CN1089035C - 用于糠醛气相加氢制2－甲基呋喃的催化剂及其用途 - Google Patents
用于糠醛气相加氢制2－甲基呋喃的催化剂及其用途 Download PDFInfo
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 9
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
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- QKICWELGRMTQCR-UHFFFAOYSA-N 4-[(7-chloroquinolin-4-yl)azaniumyl]pentyl-diethylazanium;dihydrogen phosphate Chemical compound OP(O)(O)=O.OP(O)(O)=O.ClC1=CC=C2C(NC(C)CCCN(CC)CC)=CC=NC2=C1 QKICWELGRMTQCR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- JACTTWVLMNPJQA-UHFFFAOYSA-N azane;quinoline Chemical compound N.N1=CC=CC2=CC=CC=C21 JACTTWVLMNPJQA-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种用于糠醛气相加氢制2-甲基呋喃的催化剂及其用途，催化剂的各组份重量百分比为：CuO 50-53% Cr2O3 46-49% NiO0.2-1.1%。催化剂在氢气气氛中还原活化，然后装在固定床反应器内，反应温度230-250℃，反应压力小于0.06MPa，糠醛液体空速为0.4-0.5hr-1。本发明的催化剂具有较高的活性和选择性，糠醛转化率100%，2-甲基呋喃选择性95-97%，可用于糠醛气相加氢制2-甲基呋喃工业生产。
Description
本发明属于催化剂及用途，具体地说涉及一种用于糠醛气相加氢制2-甲基呋喃的催化剂及其用途。
2-甲基呋喃是一种重要的有机化工中间体，广泛应用于医药、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。
目前工业上制取2-甲基呋喃都是采用糠醛气相催化加氢法生产。我国是糠醛生产大国，在糠醛深加工产品中，2-甲基呋喃是价值很高的一种产品。
苏联专利SU941366报导用CuO-Cr2O3/石墨或Al2O3作催化剂，进行糠醛气相加氢制2-甲基呋喃，在温度200-300℃，反应压力0.005-0.3MPa，液空0.25-0.5条件下，2-甲基呋喃收率仅为90％，这样副产物较多，增加后处理分离困难。
中国专利ZL95111759.9，“糠醛气相加氢合成2-甲基呋喃催化剂”公开的催化剂，由Al2O3、CuO、Cr2O3、为主要成份，添加碱金属和碱土金碱以及其它元素而成。催化剂组成为CuO 5-15％，Cr2O3 0.5-5％，Al2O3 80-90％ 0.001-2％的至少一种选自碱金属和碱土金属的氧化物，0.01-2％的至少一种选自P、Bi、Ce、Mo、Zn、Cr、B、Co的氧化物。在230-240℃常压，空速0.25-0.4hr-1条件下，糠醛转化率99-100％，2-甲基呋喃收率92.5-94％。该催化剂用于糠醛气相加氢制2-甲基呋喃反应虽然达到了产品收率高，副产物少的目的，但液体空速较低，催化剂组成复杂。
本发明的目的在于提供一种组成简单，用于糠醛气相加氢制2-甲基呋喃收率高、使用液体空速高的催化剂及其用途。
本发明的催化剂各组份重量百分比为：
CuO 50-53％ Cr2O3 46-49％ NiO 0.2-1.1％
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CuO 50-53％ Cr2O3 46-49％ NiO 0.2-1.1％配制成浓度为1-2M金属盐溶液；
2.将金属盐溶液和碱性沉淀剂，在温度50-60℃下，搅拌下混合，得到沉淀，搅拌时间为1小时，然后老化1小时；
3.沉淀物经洗涤过滤，在100-120℃干燥12小时，并在350℃下焙烧3小时，最后加入少于2％的石墨粉成型即得催化剂。
本发明与现有技术相比具有如下优点：
催化剂具有较高的活性和选择性，糠醛转化率100％，2-甲基呋喃选择性95-97％。
本发明的实施例如下：
实施例1
(1)催化剂制备过程：称取硝酸铜77.2g，铬酐32.2g，硝酸镍0.6g，将它们溶于600ml去离子水中，配制成溶剂。将该溶剂和氨水沉淀剂在50-60℃下搅拌，混合得到沉淀，然后老化1hr，沉淀物经洗涤过滤，在110℃干燥12hr，并在350℃焙烧3hr。最后加入1％石墨粉压片成型，得到所需催化剂样品。
(2)反应性能：
催化剂(20-40目)装填于不锈钢管式反应器(Φ12×600mm)内，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，尾气放空。
在反应温度232℃，压力0.05MPa，液体空速0.41hr-1条件下，糠醛转化率约100％，2-甲基呋喃选择性95.2％。
实施例2
(1)催化剂制备过程：
称取硝酸铜78.6g，铬酐31.3g，硝酸镍1.6g，其它同实施例1。
(2)反应性能：
在240℃，0.04MPa，气体空速0.43hr-1条件下，糠醛转化率100％，2-甲基呋喃选择性96.1％。
实施例3
(1)催化剂制备过程：
称取硝酸铜79.6g，铬酐30.6g，硝酸镍2.1g，其余同实施例1。
(2)反应性能：
在247℃，0.05MPa，气体空速0.47hr-1条件下，糠醛转化率100％，2-甲基呋喃选择性96.7％。
Claims (2)
1.一种用于糠醛气相加氢制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 50-53％ Cr2O3 46-49％ NiO 0.2-1.1％。
2.一种用于糠醛气相加氢制2-甲基呋喃的催化剂的用途，其特征在于催化剂在氢气气氛中还原活化，然后装在固定床反应器内，反应温度230-250℃，反应压力小于0.06MPa，糠醛液体空速为0.4-0.5hr-1。
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| CN00120872A CN1089035C (zh) | 2000-08-04 | 2000-08-04 | 用于糠醛气相加氢制2－甲基呋喃的催化剂及其用途 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101961652B (zh) * | 2010-10-14 | 2013-06-26 | 来安县迅能催化剂有限公司 | 一种糠醛气相加氢制2-甲基呋喃的催化剂及其制备方法 |
| CN104549319B (zh) * | 2013-10-24 | 2018-07-20 | 中国石油化工股份有限公司 | 一种糠醛气相加氢制2-甲基呋喃的催化剂及制备方法 |
| CN106902840B (zh) * | 2015-12-22 | 2019-06-11 | 中国石油天然气股份有限公司 | 一种用于糠醛气相加氢制2-甲基呋喃的催化剂及其制备方法 |
| CN106496165B (zh) * | 2016-10-31 | 2018-11-20 | 中国科学院过程工程研究所 | 一种催化转化糠醛的方法 |
| CN110054602A (zh) * | 2019-04-25 | 2019-07-26 | 黑龙江大学 | 一种糠醛加氢制2-甲基呋喃的方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5813576A (ja) * | 1981-07-14 | 1983-01-26 | Sumitomo Chem Co Ltd | ２，５−ジメチルフランの製造法 |
| CN1116610A (zh) * | 1995-08-14 | 1996-02-14 | 青岛化工医药进出口股份有限公司 | 从糠醛加氢制糠醇的废催化剂中提取重铬酸钠和硝酸铜的方法 |
| CN1145274A (zh) * | 1995-09-15 | 1997-03-19 | 中国石油化工总公司上海石油化工研究院 | 糠醛气相加氢合成2-甲基呋喃催化剂 |
| CN1256965A (zh) * | 1999-11-10 | 2000-06-21 | 天津大学 | 糠醛气相加氢生产糠醇的催化剂及其制备方法 |
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2000
- 2000-08-04 CN CN00120872A patent/CN1089035C/zh not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5813576A (ja) * | 1981-07-14 | 1983-01-26 | Sumitomo Chem Co Ltd | ２，５−ジメチルフランの製造法 |
| CN1116610A (zh) * | 1995-08-14 | 1996-02-14 | 青岛化工医药进出口股份有限公司 | 从糠醛加氢制糠醇的废催化剂中提取重铬酸钠和硝酸铜的方法 |
| CN1145274A (zh) * | 1995-09-15 | 1997-03-19 | 中国石油化工总公司上海石油化工研究院 | 糠醛气相加氢合成2-甲基呋喃催化剂 |
| CN1256965A (zh) * | 1999-11-10 | 2000-06-21 | 天津大学 | 糠醛气相加氢生产糠醇的催化剂及其制备方法 |
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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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| 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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| CP03 | Change of name, title or address | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20020814 |