CN1131655A - 1，2-丙二醇的制备方法 - Google Patents
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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
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
通过在高温和高压下甘油的催化氢化制备1，2-丙二醇的方法，包括使用水含量最高达20％(重量)的甘油和含有金属钴、铜、锰和钼的催化剂，按催化剂总重量计，该催化剂中各组分的含量为：40-70％(重量)钴，10-20％(重量)铜，0-10％(重量)锰，和0-10％(重量)钼，其中该催化活性物质还可以含有按催化剂总重量计最高达10％(重量)的无机多酸和/或杂多酸。
Description
本发明涉及通过在高温和高压下甘油的催化氢化制备1，2-丙二醇的方法，包括使用水含量最高达20％(重量)的甘油和含有金属钴、铜、锰和钼的催化剂，按催化剂总重量计，该催化剂中各组分的含量为：
40-10％(重量)钴，
10-20％(重量)铜，
0-10％(重量)锰，和
0-10％(重量)钼，其中该催化活性物质还可以含有按催化剂总重量计最高达10％(重量)的无机多酸和/或杂多酸。
甘油氢化制备1，2-丙二醇已经进行许多研究，但是由于收率不满意而未用于工业生产。最近有两份专利申请描述了用改进的载钌催化剂(EP-A-0523014)和用锌/铜催化剂(EP-A-0523015)进行甘油的氢化。虽然这些方法已取得优于现有技术的某些进展，但是还有一些缺点。
例如，这两份申请都在很稀的水溶液中进行氢解反应。使用的30％甘油水溶液被生成的反应水更进一步稀释。因此，为了分离丙二醇，必须首先用蒸馏除去大量水，这意味着消耗大量能量。
另外，选择性还不满意。实际上在消耗选择性的条件下达到定量转化。而间歇方法的选择性一般仅达到75-84％。
为了达到100转化，在用EP-A-0523014中的钌催化剂的情况下，必须另加按甘油计的10-45％的氢氧化钠。
EP-A-0415202描述了通过在高温和高压下用其活性物质主要含有金属钴、铜和锰的催化剂的蔗糖水溶液的催化氢化制备低级多元醇的方法。
本发明的目的是提供通过在高温和高压下甘油的催化氢化制备1，2-丙二醇的方法，该方法无上述缺点。
我们发现该目的由开头限定的方法达到。
新方法中使用的催化剂一般不含有催化剂载体，除了含有钴和铜外，优选含有锰和钼、磷酸和磷酸盐。
在优选方案中，催化剂含有40-70％(重量)钴(以CoO形式)，13-17％(重量)铜(以CuO形式)和3-8％(重量)锰(以MnO2形式)，和0.1-5％(重量)磷(以H3PO4形式)和0.5-5％(重量)钼(以MoO3形式)，在各种情况下均按催化剂总重量计。
特别优选的催化剂含有55-70(重量)CoO，13-17％(重量)CuO，4-6％(重量)MnO2，1-3％(重量)磷(以H3PO4形式)和1-4％(重量)MoO3。
新方法中使用的催化剂的制备一般包括用加入碱，优选无机碱水溶液，例如氢氧化钠溶液、氢氧化钾溶液或碳酸钠溶液，从这些金属的盐，例如其硝酸盐或乙酸盐的溶液中共沉淀出，例如成为这些金属的氧化物、氢氧化物、氧化物的水合物、碱式盐或碳酸盐的，分离、干燥和焙烧沉淀物。沉淀优选用DE-A-2321101中描述的方法进行。
在新方法中使用前，用该方法得到的催化剂通过用氢还原进行活化，在活化中其中存在的全部或部分金属化合物被还原成相应的金属。通常，该还原在高温，优选在200-400℃下，在氢气流中进行。
在沉淀之前通过将金属盐溶液与可形成多酸或杂多酸的无机酸或其盐混合可以得到具有特别优良机械性质的催化剂，所述的无机酸有例如硫酸、硼酸、磷酸、钼酸、钒酸或钨酸，所说的无机酸盐有例如磷酸三钠、四硼酸钠、磷酸二氢钾、磷酸氢钙、硼酸氢镁、磷酸铝、钼酸钠、钼酸铵、钒酸铵和/或钨酸钠，然后，按照EP-A-0415202中描述的方法进行沉淀，和进一步处理沉淀物。
用所述催化剂得到的氢化产物的组成取决于选择的反应温度。例如，如果在180-270℃，优选200-250℃进行新的甘油的氢化时，得到特别高的1，2-丙二醇收率。
根据本发明，甘油的氢化一般在100-700巴，优选在200-325巴的压力下进行。在较低的压力下，反应太慢且不完全，而在高于700巴的压力下愈加形成一元醇。甚至可能增加链断裂的发生。
在新方法中，优选很高浓度的甘油，例如一水合物至纯甘油的氢化。水含量最高达20％(重量)的低浓度甘油氢化就关于氢化产物的组成同样可能成功，但是由于时空收率降低其效率是低的。该方法也适用于需要更多能量的各种水溶液的浓度。
本发明的方法也可以使用非水溶液，例如在甲醇中，但是使用非水溶液与用浓甘油比较无显著优点。
由脂肪和油的酯基转移得到的甘油在用新方法氢化前应该简便地除去催化剂的毒物，例如硫。例如这可简单地用分子蒸馏的方法完成。在含有通常用作酯基转移催化剂的硫酸的粗甘油的情况下，用离子交换剂简单处理就足够了。
本发明有许多优点。例如高浓度的甘油，如含有86％(重量)甘油的一水合物，甚至纯甘油，可以选择性的氢化生成1，2-丙二醇，一般收率最高达95％。
此外，在装有颗粒催化剂的高压釜和滴流反应器中新的氢化得到收率最高达95％，转化率100％。还有少量甲醇、乙醇、异丙醇和1，3-丙二醇生成。
实施例中的百分数是重量百分数。
实施例
实施例1
将700g99.5％纯甘油和50g含有68％(重量)钴(以CoO形式)，17％(重量)铜(以CuO形式)，6％(重量)锰(以MnO2形式)，4％(重量)磷(以H3PO4形式)和5％(重量)钼(以MoO3形式)的催化剂加入装有高速气体分散搅拌器的1.2L高压釜中。催化剂预先在300℃用氢气还原。
在冷状态下，加入氢使压力达50巴，然后高压釜加热至250℃。当达到该温度时，压力升至250巴，用再加入氢保持该压力。在6小时后将高压釜冷却并放空，从内容物中过滤出催化剂。得到687g水含量23.6％的反应混合物。
通过用Aminex Hpx 87c柱和折射指数检测器的HPLC分析，显示反应混合物含有95.8％(重量)1，2-丙二醇和3.2％(重量)正丙醇。未检测出甘油。
实施例2
用于新方法的连续转化的反应器是长10m和内径4.5cm的滴流塔。该氢化塔装有21.9kg实施例1中描述的催化剂。首先在含有10％氢的H2/N2混合物中，然后增加至纯氢中，用缓慢加热至300℃，将催化剂转化为金属状态。
反应条件如下：
进料：纯度86.5％甘油(其余是水)
压力：295巴
温度：210-220℃
液体循环：35L/h＝22m3/m2h
气体循环：0-2.5m3/h
废气：2.5m3/h
进料：1.5kg/h
得到的反应混合物的水含量是29-30％。
再通过用有Aminex柱的HPLC分析有机组分，显示反应混合物含有92％(重量)1，2-丙二醇和4.3％(重量)正丙醇，和少量低级醇，但是无甘油。
Claims (1)
- 通过在高温和高压下甘油的催化氢化制备1，2-丙二醇的方法，包括使用水含量最高达20％(重量)的甘油和含有金属钴、铜、锰和钼的催化剂，按催化剂总重量计，该催化剂中各组分的含量为：40-70％(重量)钴，10-20％(重量)铜，0-10％(重量)锰，和0-10％(重量)钼，其中该催化活性物质还可以含有按催化剂总重量计最高达10％(重量)的无机多酸和/或杂多酸。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4442124A DE4442124A1 (de) | 1994-11-26 | 1994-11-26 | Verfahren zur Herstellung von Propandiol-1,2 |
| DEP4442124.9 | 1994-11-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1131655A true CN1131655A (zh) | 1996-09-25 |
| CN1061968C CN1061968C (zh) | 2001-02-14 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95121742A Expired - Fee Related CN1061968C (zh) | 1994-11-26 | 1995-11-26 | 1,2－丙二醇的制备方法 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5616817A (zh) |
| EP (1) | EP0713849B1 (zh) |
| JP (1) | JPH08208541A (zh) |
| CN (1) | CN1061968C (zh) |
| DE (2) | DE4442124A1 (zh) |
| ES (1) | ES2113151T3 (zh) |
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-
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- 1994-11-26 DE DE4442124A patent/DE4442124A1/de not_active Withdrawn
-
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- 1995-11-17 DE DE59501599T patent/DE59501599D1/de not_active Expired - Fee Related
- 1995-11-17 ES ES95118130T patent/ES2113151T3/es not_active Expired - Lifetime
- 1995-11-17 EP EP95118130A patent/EP0713849B1/de not_active Expired - Lifetime
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| CN101848884A (zh) * | 2007-08-31 | 2010-09-29 | 巴斯夫欧洲公司 | 通过在至少三个连续的反应器中将甘油氢化制备1,2-丙二醇的方法 |
| CN101848884B (zh) * | 2007-08-31 | 2013-05-01 | 巴斯夫欧洲公司 | 通过在至少三个连续的反应器中将甘油氢化制备1,2-丙二醇的方法 |
| CN101456791B (zh) * | 2007-12-13 | 2012-07-04 | 中国科学院兰州化学物理研究所 | 利用生物基甘油生产1,2-丙二醇的方法 |
| CN101925564A (zh) * | 2008-01-30 | 2010-12-22 | 花王株式会社 | 多元醇的氢解产物的制造方法 |
| CN101925564B (zh) * | 2008-01-30 | 2014-05-21 | 花王株式会社 | 多元醇的氢解产物的制造方法 |
| CN102333591A (zh) * | 2009-02-25 | 2012-01-25 | 格雷斯公司 | 从丙三醇的氢化制备1，2-丙烷二醇的方法 |
| CN101716511B (zh) * | 2009-11-27 | 2011-10-05 | 南京工业大学 | 一种催化燃烧工业有机废气催化剂及其制备方法 |
| CN104557452A (zh) * | 2015-01-04 | 2015-04-29 | 南京工业大学 | 一种利用镍基催化剂催化甘油一步氢解反应的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4442124A1 (de) | 1996-05-30 |
| EP0713849A1 (de) | 1996-05-29 |
| EP0713849B1 (de) | 1998-03-11 |
| DE59501599D1 (de) | 1998-04-16 |
| CN1061968C (zh) | 2001-02-14 |
| US5616817A (en) | 1997-04-01 |
| ES2113151T3 (es) | 1998-04-16 |
| JPH08208541A (ja) | 1996-08-13 |
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