is characterized in that: described aminosilane is the one in γ-aminopropyltriethoxy dimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, γ-divinyl triammonium hydroxypropyl methyl dimethoxysilane.
5. the preparation method of heavy metal capturing agent according to claim 2, is characterized in that: solvent for use is the one in toluene, octane, hexanaphthene or sherwood oil.
6. the preparation method of heavy metal capturing agent according to claim 2, is characterized in that: alkali used is the one in sodium hydroxide or potassium hydroxide.
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|---|---|---|---|
| CN201410828302.8A CN104609526A (en) | 2014-12-29 | 2014-12-29 | Heavy metal collector and preparation method thereof |
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| CN201410828302.8A CN104609526A (en) | 2014-12-29 | 2014-12-29 | Heavy metal collector and preparation method thereof |
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Family
ID=53144225
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961220A (en) * | 2015-06-19 | 2015-10-07 | 许昌学院 | Novel heavy metal chelating agent and preparation method thereof |
| CN105084502A (en) * | 2015-09-24 | 2015-11-25 | 泰山医学院 | Production method of broad-spectrum type heavy metal ion polymeric chelating agent |
| CN105289475A (en) * | 2015-11-20 | 2016-02-03 | 天津大学 | Modified attapulgite preparation method |
| CN110216130A (en) * | 2019-05-31 | 2019-09-10 | 湖南清之源环保科技有限公司 | For handling solidification stabilizer and its curing method containing heavy metal waste slag |
| CN110508256A (en) * | 2019-08-20 | 2019-11-29 | 杭州柏科立新材料有限公司 | One kind having adsorption selectivity composition silicate and preparation method thereof |
| CN112574047A (en) * | 2020-12-25 | 2021-03-30 | 湖州展望药业有限公司 | Production process of low-lead bulk drug esmolol hydrochloride |
| CN114100053A (en) * | 2021-11-19 | 2022-03-01 | 深圳市航天新材科技有限公司 | Long-acting treatment material for household garbage incineration fly ash and preparation method thereof |
| CN114100052A (en) * | 2021-11-19 | 2022-03-01 | 深圳市航天新材科技有限公司 | Preparation method of mineral phase coating agent |
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| CN103224472A (en) * | 2013-04-07 | 2013-07-31 | 许昌学院 | Preparation method of heavy metal capturing agent |
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| CN103224472A (en) * | 2013-04-07 | 2013-07-31 | 许昌学院 | Preparation method of heavy metal capturing agent |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961220A (en) * | 2015-06-19 | 2015-10-07 | 许昌学院 | Novel heavy metal chelating agent and preparation method thereof |
| CN105084502A (en) * | 2015-09-24 | 2015-11-25 | 泰山医学院 | Production method of broad-spectrum type heavy metal ion polymeric chelating agent |
| CN105084502B (en) * | 2015-09-24 | 2017-05-17 | 泰山医学院 | Production method of broad-spectrum type heavy metal ion polymeric chelating agent |
| CN105289475A (en) * | 2015-11-20 | 2016-02-03 | 天津大学 | Modified attapulgite preparation method |
| CN110216130A (en) * | 2019-05-31 | 2019-09-10 | 湖南清之源环保科技有限公司 | For handling solidification stabilizer and its curing method containing heavy metal waste slag |
| CN110508256A (en) * | 2019-08-20 | 2019-11-29 | 杭州柏科立新材料有限公司 | One kind having adsorption selectivity composition silicate and preparation method thereof |
| CN112574047A (en) * | 2020-12-25 | 2021-03-30 | 湖州展望药业有限公司 | Production process of low-lead bulk drug esmolol hydrochloride |
| CN114100053A (en) * | 2021-11-19 | 2022-03-01 | 深圳市航天新材科技有限公司 | Long-acting treatment material for household garbage incineration fly ash and preparation method thereof |
| CN114100052A (en) * | 2021-11-19 | 2022-03-01 | 深圳市航天新材科技有限公司 | Preparation method of mineral phase coating agent |
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