CN1137111C - 制备γ-丁内酯和2-甲基呋喃的催化剂及用途 - Google Patents
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Abstract
一种制备2-甲基呋喃和γ-丁内酯的催化剂的各组份重量百分比为：CuO 45-62%，ZnO 30-40%，Cr2O3 5-15%。催化剂装在固定床反应器内，反应温度200-225℃，反应压力0.01-0.06Mpa，本发明的催化剂具有较高的活性，糠醛转化率大于98%，1，4-丁二醇转化率大于95%，2-甲基呋喃和γ-丁内酯的总选择性大于84%。
Description
技术领域：
本发明属于一种催化剂及其用途，具体地说是一种耦合法用于1，4-丁二醇脱氢和糠醛加氢一体化制备γ-丁内酯和2-甲基呋喃的催化剂及其用途。
背景技术：
γ-丁内酯是一种重要的有机化工产品，广泛应用石油化工、医药、染料、农药及精细化工方面，近年来尤其在合成吡咯烷酮、N-甲基吡咯烷酮、乙烯基吡咯烷酮、α-乙酰基丁内酯等重要产品中应用量较大。另外γ-丁内酯还是高沸点溶剂，溶解力强，导电性和稳定性好，使用和管理安全方便。
2-甲基呋喃主要应用于医药、农药及精细化工方面；尤其在医药工业中2-甲基呋喃作为药物中间体，用于制取维生素B1，磷酸氯喹和磷酸佰氨喹等药物。
中国专利(申请号01141836.2)介绍了1，4-丁二醇脱氢和糠醛加氢为原料的耦合制备γ-丁内酯和2-甲基呋喃的原理：该过程提供一种无需氢气源，用1，4-丁二醇和糠醛为原料的耦合制备γ-丁内酯和2-甲基呋喃的方法。传统的技术路线，采用1，4-丁二醇脱氢生产γ-丁内酯副产氢气直接放空，或经过多种单元操作进行回收，增加生产成本。另外，糠醛加氢生产2-甲基呋喃企业，氢气源需从别处购买或建造制氢设备，增加了成本；所以两个过程和二为一，能充分利用氢气源。
1，4-丁二醇 糠醛 γ-丁内酯 2-甲基呋喃
从上面加氢脱氢耦合方程式可得，糠醛和1，4-丁二醇摩尔比为1∶1即可，考虑实际过程中系统漏气，惰性气体累计需要放空等因素，一般采取1，4-丁二醇少过量。
糠醛加氢制2-甲基呋喃热效应为-142KJ/mol，属强放热反应；而1，4-丁二醇脱氢制γ-丁内酯热效应为+61.6KJ/mol，为中等强度吸热反应。二者耦合后热效应为-142+61.6＝-80.4KJ/mol＝-19.2kcal/mol，即变为中等强度放热反应；若考虑实际上1，4-丁二醇过量，则热效应变为微放热或等温反应，加氢脱氢一体化无疑是一个高效过程。
发明内容：
本发明的目的在于提供一种具有活性好和选择性高的用于糠醛加氢和1，4-丁二醇脱氢耦合法制备2-甲基呋喃和γ-丁内酯的催化剂及其用途。
本发明的催化剂各组份重量百分比为：
CuO 45-62％ ZnO 30-40％ Cr2O3 5-15％
本发明的催化剂是采用沉淀法制备的，具体步骤如下：
1.按催化剂的组成配制成浓度为1M金属盐溶液；
2.将金属盐溶液和碱性沉淀剂，在温度约55℃下，搅拌下混合，得到沉淀，搅拌时间为1小时，然后老化约4小时；
3.沉淀物经洗涤过滤，在100-120℃干燥8小时，并在350℃下焙烧5小时，最后碾磨即得催化剂。
如上所述的碱性沉淀剂是氨水、碳酸钠、碳酸铵等。
本发明催化剂应用时的反应条件为温度200-225℃，压力0.01-0.06Mpa。
本发明与现有技术相比具有如下优点：
催化剂有较高的活性和选择性，糠醛转化率大于98％，1，4-丁二醇转化率大于95％，2-甲基呋喃和γ-丁内酯的总选择性大于84％。
具体实施方式：
实施例1
(1)催化剂制备过程：称取硝酸铜76g，硝酸锌67.6g，硝酸铬34.2g，其组成为CuO 50％，ZnO 37％，Cr2O3 13％。将它们溶于700ml去离子水中，配制成溶剂。将该溶液和碳酸钠沉淀剂在约55℃下搅拌，混合得到沉淀，然后老化4hr，沉淀物经洗涤过滤，在110℃干燥8hr，并在350℃焙烧5hr。最后加入1％石墨粉压片成型，碾磨为20-40目的催化剂样品。
(2)反应性能：
催化剂活性和选择性评价在固定床评价装置(俗称小试装置)上进行的。其中反应器由内径12mm、长600mm的不锈钢管制成，中心有4mm热偶套管，外有金属套管，其上缠有电炉丝。反应温度由插入中心套管的1mm铠装热电偶测量，并用温控仪(通过固态继电器)控制。每次评价装入催化剂(20-40目)15克，约12毫升。催化剂床层高度约140mm，位于反应管中部。活性评价前催化剂需用氢氮气还原，还原气空速＞500h-1。还原过程床层逐渐升温，由120℃至240℃约需12小时。还原结束，切换为氢气后，即可投料。
钢瓶氢气经定压稳压后，通过转子流量计进入汽化器，与从计量泵输送来的1，4-丁二醇和糠醛，在汽化器中混合并进行汽化，再经预热器加热至反应温度后进入反应器，产物经冷凝进入气液分离器，收集于储罐中，供分析用。反应正常后，并不需要额外补加氢气，依靠自身反应释放的氢气耦合运转。
在反应温度220℃，压力0.02MPa，氢油比40，1，4-丁二醇/糠醛摩尔比1.05条件下，1，4-丁二醇转化率约96.8％，糠醛转化率99.3％，总选择性84.2％。
实施例2
(1)催化剂制备过程：
称取硝酸铜83.6g，硝酸锌64g，硝酸铬26.3g，其组成为CuO 55％，ZnO 35％，Cr2O3 10％。其它同实施例1。
(2)反应性能：
在210℃，0.05MPa，氢油比35，1，4-丁二醇/糠醛摩尔比1.05条件下，1，4-丁二醇转化率95.6％，糠醛转化率98.6％，总选择性85.1％。
实施例3
(1)催化剂制备过程：称取硝酸铜91.2g，硝酸锌60.3g，硝酸铬18.4g，其组成为CuO 60％，ZnO 33％，Cr2O3 7％。其它同实施例1。
(2)反应性能：在205℃，0.03MPa，氢油比30，丁二醇/糠醛摩尔比1.05条件下，1，4-丁二醇转化率95.1％，糠醛转化率98.1％，总选择性86.8％。
Claims (2)
1.一种制备γ-丁内酯和2-甲基呋喃的催化剂，其特征在于催化剂的各组份重量百分比为：
CuO 45-62％ ZnO 30-40％ Cr2O3 5-15％。
2.如权利要求1所述的催化剂在制备γ-丁内酯和2-甲基呋喃中的应用，其特征在于反应条件为温度200-225℃，压力0.01-0.06Mpa。
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Owner name: ZHONGKE OIL PROJECT CO., LTD. Free format text: FORMER OWNER: SHANXI INST. OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20081017 |
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Effective date of registration: 20081017 Address after: 3, building 1, Tsinghua Science and Technology Park, No. 609, Zhongguancun East Road, Beijing, Haidian District Patentee after: SYNEFUELS CHINA Inc. Address before: 165 mailbox, Taiyuan City, Shanxi Province Patentee before: INSTITUTE OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES |
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Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee after: Synefuels China Inc. Address before: 100195, Haidian District Zhongguancun East Road, No. 1, building 3, Tsinghua Science and Technology Park, pioneering building, 609, Beijing Patentee before: Synefuels China Inc. |
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Owner name: SYNEFUELS CHINA CO., LTD. Free format text: FORMER NAME: SYNEFUELS CHINA INC. |
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Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee after: SYNFUELS CHINA Address before: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee before: Synefuels China Inc. |
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Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone Park south two Street No. 1 Patentee after: SYNEFUELS CHINA Inc. Address before: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee before: SYNFUELS CHINA |
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Granted publication date: 20040204 |