CN103055802B - 具有抗氧化性能凹凸棒黏土棕榈油脱色剂的制备方法 - Google Patents
具有抗氧化性能凹凸棒黏土棕榈油脱色剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种具有抗氧化性能凹凸棒黏土棕榈油脱色剂的制备方法,将凹凸棒黏土进行无机酸活化处理后,再用具有抗氧化性的有机酸或其盐类修饰,得到具有抗氧化性能的凹凸棒黏土棕榈油脱色剂。本发明的凹凸棒黏土棕榈油脱色剂不仅脱色效果好,还能防棕榈油储存期间氧化劣变。
Description
技术领域
本发明涉及油脂脱色用吸附剂的制备方法,具体涉及一种具有抗氧化性能的凹凸棒黏土棕榈油脱色剂的制备方法。
背景技术
棕榈油是全球第二大食用植物油,也是非常重要的精细化工原料。近年来,世界棕榈油产量以20%速率迅猛增长,使得棕榈油精炼技术的改进及产品品质的提升成为人们日益关注的问题。
毛棕榈油典型精炼工艺是物理精炼,主要工艺流程为:毛油—脱胶—脱色—脱臭—分提。其中,脱色是最为重要的精炼工序,也是决定棕榈油精炼成本和产品品质的关键因素。工业上最常用的棕榈油脱色剂是活性白土。但活性白土吸油率较高,同时脱色后油脂的酸价回升明显,影响油品储存品质。为了改善棕榈油储存品质,传统方法是精炼以后在成品油中加入抗氧化剂,这是治标不治本的方法。
凹凸棒黏土是一种具有独特纳米纤维状结构的层链状含水富镁、铝硅酸盐黏土矿物,独特的晶体结构赋予凹凸棒棒石极佳的吸附性能。由于其滞油率低,残油量少,已在棕榈油脱色方面得到应用。中国专利CN102225327A公开了一种凹凸棒黏土棕榈油脱色净化剂的生产方法,该脱色净化剂由凹凸棒黏土、硫酸铝、硫酸亚铁、硫酸钛和硫酸组成;CN 102744033 A公开了一种半干法改性凹凸棒黏土棕榈油深度脱色剂的制备方法,它是将凹凸棒黏土在搅拌槽内喷洒含磷酸盐和铝盐的硫酸溶液,经充分混合煅烧、粉碎得凹凸棒黏土棕榈油深度脱色剂。该类凹凸棒黏土脱色剂实现了棕榈油深度脱色,但任然存在油品的反色问题。
发明内容
针对棕榈油脱色后油品的反色问题,本发明提供一种具有抗氧化性能的凹凸棒黏土棕榈油土脱色剂的制备方法,其目的在于该脱色剂在实现对棕榈油高效脱色的同时,抑制油脂的氧化,解决棕榈油储存、运输中发生的氧化劣变及返色等问题。
本发明的技术原理是:通过无机酸活化凹凸棒黏土,除去凹凸棒黏土内非吸附性碳酸盐杂质及其粒间胶结物,使纤维棒晶束解聚、八面体阳离子部分溶出,增加孔道及比表面积,为凹凸棒黏土提供更多的吸附位点,提高脱色能力;在此基础上,选用具有抗氧化能力的有机酸或其盐对凹凸棒黏土加以改性,改性剂中存在的羟基、氨基、羧基等基团与凹凸棒黏土表面羟基通过氢键作用而修饰到凹凸棒黏土表面,在对油品脱色的同时螯合油脂内金属离子,及时清除油脂内过多活性氧及过剩自由基,抑制油品氧化。
本发明的技术解决方案是:在搅拌状态下,将凹凸棒黏土加入无机酸溶液中得混合溶液,在室温~90℃反应1~4h后再加入有机酸或其盐,继续搅拌反应1~4h后,过滤,洗涤,干燥,粉碎,得凹凸棒黏土棕榈油脱色剂。
本发明的工艺步骤如下:
(1)无机酸活化:在搅拌状态下,将凹凸棒黏土加入无机酸溶液中得混合溶液,室温~90℃反应1~4h;活化处理所用的酸为盐酸、硫酸、硝酸、磷酸中的一种,添加量为凹凸棒黏土质量的1~10%,无机酸活化的固液比为1:10~1:40(w/v);
(2)有机酸或盐修饰:在搅拌状态下,在凹凸棒黏土和无机酸混合溶液中,再加入有机酸或其盐,继续搅拌反应1~4h;所用的有机酸或其盐为柠檬酸、酒石酸、L-抗坏血酸、异抗坏血酸、植酸或其盐中的一种,添加量为凹凸棒黏土质量的0.1~5%;
(3)后处理:将有机酸或盐修饰的悬浮液板框式过滤后用水洗涤至pH为5,回转窑干燥,气流粉碎机粉碎至200目,得凹凸棒黏土棕榈油脱色剂。
本发明具有以下优点:
1、经过无机酸活化除去了凹凸棒黏土中的无机盐杂质及其粒间胶结物,增加了孔道及比表面积,提高了凹凸棒黏土的脱色能力;
2、有机酸改性使凹凸棒黏土在脱色的同时,可以进一步螯合油脂内金属离子,减少金属离子对油脂氧化作用的催化活性;
3、该产品安全、高效、无毒,适应范围广,不仅可使用于棕榈毛油的脱色与精炼棕榈油的深度脱色,也使用于其他植物油,动物油、矿物油的脱色。
具体实施方式
下面结合具体实施例进一步说明本发明的技术解决方案,这些实施例不能理解为是对技术方案的限制。
实施例1:在搅拌状态下,将500 kg凹凸棒黏土加入质量百分比浓度为3%的5000L硫酸溶液中,40℃反应2h后加入2 kg柠檬酸,继续搅拌反应2h,板框式过滤,用水洗涤至pH为5,回转窑干燥,气流粉碎机粉碎至200目,得产品。经脱色处理棕榈油红值由3.8降至2.1,储存6个月红值没有发生变化。
实施例2:在搅拌状态下,将500 kg凹凸棒黏土加入质量百分比浓度为6%的8000L盐酸溶液中,60℃反应3h后加入5 kg L-抗坏血酸,继续搅拌反应3h,板框式过滤,用水洗涤至pH为5,回转窑干燥,气流粉碎机粉碎至200目,得产品。经脱色处理棕榈油红值由3.8降至2.0,储存6个月红值没有发生变化。
实施例3:在搅拌状态下,将500 kg凹凸棒黏土加入质量百分比浓度为5%的8000L磷酸溶液中,80℃反应2h后加入7.5 kg 酒石酸,继续搅拌反应3h,板框式过滤,用水洗涤至pH为5,回转窑干燥,气流粉碎机粉碎至200目,得产品。经脱色处理棕榈油红值由3.8降至1.9,储存6个月红值没有变化。
实施例4:在搅拌状态下,将500 kg凹凸棒黏土加入质量百分比浓度为5%的5000L磷酸溶液中,90℃反应3h后加入5 kg异抗坏血酸和2 kg柠檬酸三钠,继续搅拌反应1h,板框式过滤,用水洗涤至pH为5,回转窑干燥,气流粉碎机粉碎至200目,得产品。经脱色处理棕榈油红值由50降至26,经脱臭处理后红值进一步降低为2.5,储存6个月红值没有发生变化。
实施例5:在搅拌状态下,将500 kg凹凸棒黏土加入质量百分比浓度为4%的5000L硝酸溶液中,20℃反应2h后加入5 kg植酸钠,继续搅拌反应4h,板框式过滤,用水洗涤至pH为5,回转窑干燥,气流粉碎机粉碎至200目,得产品。经脱色处理棕榈油红值由50降至24,再经脱臭处理后红值进一步降低为2.1,储存6个月红值没有发生变化。
Claims (1)
1.具有抗氧化性能凹凸棒黏土棕榈油脱色剂的制备方法,在搅拌状态下,将凹凸棒黏土加入无机酸溶液中得混合溶液,室温~90℃反应1~4h后再加入有机酸或其盐,继续搅拌反应1~4h,过滤,洗涤,干燥,粉碎,得凹凸棒黏土棕榈油脱色剂;其特征在于:凹凸棒黏土无机酸活化处理所用的酸为盐酸、硝酸、硫酸、磷酸中的一种,添加量为凹凸棒黏土质量的1~10%,无机酸活化的固液比1:10~1:40w/v;所用的有机酸或其盐为柠檬酸、酒石酸、L-抗坏血酸、异抗坏血酸、植酸或其盐中的一种,添加量为凹凸棒黏土质量的0.1~5%;板框式过滤后用水洗涤至pH为5,回转窑干燥,气流粉碎机粉碎至200目,得凹凸棒黏土棕榈油脱色剂。
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US5908500A (en) * | 1994-09-29 | 1999-06-01 | Oil-Dri Corporation Of America | Activated clay composition and method |
CN101658782A (zh) * | 2009-08-24 | 2010-03-03 | 淮阴师范学院 | 凹凸棒粘土改性制备吸附剂的方法 |
CN102225327A (zh) * | 2011-04-21 | 2011-10-26 | 郑玥 | 凹凸棒棕榈油脱色净化剂的生产方法 |
CN102806063A (zh) * | 2012-09-04 | 2012-12-05 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | 棕榈油脱胶脱色用凹凸棒黏土吸附剂的制备方法 |
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