CN104743686A - 一种新型可再生鱼缸杀菌放氧包 - Google Patents
一种新型可再生鱼缸杀菌放氧包 Download PDFInfo
- Publication number
- CN104743686A CN104743686A CN201510160355.1A CN201510160355A CN104743686A CN 104743686 A CN104743686 A CN 104743686A CN 201510160355 A CN201510160355 A CN 201510160355A CN 104743686 A CN104743686 A CN 104743686A
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- Prior art keywords
- oxygen
- sterilization
- oxygen bag
- fish
- agent
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Abstract
本发明采用高量子产率的磷酸银纳米粉体材料作为主要原料,设计出一种新型的可再生的鱼缸杀菌放氧包。在可见光照射下,能够产生纳米银和氧气,它不仅能够借助鱼儿的游动,使水与杀菌成分接触实现对水质的杀菌,而且还能够放出氧气。光解产生的纳米银被束缚在半透膜中,不会“流失”到鱼缸中。磷酸根有优异的软化水质、分散污垢、缓冲碱剂及抗结块性能等特点,会和鱼儿产生的粪便中的胺类物质发生作用,生成磷酸盐,又为鱼缸中的水草提供了养分。使用过一段时间后,可以将杀菌放氧包取出,放入双氧水中再生,重新获得杀菌放氧功能。
Description
技术领域
本发明属于应用无机化学领域,具体涉及一种新型可再生鱼缸杀菌放氧包及其制备方法。
背景技术
随着人民生活水平的不断提高,养殖鱼类的家庭越来越多,对鱼缸用杀菌剂和放氧剂的需求量不断增加,要求也不断提高。因此,很多有趣的技术被研发出来。
在放氧剂研究方面,黄泽平在专利《水产品养殖用供氧净化剂》(申请号:CN201110253976.6)中提供一种化学供氧净化剂,它的配方为(重量比):供氧剂10-70%;固化剂0-30%;P值调整剂10-15%;脱腆剂2-8%;稳定剂0-2%;催化剂0-10%,本供氧净水剂溶于水呈中性,既能有效供养,又不含有害物质,并且使用方便;邵东宏等在《一种可控供氧的活鱼箱》(申请号:CN201120524395.7)提到一种渔业用具,具体为一种可控供氧的活鱼箱。本实用新型包括箱体(1)和箱体(1)内分开储放的氧气发生剂(10)和水(11),其主要通过相对隔离的储鱼室和供氧室分别完成对活鱼的储存和供氧,储存时还可以通过充氧口(6)对储鱼室进行充氧,携带和运输时,通过控制闸板(4)来使得供氧室内的氧气发生剂(10)加入水(11)中产生氧气,经输氧管(5)为活鱼输氧,保证其不会因缺氧死亡,并且可以根据不同的鱼类,调节控制每次的输氧量;牛化欣等在《一种便携式水生生物活体运输箱》(申请号:CN201320263507.7)中提到一种便携式水生生物活体运输箱,它由提手和箱体组成,箱体由外保温箱体和内保温箱体组成,提手与外保温箱体相连接,外保温箱体上端面是一自由开合的外扣盖,合上外扣盖,外保温箱体处于密封状态;内保温箱体的上端面具有一内保温密封盖,能使内保温箱体处于密封状态,内保温箱体与外保温箱体具有同一底面,内保温箱体与外保温箱体四周壁及上端面之间有空隙,空隙可根据运输生物需要放置制冷剂和供氧瓶,内保温箱一侧壁上具有一进气孔,连接供氧瓶的供氧管通过进气孔通入内保温箱体内,对运输水生生物进行供氧;宋国强在专利《活鱼贝类贮运用氧气发生剂》(申请号:CN200710060280.5)中提到一种专用于活鱼、活甲壳类及贝等贮运的氧气发生剂。活鱼贝类贮运用氧气发生剂的主要成份由过碳酸钠、酒石酸、活性炭、硅砂组成;郑冀澄在《供氧体及其制造方法》(申请号:CN03102863.2)中涉及一种供氧体及其制造方法的发明创造。它是将过氧化物、粘合剂按一定比例混合,再放入模具中成型,脱模后将成型的混和体放入水中浸泡,使其内部含有水分,或在混合的同时,直接加入已吸收水分的高吸水树脂,然后在所述的混和体的外表面均匀喷涂一层树脂或漆作为透气隔离层,待所述的透气隔离层干固后即可使用;金利通等在《鱼类供氧装置》(申请号:CN96230755.6)中涉及一种鱼类供氧装置,其容器的下部装有配重块,容器内配重块的上面是一盛装制氧剂、催化剂和水的制氧室,在制氧室的上口内套装有过滤网罩,在制氧室的上口端面套装有带排氧孔的容器盖子。本实用新型产氧缓释可控,流量均衡,放氧持续时间长,制氧量大,可为鱼类在长途运输及市场销售中供氧所用,携带、使用方便;范晓等在《鱼虾保活放氧器》(申请号:CN93232385.5)中涉及一种鱼虾保活放氧器,属鲜活水产品储运装置,用于活体鱼虾等蓄养和运输中。其特征是:该放氧器由砂芯放氧嘴、软胶管、封口盖、其内装释氧剂和水的氧气发生容器及内装泥沙的球面形加重室构成;卜志洁等在《过氧化氢碳酸酰胺用于鱼虾增氧》(申请号:CN89101077.7)中提到一种鱼虾人工养殖的化学增氧剂。本发明采用过氧化氢碳酸酰胺作为鱼虾养殖增氧剂;张南伟在《鱼虾颗粒增氧剂及其制备方法》(申请号:CN200410041479.X)中提到一种鱼虾颗粒增氧剂,由化学增氧剂与粘合剂组成,所述化学增氧剂与粘合剂的重量百分比为85~95∶15~5。鱼虾颗粒增氧剂的制备方法,将按照前述重量百分比的化学增氧剂与粘合剂混合均匀后,将混合物放入压片机内,由压片机的压片模具将混合物压成颗粒状物料再干燥而成;周永康在《海水养殖增氧剂》(申请号:CN02134516.3)中提到一种海水养殖增氧剂,其组成成份是碳酸钠、碳酸氢钠和乙二胺四乙酸二钠盐,按重量百分比为:碳酸钠25~50%、碳酸氢钠50~70%和乙二胺四乙酸二钠盐0~10%。上述海水养殖增氧剂的使用方法为:每30M3海水虾池用量50~150g;赵晟等在《氧气发生剂包装袋》(申请号:CN201010608213.4)中公开了氧气发生剂包装袋,包括能放置制氧剂的容器,其中:容器与外界不连通;容器上连接有能通过按压使容器与外界连通的注水组件。采用上述结构,通过人为破坏注水组件实现将容器外界的水注入容器内,容器内的制氧剂与水反应产生氧气,以进行增氧,还能防止较大块状的制氧剂颗粒进入水体引起鱼类误食。
在杀菌剂研究方面,D·J·蒂希等在专利《水溶性消毒剂和杀菌剂》(申请号:200680013824.6)中涉及了消毒剂或杀菌剂组合物。在一个实施方案中,水溶性消毒剂或杀菌剂组合物可能包含水溶性载体,包括水、重量百分比从0.001%至50%的过酸、和重量百分比从0.001%至25%的过氧化物。另外,还可能存在基于水溶性载体含量的以重量计从0.001PPM至50,000PPM的过渡金属。当过渡金属或合金仅以离子金属或盐的形式存在时,组合物可以基本不含醛。另外的,过渡金属可以是胶态过渡金属的形式并且可包含或不包含醛;温震烨在《一种新型鱼种消毒剂》(申请号:CN201410131219.5)中公开了一种新型鱼种消毒剂。以重量份计,本发明由以下组分组成:氯化钾:2~4,硝酸钾:1~3,硫酸铜:2~4,氯化钠:1~3,氢氧化钠:0.3~0.6,草酸钠:3~5,过硫酸铵:1~3,水:300~400;于良民等在《烷氧基丙基异噻唑啉酮作为杀菌剂的应用》(申请号:CN200410035990.9)中以烷氧基丙基异噻唑啉酮用作杀菌剂。所述的烷氧基丙基异噻唑啉酮的分子式为C6H6Cl2NO2SR,式中R为CH3、CH2CH3、CH(CH3)2、CH2CH2CH2CH3、CH2CH2OCH3或CH2CH2OC6H5。本发明的烷氧基丙基异噻唑啉酮作为杀菌剂具有高效、广谱、低毒、低残留等优点;李安民等在《杀菌剂酯基季铵盐复合碘的制备方法》(申请号:CN200710100402.9)中涉及一种杀菌剂酯基季铵盐复合碘的制备方法,先由三乙醇胺、脂肪酸、硫酸二甲酯等制备酯基季铵盐,再与碘复合制成酯基季铵盐复合碘杀菌剂原药液。经稀释后可适用于蓄舍、禽舍、鱼池和其它需要杀菌、消毒的场所;赵峡等在《一种低分子壳聚糖季铵盐络合碘消毒液的制备方法》(申请号:CN03112578.6)中涉及一种低分子壳聚糖季铵盐络合碘消毒液的制备方法,其特征是将低分子壳聚糖季铵盐或低分子壳聚糖溶液在搅拌条件下,与双烷基双季铵盐、双烷基季铵盐、单烷基季铵盐中一种、两种或全部混合搅拌,将此混合液加热后,加入碘或碘和碘酸盐,保温反应,冷却至室温;陈玉成等在《水质净化器》(申请号:CN200410100800.7)中提到一种水质净化器,利用臭氧气体为消毒剂,通过臭氧气体向水中鼓泡,水中的杂质和有机大分子物质在循环过程中得到过滤和收集;丁蕴峰在《一种缓释性固体ClO2消毒剂及其制备方法和应用》(申请号:CN201310254124.8)中涉及一种杀菌消毒剂,特别涉及一种缓释性固体ClO2消毒剂及其制备方法和应用,制备方法为:将食用明胶、ClO2溶液、β-环糊精及蒸馏水搅拌均匀,加热至100-120℃,保持5-30秒,然后将样品冷藏20-28小时即可。所述食用明胶、ClO2、β-环糊精及蒸馏水的用量比为1g:0.1-5mg:0.01-0.8g:0.1-2mL。所述缓释性固体ClO2消毒剂采用β-环糊精和鱼胶二者混合制成固体;潘运平等在《一种水产专用挂袋胶体碘消毒药品》(申请号:CN201210210636.X)中涉及一种水产用消毒剂,用于鱼、虾、蟹、蛙、黄鳝、泥鳅、龟、鳖等水产动物养殖的专用挂袋消毒剂。该消毒剂含有下述成分:稀碱液1-5g;干酪素2-16g;凝胶剂6-20g;聚乙烯吡咯烷酮碘15-30g;柔软剂1-15g;缓释剂1-20g;羧甲基纤维素钠2-12g,余为助剂;各个组分之和为100g;杨斌等在《纯天然水产养殖专用消毒剂》(申请号:CN201110364144.1)中涉及一种纯天然水产养殖专用消毒剂,其特征在于具有如下配方(组分及其重量百分比%):乙酰壳聚糖10.0-15.0;褐藻多糖1.2-2.0;蜂胶提取物2.0-5.0;迷迭香酸2.0-5.0;复合维生素C衍生物1.0-1.5,海洋生物复合溶菌酶0.5-0.8;去离子水加至100;江苏胜意药业有限公司在《一种鱼血康的制备方法》(申请号:CN201210207559.2)中公开了一种鱼血康的制备方法,该产品属于消毒剂领域,本发明是以戊二醛、苯扎溴铵、药用强化剂、饮用水为原料,通过原材料的检验、溶解、分装等工序来制得到成品;李德彬在《一种用于养殖业中的消毒剂》(申请号:CN201410291548.6)中公开了一种用于养殖业中的消毒剂,包括的组分有:以体积百分比计,质量分数为15-25%的氢氧化钙悬浊液35-45mL、环氧乙烷4-10mL、含有质量分数为38-48%甲醛的水溶液20-35mL、高锰酸钾溶液3-12mL,将所述各组分混合并加热搅拌,再分装、塑封即得到所述消毒剂;张兴山在《一种水质改良杀菌消毒剂》(申请号:CN201310039986.9)中公开了一种水质改良杀菌消毒剂,包括硫酸钙、亚氯酸钠、焦硫酸钠、酒石酸、工业盐(氯化钠)、硫酸钠、次氯酸钙和氨基磺酸,其配比是:硫酸钙15%、亚氯酸钠12%、焦硫酸钠21%、酒石酸1%、工业盐(氯化钠)10%、硫酸钠20%、次氯酸钙20%和氨基磺酸1%;喻果等在《海水软体动物杀菌剂》(申请号:CN201310673546.9)中提供了一种海水软体动物杀菌剂,海水软体动物杀菌剂由去离子水、醇类、胍类和季铵盐类复配而成,去离子水、醇类、胍类和季铵盐类的质量比为40~60:20~40:1~15:1~15。本发明同时提供了海水软体杀菌剂的生产方法;李来好等在《一种用于水产品加工厂的消毒方法》(申请号:CN200410026670.7)中公开了一种用于水产品加工厂的消毒方法,其特征在于:用0.01%~0.03%的复方消毒剂对水产品加工厂中的所需消毒对象进行消毒20秒~10分钟,最后用清水冲洗干净;所述的复方消毒剂由苯扎溴铵和聚氧化乙烯按15~25∶1~1.5的体积比混合,加水稀释而成;李灿在《大鲵养殖池中药消毒剂》(申请号:CN201010127448.1)中公开了一种大鲵养殖池中药消毒剂,属于中药消毒剂。其特征在于是由下列中药材配制而成的散剂、汤剂或水剂:大青叶、板蓝根、鱼腥草、连翘、黄连、贯众;高旭在《一种固态季铵盐消毒除臭组合物及制备方法》(申请号:CN200510089903.2)中供一种固态季铵盐消毒除臭组合物及制备方法,它可以是以粉剂、颗粒剂、片剂、缓释剂和泡腾剂等控制有效成分释放的体系。其组合物主要成分按质量百分比构成如下:乙二胺四乙酸及盐 0.20%-6%多聚磷酸盐 0.2%-10%润滑剂 0.01%-3%无机酸及其盐 0.5%-9%苯甲酸及其盐 0.5%-10%碳酸盐 1%-50%聚合物 1%-12%有机酸 0.1%-35%锌化合物 0.05%-4%硫酸盐 6%-70%缓蚀剂 0.01%-5%季铵盐 0.01%-55%;高旭在《一种新型二氧化氯组合物及制备方法》(申请号:CN200410098674.6)中提供一套制备二氧化氯固态消毒剂的方法,其特征在于,是由氯化异氰尿酸、溴氯海因及其盐、次氯酸盐等组成的泡腾速溶剂作为次氯酸提供剂组分与氯酸盐、亚氯酸盐反应得到稳定态二氧化氯消毒剂的方法在粉剂、颗粒剂和片剂等制备中的应用;王连民等在《二氧化氯消毒剂》(申请号:CN200610015379.9)中提供一种二氧化氯消毒剂本发明的技术方案如下:组份A:亚氯酸钠:180-235份,无水硫酸钠或沸石粉:165-220份;组份B:柠檬酸或硫酸氢钠:300-500份;将A组份中的亚氯酸钠与无水硫酸钠或沸石粉混合,单独组装;组份B单独组装;A、B两种组份分开放置,使用时需取A组份和B组份分别溶于盛有清水的容器中,搅拌使之完全溶解,再在搅拌下将A组份溶液慢慢倒入B组份溶液中,溶液呈黄色,此时即产生了二氧化氯;孙保兴在《甜菜碱络合碘消毒剂》(申请号:CN200710028427.2)中提供一种用于畜禽、鱼虾、蟹养殖的碘消毒剂,各组份的重量百分比如下:甜菜碱10-50%,增效剂双癸基二甲基溴化铵1-20%,碘0.5-1.5%,乙二胺四乙酸0.1-0.8%,助剂磷酸0.5-5%,去离子水1-65%,用胶体磨混合各组分之后的均匀液体流入到反应釜,然后搅拌混合2-5小时左右,成为均相透明的粘稠液体;孙保兴在《复合氧化胺络合碘消毒剂》(申请号:CN200710028424.9)中涉及一种水产业用消毒剂,复合氧化胺络合碘消毒剂含有下述组分,氧化胺10-30%,增效剂双癸基二甲基溴化铵1-20%,碘0.5-1.5%,乙二胺四乙酸0.1-0.8%,助剂磷酸0.5-5%,去离子水1-65%,按重量百分比配制,用胶体磨混合各组分之后的均匀液体流入到反应釜,然后搅拌混合2-5小左右,成为均相透明的粘稠液体。
通过文献查询、对比发现,鱼缸用杀菌剂大多采用化学药物的方式,而供氧方面,更多依赖于通入空气供养或者加入多种化学试剂进行反应。本发明首次提出以磷酸银和半透膜为主要原料制备鱼缸杀菌放氧包,兼具杀菌和放氧的功能,目前国内外尚未发现有类似的研究成果报导。
2010年,日本的叶金花课题组在《Nature Materials》上报道了关于Ag3PO4晶体在可见光下光催化活性的研究,报道指出:Ag3PO4晶体的分解水制氧的效率很高。因此,Ag3PO4作为一种极具潜力的可见光光催化剂受到了很大的关注。 相关的化学反应方程式为: 4Ag3PO4 + 6H2O + 12e- +12h+ → 12Ag + 4H3PO4 + 3O2 ↑
从上式可以看出,体系在放出氧气的同时,产生单质银,具有杀菌效果。反应中还会有少量的磷酸产生,磷酸为中强酸,会和鱼儿产生的粪便中的胺类物质发生作用,生成磷酸盐,又为鱼缸中的水草提供了养分。使用一段时间后,可以取出来,放到含有磷酸盐的双氧水中,即可实现杀菌放氧包的再生。
发明内容
本发明采用高量子产率的磷酸银纳米粉体材料作为主要原料,设计出一种新型的可再生的鱼缸杀菌放氧包;该杀菌放氧包在可见光照射下,能够产生纳米银,对水质具有杀菌作用;与水作用释放出氧气,提高水中的含氧量。
本发明涉及的鱼缸杀菌放氧包的制备工艺分为两步完成:
第一步:采用注射沉淀法制备磷酸银纳米粉体,将获得的产物烘干,备用。磷酸银纳米粉体的具体制备步骤为:使用硝酸银溶液和氨水配制银氨溶液置于烧杯A中,将配制好的磷酸根源溶液放入到烧杯中B,分别向两个烧杯中加入适量的表面活性剂,使用量程为1 μL的微量注射器将烧杯A中的银氨溶液加入到盛有磷酸根源溶液的烧杯B中,在烧杯B中生成磷酸银粉体沉淀,沉淀经离心洗涤后收集,干燥,即得到磷酸银纳米粉体。 第二步:以不同形状的半封闭器皿为模具,将其浸渍于胶棉液中,提拉后置于空气中自然干燥,剥离,获得不同形状的半透膜,然后将第一步制备的磷酸银纳米粉体放入半透膜中,将开口端用细线系紧,即可获得一种新型鱼缸杀菌放氧包。
该杀菌放氧包可以根据需要,选择不同的模具,从而获得不同形状的杀菌放氧包。在使用时,可以根据鱼缸中水量的多少,调整磷酸银粉体的用量。
研究发现,杀菌放氧包中磷酸银纳米粉体较为合适的用量为每升水0.01~0.1g。
本发明同现有技术相比,具有如下优点:本发明提出的鱼缸杀菌放氧包,兼具杀菌和制氧两种功能。在可见光照射下,能够产生纳米银和氧气,它不仅能够借助鱼儿的游动,使水与杀菌成分接触实现对水质的杀菌,而且还能够放出氧气。光解产生的纳米银被束缚在半透膜中,不会“流失”到鱼缸中。磷酸根有优异的软化水质、分散污垢、缓冲碱剂及抗结块性能等特点,会和鱼儿产生的粪便中的胺类物质发生作用,生成磷酸盐,又为鱼缸中的水草提供了养分。使用过一段时间后,可以将杀菌放氧包取出,放入双氧水中再生,重新获得杀菌放氧功能。
综上,本发明具有科学依据,且经过实验验证,因此,具有推广可行性。
具体实施方式
实施例1
第一步:采用注射沉淀法制备磷酸银纳米粉体,将获得的产物烘干,备用。磷酸银纳米粉体的具体制备步骤为:使用硝酸银溶液和氨水配制银氨溶液置于烧杯A中,将配制好的磷酸根源溶液放入到烧杯中B,分别向两个烧杯中加入适量的表面活性剂聚乙二醇600,其用量为银氨溶液质量的0.2%,使用量程为1 μL的微量注射器将烧杯A中的银氨溶液加入到盛有磷酸根源溶液的烧杯B中,在烧杯B中生成磷酸银粉体沉淀,沉淀经离心洗涤后收集,干燥,即得到磷酸银纳米粉体。第二步:以锥形瓶为模具,将其浸渍于胶棉液中,提拉后置于空气中自然干燥,剥离,获得不同形状的半透膜,然后将第一步制备的磷酸银纳米粉体放入半透膜中,将开口端用细线系紧,即可获得一种新型鱼缸杀菌放氧包。
实施例2
第一步:采用注射沉淀法制备磷酸银纳米粉体,将获得的产物烘干,备用。磷酸银纳米粉体的具体制备步骤为:使用硝酸银溶液和氨水配制银氨溶液置于烧杯A中,将配制好的磷酸根源溶液放入到烧杯中B,分别向两个烧杯中加入适量的表面活性剂曲拉通X-100,其用量为银氨溶液质量的0.2%,使用量程为1 μL的微量注射器将烧杯A中的银氨溶液加入到盛有磷酸根源溶液的烧杯B中,在烧杯B中生成磷酸银粉体沉淀,沉淀经离心洗涤后收集,干燥,即得到磷酸银纳米粉体。第二步:以圆底烧瓶为模具,将其浸渍于胶棉液中,提拉后置于空气中自然干燥,剥离,获得不同形状的半透膜,然后将第一步制备的磷酸银纳米粉体放入半透膜中,将开口端用细线系紧,即可获得一种新型鱼缸杀菌放氧包。
实施例3
第一步:采用注射沉淀法制备磷酸银纳米粉体,将获得的产物烘干,备用。磷酸银纳米粉体的具体制备步骤为:使用硝酸银溶液和氨水配制银氨溶液置于烧杯A中,将配制好的磷酸根源溶液放入到烧杯中B,分别向两个烧杯中加入适量的表面活性剂吐温80,其用量为银氨溶液质量的0.2%,使用量程为1 μL的微量注射器将烧杯A中的银氨溶液加入到盛有磷酸根源溶液的烧杯B中,在烧杯B中生成磷酸银粉体沉淀,沉淀经离心洗涤后收集,干燥,即得到磷酸银纳米粉体。第二步:以圆底烧瓶为模具,将其浸渍于胶棉液中,提拉后空气中置于自然干燥,剥离,获得不同形状的半透膜,然后将第一步制备的磷酸银纳米粉体放入半透膜中,将开口端用细线系紧,即可获得一种新型鱼缸杀菌放氧包。
Claims (3)
1.一种新型可再生鱼缸杀菌放氧包,其特征在于本发明涉及的鱼缸杀菌放氧包制备工艺分为两步完成:
第一步:采用注射沉淀法制备磷酸银纳米晶,将获得的产物烘干,备用,其具体步骤为:使用硝酸银溶液和氨水配制银氨溶液后,将配制好的磷酸根源溶液放入到烧杯中,加入适量表面活性剂,使用量程为1 μL的微量注射器将银氨溶液加入到磷酸根源溶液中,生成磷酸银晶体沉淀,沉淀经离心洗涤后收集,干燥,即得到磷酸银纳米粉体;
第二步:以不同形状的半封闭器皿为模具,将其浸渍于胶棉液中,提拉后自然干燥,剥离,获得不同形状的半透膜,然后将第一步制备的磷酸银粉体放入其中,将开口端用细线系紧,即可获得一种新型鱼缸杀菌放氧包。
2.根据权利要求1所述的一种新型可再生鱼缸杀菌放氧包,其特征在于该杀菌放氧包可以根据需要,选择不同的模具,从而获得不同形状的杀菌放氧包。
3.根据权利要求1所述的一种新型可再生鱼缸杀菌放氧包,其特征在于杀菌放氧包中磷酸银纳米粉体较为合适的用量为每升水0.01~0.1g。
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