CN115722202A - Yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, preparation method and application thereof - Google Patents
Yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, preparation method and application thereof Download PDFInfo
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 108
- -1 Yttrium-zirconium-terephthalic acid Chemical compound 0.000 title claims abstract description 96
- 239000002131 composite material Substances 0.000 title claims abstract description 92
- 239000000463 material Substances 0.000 title claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 97
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 239000012692 Fe precursor Substances 0.000 claims abstract description 15
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims abstract description 12
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract 6
- 238000005406 washing Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000011790 ferrous sulphate Substances 0.000 claims description 15
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 15
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 15
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 10
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 102000012440 Acetylcholinesterase Human genes 0.000 description 1
- 108010022752 Acetylcholinesterase Proteins 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 206010053159 Organ failure Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229940022698 acetylcholinesterase Drugs 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- MTRJKZUDDJZTLA-UHFFFAOYSA-N iron yttrium Chemical compound [Fe].[Y] MTRJKZUDDJZTLA-UHFFFAOYSA-N 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- RVRKDGLTBFWQHH-UHFFFAOYSA-N yttrium zirconium Chemical compound [Y][Zr][Y] RVRKDGLTBFWQHH-UHFFFAOYSA-N 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
技术领域technical field
本发明属于水处理技术领域，特别是涉及一种用于去除水中有机膦的钇-锆-对苯二甲酸基复合磁性吸附材料、制备方法及其应用。The invention belongs to the technical field of water treatment, and in particular relates to a yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material for removing organic phosphine in water, a preparation method and an application thereof.
背景技术Background technique
全球对向水体释放磷的限制越来越严格，关于磷排放，除无机磷，还应考虑其他定量相关的含磷化合物，如有机膦。有机膦是含有一个或多个C-PO(OH)2基团，其C-P键的化学稳定性优于无机磷中的P-O-P键。有机膦是用于造纸和纺织工业等许多不同工业部门的络合剂，作为漂白剂稳定剂、冷却设备中的硬度稳定剂、膜设备或家庭中的阻垢剂和清洁剂等，它们还广泛用于农业领域，由于其高效和低成本，在保护农作物和消灭昆虫方面发挥着至关重要的作用。然而，有机膦的广泛应用会造成在水体中的残留，导致环境污染，由于其残留物会抑制乙酰胆碱酯酶的活性并导致器官衰竭，对公众健康构成了极大的危害。此外，有机膦还促成了水体的藻华和富营养化，因此，开发有效的技术从水体中去除有机膦是非常必要的。The global restrictions on the release of phosphorus to water bodies are becoming more and more stringent. Regarding phosphorus discharge, in addition to inorganic phosphorus, other quantitatively relevant phosphorus-containing compounds, such as organic phosphines, should also be considered. Organic phosphine contains one or more C-PO(OH) 2 groups, and the chemical stability of its CP bond is better than that of the POP bond in inorganic phosphorus. Organophosphines are complexing agents used in many different industrial sectors such as the paper and textile industries, as bleach stabilizers, hardness stabilizers in cooling equipment, scale inhibitors and cleaning agents in membrane equipment or households, etc. They are also widely used in Used in the field of agriculture, due to its high efficiency and low cost, it plays a vital role in protecting crops and exterminating insects. However, the widespread use of organophosphine will cause residues in water bodies, leading to environmental pollution, and pose a great hazard to public health because their residues will inhibit the activity of acetylcholinesterase and cause organ failure. In addition, organophosphine also contributes to algal blooms and eutrophication of water bodies. Therefore, it is very necessary to develop effective technologies to remove organophosphine from water bodies.
与其他去除有机膦的方法相比，吸附法具有易于实施、选择性和可重复使用等优点，是最有前途的候选方法之一。以前的研究表明，过渡金属元素的羟基氧化物或氢氧化物，如针铁矿(a-FeOOH)和粒状氢氧化铁可用于去除有机膦；然而，此类吸附剂需要较长时间才能达到吸附平衡(9小时至7天)，并且对有机膦的吸附能力较差，截止目前为止，吸附材料对有机膦的吸附量较低，一般为30mg/g以下。Compared with other methods for the removal of organophosphine, the adsorption method is one of the most promising candidates due to its advantages of ease of implementation, selectivity, and reusability. Previous studies have shown that oxyhydroxides or hydroxides of transition metal elements such as goethite (a-FeOOH) and granular ferric hydroxide can be used for the removal of organophosphine; however, such adsorbents take a long time to reach adsorption Equilibrium (9 hours to 7 days), and the adsorption capacity of organic phosphine is poor. So far, the adsorption capacity of adsorption materials for organic phosphine is low, generally below 30mg/g.
钇作为稀土元素，具有较大的配位数，从而使其对于含氧阴离子(磷酸盐、砷酸盐等)具有良好的亲和能力和吸附选择性，而锆也具有较大的配位数，但目前仍未见以钇-锆基复合稀土材料为吸附材料作为主要活性成分来去除水中有机膦的报道；另外，吸附材料即使吸附了有机膦，通常也很难从溶液中分离出来，不利于后续处理。As a rare earth element, yttrium has a large coordination number, which makes it have good affinity and adsorption selectivity for oxyanions (phosphate, arsenate, etc.), and zirconium also has a large coordination number. , but there is still no report on the use of yttrium-zirconium-based composite rare earth materials as the main active ingredient to remove organic phosphine from water; in addition, even if the adsorption material adsorbs organic phosphine, it is usually difficult to separate it from the solution. Useful for subsequent processing.
因此，需要提供一种针对上述现有技术不足的改进技术方案。Therefore, it is necessary to provide an improved technical solution for the above-mentioned deficiencies in the prior art.
发明内容Contents of the invention
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种用于去除水中有机膦的钇-锆-对苯二甲酸基复合磁性吸附材料、制备方法及其应用，用于解决现有技术中的吸附材料对有机膦的吸附能力差、吸附量低的问题，以及现有技术中吸附材料吸附有机膦之后难以从溶液中分离、不利于后续处理的问题。In view of the shortcomings of the prior art described above, the object of the present invention is to provide a yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material for removing organic phosphine in water, a preparation method and its application, to solve the existing problems. The adsorption material in the technology has poor adsorption capacity and low adsorption capacity for organic phosphine, and the adsorption material in the prior art is difficult to separate from the solution after adsorbing organic phosphine, which is not conducive to subsequent treatment.
为实现上述目的及其他相关目的，本发明提供一种用于去除水中有机膦的钇-锆-对苯二甲酸基复合磁性吸附材料的制备方法，所述制备方法包括以下步骤：In order to achieve the above object and other related objects, the present invention provides a method for preparing a yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material for removing organic phosphine in water, the preparation method comprising the following steps:
S1、将硝酸钇、氯化锆和对苯二甲酸加入DMF溶剂中，形成混合溶液，然后于120℃下反应24h，得到钇-锆-对苯二甲酸基复合材料；S1, adding yttrium nitrate, zirconium chloride and terephthalic acid into a DMF solvent to form a mixed solution, and then reacting at 120° C. for 24 hours to obtain a yttrium-zirconium-terephthalic acid-based composite material;
S2、将一定量的粉末活性炭分散于去离子水中，得到活性炭分散液；S2, a certain amount of powdered activated carbon is dispersed in deionized water to obtain an activated carbon dispersion;
S3、于步骤S2中得到的所述活性炭分散液中加入铁前驱物和所述钇-锆-对苯二甲酸基复合材料，得到反应溶液，调节所述反应溶液的pH值后，加热下搅拌反应3h；S3. Add an iron precursor and the yttrium-zirconium-terephthalic acid-based composite material to the activated carbon dispersion obtained in step S2 to obtain a reaction solution, adjust the pH value of the reaction solution, and stir under heating Reaction 3h;
S4、待反应结束后离心并洗涤至中性，然后经烘干，得到钇-锆-对苯二甲酸基复合磁性吸附材料。S4. After the reaction is completed, centrifuge and wash until neutral, and then dry to obtain a yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material.
优选地，步骤S1中所述硝酸钇、氯化锆和对苯二甲酸在所述混合溶液中的浓度一致，且均为0.04mol/L。Preferably, the concentrations of yttrium nitrate, zirconium chloride and terephthalic acid in the mixed solution in step S1 are the same, and are all 0.04mol/L.
优选地，步骤S2中所述粉末活性炭的比表面积为1000～1500m2/g，所述粉末活性炭的粒径大小为150～300目。Preferably, the specific surface area of the powdered activated carbon in step S2 is 1000-1500 m 2 /g, and the particle size of the powdered activated carbon is 150-300 mesh.
优选地，步骤S2中所述活性炭分散液的质量浓度为1～4g/L。Preferably, the mass concentration of the activated carbon dispersion in step S2 is 1-4 g/L.
优选地，步骤S3中所述铁前驱物为硫酸亚铁和三氯化铁的混合物，其中，所述硫酸亚铁与所述三氯化铁的摩尔比为1：2。Preferably, the iron precursor in step S3 is a mixture of ferrous sulfate and ferric chloride, wherein the molar ratio of ferrous sulfate to ferric chloride is 1:2.
优选地，步骤S3中所述活性炭分散液中的粉末活性炭与铁前驱物的质量比为0.06～0.25。Preferably, the mass ratio of the powdered activated carbon to the iron precursor in the activated carbon dispersion in step S3 is 0.06-0.25.
优选地，步骤S3中加入的所述铁前驱物中的铁元素与所述钇-锆-对苯二甲酸的摩尔比为(1～4)：1。Preferably, the molar ratio of the iron element in the iron precursor added in step S3 to the yttrium-zirconium-terephthalic acid is (1-4):1.
优选地，步骤S3中调节所述反应溶液的pH值，具体包括：采用2mol/L的氢氧化钠溶液将所述反应溶液的pH值调节至11。Preferably, adjusting the pH value of the reaction solution in step S3 specifically includes: adjusting the pH value of the reaction solution to 11 with 2 mol/L sodium hydroxide solution.
优选地，步骤S3中所述加热的温度为70～80℃。Preferably, the heating temperature in step S3 is 70-80°C.
优选地，步骤S4中所述烘干的温度为60～65℃。Preferably, the drying temperature in step S4 is 60-65°C.
一种用于去除水中有机膦的钇-锆-对苯二甲酸基复合磁性吸附材料，所述钇-锆-对苯二甲酸基复合磁性吸附材料为采用上述的制备方法制备而成的。A yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material for removing organic phosphine in water is prepared by the above-mentioned preparation method.
一种采用上述制备方法制备而成的钇-锆-对苯二甲酸基复合磁性吸附材料的应用，所述钇-锆-对苯二甲酸基复合磁性吸附材料应用于吸附去除水中的有机膦。An application of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material prepared by the above preparation method, and the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material is applied to adsorb and remove organic phosphine in water.
如上所述，本发明的用于去除水中有机膦的钇-锆-对苯二甲酸基复合磁性吸附材料、制备方法及其应用，具有以下有益效果：As mentioned above, the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material, preparation method and application of the present invention for removing organic phosphine in water have the following beneficial effects:
本发明采用硝酸钇、氯化锆和对苯二甲酸制备出钇-锆-对苯二甲酸基复合材料，硫酸亚铁和三氯化铁原位反应形成四氧化三铁，通过四氧化三铁对钇-锆-对苯二甲酸基复合材料进行修饰，使其具有磁性，同时还利用了活性炭的多孔结构和较大比表面积的优点，有效分散钇-锆-对苯二甲酸基复合材料和四氧化三铁粒子，最终制备出钇-锆-对苯二甲酸基复合磁性吸附材料，制备过程简单、易操作，具有良好的重复性。The present invention adopts yttrium nitrate, zirconium chloride and terephthalic acid to prepare yttrium-zirconium-terephthalic acid-based composite material, ferrous sulfate and ferric chloride react in situ to form ferric oxide, and ferric oxide The yttrium-zirconium-terephthalic acid-based composite is modified to make it magnetic, and the advantages of the porous structure and large specific surface area of activated carbon are also used to effectively disperse the yttrium-zirconium-terephthalic acid-based composite and The ferric oxide particles are used to finally prepare the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material. The preparation process is simple, easy to operate, and has good repeatability.
本发明中钇-锆-对苯二甲酸基复合磁性吸附材料是利用了稀土钇-锆-对苯二甲酸基复合材料对有机膦的吸附选择性与四氧化三铁的磁分离的特性，使其应用于水中去除有机膦时具有较高吸附性能的同时兼有磁分离的特性，高比表面积活性炭的加入，进一步提高了吸附材料活性成分的吸附效率和磁分离性能，从而提高了吸附材料对水中有机膦的吸附选择性，实现对其进行高效去除，显著提高了水中有机膦的吸附量和去除率，且由于磁分离特性，使得吸附材料吸附有机膦后易从水中分离，利于后续处理，在吸附法处理水中有机膦领域具有广泛的应用前景。In the present invention, the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material utilizes the characteristics of the adsorption selectivity of the rare earth yttrium-zirconium-terephthalic acid-based composite material to organic phosphine and the magnetic separation of ferroferric oxide. When it is applied to remove organic phosphine in water, it has high adsorption performance and also has the characteristics of magnetic separation. The addition of high specific surface area activated carbon further improves the adsorption efficiency and magnetic separation performance of the active components of the adsorption material, thereby improving the adsorption of the adsorption material. The adsorption selectivity of organic phosphine in water enables efficient removal of it, significantly improving the adsorption capacity and removal rate of organic phosphine in water, and due to the magnetic separation characteristics, the adsorption material is easy to separate from water after adsorbing organic phosphine, which is beneficial to subsequent treatment. It has broad application prospects in the field of organic phosphine treatment in water by adsorption method.
具体实施方式Detailed ways
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。Embodiments of the present invention are described below through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various modifications or changes can be made to the details in this specification based on different viewpoints and applications without departing from the spirit of the present invention.
本发明采用硝酸钇、氯化锆和对苯二甲酸制备出钇-锆-对苯二甲酸基复合材料，硫酸亚铁和三氯化铁原位反应形成四氧化三铁，通过四氧化三铁对钇-锆-对苯二甲酸基复合材料进行修饰，使其具有磁性，同时还利用了活性炭的多孔结构和较大比表面积的优点，有效分散钇-锆-对苯二甲酸基复合材料和四氧化三铁粒子，最终制备出钇-锆-对苯二甲酸基复合磁性吸附材料，制备过程简单、易操作，具有良好的重复性；本发明中钇-锆-对苯二甲酸基复合磁性吸附材料是利用了稀土钇-锆-对苯二甲酸基复合材料对有机膦的吸附选择性与四氧化三铁的磁分离的特性，使其应用于水中去除有机膦时具有较高吸附性能的同时兼有磁分离的特性，高比表面积活性炭的加入，进一步提高了吸附材料活性成分的吸附效率和磁分离性能，从而提高了吸附材料对水中有机膦的吸附选择性，实现对其进行高效去除，显著提高了水中有机膦的吸附量和去除率，且由于磁分离特性，使得吸附材料吸附有机膦后易从水中分离，利于后续处理，在吸附法处理水中有机膦领域具有广泛的应用前景。The present invention adopts yttrium nitrate, zirconium chloride and terephthalic acid to prepare yttrium-zirconium-terephthalic acid-based composite material, ferrous sulfate and ferric chloride react in situ to form ferric oxide, and ferric oxide The yttrium-zirconium-terephthalic acid-based composite is modified to make it magnetic, and the advantages of the porous structure and large specific surface area of activated carbon are also used to effectively disperse the yttrium-zirconium-terephthalic acid-based composite and Ferriferric oxide particles finally prepare the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material, the preparation process is simple, easy to operate, and has good repeatability; in the present invention, the yttrium-zirconium-terephthalic acid-based composite magnetic The adsorption material is based on the adsorption selectivity of rare earth yttrium-zirconium-terephthalic acid-based composite materials for organic phosphine and the magnetic separation characteristics of ferroferric oxide, so that it has high adsorption performance when it is applied to remove organic phosphine in water. At the same time, it has the characteristics of magnetic separation, and the addition of activated carbon with high specific surface area further improves the adsorption efficiency and magnetic separation performance of the active components of the adsorption material, thereby improving the adsorption selectivity of the adsorption material for organic phosphine in water and realizing its efficient removal. , significantly improved the adsorption capacity and removal rate of organic phosphine in water, and due to the magnetic separation characteristics, the adsorption material is easy to separate from water after adsorbing organic phosphine, which is beneficial to subsequent treatment. It has a wide application prospect in the field of organic phosphine in water treated by adsorption method.
本发明提供一种用于去除水中有机膦的钇-锆-对苯二甲酸基复合磁性吸附材料的制备方法，该制备方法包括以下步骤：The invention provides a method for preparing a yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material for removing organic phosphine in water. The preparation method comprises the following steps:
S1、将硝酸钇、氯化锆和对苯二甲酸加入DMF溶剂中，形成混合溶液，然后于120℃下反应24h，得到钇-锆-对苯二甲酸基复合材料；S1, adding yttrium nitrate, zirconium chloride and terephthalic acid into a DMF solvent to form a mixed solution, and then reacting at 120° C. for 24 hours to obtain a yttrium-zirconium-terephthalic acid-based composite material;
S2、将一定量的粉末活性炭分散于去离子水中，得到活性炭分散液；S2, a certain amount of powdered activated carbon is dispersed in deionized water to obtain an activated carbon dispersion;
S3、于步骤S2中得到的活性炭分散液中加入铁前驱物和钇-锆-对苯二甲酸基复合材料，得到反应溶液，调节反应溶液的pH值后，加热下搅拌反应3h；S3. Add iron precursor and yttrium-zirconium-terephthalic acid-based composite material to the activated carbon dispersion obtained in step S2 to obtain a reaction solution. After adjusting the pH value of the reaction solution, stir and react for 3 hours under heating;
S4、待反应结束后离心并洗涤至中性，然后经烘干，得到钇-锆-对苯二甲酸基复合磁性吸附材料。S4. After the reaction is completed, centrifuge and wash until neutral, and then dry to obtain a yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material.
具体的，由于钇和锆均具有较大的配位数，使其对于含氧阴离子具有良好的亲和能力和吸附选择性，步骤S1中采用硝酸钇、氯化锆和对苯二甲酸在DMF溶剂中发生溶剂热反应，在120℃下反应生成的化合物会发生结晶，从而得到钇-锆-对苯二甲酸基复合材料，并以其作为吸附材料的主要活性成分。Specifically, since both yttrium and zirconium have relatively large coordination numbers, they have good affinity and adsorption selectivity for oxyanions. In step S1, yttrium nitrate, zirconium chloride and terephthalic acid are used in DMF Solvothermal reaction occurs in the solvent, and the compound formed by the reaction at 120°C will crystallize, thereby obtaining the yttrium-zirconium-terephthalic acid-based composite material, which is used as the main active component of the adsorption material.
作为示例，步骤S1中硝酸钇、氯化锆和对苯二甲酸在混合溶液中的浓度一致，且均为0.04mol/L。As an example, the concentrations of yttrium nitrate, zirconium chloride and terephthalic acid in the mixed solution in step S1 are consistent and all are 0.04mol/L.
作为示例，步骤S2中粉末活性炭的比表面积为1000～1500m2/g，粉末活性炭的粒径大小为150～300目。As an example, the specific surface area of the powdered activated carbon in step S2 is 1000-1500 m 2 /g, and the particle size of the powdered activated carbon is 150-300 mesh.
具体的，步骤S2中粉末活性炭的比表面积可包括1000m2/g、1100m2/g、1200m2/g、1300m2/g、1400m2/g、1500m2/g等任何范围内的数值，具体可根据实际进行调节；粉末活性炭的粒径大小可包括150目、180目、200目、250目、280目、300目等任何范围内的数值，具体可根据实际进行调节；在本发明具体实施例中，粉末活性炭的多孔结构和较大比表面积的优点，有效分散钇-锆-对苯二甲酸基复合材料和四氧化三铁粒子，提高吸附材料活性成分的吸附效率和磁分离性能。Specifically, the specific surface area of powdered activated carbon in step S2 may include values within any range such as 1000m 2 /g, 1100m 2 /g, 1200m 2 /g, 1300m 2 /g, 1400m 2 /g, 1500m 2 /g, etc., specifically It can be adjusted according to the actual situation; the particle size of the powdered activated carbon can include values in any range such as 150 mesh, 180 mesh, 200 mesh, 250 mesh, 280 mesh, 300 mesh, etc., which can be adjusted according to the actual situation; in the specific implementation of the present invention In the example, the advantages of the porous structure and large specific surface area of powdered activated carbon can effectively disperse the yttrium-zirconium-terephthalic acid-based composite material and ferric oxide particles, and improve the adsorption efficiency and magnetic separation performance of the active components of the adsorption material.
另外，在本发明具体实施例中可直接采用商用的粉末活性炭，也可以采用商用粒状活性炭，但需要对商用粒状活性炭进行处理，具体为：采用球磨机将商用粒状活性炭进行研磨，制成粉末状，再对其超声分散进行清洗，离心烘干后备用，但必须保证最终所制备的粉末活性炭的比表面积为1000～1500m2/g，粒径大小为150～300目。In addition, in the specific embodiment of the present invention, commercial powdered activated carbon can be directly used, and commercial granular activated carbon can also be used, but the commercial granular activated carbon needs to be processed, specifically: use a ball mill to grind the commercial granular activated carbon into powder, Then it is cleaned by ultrasonic dispersion, centrifuged and dried for later use, but it must be ensured that the specific surface area of the finally prepared powdered activated carbon is 1000-1500m 2 /g, and the particle size is 150-300 mesh.
作为示例，步骤S2中得到的活性炭分散液的质量浓度为1～4g/L。As an example, the mass concentration of the activated carbon dispersion obtained in step S2 is 1-4 g/L.
具体的，活性炭分散液的质量浓度包括1g/L、2g/L、3g/L、4g/L等任何范围内的数值，具体可根据实际进行调节。Specifically, the mass concentration of the activated carbon dispersion includes values within any range such as 1g/L, 2g/L, 3g/L, 4g/L, etc., which can be adjusted according to actual conditions.
作为示例，步骤S3中所述铁前驱物为硫酸亚铁和三氯化铁的混合物，其中，硫酸亚铁与三氯化铁的摩尔比为1：2。As an example, the iron precursor in step S3 is a mixture of ferrous sulfate and ferric chloride, wherein the molar ratio of ferrous sulfate to ferric chloride is 1:2.
具体的，硫酸亚铁和三氯化铁在步骤S3中经加热反应，会原位生成四氧化三铁，通过四氧化三铁对钇-锆-对苯二甲酸基复合材料进行修饰，使其具有磁性，得到同时具有吸附性能和磁性的钇-锆-对苯二甲酸基复合磁性吸附材料，当其用于水中对有机膦进行吸附时，便于从水中分离并进行后续处理；其中，在本发明具体实施例中，所采用的硫酸亚铁和三氯化铁均为粉末状。Specifically, ferrous sulfate and ferric chloride are heated and reacted in step S3 to generate ferric oxide in situ, and the yttrium-zirconium-terephthalic acid-based composite material is modified by ferric oxide to make it With magnetism, a yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material with both adsorption properties and magnetism is obtained. When it is used to adsorb organic phosphine in water, it is easy to separate from water and carry out subsequent treatment; among them, in this In the specific embodiment of the invention, the ferrous sulfate and ferric chloride used are all powdery.
作为示例，步骤S3中活性炭分散液中的粉末活性炭与铁前驱物的质量比为0.06～0.25。As an example, the mass ratio of the powdered activated carbon to the iron precursor in the activated carbon dispersion in step S3 is 0.06˜0.25.
具体的，步骤S3中活性炭分散液中的粉末活性炭与铁前驱物的质量比可包括0.06、0.1、0.15、0.2、0.25等任何范围内的数值，具体根据实际进行调节。Specifically, the mass ratio of the powdered activated carbon in the activated carbon dispersion to the iron precursor in step S3 may include values in any range such as 0.06, 0.1, 0.15, 0.2, 0.25, etc., and be adjusted according to actual conditions.
作为示例，步骤S3中加入的铁前驱物中的铁元素与钇-锆-对苯二甲酸的摩尔比为(1～4)：1。As an example, the molar ratio of iron element to yttrium-zirconium-terephthalic acid in the iron precursor added in step S3 is (1˜4):1.
具体的，步骤S3中加入的铁前驱物中的铁与钇-锆-对苯二甲酸的摩尔比可包括1：1、2：1、3：1、4：1等任何范围内的数值，具体可根据实际进行调节。Specifically, the molar ratio of iron in the iron precursor added in step S3 to yttrium-zirconium-terephthalic acid may include values within any range of 1:1, 2:1, 3:1, 4:1, etc., Specifically, it can be adjusted according to the actual situation.
作为示例，步骤S3中调节反应溶液的pH值，具体包括：采用2mol/L的氢氧化钠溶液将所述反应溶液的pH值调节至11。As an example, adjusting the pH value of the reaction solution in step S3 specifically includes: adjusting the pH value of the reaction solution to 11 with 2 mol/L sodium hydroxide solution.
作为示例，步骤S3中加热的温度为70～80℃。As an example, the heating temperature in step S3 is 70-80°C.
具体的，步骤S3中加热的温度可包括70℃、72℃、74℃、76℃、78℃、80℃等任何范围内的数值，具体可根据实际进行调节。Specifically, the heating temperature in step S3 may include values within any range such as 70° C., 72° C., 74° C., 76° C., 78° C., 80° C., and may be adjusted according to actual conditions.
作为示例，步骤S4中烘干的温度为60～65℃。As an example, the drying temperature in step S4 is 60-65°C.
具体的，步骤S4中烘干的温度可包括60℃、61℃、62℃、63℃、64℃、65℃等任何范围内的数值，具体可根据实际进行调节。Specifically, the drying temperature in step S4 may include values within any range such as 60° C., 61° C., 62° C., 63° C., 64° C., 65° C., and may be adjusted according to actual conditions.
本发明还提供一种用于去除水中有机膦的钇-锆-对苯二甲酸基复合磁性吸附材料，该磁性吸附材料是采用上述制备方法制备而成的。The present invention also provides a yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, which is prepared by the above preparation method.
为了更好的理解本发明中钇-锆-对苯二甲酸基复合磁性吸附材料及其制备方法，本发明还提供一种钇-锆-对苯二甲酸基复合磁性吸附材料的应用，将其应用于吸附去除水中的有机膦。In order to better understand the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material and its preparation method in the present invention, the present invention also provides an application of a yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material, which Applied to adsorption and removal of organic phosphine in water.
下面参考具体实施例对本发明中用于去除水中有机膦的钇-锆-对苯二甲酸基复合磁性吸附材料、制备方法及其应用进行描述，需要说明的是，这些实施例仅仅是描述性的，而不以任何方式限制本发明。The yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material for removing organic phosphine in water, the preparation method and its application in the present invention are described below with reference to specific examples. It should be noted that these examples are only descriptive , without limiting the invention in any way.
其中，实施例1～实施例4中所用的粉末活性炭均为商用粒状活性炭经处理后得到的，采用球磨机对商用粒状活性炭进行研磨，再对其超声分散进行清洗，离心烘干后，过200目筛，得到200目的粉末活性炭，且比表面积为1000～1500m2/g。Among them, the powdered activated carbon used in Examples 1 to 4 is obtained after the treatment of commercial granular activated carbon. The commercial granular activated carbon is ground by a ball mill, and then cleaned by ultrasonic dispersion. After centrifugal drying, pass through 200 mesh Sieve to obtain 200-mesh powdered activated carbon with a specific surface area of 1000-1500 m 2 /g.
实施例1Example 1
本实施例提供一种用于去除水中有机膦的钇-锆-对苯二甲酸基复合磁性吸附材料及其制备方法，其制备方法包括以下步骤：This embodiment provides a yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material for removing organic phosphine in water and a preparation method thereof. The preparation method includes the following steps:
S1、将硝酸钇、氯化锆和对苯二甲酸加入DMF溶剂中，使各原料的浓度均为0.04mol/L，然后于120℃下反应24h，得到钇-锆-对苯二甲酸基复合材料；S1. Add yttrium nitrate, zirconium chloride and terephthalic acid into the DMF solvent so that the concentration of each raw material is 0.04mol/L, and then react at 120°C for 24 hours to obtain the yttrium-zirconium-terephthalic acid-based composite Material;
S2、将粉末活性炭分散于去离子水中，得到质量浓度为1g/L的活性炭分散液；S2. Dispersing the powdered activated carbon in deionized water to obtain an activated carbon dispersion with a mass concentration of 1 g/L;
S3、于1L质量浓度为1g/L的活性炭分散液中加入5.56g硫酸亚铁、10.81g三氯化铁和钇-锆-对苯二甲酸基复合材料(其中，铁元素与钇-锆-对苯二甲酸基复合材料的摩尔比为4：1)，得到反应溶液，然后使用2mol/L的氢氧化钠溶液调节反应溶液的pH值为11后，加热至80℃下搅拌反应3h；S3. Add 5.56g ferrous sulfate, 10.81g ferric chloride and yttrium-zirconium-terephthalic acid-based composite material (wherein, iron element and yttrium-zirconium- The molar ratio of the terephthalic acid-based composite material is 4:1) to obtain a reaction solution, and then use 2mol/L sodium hydroxide solution to adjust the pH value of the reaction solution to 11, then heat to 80°C and stir for 3 hours;
S4、待反应结束后离心并洗涤至中性，然后在60℃下烘干，得到钇-锆-对苯二甲酸基复合磁性吸附材料。S4. Centrifuge and wash until neutral after the reaction, and then dry at 60° C. to obtain a yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material.
本发明还提供一种钇-锆-对苯二甲酸基复合磁性吸附材料的应用，将本实施例中所制备的钇-锆-对苯二甲酸基复合磁性吸附材料加入含有羟基乙叉二膦酸(HEDP)的水中，其中，钇-锆-对苯二甲酸基复合磁性吸附材料在水中的质量浓度为0.4g/L，水中羟基乙叉二膦酸的浓度为18mg/L。The present invention also provides an application of a yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material. The yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material prepared in this example is added acid (HEDP) water, wherein the mass concentration of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material in the water is 0.4g/L, and the concentration of hydroxyethylidene diphosphonic acid in the water is 18mg/L.
在温度为25℃的条件下，本实施例中所制备的钇-锆-对苯二甲酸基复合磁性吸附材料对HEDP的吸附量为100.9mg/g，去除率为99.3％，即本实施例中的吸附材料具有良好的HEDP吸附性能。Under the condition of a temperature of 25°C, the adsorption amount of HEDP by the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material prepared in this example is 100.9 mg/g, and the removal rate is 99.3%, that is, this example The adsorbent material in has good HEDP adsorption performance.
实施例2Example 2
本实施例提供一种用于去除水中有机膦的钇-锆-对苯二甲酸基复合磁性吸附材料及其制备方法，其制备方法同实施例1中的不同在于：步骤S2中活性炭分散液的质量浓度为2g/L；步骤S3中是于1L质量浓度为2g/L的活性炭分散液中加入5.56g硫酸亚铁、10.81g三氯化铁和钇-锆-对苯二甲酸基复合材料(其中，铁元素与钇-锆-对苯二甲酸基复合材料的摩尔比为3：1)，得到反应溶液，然后使用2mol/L的氢氧化钠溶液调节反应溶液的pH值为11后，加热至80℃下搅拌反应3h；其他步骤和方法同实施例1中的相同，在此不再赘述。This embodiment provides a kind of yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material and its preparation method for removing organic phosphine in water. Mass concentration is 2g/L; Be to add 5.56g ferrous sulfate, 10.81g iron trichloride and yttrium-zirconium-terephthalic acid-based composite material ( Wherein, the molar ratio of the iron element to the yttrium-zirconium-terephthalic acid-based composite material is 3:1) to obtain the reaction solution, and then use 2mol/L sodium hydroxide solution to adjust the pH value of the reaction solution to 11, then heat Stir and react at 80° C. for 3 h; other steps and methods are the same as those in Example 1, and will not be repeated here.
本发明还提供一种钇-锆-对苯二甲酸基复合磁性吸附材料的应用，将本实施例中所制备的钇-锆-对苯二甲酸基复合磁性吸附材料加入含有羟基乙叉二膦酸(HEDP)的水中，其中，钇-锆-对苯二甲酸基复合磁性吸附材料在水中的质量浓度为0.4g/L，水中羟基乙叉二膦酸的浓度为18mg/L。The present invention also provides an application of a yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material. The yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material prepared in this example is added acid (HEDP) water, wherein the mass concentration of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material in the water is 0.4g/L, and the concentration of hydroxyethylidene diphosphonic acid in the water is 18mg/L.
在温度为25℃的条件下，本实施例中所制备的钇-锆-对苯二甲酸基复合磁性吸附材料对HEDP的吸附量为105.1mg/g，去除率为99.6％，即本实施例中的吸附材料具有良好的HEDP吸附性能。Under the condition of a temperature of 25°C, the adsorption amount of HEDP by the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material prepared in this example is 105.1 mg/g, and the removal rate is 99.6%, that is, this example The adsorbent material in has good HEDP adsorption performance.
实施例3Example 3
本实施例提供一种用于去除水中有机膦的钇-锆-对苯二甲酸基复合磁性吸附材料及其制备方法，其制备方法同实施例1中的不同在于：步骤S2中活性炭分散液的质量浓度为3g/L；步骤S3中是于1L质量浓度为3g/L的活性炭分散液中加入5.56g硫酸亚铁、10.81g三氯化铁和钇-锆-对苯二甲酸基复合材料(其中，铁元素与钇-锆-对苯二甲酸基复合材料的摩尔比为2：1)，得到反应溶液，然后使用2mol/L的氢氧化钠溶液调节反应溶液的pH值为11后，加热至80℃下搅拌反应3h；其他步骤和方法同实施例1中的相同，在此不再赘述。This embodiment provides a kind of yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material and its preparation method for removing organic phosphine in water. Mass concentration is 3g/L; Be to add 5.56g ferrous sulfate, 10.81g iron trichloride and yttrium-zirconium-terephthalic acid-based composite material ( Wherein, the molar ratio of the iron element to the yttrium-zirconium-terephthalic acid-based composite material is 2:1) to obtain the reaction solution, and then use 2mol/L sodium hydroxide solution to adjust the pH value of the reaction solution to 11, then heat Stir and react at 80° C. for 3 h; other steps and methods are the same as those in Example 1 and will not be repeated here.
本发明还提供一种钇-锆-对苯二甲酸基复合磁性吸附材料的应用，将本实施例中所制备的钇-锆-对苯二甲酸基复合磁性吸附材料加入含有羟基乙叉二膦酸(HEDP)的水中，其中，钇-锆-对苯二甲酸基复合磁性吸附材料在水中的质量浓度为0.4g/L，水中羟基乙叉二膦酸的浓度为18mg/L。The present invention also provides an application of a yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material. The yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material prepared in this example is added acid (HEDP) water, wherein the mass concentration of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material in the water is 0.4g/L, and the concentration of hydroxyethylidene diphosphonic acid in the water is 18mg/L.
在温度为25℃的条件下，本实施例中所制备的钇-锆-对苯二甲酸基复合磁性吸附材料对HEDP的吸附量为109.2mg/g，去除率为99.3％，即本实施例中的吸附材料具有良好的HEDP吸附性能。Under the condition of a temperature of 25°C, the adsorption amount of HEDP by the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material prepared in this example is 109.2mg/g, and the removal rate is 99.3%, that is, this example The adsorbent material in has good HEDP adsorption performance.
实施例4Example 4
本实施例提供一种用于去除水中有机膦的钇-锆-对苯二甲酸基复合磁性吸附材料及其制备方法，其制备方法同实施例1中的不同在于：步骤S2中活性炭分散液的质量浓度为4g/L；步骤S3中是于1L质量浓度为4g/L的活性炭分散液中加入5.56g硫酸亚铁、10.81g三氯化铁和钇-锆-对苯二甲酸基复合材料(其中，铁元素与钇-锆-对苯二甲酸基复合材料的摩尔比为1：1)，得到反应溶液，然后使用2mol/L的氢氧化钠溶液调节反应溶液的pH值为11后，加热至80℃下搅拌反应3h；其他步骤和方法同实施例1中的相同，在此不再赘述。This embodiment provides a kind of yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material and its preparation method for removing organic phosphine in water. Mass concentration is 4g/L; Be to add 5.56g ferrous sulfate, 10.81g iron trichloride and yttrium-zirconium-terephthalic acid-based composite material ( Wherein, the molar ratio of the iron element to the yttrium-zirconium-terephthalic acid-based composite material is 1:1) to obtain the reaction solution, and then use 2mol/L sodium hydroxide solution to adjust the pH value of the reaction solution to 11, then heat Stir and react at 80° C. for 3 h; other steps and methods are the same as those in Example 1 and will not be repeated here.
本发明还提供一种钇-锆-对苯二甲酸基复合磁性吸附材料的应用，将本实施例中所制备的钇-锆-对苯二甲酸基复合磁性吸附材料加入含有2-膦酸丁烷-1,2,4-三羧酸(PBTCA)的水中，其中，钇-锆-对苯二甲酸基复合磁性吸附材料在水中的质量浓度为0.4g/L，水中2-膦酸丁烷-1,2,4-三羧酸(PBTCA)的浓度为18mg/L。The present invention also provides an application of a yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material. The yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material prepared in this example is added Alkane-1,2,4-tricarboxylic acid (PBTCA) in water, wherein the mass concentration of yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material in water is 0.4g/L, 2-phosphonic acid butane in water The concentration of -1,2,4-tricarboxylic acid (PBTCA) was 18mg/L.
在温度为25℃的条件下，本实施例中所制备的钇-锆-对苯二甲酸基复合磁性吸附材料对PBTCA的吸附量为119.4mg/g，去除率为99.5％，即本实施例中的吸附材料具有良好的PBTCA吸附性能。Under the condition of a temperature of 25°C, the adsorption capacity of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material prepared in this example to PBTCA is 119.4 mg/g, and the removal rate is 99.5%, that is, this example The adsorbent material in has good PBTCA adsorption performance.
综上所述，本发明采用硝酸钇、氯化锆和对苯二甲酸制备出钇-锆-对苯二甲酸基复合材料，硫酸亚铁和三氯化铁原位反应形成四氧化三铁，通过四氧化三铁对钇-锆-对苯二甲酸基复合材料进行修饰，使其具有磁性，同时还利用了活性炭的多孔结构和较大比表面积的优点，有效分散钇-锆-对苯二甲酸基复合材料和四氧化三铁粒子，最终制备出钇-锆-对苯二甲酸基复合磁性吸附材料，制备过程简单、易操作，具有良好的重复性；本发明中钇-锆-对苯二甲酸基复合磁性吸附材料是利用了稀土钇-锆-对苯二甲酸基复合材料对有机膦的吸附选择性与四氧化三铁的磁分离的特性，使其应用于水中去除有机膦时具有较高吸附性能的同时兼有磁分离的特性，高比表面积活性炭的加入，进一步提高了吸附材料活性成分的吸附效率和磁分离性能，从而提高了吸附材料对水中有机膦的吸附选择性，实现对其进行高效去除，显著提高了水中有机膦的吸附量和去除率，且由于磁分离特性，使得吸附材料吸附有机膦后易从水中分离，利于后续处理，在吸附法处理水中有机膦领域具有广泛的应用前景。所以，本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。In summary, the present invention adopts yttrium nitrate, zirconium chloride and terephthalic acid to prepare yttrium-zirconium-terephthalic acid-based composite material, ferrous sulfate and ferric chloride react in situ to form ferric oxide, The yttrium-zirconium-terephthalic acid-based composite material is modified by ferroferric oxide to make it magnetic, and the advantages of the porous structure and large specific surface area of activated carbon are also used to effectively disperse the yttrium-zirconium-terephthalic acid Formic acid-based composite materials and iron ferric oxide particles are finally prepared to produce yttrium-zirconium-terephthalic acid-based composite magnetic adsorption materials. The preparation process is simple, easy to operate, and has good repeatability; in the present invention, yttrium-zirconium-terephthalic acid The diformic acid-based composite magnetic adsorption material utilizes the adsorption selectivity of the rare earth yttrium-zirconium-terephthalic acid-based composite material for organic phosphine and the magnetic separation characteristics of ferroferric oxide, making it suitable for removing organic phosphine in water. The high adsorption performance also has the characteristics of magnetic separation. The addition of activated carbon with high specific surface area further improves the adsorption efficiency and magnetic separation performance of the active components of the adsorption material, thereby improving the adsorption selectivity of the adsorption material for organic phosphine in water. Efficient removal of it significantly improves the adsorption capacity and removal rate of organic phosphine in water, and due to the magnetic separation characteristics, the adsorption material is easy to separate from water after adsorbing organic phosphine, which is beneficial to subsequent treatment. Wide application prospects. Therefore, the present invention effectively overcomes various shortcomings in the prior art and has high industrial application value.
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。The above-mentioned embodiments only illustrate the principles and effects of the present invention, but are not intended to limit the present invention. Anyone skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those skilled in the art without departing from the spirit and technical ideas disclosed in the present invention shall still be covered by the claims of the present invention.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080121105A1 (en) * | 2006-11-24 | 2008-05-29 | Basf Aktiengesellschaft | Method for the separation of carbon dioxide using a porous metal-organic framework material |
| CN103495390A (en) * | 2013-08-30 | 2014-01-08 | 蚌埠凤凰滤清器有限责任公司 | Zirconium oxide modified activated carbon adsorbent for removing phosphates and its preparation method |
| WO2016192311A1 (en) * | 2015-06-05 | 2016-12-08 | 中国科学院生态环境研究中心 | Hollow iron-manganese composite material prepared by etching template process and application thereof |
| CN107876053A (en) * | 2017-11-21 | 2018-04-06 | 中国科学院上海硅酸盐研究所湖州先进材料产业创新中心 | A high-strength wastewater treatment catalyst and its preparation method and application |
| WO2018159724A1 (en) * | 2017-02-28 | 2018-09-07 | 東レ株式会社 | Organic-inorganic mixture, use thereof, and method for producing same |
| CN110302758A (en) * | 2019-05-07 | 2019-10-08 | 西南大学 | A bimetallic organic framework material for phosphorus removal, its preparation method and application |
| CN110947365A (en) * | 2019-12-18 | 2020-04-03 | 成都理工大学 | Preparation method and application of Form-Ce-MOFS phosphorus removal material |
| CN113060731A (en) * | 2021-03-18 | 2021-07-02 | 黑龙江工程学院 | Preparation method and application of a ternary metal carbide MOFs material |
| CN113101891A (en) * | 2021-04-16 | 2021-07-13 | 中北大学 | A kind of high nitrogen carbon-based zirconium phosphate broad-spectrum gas adsorbent and its preparation method and application |
| CN114225905A (en) * | 2021-12-07 | 2022-03-25 | 珠海兴业新材料科技有限公司 | Adsorbing material and preparation method and application thereof |
| CN114832785A (en) * | 2022-06-08 | 2022-08-02 | 佛山(华南)新材料研究院 | Novel formaldehyde adsorption composite material and preparation method thereof |
| CN115069218A (en) * | 2021-03-12 | 2022-09-20 | 四川大学 | Preparation method of metal organic framework composite GO/waste spinning cellulose aerogel |
| CN115254031A (en) * | 2022-01-07 | 2022-11-01 | 南开大学 | Preparation method and application of a hollow structure microporous network adsorption material |
-
2022
- 2022-11-08 CN CN202211393412.7A patent/CN115722202B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080121105A1 (en) * | 2006-11-24 | 2008-05-29 | Basf Aktiengesellschaft | Method for the separation of carbon dioxide using a porous metal-organic framework material |
| CN103495390A (en) * | 2013-08-30 | 2014-01-08 | 蚌埠凤凰滤清器有限责任公司 | Zirconium oxide modified activated carbon adsorbent for removing phosphates and its preparation method |
| WO2016192311A1 (en) * | 2015-06-05 | 2016-12-08 | 中国科学院生态环境研究中心 | Hollow iron-manganese composite material prepared by etching template process and application thereof |
| WO2018159724A1 (en) * | 2017-02-28 | 2018-09-07 | 東レ株式会社 | Organic-inorganic mixture, use thereof, and method for producing same |
| CN107876053A (en) * | 2017-11-21 | 2018-04-06 | 中国科学院上海硅酸盐研究所湖州先进材料产业创新中心 | A high-strength wastewater treatment catalyst and its preparation method and application |
| CN110302758A (en) * | 2019-05-07 | 2019-10-08 | 西南大学 | A bimetallic organic framework material for phosphorus removal, its preparation method and application |
| CN110947365A (en) * | 2019-12-18 | 2020-04-03 | 成都理工大学 | Preparation method and application of Form-Ce-MOFS phosphorus removal material |
| CN115069218A (en) * | 2021-03-12 | 2022-09-20 | 四川大学 | Preparation method of metal organic framework composite GO/waste spinning cellulose aerogel |
| CN113060731A (en) * | 2021-03-18 | 2021-07-02 | 黑龙江工程学院 | Preparation method and application of a ternary metal carbide MOFs material |
| CN113101891A (en) * | 2021-04-16 | 2021-07-13 | 中北大学 | A kind of high nitrogen carbon-based zirconium phosphate broad-spectrum gas adsorbent and its preparation method and application |
| CN114225905A (en) * | 2021-12-07 | 2022-03-25 | 珠海兴业新材料科技有限公司 | Adsorbing material and preparation method and application thereof |
| CN115254031A (en) * | 2022-01-07 | 2022-11-01 | 南开大学 | Preparation method and application of a hollow structure microporous network adsorption material |
| CN114832785A (en) * | 2022-06-08 | 2022-08-02 | 佛山(华南)新材料研究院 | Novel formaldehyde adsorption composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| RUBINA ALTAF等: "Modified magnetite adsorbent (Zr-La@Fe3O4) for nitrilotrismethylenephosphonate (NTMP) removal and recovery from wastewater", 《JOURNAL OF CLEANER PRODUCTION 》, vol. 278, pages 123960 * |
| TAO LIU等: "Magnetic zirconium-based metal–organic frameworks for selective phosphate adsorption from water", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》, vol. 552, pages 134 - 141 * |
| 孙清燕: "柔性羧酸类配体构筑的稀土配合物及其识别、吸附性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 03, pages 014 - 353 * |
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