CN102099320A - 通过裂化在制造过程中形成的高沸物来获得新戊二醇的方法 - 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
本发明涉及通过将在制造过程中形成的高沸物在铜-铬催化剂存在下氢化裂化来获得新戊二醇的方法。该氢化裂化在不存在溶剂的情况下在140至220℃的温度和7至28MPa的压力下进行。
Description
本发明涉及通过在制造过程中形成的高沸物在铜-铬(Kupfer-Chromit)催化剂存在下的氢化裂化来获得新戊二醇的方法。
多羟基醇或多元醇作为形成聚酯或聚氨酯、合成树脂涂料、润滑剂和增塑剂用的缩合组分具有相当大的经济重要性。通过甲醛与异丁醛或正丁醛的混合醛醇缩合获得的多元醇在此特别有用。在甲醛与适当的丁醛的醛醇缩合中,首先形成醛式中间体,其随后必须还原成多元醇。可通过这种方法获得的一种工业上重要的多元醇是由甲醛与异丁醛的混合醛醇缩合反应形成的新戊二醇[NPG,2,2-二甲基丙-1,3-二醇]。
在碱性催化剂,例如碱金属氢氧化物或脂族胺存在下使用等摩尔量进行该醛醇缩合反应,并首先产生可分离的中间体羟基新戊醛(HPA)。这种中间体可随后如DE 1800506A1中所述通过在Cannizzaro反应中与过量甲醛反应来转化成新戊二醇并形成1当量甲酸盐。但是,在工业上也使用羟基新戊醛在金属催化剂上的气相或液相催化氢化。如EP 0278106A1中所述的镍催化剂已被发现是合适的氢化催化剂。在EP 0484800A2的方法中的氢化步骤中使用基于铜、锌和锆的催化剂。根据EP 0522368A1的教导,当使用铜-铬催化剂时,可以在特别温和的压力和温度条件下进行氢化步骤。根据US 4,855,515A1,锰掺杂的铜-铬催化剂特别可用作甲醛与异丁醛反应的醛醇缩合产物的氢化中的氢化催化剂。
从EP 0522368A1中获知的氢化法在至少20重量%的低级醇存在下进行,所示的量基于醇和醛醇缩合产物的混合物。现有技术还提出,羟基新戊醛及其通过Tishchenko反应形成的歧化产物,即2,2-二甲基-1,3-丙二醇单羟基新戊酸酯(HPN)都在反应条件下离解成新戊二醇。
无论通过Cannizzaro法还是氢化法制备新戊二醇,都在醛醇缩合步骤中形成可视为新戊二醇衍生物的一系列次级组分。由于甲醛和异丁醛的高反应性以及由于形成的产物,例如羟基醛和多元醇的高官能度,可发生一系列次级反应,如Tishchenko反应、缩醛化或成酯反应并导致形成高沸物。
在甲醛与异丁醛反应的情况下,高沸物尤其是下列化合物:
NPG单甲酸酯 Tishchenko酯(HPN)
NPG异丁酸酯 HPN羟基新戊酸酯
NPG二羟基新戊酸酯
NPG/HPA环状缩醛
因此在来自新戊二醇制备的高沸物中存在含氧化合物,如相对高沸点的酯或缩醛。
可以从该制造法中在各种位置排出高沸物,例如在醛醇缩合步骤后作为底部产物从氢化步骤前的汽化器排出,从汽化器顶部取出的粗制醛醇缩合产物在气相中在金属催化剂上用氢气氢化以产生新戊二醇。在蒸馏提纯以提供所需新戊二醇时也获得高沸物,例如作为最终纯蒸馏塔的底部产物。
高沸物的这种形成是不合意的,因为多元醇单元化学键合在该高沸物中并显著降低所需新戊二醇的收率。此外,显著量的新戊二醇物理夹带在该高沸物中。此外,最终产物中的痕量高沸物也对应用性能具有不利影响。
WO 97/01523A1公开了,在通过与甲醛反应制备新戊二醇时形成的环状缩醛可以在酸性水溶液或悬浮液中在金属催化剂存在下在升高的温度和升高的压力下用氢裂化产生相应的二醇和甲醛。释放出的甲醛在反应条件下氢化成甲醇。
根据DE 1518784A1的教导,在新戊二醇制备中的最终纯蒸馏塔中提纯氢化产物获得的高沸物至少部分再循环到氢化反应器中,而待氢化的粗制醛醇缩合产物在已知运行模式中含有过量异丁醛。在铜-铬催化剂存在下进行该粗制醛醇缩合产物的催化氢化。
由新戊二醇制备中形成的高沸物获得新戊二醇的已知方法要求酸处理和添加水并随后氢化,或在将这些高沸物再循环到氢化步骤(其中同时氢化最初获得的粗制醛醇缩合产物)时要求存在溶剂。
已经令人惊讶地发现,如果在单独的氢化反应器中在不存在溶剂的情况下和在铜-铬催化剂存在下用氢处理高沸物并通过蒸馏处理所得裂化产物,可以由新戊二醇制备中形成的高沸物以简单方式大量回收新戊二醇。
本发明因此提供由制造过程中形成的高沸物获得新戊二醇的方法。在这种方法中,在单独的氢化反应器中在不存在溶剂的情况下和在铜-铬催化剂存在下,在140至220℃的温度和7至28MPa的压力下在液相中用氢处理该高沸物,并通过蒸馏处理所得裂化产物。
与将高沸物再循环到氢化步骤中的已知方法(其中同时氢化来自甲醛与异丁醛的反应的粗制醛醇缩合产物)不同,在本发明的方法中,氢处理(这也可以视为高沸物的氢化裂化)在单独的氢化反应器中进行。这种分开的工艺构造能以指定方式和不依赖于粗制醛醇缩合产物的氢化中所选的反应条件而设定高沸物的氢化裂化的反应条件。此外,在单独的氢化反应器中进行氢化裂化也允许处理在通过Cannizzaro法制备和提纯新戊二醇中形成的高沸物,在所述方法中醛醇缩合产物与另一当量的甲醛反应并且不用氢氢化。
在不存在溶剂的情况下进行高沸物的氢化裂化。对本发明而言,“不存在溶剂”是指在用氢处理中既不添加有机溶剂,也不添加水。但是,该高沸物中可存在具有溶剂性质并在在先工艺步骤中添加或形成的少量低沸点化合物,例如异丁醇或正丁醇或水。
在新戊二醇(NPG)制备中形成的高沸物含有上述含氧化合物,如NPG单甲酸酯、NPG异丁酸酯、HPA Tishchenko酯、NPG/HPA环状缩醛、NPG二异丁酸酯和NPG二羟基新戊酸酯,以及其它酯、醚和缩醛化合物。HPA Tishchenko酯和NPG二羟基新戊酸酯的含量特别高。该高沸物还含有显著量的新戊二醇和羟基新戊醛。
可以在各种工艺阶段从新戊二醇制备法中分离出要用于氢化裂化的高沸物。它们随后可以单独或以合并形式引入要单独进行的氢化裂化步骤中以获得所需多元醇。在新戊二醇的制备中,高沸物例如从在粗制醛醇缩合产物的氢化之前的汽化器中作为塔底物获得。另外的高沸物可以在氢化后获得的粗制新戊二醇蒸馏提纯以提供纯化产物时排出。来自新戊二醇制备的该合并的高沸物流可随后通过本发明的方法氢化。
在市售铜-铬催化剂存在下进行根据本发明的方法的氢化裂化。从一般现有技术(Ullmann’s Encyclopedia of Industrial Chemistry,第5版,第9卷,VCH-Verlag)中获知它们适用于酯化合物的氢化裂化。铜-铬催化剂根据H.Adkin,Org.React.8,1954,1-27被描述为氧化铜和亚铬酸铜的等摩尔组合,尽管它们不一定含有亚铬酸铜。例如在DE 2611374A1、DE 1518784A1、US 4,855,515A1或EP 0522368A1中描述了此类氢化催化剂。该铜-铬催化剂常常进一步包含活化剂,如钡、镉、镁、锰和/或稀土金属。适用于本发明的方法的铜-铬催化剂可以在无载体材料或有载体材料,例如硅藻土、硅胶或氧化铝的情况下,以粉末或丸粒、星形物、挤出物、环或具有相对较大表面积的其它粒子形式使用。
锰掺杂的铜-铬催化剂特别适用于本发明的氢处理。
在不添加溶剂和不添加水的情况下,在140至220℃,优选160至200℃的温度和7至28MPa,优选7至20MPa的压力下进行高沸物的氢处理或氢化裂化。不适合使用更高温度,因为会更大程度发生多元醇的非选择性离解。尽管更高压力对铜-铬催化剂的氢化性能具有积极作用并对所需多元醇具有高选择性,但在高压下操作也要求高能量输入以将反应气体压缩至适当高压。
本发明的氢处理在固定床催化剂上在液相中连续或分批进行,例如在下行流或上行流氢化中进行。此外,也可以使用悬浮催化剂进行该氢处理。在连续运行模式中,0.2至1.2h-1,优选0.4至1h-1的在该催化剂上的空速V/Vh被认为是有利的,以每单位催化剂体积和时间的体积处理量表示。
在分批运行模式中,基于无溶剂的原材料,使用1至10,优选2至6重量%的上述铜-铬催化剂。
从氢化反应器中取出的裂化产物首先引入高压分离器并减压至大气压。该裂化产物随后通过已知蒸馏法,例如通过从EP 0278106A1中获知的程序处理以提供纯化的新戊二醇。在一个具体实施方案中,裂化产物首先与粗制新戊二醇混合,随后通过蒸馏处理该混合物。
通过本发明的氢处理可以由所用高沸物以基于高沸物输入量的多于80重量%的收率回收新戊二醇。通过下列实施例举例说明本发明方法,但本发明方法不限于这些实施方案。
实施例
将600毫升3×3毫米丸粒形式的市售铜-铬催化剂置于管式反应器中。在借助氮气的压力测试后,用流经该反应器的氮气流将温度缓慢升至180℃以活化该催化剂。将氢气逐渐引入该氮气流直至在不变的氮气流速下达到60升/小时的氢气流速。随后在这些条件下经5小时活化该催化剂。
在催化剂活化后,在管式反应器中设定根据表1和2中的条件的氢压和反应温度。以在每种情况中设定的排气流速,将来自新戊二醇制备的适当量的高沸物混合物连续引入该管式反应器并将该排出的排气流引入高压分离器并经由料位控制排出到大气压接收器中。将该裂化产物与粗制新戊二醇混合并蒸馏该混合物以提供纯化新戊二醇。
在各种温度和压力下的实施例:
来自新戊二醇制备的具有下列组成的高沸物材料用于氢化裂化实验(气相色谱分析,数字以百分比计):
在各种温度和压力下的裂化实验结果概括在下表中。
表1:
来自新戊二醇制备的高沸物(NPG进料)在各种温度下的氢化裂化
如温度变化所示,裂化温度的提高导致氢化产物中NPG含量的降低,但同时,异丁醇和初馏分组分的比例提高。这一系列分析数据表明当温度提高时新戊二醇和羟基新戊醛Tishchenko酯/NPG二异丁酸酯的提高的非选择性离解,尤其形成异丁醇和初馏分组分。
表2:
来自新戊二醇制备的高沸物(NPG进料)在各种压力下的氢化裂化。
该系列分析数据表明氢化催化剂的裂化速率的压力依赖性。在20MPa的压力下,Tishchenko酯和NPG二异丁酸酯几乎完全裂化和氢化成新戊二醇。
进行后续蒸馏的氢化实验:
在与上述实验相同的装置条件下进行来自新戊二醇制备的具有上述组成的高沸物的氢化裂化。在8MPa的压力和180℃的温度下使用300克/小时的高沸物的进料速率(相当于0.5h-1的在催化剂上的空速V/Vh)进行氢化裂化。裂化产物具有下列组成(以百分比计),通过气相色谱法测得:
初馏分(含有甲醇、异丁醇) | 7.4 |
HPA | 0.0 |
NPG | 82.0 |
NPG单甲酸酯 | 0.0 |
NPG二甲酸酯 | 0.0 |
中间馏分 | 0.3 |
NPG单异丁酸酯 | 0.9 |
环状缩醛{HPA/NPG} | 0.3 |
HPA Tishchenko酯/NPG二异丁酸酯 | 6.2 |
尾渣 | 2.9 |
在这些条件下,基于高沸物的进料速率,裂化以91%的转化率进行,且新戊二醇选择性为97.1%,相当于89.0%的新戊二醇收率。
将所得裂化产物与粗制新戊二醇以1∶10的重量比混合,随后在40板式塔中在大气压和1∶1回流率下通过蒸馏处理以提供纯化新戊二醇。在87至100℃范围内的顶部温度和100至125℃范围内的底部温度下取出第一馏分后,在210℃的顶部温度和210至260℃范围内的底部温度下获得纯化的新戊二醇。进料混合物、纯化的新戊二醇和蒸馏残渣具有下列组成(以百分比计),通过气相色谱法测得:
Claims (4)
1.由制造过程中形成的高沸物获得新戊二醇的方法,其特征在于在单独的氢化反应器中在不存在溶剂的情况下和在铜-铬催化剂存在下,在140至220℃的温度和7至28MPa的压力下在液相中用氢处理该高沸物,并通过蒸馏处理所得裂化产物。
2.如权利要求1所述的方法,其特征在于在160至200℃的温度和7至20MPa的压力下进行氢处理。
3.如权利要求1或2所述的方法,其特征在于所述铜-铬催化剂进一步包含钡、镁或锰或其混合物作为活化剂。
4.如权利要求1至3中任一项所述的方法,其特征在于将所得裂化产物与粗制新戊二醇混合,并通过蒸馏处理该混合物以提供纯化的新戊二醇。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3340312A (en) * | 1964-10-21 | 1967-09-05 | Eastman Kodak Co | Manufacture of neopentyl glycol and isobutanol |
US4250337A (en) * | 1978-06-24 | 1981-02-10 | Chemische Werke Huls Aktiengesellschaft | Two stage hydrogenation to make neopentyl glycol |
US6380443B1 (en) * | 1999-10-06 | 2002-04-30 | Basf Aktiengesellschaft | Preparation of 1,3-diols |
US20080167506A1 (en) * | 2007-01-05 | 2008-07-10 | Basf Aktiengesellschaft | Process for preparing polyalcohols from formaldehyde having a low formic acid content |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1269605B (de) * | 1966-06-25 | 1968-06-06 | Basf Ag | Verfahren zur Herstellung gesaettigter Alkohole durch Hydrieren von Aldehyden oder Ketonen |
DE1800506A1 (de) | 1968-10-02 | 1970-05-21 | Basf Ag | Verfahren zur Herstellung von 2,2-Dimethylpropandiol-1,3 |
DE2611374A1 (de) | 1976-03-18 | 1977-09-29 | Basf Ag | Katalysator zur hydrierung von estern |
DE3644675A1 (de) | 1986-12-30 | 1988-07-14 | Ruhrchemie Ag | Verfahren zur herstellung von 2,2-dimethylpropandiol-(1,3) |
US4855515A (en) | 1987-08-12 | 1989-08-08 | Eastman Kodak Company | Process for the production of neopentyl glycol |
JP2964621B2 (ja) | 1990-11-06 | 1999-10-18 | 三菱瓦斯化学株式会社 | ネオペンチルグリコールの製造方法 |
US5144088A (en) * | 1991-04-26 | 1992-09-01 | Aristech Chemical Corporation | Manufacture of neopentyl glycol (I) |
EP0522368B2 (en) | 1991-06-28 | 2000-03-15 | Aristech Chemical Corporation | Manufacture of neopentyl glycol (IV) |
SE9502355L (sv) | 1995-06-29 | 1996-12-30 | Perstorp Ab | Spaltning av cykloalkyletrar |
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Publication number | Priority date | Publication date | Assignee | Title |
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US3340312A (en) * | 1964-10-21 | 1967-09-05 | Eastman Kodak Co | Manufacture of neopentyl glycol and isobutanol |
US4250337A (en) * | 1978-06-24 | 1981-02-10 | Chemische Werke Huls Aktiengesellschaft | Two stage hydrogenation to make neopentyl glycol |
US6380443B1 (en) * | 1999-10-06 | 2002-04-30 | Basf Aktiengesellschaft | Preparation of 1,3-diols |
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