CN114031715B - Sulfur-containing amido resin, preparation method and application thereof - Google Patents
Sulfur-containing amido resin, preparation method and application thereof Download PDFInfo
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- CN114031715B CN114031715B CN202111212779.XA CN202111212779A CN114031715B CN 114031715 B CN114031715 B CN 114031715B CN 202111212779 A CN202111212779 A CN 202111212779A CN 114031715 B CN114031715 B CN 114031715B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/50—Nitriles containing four or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a cross-linked polymer resin containing thioamide groups, which is prepared by copolymerizing functional monomers containing double bonds and cyano groups and cross-linking agents containing more than 2 double bonds to obtain the cyano group-containing resin, wherein the obtained cyano group-containing cross-linked polymer resin reacts with a compound containing sulfhydryl ions to obtain the thioamide group-containing resin, and the obtained thioamide group-containing resin has good adsorption effect on mercury ions. The resin containing thioamide groups has the advantages of high adsorption quantity to mercury ions, simple synthesis process and low cost.
Description
Technical Field
The invention relates to the field of resin for adsorbing mercury ions, in particular to a resin containing thioamide groups as an adsorbent for mercury ions.
Background
With the development of modern industry, some toxic and harmful substances inevitably pollute the environment, for example, a large amount of waste water containing mercury ions is often generated in the production process of certain industries, particularly mining industries. Mercury ions have very serious toxic and side effects on animals and plants, mercury ions in water bodies can be enriched in human bodies through food chains, and the mercury ions enriched in the human bodies are difficult to discharge out of the body through metabolism, so that the human bodies are healthily and irreversibly injured, and symptoms such as nerve injury, movement disorder, vision decline, hearing attenuation, mood fluctuation, heart failure and the like are caused. Therefore, how to treat the waste water containing mercury ions economically and effectively is an urgent problem to be solved.
The treatment method of the mercury ion-containing wastewater mainly comprises a chemical precipitation method, an electrolytic method, an adsorption method and the like. The chemical precipitation method is a mercury treatment method which is generally applied, and is suitable for treating wastewater with high mercury ion concentration, and the common methods are a coagulating sedimentation method and a sulfide sedimentation method. But the method is not suitable for treating wastewater with smaller mercury ion concentration; electrolytic processes are processes in which mercury ions are reduced to metallic mercury at the cathode under the action of direct current, thereby minimizing the concentration of mercury ions in wastewater. However, the method has poor effect on the treatment of wastewater containing low-concentration mercury ions, and the method has high energy consumption and high investment. In addition, mercury vapor is easy to generate by the method to form secondary pollution; the adsorption method for treating the mercury-containing wastewater is the most studied and widely applied method at present, and the method enriches mercury ions with low concentration through adsorption, so that the concentration of the mercury ions in the treated water is reduced below the allowable concentration of emission standard. The adsorption method is suitable for treating the wastewater containing low-concentration mercury ions, particularly when the concentration of mercury ions in the wastewater is high, the concentration of mercury ions can be reduced to a lower concentration by adopting a chemical precipitation method or an electrolytic method and other treatment methods, and then the wastewater is treated by the adsorption method, so that the advantages of the methods are fully exerted, the defects of the methods are overcome, and the optimal treatment effect is achieved.
The most used adsorbents in the adsorption method are chelate resins, and a plurality of groups containing sulfur, nitrogen, oxygen and the like, particularly sulfur-containing groups, can form stable complexes with heavy metal ions such as mercury ions and the like, so that a plurality of chelate resins containing the groups are developed for adsorbing heavy metal ions such as mercury ions and the like. However, the chelating resin containing sulfur groups reported in the literature often has the defects of complex preparation process, high preparation cost, low adsorption capacity and the like, and limits the practical application of the chelating resin in mercury ion-containing wastewater treatment.
Disclosure of Invention
The invention aims to overcome the defects of sulfur-containing chelate resin reported in the above documents and provides an adsorbent for preparing a polymer resin containing thioamide as mercury ions. The thioamide mercury ion adsorbent is prepared by reacting cyano-containing resin with sulfhydryl ions, and the reaction formula can be represented by the following formula:
the cyano-containing resin is obtained by conventional suspension free radical polymerization of a functional group monomer containing double bonds and cyano groups and a cross-linking agent containing 2 or more double bonds, and the cyano-containing resin obtained by polymerization can be gel resin or macroporous resin. I.e., if no porogen is added during the polymerization, a gel-type resin is obtained. If a porogen is added during the polymerization process, a macroporous resin is obtained. Porogens are inert compounds that are insoluble or sparingly soluble in water and do not participate in free radical polymerization.
Functional group monomers containing double bonds and cyano groups include, but are not limited to, acrylonitrile, methacrylonitrile, and 2-butenenitrile; crosslinking agents containing 2 or more double bonds include, but are not limited to, divinylbenzene, ethylene glycol dimethacrylate, triallyl isocyanurate, and the like. The cross-linking agent can be used singly or as a mixture of 2 or more cross-linking agents in any proportion; the pore-forming agent comprises toluene, ethylbenzene, n-hexane, cyclohexane, heptane, liquid paraffin, solvent oil, butanol, hexanol, cyclohexanol and the like. The pore-forming agent can be used singly or by mixing 2 or more pore-forming agents in any proportion.
The cyano group-containing resin is reacted with a compound containing a sulfhydryl group to obtain a thioamide group-containing resin. The sulfhydryl-containing compounds used include sodium hydrosulfide, potassium hydrosulfide and ammonium hydrosulfide. The reaction may be carried out using water, methanol, ethanol, dimethylformamide, dimethylsulfoxide, etc., as a solvent, either a single solvent or a mixed solvent may be used. The reaction temperature is from room temperature to reflux temperature. The particle diameter of the resulting crosslinked polymer resin is controlled to be 0.05 to 1.5mm, preferably 0.2 to 1.2mm.
The invention further provides application of the thioamide-based resin as an adsorbent, in particular to adsorption of mercury ions in water.
The invention has the advantages and beneficial effects that:
the thioamide-based resin disclosed by the invention has the advantages of simple preparation process, low cost and large mercury ion adsorption capacity.
Detailed Description
The invention is further illustrated by the following examples, which are only intended to provide a better understanding of the invention. It is to be understood that the inventive content is not to be limited to the scope of the embodiments, which is defined by the scope of the appended claims.
Example 1
34.8g of acrylonitrile and 5.2g of divinylbenzene (content: 63%) were uniformly mixed, and 0.2g of azobisisobutyronitrile was added and dissolved by stirring, called an oil phase. 1.5g of polyvinyl alcohol (model 1788) and 15g of sodium chloride are dissolved in 300mL of deionized water, called the aqueous phase. The oil phase was added to the water phase, mechanical stirring was started, stirring speed was adjusted to disperse the oil phase into small oil droplets, the peak value of the diameter distribution of the oil droplets was about 0.4mm, heating was performed to bring the temperature of the system to 65 ℃ and hold for 6 hours, and then heating was performed to 75 ℃ and hold for 4 hours. The heating was stopped, the system was cooled, the resulting resin was collected by filtration, and the resin was washed with hot water several times and dried in the air, and the resulting resin was called white ball PCN-1.
18g of sodium hydrosulfide was added to 50mL of water, followed by 10g of white ball PCN-1, and the reaction was heated at reflux for 4 hours. Cooling, filtering, and washing the obtained resin with water to obtain thioamide resin PCNS-1.
Example 2
71.6g of acrylonitrile, 5.2g of divinylbenzene (content: 63%), 3.2g of triallyl isocyanurate and 40g of toluene were uniformly mixed, and 0.4g of azobisisobutyronitrile was added and dissolved by stirring, which was called an oil phase. 2.5g of polyvinyl alcohol (model 1788) and 25g of sodium chloride are dissolved in 500mL of deionized water, called the aqueous phase. The oil phase was added to the water phase, mechanical stirring was started, and stirring speed was adjusted so that the oil phase was dispersed into small oil droplets, the peak value of the diameter distribution of the oil droplets was about 0.4mm, the system was heated to 65℃and held for 6 hours, and then heated to 75℃and held for 4 hours. Stopping heating, cooling the system, filtering and collecting the obtained resin, washing the resin with hot water for multiple times, airing, extracting with acetone for 8 hours by using a Soxhlet extractor, airing, and obtaining the resin called white ball PCN-2.
18g of sodium hydrosulfide was added to 50mL of water, followed by 10g of white ball PCN-2, and the reaction was heated at reflux for 4 hours. Cooling, filtering, and washing the obtained resin with water to obtain thioamide resin PCNS-2-1.
20g of potassium bisulfide was added to 50mL of water, followed by 10g of white ball PCN-2, and the reaction was heated under reflux for 4 hours. Cooling, filtering, and washing the obtained resin with water to obtain thioamide resin PCNS-2-2.
Example 3
71.6g of acrylonitrile, 5.2g of divinylbenzene (content: 63%), 3.2g of triallyl cyanurate, 20g of toluene and 20g of cyclohexanol were uniformly mixed, and 0.4g of azobisisobutyronitrile was added and dissolved by stirring, which was called an oil phase. 2.5g of polyvinyl alcohol (model 1788) and 25g of sodium chloride are dissolved in 500mL of deionized water, called the aqueous phase. The oil phase was added to the water phase, mechanical stirring was started, and stirring speed was adjusted so that the oil phase was dispersed into small oil droplets, the peak value of the diameter distribution of the oil droplets was about 0.4mm, the system was heated to 65℃and held for 6 hours, and then heated to 75℃and held for 4 hours. Stopping heating, cooling the system, filtering and collecting the obtained resin, washing the resin with hot water for multiple times, airing, extracting with acetone for 8 hours by using a Soxhlet extractor, airing, and obtaining the resin called white ball PCN-3.
18g of ammonium bisulfide was added to a mixed solvent of 25mL of water and 25mL of ethanol, followed by 10g of white ball PCN-3, and the reaction was heated under reflux for 8 hours. Cooling, filtering, and washing the obtained resin with water to obtain thioamide resin PCNS-3-1.
18g of ammonium bisulfide was added to 50mL of ethanol, followed by 10g of white ball PCN-3, and the reaction was heated under reflux for 15 hours. Cooling, filtering, and washing the obtained resin with water to obtain thioamide resin PCNS-3-2.
Example 4
90.6g of 2-butenenitrile, 5.2g of divinylbenzene (content: 63%), 6.1g of ethylene glycol dimethacrylate and 40g of toluene were homogenized, and 0.4g of azobisisobutyronitrile was added and dissolved by stirring, which was called an oil phase. 5g of gelatin, 50g of sodium chloride, was dissolved in 500mL of deionized water, referred to as the aqueous phase. The oil phase was added to the water phase, mechanical stirring was started, and stirring speed was adjusted so that the oil phase was dispersed into small oil droplets, the peak value of the diameter distribution of the oil droplets was about 0.4mm, the system was heated to 65℃and held for 6 hours, and then heated to 75℃and held for 4 hours. Stopping heating, cooling the system, filtering and collecting the obtained resin, washing the resin with hot water for multiple times, airing, extracting with acetone for 8 hours by using a Soxhlet extractor, airing, and obtaining the resin called white ball PCN-4.
18g of sodium hydrosulfide was added to 50mL of water, followed by 10g of white ball PCN-4, and the reaction was heated at reflux for 4 hours. Cooling, filtering, and washing the obtained resin with water to obtain thioamide resin PCNS-4.
Example 5
34.8g of methacrylonitrile, 5.2g of divinylbenzene (content: 63%), 10g of toluene and 10g of n-heptane were mixed homogeneously, 0.3g of benzoyl peroxide was added and dissolved by stirring, called oil phase. 1.25g gelatin and 15g sodium chloride were dissolved in 250mL deionized water, referred to as the aqueous phase. Adding the oil phase into the water phase, starting mechanical stirring, regulating stirring speed to disperse the oil phase into oil beads with proper size, heating to 70 ℃ and keeping the temperature of the system for 6 hours, and then heating to 75 ℃ and keeping the temperature for 4 hours. Stopping heating, cooling the system, filtering and collecting the obtained resin, washing the resin with hot water for multiple times, airing, extracting with acetone for 8 hours by using a Soxhlet extractor, airing, and obtaining the resin called white ball PCN-5.
18g of sodium hydrosulfide was added to 50mL of methanol, followed by 10g of white ball PCN-5, and the reaction was heated at reflux for 15 hours. Cooling, filtering, and washing the obtained resin with water to obtain thioamide resin PCNS-5.
Application examples
About 0.06g of the thioamide-based resin was dispersed in 25mL of mercury sulfate solution having an initial mercury ion concentration of 150mg/L and shaken at room temperature for 24 hours. The supernatant was measured for the concentration of mercury ions by ICP method, and then the amount of mercury ions adsorbed was calculated, as shown in the following table.
Table 1: adsorption amount of mercuric ions of thioamide resin
Resin composition | Adsorption quantity (mg/g) | Resin composition | Adsorption quantity (mg/g) |
PCNS-1 | 28.7 | PCNS-3-2 | 32.8 |
PCNS-2-1 | 30.5 | PCNS-4 | 26.7 |
PCNS-2-2 | 31.2 | PCNS-5 | 29.2 |
PCNS-3-1 | 29.6 |
Description: the above embodiments are only for illustrating the present invention and not for limiting the technical solution described in the present invention; thus, while the invention has been described in detail with reference to the various embodiments described above, it will be understood by those skilled in the art that the invention may be modified or equivalents; all technical solutions and modifications thereof that do not depart from the spirit and scope of the present invention are intended to be included in the scope of the appended claims.
Claims (1)
1. A method for producing a cross-linked polymer resin containing thioamide groups, which is an adsorbent for adsorbing mercury ions from an aqueous solution, characterized by: the functional thioamide group of the crosslinked polymer resin is represented by the following structural formula:
the cross-linked polymer resin containing thioamide groups is obtained by reacting a cyano-containing cross-linked polymer resin with a compound containing sulfhydryl ions, and the reaction water is used as a solvent;
the reaction formula can be represented by the following formula:
the cyano-containing crosslinked polymer resin is prepared by carrying out suspension free radical copolymerization on a functional monomer containing double bonds and cyano groups and a crosslinking agent containing more than two double bonds, wherein a pore-forming agent is added in the copolymerization of the functional monomer containing double bonds and cyano groups and the crosslinking agent containing more than two double bonds, and the obtained cyano-containing crosslinked polymer resin is macroporous; the monomer containing double bond and cyano is one or more than two of acrylonitrile, methacrylonitrile and 2-butenenitrile;
the cross-linking agent containing more than two double bonds is a composition containing more than two of divinylbenzene, ethylene glycol dimethacrylate, triallyl cyanurate and triallyl isocyanurate;
the compound containing the sulfhydryl ions is one or a combination of more than two of sodium hydrosulfide, potassium hydrosulfide and ammonium hydrosulfide;
the pore-forming agent is one or more of toluene, ethylbenzene, n-hexane, cyclohexane, heptane, liquid paraffin, solvent oil, butanol, hexanol and cyclohexanol;
the particle size of the obtained crosslinked polymer resin is controlled to be 0.2-1.2mm.
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Citations (6)
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US3423336A (en) * | 1965-10-18 | 1969-01-21 | Diamond Shamrock Corp | Weak base anion exchange resin and process of preparing same |
GB1377880A (en) * | 1971-12-01 | 1974-12-18 | Akzo Nv | Removal of mercury ions from solutions which contain mercury in the form of soluble salts |
US3998797A (en) * | 1974-10-24 | 1976-12-21 | Labofina S.A. | Posttreatment of copolymer of styrene and acrylonitrile |
CN102140705A (en) * | 2010-12-24 | 2011-08-03 | 吉林大学 | Method for preparing thioamide-based chelating nanofiber for adsorbing heavy metal ions |
CN105837742A (en) * | 2016-05-17 | 2016-08-10 | 张国华 | Preparation method of polyamide adsorption resin |
CN109289807A (en) * | 2018-10-31 | 2019-02-01 | 扬州金珠树脂有限公司 | A kind of preparation method of mercury ion absorption resin |
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2021
- 2021-10-18 CN CN202111212779.XA patent/CN114031715B/en active Active
Patent Citations (6)
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US3423336A (en) * | 1965-10-18 | 1969-01-21 | Diamond Shamrock Corp | Weak base anion exchange resin and process of preparing same |
GB1377880A (en) * | 1971-12-01 | 1974-12-18 | Akzo Nv | Removal of mercury ions from solutions which contain mercury in the form of soluble salts |
US3998797A (en) * | 1974-10-24 | 1976-12-21 | Labofina S.A. | Posttreatment of copolymer of styrene and acrylonitrile |
CN102140705A (en) * | 2010-12-24 | 2011-08-03 | 吉林大学 | Method for preparing thioamide-based chelating nanofiber for adsorbing heavy metal ions |
CN105837742A (en) * | 2016-05-17 | 2016-08-10 | 张国华 | Preparation method of polyamide adsorption resin |
CN109289807A (en) * | 2018-10-31 | 2019-02-01 | 扬州金珠树脂有限公司 | A kind of preparation method of mercury ion absorption resin |
Non-Patent Citations (1)
Title |
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聚丙烯腈螯合纳米纤维的制备及其吸附性能研究;崔振峰;杨华;王永芝;;长春工程学院学报(自然科学版)(第03期);165-168 * |
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