CN1562474A - 一种耦合法制备γ－丁内酯的催化剂及其用途 - Google Patents
一种耦合法制备γ－丁内酯的催化剂及其用途 Download PDFInfo
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- 238000000034 method Methods 0.000 title description 10
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 44
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000010168 coupling process Methods 0.000 claims abstract description 14
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 17
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 8
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 6
- 230000008878 coupling Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
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- 239000002244 precipitate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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Abstract
一种耦合法制备γ－丁内酯的催化剂各组份重量百分比为：CuO 45－62％，ZnO 30－40％，Cr2O3 5－15％。顺酐加氢和1，4－丁二醇脱氢耦合法制备γ－丁内酯时，催化剂装在固定床反应器，液体空速为0.2－0.4h－1，反应条件为温度270－285℃，压力0.01－0.05MPa。本发明的催化剂具有较高的活性，顺酐转化率大于99％，1，4－丁二醇转化率100％，γ－丁内酯的总选择性大于95％。
Description
技术领域
本发明属于催化剂及其用途，具体地说是一种耦合法用于1，4-丁二醇脱氢和顺酐加氢一体化耦合制备γ-丁内酯的催化剂及其用途。
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。
中国专利(ZL00135620.8)介绍了1，4-丁二醇脱氢和顺酐加氢为原料的耦合制备γ-丁内酯的原理：该过程提供一种无需氢气源，用1，4-丁二醇和顺酐为原料的耦合制备γ-丁内酯的方法。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，顺酐加氢生产γ-丁内酯企业，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。
发明内容
本发明的目的是提供一种耦合法用于1，4-丁二醇脱氢和顺酐加氢一体化耦合制备γ-丁内酯的催化剂及其用途。
耦合反应方程式为：
1.5
1，4-丁二醇 顺酐 丁内酯
从上面的方程式可得，1，4-丁二醇和顺酐摩尔比1.5∶1，考虑实际过程中系统泄漏等因素，一般采取丁二醇少微过量比较合理。
加氢是放热反应，而脱氢则是吸热反应，二者结合可缓解反应过程中的热效应。顺酐加氢制γ-丁内酯热效应为-212KJ/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：
-212+61.6×1.5＝-119.6KJ/mol＝-28.6kcal/mol，即变为中等强度放热反应。加氢脱氢一体化是一个高效过程，节约了能源；耦合无疑将是一个高效的过程。
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约1-2M金属盐溶液；
2.将金属盐溶液和碱性沉淀剂，在温度约60℃下，搅拌下混合，得到沉淀，搅拌时间为1小时，然后老化约8小时；
3.沉淀物经洗涤过滤，在110-120℃干燥20小时，并在380℃下焙烧4小时，最后碾磨即得催化剂。
本发明的催化剂用于顺酐加氢和1，4-丁二醇脱氢耦合法制备2-甲基呋喃和γ-丁内酯，是将催化剂装在固定床反应器，液体空速为0.2-0.4h-1，反应条件为温度270-285℃，压力0.01-0.05Mpa。
本发明的目的在于提供一种制备方便、有较好的活性和选择性，用于顺酐加氢和1，4-丁二醇脱氢耦合法制备γ-丁内酯的催化剂。顺酐转化率大于99％，1，4-丁二醇转化率约100％，γ-丁内酯的总选择性大于95％。
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温度约60℃下，搅拌下混合，得到共沉淀物，继续搅拌时间为1小时，然后老化约8小时；沉淀物经洗涤过滤，在110℃干燥20hr，并在380℃焙烧4hr。最后加入1％石墨粉压片成型，碾磨为40-60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10mm、长650mm的不锈钢管制成，中心有ø3mm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ø1mm铠装热电偶测量，并用温控仪控制。每次评价装入催化剂(40-60目)15克，约13毫升。催化剂床层高度约150mm，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＞800h-1。还原时催化剂床层逐渐升温，由120℃至290℃约需20小时。还原结束，切换为氢气后，即可投料。
钢瓶氢气经过稳压后，通过转子流量计分别进入1，4-丁二醇和顺酐的汽化器，在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。
在反应温度270℃，压力0.02MPa，氢油摩尔比(即氢气摩尔数比上顺酐和1，4-丁二醇摩尔数总合)105，1，4-丁二醇/糠醛摩尔比1.55条件下，1，4-丁二醇转化率约100％，顺酐转化率99.1％，γ-丁内酯总选择性97.5.2％。
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280℃，0.04MPa，氢油摩尔比135，1，4-丁二醇/糠醛摩尔比1.65条件下，1，4-丁二醇转化率100％，顺酐转化率99.6％，γ-丁内酯总选择性96.3％。
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285℃，0.03MPa，氢油摩尔比160，丁二醇/糠醛摩尔比1.75条件下，1，4-丁二醇转化率100％，顺酐转化率99.8％，γ-丁内酯总选择性95.8％。
Claims (2)
1.一种耦合法制备γ-丁内酯的催化剂，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所述的一种耦合法制备γ-丁内酯的催化剂的用途，其特征在于顺酐加氢和1，4-丁二醇脱氢耦合法制备γ-丁内酯时，催化剂装在固定床反应器，液体空速为0.2-0.4h-1，反应条件为温度270-285℃，压力0.01-0.05Mpa。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380391A (zh) * | 2010-08-26 | 2012-03-21 | 中科合成油技术有限公司 | 选择性脱酸催化剂及其制备方法、以及其在对费托合成油进行选择性加氢脱酸处理中的应用 |
| CN112517013A (zh) * | 2020-12-23 | 2021-03-19 | 中科合成油技术有限公司 | Cu基催化剂以及用其制备γ-戊内酯和δ-环戊内酯的方法 |
| CN114539191A (zh) * | 2022-03-22 | 2022-05-27 | 滨州裕能化工有限公司 | 一种顺酐马来酐加氢和1,4丁二醇脱氢耦合法制备gbl的方法 |
-
2004
- 2004-03-16 CN CN 200410012192 patent/CN1255214C/zh not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380391A (zh) * | 2010-08-26 | 2012-03-21 | 中科合成油技术有限公司 | 选择性脱酸催化剂及其制备方法、以及其在对费托合成油进行选择性加氢脱酸处理中的应用 |
| CN112517013A (zh) * | 2020-12-23 | 2021-03-19 | 中科合成油技术有限公司 | Cu基催化剂以及用其制备γ-戊内酯和δ-环戊内酯的方法 |
| CN112517013B (zh) * | 2020-12-23 | 2023-07-28 | 中科合成油技术股份有限公司 | Cu基催化剂以及用其制备γ-戊内酯和δ-环戊内酯的方法 |
| CN114539191A (zh) * | 2022-03-22 | 2022-05-27 | 滨州裕能化工有限公司 | 一种顺酐马来酐加氢和1,4丁二醇脱氢耦合法制备gbl的方法 |
| CN114539191B (zh) * | 2022-03-22 | 2023-09-05 | 滨州裕能化工有限公司 | 一种顺酐马来酐加氢和1,4丁二醇脱氢耦合法制备gbl的方法 |
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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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| C56 | Change in the name or address of the patentee | ||
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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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| CP01 | Change in the name or title of a patent holder |
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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| CP03 | Change of name, title or address |
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: 20060510 |