CN114890523A - Embedding flocculant and preparation method and application thereof - Google Patents
Embedding flocculant and preparation method and application thereof Download PDFInfo
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- CN114890523A CN114890523A CN202210348832.7A CN202210348832A CN114890523A CN 114890523 A CN114890523 A CN 114890523A CN 202210348832 A CN202210348832 A CN 202210348832A CN 114890523 A CN114890523 A CN 114890523A
- Authority
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- China
- Prior art keywords
- sodium alginate
- flocculant
- triethylene tetramine
- reacting
- reaction
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- 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.)
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- 238000002360 preparation method Methods 0.000 title claims description 9
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 54
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 51
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 51
- 239000000661 sodium alginate Substances 0.000 claims abstract description 51
- 229960001124 trientine Drugs 0.000 claims abstract description 26
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 14
- 239000010865 sewage Substances 0.000 claims abstract description 7
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 6
- -1 triethylene tetramine modified sodium alginate Chemical class 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract 2
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008394 flocculating agent Substances 0.000 abstract description 15
- 230000009471 action Effects 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 238000010408 sweeping Methods 0.000 abstract description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 5
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses an embedded flocculant, which is a triethylene tetramine modified sodium alginate flocculant, wherein sodium alginate is oxidized and subjected to ring opening to obtain aldehyde groups, amino groups are introduced through Schiff reaction with triethylene tetramine, and dithio carboxyl groups are introduced through reaction with carbon disulfide to obtain a sodium alginate based chelating flocculant. The invention uses triethylene tetramine (TETA) and carbon disulfide (CS) 2 ) A series of novel sodium alginate chelating flocculants with different contents of dithio carboxyl (C (═ S) -S-) are prepared for modifying reagents, heavy metal ions in sewage are flocculated through the chelating action of O, N, S element and heavy metal, the electric neutralization action and the net trapping and sweeping action, the sodium alginate based chelating flocculants can be used for treating wastewater containing the heavy metal ions, the environment is friendly, no secondary pollution is caused, the post-treatment is simple, and the method is used for treating wastewater containing the heavy metal ionsBelongs to ion wastewater and provides a new method.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to an embedded flocculant and a preparation method and application thereof.
Background
With the rapid development of industrial technology, the amount of various sewage in China is greatly increased, and the water quality resources in China are seriously influenced. Water is a valuable resource left by nature to mankind, and is closely related to the health and ecosystem of people. According to the detection of various large water quality conditions by the environmental protection department in China, most water systems in China are polluted to different degrees. Therefore, with the development of science and technology, a plurality of water treatment technologies are produced, and the flocculation technology has the advantages of low investment, simple and convenient operation, reduction of wastewater pollution and the like, and has great influence on the final effluent quality of the treated wastewater. Therefore, the development of a flocculating agent which has high flocculation efficiency, convenient use, no toxicity, low price and environmental friendliness is a development trend in the future.
The continuous enhancement of the environment protection requirement of the society nowadays has application prospect in the development of organic natural polymeric flocculant. Among various natural organic high polymer materials, the starch has the advantages of rich yield, low price, no toxicity, unique chain structure, certain flocculation performance and the like, is popular with multiple students, but the flocculant has fatal defects in the use process, such as low molecular weight, and is easy to biodegrade in the use and storage processes so as to lose the original flocculation activity. Therefore, it is highly desirable to develop a new polymeric flocculant.
Disclosure of Invention
In order to solve the defects in the background technology, the invention aims to provide an embedding flocculant and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
an embedding flocculating agent is a triethylene tetramine modified sodium alginate flocculating agent, the sodium alginate is oxidized and subjected to ring opening to obtain aldehyde group, then the aldehyde group is introduced with triethylene tetramine through Schiff reaction, finally the aldehyde group is reacted with carbon disulfide to introduce dithio carboxyl, and the sodium alginate-based chelating flocculating agent is obtained, wherein the preparation method comprises the following steps:
s1, adding sodium alginate powder into absolute ethyl alcohol, magnetically stirring and dispersing, and adding NalO 4 Reacting the aqueous solution for 3 to 8 hours at room temperature in a dark place, then adding glycol for continuous reaction, and filtering to obtain oxidized sodium alginate;
s2, completely dissolving oxidized sodium alginate in water, fully preheating a triethylene tetramine solution in a water bath, slowly adding the oxidized sodium alginate solution into the triethylene tetramine solution while magnetically stirring, and reacting for 10-14 hours;
s3, cooling to room temperature, adding NaBH in batches while stirring 4 Continuously reacting for 10-14h, adding NaOH and CS according to a certain proportion 2 Firstly, reacting for 20-40min at 20-30 ℃, then transferring into water bath at 30-50 ℃ to continue reacting for 3-8h, stopping the reaction, and cooling to room temperature;
s4, adding absolute ethyl alcohol, standing at the low temperature of 2-4 ℃ for 6-10h, and freeze-drying the precipitate to obtain the sodium alginate-based integrated flocculant.
Further preferably, NalO is added in step S1 4 The concentration of (A) is 0.2-0.4 mol/L.
Further preferably, the triethylene tetramine solution in the step S2 is preheated to 40-60 ℃ in a water bath.
Further preferably, NaOH and CS in step S3 2 The mol ratio of the sodium alginate to the raw material sodium alginate is 1-5:1-5: 1.
An embedding flocculant for treating sewage features that the embedding flocculant is used to select Hg ions as the priority order of mixed metal ions 2+ ＞Pb 2+ ＞Cd 2+ 、Cu 2+ 、Zn 2+ 。
The invention has the beneficial effects that:
the invention uses triethylene tetramine (TETA) and carbon disulfide (CS) 2 ) Modifying natural high-molecular sodium alginate by a three-step synthesis method for modifying a reagent, introducing amido and dithio carboxyl on a molecular chain, and adding different amounts of reaction raw materials to prepare a series of modified sodium alginate with different contents of dithio carboxyl (C (═ S) -S-)The novel sodium alginate chelating flocculant flocculates heavy metal ions in sewage through the chelating action of element O, N, S and heavy metals, the electric neutralization action and the net catching and rolling sweeping action.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "opening," "upper," "lower," "thickness," "top," "middle," "length," "inner," "peripheral," and the like are used in an orientation or positional relationship that is merely for convenience in describing and simplifying the description, and do not indicate or imply that the referenced component or element must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be considered as limiting the present invention.
Example 1
An embedding flocculating agent is a triethylene tetramine modified sodium alginate flocculating agent, the sodium alginate is oxidized and subjected to ring opening to obtain aldehyde group, then the aldehyde group is introduced with triethylene tetramine through Schiff reaction, finally the aldehyde group is reacted with carbon disulfide to introduce dithio carboxyl, and the sodium alginate-based chelating flocculating agent is obtained, wherein the preparation method comprises the following steps:
s1, adding sodium alginate powder into absolute ethyl alcohol, magnetically stirring and dispersing, and adding NalO with the concentration of 0.2mol/L 4 Reacting the aqueous solution at room temperature in a dark place for 8 hours, then adding ethylene glycol for continuous reaction, and filtering to obtain oxidized sodium alginate;
s2, completely dissolving oxidized sodium alginate in water, fully preheating a triethylene tetramine solution in a water bath at 60 ℃, slowly adding the oxidized sodium alginate solution into the triethylene tetramine solution while magnetically stirring, and reacting for 10 hours;
s3, cooling to room temperature, adding NaBH in batches while stirring 4 Continuously reacting for 10 hours, adding NaOH and CS according to a certain proportion 2 Firstly reacting at 20 ℃ for 30min, then transferring into 30 ℃ water bath to continue reacting for 5h, stopping the reaction, and cooling to room temperature, wherein NaOH and CS 2 The mol ratio of the sodium alginate to the raw material sodium alginate is 5:5: 1;
and S4, adding absolute ethyl alcohol, standing at the low temperature of 4 ℃ for 10 hours, and freeze-drying the precipitate to obtain the sodium alginate-based integrated flocculant.
Example 2
An embedding flocculating agent is a triethylene tetramine modified sodium alginate flocculating agent, the sodium alginate is oxidized and subjected to ring opening to obtain aldehyde group, then the aldehyde group is introduced with triethylene tetramine through Schiff reaction, finally the aldehyde group is reacted with carbon disulfide to introduce dithio carboxyl, and the sodium alginate-based chelating flocculating agent is obtained, wherein the preparation method comprises the following steps:
s1, adding sodium alginate powder into absolute ethyl alcohol, magnetically stirring and dispersing, and adding NalO with the concentration of 0.4mol/L 4 Reacting the aqueous solution at room temperature in a dark place for 5 hours, then adding ethylene glycol for continuous reaction, and filtering to obtain oxidized sodium alginate;
s2, completely dissolving oxidized sodium alginate in water, fully preheating a triethylene tetramine solution in a water bath at 50 ℃, slowly adding the oxidized sodium alginate solution into the triethylene tetramine solution while magnetically stirring, and reacting for 12 hours;
s3, cooling to room temperature, adding NaBH in portions while stirring 4 Continuously reacting for 14h, adding NaOH and CS according to a certain proportion 2 Reacting at 20 deg.C for 40min, transferring into 50 deg.C water bath, reacting for 3-8 hr, cooling to room temperature, wherein NaOH and CS 2 The mol ratio of the sodium alginate to the raw material sodium alginate is 3:3: 1;
and S4, adding absolute ethyl alcohol, standing at the low temperature of 3 ℃ for 6 hours, and freeze-drying the precipitate to obtain the sodium alginate-based integrated flocculant.
Example 3
An embedding flocculating agent is a triethylene tetramine modified sodium alginate flocculating agent, the sodium alginate is oxidized and subjected to ring opening to obtain aldehyde group, then the aldehyde group is introduced with triethylene tetramine through Schiff reaction, finally the aldehyde group is reacted with carbon disulfide to introduce dithio carboxyl, and the sodium alginate-based chelating flocculating agent is obtained, wherein the preparation method comprises the following steps:
s1, adding sodium alginate powder into absolute ethyl alcohol, magnetically stirring and dispersing, and adding NalO with the concentration of 0.3mol/L 4 Reacting the aqueous solution at room temperature in a dark place for 3 hours, then adding ethylene glycol for continuous reaction, and filtering to obtain oxidized sodium alginate;
s2, completely dissolving oxidized sodium alginate in water, fully preheating a triethylene tetramine solution in a water bath at 45 ℃, slowly adding the oxidized sodium alginate solution into the triethylene tetramine solution while magnetically stirring, and reacting for 14 hours;
s3, cooling to room temperature, adding NaBH in batches while stirring 4 Continuously reacting for 10 hours, adding NaOH and CS according to a certain proportion 2 Firstly reacting at 25 ℃ for 30min, then transferring into 45 ℃ water bath for continuous reaction for 8h to stop the reaction, and cooling to room temperature, wherein NaOH and CS 2 The mol ratio of the sodium alginate to the raw material sodium alginate is 1:1: 1;
and S4, adding absolute ethyl alcohol, standing at the low temperature of 4 ℃ for 10 hours, and freeze-drying the precipitate to obtain the sodium alginate-based integrated flocculant.
An embedding flocculant for treating sewage features that the embedding flocculant is used to select Hg ions as the priority order of mixed metal ions 2+ ＞Pb 2+ ＞Cd 2+ 、Cu 2+ 、Zn 2+ 。
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are within the scope of the invention as claimed.
Claims (5)
1. An embedded flocculant is characterized in that the embedded flocculant is a triethylene tetramine modified sodium alginate flocculant, sodium alginate is oxidized and subjected to ring opening to obtain aldehyde groups, then amino groups are introduced through Schiff reaction with triethylene tetramine, and finally dithio carboxyl groups are introduced through reaction with carbon disulfide to obtain a sodium alginate-based chelating flocculant, and the preparation method comprises the following steps:
s1, adding sodium alginate powder into absolute ethyl alcohol, magnetically stirring and dispersing, and adding NalO 4 Reacting the aqueous solution for 3 to 8 hours at room temperature in a dark place, then adding glycol for continuous reaction, and filtering to obtain oxidized sodium alginate;
s2, completely dissolving oxidized sodium alginate in water, fully preheating a triethylene tetramine solution in a water bath, slowly adding the oxidized sodium alginate solution into the triethylene tetramine solution while magnetically stirring, and reacting for 10-14 hours;
s3, cooling to room temperature, adding NaBH in portions while stirring 4 Continuously reacting for 10-14h, adding NaOH and CS according to a certain proportion 2 Firstly, reacting for 20-40min at 20-30 ℃, then transferring into water bath at 30-50 ℃ to continue reacting for 3-8h, stopping the reaction, and cooling to room temperature;
s4, adding absolute ethyl alcohol, standing at the low temperature of 2-4 ℃ for 6-10h, and freeze-drying the precipitate to obtain the sodium alginate-based integrated flocculant.
2. The embedded flocculant as claimed in claim 1, wherein NalO in step S1 4 The concentration of (A) is 0.2-0.4 mol/L.
3. The embedded flocculant according to claim 1, wherein the triethylene tetramine solution in the step S2 is preheated to 40-60 ℃ in a water bath.
4. The embedded flocculant of claim 1, wherein NaOH and CS are used in step S3 2 The mol ratio of the sodium alginate to the raw material sodium alginate is 1-5:1-5: 1.
5. Use of an embedding flocculant according to any one of claims 1 to 4 in sewage treatment, wherein the embedding flocculant is selected for mixed metal ions in the order of preference of Hg 2+ ＞Pb 2+ ＞Cd 2+ 、Cu 2+ 、Zn 2+ 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210348832.7A CN114890523A (en) | 2022-04-01 | 2022-04-01 | Embedding flocculant and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210348832.7A CN114890523A (en) | 2022-04-01 | 2022-04-01 | Embedding flocculant and preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN114890523A true CN114890523A (en) | 2022-08-12 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359816A (en) * | 2012-03-29 | 2013-10-23 | 江南大学 | Method for synthesizing modified sodium alginate flocculating agent and application of flocculating agent |
| CN104907051A (en) * | 2015-05-21 | 2015-09-16 | 江南大学 | Preparation method and application of heavy metal ion absorbent |
| CN108855014A (en) * | 2018-08-05 | 2018-11-23 | 广州小众环保科技有限公司 | A kind of heavy metal absorbent and the preparation method and application thereof |
| US20190143302A1 (en) * | 2017-11-13 | 2019-05-16 | Honeywell International Inc. | Gels for removing air pollutants |
| CN113620534A (en) * | 2021-08-24 | 2021-11-09 | 珠海市科立鑫金属材料有限公司 | Process for removing oil from cobalt sulfate extraction waste liquid |
-
2022
- 2022-04-01 CN CN202210348832.7A patent/CN114890523A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359816A (en) * | 2012-03-29 | 2013-10-23 | 江南大学 | Method for synthesizing modified sodium alginate flocculating agent and application of flocculating agent |
| CN104907051A (en) * | 2015-05-21 | 2015-09-16 | 江南大学 | Preparation method and application of heavy metal ion absorbent |
| US20190143302A1 (en) * | 2017-11-13 | 2019-05-16 | Honeywell International Inc. | Gels for removing air pollutants |
| CN108855014A (en) * | 2018-08-05 | 2018-11-23 | 广州小众环保科技有限公司 | A kind of heavy metal absorbent and the preparation method and application thereof |
| CN113620534A (en) * | 2021-08-24 | 2021-11-09 | 珠海市科立鑫金属材料有限公司 | Process for removing oil from cobalt sulfate extraction waste liquid |
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Application publication date: 20220812 |