CN111849646A - 一种基于地沟油的蜡及其制备方法 - Google Patents
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
本发明公开了一种基于地沟油的蜡及其制备方法。所述地沟油基蜡在室温下为接近白色的蜡状固体,在空气和日光下能保持性状稳定,无地沟油特有的酸败油脂或煎炸油脂等异味,无有毒有害成分,具有较高的熔点和硬度,较浅的色泽以及较好的光安定性,其制备方法为:将地沟油经过环氧化获得环氧地沟油,而后加入硬脂酸共熔,混合形成均相后,冷却注模获得。该蜡能够替代市场上的半精炼石蜡,用于制备蜡烛、蜡笔、蜡纸、打光用蜡等产品。与其他市场上的半精炼石蜡相比,本发明的基于地沟油的蜡材料具有价格低廉,绿色环保的特点,且可以有效回收利用地沟油,具有较好的经济意义和社会价值。
Description
【技术领域】
本发明具体涉及一种基于地沟油的蜡及其制备方法,属于地沟油回收利用和应用化学领域。
【背景技术】
地沟油是各类劣质废油脂的统称,不仅营养价值低下,还含有多种对人体有害的成分,如酚类、酮类、游离脂肪酸、脂肪酸聚合物、黄曲霉素等,不可用于食用。地沟油若不加以回收利用,不但浪费宝贵的自然资源,还会对水体等自然环境造成二次污染,或通过不法分子加工提炼后重新流入餐桌,对人民群众的健康造成巨大威胁。当前,我国对地沟油的回收利用主要有以下几个途径:(1)将地沟油进行预处理后,经过皂化、盐析、水洗、干燥定型等工序,生产肥皂和洗衣粉(梁芳慧,尹平河,赵玲,王耀.地沟油生产无磷洗衣粉的研究[J].广东化工,2005,9:5-8;魏正妍,尚雪岭.餐饮废油和柑橘皮制肥皂的工艺研究[J].新乡学院学报:自然科学版,2010,4:49-50);(2)将地沟油在适当催化剂的作用下,与甲醇等发生酯交换反应制备生物柴油燃料(王振斌,姜美花,王倩倩,赵帅.响应面法优化餐饮废油制备生物柴油的研究[J].中国油脂,2013,38:59-63;M.Farooq,A.Ramli,A.Naeem,Biodiesel production from low FFA waste cooking oil using heterogeneouscatalyst derived from chicken bones[J].Renewable Energy,2015,76:362-368);(3)将地沟油在适当的条件下水解、精制获得硬脂酸、油酸、甘油等化工产品,或进一步生产脂肪酸酰胺等表面活性剂或中间体(郭涛,杜蕾蕾,万辉,何东平.餐饮废油制备硬脂酸与油酸的研究[J].食品科技,2009,34:109-112;刘先杰,陈立功,曹书翰.餐饮废油制取脂肪酸二乙醇酰胺的研究[J].中国油脂,2013,38:55-59;苗宗成,翟鹏飞,吴玮,冀静,赵阳.基于废弃地沟油制备双酯基季铵盐型阳离子表面活性剂[J].应用化工,2016,45:2095-2097)。(4)将地沟油与适当有机酸发生酯交换反应生产醛酸树脂(梁建新,徐家燕,梁善成,谢尚业,李崇铭,王维熙,袁爱群.利用地沟油和对苯二甲酸废料生产醇酸树脂的理论和实践[J].中国涂料,2013,4:72-76);(5)将地沟油进行环氧化、酯交换等步骤制备塑料增塑剂等吴锦京,张晓燕,李季衡.(环氧地沟油基PVC人造革增塑剂的制备与应用[J].上海塑料,2016,(04):58-61)。这几种途径虽然都能够回收利用地沟油,但都存在某些不足:如产品附加值过低、但生产设备复杂,工艺技术难度较高、地沟油预处理步骤繁琐等。这些缺点都不同程度阻碍了地沟油的大规模工业化回收利用。因此,有必要进一步探索地沟油回收利用的新途径。
石蜡为碳原子数约为18~30的烃类混合物,主要组分为直链烷烃,还有少量带个别支链的烷烃和带长侧链的单环环烷烃,石蜡尤其是全精炼石蜡和半精炼石蜡用途很广,主要用做食品、口服药品及某些商品(如蜡纸、蜡笔、蜡烛、复写纸)的组分及包装材料,烘烤容器的涂敷料,用于水果保鲜,电器元件绝缘,提高橡胶抗老化性和增加柔韧性等。地沟油的主要成分为甘油三酯,和石油蜡能够相溶,但地沟油含有太多杂质和有毒有害物质,色泽较深,熔点低,光安定性很差室温下为液态或半固态,不能直接作为蜡或者石蜡的添加剂使用,
【发明内容】
为了解决上述现有技术存在的问题并发明新型地沟油基材料,本发明提供一种地沟油基蜡及其合成方法,可以获得熔点较高、硬度较大、色泽较浅、光安定性好的地沟油基蜡,该蜡可以替代普通石蜡,作为蜡烛、蜡笔、蜡纸和打光用蜡使用。
本发明采用的技术方案为:
一种基于地沟油的蜡,包含以下质量百分比的组分:
环氧地沟油 25%~75%
脂肪酸 25%~75%
将上述配比的环氧地沟油和脂肪酸在70℃~90℃下加热熔化,混合搅拌5~20分钟形成均相,注模冷却成型,即可获得基于地沟油的蜡材料。
所述的环氧地沟油环氧值不大于2,在不大于30℃时为浅黄色固体。
所述脂肪酸为硬脂酸、软脂酸其中的一种或一种以上组合。所述脂肪酸优选硬脂酸。
其中,所述环氧地沟油,由如下质量份的原料合成:
所述的环氧地沟油合成过程如下:
将上述冰乙酸、30%过氧化氢溶液、浓硫酸和尿素混合,避光放置于35℃~45℃的烘箱中反应12~24小时,获得环氧化试剂。将半固态地沟油加入反应釜中,加热至35℃~45℃令其溶解,然后将配制好的环氧化试剂用恒压漏斗缓慢滴加到反应釜中。滴加完毕后,将温度升至65℃~75℃,恒温搅拌反应2~4小时。反应完成后,静置4~24小时,直到油水层明显分离,将下层水层去掉后,用5%碳酸氢钠溶液洗涤油层1次,再用70℃去离子水洗涤油层2次。随后收集油层,用真空旋转蒸发器在65℃~75℃下旋转蒸发1~2小时,冷却到室温后,获得淡黄色固体,即为环氧地沟油。
所采用的地沟油可为以下一种或一种以上油脂的组合:下水道中的油腻漂浮物或者餐饮企业的泔水经过简单加工提炼出的油;餐饮单位或食品加工企业在多次烹饪作业后的油底;煎炸烧烤食材后淘汰的废油;居民抽油烟机集油器中的废油。优选餐饮单位或食品加工企业煎炸烧烤食材后淘汰的废油。所用地沟油原料的碘值需在50以下。若地沟油碘值超过此值,需将原料油脂在离心机上以6000~10000rpm转速离心3~5分钟,冷却后,地沟油被分离成为室温下固态的油底和液态的上清油,将上清油以倾泻法与油底分离,取油底进行碘值检测,直到碘值合格方可进行后续制备。
所述的一种基于地沟油的蜡,在室温下为接近白色的蜡状固体,在空气和日光下能保持性状稳定,无地沟油特有的酸败油脂或煎炸油脂等异味,无有毒有害成分,具有较高的熔点和硬度,较浅的色泽以及较好的光安定性,其熔点范围为38℃~54℃,针入度58~21,赛波特颜色号大于8,光安定性号数不大于6。
本发明的有益效果是:本发明首先通过将地沟油环氧化,去除其中有害成分和杂质,并同时对其除色除味,获得了安全无毒、色泽浅、光安定性好的环氧地沟油,而后加入脂肪酸提升熔点和硬度,获得了具有较高的熔点和硬度,较浅的色泽、较好的光安定性、成本低廉的地沟油基蜡。
该蜡能够替代市场上的半精炼石蜡,用于制备蜡烛、蜡笔、蜡纸、打光用蜡等产品。与其他市场上的半精炼石蜡相比,本发明的基于地沟油的蜡材料具有价格低廉,绿色环保的特点,且可以有效回收利用地沟油,具有较好的经济意义和社会价值。
具体实施方式
下面列举具体实施例对本发明进行说明:
实施例1:
取冰乙酸160g,30%过氧化氢溶液620g,浓硫酸4g,尿素4g混合于大烧杯中,避光放置于40℃的烘箱中反应12小时,获得环氧化试剂。将碘值为40的地沟油加入反应釜中,加热至40℃,然后将配制好的环氧化试剂用恒压漏斗缓慢滴加到反应釜中。滴加完毕后,将温度升至70℃,恒温搅拌反应3小时。反应完成后,静置12小时,令油水层明显分离,将下层水层去掉后,用5%碳酸氢钠溶液洗涤油层1次,再用70℃去离子水洗涤油层2次。随后收集油层,用真空旋转蒸发器在70℃下旋转蒸发2小时,冷却到室温,即可得淡黄色的固态环氧地沟油,此油环氧值1.1。称取环氧地沟油100g、硬脂酸100g于烧杯中,升温到80℃熔化,混合搅拌5分钟形成均相浅黄色熔液,注模冷却成型,即可获得基于地沟油的蜡材料。
根据国家标准GB/T 2539-2008《石油蜡熔点的测定(冷却曲线法)》、GB/T 4985-2010《石油蜡针入度测定法》、GB/T 3555-92《石油产品赛波特颜色测定法(赛波特比色计法)》、石油化工行业标准SH/T 0404-2008《石蜡光安定性测定法》分别测试其熔点、针入度、色号和光安定性。测试结果表明,该蜡熔点47~51℃,针入度41,赛波特颜色号12,光安定性值4。
实施例2:
取冰乙酸150g,30%过氧化氢溶液620g,浓硫酸3g,尿素3g混合于大烧杯中,避光放置于40℃的烘箱中反应24小时,获得环氧化试剂。将碘值为44的地沟油加入反应釜中,加热至40℃,然后将配制好的环氧化试剂用恒压漏斗缓慢滴加到反应釜中。滴加完毕后,将温度升至70℃,恒温搅拌反应3小时。反应完成后,静置12小时,令油水层明显分离,将下层水层去掉后,用5%碳酸氢钠溶液洗涤油层1次,再用70℃去离子水洗涤油层2次。随后收集油层,用真空旋转蒸发器在70℃下旋转蒸发2小时,冷却到室温,即可得淡黄色的固态环氧地沟油,此油环氧值1.4。称取环氧地沟油75g、软脂酸25g于烧杯中,升温到70℃熔化,混合搅拌10分钟形成均相浅黄色熔液,注模冷却成型,即可获得基于地沟油的蜡材料。
根据国家标准GB/T 2539-2008《石油蜡熔点的测定(冷却曲线法)》、GB/T 4985-2010《石油蜡针入度测定法》、GB/T 3555-92《石油产品赛波特颜色测定法(赛波特比色计法)》、石油化工行业标准SH/T 0404-2008《石蜡光安定性测定法》分别测试其熔点、针入度、色号和光安定性。测试结果表明,该蜡熔点38~44℃,针入度58,赛波特颜色号9,光安定性值5。
实施例3:
取冰乙酸170g,30%过氧化氢溶液620g,浓硫酸3g,尿素3g混合于大烧杯中,避光放置于40℃的烘箱中反应24小时,获得环氧化试剂。将碘值为38的地沟油加入反应釜中,加热至40℃,然后将配制好的环氧化试剂用恒压漏斗缓慢滴加到反应釜中。滴加完毕后,将温度升至70℃,恒温搅拌反应3小时。反应完成后,静置12小时,令油水层明显分离,将下层水层去掉后,用5%碳酸氢钠溶液洗涤油层1次,再用70℃去离子水洗涤油层2次。随后收集油层,用真空旋转蒸发器在70℃下旋转蒸发1小时,冷却到室温,即可得淡黄色的固态环氧地沟油,此油环氧值0.9。称取环氧地沟油25g、硬脂酸75g于烧杯中,升温到85℃熔化,混合搅拌10分钟形成均相浅黄色熔液,注模冷却成型,即可获得基于地沟油的蜡材料。
根据国家标准GB/T 2539-2008《石油蜡熔点的测定(冷却曲线法)》、GB/T 4985-2010《石油蜡针入度测定法》、GB/T 3555-92《石油产品赛波特颜色测定法(赛波特比色计法)》、石油化工行业标准SH/T 0404-2008《石蜡光安定性测定法》分别测试其熔点、针入度、色号和光安定性。测试结果表明,该蜡熔点51~54℃,针入度21,赛波特颜色号17,光安定性值4。
Claims (5)
1.一种基于地沟油的蜡,其特征在于,由以下百分比的物质组成:环氧地沟油,质量占比25%~75%;脂肪酸,质量占比25%~75%。
2.如权利要求1所述的一种基于地沟油的蜡,其特征在于:在室温下为接近白色的蜡状固体,在空气和日光下能保持性状稳定,无地沟油特有的酸败油脂或煎炸油脂等异味,无有毒有害成分,具有较高的熔点和硬度,较浅的色泽以及较好的光安定性,其熔点范围为38℃~54℃,针入度58~21,赛波特颜色号大于8,光安定性号数不大于6。
3.如权利要求1所述的一种基于地沟油的蜡的制备方法,其特征在于具体步骤为:将环氧地沟油和脂肪酸以质量比(25~75):(25~75)混合,在70℃~90℃下加热熔化,混合搅拌5~20分钟形成均相,注模冷却成型,即可获得基于地沟油的蜡材料;
所述的环氧地沟油环氧值不大于2,在不大于30℃时为浅黄色固体;
所述脂肪酸为硬脂酸、软脂酸其中的一种或一种以上组合;
其中,所述环氧地沟油,由如下质量份的原料合成:地沟油100份;冰乙酸150~180份;30%过氧化氢溶液500~700份;浓硫酸3~6份;尿素3~6份,所述的环氧地沟油合成过程如下:
将冰乙酸、30%过氧化氢溶液、浓硫酸和尿素混合,避光放置于35℃~45℃的烘箱中反应12~24小时,获得环氧化试剂,将半固态地沟油加入反应釜中,加热至35℃~45℃令其溶解,然后将配制好的环氧化试剂用恒压漏斗缓慢滴加到反应釜中,滴加完毕后,将温度升至65℃~75℃,恒温搅拌反应2~4小时,反应完成后,静置4~24小时,直到油水层明显分离,将下层水层去掉后,用5%碳酸氢钠溶液洗涤油层1次,再用70℃去离子水洗涤油层2次,随后收集油层,用真空旋转蒸发器在65℃~75℃下旋转蒸发1~2小时,冷却到室温后,获得淡黄色固体,即为环氧地沟油。
4.如权利要求3所述的一种基于地沟油的蜡的制备方法,其特征在于所采用的地沟油为以下一种或一种以上油脂的组合:下水道中的油腻漂浮物或者餐饮企业的泔水经过简单加工提炼出的油;餐饮单位或食品加工企业在多次烹饪作业后的油底;煎炸烧烤食材后淘汰的废油;居民抽油烟机集油器中的废油。
5.如权利要求3-4任一项所述的一种基于地沟油的蜡的制备方法,所采用的地沟油特征为:地沟油原料的碘值需在50以下,若地沟油碘值超过此值,需将原料油脂在离心机上以6000~10000rpm转速离心3~5分钟,冷却后,地沟油被分离成为室温下固态的油底和液态的上清油,将上清油以倾泻法与油底分离,取油底进行碘值检测,直到碘值合格方可进行后续制备。
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