CN117447630B - Mercapto resin, and preparation method and application thereof - Google Patents

Mercapto resin, and preparation method and application thereof Download PDF

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Publication number
CN117447630B
CN117447630B CN202311780724.8A CN202311780724A CN117447630B CN 117447630 B CN117447630 B CN 117447630B CN 202311780724 A CN202311780724 A CN 202311780724A CN 117447630 B CN117447630 B CN 117447630B
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resin
cadmium
copper
acid solution
extraction
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CN117447630A (en
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林荣文
陈亮
李可来
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Shanghai Haoyi Material Technology Co ltd
Shanghai Xigu Technology Co ltd
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Shanghai Haoyi Material Technology Co ltd
Shanghai Xigu Technology Co ltd
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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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
    • 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
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Analytical Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention provides a sulfhydryl resin and a preparation method and application thereof. The invention relates to the field of organic synthesis, wherein the sulfhydryl resin has a structure shown in a formula I, wherein P is a resin matrix; n is any integer from 1 to 9. The sulfhydryl resin provided by the invention is simple to prepare, has high selectivity to metals such as copper, cadmium and the like, has good cycle performance, can be used in an actual extraction process, and realizes a more efficient separation effect.

Description

Mercapto resin, and preparation method and application thereof
Technical Field
The invention relates to the field of organic synthesis, in particular to a sulfhydryl resin and a preparation method and application thereof.
Background
The resin solid phase extraction is a metal separation and purification process in development, has wide prospect in the field of metal extraction, and has certain application in the fields of chemical industry, electroplating, metallurgy, mining and new energy.
The specific functional groups are grafted on the resin, so that the specific selectivity of certain metals can be obtained, and the aim of separating and purifying the specific metals is fulfilled.
Compared with the traditional method, the resin solid-phase extraction method has the advantages of quick phase separation, low loss, simple operation, small pollution, low cost, multiple circulation times and the like.
However, the resin used for solid phase extraction at present has no high selectivity and can not achieve the purposes of selective adsorption and purification; therefore, it is necessary to provide a new adsorbent to further improve the selectivity in the solid phase extraction process, thereby improving the separation and purification effects of certain metal elements (especially copper and cadmium).
Disclosure of Invention
The invention aims to provide a novel adsorbent which has higher selectivity to copper and cadmium metals.
Thus, according to a first aspect, the present invention provides a mercapto resin having a structure of formula i:
a method for preparing the compound of formula I,
wherein:
p is a resin matrix;
n is any integer from 1 to 9.
According to a second aspect, the present invention provides a method for producing the mercapto resin, comprising the steps of:
condensing resin containing primary amine groups with mercapto carboxylic acid derivative X with a structure of formula II in the presence of a catalyst and a condensing agent at a temperature of 40-120 ℃ to obtain the mercapto resin,
II type
Wherein:
R 3 is oxygen anion, C 1 -C 10 Alkoxy or chlorine;
n is any integer from 1 to 9.
According to a third aspect, the present invention provides the use of the mercapto resin for adsorbing a metal, the metal being one or a combination of two of copper and cadmium.
According to a fourth aspect, the present invention provides an extractant for solid phase extraction of metal elements, the extractant comprising the thiol resin.
According to a fifth aspect, the present invention provides a method for solid phase extraction of metal elements, using an extractant containing the mercapto resin, the metal being one or a combination of two of copper and cadmium.
The sulfhydryl resin has high selectivity to copper and cadmium, simple preparation, good effect when used for separation and purification, environmental friendliness and low cost.
Detailed Description
Hereinafter, aspects and further objects, features and advantages of the present invention will be described in more detail.
Mercapto resin
According to a first aspect, the present invention provides a mercapto resin having a structure represented by formula i:
a method for preparing the compound of formula I,
wherein:
p is a resin matrix;
n is any integer from 1 to 9.
The resin substrate P is not particularly limited, and is preferably selected from polystyrene resin, a copolymer of styrene and divinylbenzene, a phenol resin, a polyacrylic resin, or a silicon-based resin. More preferably, the resin matrix P is selected from polystyrene resins or copolymers of styrene and divinylbenzene.
n is any integer from 1 to 9, i.e. 1, 2, 3, 4, 5, 6, 7, 8 or 9.
Preferably, n is 1, 2 or 3.
Preferably, the mercapto resin is selected from the following structures:
、/>、/>，
wherein P is selected from polystyrene resin, copolymer of styrene and divinylbenzene, phenolic resin, polyacrylic resin or silicon-based resin.
The sulfhydryl resin obtained by the invention has high selectivity to metal elements (especially copper and cadmium), can adsorb the two metal elements of copper and cadmium in an acidic solution, and provides a new extractant for the extraction and purification process.
Method for preparing the mercapto resin
According to a second aspect, the present invention provides a method for producing the mercapto resin, comprising the steps of:
condensing resin containing primary amine group with mercapto carboxylic acid derivative X with structure of formula II in the presence of catalyst at 40-120 deg.c,
II type
Wherein:
R 3 is oxygen anion, C 1 -C 10 Alkoxy or chlorine;
n is any integer from 1 to 9.
The resin matrix may be pretreated prior to the reaction.
Specifically, the pretreatment includes rinsing the resin matrix with a solvent, stirring and shaking the resin, followed by removal of excess solvent.
Preferably, the solvent used in the pretreatment is selected from one or more solvents selected from the group consisting of water, ethanol, toluene, dioxane, N-dimethylformamide, ethyl acetate.
Preferably, the mercaptocarboxylic acid derivative is selected from the group consisting of sodium 2-mercaptoacetate, sodium 3-mercaptopropionate, sodium 4-mercaptobutyrate, methyl 2-mercaptoacetate, methyl 3-mercaptopropionate, ethyl 4-mercaptobutyrate, 2-mercaptoacetyl chloride.
Condensing agents may also be added during the condensation reaction to facilitate the reaction.
Preferably, the condensing agent is selected from one or a combination of at least two of N, N-dicyclohexylcarbodiimide, N-diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide.
Preferably, the catalyst is 4-dimethylaminopyridine.
Preferably, the molar ratio of primary amine groups, mercapto carboxylic acid derivative X, condensing agent and catalyst of the resin matrix is 1 (1-1.5): 1-1.6): 0.1-0.5.
Preferably, the solvent of the condensation reaction is selected from one or more solvents selected from methanol, ethanol, diethyl ether, toluene, dioxane, N-dimethylformamide, dichloromethane and ethyl acetate.
Preferably, the solvent is used in an amount of 1 to 30 times by mass based on the mass of the resin.
Preferably, the time of the condensation reaction is 2 to 48 hours.
Application of sulfhydryl resin
According to a third aspect, the present invention provides the use of the mercapto resin for adsorbing a metal, the metal being one or a combination of two of copper and cadmium.
The sulfhydryl resin can be used for adsorbing metal in hydrometallurgy and electroplating wastewater treatment industry. According to a fourth aspect, the present invention provides an extractant for solid phase extraction of metal elements, the extractant comprising the thiol resin.
According to a fifth aspect, the present invention provides a method for solid phase extraction of metal elements, using an extractant containing the mercapto resin, the metal being one or a combination of two of copper and cadmium.
The sulfhydryl resin of the invention can effectively adsorb copper and cadmium metals, and has higher selectivity.
In some embodiments, the method comprises the steps of:
s1, contacting the sulfhydryl resin composition with a copper-cadmium-containing solution for extraction, and then carrying out solid-liquid separation to obtain a copper-cadmium-loaded sulfhydryl resin composition and raffinate;
s2, back-extracting the sulfhydryl resin composition loaded with copper and cadmium by using an acid solution, and then performing solid-liquid separation to obtain the back-extracted sulfhydryl resin composition and copper and cadmium back-extracting solution.
The copper-cadmium-containing solution contains one or two of copper and cadmium.
Advantageously, the extraction time is more than l min, for example from 1 to 120min, for example from 5 to 100min, for example from 10 to 80min, preferably from 10 to 60min.
Advantageously, the pH of the copper-containing, cadmium-containing solution is in the range of 0.2 to 3, such as 1 to 2.5, such as 1.5 to 2.
Advantageously, the copper-cadmium loaded sulfhydryl resin is washed with dilute acid solution prior to back extraction, and the impurity metals are washed down.
Advantageously, the acid solutions used for washing and stripping are each independently selected from sulfuric acid solutions and hydrochloric acid solutions, preferably the concentration of the sulfuric acid solution used for stripping is 0.5-6 mol/L, the concentration of the hydrochloric acid solution is 1-8 mol/L; the pH value of the acid solution adopted in the washing is between 0.5 and 2.5.
The sulfhydryl resin composition has improved selectivity to metal elements, especially copper and cadmium metal elements, and can effectively separate copper and cadmium from metals such as iron, aluminum, chromium, nickel, cobalt, manganese, zinc and the like.
As used herein, "selectivity" is defined by the separation coefficient of the metallic elementβFurther, the separation coefficient is expressed by the following formula:
β A/B =D A /D B =E A ×(1-E B )/((1-E A )×E B )
wherein D is A Representing the ratio of the content of the metal element A in the resin to the content of the metal element A in the raffinate water phase after the primary extraction is completed;
D B representing the ratio of the content of the metal element B in the resin to the content of the metal element B in the raffinate phase after the primary extraction is completed;
E A and E is B The extraction rates of the metal element a and the metal element B are shown respectively (extraction rate e=the content of the metal element in the resin after the completion of one extraction/the content of the metal element in the initial aqueous phase×100%).
Wherein the metal extraction rate in the formula can be measured by the following method:
pretreatment of resin: mixing 2 mol/L sulfuric acid with resin, stirring, washing with pure water at 250 rpm/min for 30 min until the supernatant is colorless, washing with 0.25 mol/L sodium hydroxide solution until the supernatant is alkaline, washing the resin with pure water to neutrality, and filtering to obtain pretreated resin;
preparing a sulfate solution 30 mL containing 0.05 g/L of each metal element as an initial water phase, adjusting the pH value of the initial water phase, mixing and stirring the initial water phase with the resin pretreated by 5 g at room temperature for 60min, and carrying out solid-liquid separation after stirring to balance the adsorption, obtaining a raffinate (balanced) water phase, measuring the concentration of each metal element in the raffinate water phase by using an inductively coupled plasma emission spectrometry (ICP), and obtaining the content of each metal element in the resin by using a difference method.
The "loading" as described herein can be measured by the following method:
preparing 0.5 mol/L sulfate solution of each metal element, adjusting the pH value of an initial aqueous phase, respectively taking pretreated resin 2 g in a beaker, respectively adding 20 mL prepared metal element solutions, stirring at room temperature for 60min, stirring at 250 rpm/min, performing solid-liquid separation after stirring to obtain a raffinate aqueous phase, repeating for three times, and contacting with fresh initial aqueous phase each time. And (3) measuring the concentration of each metal element in the raffinate water phase by adopting an inductively coupled plasma emission spectrum (ICP), and solving the content of the metal element in the resin by using a subtraction method to obtain the loading capacity of the resin on each metal element.
In this application, the terms "comprising" and "including" are intended to cover the instances where additional elements not explicitly mentioned are included or included, as well as the instances where such elements are comprised of those elements.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. To the extent that the definitions of terms in this specification are inconsistent with the ordinary understanding of those skilled in the art to which this invention pertains, the definitions described herein control.
Unless otherwise indicated, all numbers expressing quantities of ingredients, temperatures, times, and so forth used in the specification are to be understood as being modified in the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that may vary depending upon the desired properties to be obtained.
Examples
The conception and the technical effects produced by the present invention will be further described with reference to examples so that those skilled in the art can fully understand the objects, features and effects of the present invention. It will be readily appreciated by those skilled in the art that the embodiments herein are for illustrative purposes only and that the scope of the present invention is not limited thereto.
Example 1: preparation of resin 1
10g of polystyrene resin with primary amino groups, 3.71g (35 mmol) of methyl 2-mercaptoacetate and 0.48g (4 mmol) of 4-dimethylaminopyridine are added into a three-necked flask, 100mL of N, N-dimethylformamide are added, and the mixture is heated and reacted for 12 hours at 100 ℃ under the condition of mechanical stirring, so that resin 1 is obtained.
Example 2: preparation of resin 2
Into a three-necked flask, 10g of a polystyrene resin having a primary amine group, 4.48g (35 mmol) of sodium 3-mercaptopropionate (CAS number: 42267-40-3), 0.48g (4 mmol) of 4-dimethylaminopyridine and 8.24g (40 mmol) of N, N-dicyclohexylcarbodiimide were placed, and 50mL of toluene was further added thereto, followed by thermal reaction at 80℃for 24 hours under mechanical stirring to give resin 2.
Example 3: preparation of resin 3
Into a three-necked flask, 10g of a polystyrene resin having a primary amine group, 5.18g (35 mmol) of ethyl 4-mercaptobutyrate (CAS number: 70124-54-8), 0.48g (4 mmol) of 4-dimethylaminopyridine and 5.04g (40 mmol) of N, N-diisopropylcarbodiimide were placed, and 100mL of N, N-dimethylformamide were added thereto, followed by heating and reacting at 100℃for 12 hours under mechanical stirring to obtain resin 3.
Example 4
Configuration 30 mL contains Fe 3+ 、Al 3+ 、Cr 3+ 、Cu 2+ 、Ni 2+ 、Cd 2+ 、Co 2+ 、Mn 2+ 、Zn 2+ The sulfate solutions of 0.05/g/L each were used as an initial aqueous phase, the pH value of the initial aqueous phase was adjusted to 2, and then the aqueous phase was mixed with the resin of 5 g at room temperature and stirred for 60 minutes at 250 rpm/min, after the completion of the extraction, the concentration of each metal element in the aqueous phase of the extract was measured by inductively coupled plasma emission spectrometry (ICP), the content of the metal element in the resin was determined by difference subtraction, and the results are summarized in Table 1.
TABLE 1 Metal element content in each resin raffinate
The extraction rate of each ion from each resin was calculated, and the results are summarized in table 2.
Table 2. Extraction ratio of each resin to metal element.
The metal element separation coefficients of the resins 1, 2 and 3 were calculated, and the results are summarized in tables 3, 4 and 5.
TABLE 3 separation coefficient of resin 1
TABLE 4 separation coefficient of resin 2
TABLE 5 separation coefficient of resin 3
It can be seen from tables 3-5 that resins 1, 2, 3 have high selectivity for both copper and cadmium.
Further detecting the loading of the resins 1, 2 and 3 on copper and cadmium.
Preparing 0.5 mol/L copper sulfate and cadmium sulfate solution, regulating the pH value of an initial aqueous phase to be 2, respectively taking 2 g pretreated resin in a beaker, respectively adding 20 mL prepared metal element solutions, stirring at room temperature for 60min, stirring at 250 rpm/min, performing solid-liquid separation to obtain a raffinate aqueous phase, repeating the steps for three times, each time contacting with a new initial aqueous phase, measuring the concentration of each metal element in the raffinate aqueous phase by using inductively coupled plasma emission spectrometry (ICP), obtaining the loading amounts of the metal elements in the resin 1, 2 and 3 pairs of copper and cadmium by using a difference method, and summarizing the results in Table 6.
TABLE 6 copper and cadmium loadings of resins 1, 2, 3
The resin is repeatedly extracted and regenerated for 10 times, and the metal loading is hardly changed, so that the resin has better reusability.
The foregoing describes only exemplary embodiments or examples of the present invention and is not intended to limit the present invention. The present invention is susceptible to various modifications and changes by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the scope of the present application.

Claims (9)

1. The use of a mercapto resin having the structure of formula I for adsorbing metals,
the compound of the formula I,
wherein:
p is a resin matrix;
n is any integer from 1 to 3,
the method is characterized in that the metal is one or the combination of two of copper and cadmium;
and the P is selected from any one or more of polystyrene resin, copolymer of styrene and divinylbenzene, phenolic resin, polyacrylic resin and silicon-based resin.
2. A method for solid phase extraction of metal elements, characterized in that an extractant containing the mercapto resin according to claim 1 is used, wherein the metal is one or a combination of two of copper and cadmium.
3. The method according to claim 2, characterized in that it comprises the steps of:
s1, contacting the sulfhydryl resin with a copper-cadmium-containing solution for extraction, and then carrying out solid-liquid separation to obtain a copper-cadmium-loaded sulfhydryl resin composition and raffinate;
s2, back-extracting the sulfhydryl resin composition loaded with copper and cadmium by using an acid solution, and then carrying out solid-liquid separation to obtain the back-extracted sulfhydryl resin composition and copper and cadmium back-extraction liquid.
4. A method according to claim 3, characterized in that the extraction time is more than l min.
5. A method according to claim 3, characterized in that the pH of the copper-and cadmium-containing solution is 0.2-3.
6. A method according to claim 3, wherein the copper-cadmium-loaded mercapto resin composition is washed with a dilute acid solution prior to stripping, and the impurity metals are washed off.
7. The method of claim 6, wherein the acid solutions used for washing and stripping are each independently selected from sulfuric acid solution and hydrochloric acid solution.
8. The method according to claim 7, wherein the concentration of sulfuric acid solution used for back extraction is 0.5-6 mol/L and the concentration of hydrochloric acid solution is 1-8 mol/L; the pH value of the acid solution adopted in the washing is between 0.5 and 2.5.
9. A method according to claim 3, characterized in that the copper-cadmium-containing solution comprises copper, cadmium, iron, aluminum, chromium, nickel, cobalt, manganese and zinc metals.
CN202311780724.8A 2023-12-22 2023-12-22 Mercapto resin, and preparation method and application thereof Active CN117447630B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103998135A (en) * 2011-12-22 2014-08-20 朗盛德国有限责任公司 Thiol group-containing acrylate 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
CN109970609A (en) * 2019-03-20 2019-07-05 广州同隽医药科技有限公司 A kind of composition and its application
CN112979867A (en) * 2021-02-07 2021-06-18 中铝环保生态技术(湖南)有限公司 Heavy metal sulfydryl adsorption material and preparation method thereof
CN114632498A (en) * 2020-12-15 2022-06-17 中国科学院大连化学物理研究所 Hyperbranched sulfhydryl sponge adsorbent as well as preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103998135A (en) * 2011-12-22 2014-08-20 朗盛德国有限责任公司 Thiol group-containing acrylate 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
CN109970609A (en) * 2019-03-20 2019-07-05 广州同隽医药科技有限公司 A kind of composition and its application
CN114632498A (en) * 2020-12-15 2022-06-17 中国科学院大连化学物理研究所 Hyperbranched sulfhydryl sponge adsorbent as well as preparation method and application thereof
CN112979867A (en) * 2021-02-07 2021-06-18 中铝环保生态技术(湖南)有限公司 Heavy metal sulfydryl adsorption material and preparation method thereof

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