CN107699280B - 一种废弃油提质再生的方法 - Google Patents

一种废弃油提质再生的方法 Download PDF

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CN107699280B
CN107699280B CN201710983003.5A CN201710983003A CN107699280B CN 107699280 B CN107699280 B CN 107699280B CN 201710983003 A CN201710983003 A CN 201710983003A CN 107699280 B CN107699280 B CN 107699280B
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oil
waste
oxidant
waste oil
upgrading
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CN107699280A (zh
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李学兵
陈松
蔡恒吉
程斌
李广慈
陈磊
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Qingdao Aikcan Environmental Protection Technology Co ltd
Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Abstract

本发明属于环境保护和能源技术领域，涉及到一种废弃油催化氧化提质再生的方法。废弃油经预处理后在0‑40℃条件下经催化氧化‑萃取过程脱除颜色、金属杂质及硫化物，得到再生油；其中，氧化剂为气体氧化剂或气体氧化剂和液体氧化剂。本发明方法在降低温度下即可有效脱除脱色、脱金属和脱硫，过程中无需氢气，无酸碱废弃物排放，环保无污染，投资成本低，氧化‑萃取过程油收率97％以上，废油再生回收率85％以上，具有良好的应用前景。

Description

一种废弃油提质再生的方法
技术领域
本发明属于环境保护和能源技术领域，涉及到一种废弃油催化氧化提质再生的方法。
背景技术
废弃油是指在使用、运输和储存过程中因氧化、分解和物理杂质污染产生的变质油，主要分为三大类：1、合成废油，如使用过的润滑油、液压油、变压器油等；2、矿物废油，如被污染的汽油、柴油和煤油等；3、生物废油，如被污染或变质的动物油和植物油。对于这些废弃油，传统的做法是将其直接倒掉或是燃烧，由于废油中均不同程度的含有有害物质，这样的做法是对环境和人类健康造成极大危害，也是对油类资源的极大浪费。因此合理高效的回收利用各种废弃油，对于弥补我国石油资源短缺、防止环境污染、促进我国资源循环利用和经济的可持续发展具有积极意义。
国内目前对于生物废油的回收利用方法主要是将其转化成生物柴油及其脂类衍生物，而对于合成废油及矿物废油的处理，已报道较为成熟的工艺包括：蒸馏-酸洗-白土精制；沉降-酸洗-白土精制；沉降-蒸馏-酸洗-白土精制；白土高温接触无酸再生；沉降-絮凝-白土精制；蒸馏-白土精制等(如中国专利CN101988024B、CN101362982B、CN101445763A)。这些工艺存在较多问题，如操作复杂、工艺繁琐、收率较低等，而且多数再生过程会产生新的危险废弃物，如含油白土、酸渣、废气、高粘度渣油等。此外，这些工艺没有加氢过程，再生油中硫、氮含量超标。中国专利201410185259.8介绍了一种废机油催化提质再生的方法，该专利采用加氢脱硫工艺可以显著降低产品中的硫、氮含量。中国专利200610134148.X介绍了一种废润滑油的回收利用方法，采用过滤、电脱水脱金属、沸腾床加氢脱金属、沸腾床加氢精制等工艺组合，可将废润滑油中大部分的杂质有效脱除，并且改善了润滑油的色度、安定性等，同时提高了润滑油基础油的收率。但涉及加氢过程的工艺必须要有氢气，或建立配套的制氢装置，投资大费用高，不适用于小规模废弃油处理再生项目。
由于现有工艺方法均存在一些缺陷，很难进行大规模推广，因此需要开发一种操作过程简单、废弃物少、投资成本可接受的新方法和新技术以满足不同规模处理要求。
发明内容
本发明的目的在于，针对上述不足提供一种适用于工业化的废弃油催化氧化提质再生的方法。
为实现上述目的，本发明采用的技术方案为：
一种废弃油提质再生的方法，在0-40℃条件下经催化氧化-萃取过程脱除颜色、金属杂质及硫化物，得到再生油；其中，氧化剂为气体氧化剂或气体氧化剂和液体氧化剂。
所述液体氧化剂为双氧水；气体氧化剂为臭氧含量为2-10％的空气，进一步的说将空气通过现有方式进行处理使其臭氧含量达到2-10％，同时空气中并未转化的气体(未转化的空气、氮气和氦气)作为臭氧的稀释剂一并进入废弃油提质再生反应中。
所述经预处理的废弃油于0-40℃与抑制剂在过量的氧化剂的存在下进行催化氧化反应0.5-24h，而后在萃取塔中使氧化后的废弃油与萃取剂逆流接触进行萃取，萃取后分离，得到再生油；其中，抑制剂占原料的重量的1-5％；所述抑制剂为游离脂肪酸、乙醇胺、甲醇、乙醇异丁醇的一种或几种；所述萃取剂是甲醇、乙醇、异丁醇、乙醇胺、N，N-二甲基甲酰胺或N-甲基吡咯烷酮。
所述萃取剂用量为氧化后的废弃油质量的1.5-3倍；所述抑制剂溶液的pH值为1-5或8-13。
所述废弃油为废内燃机油、废齿轮油、废液压油、废变压器油、废压缩机油、废汽轮机油、废热处理油、废矿物油、废生物质油在内的，在化石能源和生物质资源的炼制、加工和使用过程中因氧化、热分解和杂质污染变质后产生的废油。
废弃油提质再生的方法进一步的说是：
(1)废弃油原料经沉降、过滤除去水和大颗粒机械杂质，而后进行减压蒸馏，除去胶质和剩余杂质得到粗馏分油；
(2)步骤(1)得到的粗馏分油于0-40℃与抑制剂在过量的氧化剂的存在下进行催化氧化反应0.5-24h，然后分离除去生成的胶质及少量的水，获得氧化后的废弃油；
(3)步骤(2)中的氧化后废弃油进入萃取塔中，与萃取塔由上至下流入的萃取剂逆流接触，脱除氧化反应中产生的极性硫化物及其衍生物得到脱硫油；
(4)步骤(3)中的脱硫油与含硫萃取剂的混合物进入分馏塔进行分离，得到的脱硫油即为再生油；分离后的含硫萃取剂进入溶剂再生塔中进行再生。
所述步骤4)分馏塔在120-180℃，0.08-0.09MP压力下进行分离。
所述步骤(1)中废弃油原料经沉降、过滤除去水和大颗粒机械杂质，而后加热至350℃左右，进入减压蒸馏塔在0.01MPa的绝对压力下蒸馏，溜出的蒸馏油为粗馏分油，塔底的残留油为胶质等重组分。
本发明的优点在于：本发明在常温、常压下通过催化氧化过程即可有效降低色度、脱除废弃油中的杂质，不会像传统的采用酸洗-白土精制工艺产生污染废弃物，具有环境友好的特点。此外，该方法无需加氢过程也可降低原料中的硫、氮含量，在提高再生油品质的同时大大降低了投资和操作成本，也避免了硫化氢、氨气等有毒废气的产生。
具体实施方式
下面结合实施例进一步说明本发明，但本发明并不局限于实施例。
本发明方法将废弃油经减压分离除胶、除杂后，在室温下进入氧化装置进行脱色、脱金属并分离出生成的胶质，氧化后的废弃油进入萃取塔通过萃取分离出氧化过程中产生的砜类硫化物及其衍生物，脱硫油进入分馏塔分离萃取剂后进行冷却，得到再生油。该方法在降低温度下即可有效脱除脱色、脱金属和脱硫，过程中无需氢气，无酸碱废弃物排放，环保无污染，投资成本低，氧化-萃取过程油收率97％以上，废油再生回收率85％以上，具有良好的应用前景。
实施例1.废弃油脱胶除杂质过程
废弃油原料为废弃机动车润滑油，由山东省本地一家地方炼厂提供，其为该废弃油混合物，包括各类废机油和废矿物油；原料首先在分离罐中经过自然沉降、滤网过滤(100目)后除去游离水和大颗粒机械杂质，之后进入分馏塔中经减压蒸馏获得粗馏分油，塔底残留的是重组分的胶质(参见表1)；蒸馏过程中系统真空度为0.095MPa,粗馏分油温度在170-190℃。
表1废弃油脱胶除杂后产物的物理性能检测结果
Figure BDA0001439862070000031
实施例2.粗馏分油的催化氧化过程1
将上述处理所得脱胶除杂得到的粗馏分油进入间歇式反应器，在含臭氧的空气存在下室温进行氧化脱色、脱金属反应，具体过程是：向反应器中加入10L粗馏分油，之后加入50L水和丙酮酸的混合溶液作为抑制剂，充分混合后自下而上通入含臭氧的空气(流速为2L/min)，在20℃下持续反应1.5h，反应结束后，产物以3000转/分钟离心10分钟进行离心，分离出去下层的水、絮状沉淀和少量胶质，得到氧化油(参见表2)，收率为98.8％。其中丙酮酸在水中的质量分数为4％，臭氧的体积分数为7％。
含臭氧的空气是将空气通过现有方式进行处理使其臭氧含量达到7％，同时空气中并未转化的气体(未转化的空气、氮气和氦气)作为臭氧的稀释剂一并进入废弃油提质再生反应中。
表2氧化油的物理性能检测结果
Figure BDA0001439862070000041
实施例3.粗馏分油的催化氧化过程2
脱胶除杂得到的粗馏分油进入间歇式反应器，在含臭氧的空气存在下室温进行氧化脱色、脱金属反应，具体过程是：向反应器中加入10L粗馏分油，之后加入50L水和丙酮酸的混合溶液作为抑制剂，充分混合后自下而上通入含臭氧的空气(流速为2L/min)，在20℃下连续反应3h，反应结束后，产物经过离心分离出去下层的水、絮状沉淀和少量胶质，得到氧化油(参见表3)，收率为97.7％。其中丙酮酸在水中的质量分数为4％，臭氧的体积分数为7％。
同时上述氧化剂含臭氧的空气可由含臭氧的空气和双氧水的混合物进行替换。
表3氧化油的物理性能检测结果
Figure BDA0001439862070000042
Figure BDA0001439862070000051
实施例4.氧化油的萃取分离
经实施例3过程得到的氧化油进入萃取塔中通过萃取的方法除去氧化过程中可能生成的砜类硫化物及其衍生物，具体过程是：离心分离后的氧化油经萃取塔下部注入，伴随着搅拌过程与上部喷淋而下的萃取液进行充分接触，萃取后含有少量萃取剂的脱硫油从萃取塔上部流出进入分馏塔在180℃，0.08MP压力下进行分离，得到的脱硫油即为再生油；分离后的含硫萃取剂进入溶剂再生塔中进行再生(参见表4)。其中，萃取塔的操作温度为30℃，萃取液为乙醇胺与异丁醇的混合物(乙醇胺与异丁醇的体积比＝2/7)，萃取液的用量为氧化油的2.5倍。
表4再生油的物理性能检测结果
Figure BDA0001439862070000052
Figure BDA0001439862070000061
由萃取后所得再生油的检测结果可知，本发明提供的方法可以有效减少废弃油原料中可能存在的污染物和杂质，特别是对于高含硫、金属杂原子的原料效果显著，同是本发明操作简单、投资成本低、污染废弃物产量少，是一种高效环保的废弃油处理工艺，具有重要的推广价值。

Claims (3)

1.一种废弃油提质再生的方法，其特征在于：废弃油经预处理的废弃油于0-40℃与抑制剂在过量的氧化剂的存在下进行催化氧化反应0.5-24h，而后在萃取塔中使氧化后的废弃油与萃取剂逆流接触进行萃取，萃取后分离，得到再生油；其中，抑制剂占原料的重量的1-5%；
所述抑制剂为丙酮酸；
所述萃取剂是乙醇胺与异丁醇的混合物，乙醇胺与异丁醇的体积比为2:7；
所述氧化剂为气体氧化剂或气体氧化剂和液体氧化剂；
所述气体氧化剂为臭氧体积含量为2-10%的空气；
所述液体氧化剂为双氧水；
所述萃取剂用量为氧化后的废弃油质量的2.5倍；
所述废弃油为废内燃机油、废齿轮油、废液压油、废变压器油、废压缩机油、废汽轮机油、废热处理油、废矿物油或废生物质油。
2.按权利要求1所述的废弃油提质再生的方法，其特征在于：
（1）废弃油原料经沉降、过滤除去水和大颗粒机械杂质，而后进行减压蒸馏，除去胶质和剩余杂质得到粗馏分油；
（2）步骤（1）得到的粗馏分油于0-40℃与抑制剂在过量的氧化剂的存在下进行催化氧化反应0.5-24h，然后分离除去生成的胶质及少量的水，获得氧化后的废弃油；
（3）步骤（2）中的氧化后废弃油进入萃取塔中，与萃取塔由上至下流入的萃取剂逆流接触，脱除氧化反应中产生的极性硫化物及其衍生物得到脱硫油；
（4）步骤（3）中的脱硫油与含硫萃取剂的混合物进入分馏塔进行分离，得到的脱硫油即为再生油；分离后的含硫萃取剂进入溶剂再生塔中进行再生。
3.按权利要求2所述的废弃油提质再生的方法，其特征在于：所述步骤4）分馏塔在120-180℃，0.08-0.09MP压力下进行分离。
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