CN106187690A - 一种杂醇油臭味去除剂的制备方法及应用 - Google Patents
一种杂醇油臭味去除剂的制备方法及应用 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
煤制甲醇杂醇油主要成分是甲醇、乙醇、丙醇、异丙醇等多种醇类的混合物,还含有极少量的硫化物,具有难闻刺鼻的臭味。使用煤制甲醇杂醇油臭味去除剂,除臭效果明显,工艺简单,容易操作,无任何排放,环保无污染;使用量少,成本低;经济效益和社会效益显著。
Description
技术领域
本发明属于化工生产领域,具体涉及一种杂醇油臭味去除剂的制备方法及应用。
背景技术
杂醇油是发酵法生产酒精副产物之一,是含有多种醇类混合液的统称。杂醇油是一种淡黄色油状液体有特殊臭味和毒性。杂醇油的主要成分是乙醇、正丙醇、正丁醇、异丁醇、仲丁醇、戊醇、异戊醇、水及少量沸点大于135℃的醛、醇、酯、酸、不饱和萜烯类化合物、吡啶、生物碱等二十多种成分。杂醇油所含C2—C5醇均能与水形成恒沸物,各恒沸物间的恒沸点差小于相应醇间的沸点差,使得各组分的分离变得非常困难。因在酒精工业上高级醇被视为杂质,且易溶于酒精不溶于水,酒度低时类似油状,所以习惯上称高级醇作“杂醇油”。
发酵法产生的杂醇油臭味主要采用冷冻过滤法、淀粉吸附法、活性炭吸附法等方法除去。冷冻法是根据溶解度特性,在低温下杂醇油中的高级醇溶解度降低而被析出、凝集沉淀的原理,将白酒冷冻到-12~-15℃,并保持数小时,有絮凝、析出,颗粒增大,并在低温度条件下过滤除去。淀粉吸附是淀粉膨胀后颗粒表面形成许多微孔,与白酒中的混浊物相遇,即可将它们吸附在淀粉颗粒上,然后通过机械过滤的方法除去。活性炭是选择适宜的酒用活性炭搅拌均匀后,经8~24h放置沉降处理,过滤后使用。
煤制甲醇是煤化工项目的重要组成部分。我国煤炭资源丰富,发展煤制甲醇不仅合理利用了煤炭,而且可以减轻粗放式开采利用过程中对环境的污染破坏。甲醇是一种基础化工原料,在化工、医药、轻纺等领域有着广泛的用途。甲醇可以用来直接合成含氧化工产品,主要用于制造甲醛、甲胺、二甲醚等一系列有机化工产品,而且还可以加入汽油掺烧或代替汽油作为动力燃料以及用来合成甲醇蛋白。在世界基础有机化工原料中,甲醇消耗量却仅次于C2H4,C3H6和C6H6,居于第4位。
2014年我国煤制甲醇约500万吨,同时产有10万吨杂醇油。在煤制甲醇工艺中,经蒸馏甲醇后剩余的杂醇油主要成分是甲醇、乙醇、丙醇、异丙醇、丁醇等,还含有异丁醇、2-丁醇、戊醇、异戊醇、2-戊醇、3-甲基-2-丁醇、2-甲基-1-丁醇、己醇、2-己醇、3-己醇、庚醇、2-庚醇、3-庚醇、2-甲基-1-己醇、2-乙基-1-戊醇、2-甲基-3-己醇、癸烷、十一烷、十二烷、十三烷、十四烷、十五烷、十六烷、十七烷、十八烷、十九烷、二十烷、二十一烷等共40多种化合物,其中含有极少量的甲硫醇、乙硫醇、硫化氢等。由于含有极少量的硫化物,具有难闻刺鼻的臭味。由于硫化物的含量少,处理成本较高,完全清除这种臭味困难。目前煤制甲醇这些副产物杂醇油,大都没有经过认真、系统的回收和处理,或送入它系统裂解燃烧,或随残液直接排放,或简单处理后送进污水处理系统。其结果是既污染了环境,增大了污水处理系统负荷,又减少了企业的副产品和效益。
煤制甲醇的杂醇油与发酵法生产酒精的杂醇油,都具有刺鼻的难闻臭味,它们的名称相同,但是它们的化学成分有很大的区别,性质完全不同。对于来源不同的臭味,常采用不同的处理方法。发明人把发酵法生产酒精的杂醇油处理方法,应用于煤制甲醇的杂醇油,即使用冷冻过滤法、淀粉吸附法、活性炭吸附法等方法处理煤制甲醇的杂醇油效果很差,即处理后的杂醇油仍然有刺激的臭味。
目前国内的除臭剂主要有:物理除臭剂、化学除臭剂、微生物型除臭剂等。物理除臭剂是通过物理方法进行除臭,利用除臭剂或者臭气的物理性质,不改变臭气组分,只改变臭气的局部浓度,或者说是相对浓度。常见的有吸附除臭剂、遮掩除臭剂等。吸附性除臭剂常采用活性炭,通常能吸附减少空气中恶臭浓度以达到除臭的目的。掩蔽除臭剂是用天然芳香油、香料等物质掩蔽恶臭,例如酒店卫生间喷洒香水,放置卫生球等;化学除臭剂是利用氧化还原、中和、加成、缩合反应等将产生的恶臭物质变为无臭物质从而消除臭气。常见的有氧化除臭剂、盐类化合物除臭剂、酸、碱制剂除臭剂等。氧化除臭剂是采用氧化剂将臭气中的有机硫等物质氧化成臭味较轻或溶解度较高的化合物,然后使用酸碱吸收净化。盐类化合物除臭剂,例如二价铁离子和抗坏血酸在一起抑制氧化,与硫醇等恶臭物质反应使之变成无臭物质;酸碱除臭剂,例如氧化锌与硫化氢发生反应,可以去除空气中的硫化氢气体等;微生物法脱硫除臭是在水、微生物和氧存在的条件下,利用微生物的代谢作用氧化分解发臭物质,以达到净化气体的目的。微生物处理大致可以分为3个过程:发臭物质被载体(固定有微生物)吸附;发臭物质向微生物表面扩散、被微生物吸附;微生物将发臭物质氧化分解。不含氮的恶臭物质被分解成CO2和H2O,含硫恶臭物质被分解成S、SO3 2-、SO4 2-,含氮恶臭物质则被分解成NH4 +,NO2 -,NO3 -。现有的除臭剂,功能单一,都不能适用于煤制甲醇的杂醇油的脱硫除臭。
针对煤制甲醇所产生的杂醇油刺鼻的臭味,提出了一种煤制甲醇的杂醇油臭味的去除方法。
发明内容
煤制甲醇的杂醇油的主要成分是各种醇的混合物,还含有极少量的硫醇、硫化氢等含硫化合物。煤制甲醇的杂醇油的刺鼻难闻臭味就是硫化物引起的。脱硫除臭方法很多,对于空气中的臭味、垃圾场的臭味、粪便的臭味、养殖场的臭味等等,不同的臭味采用不同的除臭方法。经过千百万次的试验,针对煤制甲醇杂醇油的臭味,使用次氯酸钙、亚氯酸钠、三氟甲烷磺酸钠、膨润土、明矾、硫酸锌、硫酸钠、氧化锌的试剂处理效果较好。煤制甲醇杂醇油臭味去除剂,其质量百分比如下:
把上述原料按照膨润土、明矾、硫酸锌、硫酸钠、氧化锌的顺序放入混合容器内,混合均匀,加入次氯酸钙、亚氯酸钠和三氟甲烷磺酸钠,混合均匀备用。
取杂醇油臭味去除剂1—20g,加入到1000—20000ml杂醇油中,充分搅拌,过滤,可得到无味的杂醇油。
杂醇油臭味去除剂除臭效果明显,成本低,工艺简单,容易操作,用户愿意使用,无任何排放,无污染、环保,可推广。
具体实施方式
实施例一
按照膨润土、明矾、硫酸锌、硫酸钠、氧化锌的顺序放入混合容器内,混合均匀,加入次氯酸钙、亚氯酸钠和三氟甲烷磺酸钠,混合均匀备用。
取杂醇油臭味去除剂1g,加入到1000ml杂醇油中,充分搅拌,过滤,可得到无味的杂醇油。
实施例二
按照膨润土、明矾、硫酸锌、硫酸钠、氧化锌的顺序放入混合容器内,混合均匀,加入次氯酸钙、亚氯酸钠和三氟甲烷磺酸钠,混合均匀备用。
取杂醇油臭味去除剂2g,加入到2500ml杂醇油中,充分搅拌,过滤,可得到无味的杂醇油。
Claims (2)
1.一种杂醇油臭味去除剂的制备方法及应用,其特征在于具有下列百分组成:
以上各组分之和等于100。
2.根据权利要求1所述,其特征还在于,按照膨润土、明矾、硫酸锌、硫酸钠、氧化锌的顺序放入混合容器内,混合均匀,加入次氯酸钙、亚氯酸钠和三氟甲烷磺酸钠,混合均匀备用。
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