CN114160107B - Hydrazine waste water adsorbent and preparation method thereof - Google Patents

Hydrazine waste water adsorbent and preparation method thereof Download PDF

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CN114160107B
CN114160107B CN202111537878.5A CN202111537878A CN114160107B CN 114160107 B CN114160107 B CN 114160107B CN 202111537878 A CN202111537878 A CN 202111537878A CN 114160107 B CN114160107 B CN 114160107B
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vinyl alcohol
ethylene
alcohol copolymer
hydrazine
adsorbent
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CN114160107A (en
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陈通
耿葵
韩俊杰
高缨
温伟伟
王庆波
程金星
吴友朋
李浪
高鑫
张悦
郑承银
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23 Units Of Chinese People's Liberation Army 96901 Force
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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
    • C08F8/14—Esterification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen 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
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • 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 hydrazine wastewater adsorbent, which is a maleic anhydride grafted ethylene-vinyl alcohol copolymer polymer material, and the ring-opening esterification reaction of maleic anhydride is realized through the reaction between maleic anhydride and the hydroxyl of the high molecular side chain of the ethylene-vinyl alcohol copolymer, so as to obtain the maleic acid-carboxyl grafted polyethylene-vinyl alcohol adsorbent material. The maleic anhydride grafted ethylene-vinyl alcohol copolymer adsorbent can efficiently adsorb hydrazine substances in wastewater by utilizing the ionization between carboxyl and amino of the side chain of the maleic anhydride grafted ethylene-vinyl alcohol copolymer adsorbent, and effectively reduce the concentration of the hydrazine substances. The hydrazine wastewater adsorbent of the invention not only has excellent adsorption performance on hydrazine substances in wastewater, but also has excellent adsorption performance on toxic metal elements such as Pb in wastewater 2+ ，Cs + ，Sr 3+ The adsorbent has obvious adsorption capacity and wide application prospect.

Description

Hydrazine waste water adsorbent and preparation method thereof
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a hydrazine wastewater adsorbent and a preparation method thereof.
Background
The unsymmetrical dimethylhydrazine, methyl hydrazine and hydrazine are common fuel of liquid propellant, wherein the unsymmetrical dimethylhydrazine is the main fuel of launching tests of missiles, satellites, spacecraft and the like and carrier rockets, and is a high toxic substance. During the storage and use of the unsymmetrical dimethylhydrazine, a large amount of unsymmetrical dimethylhydrazine wastewater can be generated due to the cleaning of the container during running, bubbling, dripping, leaking and transportation. The treatment method of the unsymmetrical dimethylhydrazine mainly comprises a chemical method, a physical method and a biological method.
The chemical method mainly adopts an oxidation process to degrade the unsymmetrical dimethylhydrazine, and adopts a traditional chemical oxidation method to treat, the unsymmetrical dimethylhydrazine can be decomposed into a series of intermediate products, and some intermediate products such as nitrosodimethylamine and cyanide have higher toxicity, so that the unsymmetrical dimethylhydrazine wastewater must be scientifically treated. The biological method adopts microorganisms or aquatic plants to carry out biodegradation on the unsymmetrical dimethylhydrazine wastewater, is easily influenced by surrounding environment, and has the problems of difficult operation control, unstable treatment effect and the like.
The traditional physical adsorption method for treating wastewater has the advantages of simple treatment process and mild treatment condition. Various methods for treating unsymmetrical dimethylhydrazine wastewater by adsorption are presented in the literature. The most commonly used porous adsorbents mainly comprise active carbon, attapulgite, carbon nano tubes and the like, and the adsorption effect mainly utilizes the porous physical adsorption force of the adsorbent, so that the effect of adsorbing hydrazine substances in wastewater is poor. To improve its adsorption properties, the surface of the adsorbent pores is generally chemically modified. Traditional ion exchange resins are also used for adsorbing the unsymmetrical dimethylhydrazine in the wastewater, and the adsorption of the unsymmetrical dimethylhydrazine in the wastewater is realized mainly by utilizing the exchange of the indicated cation exchange groups, such as sulfonate groups and amino groups, of the ion exchange resins, but the adsorption effect is not very ideal, and the macroscopic structural modification of the adsorbent is also difficult.
Disclosure of Invention
The invention provides a hydrazine wastewater adsorbent and a preparation method thereof, which solve the problem of unsatisfactory adsorption effect of unsymmetrical dimethylhydrazine in wastewater treated by a physical adsorption method in the prior art. The adsorbent not only has excellent adsorption effect on hydrazine substances in wastewater, but also has obvious adsorption effect on hydrazine substances.
The technical scheme of the invention is that the invention provides a hydrazine wastewater adsorbent which is a high polymer material of maleic anhydride grafted ethylene-vinyl alcohol copolymer, and the structural formula of the adsorbent is shown as the following formula I:
wherein n is the average polymerization degree of ethylene-vinyl alcohol copolymer ethylene chain segment, m is the average polymerization degree of ethylene-vinyl alcohol copolymer vinyl alcohol chain segment, and k is the average grafting number of vinyl alcohol chain segment in the ethylene-vinyl alcohol copolymer.
Preferably, the grafting ratio of the ethylene-vinyl alcohol copolymer in the adsorbent is adjusted by adding the amount of maleic anhydride.
Preferably, the mass ratio of the ethylene-vinyl alcohol copolymer to the maleic anhydride in the adsorbent is (1-4): 1.
the invention also provides a preparation method of the hydrazine wastewater adsorbent, which comprises the steps of dissolving maleic anhydride and ethylene-vinyl alcohol copolymer in a solvent, carrying out ring-opening esterification reaction to obtain maleic anhydride grafted ethylene-vinyl alcohol copolymer solution, and removing the solvent to obtain the maleic anhydride grafted ethylene-vinyl alcohol copolymer material.
Preferably, the content of the ethylene-vinyl alcohol copolyester is 5 to 20 parts and the content of the maleic anhydride is 1.25 to 20 parts per 100 parts of the solvent by mass.
Preferably, the solvent is one or more of dioxane, dimethyl sulfoxide and dimethylacetamide.
Preferably, the reaction temperature of the ring-opening esterification reaction is 20-90 ℃.
Preferably, the reaction time of the ring-opening esterification reaction is 12-120 h.
Preferably, the solvent is removed by precipitation with the addition of a poor solvent, which is one or more of methanol, ethanol, and isopropanol.
Preferably, the solvent is removed by a vacuum volatilizing solvent method, the solvent is removed under the conditions that the temperature is 60-90 ℃ and the vacuum degree is 100-2000 Pa, and the removed solvent is collected by a cold trap and recycled.
The beneficial effects are that:
in the maleic acid-carboxyl grafted ethylene-vinyl alcohol copolymer high molecular adsorbent provided by the invention, in the aqueous solution, a vinyl chain segment in a high molecular chain forms a hydrophobic part, so that the high molecular can not be completely swelled and dissolved in water; and the maleic anhydride grafted vinyl alcohol part promotes the dissolution of the vinyl alcohol chain segment due to the introduction of carboxyl, so as to form a phase structure shown in figure 1, and the phase structure realizes the dual characteristics of easy separation and high-efficiency adsorption of the adsorbent in water. That is, the vinyl chain segment crystallization and the hydrophobic property of the adsorbent are utilized to form physical crosslinking points, so that the adsorbent can not be dissolved; meanwhile, the strong interaction of maleic acid-carboxyl groups of the adsorbent on primary amino groups of hydrazine substances in the wastewater is utilized, so that the efficient adsorption of the hydrazine substances in the wastewater is realized. In addition, the structure of the adsorbent after swelling in water and the number of adsorption sites of the adsorbent can be conveniently adjusted, and the adsorbent has an excellent adsorption effect on hydrazine substances in wastewater. The adsorbent of the invention not only has adsorption effect on hydrazine substances in water, but also has adsorption effect on metal ions such as Pb in wastewater 2+ ，Cs + ，Sr 3+ ，Fe 3+ The maleic anhydride grafted ethylene-vinyl alcohol copolymer high molecular adsorbent has an adsorption effect, so that the maleic anhydride grafted ethylene-vinyl alcohol copolymer high molecular adsorbent has potential application prospect in the field of wastewater treatment.
The preparation method of the hydrazine wastewater adsorbent is simple, the maleic anhydride grafted ethylene-vinyl alcohol copolymer high-molecular adsorbent is successfully prepared, the structural designability of the adsorbent is strong, and the number of adsorption sites can be conveniently adjusted. The ethylene-vinyl alcohol copolymer containing maleic anhydride grafting is successfully prepared by grafting reaction of the ethylene-vinyl alcohol copolymer by adopting a solution low-temperature homogeneous phase method, and meanwhile, chemical crosslinking of the adsorbent caused by a high Wen Jiezhi method is avoided. According to the method, the adsorbent which forms an 'amphiphilic' structure in water is successfully prepared, and the polyethylene chain segment of the adsorbent forms physical crosslinking points in water; maleic anhydride grafted vinyl alcohol segments, forming hydrophilic segments. When the carboxyl group in maleic acid in the hydrophilic chain segment of the adsorbent is contacted with the unsymmetrical dimethylhydrazine, methylhydrazine, hydrazine and the like in water, positive-negative ion pairs of the carboxyl group and the amino group are formed. Compared with the ion pairing effect of sulfonic acid-amino of the traditional adsorbent, the grafting carboxyl is connected with carbon-carbon double bond, so that the acting force of maleic acid carboxyl-amino is stronger, and the adsorption effect is better. The grafting rate of the adsorbent can be conveniently adjusted by controlling the addition amount of maleic anhydride.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings.
FIG. 1 is a schematic representation of the adsorption of unsymmetrical dimethylhydrazine in water for maleic anhydride grafted polyethylene-vinyl alcohol.
Detailed Description
In order to describe the technical contents, the achieved objects and effects of the present invention in detail, the following description will be made with reference to the embodiments.
The reagents used in this specification are commercially available products unless specified otherwise. The ethylene-vinyl alcohol copolymer used was purchased from Kuraray corporation, japan.
The hydrazine waste water adsorbent is a high molecular material of maleic anhydride grafted ethylene-vinyl alcohol copolymer. The grafting ratio of the adsorbent ethylene-vinyl alcohol copolymer is adjusted by adding the amount of maleic anhydride. Wherein the mass ratio of the ethylene-vinyl alcohol copolymer to the maleic anhydride is (1-4): 1.
the preparation method of the hydrazine wastewater adsorbent comprises the following steps:
s100: 100 parts of solvent is weighed and added into a three-neck round bottom flask, and 5-20 parts of ethylene-vinyl alcohol copolymer polymer content is added for dissolution until a homogeneous solution is formed. Preferably, the molar content of vinyl alcohol monomer of ethylene-vinyl alcohol copolymer polymer is 20% -30%, so that the prepared modified material reaches the optimal adsorption state;
s200: continuously adding 1.25-20 parts of maleic anhydride into a three-neck round-bottom flask, preferably, 50-100% of maleic anhydride in molar content of hydroxyl in ethylene-vinyl alcohol copolymer polymer, more preferably 75-100%, and uniformly mixing to form a homogeneous solution;
s300: the three-mouth bottle is put into a water bath with oscillation function, the temperature of the water bath is controlled to be 20-90 ℃, the water bath temperature is preferably 20-60 ℃, and the water bath temperature is more preferably 35 ℃. The reaction time is 24-72 h, preferably 36-60 h, more preferably 48h;
s400: adding a large amount of poor solvent, preferably ethanol, into the reacted solution to fully precipitate maleic anhydride grafted polyethylene-vinyl alcohol polymer; the solvent can be removed from the reacted solution by a method of removing the solvent in vacuum, the vacuum degree is controlled to be 100 Pa-2000 Pa, the solvent is collected by a cold trap, and the collected solvent can be reused.
Referring to FIG. 1, a schematic representation of the adsorption of unsymmetrical dimethylhydrazine in water of a maleic anhydride grafted ethylene vinyl alcohol copolymer is shown. A maleic acid-carboxyl grafted vinyl alcohol chain segment forms a hydrophilic chain segment, and positive and negative ion pairs of carboxyl and amino can be formed when maleic acid-carboxyl in the hydrophilic chain segment contacts with unsymmetrical dimethylhydrazine, methylhydrazine, hydrazine and the like in water; the vinyl chain segment in the polymer chain forms a hydrophobic part, so that the polymer in water can not be completely swelled and dissolved; the physical crosslinking point is formed by utilizing the vinyl chain segment crystallization and hydrophobic property of the adsorbent, so that the adsorbent can not be dissolved; meanwhile, the strong interaction of maleic acid-carboxyl groups of the adsorbent on primary amino groups of hydrazine substances in the wastewater is utilized, so that the efficient adsorption of the hydrazine substances in the wastewater is realized.
In addition, the structural designability of the adsorbent is strong, the structure of the adsorbent after swelling in water and the number of adsorption sites of the adsorbent can be adjusted, for example, by selecting materials with different ethylene chain segments occupying the mole ratio of ethylene-vinyl alcohol copolymer, or simultaneously by controlling the grafting rate of maleic anhydride, the adsorbent has an excellent adsorption effect on hydrazine substances in wastewater.
The inventor has found through experiments that the adsorbent of the invention not only has adsorption effect on hydrazine substances in wastewater, but also has adsorption effect on metal ions such as Pb in wastewater 2+ ，Cs + ，Sr 3+ ，Fe 3+ The maleic anhydride grafted ethylene-vinyl alcohol copolymer high molecular adsorbent has an adsorption effect, so that the maleic anhydride grafted ethylene-vinyl alcohol copolymer high molecular adsorbent has potential application prospect in the field of wastewater treatment.
Example 1
The embodiment provides a hydrazine wastewater adsorbent, and the preparation method comprises the following steps:
(1) Weighing 100g of dimethylacetamide solvent, adding into a three-neck round-bottom flask, and then adding 10g of ethylene-vinyl alcohol copolymer for dissolution until a homogeneous solution is formed; wherein the ethylene-vinyl alcohol copolymer polymer has a vinyl alcohol monomer molar content of 20%;
(2) Continuously adding 5.02g of maleic anhydride into the three-neck round-bottom flask, wherein the molar content of maleic acid is 80% of the molar content of hydroxyl in the ethylene-vinyl alcohol copolymer polymer, and uniformly mixing to form a homogeneous solution;
(3) Placing the three-mouth bottle into a water bath, controlling the temperature of the water bath to be 35 ℃ and the reaction time to be 72 hours;
(4) And (3) removing the dimethylacetamide solvent from the reacted solution under the vacuum condition, collecting the solvent by using a cold trap, and volatilizing the solvent to obtain the maleic anhydride grafted and modified ethylene-vinyl alcohol copolymer polymer.
Cutting the adsorbent into granular substances with the diameter smaller than 5mm, adding 1g of the adsorbent into 1000mL of a unsymmetrical dimethylhydrazine aqueous solution with the concentration of 200mg/L for adsorption, wherein the adsorption temperature is 35 ℃, the adsorption time is 1h, and the concentration of methylhydrazine in the adsorbed wastewater is lower than 0.2mg/L.
Example 2
The embodiment provides a hydrazine wastewater adsorbent, and the preparation method comprises the following steps:
(1) Weighing 100g of dimethylacetamide solvent, adding into a three-neck round-bottom flask, and then adding 10g of ethylene-vinyl alcohol copolymer for dissolution until a homogeneous solution is formed; wherein the molar content of vinyl alcohol monomer in the ethylene-vinyl alcohol copolymer macromolecule is 20%;
(2) Continuously adding 6.28g of maleic anhydride into the three-neck round-bottom flask, wherein the molar content of maleic acid is 100% of the molar content of hydroxyl in the ethylene-vinyl alcohol copolymer polymer, and uniformly mixing to form a homogeneous solution;
(3) Placing the three-mouth bottle into a water bath, controlling the temperature of the water bath to be 90 ℃ and the reaction time to be 24 hours;
(4) And (3) removing the dimethylacetamide solvent from the reacted solution under the vacuum condition, collecting the solvent by using a cold trap, and volatilizing the solvent to obtain the maleic anhydride grafted and modified ethylene-vinyl alcohol copolymer polymer.
Cutting the adsorbent into granular substances with the diameter smaller than 5mm, adding 1.5g of the adsorbent into 1000mL of a 300 mg/L-concentration unsymmetrical dimethylhydrazine solution, adsorbing at 35 ℃ for 1h, wherein the concentration of methylhydrazine in the adsorbed wastewater is lower than 0.2mg/L.
Example 3
The embodiment provides a hydrazine wastewater adsorbent, and the preparation method comprises the following steps:
(1) Weighing 100g of dimethyl sulfoxide solvent, adding into a three-neck round-bottom flask, and then adding 10g of ethylene-vinyl alcohol copolymer for dissolution until a homogeneous solution is formed; wherein the molar content of vinyl alcohol monomer in the ethylene-vinyl alcohol copolymer is 25%;
(2) Continuously adding 7.7g of maleic anhydride into the three-neck round-bottom flask, wherein the molar content of maleic acid is 100% of the molar content of hydroxyl in the ethylene-vinyl alcohol copolymer polymer, and uniformly mixing to form a homogeneous solution;
(3) Placing the three-mouth bottle into a water bath, controlling the temperature of the water bath to be 35 ℃ and the reaction time to be 48 hours;
(4) Adding a large amount of ethanol into the reacted solution, precipitating maleic anhydride grafted ethylene-vinyl alcohol copolymer, and drying in a vacuum oven to obtain maleic anhydride grafted ethylene-vinyl alcohol copolymer.
Cutting the modified adsorbent into granular substances with the diameter smaller than 5mm, adding 1g of the adsorbent into 1000mL of a unsymmetrical dimethylhydrazine aqueous solution with the concentration of 200mg/L for adsorption, wherein the adsorption temperature is 35 ℃, the adsorption time is 1h, and the unsymmetrical dimethylhydrazine concentration in the adsorbed wastewater is lower than 0.5mg/L.
Example 4
The embodiment provides a hydrazine wastewater adsorbent, and the preparation method comprises the following steps:
(1) Weighing 100g of dimethyl sulfoxide solvent, adding into a three-neck round-bottom flask, adding 10g of ethylene-vinyl alcohol copolymer, and dissolving until a homogeneous solution is formed; wherein, in the polyethylene-vinyl alcohol polymer, the molar content of vinyl alcohol monomer is 25%;
(2) Continuously adding 5.78g of maleic anhydride into the three-neck round-bottom flask, wherein the molar content of maleic acid is 75% of the molar content of hydroxyl in the ethylene-vinyl alcohol copolymer polymer, and uniformly mixing to form a homogeneous solution;
(3) Placing the three-mouth bottle into a water bath, controlling the temperature of the water bath to be 40 ℃ and the reaction time to be 48 hours;
(4) Adding a large amount of ethanol into the reacted solution to precipitate maleic acid grafted ethylene-vinyl alcohol copolymer polymer, and drying in a vacuum oven to obtain maleic anhydride grafted modified ethylene-vinyl alcohol copolymer polymer.
Cutting the adsorbent into granular substances with the diameter smaller than 5mm, adding 1.5g of the adsorbent into 1000mL of a unsymmetrical dimethylhydrazine aqueous solution with the concentration of 200mg/L for adsorption, wherein the adsorption temperature is 35 ℃, the adsorption time is 1h, and the unsymmetrical dimethylhydrazine concentration in the adsorbed wastewater is lower than 0.5mg/L.
Example 5
The embodiment provides a hydrazine wastewater adsorbent, and the preparation method comprises the following steps:
(1) Weighing 100g of dioxane solvent, adding the dioxane solvent into a three-neck round bottom flask, adding 10g of ethylene-vinyl alcohol copolymer, and dissolving until a homogeneous solution is formed; wherein the ethylene-vinyl alcohol copolymer polymer has a vinyl alcohol monomer molar content of 30%;
(2) Continuously adding 8.06g of maleic anhydride into the three-neck round-bottom flask, wherein the molar content of maleic acid is 90% of the molar content of hydroxyl in the polyethylene-vinyl alcohol polymer, and uniformly mixing to form a homogeneous solution;
(3) Placing the three-mouth bottle into a water bath, controlling the temperature of the water bath to be 35 ℃ and the reaction time to be 72 hours;
(4) And (3) removing dioxane solvent from the reacted solution under a vacuum condition, collecting the solvent by using a cold trap, and volatilizing the solvent to obtain the maleic anhydride grafted modified polyethylene-vinyl alcohol polymer.
Cutting the polymer into granular substances with the diameter smaller than 5mm, taking 1g of adsorbent, adding the adsorbent into 1000mL of a 100mg/L aqueous solution of the unsymmetrical dimethylhydrazine for adsorption, wherein the adsorption temperature is 35 ℃, the adsorption time is 1h, and the concentration of the unsymmetrical dimethylhydrazine in the adsorbed wastewater is lower than 0.1mg/L.
Example 6
The embodiment provides a hydrazine wastewater adsorbent, and the preparation method comprises the following steps:
(1) Weighing 100g of dioxane solvent, adding the dioxane solvent into a three-neck round bottom flask, adding 10g of ethylene-vinyl alcohol copolymer, and dissolving until a homogeneous solution is formed; wherein the mol content of vinyl alcohol monomer in the polyethylene-vinyl alcohol polymer is 30%;
(2) Continuously adding 4.43g of maleic anhydride into the three-neck round-bottom flask, wherein the molar content of maleic acid is 50% of the molar content of hydroxyl in the ethylene-vinyl alcohol copolymer polymer, and uniformly mixing to form a homogeneous solution;
(3) Placing the three-mouth bottle into a water bath, controlling the temperature of the water bath to be 35 ℃ and the reaction time to be 72 hours;
(4) And (3) removing dioxane solvent from the reacted solution under a vacuum condition, collecting the solvent by using a cold trap, and volatilizing the solvent to obtain the maleic anhydride grafted modified ethylene-vinyl alcohol copolymer polymer.
Cutting the adsorbent into granular substances with the diameter smaller than 5mm, adding 1.5g of the adsorbent into 1000mL of hydrazine aqueous solution, adsorbing at 35 ℃ for 1h, wherein the concentration of hydrazine in the adsorbed wastewater is lower than 0.1mg/L.
Example 7
The embodiment provides a hydrazine wastewater adsorbent, and the preparation method comprises the following steps:
(1) Weighing 100g of dimethylacetamide solvent, adding into a three-neck round-bottom flask, and then adding 10g of ethylene-vinyl alcohol copolymer for dissolution until a homogeneous solution is formed; wherein the ethylene-vinyl alcohol copolymer polymer has a vinyl alcohol monomer molar content of 30%;
(2) Continuously adding 7.57g of maleic anhydride into the three-neck round-bottom flask, wherein the molar content of maleic acid is 85% of the molar content of hydroxyl in the ethylene-vinyl alcohol copolymer polymer, and uniformly mixing to form a homogeneous solution;
(3) Placing the three-mouth bottle into a water bath, controlling the temperature of the water bath to be 90 ℃ and the reaction time to be 12 hours;
(4) And (3) removing the dimethylacetamide solvent from the reacted solution under the vacuum condition, collecting the solvent by using a cold trap, and volatilizing the solvent to obtain the maleic anhydride grafted and modified ethylene-vinyl alcohol copolymer polymer.
Cutting the adsorbent into granular substances with the diameter smaller than 5mm, adding 1g of the adsorbent into 1000mL of a 150mg/L aqueous solution of the unsymmetrical dimethylhydrazine for adsorption, wherein the adsorption temperature is 35 ℃, the adsorption time is 1h, and the concentration of the unsymmetrical dimethylhydrazine in the adsorbed wastewater is lower than 0.2mg/L.
Example 8
The embodiment provides a hydrazine wastewater adsorbent, and the preparation method comprises the following steps:
(1) Weighing 100g of dimethylacetamide solvent, adding into a three-neck round-bottom flask, and then adding 10g of ethylene-vinyl alcohol copolymer for dissolution until a homogeneous solution is formed; wherein the molar content of vinyl alcohol monomer in the ethylene-vinyl alcohol copolymer macromolecule is 30%;
(2) Continuously adding 8.9g of maleic anhydride into the three-neck round-bottom flask, wherein the molar content of maleic acid is 100% of the molar content of hydroxyl in the ethylene-vinyl alcohol copolymer polymer, and uniformly mixing to form a homogeneous solution;
(3) Placing the three-mouth bottle into a water bath, controlling the temperature of the water bath to be 25 ℃ and the reaction time to be 120 hours;
(4) And (3) removing the dimethylacetamide solvent from the reacted solution under the vacuum condition, collecting the solvent by using a cold trap, and volatilizing the solvent to obtain the maleic anhydride grafted and modified ethylene-vinyl alcohol copolymer polymer.
Cutting the adsorbent into granular substances with the diameter smaller than 5mm, adding 1g of the adsorbent into 1000mL of hydrazine solution with the concentration of 200mg/L, adsorbing at 35 ℃ for 1h, and keeping the concentration of hydrazine in the adsorbed wastewater below 0.1mg/L.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (9)

1. The preparation method of the hydrazine wastewater adsorbent is characterized in that maleic anhydride and ethylene-vinyl alcohol copolymer are dissolved in a solvent to carry out ring opening esterification reaction, the reaction temperature is 20-90 ℃, a maleic anhydride grafted ethylene-vinyl alcohol copolymer solution is obtained, and then the solvent is removed, so that a maleic anhydride grafted ethylene-vinyl alcohol copolymer material is obtained, wherein the structural formula of the maleic anhydride grafted ethylene-vinyl alcohol copolymer material is shown as the following formula I:
wherein n is the average polymerization degree of ethylene-vinyl alcohol copolymer ethylene chain segment, m is the average polymerization degree of ethylene-vinyl alcohol copolymer vinyl alcohol chain segment, and k is the average grafting number of vinyl alcohol chain segment in the ethylene-vinyl alcohol copolymer.
2. The method for producing a hydrazine-based wastewater adsorbent according to claim 1, wherein the content of the ethylene-vinyl alcohol copolymer is 5 to 20 parts by mass and the content of the maleic anhydride is 1.25 to 20 parts by mass per 100 parts by mass of the solvent.
3. The method for preparing the hydrazine wastewater adsorbent according to claim 1, wherein the solvent is one or more of dioxane, dimethyl sulfoxide and dimethylacetamide.
4. The method for preparing the hydrazine wastewater adsorbent according to claim 1, wherein the reaction time of the ring-opening esterification reaction is 12-120 hours.
5. The method for preparing the hydrazine wastewater adsorbent according to claim 1, wherein the solvent is removed by precipitation with the addition of a poor solvent, and the poor solvent is one or more of methanol, ethanol and isopropanol.
6. The method for preparing the hydrazine wastewater adsorbent according to claim 1, wherein the solvent is removed by a vacuum evaporation solvent method, the solvent is removed under the conditions that the temperature is 60-90 ℃ and the vacuum degree is 100-2000 Pa, and the removed solvent is collected by a cold trap and recycled.
7. A hydrazine-based wastewater adsorbent prepared by the preparation method according to any one of claims 1 to 6.
8. The hydrazine-based wastewater adsorbent according to claim 7, wherein the grafting ratio of the ethylene-vinyl alcohol copolymer in the adsorbent is adjusted by adding maleic anhydride in an amount.
9. The hydrazine-based wastewater adsorbent according to claim 8, wherein the mass ratio of the ethylene-vinyl alcohol copolymer to the maleic anhydride in the adsorbent is (1-4): 1.
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