CN116514653A - 一种醋酸乙酯的生产工艺 - Google Patents
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 119
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 87
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract
本发明属于醋酸乙酯合成技术领域,尤其是一种醋酸乙酯的生产工艺,本发明合成方法使用的离子液体接枝硅胶催化剂具有选择性好,反应速率快,对设备腐蚀小对环境污染小。催化剂稳定不挥发,对热稳定,环境污染小的优势。比于传统反应精馏,操作成本降低,以往离子液体在反应过程中活性组分会逐渐流失,离子液体接枝硅胶催化剂便于离子液体的重复使用,将酸性离子液体接枝到硅胶微球上,用于醋酸和乙醇的酯化反应,表现出良好的催化活性,催化剂重复使用后,反应活性和收率未明显降低。
Description
技术领域
本发明属于醋酸乙酯合成技术领域,尤其是一种醋酸乙酯的生产工艺。
背景技术
醋酸乙酯是一种具有水果香味,外观为无色透明的油状液体。在有机合成领域,醋酸乙酯既可以在涂料、纤维、人造革的生产过程中作为溶剂被使用,又可以在印刷油墨生产领域被用作为一种性能优良的黏合剂,在精细化学品的生产中它还可以作为香料、表面活性剂和食品添加剂被使用。中国专利CN201711152064.3公开了一种醋酸乙酯的合成方法,依次按醋酸、氢氧化钠和醋酸浸泡的顺序对大孔型阳离子交换树脂浸泡,但工序繁琐,纯度不高,催化剂易破碎粉化以及杂质积累而流失或催化活性降低,导致后续工程难题。醋酸乙酯的传统工业生产方法主要是以浓硫酸为催化剂,不足之处在于此反应以浓硫酸为催化剂,对设备腐蚀严重,反应产生的废液成分复杂且分离困难容易造成环境污染;转化率不高且在常温下反应物与产物容易混合形成共沸物,分离与提纯的难度大。该工艺粗放,与当前绿色化工理念相悖。乙醇脱氢法采用铜基催化剂不会生成大量的含酸废水,对环境污染小,且对设备腐蚀较小,设备费较乙酸酯化法,但是催化剂使用后为避免氧化需用保护气保护,过程繁琐。本领域技术人员为解决上述问题,亟待开发一种醋酸乙酯的生产工艺及其应用以满足现有的市场需求和性能要求。
发明内容
针对上述问题,本发明旨在提供一种醋酸乙酯的生产工艺及其应用。
一种醋酸乙酯的生产工艺,包括以下步骤:
(2)按一定比例将醋酸从醋酸储罐通过醋酸加料泵送往醋酸乙酯合成塔上部,同时也按一定比例将乙醇从乙醇储罐通过乙醇加料泵送往乙醇回收塔中与乙醇回收塔塔顶产生的气相乙醇一起再通过泵送往醋酸乙酯合成塔下部,对合成塔进行蒸汽套夹加热,将合成塔内温度升高,气压为130~140kPa,乙醇和醋酸在合成塔内经离子液体接枝硅胶催化剂催化生成醋酸乙酯和水,塔顶气相物料首先进入合成塔馏出冷凝器冷凝后得到冷凝液,即醋酸乙酯粗品,送往醋酸乙酯精制塔进行精制;
由于醋酸乙酯的沸点为77℃,因此合成塔塔顶出来的气相物料主要为醋酸乙酯、少量的乙醇、微量的醋酸和水,送入萃取塔进料罐。
进行一级冷凝,一级冷凝冷却水进水温度为32℃,再进入合成塔尾气冷凝器进行二级冷凝,二级冷凝冷冻水进水温度为5℃,两级冷凝,冷凝效率99.9%,醋酸乙酯连续从反应精馏塔塔顶采出。
(2)进入乙酯精制塔,在塔底得到精制醋酸乙酯。
进一步的,所述反应精馏塔中进行常压操作,回流比2.3~2.5,顶温67~68.5℃,釜温92~96℃。
进一步的,乙醇与醋酸的摩尔比=1.1~1.2∶1
进一步的,所述离子液体接枝硅胶催化剂按照以下步骤制备:(1)按重量份数计,将19~20份氯甲基化硅胶球加入反应釜中,再加入37~40份无水乙醇和18~20份咪唑,然后将该混合物在90℃搅拌下反应24小时,反应完成后,过滤该混合物得到固体产物;(2)将得到的固体产物用去离子水洗涤,并在60℃真空干燥6小时后再与18份的1,4-丁磺酸内酯和80~90份无水乙醇在55~60℃反应24小时,得到接枝硅胶球;(3)将接枝硅胶球用去离子水反复洗涤,并在50~60℃下真空干燥6小时后,在55~60℃的500rpm搅拌条件下,用硫酸45~50份和无水乙醇45~50份直接酸化12小时,通过过滤收集,并用大量去离子水洗涤,并在60℃下真空干燥12小时,即得离子液体接枝硅胶催化剂。先将氯甲基三乙氧基硅烷溶于甲苯中,加入干燥后的硅胶,加热回流6h过滤,用索氏提取法除去未反应的氯甲基三乙氧基硅烷,真空干燥后即得氯甲基化硅胶。
反应简式如下所示:
本发明合成方法使用的离子液体接枝硅胶催化剂具有选择性好,反应速率快,对设备腐蚀小对环境污染小,催化剂稳定的优点,不挥发,对热稳定,环境污染小的优势。比于传统反应精馏,操作成本降低,以往离子液体在反应过程中活性组分会逐渐流失,离子液体接枝硅胶催化剂便于离子液体的重复使用,将酸性离子液体接枝到硅胶微球上,用于醋酸和乙醇的酯化反应,表现出良好的催化活性,催化剂重复使用后,反应活性和收率未明显降低。将离子液体接枝硅胶催化剂用于催化合成乙酸乙酯,与未接枝的离子液体接枝硅胶催化剂相比,具有较高的活性,在产物分离及重复使用方面具有优势,反应后催化剂通过简单分离即可重复使用。
实施方式
下面用具体实施例说明本发明,但并不是对本发明的限制。
实施例
河北宏林硅胶有限公司的平均粒径150μm,总孔容0.35ml/g、比表面积600m²/g、孔径分布1.5~8.0nm、堆积密度790g/L、磨损率0.8%、含水率1%、二氧化硅含量99%、比电阻≥3000Ω·㎝。
第一步、硅胶氯甲基化:先将氯甲基三乙氧基硅烷溶于甲苯中,形成质量分数20%的溶液,加入干燥后的硅胶球且浴比1∶3,加热回流6h过滤,用索氏提取法除去未反应的氯甲基三乙氧基硅烷,50℃真空干燥后得氯甲基化硅胶;第二步、离子液体接枝硅胶催化剂的制备:按重量份数计,将19份氯甲基化硅胶球加入反应釜中,再加入37份无水乙醇和18份咪唑,然后将该混合物在90℃500rpm搅拌下反应24小时,反应完成后,过滤该混合物以得到固体产物;第三步、将得到的固体产物用去离子水洗涤,并在55℃真空干燥6小时后再与18份的1,4-丁磺酸内酯和90份无水乙醇在55℃反应24小时,得到接枝硅胶球,将接枝硅胶球用去离子水反复洗涤,并在50℃下真空干燥6小时后,在55℃的500rpm搅拌条件下,用硫酸45份和无水乙醇45份直接酸化12小时,通过过滤收集,并用大量去离子水洗涤,并在55℃下真空干燥12小时,即得离子液体接枝硅胶催化剂。
第四步、醋酸乙酯合成:乙醇与醋酸的摩尔比=1.1∶1,将醋酸从醋酸储罐通过醋酸加料泵送往醋酸乙酯合成塔上部,同时将乙醇从乙醇储罐通过乙醇加料泵送往乙醇回收塔中与乙醇回收塔塔顶产生的气相乙醇一起再通过泵送往醋酸乙酯合成塔下部,离子液体接枝硅胶催化剂占乙醇与醋酸反应物总质量的6%,对合成塔进行蒸汽套夹加热,将合成塔内温度升高至96℃,气压为140KPa,回流比2.3,顶温67℃,乙醇和醋酸在合成塔内经离子液体接枝硅胶催化剂催化生成醋酸乙酯和水。由于醋酸乙酯的沸点为77℃,因此合成塔塔顶出来的气相物料主要为醋酸乙酯、少量的乙醇、微量的醋酸和水,送入萃取塔进料罐。塔顶气相物料首先进入合成塔馏出冷凝器进行一级冷凝,一级冷凝冷却水进水温度为32℃,再进入合成塔尾气冷凝器进行二级冷凝,二级冷凝冷冻水进水温度为5℃,两级冷凝(冷凝效率99.9%)后得到冷凝液,即醋酸乙酯粗品,送往醋酸乙酯精制塔进行精制。水相送往脱轻塔进料罐。40℃萃取塔主要处理合成塔馏出、精制塔馏出和脱轻塔馏出的物料,三者物料进入萃取塔进料罐,经泵送入萃取塔底部,与塔顶加入的水逆流接触后,油相从顶部馏出至萃取塔顶罐,经泵送往精制塔处理,萃取塔底部为水相,送往脱轻塔进料罐。萃取塔油相进入精制塔分离,控制塔压力至0.4MPa,塔顶为乙酯、水及少量乙醇,冷却至常温后进入精制塔分相罐,油相进入馏出槽,水相进入脱轻塔进料罐,油相经泵一部分回流,一部分送往精制塔进料罐,总收率96.8%。
实施例
硅胶购自皖西硅源材料厂的平均粒径150μm,总孔容0.35ml/g、比表面积600m²/g、孔径分布1.2~8.0nm、堆积密度780g/L、磨损率1.0%、含水率1%、二氧化硅含量99%、比电阻≥3000Ω·㎝,泰丰化工95%氯甲基三乙氧基硅烷。
第一步、硅胶氯甲基化:先将氯甲基三乙氧基硅烷溶于甲苯中,形成质量分数20%的溶液,加入干燥后的硅胶球且浴比1∶3,加热回流6h过滤,用索式提取法除去未反应的氯甲基三乙氧基硅烷,50℃真空干燥后得氯甲基化硅胶;第二步、离子液体接枝硅胶催化剂的制备:按重量份数计,将20份氯甲基化硅胶球加入反应釜中,再加入40份无水乙醇和20份咪唑,然后将该混合物在90℃500rpm搅拌下反应24小时,反应完成后,过滤该混合物以得到固体产物;第三步、将得到的固体产物用去离子水洗涤,并在60℃真空干燥6小时后再与20份的1,4-丁磺酸内酯和100份无水乙醇在60℃反应24小时,得到接枝硅胶球,将接枝硅胶球用去离子水反复洗涤,并在60℃下真空干燥6小时后,在60℃的500rpm搅拌条件下,用硫酸50份和无水乙醇50份直接酸化12小时,通过过滤收集,并用大量去离子水洗涤,并在60℃下真空干燥12小时,即得离子液体接枝硅胶催化剂。
第四步、醋酸乙酯合成:乙醇与醋酸的摩尔比=1.2∶1,将醋酸从醋酸储罐通过醋酸加料泵送往醋酸乙酯合成塔上部,同时将乙醇从乙醇储罐通过乙醇加料泵送往乙醇回收塔中与乙醇回收塔塔顶产生的气相乙醇一起再通过泵送往醋酸乙酯合成塔下部。对合成塔进行蒸汽套夹加热,将合成塔内温度升高至92℃,气压为130KPa,回流比2.5,顶温68.5℃,乙醇和醋酸在合成塔内经离子液体接枝硅胶催化剂催化生成醋酸乙酯和水,离子液体接枝硅胶催化剂占乙醇与醋酸反应物总质量的5%,由于醋酸乙酯的沸点为77℃,因此合成塔塔顶出来的气相物料主要为醋酸乙酯、少量的乙醇、微量的醋酸和水,送入萃取塔进料罐。塔顶气相物料首先进入合成塔馏出冷凝器进行一级冷凝,一级冷凝冷却水进水温度为32℃,再进入合成塔尾气冷凝器进行二级冷凝,二级冷凝冷冻水进水温度为5℃,两级冷凝,冷凝效率99.9%,后得到冷凝液,即醋酸乙酯粗品,送往醋酸乙酯精制塔进行精制。水相送往脱轻塔进料罐。40℃萃取塔主要处理合成塔馏出、精制塔馏出和脱轻塔馏出的物料,三者物料进入萃取塔进料罐,经泵送入萃取塔底部,与塔顶加入的水逆流接触后,油相从顶部馏出至萃取塔顶罐,经泵送往精制塔处理,萃取塔底部为水相,送往脱轻塔进料罐。萃取塔油相进入精制塔分离,控制塔压力至0.4MPa,塔顶为乙酯、水及少量乙醇,冷却至常温后进入精制塔分相罐,油相进入馏出槽,水相进入脱轻塔进料罐,油相经泵,一部分回流,一部分送往精制塔进料罐,乙酸乙酯总收率96.2%。
实施例
实施例1重复使用8次后的离子液体接枝硅胶催化剂,按照实施例1的合成方法进行合成,乙酸乙酯总收率91.2%。
将实施例1~3得到的醋酸乙酯进行性能检测,检测结果见表1
表1实施例1~3得到的醋酸乙酯进行性能检测结果
注:含量的测定检测器(FID):温度(℃)250、氢气流量(mL/min)30、空气流量(mL/min)300、尾吹气流量(mL/min)25、载气及流量(mL/min)氮气25、进样口:温度(℃)220、进样模式分流、分流比150:1、隔垫吹扫流量(mL/min)3、柱温:程序升温、初始温度(℃)40、保持时间(min)0、升温速率(℃/min)15、结束温度(℃)90、保持时间(min)0、升温速率(℃/min)25、结束温度(℃)230、保持时间(min)2、进样量(μL)1、色谱柱指标Heff≤12mm、色谱柱J&W122-1334;260℃:30m×250μm×1.4μm;DB-624:1181.59898。蒸发残渣量取100g样品,按GB/T9740的规定测定;水分量取5g样品(5.55mL)须量准至0.1mL,注入梅特勒-托利多V20型卡尔费休滴定仪。
Claims (5)
1.一种醋酸乙酯的生产工艺,其特征在于,包括以下步骤:
(1)按一定比例将醋酸送往醋酸乙酯合成塔上部,同时也按一定比例将乙醇送往醋酸乙酯合成塔下部,对合成塔进行蒸汽套夹加热,将合成塔内温度升高至92~96℃,气压为135~140KPa,乙醇和醋酸在合成塔内经离子液体接枝硅胶催化剂催化生成醋酸乙酯和水,塔顶气相物料进入合成塔馏出冷凝器进行冷凝后得到冷凝液,即醋酸乙酯粗品,送往醋酸乙酯精制塔进行精制;(2)进入醋酸乙酯精制塔,在塔底得到精制醋酸乙酯。
2.根据权利要求1所述的醋酸乙酯的生产工艺,其特征在于,所述醋酸乙酯合成塔回流比2.3~2.5,顶温67~68.5℃。
3.根据权利要求1所述的醋酸乙酯的生产工艺,其特征在于,所述乙醇与醋酸的摩尔比=1.1~1.2∶1。
4.根据权利要求1所述的醋酸乙酯的生产工艺,其特征在于,所述离子液体接枝硅胶催化剂占乙醇与醋酸反应物总质量的5%~6%。
5.根据权利要求1所述的醋酸乙酯的生产工艺,其特征在于:所述离子液体接枝硅胶催化剂按照以下步骤制备:(1)按重量份数计,将19~20份氯甲基化硅胶球加入反应釜中,再加入37~40份无水乙醇和18~20份咪唑,然后将该混合物在90℃搅拌下反应24小时,反应完成后,过滤该混合物得到固体产物;(2)将得到的固体产物用去离子水洗涤,并在60℃真空干燥6小时后再与18份的1,4-丁磺酸内酯和80~90份无水乙醇在55~60℃反应24小时,得到接枝硅胶球;(3)将接枝硅胶球用去离子水反复洗涤,并在50~60℃下真空干燥6小时后,在55~60℃的500rpm搅拌条件下,用硫酸45~50份和无水乙醇45~50份直接酸化12小时,通过过滤收集,并用大量去离子水洗涤,并在60℃下真空干燥12小时,即得离子液体接枝硅胶催化剂。
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