CN111375307B - 一种液体除臭剂及其制备方法 - Google Patents
一种液体除臭剂及其制备方法 Download PDFInfo
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- CN111375307B CN111375307B CN202010278052.0A CN202010278052A CN111375307B CN 111375307 B CN111375307 B CN 111375307B CN 202010278052 A CN202010278052 A CN 202010278052A CN 111375307 B CN111375307 B CN 111375307B
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- liquid deodorant
- essential oil
- zinc
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- 239000002781 deodorant agent Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229930182478 glucoside Natural products 0.000 claims abstract description 15
- 150000008131 glucosides Chemical class 0.000 claims abstract description 15
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
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- AFWTZXXDGQBIKW-UHFFFAOYSA-N C14 surfactin Natural products CCCCCCCCCCCC1CC(=O)NC(CCC(O)=O)C(=O)NC(CC(C)C)C(=O)NC(CC(C)C)C(=O)NC(C(C)C)C(=O)NC(CC(O)=O)C(=O)NC(CC(C)C)C(=O)NC(CC(C)C)C(=O)O1 AFWTZXXDGQBIKW-UHFFFAOYSA-N 0.000 claims abstract description 11
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- NJGWOFRZMQRKHT-WGVNQGGSSA-N surfactin C Chemical compound CC(C)CCCCCCCCC[C@@H]1CC(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC(C)C)C(=O)N[C@H](CC(C)C)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(=O)O1 NJGWOFRZMQRKHT-WGVNQGGSSA-N 0.000 claims abstract description 11
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- WMBWREPUVVBILR-WIYYLYMNSA-N (-)-Epigallocatechin-3-o-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=C(O)C=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-WIYYLYMNSA-N 0.000 claims description 21
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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Abstract
本发明公开了一种液体除臭剂及其制备方法。所述的液体除臭剂包含以下质量百分比计的组分：纳米二氧化钛6～9％、EGCG‑ZnO纳米颗粒5～10％、壳聚糖季铵盐6～10％、锌盐3～6％、植物精油1～4％、γ‑己内酯3～5％、枯草菌脂肽钠1～3％、鲸蜡硬脂基葡糖苷3～5％、助剂2～6％，余量为水。本发明的液体除臭剂综合多种除臭技术，除臭效果全面，具有高效、速效的除臭特点，能从源头上扼制臭气的产生，从根本上彻底消除臭气，并且对人体无害，适用于家居、酒店、医院、会场和其它公共场所及其设施的抗菌除异味、臭味的处理，应用范广。
Description
技术领域
本发明涉及除臭领域，尤其涉及液体除臭剂，具体涉及一种液体除臭剂及其制备方法。
背景技术
呈臭物质是一类挥发性极强的物质，其具有多种化学特性，如酸性、碱性、极性和非极性，主要存在于污水处理厂、垃圾场、养殖场等场所。恶臭污染对周边生态环境影响很大，且还会对人的身体健康造成严重危害，导致人们出现嗅觉失调、恶心、头痛、癌变、畸变等症状。随着环保要求越来越高，臭气污染问题受到了人们的广泛关注和高度重视，除臭研究意义重大，且应用前景广阔。
臭气的成分复杂，治理难度较大。目前，国内外消除臭味的一般方法有掩盖法、吸附法、臭氧除臭、金属氧化物或者酶反应除臭等。掩盖法除臭是用一些怡人的芳香剂掩盖臭味，但是当芳香剂挥发后，臭气分子依然存在，不能彻底消除；吸附法除臭是用一些类似活性炭、硅藻土的多孔物质吸附住臭气分子，该方法的缺点是吸附具有选择性(如活性炭对氨气、三甲胺等胺类物质的消臭作用就极不理想)。而且活泼炭需要定期更换或者再生，成本较高；利用臭气或酶反应除臭的可行性不高。因此迫切需要寻求一种从多个方面消除臭味并且同时有效地抑制微生物繁殖，防止恶臭分子的再生成，从根本上解决臭味来源的液体除臭剂。
发明内容
本发明的目的是提供一种液体除臭剂及其制备方法。所述的液体除臭剂除臭效果全面，对人体无害，具有高效、速效的除臭特点，能防止恶臭分子的再生成，从根本上解决臭味来源。
本发明是通过以下技术方案予以实现的：
一种液体除臭剂，包含以下质量百分比计的组分：纳米二氧化钛6～9％、EGCG-ZnO纳米颗粒5～10％、壳聚糖季铵盐6～10％、锌盐3～6％、植物精油1～4％、γ-己内酯3～5％、枯草菌脂肽钠1～3％、鲸蜡硬脂基葡糖苷3～5％、助剂2～6％，余量为水。
优选，所述的液体除臭剂，包含以下质量百分比计的组分：纳米二氧化钛8％、EGCG-ZnO纳米颗粒8％、壳聚糖季铵盐9％、锌盐4％、植物精油3％、γ-己内酯4％、枯草菌脂肽钠2％、鲸蜡硬脂基葡糖苷5％、助剂4％，余量为水。
优选，所述的EGCG-ZnO纳米颗粒为表没食子儿茶素没食子酸酯(EGCG)和ZnO按摩尔比1:50～60组成。
所述的EGCG-ZnO纳米颗粒的制备包括以下步骤：按EGCG和ZnO的摩尔比为1:50～60，分别准确称取EGCG和氯化锌，将EGCG和氯化锌溶于水，用氢氧化钠溶液调节体系的pH至7.0～7.5，将混合溶液在100℃下回流2～3h，室温下静置24～72h，于12000～15000rpm下离心15～20min，取沉淀，将沉淀用水反复清洗多次，干燥，得到EGCG-ZnO纳米颗粒。
优选，所述的锌盐选自乳酸锌、蓖麻醇酸锌、4-羟基苯磺酸锌、葡萄糖酸锌中的至少一种。
优选，所述的壳聚糖季铵盐为羟丙基三甲基氯化铵壳聚糖。
优选，所述的植物精油选自佛手柑精油、罗马洋甘菊精油、橙花精油、柠檬精油、玫瑰精油、葡萄柚精油中的至少一种。
优选，所述的助剂为氨基己酸。
本发明的液体除臭剂的制备方法，包括以下步骤：将壳聚糖季铵盐、锌盐、助剂和水，混合，搅拌溶解，然后加入枯草菌脂肽钠、鲸蜡硬脂基葡糖苷，搅拌均匀，加入纳米二氧化钛、EGCG-ZnO纳米颗粒、植物精油和γ-己内酯，使用高速均质机进行均质处理2～3min，得到液体除臭剂。
本发明的液体除臭剂为性质稳定的乳状液，纳米二氧化钛(1～100nm)和EGCG-ZnO纳米颗粒(20～50nm)以单分散的形式悬浮于溶液中，协同发挥高效的光触媒催化降解以及抗菌活性，所述的EGCG-ZnO纳米颗粒将表没食子儿茶素没食子酸酯和ZnO结合一起，一方面改善ZnO的分散乳化性能，使ZnO粒子稳定存在于溶液中，提升ZnO和TiO2的的光催化降解活性，所述的ZnO纳米粒子在可见光下仍具有显著的光触媒作用，可克服TiO2纳米粒子的光催化降解效果受限于紫外光的缺陷，提升除臭剂的应用范围。另一方面，EGCG的结构中具有6个邻位酚羟基，易发生降解、异构化及氧化，大大削弱其抗菌活性，EGCG和ZnO的结合可明显改善EGCG的稳定性，使其能发挥长效的杀菌作用。光触媒能催化恶臭气体中的有机物分解为CO2和H2O，通过杀菌作用抑制病原微生物释放臭气，从源头上扼制臭气的产生，从根本上彻底消除臭气。
进一步的。配方中的壳聚糖季铵盐和锌盐通过物理吸附作用和化学键合作用，协同发挥显著的除臭作用。所述的羟丙基三甲基氯化铵壳聚糖为水溶性壳聚糖，具有良好的抗菌性、成膜性、阳离子吸附性能，一方面提升了液体除臭剂的杀菌性能，另一方面阳离子吸附性能对酸性呈臭物质(硫化氢和低分子量有机酸)具有良好的吸附作用；水溶性和成膜性使液体除臭剂易于在除臭物体表面上形成良好的镀膜，有效阻止甲醛等有害物质释放，发挥物理性吸附作用。
锌盐为含锌原子的阴离子表面活性剂，通过成键的机理来除臭，活化的锌原子与臭味中的氮、硫原子形成很强的化合键从而彻底消除臭味，有效阻止呈臭物质释放的同时还能与空气中已存在的呈臭物质反应，达到快速除臭的目的。
本发明选用新型的生物表面活性剂枯草菌脂肽钠和糖苷型非离子表面活性剂鲸蜡硬脂基葡糖苷(INCI：鲸蜡硬脂醇(和)鲸蜡硬脂基葡糖苷)复配作为乳化剂，在氨基己酸助剂的作用下，能促使纳米二氧化钛、EGCG-ZnO纳米颗粒、植物精油及其它成分乳化形成性质稳定的微乳液，增加植物精油在溶液中的溶解度，其中纳米二氧化钛、EGCG-ZnO纳米颗粒是以单分散的形式悬浮于溶液中，经长时间的放置，不会发生沉淀或团结现象，呈高度分散状态。
与现有技术相比，本发明具有以下有益效果：
(1)本发明的液体除臭剂综合多种除臭技术，除臭效果全面，具有高效、速效的除臭特点，能从源头上扼制臭气的产生，从根本上彻底消除臭气，适用于家居、酒店、医院、会场和其它公共场所及其设施的抗菌除异味、臭味的处理，应用范广。
(2)本发明的液体除臭剂使用方便，配制简单，成本低，除臭效果全面，对人体无害、安全，不会对人体产生不利影响。
具体实施方式
以下实施例是对本发明的进一步说明，而不是对本发明的限制。下述实施例中配方的组分，若无特别说明，均为常规市售产品。
实施例1：EGCG-ZnO纳米颗粒的制备
按EGCG和ZnO的摩尔比为1:50，分别准确称取4.58g EGCG和68.2g氯化锌，将EGCG和氯化锌溶于水，用1.25M的氢氧化钠溶液调节体系的pH至7.0，将混合溶液在100℃下回流3h，室温下静置72h，于15000rpm下离心15min，取沉淀，将沉淀用水反复清洗多次，干燥，得到EGCG-ZnO纳米颗粒。
实施例2：EGCG-ZnO纳米颗粒的制备
按EGCG和ZnO的摩尔比为1:60，分别准确称取4.58g EGCG和81.8g氯化锌，将EGCG和氯化锌溶于水，用1.25M的氢氧化钠溶液调节体系的pH至7.5，将混合溶液在100℃下回流2h，室温下静置24h，于12000rpm下离心20min，取沉淀，将沉淀用水反复清洗多次，干燥，得到EGCG-ZnO纳米颗粒。
实施例3-7液体除臭剂的制备
实施例3-7的液体除臭剂包含下表所示质量百分比计的组分：
制备步骤：将羟丙基三甲基氯化铵壳聚糖、锌盐、氨基己酸和水，混合，搅拌溶解，然后加入枯草菌脂肽钠、鲸蜡硬脂基葡糖苷，搅拌均匀，加入纳米TiO2、EGCG-ZnO纳米颗粒、植物精油和γ-己内酯，使用高速均质机进行均质处理3min，得到液体除臭剂。
对比例1：液体除臭剂的制备
本对比例的液体除臭剂与实施例3比较，区别在于，不含EGCG-ZnO纳米颗粒，并相应增加纳米TiO2的用量，其余组成与实施例3相同。制备步骤参考上述实施例。
对比例2：液体除臭剂的制备
本对比例的液体除臭剂与实施例3比较，区别在于，以纳米ZnO(20～50nm)替换EGCG-ZnO纳米颗粒，其余组成与实施例3相同。制备步骤参考上述实施例。
对比例3：液体除臭剂的制备
本对比例的液体除臭剂包含以下质量百分比计的组分：
纳米TiO2 8％、纳米ZnO 7.2％、EGCG 0.8％、羟丙基三甲基氯化铵壳聚糖10％、蓖麻醇酸锌4％、橙花精油3％、γ-己内酯4％、枯草菌脂肽钠2％、鲸蜡硬脂基葡糖苷5％、氨基己酸4％，余量为水。制备步骤参考上述实施例。
对比例4：液体除臭剂的制备
本对比例的液体除臭剂与实施例3比较，区别在于，不含羟丙基三甲基氯化铵壳聚糖，其余组成与实施例3相同。制备步骤参考上述实施例。
对比例5：液体除臭剂的制备
本对比例的液体除臭剂与实施例3比较，区别在于，不含枯草菌脂肽钠，并相应增加鲸蜡硬脂基葡糖苷的用量，其余组成与实施例3相同。制备步骤参考上述实施例。
对比例6：液体除臭剂的制备
本对比例的液体除臭剂与实施例2比较，区别在于，不含氨基己酸，其余组成与实施例3相同。制备步骤参考上述实施例。
试验例一、稳定性检测
分别将实施例3-7和对比例5-6制得的液体除臭剂在室温下放置60天，以及在45℃的高温环境放置72h，进行加速试验，观察液体除臭剂是否分层现象，结果见表1。
表1稳定性检测结果
| 组别 | 室温静置60天 | 45℃静置72h |
| 实施例3 | 无团结、无分层 | 无团结、无分层 |
| 实施例4 | 无团结、无分层 | 无团结、无分层 |
| 实施例5 | 无团结、无分层 | 无团结、无分层 |
| 实施例6 | 无团结、无分层 | 无团结、无分层 |
| 实施例7 | 无团结、无分层 | 无团结、无分层 |
| 对比例5 | 无团结、无分层 | 分层 |
| 对比例6 | 无团结、无分层 | 分层 |
结果显示，实施例3-7制得的液体除臭剂在室温下放置60天或在高温45℃下放置72h，均无出现团结、分层现象，溶液体系的稳定。由对比例5和6可知，仅以鲸蜡硬脂基葡糖苷作为乳化剂，或不含助剂氨基己酸，溶液在室温下稳定，但在加速条件下不稳定，有沉淀分层团结现象。以上结果表明，溶液体系选用新型的生物表面活性剂枯草菌脂肽钠和糖苷型非离子表面活性剂鲸蜡硬脂基葡糖苷复配作为乳化剂，在氨基己酸助剂的作用下，能促使纳米二氧化钛、EGCG-ZnO纳米颗粒、植物精油及其它成分乳化形成性质稳定的微乳液，促使纳米二氧化钛、EGCG-ZnO纳米颗粒是以单分散的形式悬浮于溶液中，经长时间的放置，不会发生沉淀或团结现象，呈高度分散状态。
试验例二、除臭效果检测
按照QB/T 2761《室内空气净化产品净化效果测定方法》，使用本发明实施例3-7和对比例1-4制备的液体除臭剂对环境中的大部分臭气进行检测，包括氨气、硫化氢、甲硫醇和乙醛，进而评估本发明液体除臭剂对臭气的去除能力，结果见表2。
表2除臭效果检测结果
| 组别 | 氨气去除率(％) | 硫化氢去除率(％) | 甲硫醇去除率(％) | 乙醛去除率(％) |
| 实施例3 | 92.7 | 93.2 | 88.6 | 90.4 |
| 实施例4 | 91.2 | 94.6 | 87.4 | 89.6 |
| 实施例5 | 92.4 | 92.1 | 89.5 | 90.7 |
| 实施例6 | 91.8 | 92.5 | 87.0 | 90.0 |
| 实施例7 | 93.3 | 93.0 | 89.8 | 91.5 |
| 对比例1 | 81.4 | 80.7 | 78.2 | 79.3 |
| 对比例2 | 86.7 | 86.0 | 80.7 | 82.2 |
| 对比例3 | 88.5 | 87.4 | 82.5 | 84.8 |
| 对比例4 | 86.0 | 85.2 | 80.1 | 83.6 |
结果显示，实施例3-7制得的液体除臭剂对氨气、硫化氢、甲硫醇和乙醛均具有较佳的清除效果，去除率达到87％以上，效果明显优于对比例1-4制得的液体除臭剂。
试验例三、抑菌效果检测
按照2017版《消毒技术规范》中抑菌效果的测试方法对本发明实施例3和对比例1-4制备的液体除臭剂进行抑菌性能测试，试验菌种为大肠杆菌ATCC 8739、金黄色葡萄球菌ATCC 25923、枯草芽孢杆菌ATCC 9372，作用时间为1min。结果见表3。
表3抑菌效果检测结果
| 组别 | 大肠杆菌抑菌率(％) | 金黄色葡萄球菌抑菌率(％) | 枯草芽孢杆菌抑菌率(％) |
| 实施例3 | 99.7 | 99.5 | 99.1 |
| 对比例1 | 96.3 | 95.7 | 95.2 |
| 对比例2 | 97.4 | 97.0 | 96.8 |
| 对比例3 | 98.8 | 98.4 | 98.0 |
| 对比例4 | 97.0 | 96.8 | 96.4 |
结果显示，实施例3得的液体除臭剂对大肠杆菌、金黄色葡萄球菌和枯草芽孢杆菌均具有较佳的抑菌作用，抑菌率高达99％以上，效果明显优于对比例1-4制得的液体除臭剂。
以上仅是本发明的优选实施方式，应当指出的是，上述优选实施方式不应视为对本发明的限制，本发明的保护范围应当以权利要求所限定的范围为准。对于本技术领域的普通技术人员来说，在不脱离本发明的精神和范围内，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (7)
1.一种液体除臭剂，其特征在于，包含以下质量百分比计的组分：纳米二氧化钛6～9％、EGCG-ZnO纳米颗粒5～10％、壳聚糖季铵盐6～10％、锌盐3～6％、植物精油1～4％、γ-己内酯3～5％、枯草菌脂肽钠1～3％、鲸蜡硬脂基葡糖苷3～5％、助剂2～6％，余量为水；所述的EGCG-ZnO纳米颗粒为表没食子儿茶素没食子酸酯和ZnO按摩尔比1:50～60组成。
2.根据权利要求1所述的液体除臭剂，其特征在于，所述的EGCG-ZnO纳米颗粒的制备包括以下步骤：按EGCG和ZnO的摩尔比为1:50～60，分别准确称取EGCG和氯化锌，将EGCG和氯化锌溶于水，用氢氧化钠溶液调节体系的pH至7.0～7.5，将混合溶液在100℃下回流2～3h，室温下静置24～72h，于12000～15000rpm下离心15～20min，取沉淀，将沉淀用水反复清洗多次，干燥，得到EGCG-ZnO纳米颗粒。
3.根据权利要求1所述的液体除臭剂，其特征在于，所述的锌盐选自乳酸锌、蓖麻醇酸锌、4-羟基苯磺酸锌、葡萄糖酸锌中的至少一种。
4.根据权利要求1所述的液体除臭剂，其特征在于，所述的壳聚糖季铵盐为羟丙基三甲基氯化铵壳聚糖。
5.根据权利要求1所述的液体除臭剂，其特征在于，所述的植物精油选自佛手柑精油、罗马洋甘菊精油、橙花精油、柠檬精油、玫瑰精油、葡萄柚精油中的至少一种。
6.根据权利要求1所述的液体除臭剂，其特征在于，所述的助剂为氨基己酸。
7.一种制备权利要求1-6任一项所述的液体除臭剂的方法，其特征在于，包括以下步骤：
将壳聚糖季铵盐、锌盐、助剂和水，混合，搅拌溶解，然后加入枯草菌脂肽钠、鲸蜡硬脂基葡糖苷，搅拌均匀，加入纳米二氧化钛、EGCG-ZnO纳米颗粒、植物精油和γ-己内酯，使用高速均质机进行均质处理2～3min，得到液体除臭剂。
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