CN104209094A - Preparation method of sepiolite heavy metal absorbent modified with amino acid carboxylic acid - Google Patents
Preparation method of sepiolite heavy metal absorbent modified with amino acid carboxylic acid Download PDFInfo
- Publication number
- CN104209094A CN104209094A CN201410504697.6A CN201410504697A CN104209094A CN 104209094 A CN104209094 A CN 104209094A CN 201410504697 A CN201410504697 A CN 201410504697A CN 104209094 A CN104209094 A CN 104209094A
- Authority
- CN
- China
- Prior art keywords
- sepiolite
- gel
- carboxylic acid
- ethyl alcohol
- absolute ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004113 Sepiolite Substances 0.000 title claims abstract description 60
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 60
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 59
- -1 amino acid carboxylic acid Chemical group 0.000 title claims abstract description 30
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000002745 absorbent Effects 0.000 title claims abstract description 7
- 239000002250 absorbent Substances 0.000 title claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012266 salt solution Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000012065 filter cake Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 229920001971 elastomer Polymers 0.000 claims description 7
- RTQKKSJHZQNXHG-UHFFFAOYSA-K [Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.NCCN Chemical compound [Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.NCCN RTQKKSJHZQNXHG-UHFFFAOYSA-K 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- FRGBDYDAIWEXJX-UHFFFAOYSA-K trisodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(3-trimethoxysilylpropyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].CO[Si](OC)(OC)CCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O FRGBDYDAIWEXJX-UHFFFAOYSA-K 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- LWOZJYLVHAJSBS-UHFFFAOYSA-K [Na+].[Na+].[Na+].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].COC(CC([SiH3])(OC)OC)NCCN Chemical compound [Na+].[Na+].[Na+].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].COC(CC([SiH3])(OC)OC)NCCN LWOZJYLVHAJSBS-UHFFFAOYSA-K 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000012224 working solution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009938 salting Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a preparation method of a sepiolite heavy metal absorbent modified with amino acid carboxylic acid and belongs to the technical field of environment protection. According to the proportion of sepiolite: deionized water: absolute ethyl alcohol (2.5-5 : 40-70 : 35-55 (w/v/v)), preparing sepiolite turbid liquid, and stirring to form gel; under a stirring condition of 7000 to 10000rpm, adding N-(triethoxy silicyl propyl) ethylenediamine nitrilotriacetic acid trisodium salt solution with the mass concentration of 10-20%, wherein the proportion of N-(triethoxy silicyl propyl) ethylenediamine nitrilotriacetic acid trisodium salt to sepiolite is 4.5-9 : 2-3 (v/w); adding absolute ethyl alcohol, constantly stirring to form a gel system, filtering it with absolute ethyl alcohol and collecting gel filtering cakes; placing the cakes into an oven for 18 hours under constant temperature of 70 to 80 degrees centigrade, drying and grinding them to prepare the sepiolite modified with amino acid carboxylic acid. The preparation method has the advantages of simple process, low cost and wide application range, without secondary pollution.
Description
Technical field
The present invention relates to the technology of preparing of heavy metal adsorption material, particularly a kind of amido carboxylic acid is modified the preparation method of sepiolite heavy metal absorbent, belongs to environmental technology field.
Background technology
Industry is as the important support of China's economy, when high speed development, bring day by day serious problem of environmental pollution, especially along with opening a mine frequently, metal smelt and processing, waste gas, waste water and the solid waste such as leaded, mercury, cadmium, cobalt, copper is discharged in environment in a large number, causes serious harm.According to incompletely statistics, at present approximately 1.5 ten thousand tons of mercury are discharged in the whole world every year on average, approximately 3,400,000 tons of copper, and plumbous approximately 5,000,000 tons, approximately 1,500 ten thousand tons, manganese, approximately 1,000,000 tons, nickel etc., the discarded object of discharge makes the heavy metal-polluted soil concentration in a lot of regions apparently higher than background value.Heavy metal pollution meeting not only can have a strong impact on and change the ecological functions of water body, soil etc., also can cause the decline of crop yield and quality, the excessive enrichment meeting of heavy metal in food chain causes very large harm to natural environment and health, affects Sustainable Socioeconomic Development.
At present, people utilize several different methods, as: chemical precipitation method, absorption method, By Bubble-floating Method, oxidation-reduction method etc., process the heavy metal ion in waste water, wherein, be most widely used with chemical precipitation method and absorption method.
Sepiolite (Sepiolite) chemical formula is Mg
8si
12o
30(OH)
4(OH
2)
48H
2o, is a kind of fibrous rich magnesium silicate mineral of 2:1 type chain type layer structure, is conventionally white, light gray, the color such as pale yellow, opaque also lackluster, hardness 2～3, density 2～2.5g/cm
3, there is shrinkage factor low, the advantage such as plasticity is good, and specific surface is large, and adsorptivity is strong and thermally-stabilised.China is one of a few rich country that produces sepiolite in the world, in Hunan, all there is extensive distribution in Jiangxi, Hebei, but develop very backward, at present still taking outlet raw material as main.The theoretical specific area of sepiolite is 900m
2/ g, approaches active carbon, but price is only its ten part.In recent years, improve material property by surface modification method, preparation function advanced person, the exsertile material of property and composite become the focus of research.Therefore strengthen the exploitation to sepiolite, the absorption property that particularly improves sepiolite by finishing has extremely important meaning.
2000, scholar Mercier utilized 3-mercaptopropyl trimethoxysilane (3-mercapto-pro-pyltrimethoxysilane) to carry out finishing to sepiolite in toluene solution, and the material after modification is to Pb
2+and Cd
2+maximal absorptive capacity be respectively 0.31mmol/g and 0.21mmol/g.But because this reaction is to carry out, unavoidably can cause certain pollution and harm in organic solution toluene.Therefore need that exploitation is a kind of fast badly, the synthesis technique of low cost, environmental protection carries out finishing to improve its absorption property to sepiolite.
Summary of the invention
The object of this invention is to provide that a kind of technique is simple, cost is low, amido carboxylic acid applied widely, non-secondary pollution modifies the preparation method of sepiolite as heavy metal absorbent.
For achieving the above object, the invention provides a kind of nanometer texturing method and prepare amido carboxylic acid sepiolite, this amido carboxylic acid sepiolite can be used as heavy metal absorbent, and preparation method is as follows:
(1) get sepiolite powder, be scattered in deionized water, add absolute ethyl alcohol, form sepiolite suspension, wherein, sepiolite: deionized water: absolute ethyl alcohol=2.5～5:40～70:35～55 (w/v/v/);
(2) N-(trimethoxy-silylpropyl) the ethylenediamine triacetic acid trisodium-salt solution that preparation quality concentration is 10～20%, for subsequent use;
(3) sepiolite suspension is stirred on dispersion machine and form after gel, under 7000～10000rpm stirring condition, add N-(trimethoxy-silylpropyl) the ethylenediamine triacetic acid trisodium-salt solution preparing in step (2), N-(trimethoxy-silylpropyl) the ethylenediamine triacetic acid trisodium-salt solution that mass concentration is 10～20% and the ratio of sepiolite are 4.5～9:2～3 (v/w);
(4) add absolute ethyl alcohol, continue to stir and form amido carboxylic acid and modify sepiolite gel rubber system, this gel rubber system is transferred to Buchner funnel, with absolute ethyl alcohol suction filtration and collect gel filter cake;
(5) above-mentioned gel filter cake is transferred to wide-mouth bottle, is placed in 70～80 DEG C of baking oven constant temperature, continue after 18h, gel in wide-mouth bottle to be taken out, dry, after grinding, obtain amido carboxylic acid and modify sepiolite (TMS-EDTA-sepiolite).
Tool of the present invention has the following advantages:
(1) applied widely: sorbing material prepared by the present invention is mainly used in containing the wastewater treatment of heavy metal ion, the reparation of water body, and the reparation of heavy-metal contaminated soil etc., also there is significant effect for the combined pollution being caused by detection device for multi metallic elements such as lead, cadmium, copper.
(2) advantages of good adsorption effect: heavy metal adsorption parting material amido carboxylic acid prepared by the present invention is modified sepiolite, contain a large amount of activity functional groups, can, by surface complex reaction Adsorption of Heavy Metals such as chemisorbed, modify sepiolite through evidence amido carboxylic acid plumbous (Pb), cadmium (Cd) and copper (Cu) are all had to good adsorption effect.
(3) consumption few, easily promote: material of the present invention can be obtained good effect in the situation that dosage is less, and cost is lower, can not produce secondary pollution, is easily accepted by society, and simultaneously using method is simple, can large-scale promotion application.
(4) the present invention adopt fast, one-step synthesis process cheaply, utilize water to do reaction medium, environmental protection; The absorption property of product is further promoted, to Pb
2+, Cd
2+and Cu
2+maximal absorptive capacity be respectively 0.338,0.357 and 0.469mmol/g; Simple to operate, productive rate is high, is conducive to advance large-scale production.
Detailed description of the invention
Embodiment 1
Take sepiolite powder 3g, add 50ml deionized water, 40ml absolute ethyl alcohol, forms sepiolite suspension; Sepiolite suspension speed high-speed stirred 8min with 8000rpm on dispersion machine is formed to gel, (I) for subsequent use; The N-that is 45% by the mass concentration of purchase (trimethoxy-silylpropyl) ethylenediamine triacetic acid trisodium-salt solution 2ml is dissolved in deionized water, the salting liquid (II) for subsequent use that preparation quality concentration is 10%; Continuing N-(trimethoxy-silylpropyl) the ethylenediamine triacetic acid trisodium-salt solution consumption 9ml (II) that is 10% by mass concentration under 8000rpm stirring condition pours in (I), add 1ml absolute ethyl alcohol, continue 8000rpm and stir 25min, form amido carboxylic acid and modify sepiolite gel rubber system, wherein the ratio of sodium salt solution and sepiolite is 9:3 (v/w); This reaction gel system is transferred to Buchner funnel, with absolute ethyl alcohol suction filtration and collect gel filter cake, gel filter cake is transferred to wide-mouth bottle, be placed in 70 DEG C of baking oven constant temperature, continue, after 18h, gel in wide-mouth bottle to be taken out, 80 DEG C of oven dry, obtain amido carboxylic acid and modify sepiolite 3.17g after grinding.
Embodiment 2
Take sepiolite powder 2.5g, add 70ml deionized water, 55ml absolute ethyl alcohol, forms sepiolite suspension; Sepiolite suspension speed high-speed stirred 8min with 7000rpm on dispersion machine is formed to gel, (I) for subsequent use; The N-that is 45% by the mass concentration of purchase (trimethoxy-silylpropyl) ethylenediamine triacetic acid trisodium-salt solution 2.5ml is dissolved in deionized water, the salting liquid (II) for subsequent use that preparation quality concentration is 15%; The N-that is 15% by mass concentration under 10000rpm stirring condition (trimethoxy-silylpropyl) ethylenediamine triacetic acid trisodium-salt solution consumption 7.5ml (II) pours in (I), add 3ml absolute ethyl alcohol, continue 8000rpm and stir 25min, form amido carboxylic acid and modify sepiolite gel rubber system, wherein the ratio of sodium salt solution and sepiolite is 7.5:2.5 (v/w); This reaction gel system is transferred to Buchner funnel, with absolute ethyl alcohol suction filtration and collect gel filter cake, gel filter cake is transferred to wide-mouth bottle, be placed in 80 DEG C of baking oven constant temperature, continue, after 18h, gel in wide-mouth bottle to be taken out, 80 DEG C of oven dry, obtain amido carboxylic acid and modify sepiolite 2.55g after grinding.
Embodiment 3
Take sepiolite 4g, add 40ml deionized water, 35ml absolute ethyl alcohol, forms sepiolite suspension; Sepiolite suspension speed high-speed stirred 7min with 9000rpm on dispersion machine is formed to gel, (I) for subsequent use; The N-that is 45% by the mass concentration of purchase (trimethoxy-silylpropyl) ethylenediamine triacetic acid trisodium-salt solution 4ml is dissolved in deionized water, the salting liquid (II) for subsequent use that preparation quality concentration is 20%; The N-that is 20% by mass concentration under 9000rpm stirring condition (trimethoxy-silylpropyl) ethylenediamine triacetic acid trisodium-salt solution consumption 9ml (II) pours in (I), add 2ml absolute ethyl alcohol, continue 9000rpm and stir 25min, form amido carboxylic acid and modify sepiolite gel rubber system, wherein the ratio of sodium salt solution and sepiolite is 4.5:2 (v/w); This reaction gel system is transferred to Buchner funnel, with absolute ethyl alcohol suction filtration and collect gel filter cake, gel filter cake is transferred to wide-mouth bottle, be placed in 80 DEG C of baking oven constant temperature, continue, after 18h, gel in wide-mouth bottle to be taken out, 65 DEG C of oven dry, obtain amido carboxylic acid and modify sepiolite 4.20g after grinding.
Embodiment 4
Amido carboxylic acid is modified sepiolite adsorption aqueous solution Pb
2+, Cd
2+and Cu
2+application.
Configuration concentration is the Pb of 100mg/L
2+, Cd
2+and Cu
2+solution, as working solution, respectively measures 25ml and is placed in 50ml centrifuge tube, takes respectively amido carboxylic acid prepared by embodiment 1 and modifies sepiolite 0.025g and add and add Pb
2+, Cd
2+and Cu
2+pollute in the centrifuge tube of working solution, it is 1g/L with the ratio of polluting working solution that amido carboxylic acid is modified sepiolite, and 25 DEG C of isothermal vibration 6h, get supernatant liquor after 3800rpm is centrifugal, with Pb in atomic absorption spectrophotometer mensuration solution
2+, Cd
2+and Cu
2+concentration, according to Pb in working solution
2+and Cd
2+before and after concentration, concentration difference is calculated the adsorbance of amido carboxylic acid modification sepiolite.
Result shows: amido carboxylic acid is modified sepiolite lead, cadmium and copper in solution are polluted and all has good adsorption effect, and its saturated extent of adsorption is: plumbous 0.338mmol/g, cadmium 0.357mmol/g and copper 0.469mmol/g.
Claims (1)
1. amido carboxylic acid is modified the preparation method of sepiolite heavy metal absorbent, it is characterized in that: comprise the following steps:
(1) get sepiolite powder, be scattered in deionized water, add absolute ethyl alcohol, form sepiolite suspension, wherein, sepiolite: deionized water: absolute ethyl alcohol=2.5～5:40～70:35～55 (w/v/v/);
(2) N-(trimethoxy-silylpropyl) the ethylenediamine triacetic acid trisodium-salt solution that preparation quality concentration is 10～20%, for subsequent use;
(3) sepiolite suspension is stirred on dispersion machine and form after gel, under 7000～10000rpm stirring condition, add N-(trimethoxy-silylpropyl) the ethylenediamine triacetic acid trisodium-salt solution preparing in step (2), the ratio of N-(trimethoxy-silylpropyl) ethylenediamine triacetic acid trisodium-salt solution and sepiolite is 4.5～9:2～3 (v/w);
(4) add absolute ethyl alcohol, continue to stir and form amido carboxylic acid and modify sepiolite gel rubber system, this gel rubber system is transferred to Buchner funnel, with absolute ethyl alcohol suction filtration and collect gel filter cake;
(5) above-mentioned gel filter cake is transferred to wide-mouth bottle, is placed in 70～80 DEG C of baking oven constant temperature, continue after 18h, gel in wide-mouth bottle to be taken out, dry, after grinding, obtain amido carboxylic acid and modify sepiolite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410504697.6A CN104209094B (en) | 2014-09-28 | 2014-09-28 | Amido carboxylic acid modifies the preparation method of meerschaum heavy metal absorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410504697.6A CN104209094B (en) | 2014-09-28 | 2014-09-28 | Amido carboxylic acid modifies the preparation method of meerschaum heavy metal absorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104209094A true CN104209094A (en) | 2014-12-17 |
| CN104209094B CN104209094B (en) | 2016-08-24 |
Family
ID=52091237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410504697.6A Expired - Fee Related CN104209094B (en) | 2014-09-28 | 2014-09-28 | Amido carboxylic acid modifies the preparation method of meerschaum heavy metal absorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104209094B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105195085A (en) * | 2015-09-24 | 2015-12-30 | 北京新源环境有限公司 | Preparation method of dopamine modified sepiolite adsorbent |
| CN106902745A (en) * | 2017-03-08 | 2017-06-30 | 江苏大学 | A kind of preparation method and applications of lithium/rubidium ion synchronization adsorbent |
| CN111167409A (en) * | 2019-12-04 | 2020-05-19 | 甘肃省科学院传感技术研究所 | Preparation method and application of Ni-NTA modified silicon dioxide coated ferroferric oxide magnetic nano functional assembly |
| CN111186874A (en) * | 2020-01-17 | 2020-05-22 | 厦门大学 | Silanization reduction graphene oxide titanium dioxide composite material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130095025A1 (en) * | 2011-10-12 | 2013-04-18 | Gwangju Institute Of Science And Technology | Granular mesoporous silica and preparation method thereof |
| CN104041362A (en) * | 2014-05-13 | 2014-09-17 | 农业部环境保护科研监测所 | Method for safely producing rice in rice field with serious Cd pollution |
-
2014
- 2014-09-28 CN CN201410504697.6A patent/CN104209094B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130095025A1 (en) * | 2011-10-12 | 2013-04-18 | Gwangju Institute Of Science And Technology | Granular mesoporous silica and preparation method thereof |
| CN104041362A (en) * | 2014-05-13 | 2014-09-17 | 农业部环境保护科研监测所 | Method for safely producing rice in rice field with serious Cd pollution |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105195085A (en) * | 2015-09-24 | 2015-12-30 | 北京新源环境有限公司 | Preparation method of dopamine modified sepiolite adsorbent |
| CN106902745A (en) * | 2017-03-08 | 2017-06-30 | 江苏大学 | A kind of preparation method and applications of lithium/rubidium ion synchronization adsorbent |
| CN106902745B (en) * | 2017-03-08 | 2019-06-28 | 江苏大学 | A kind of lithium/rubidium ion synchronizes the preparation method and applications of adsorbent |
| CN111167409A (en) * | 2019-12-04 | 2020-05-19 | 甘肃省科学院传感技术研究所 | Preparation method and application of Ni-NTA modified silicon dioxide coated ferroferric oxide magnetic nano functional assembly |
| CN111167409B (en) * | 2019-12-04 | 2021-01-08 | 甘肃省科学院传感技术研究所 | Preparation method and application of Ni-NTA modified silicon dioxide coated ferroferric oxide magnetic nano functional assembly |
| CN111186874A (en) * | 2020-01-17 | 2020-05-22 | 厦门大学 | Silanization reduction graphene oxide titanium dioxide composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104209094B (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102190345B (en) | Method for enriching low-concentration heavy metal in water by recyclable magnesium hydroxide adsorbent | |
| CN110559991B (en) | Modified biochar and preparation method and application thereof | |
| CN105597668B (en) | A kind of preparation method and application of modified zeolite | |
| CN104923163B (en) | A kind of silica gel absorber of Adsorption of Heavy Metal Ions and preparation method thereof | |
| CN104209094A (en) | Preparation method of sepiolite heavy metal absorbent modified with amino acid carboxylic acid | |
| CN109012565A (en) | A kind of method of the magnetic carbon material Adsorption heavy metal ions in wastewater of nitrating | |
| CN105195085A (en) | Preparation method of dopamine modified sepiolite adsorbent | |
| CN112707509B (en) | Method for removing heavy metals in water body by using marine microalgae | |
| CN102489245A (en) | Modified pumice absorbing material and preparation method as well as application thereof | |
| CN104355497B (en) | A kind of method processing electroplating wastewater | |
| CN103752280B (en) | Composite modified walnut shell adsorbent and its preparation method and application | |
| CN100536983C (en) | Nano granule water purifying material for removing heavy metal and preparation thereof | |
| CN106345397A (en) | Novel adsorbing material for efficiently removing phosphorus out of water | |
| CN105174403B (en) | A kind of functional amido graphene quantum dot and its preparation and application | |
| CN105417614A (en) | Heavy metal removal agent for mariculture water | |
| CN103818969A (en) | Iron oxide red and preparation method thereof | |
| CN105753219A (en) | Process for purifying and treating vanadium-containing wastewater in advanced manner and process for recycling vanadium and chromium | |
| CN108201876B (en) | Method for deeply adsorbing zinc ions by using NaP molecular sieve | |
| CN102173602A (en) | Glass fiber subjected to surface treatment, preparation method and application | |
| CN104549172B (en) | Method for preparing sulfydryl-modified chitosan short hole microspheres | |
| CN106745592B (en) | It is a kind of with heavy metal ion adsorbed and detection function composite flocculation agent and preparation method thereof | |
| CN101757890A (en) | Preparation method of attapulgite filter material for selectively absorbing calcium ions and magnesium ions | |
| CN109534533A (en) | A kind of administering method of molybdenum calcining pickling waste waters | |
| CN109012571B (en) | Modified electrolytic manganese waste residue, preparation method thereof and industrial wastewater treatment method | |
| CN103395825A (en) | Method for producing nanometer zinc oxide by using steelmaking electric-furnace flue dust |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160824 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |