CN109304225A - 农药残留去除剂的生产制备方法 - Google Patents
农药残留去除剂的生产制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 5
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- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 5
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
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- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims description 2
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- 238000010438 heat treatment Methods 0.000 claims description 2
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- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 235000013772 propylene glycol Nutrition 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 11
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
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- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 3
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
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- 150000001298 alcohols Chemical class 0.000 description 3
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 241000345998 Calamus manan Species 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 238000012271 agricultural production Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical group [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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Abstract
本发明提供了一种农药残留去除剂的生产制备方法。本发明通过预先形成氧化硅溶胶水溶液，并在氧化硅溶胶水溶液中加入含银的氧化钛前驱体溶液，使得氧化钛前驱体的水解过程和氧化钛粒子的生成受限于氧化硅溶胶网络，从而控制了氧化钛粒子的过度生长。本发明制得的纳米二氧化钛粒径小于3纳米，催化活性强，分散稳定。本发明在制备过程中引入氧化铁纳米粒子，与二氧化钛粒子形成了复合体，增强了反应催化活性，并能够将部分反应产物絮凝沉淀，便于除去。
Description
技术领域
本发明属于污染物处理领域，具体涉及一种农药残留去除剂的生产制备方法。
背景技术
在农业现代化过程中，随着大量农药的使用，在保证了农产物高产丰收的同时，有这些农药所引发的水污染、土地污染等诸多环境问题已经日益凸显，在农业生产中，杀虫剂和除草剂等广泛应用，这些农药一般都直接排放到江河中，甚至进入地下水系统，引起严重的环境污染。近几年来，科学家开始研究采用光催化剂分解农药，解决环境污染的问题。
1967年，日本东京大学的本多建一教授和博士班学生藤岛昭发现，用光照射二氧化钛电极可进行水的电解反应。这就是著名的“本多作用的光催化反应”。在科学技术不断发展条件下，二氧化钛技术也不断提高。目前，制备纳米TiO2的方法很多，基本上可归纳为物理法和化学法，物理法主要为机械粉碎法，对粉碎设备要求很高；化学法主要为气相法(CVD)、液相法和固相法，但是现有技术中的制备方法存在以下不足：
一、制备出的二氧化钛粒径偏大，一般在5-100纳米，其比表面积小，表面原子数少，超微粒子的表面效应不显著，一方面吸收的光能愈少，产生的e-和h+对的密度愈小，另一方面吸附的反应物也愈少，被氧化或还原的物质浓度也愈少，因此可见光催化活性会降低。
二、制造成本高，处理效果低、处理速度慢，直接造成处理使用成本增加，经济价值大打折扣。
三、粒径大造成附着力低，现有技术制备出的纳米二氧化钛需添加粘合剂，粘合剂对人体、牲畜会有毒害，所以在应用领域受到限制。
另外，虽然也有不少文献提出使用各类金属掺杂方法来改进TiO2的光催化活性，例如使用铜掺杂、钴掺杂、镍掺杂等，但一方面，这些掺杂手段尽管在实验室的检测中体现了一定的提升，但由于在实际使用环境非常复杂，也容易进一步团聚，中实际产生的提升效应有限，另一方面，这些掺杂元素大多是对人体有害的，在使用过程中可能对水质或土壤造成二次污染。
发明内容
针对现有技术存在的上述问题，本发明提供了一种光催化活性高、制造成本低、吸附效果好、不会带来二次污染的农药残留去除剂的制备方法。
本发明的制备方法包括：
(1)原料准备：
制备含氧化钛前驱体的醇溶液A；
制备含银盐的醇溶液B；
制备含氧化硅溶胶的溶液C；
制备硅烷偶联剂溶液D；
制备含氧化铁前驱体的醇溶液E；
(2)混合与反应
将溶液A和溶液B加入部分溶液C中，搅拌1-12小时，得到混合溶液H1，再将溶液D和混合溶液H1混合，搅拌1-12小时，得到含氧化钛的醇分散溶液H2；
将溶液E加入剩余的部分溶液C中，水热或高温加热反应2-8小时，得到溶液H3
将溶液H2和H3混和，得到溶液H4；
(3)减压蒸馏
将溶液H4减压蒸馏醇，同时慢慢补加水溶剂替换，制得含有0.1-5wt％二氧化钛和0.5-1wt％氧化铁纳米粒子的分散液；
然后在该分散液中加入0.1-0.5wt％的表面活性剂、5-10wt％的有机载体剂，并搅拌，得到产物。
其中，优选地：
所述氧化钛前驱体选自钛酸乙酯、钛酸丁酯、钛酸丙酯；所述银盐选自硝酸银、氯化盐；
所述溶液A和溶液B中的醇分别单独地选择甲醇、乙醇、乙二醇、丙醇、丙二醇、丙三醇，所述溶液A和溶液B中醇相同或不同，特别优选地是，从成本考虑，均使用乙醇；
所述含氧化硅溶胶的溶液C由硅酸乙酯的醇溶液进行酸水解后制成，所述酸选自甲酸、乙酸、乙二酸、盐酸、硝酸，优选使用盐酸，并优选使用浓度为10-50％的盐酸水溶液；
所述硅烷偶联选自乙氧基硅烷、甲氧基硅烷、氨基硅烷，优选为甲氧基硅烷，最优选为二乙烯三胺基丙基三甲氧基硅烷。
所述氧化铁前驱体选自氯化铁、硫酸铁；
所述有机载体选自壳聚糖、甲基纤维素、聚乳酸微球或其组合，所述表面活性剂优选为阳离子表面活性剂。
本发明通过预先形成氧化硅溶胶水溶液，并在氧化硅溶胶水溶液中加入含银的氧化钛前驱体溶液，使得氧化钛前驱体的水解过程和氧化钛粒子的生成受限于氧化硅溶胶网络，从而控制了氧化钛粒子的过度生长，同时在氧化钛粒子生长过程中很快被氧化硅所包覆，也阻止了彼此之间的碰撞长大。进一步，硅烷偶联剂的加入在粒子表面形成接枝层，靠电性相斥作用，使纳米二氧化钛一次粒子不团聚。
本发明制得的纳米二氧化钛粒径小于3纳米，纳米颗粒外部有两层自组装结构，第一层是二氧化硅结晶，第二层是氨基硅烷树枝状接枝。二氧化钛水解时，添加银盐溶液，在水解过程中银离子被乙醇还原为纳米银，与二氧化钛共结晶，促进二氧化钛结晶形貌转变为锐钛矿晶型。在减压蒸馏溶剂替换过程中，醇浓度逐渐降低，水溶液越来越多，这时，促进水解体系逐渐由醇解体系逐渐演变为水解体系，水解更加深入。由于氨基硅烷和二氧化硅的阻隔包覆作用，二氧化钛粒子不能二次团聚，制得的纳米二氧化钛粒径小，分散稳定。同时，本发明中在纳米二氧化钛纳米粒子表面的纳米银粒子具有杀菌作用，有助于农药污染物的去除。
采用本发明技术制备的纳米二氧化钛纳米粒径小于5纳米(3-5纳米)，光催化活性高于粒径5-100纳米的产品。粒子愈小，比表面积愈大，表面原子数增多，超微粒子的表面效应愈显著，一方面吸收的光能愈多，产生的e-和h+对的密度愈大，另一方面吸附的反应物也愈多，被氧化或还原的物质浓度也愈大，因此可见光催化活性显著提高。
本发明在制备过程中引入的氧化铁纳米粒子，其与二氧化钛粒子形成了复合体，氧化铁本粒子本身具有一定的反应催化活性作用，同时，氧化铁在粒子还具有一定的絮凝作用，能够将部分反应产物絮凝沉淀，便于除去。
另外，通过加入表面活性剂和有机载体，增大了其中的有效成分在溶液中的稳定性以及和农药成分的接触几率，提高了处理效率。
总之，本发明的制造成本低于，处理效果高，处理速度快，直接造成处理使用成本大幅降低。而且，未使用其他有害金属元素，不会产生二次毒害和污染，反应产物易于除去。
具体实施方式
实施例1
第一步：将钛酸异丙酯2.35克溶于40克无水乙醇中，制得A溶液。同时，将0.0015克硝酸银溶于1克甘油中，搅拌醇解90分钟，制得B溶液。
第二步：将正硅酸乙酯0.3克，溶于20克无水乙醇中，搅拌醇解80分钟后，加入0.08克10％wt盐酸和5克水，搅拌水解42分钟。制得C溶液。
第三步，将A溶液和B溶液以每秒3-10的滴速度滴加到部分C溶液中，快速搅拌水解。使钛酸异丙酯缓慢水解为二氧化钛，并被正硅酸乙酯水解物单层包覆。滴加结束搅拌12小时，制得混合溶液H1。
第四步，取二乙烯三胺基丙基三甲氧基硅烷0.3克，加入1克水中，搅拌水解后，加入30克无水乙醇，搅拌均匀后，将溶液H1以每秒3-10滴的速度滴加到二乙烯三胺基丙基三甲氧基硅烷水解。滴加结束后，继续搅拌12小时。制得二氧化钛乙醇分散液H2。
第四步，将氯化铁水溶液加入到剩余的部分C溶液中，在200℃水热反应2小时，得到含氧化铁纳米粒子的分散液H3。然后将分散液H2和H3混合得到混合溶液H4
第五步，将溶液H4减压蒸馏乙醇，同时慢慢补加蒸馏水至100克进行溶剂替换，制得含二氧化钛0.5wt％、含氧化铁0.1wt％的溶液，在其中加入0.05wt％的阳离子表面活性剂和5wt％的甲基纤维素，充分搅拌，得到本发明的农药残留去除剂。
实施例2
将实施例1中的2.35克钛酸异丙酯替换为4克钛酸丁酯，其他与实施例1相同，制得二氧化钛浓度为0.8％的水分散液。
实施例3
将实施例2中的0.0015克硝酸银替换为0.002克氯化银，其他与实施例1相同，制得二氧化钛浓度为0.8％的水分散液。
Claims (10)
1.一种农药残留去除剂的制备方法，包括：
(1)原料准备：
制备含氧化钛前驱体的醇溶液A；
制备含银盐的醇溶液B；
制备含氧化硅溶胶的溶液C；
制备硅烷偶联剂溶液D；
制备含氧化铁前驱体的醇溶液E；
(2)混合与反应
将溶液A和溶液B加入部分溶液C中，搅拌1-12小时，得到混合溶液H1，再将溶液D和混合溶液H1混合，搅拌1-12小时，得到含氧化钛的醇分散溶液H2；
将溶液E加入剩余的部分溶液C中，水热或高温加热反应2-8小时，得到溶液H3
将溶液H2和H3混和，得到溶液H4；
(3)减压蒸馏
将溶液H4减压蒸馏醇，同时慢慢补加水溶剂替换，制得含有0.1-5wt％二氧化钛和0.5-1wt％氧化铁纳米粒子的分散液；
然后在该分散液中加入0.1-0.5wt％的表面活性剂、5-10wt％的有机载体剂，并搅拌，得到产物。
2.根据权利要求1所述的农药残留去除剂的制备方法，其特征在于：
所述氧化钛前驱体选自钛酸乙酯、钛酸丁酯、钛酸丙酯或其组合；
所述银盐选自硝酸银、氯化银或其组合；
所述溶液A和溶液B中的醇分别单独地选择甲醇、乙醇、乙二醇、丙醇、丙二醇、丙三醇，所述溶液A和溶液B中醇相同或不同。
3.根据权利要求1所述的农药残留去除剂的制备方法，其特征在于：
所述含氧化硅溶胶的溶液C由硅酸乙酯的醇溶液进行酸水解后制成，所述酸选自甲酸、乙酸、乙二酸、盐酸、硝酸或其组合。
4.根据权利要求1或2所述的农药残留去除剂的制备方法，其特征在于：
所述硅烷偶联选自乙氧基硅烷、甲氧基硅烷、氨基硅烷或其组合，优选为甲氧基硅烷，最优选为二乙烯三胺基丙基三甲氧基硅烷。
5.根据权利要求1-4任一所述的农药残留去除剂的制备方法，其特征在于：
产物中，以氧化钛为基准，含有1-5％wt％的银。
6.根据权利要求1-4任一所述的农药残留去除剂的制备方法，其特征在于：
产物中，以氧化钛为基准，含有1-10％wt％的氧化硅，所述氧化硅为结晶态、无定形态或二者混合物。
7.根据权利要求1-4任一所述的农药残留去除剂的制备方法，其特征在于：
所述氧化铁前驱体选自氯化铁、硫酸铁或其组合；
8.根据权利要求1-4任一所述的农药残留去除剂的制备方法，其特征在于：
所制得的农药残留去除剂中氧化钛纳米粒子的平均直径为3-8纳米，其中60％的粒子的直径小于5纳米。
9.根据权利要求1-4任一所述的农药残留去除剂的制备方法，其特征在于：
所述有机载体选自壳聚糖、甲基纤维素、聚乳酸微球或其组合，所述表面活性剂优选为阳离子表面活性剂。
10.一种农药残留去除剂，其包括权利要求1-9制备得到的产物。
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