WO2016161824A1 - 一种可用于海水淡化的水凝胶及其制备方法 - Google Patents

一种可用于海水淡化的水凝胶及其制备方法 Download PDF

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WO2016161824A1
WO2016161824A1 PCT/CN2015/100039 CN2015100039W WO2016161824A1 WO 2016161824 A1 WO2016161824 A1 WO 2016161824A1 CN 2015100039 W CN2015100039 W CN 2015100039W WO 2016161824 A1 WO2016161824 A1 WO 2016161824A1
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hydrogel
seawater desalination
acrylate
monomer
methacrylate
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French (fr)
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樊栓狮
于驰
郎雪梅
王燕鸿
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South China University of Technology SCUT
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South China University of Technology SCUT
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    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • 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
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
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    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
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    • C08J2201/00—Foams characterised by the foaming process
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    • C08J2201/026—Crosslinking before of after foaming
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    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
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    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
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    • C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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    • C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Definitions

  • the invention relates to the technical field of seawater desalination, in particular to a hydrogel which can be used for seawater desalination and a preparation method thereof.
  • seawater desalination is an effective way to solve the shortage of fresh water.
  • the current desalination technology has 20 A variety of, including forward and reverse osmosis, multi-stage flash, electrodialysis, dew point evaporation and the use of nuclear energy, solar desalination technology.
  • these methods have the disadvantage of being too costly, which limits the large-scale application of seawater desalination technology.
  • current technologies often require large-scale equipment and have limitations in some sudden, small-scale applications.
  • Hydrogels are shorthand for a class of polymers that are lightly crosslinked, water absorbing but insoluble in water.
  • the dried hydrogel is extremely water-absorptive, and its water absorption and water absorption rate are surprising.
  • Monash University, Australia Amir Razmjou et al. used a hydrogel loaded with nano-sized iron oxide particles as a carrier. Under the combined action of magnetic field and heating, the strong water absorption by hydrogel was 3.5% by weight of sodium chloride.
  • the seawater provides driving force through the semi-permeable membrane, thereby achieving the purpose of improving the recovery rate of desalinated water.
  • Amir Razmjou The team of et al. also reported a method for extracting fresh water from seawater through a two-layer hydrogel.
  • these methods utilize a semi-permeable membrane to substantially desalinate seawater, and the hydrogel plays only a role in providing driving force and increasing water recovery rate.
  • the above method requires magnetic field heating or a certain intensity of solar irradiation in operation, which adversely affects the convenience of the application of the technology.
  • KIT Korean of the Düsseldorf Institute of Technology
  • the team of opfner et al. used sodium polyacrylate to absorb sodium chloride solution, squeezed the hydrogel to obtain the extrusion and tested its sodium chloride concentration. When the raw water concentration was 35g/L NaCl solution, the salt rejection rate was only 25 % .
  • the object of the present invention is to provide a hydrogel which can be used for seawater desalination and a preparation method thereof, in view of the deficiencies of the prior art.
  • the invention does not need to use a semi-permeable membrane to desalinate seawater, and achieves the purpose of desalinating seawater by utilizing the structural properties of the hydrogel itself.
  • the hydrogel used in the present invention may be hydroxyethyl methacrylate (HEMA) or sodium acrylate (SA).
  • HEMA hydroxyethyl methacrylate
  • SA sodium acrylate
  • the monomer which can be used for synthesizing a hydrogel which can desalinate seawater is not limited thereto, and an acrylate or methacrylate monomer having a carbon-carbon double bond and an ester group is satisfactory.
  • water is a pore former. Hydrogels with different water contents have different shapes and sizes of internal pore structures.
  • the hydrogel pore size used in the present invention is from 0.1 ⁇ m to 20 ⁇ m. Between. This pore size range ensures that the hydrogel has a strong water absorption and a certain filtration effect on the ion hydrate formed by ions in seawater. In addition, the hydrogel absorbs water and dehydrates with good reversibility. Therefore, under suitable operating conditions, the hydrogel used to desalinate seawater can be reused many times, which plays a role in energy conservation and environmental protection.
  • a hydrogel which can be used for seawater desalination which is a polymer obtained by polymerizing a monomer having a hydrophilic group and a carbon-carbon double bond through a carbon-carbon double bond; Crosslinking degree is 0.01 to 0.2 The monomer accounts for 5 wt% to 50 wt% of the hydrogel.
  • the monomer is at least one of methacrylic acid, acrylic acid, sodium acrylate, methacrylate, and acrylate compound.
  • the methacrylates include hydroxyethyl methacrylate (HEMA), methacrylic acid (2- Hydroxyethoxy)ethyl ester, methoxyethyl methacrylate, (2-methoxyethoxy)ethyl methacrylate, ethylene glycol dimethacrylate (EDMA), methacrylic acid-2 - Ethoxyethyl ester ( More than one of EEMA).
  • HEMA hydroxyethyl methacrylate
  • methacrylic acid (2- Hydroxyethoxy)ethyl ester
  • methoxyethyl methacrylate methoxyethyl methacrylate
  • EDMA ethylene glycol dimethacrylate
  • methacrylic acid-2 - Ethoxyethyl ester More than one of EEMA.
  • the acrylates include one or more of methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, and methoxyethyl acrylate.
  • the hydrogel is a homopolymer polymerized from a monomer or a copolymer obtained by polymerizing two or more monomers; the hydrogel pore size is 0.1 ⁇ m to 20 ⁇ m.
  • a method for preparing a hydrogel which can be used for seawater desalination It is synthesized from a monomer, a pore former, a crosslinking agent, an initiator and a catalyst, and the specific steps thereof are: uniformly mixing a monomer, a pore former, a crosslinking agent, an initiator, and a catalyst to obtain a mixture, and then transferring to a mold. Medium, first at 20 °C ⁇ The polymerization is carried out at a temperature of 30 ° C for 2 to 3 hours, and then the temperature is increased to continue the polymerization until the polymerization is completed, and a hydrogel which can be used for seawater desalination is obtained.
  • the crosslinking agent is ethylene glycol dimethacrylate (EDMA ), N, N-methylene bis acrylamide ( MBA And one or more of 1,5-hexadiene-3,4-diol (DVG), and the ratio of the amount of the crosslinking agent to the monomer is 0.01 to 0.2.
  • EDMA ethylene glycol dimethacrylate
  • MBA N, N-methylene bis acrylamide
  • DVG 1,5-hexadiene-3,4-diol
  • the initiator is ammonium persulfate (APS), azobisisobutyronitrile (AIBN) and benzoyl peroxide (BPO).
  • APS ammonium persulfate
  • AIBN azobisisobutyronitrile
  • BPO benzoyl peroxide
  • One or more of the initiators are used in a concentration of 1.0 mmol/L to 3.0 mmol/L in the mixture
  • the catalyst is N,N,N',N'-tetramethylethylenediamine ( TEMED)
  • the amount of catalyst is 0.2% (V/V) to 0.5% (V/V) of the total volume of the mixture
  • the pore-forming agent is deionized water, and the amount of pore-forming agent accounts for the total mass of the hydrogel. 50wt% to 95wt%.
  • the polymerization temperature is 40 ° C to 120 ° C during the temperature polymerization, and the polymerization time is 1 hour to 48 hours.
  • the initiator In order to ensure sufficient contact of the materials and uniformity of the properties of the various parts of the hydrogel, the initiator needs to be dispersed into an aqueous solution before the experiment.
  • the pore former is deionized water.
  • the pore former should be thoroughly mixed with the monomer to form a homogeneous system prior to the addition of other materials.
  • the ratio of monomer, pore former to crosslinker determines the pore structure of the hydrogel and the performance of desalinated seawater.
  • the initiator used in the synthetic hydrogel of the invention needs to be made A 10 wt% aqueous solution of ammonium persulfate was used in an amount of 1.75 mM after the addition of the reaction system.
  • the calibration method of sodium chloride concentration is ion chromatography.
  • the concentration of sodium chloride in the obtained solution is quantitatively analyzed by the linear relationship between the peak area of the chloride ion in the solution and the concentration.
  • the hydrogel dry glue first swells in seawater, and then the hydrogel that absorbs seawater is mechanically squeezed by a piston extrusion device, and the extrusion liquid is collected, which is obtained after the hydrogel is desalinated. Fresh water, then test the concentration in the extrusion. In practical applications, the hydrogel that absorbs seawater can also be directly squeezed by hand to obtain fresh water.
  • the spatial network structure of the hydrogel molecules has a certain filtering effect on the ion hydrate in the brine, so when the seawater passes through the hydrogel, part of the ion hydrate is blocked by the pores of the hydrogel, while the water molecules are free. Pass through to achieve the purpose of separation.
  • the hydrogel can handle total dissolved solids ( TDS ) ⁇ 35.00g/L Sea water or salt solution. The entire process of absorbing seawater is driven by the attraction of hydrogels to seawater, and the hydrogels can be recycled, thus reducing energy consumption and costs and meeting energy conservation and environmental requirements.
  • the invention discloses a hydrogel which can be used for seawater desalination, and utilizes the feature that the hydrogel pores have certain filtering and repelling effects on ions in seawater, thereby realizing the seawater desalination by replacing the semipermeable membrane with hydrogel.
  • the hydrogel has a strong water absorption, which provides the power for seawater to be absorbed into the hydrogel, compared to traditional reverse osmosis processes.
  • a high pressure of 3 MPa to 5 MPa is used to provide a film driving force, and the method described in the invention can save energy consumption in this part.
  • Hydrogel obtained by the present invention The degree of crosslinking of the polymer and the weight of the monomer in the preparation process as a final product are decisive for the desalination of the product.
  • the hydrogel used in the present invention meets the hygienic standard of direct contact of the human body, and the desalination process is convenient and quick. Therefore, the operation method of the present invention can directly squeeze the hydrogel by hand to obtain fresh water if necessary. In the case of rescue and disaster relief, long-distance navigation, outdoor adventures, etc., it is convenient and quick to get fresh water from seawater or brackish water to supplement the needs of the human body.
  • the seawater in the example of the present invention is replaced by an aqueous solution of sodium chloride, a main component in seawater, at a concentration of 35.00 g / L. , but not limited to this.
  • the hydrogels selected were polyhydroxyethyl methacrylate, polyhydroxyethyl methacrylate - sodium acrylate, sodium polyacrylate and polyhydroxyethyl methacrylate - Methacrylate.
  • the mass fraction of hydroxyethyl methacrylate in polyhydroxyethyl methacrylate is 10wt%, 15wt%, 20wt%, respectively; polyhydroxyethyl methacrylate -
  • the mass fraction of hydroxyethyl methacrylate in sodium acrylate is 15wt% and 10wt%, respectively, and the mass fraction of sodium acrylate is 5wt% and 10wt%, respectively, that is, the monomer after polymerization accounts for the total mass of hydrogel. 20wt%.
  • the hydrogel of the present invention is not limited thereto.
  • HEMA hydroxyethyl methacrylate
  • SA sodium acrylate
  • HEMA15/SA5 Polyhydroxyethyl methacrylate - sodium acrylate
  • EDMA ethylene glycol dimethacrylate
  • APS ammonium persulfate
  • TEMED Tetramethylethylenediamine
  • the polymerized hydrogel was thoroughly washed with deionized water and then freeze-dried at -45 °C in a freeze dryer. In the hour, the hydrogel of the present invention is obtained.
  • the hydrogel was extruded after being swollen in seawater, and the concentration of sodium chloride in the extruded solution was 12.40 g / L, and the salt rejection was 64.57%.
  • HEMA10/SA10 polyhydroxyethyl methacrylate-sodium acrylate containing 10% by weight of hydroxyethyl methacrylate and 10% by weight of sodium acrylate
  • the polymerized hydrogel was thoroughly washed with deionized water and then freeze-dried at -45 °C in a freeze dryer.
  • the hydrogel of the present invention is obtained.
  • the hydrogel was extruded after being swollen in seawater, and the concentration of sodium chloride in the extruded solution was 15.28 g / L, and the salt rejection was 56.34%.
  • HEMA20 Poly(hydroxyethyl methacrylate) containing 20% by weight of hydroxyethyl methacrylate was prepared. Weigh 10g HEMA and 40g water, placed in a conical flask and stirred evenly, then add 50 ⁇ l EDMA, 400 ⁇ l 10% APS solution and 100 ⁇ l TEMED And mix well. Transfer the mixed solution to the mold, place the mold in a thermostat, and polymerize at 25 °C for 3 hours and then at 80 °C. After a few hours, the polymerized hydrogel was thoroughly washed with deionized water and placed in a freeze dryer at -45 °C for lyophilization 24 In the hour, the hydrogel of the present invention is obtained. The hydrogel was squeezed in seawater and then squeezed. The concentration of sodium chloride in the test extrusion was 25.33 g / L, and the salt rejection was 27.63%.
  • HEMA15 Poly(hydroxyethyl methacrylate) containing 15% by weight of hydroxyethyl methacrylate was prepared. Weigh 7.5g HEMA And 42.5g of water, placed in a conical flask and stirred evenly, then add 37.5 ⁇ l EDMA, 300 ⁇ l 10% APS solution and 75 ⁇ l TEMED And mix well. Transfer the mixed solution to the mold, place the mold in a thermostat, and polymerize at 25 °C for 3 hours and then at 80 °C. After a few hours, the polymerized hydrogel was thoroughly washed with deionized water and placed in a freeze dryer at -45 °C for lyophilization 24 In the hour, the hydrogel of the present invention is obtained. The hydrogel was extruded after being swollen in seawater, and the concentration of sodium chloride in the extruded solution was 26.50 g / L, and the salt rejection was 32.08%.
  • HEMA10 Poly(hydroxyethyl methacrylate) (HEMA10) containing 10% by weight of hydroxyethyl methacrylate was prepared. Weigh 5g HEMA and 45g water, place in a conical flask and stir evenly, then add 25 ⁇ l EDMA, 200 ⁇ l 10% APS solution and 50 ⁇ l TEMED And mix well. Transfer the well-mixed solution to the mold and place the mold in a thermostat, polymerize at 25 °C for 3 hours and then polymerize at 80 °C. After a few hours, the polymerized hydrogel was thoroughly washed with deionized water and placed in a freeze dryer at -45 °C for lyophilization 24 In the hour, the hydrogel of the present invention is obtained. The hydrogel was extruded after being swollen in seawater, and the concentration of sodium chloride in the extruded solution was 27.50 g / L, and the salt rejection was 21.42%.
  • SA10 Sodium polyacrylate (SA10) containing 10% by weight of sodium acrylate was prepared. Weigh 5g SA and 45g Water, place in a conical flask and stir evenly, then add 25 ⁇ l N-N' methylene bisacrylamide (MBA), 200 ⁇ l 10% APS solution and 50 ⁇ l TEMED. And mix well. Transfer the mixed solution to the mold, place the mold in a thermostat, and polymerize at 25 °C for 3 hours and then at 70 °C. After a few hours, the polymerized hydrogel was thoroughly washed with deionized water and placed in a freeze dryer at -45 °C for lyophilization 24 In the hour, the hydrogel of the present invention is obtained. The hydrogel was extruded after being swollen in seawater, and the concentration of sodium chloride in the extruded solution was 28.13 g / L, and the salt rejection was 19.51%.
  • MFA N-N' methylene bisacrylamide
  • the mixture was polymerized at 80 °C for 24 hours, then the polymerized hydrogel was thoroughly washed with deionized water and then freeze-dried at -45 °C in a freeze dryer. In the hour, the hydrogel of the present invention is obtained.
  • the hydrogel was extruded after being swollen in seawater, and the concentration of sodium chloride in the extruded solution was 27.69 g / L, and the salt rejection was 20.89%.
  • the formulation of the hydrogel will have a major impact on the structure of the hydrogel.
  • the hydrogel monomer mass fraction is less than 5 wt%
  • the hydrogel gel is soft, it cannot be squeezed, and in this case, the water content is high, causing the hydrogel to exhibit 20 ⁇ m.
  • the above macroporous structure cannot adsorb and sieve salt ions in seawater; and when the mass fraction of hydrogel monomer is greater than 50wt%
  • the hydrogel has a low degree of swelling, the amount of seawater treated in a single treatment is small and the swelling behavior in seawater is not obvious, and the treatment time is prolonged and the recovery rate is greatly reduced, and there is no practical application value.
  • the hydrogel When the degree of cross-linking of the hydrogel is less than 0.01 (Mole ratio), the hydrogel exhibits a viscous fluid and does not have desalination properties; and when the degree of crosslinking is greater than 0.2 At (molar ratio), excessive cross-linking of the hydrogel results in slow swelling in the brine, while the hydrogel colloid is harder, which is not conducive to extrusion.

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Abstract

本发明公开了一种可用于海水淡化的水凝胶及其制备方法。该水凝胶是由含有亲水基团和碳碳双键的单体通过碳碳双键聚合而成的一种聚合物；所述聚合物的交联度为0.01～0.2；所述单体占水凝胶的质量为5wt%～50wt%。本发明的制备方法为：将单体、造孔剂、交联剂、引发剂和催化剂混合均匀，得到混合物料，然后转移到模具中，先在20℃～30℃温度下聚合2～3小时，随后升温继续聚合直到聚合完全，得到可用于海水淡化的水凝胶。本发明所述的方法方便快捷，使得本发明具备可以在抗震救灾、海事救援、野外探险等特殊状况下使用的优点。

Description

一种可用于海水淡化的水凝胶及其制备方法
技术领域
本发明涉及海水淡化的技术领域，具体涉及一种可用于海水淡化的水凝胶及其制备方法。
背景技术
淡水资源在地表分布具有不均衡性和有限性，我国尤其明显。海水的储水量非常丰富，但是海水却不能直接供人和农作物等生物使用。因此海水淡化是解决淡水短缺的一个有效途径。现行的海水淡化技术有 20 多种，包括正反渗透、多级闪蒸、电渗析法、露点蒸发法以及利用核能、太阳能海水淡化技术等。但是这些方法都有成本过高的缺点，限制了海水淡化技术的大面积推广应用。同时现行的技术往往需要大型的设备，在某些突发性、小规模情况的应用中具有局限性。
水凝胶是一类高分子聚合物的简称，这类聚合物具有轻度交联、可吸水却不溶于水的特点。经过干燥后的水凝胶具有极强的吸水性，其吸水量和吸水速率都是惊人的。澳大利亚莫纳什大学 Amir Razmjou 等人以一种负载纳米氧化铁颗粒的水凝胶为载体，在磁场和加热共同作用的情况下，通过利用水凝胶的强吸水性为含氯化钠浓度为 3.5wt% 海水通过半透膜提供驱动力，进而达到提高海水淡化水回收率的目的。随后， Amir Razmjou 等人的团队又报告了一种通过双层结构的水凝胶从海水中提取淡水的方法。该团队通过凝胶本身的吸水性以及利用太阳能照射凝胶层使海水穿过半透膜进入凝胶层中，进而释放出淡水。但是这些方法都是利用半透膜对海水进行实质性的脱盐处理，水凝胶在其中只是起到一个提供驱动力和提高水回收率的作用。而且上述的方法在操作中需要磁场加热或达到一定强度的太阳能照射，都对该技术应用的便捷性产生了不利的影响。德国卡尔斯鲁厄理工学院（KIT）的Johannes opfner 等人的团队曾用聚丙烯酸钠吸收氯化钠溶液，通过挤压水凝胶得到挤出液并测试其氯化钠浓度，当原水浓度为 35g/L NaCl溶液时，脱盐率仅为 25% 。
发明内容
本发明的目的在于针对现有技术的不足，提供了一种可用于海水淡化的水凝胶及其制备方法。本发明无需利用半透膜对海水进行淡化处理，通过利用水凝胶自身的结构性质，达到淡化海水的目的。
本发明的技术原理如下：
本发明所用的水凝胶可以用甲基丙烯酸羟乙酯（ HEMA ）或者丙烯酸钠 (SA) 作为单体合成的均聚物或共聚物。当然可用于合成可淡化海水的水凝胶的单体并不局限于此，具备碳碳双键和酯基的丙烯酸酯类、甲基丙烯酸酯类单体都满足要求。
在水凝胶的结构中，水是造孔剂。不同含水量的水凝胶其内部孔穴结构的形状与大小也不同。本发明所采用的水凝胶孔径在 0.1μm ～ 20μm 之间。这个孔径范围可以保证水凝胶有较强的吸水性，同时对于海水中离子所形成的离子水合物有一定的过滤作用。此外水凝胶吸水、脱水有良好的可逆性，因此在控制合适的操作条件下，用于淡化海水的水凝胶可以多次重复利用，起到了节能环保的作用。
本发明目的通过以下技术方案来实现。
一种可用于海水淡化的水凝胶，所述水凝胶是由含有亲水基团和碳碳双键的单体通过碳碳双键聚合而成的一种聚合物；所述聚合物的交联度为 0.01 ～ 0.2 ；所述单体占水凝胶的质量为 5wt% ～ 50wt% 。
优选地，所述单体为甲基丙烯酸、丙烯酸、丙烯酸钠、甲基丙烯酸酯类和丙烯酸酯类化合物中的一种以上。
优选地，所述的甲基丙烯酸酯类包括甲基丙烯酸羟乙酯（ HEMA ）、甲基丙烯酸（ 2- 羟基乙氧基）乙酯、甲基丙烯酸甲氧基乙酯、甲基丙烯酸（ 2- 甲氧基乙氧基）乙酯、乙二醇二甲基丙烯酸酯（ EDMA ）、甲基丙烯酸 -2- 乙氧基乙酯（ EEMA ）中的一种以上。
优选地，所述的丙烯酸酯类包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸羟乙酯、丙烯酸甲氧基乙酯中的一种以上。
优选地，所述水凝胶是由一种单体聚合而成的均聚物，或是由两种以上单体聚合而成的共聚物；所述水凝胶孔径为 0.1 μ m ～ 20 μ m 。
一种可用于海水淡化的水凝胶的制备方法， 由单体、造孔剂、交联剂、引发剂和催化剂合成，其具体步骤为：将单体、造孔剂、交联剂、引发剂和催化剂混合均匀，得到混合物料，然后转移到模具中，先在 20 ℃～ 30 ℃温度下聚合 2 ～ 3 小时，随后升温继续聚合直到聚合完全，得到可用于海水淡化的水凝胶。
上述方法中，所述交联剂为乙二醇二甲基丙烯酸酯（ EDMA ）、 N,N- 亚甲基双丙烯酰胺（ MBA ）和 1,5- 己二烯 -3,4- 二醇（ DVG ）的一种或以上，交联剂与单体的物质的量之比为 0.01 ～ 0.2 。
上述方法中，所述引发剂为过硫酸铵（ APS ）、偶氮二异丁腈（ AIBN ）和过氧化二甲酰（ BPO ）的一种或以上，引发剂的用量在 混合物料中的浓度为 1.0mmol/L ～ 3.0mmol/L ； 所述催化剂为 N,N,N',N'- 四甲基乙二胺（ TEMED ），催化剂用量占混合物料总体积的 0.2% （ V/V ）～ 0.5% （ V/V ）；所述的造孔剂为去离子水，造孔剂的用量占水凝胶总质量的 50wt% ～ 95wt% 。
上述方法中，升温聚合时为聚合温度在 40 ℃～ 120 ℃，聚合时间在 1 小时～ 48 小时。
为保证各物料的充分接触和水凝胶各部位性质的均一稳定，所述的引发剂在实验前需被分散成水溶液。所述的造孔剂为去离子水。在加入其它原料之前，造孔剂应与单体充分混合成一均相体系。单体、造孔剂与交联剂的比例决定了水凝胶的孔穴结构和淡化海水的性能。本发明合成水凝胶所用的引发剂需制成 10wt% 的过硫酸铵水溶液，用量为加入反应体系后过硫酸铵的浓度为 1.75mM 。
氯化钠浓度标定方法为离子色谱法，通过溶液中氯离子色谱峰面积与浓度成线性关系这一特性定量分析所得溶液中氯化钠的浓度。
所述的水凝胶干胶先在海水中溶胀，随后用一个活塞挤压的装置对吸收了海水的水凝胶进行机械挤压，收集挤出液，即为经过水凝胶淡化后所得到的淡水，再测试挤出液中的浓度即可。实际应用中亦可直接用手挤压吸收海水的水凝胶来得到淡水。
本发明产品 水凝胶分子的空间网状结构对盐水中的离子水合物有一定的过滤作用，因此当海水穿过水凝胶时，一部分离子水合物被水凝胶的孔阻拦，而水分子却可以自由穿过，从而达到分离的目的。所述水凝胶可以处理总溶解固体（ TDS ）≥ 35.00g/L 的海水或盐溶液。整个吸收海水的过程由水凝胶对海水的吸引力提供驱动力，而且水凝胶可以循环使用，因此降低了能耗和成本，达到节能环保的要求。
本发明相对于现有技术所具备的优点及有益效果：
本发明公开了一种可用于海水淡化的水凝胶，利用水凝胶孔穴对海水中离子有一定过滤和排斥作用这一特征，实现了用水凝胶代替半透膜进行海水淡化。水凝胶有很强的吸水性，这为海水被吸入水凝胶提供了动力，相比传统的反渗透工艺需要 3MPa ～ 5MPa 的高压来提供过膜驱动力，该发明所述的方法能节约这部分的能耗。
本发明所得的水凝胶 聚合物的交联度以及制备过程中的单体占最终产品的重量参数对于产品的用于海水淡化其决定性的作用。
本发明所用的水凝胶达到人体直接接触的卫生标准，同时淡化过程方便快捷，因此本发明所述的操作方法在有需要的情况下可以直接用手去挤压水凝胶得到淡水，在诸如抢险救灾、长途航海、户外探险等情况下可方便、快捷的从海水或苦咸水得到淡水，补充人体所需。
具体实施方式
下面结合具体实施例对本发明作进一步地具体详细描述，但本发明的实施方式不限于此，对于未特别注明的工艺参数，可参照常规技术进行。
本发明实例中的海水由海水中的主要成分氯化钠的水溶液代替，所用浓度为 35.00g /L ，但并不限于此。所选用的水凝胶为聚甲基丙烯酸羟乙酯、聚甲基丙烯酸羟乙酯 - 丙烯酸钠、聚丙烯酸钠和聚甲基丙烯酸羟乙酯 - 甲基丙烯酸。聚甲基丙烯酸羟乙酯中甲基丙烯酸羟乙酯的质量分数分别为 10wt% 、 15wt% 、 20wt% ；聚甲基丙烯酸羟乙酯 - 丙烯酸钠中甲基丙烯酸羟乙酯的质量分数分别为 15wt% 和 10wt% ，丙烯酸钠的质量分数分别为 5wt% 和 10wt% ，即聚合后单体占水凝胶总质量的 20wt% 。本发明所述的水凝胶并不局限于此。
实施例 1
制备含 15wt% 甲基丙烯酸羟乙酯（ HEMA ）和 5wt% 丙烯酸钠 (SA) 的聚甲基丙烯酸羟乙酯 - 丙烯酸钠（ HEMA15/SA5 ）。称取 7.5g HEMA 、 2.5gSA 和 40g 水，放置锥形瓶中均匀搅拌，然后依次加入 150 μ l 乙二醇二甲基丙烯酸酯（ EDMA ）、 200 μ l 10% 过硫酸铵（ APS ）溶液和 100 μ l N,N,N',N'- 四甲基乙二胺（ TEMED ）并混合均匀。将混合均匀的溶液转移到模具中，并将模具至于恒温器中，在 30 ℃ 下恒温聚合 3 小时后再在 75 ℃ 下恒温聚合 24 小时，然后将聚合好的水凝胶用去离子水充分洗净，再置于冷冻干燥机中在 -45 ℃ 冷冻干燥 24 小时，即得到本发明所述的水凝胶。将水凝胶放到海水中溶胀之后挤压，经测试挤出液中氯化钠的浓度为 12.40g /L ，脱盐率为 64.57% 。
实施例 2
制备含 10wt% 甲基丙烯酸羟乙酯和 10wt% 丙烯酸钠的聚甲基丙烯酸羟乙酯 - 丙烯酸钠（ HEMA10/SA10 ）。称取 5g HEMA 、 5gSA 和 40g 水，放置锥形瓶中均匀搅拌，然后依次加入 175 μ l EDMA 、 200 μ l 10% APS 溶液和 100 μ l TEMED 并混合均匀。将混合均匀的溶液转移到模具中，并将模具至于恒温器中，在 30 ℃ 下恒温聚合 3 小时后再在 75 ℃ 下恒温聚合 24 小时，然后将聚合好的水凝胶用去离子水充分洗净，再置于冷冻干燥机中在 -45 ℃ 冷冻干燥 24 小时，即得到本发明所述的水凝胶。将水凝胶放到海水中溶胀之后挤压，经测试挤出液中氯化钠的浓度为 15.28g /L ，脱盐率为 56.34% 。
实施例 3
制备含 20wt% 甲基丙烯酸羟乙酯的聚甲基丙烯酸羟乙酯（ HEMA20 ）。称取 10g HEMA 和 40g 水，放置锥形瓶中均匀搅拌，然后依次加入 50μl EDMA 、 400μl 10%APS 溶液和 100μlTEMED 并混合均匀。将混合均匀的溶液转移到模具中，并将模具至于恒温器中，在 25 ℃ 下恒温聚合 3 小时后再在 80 ℃ 下恒温聚合 24 小时，然后将聚合好的水凝胶用去离子水充分洗净，再置于冷冻干燥机中在 -45 ℃ 冷冻干燥 24 小时，即得到本发明所述的水凝胶。将水凝胶放到海水中溶胀之后挤压，经试挤出液中氯化钠的浓度为 25.33g /L ，脱盐率为 27.63% 。
实施例 4
制备含 15wt% 甲基丙烯酸羟乙酯的聚甲基丙烯酸羟乙酯（ HEMA15 ）。称取 7.5g HEMA 和 42.5g 水，放置锥形瓶中均匀搅拌，然后依次加入 37.5μl EDMA 、 300μl 10%APS 溶液和 75μlTEMED 并混合均匀。将混合均匀的溶液转移到模具中，并将模具至于恒温器中，在 25 ℃ 下恒温聚合 3 小时后再在 80 ℃ 下恒温聚合 24 小时，然后将聚合好的水凝胶用去离子水充分洗净，再置于冷冻干燥机中在 -45 ℃ 冷冻干燥 24 小时，即得到本发明所述的水凝胶。将水凝胶放到海水中溶胀之后挤压，经测试挤出液中氯化钠的浓度为 26.50g /L ，脱盐率为 32.08% 。
实施例 5
制备含 10wt% 甲基丙烯酸羟乙酯的聚甲基丙烯酸羟乙酯（ HEMA10 ）。称取 5g HEMA 和 45g 水，放置锥形瓶中均匀搅拌，然后依次加入 25μl EDMA 、 200μl 10%APS 溶液和 50μlTEMED 并混合均匀。将混合均匀的溶液转移到模具中，并将模具至于恒温器中，在 25 ℃ 下聚合 3 小时后再在 80 ℃ 下聚合 24 小时，然后将聚合好的水凝胶用去离子水充分洗净，再置于冷冻干燥机中在 -45 ℃ 冷冻干燥 24 小时，即得到本发明所述的水凝胶。水凝胶放到海水中溶胀之后挤压，经测试挤出液中氯化钠的浓度为 27.50g /L ，脱盐率为 21.42% 。
实施例 6
制备含 10wt% 丙烯酸钠的聚丙烯酸钠（ SA10 ）。称取 5g SA 和 45g 水，放置锥形瓶中均匀搅拌，然后依次加入 25μl N-N' 亚甲基双丙烯酰胺（ MBA ）、 200μl 10%APS 溶液和 50μlTEMED 并混合均匀。将混合均匀的溶液转移到模具中，并将模具至于恒温器中，在 25 ℃ 下恒温聚合 3 小时后再在 70 ℃ 下恒温聚合 24 小时，然后将聚合好的水凝胶用去离子水充分洗净，再置于冷冻干燥机中在 -45 ℃ 冷冻干燥 24 小时，即得到本发明所述的水凝胶。水凝胶放到海水中溶胀之后挤压，经测试挤出液中氯化钠的浓度为 28.13g /L ，脱盐率为 19.51% 。
实施例 7
制备含 19.9wt% 的甲基丙烯酸羟乙酯和 0.2wt% 的甲基丙烯酸（ MA ）共聚而成的聚甲基丙烯酸羟乙酯 - 甲基丙烯酸。称取 10g HEMA 、 0.1gMA 和 40g 水，放置锥形瓶中均匀搅拌，然后依次加入 50μl EDMA 、 400μl 10%APS 溶液和 100μlTEMED 并混合均匀。将混合均匀的溶液转移到模具中，并将模具至于恒温器中，在 25 ℃ 下恒温聚合 3 小时后再在 80 ℃ 下恒温聚合 24 小时，然后将聚合好的水凝胶用去离子水充分洗净，再置于冷冻干燥机中在 -45 ℃ 冷冻干燥 24 小时，即得到本发明所述的水凝胶。水凝胶放到海水中溶胀之后挤压，经测试挤出液中氯化钠的浓度为 27.69g /L ，脱盐率为 20.89% 。
制备水凝胶的配方会对水凝胶的结构产生重大的影响。当水凝胶的单体的质量分数低于 5wt% 时，水凝胶成胶较软无法挤压，同时该情况下含水率大导致水凝胶呈现出 20 μ m 以上的大孔结构，没法对海水中的盐离子进行吸附和筛分；而当水凝胶单体的质量分数大于 50wt% 时，水凝胶整体的溶胀度低，单次处理海水量小而且在海水中溶胀行为不明显，延长处理时间同时大幅降低了回收率，没有实际应用价值。当水凝胶的交联度小于 0.01 （摩尔比）时，水凝胶呈现出粘稠状流体，不具备淡化性能；而当交联度大于 0.2 （摩尔比）时，水凝胶过度交联导致在盐水中溶胀缓慢，同时水凝胶胶体较硬，不利于挤压。
本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (9)

  1. 一种可用于海水淡化的水凝胶，其特征在于，所述水凝胶是由含有亲水基团和碳碳双键的单体通过碳碳双键聚合而成的一种聚合物；所述聚合物的交联度为0.01～0.2；所述单体占水凝胶的质量为5wt%～50wt%。
  2. 根据权利要求1所述的可用于海水淡化的水凝胶，其特征在于，所述单体为甲基丙烯酸、丙烯酸、丙烯酸钠、甲基丙烯酸酯类和丙烯酸酯类化合物中的一种以上。
  3. 根据权利要求2所述的可用于海水淡化的水凝胶，其特征在于，所述的甲基丙烯酸酯类包括甲基丙烯酸羟乙酯（HEMA）、甲基丙烯酸（2-羟基乙氧基）乙酯、甲基丙烯酸甲氧基乙酯、甲基丙烯酸（2-甲氧基乙氧基）乙酯、乙二醇二甲基丙烯酸酯（EDMA）、甲基丙烯酸-2-乙氧基乙酯（EEMA）中的一种以上。
  4. 根据权利要求2所述的可用于海水淡化的水凝胶，其特征在于，所述的丙烯酸酯类包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸羟乙酯、丙烯酸甲氧基乙酯中的一种以上。
  5. 根据权利要求1所述的可用于海水淡化的水凝胶，其特征在于，所述水凝胶是由一种单体聚合而成的均聚物，或是由两种以上单体聚合而成的共聚物；所述水凝胶孔径为0.1μm～20μm。
  6. 制备权利要求1所述可用于海水淡化的水凝胶的方法，其特征在于，具体步骤为：将单体、造孔剂、交联剂、引发剂和催化剂混合均匀，得到混合物料，然后转移到模具中，先在20℃～30℃温度下聚合2～3小时，随后升温继续聚合直到聚合完全，得到可用于海水淡化的水凝胶。
  7. 根据权利要求6所述的方法，其特征在于，所述交联剂为乙二醇二甲基丙烯酸酯（EDMA）、N,N-亚甲基双丙烯酰胺（MBA）和1,5-己二烯-3,4-二醇（DVG）的一种以上，交联剂与单体的物质的量之比为0.01～0.2。
  8. 根据权利要求6所述的方法，其特征在于，所述引发剂为过硫酸铵（APS）、偶氮二异丁腈（AIBN）和过氧化二甲酰（BPO）的一种以上，引发剂的用量在混合物料中的浓度为1.0mmol/L～3.0mmol/L；所述催化剂为N,N,N’,N’-四甲基乙二胺（TEMED），催化剂用量占混合物料总体积的0.2%（V/V）～0.5%（V/V）；所述的造孔剂为去离子水，造孔剂的用量占水凝胶总质量的50wt%～95wt%。
  9. 根据权利要求6所述的方法，其特征在于，升温聚合时为聚合温度在40℃～120℃，聚合时间在1小时～48小时。
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