CN111036217B - 癸二酸二甲酯连续加氢制备癸二醇用催化剂 - Google Patents
癸二酸二甲酯连续加氢制备癸二醇用催化剂 Download PDFInfo
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- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 229940014772 dimethyl sebacate Drugs 0.000 title claims abstract description 52
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
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- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 3
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- 229910052708 sodium Inorganic materials 0.000 description 3
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- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种癸二酸二甲酯连续加氢制备癸二醇的催化剂,其特征在于催化剂为三叶草形铜系催化剂。催化剂主要活性组分为Cu,Cu质量百分比含量为30~50%,辅助活性组为Zn、Cr、Al、Ni中的一种或者几种的混合物,质量百分比含量为0.5~30%。本发明公开的三叶草形铜系催化剂,能有效消除反应内扩散的影响,明显的提高癸二酸二甲酯加氢反应性能,温和反应条件,降低反应成本。
Description
技术领域
本发明属于催化剂领域,本发明涉及一种癸二酸二元酯加氢制备癸二醇用催化剂。
背景技术
1,10-癸二醇是一种新兴的精细化工原料,其拥有两个位于碳链两端的羟基,具有较高的反应活性,能与有机酸、异氰酸酯、酸酐等反应生成不同类型的衍生物。由于其性能独特,并可生产一系列新型的精细化工产品,应用在功能新材料、农药、医药以及香精添加剂等领域。常被用于制备香精香料、粘合剂和高分子特种材料、医药及材料。如:用于生产抗细菌和抗霉菌药(双)克菌定及奥替尼啶;用于制备外消旋药喇叭酸甲酯、艾地苯醌药物;用于合成含手性碳的串型液晶共聚物。
文献报道的癸二醇的合成技术主要有3种方法:(1)、金属钠还原法;(2)、有机高活性还原剂还原法;(3)、催化加氢法。金属钠还原法,Chuit首次利用Bouveault-Blan反应,用金属钠还原癸二酸二乙酯,合成1,10-癸二醇;Carothers等也相继对该方法进行了深入的研究,但在实际生产过程中,由于该方法需要大量无水乙醇,且难以回收,造成废水量大,污染严重。有机高活性还原剂还原法,这类方法通常是以癸二酸二乙酯或癸二酰氯为原料,用有机高活性还原剂如硼氢化钾钠、氢化铝锂等还原制备癸二醇,该方法因成本高,且硼氢化钾钠不易储存,生产时危险性高;催化剂加氢法,Jones首次用本方法制备癸二醇,采用的是铜铬催化剂,在250℃、35MPa的条件下,获得1,10-癸二醇,之后人们相继开发了铜铬钡催化剂、铜铬钡锰等催化剂。因工业放大转化率高,污染小,且易工业化生产,在工业放大中被广泛应用。但该方法的缺点在于,反应加氢压力较高,最高可达到30MPa,高的加氢反应压力在生产运行过程中难以保证安全;该反应液体空速一般在0.01~0.15h-1之间,而氢气与癸二酸二甲酯的物质的量之比一般高达300。这降低了装置产能、而且大量氢气循环浪费运行动力,这些都导致生产成本升高。
目前癸二醇合成技术主要采用催化加氢法。发展趋势在于寻求高性能酯加氢催化剂,通过催化剂促进反应性能,温和生产工艺条件,降低生产成本。国内外研究机构对酯加氢反应进行了大量的研究,通常采用铜系催化剂,根据原料的不同来调整催化剂的组成及反应工艺条件。
发明内容
本发明目的在于提供一种高效三叶草形铜系催化剂,提高癸二酸二甲酯连续加氢制备癸二醇的反应性能,温和反应工艺条件,降低生产成本。
本发明的目的通过以下技术方案实现的:癸二酸二甲酯连续加氢制备癸二醇用催化剂,其特征在于催化剂为三叶草形铜系催化剂。
所述的催化剂主要活性组分为Cu,Cu质量百分比含量为30~50%,辅助活性组分为Zn、Cr、Al、Co、Ni中的一种或者几种的混合物,质量百分比含量为0.5~30%,余量为催化剂制造成型的辅助材料。
所述催化剂为三叶草形,其径向横截面呈三个圆所组成的三叶草形状,三个圆中任意两个圆相互外切,三个圆的排布与正三角形内切。
所述的三叶草形催化剂,所述的三个圆的大小相等。
所述的三叶草形催化剂,所述的三个圆的直径为0.5-10mm。
所述的三叶草形催化剂,所述的催化剂长度为三个圆中任意一个圆的直径的2-30倍。
所述的三叶草形催化剂,所述的三个圆内可设计不含孔道或者含均匀分布的孔道这两种结构,孔道可呈圆形或者正三角形。
本发明提供了采用上述催化剂,癸二酸二甲酯连续加氢制备癸二醇的方法,包含以下步骤:
(1)、以甲醇作为反应溶剂,在配料罐将甲醇与癸二酸二甲酯混合均匀,温度控制在30~40℃,甲醇与癸二酸二甲酯质量比为(0.2~5):1;
(2)、将氢气与配料罐中的混合液送入装有三叶草形铜系催化剂的固定床反应器中反应,控制氢气与癸二酸二甲酯物质的量之比为(50~160):1,反应压力为3~8MPa、反应温度170~220℃、体积空速(0.4~2.0)h-1;
(3)、反应结束后,反应液通过精馏等后处理工艺,分离提纯癸二醇,通过气相色谱分析癸二醇的纯度,癸二酸二甲酯转化率为95~100%,癸二醇选择性为95~99%。
优选地,所述的氢气与癸二酸二甲酯物质的量之比为(80~160):1。
所述反应压力为4~6MPa;温度为190~205℃;积空速为(0.5~1.2)h-1。
本发明公开的三叶草形铜系催化剂,能有效消除反应内扩散的影响,明显的提高1,10-癸二酸二甲酯加氢反应性能,温和反应条件,降低反应成本。
附图说明
图1 为实施例中三叶草形催化剂径向横截面图示意图(R为圆的直径,0.5-10mm)。
图2 为实施例中三叶草形催化剂整体外形示意图(L为催化剂的长度)。
具体实施方式
为了更好的理解本发明,下面结合实施例和附图进一步阐明发明的内容,但本发明的内容不仅限于下面的实施例。
实施例1
三叶草形铜系催化剂外形示意图参照图1、图2。图1是三叶草形催化剂径向横截面图示意图,横截面的三个叶片由三个两两相外切的圆构成,三个圆内设置多个均匀孔道;图2是三叶草形催化剂整体外形示意图。
实施例2
根据设计要求,制备如下三叶草形铜系催化剂,催化剂具体型号见表1。
表1 三叶草形铜系催化剂
编号 | 描述 |
<![CDATA[1<sup>#</sup>]]> | 圆直径0.5mm,催化剂长度为15 mm,圆内含正三角形孔道;Cu含量为40%,Zn含量为4%,Al含量为15%。 |
<![CDATA[2<sup>#</sup>]]> | 圆直径1mm,催化剂长度为2mm,圆内不含孔道;Cu含量为30%,Al含量为30%。 |
<![CDATA[3<sup>#</sup>]]> | 圆直径5mm,催化剂长度为20mm,圆内含正三角形孔道;Cu含量为50%,Cr含量为7%,Al含量为12%。 |
<![CDATA[4<sup>#</sup>]]> | 圆直径8mm,催化剂长度为24mm,圆内含正三角形孔道;Cu含量为40%,Zn含量为4%,Al含量为14%。 |
<![CDATA[5<sup>#</sup>]]> | 圆直径3mm,催化剂长度为15mm,圆内不含孔道;Cu含量为50%,Ni含量为3%,Co含量为0.5%,Al含量为14.3%。 |
<![CDATA[6<sup>#</sup>]]> | 圆直径10mm,催化剂长度为25mm,圆内含圆形孔道;Cu含量为38%,Zn含量为10%. |
实施例3
35℃条件下,甲醇与癸二酸二甲酯按照质量比1:1混合均匀,将氢气与混合液送入装有三叶草形铜系催化剂1#的固定床反应器中,氢气与癸二酸二甲酯物质的量之比为130:1,反应压力为5MPa、反应温度195℃、体积空速0.8h-1,反应结束后,分离提纯癸二醇分析,癸二酸二甲酯转化率为99.5%,癸二醇选择性为99%。
实施例4
35℃条件下,甲醇与癸二酸二甲酯按照质量比2:1混合均匀,将氢气与混合液送入装有三叶草形铜系催化剂2#的固定床反应器中,氢气与癸二酸二甲酯物质的量之比为160:1,反应压力为3MPa、反应温度220℃、体积空速0.4h-1,反应结束后,分离提纯癸二醇分析,癸二酸二甲酯转化率为98%,癸二醇选择性为95%。
实施例5
30℃条件下,甲醇与癸二酸二甲酯按照质量比3:1混合均匀,将氢气与混合液送入装有三叶草形铜系催化剂3#的固定床反应器中,氢气与癸二酸二甲酯物质的量之比为50:1,反应压力为8MPa、反应温度210℃、体积空速0.6h-1,反应结束后,分离提纯癸二醇分析,癸二酸二甲酯转化率为99.2%,癸二醇选择性为97%。
实施例6
35℃条件下,甲醇与癸二酸二甲酯按照质量比5:1混合均匀,将氢气与混合液送入装有三叶草形铜系催化剂4#的固定床反应器中,氢气与癸二酸二甲酯物质的量之比为150:1,反应压力为7MPa、反应温度200℃、体积空速2.0h-1,反应结束后,分离提纯癸二醇分析,癸二酸二甲酯转化率为95%,癸二醇选择性为99%。
实施例7
40℃条件下,甲醇与癸二酸二甲酯按照质量比0.2:1混合均匀,将氢气与混合液送入装有三叶草形铜系催化剂5#的固定床反应器中,氢气与癸二酸二甲酯物质的量之比为80:1,反应压力为6MPa、反应温度200℃、体积空速1.0h-1,反应结束后,分离提纯癸二醇分析,癸二酸二甲酯转化率为99.8%,癸二醇选择性为98%。
实施例8
40℃条件下,甲醇与癸二酸二甲酯按照质量比0.5:1混合均匀,将氢气与混合液送入装有三叶草形铜系催化剂6#的固定床反应器中,氢气与癸二酸二甲酯物质的量之比为130:1,反应压力为4MPa、反应温度195℃、体积空速0.7h-1,反应结束后,分离提纯癸二醇分析,癸二酸二甲酯转化率为100%,癸二醇选择性为98%。
实施例9
35℃条件下,甲醇与癸二酸二甲酯按照质量比1:1混合均匀,将氢气与混合液送入装有三叶草形铜系催化剂3#的固定床反应器中,氢气与癸二酸二甲酯物质的量之比为60:1,反应压力为6MPa、反应温度200℃、体积空速0.8h-1,反应结束后,分离提纯癸二醇分析,癸二酸二甲酯转化率为99.5%,癸二醇选择性为98%。
实施例10
35℃条件下,甲醇与癸二酸二甲酯按照质量比2:1混合均匀,将氢气与混合液送入装有三叶草形铜系催化剂4#的固定床反应器中,氢气与癸二酸二甲酯物质的量之比为140:1,反应压力为7MPa、反应温度170℃、体积空速0.5h-1,反应结束后,分离提纯癸二醇分析,癸二酸二甲酯转化率为95%,癸二醇选择性为98.3%。
实施例11
30℃条件下,甲醇与癸二酸二甲酯按照质量比2.5:1混合均匀,将氢气与混合液送入装有三叶草形铜系催化剂5#的固定床反应器中,氢气与癸二酸二甲酯物质的量之比为150:1,反应压力为4MPa、反应温度200℃、体积空速0.8h-1,反应结束后,分离提纯癸二醇分析,癸二酸二甲酯转化率为100%,癸二醇选择性为99.1%。
实施例12
35℃条件下,甲醇与癸二酸二甲酯按照质量比1:1混合均匀,将氢气与混合液送入装有三叶草形铜系催化剂5#的固定床反应器中,氢气与癸二酸二甲酯物质的量之比为70:1,反应压力为8MPa、反应温度200℃、体积空速0.6h-1,反应结束后,分离提纯癸二醇分析,癸二酸二甲酯转化率为99%,癸二醇选择性为95.4%。
实施例13
35℃条件下,甲醇与癸二酸二甲酯按照质量比0.8:1混合均匀,将氢气与混合液送入装有三叶草形铜系催化剂3#的固定床反应器中,氢气与癸二酸二甲酯物质的量之比为120:1,反应压力为6MPa、反应温度200℃、体积空速1.0h-1,反应结束后,分离提纯癸二醇分析,癸二酸二甲酯转化率为99.5%,癸二醇选择性为99.0%。
Claims (1)
1.一种催化剂在癸二酸二甲酯连续加氢制备癸二醇的应用,其特征在于催化剂为三叶草形铜系催化剂,三叶草形的径向横截面呈三个圆所组成的三叶草形状,三个圆中任意两个圆相互外切,三个圆的排布与正三角形内切,三个圆的大小相等,三个圆的直径为0.5-10mm,催化剂长度为三个圆中任意一个圆的直径的2-30倍;所述的三个圆内不含孔道或者含均匀分布的孔道结构,孔道呈圆形或者正三角形;所述的催化剂主要活性组分为Cu,Cu质量百分比 含量为30 ~50%,辅助活性组分为Zn、Cr、Al、Co 、Ni中的一种或者几种的混合物,质量百分比含 量为0.5 ~30%,余量为催化剂制造成型的辅助材料;所述催化剂在癸二酸二甲酯连续加氢制备癸二醇的步骤为:
(1)以甲醇作为反应溶剂,将甲醇与癸二酸二甲酯混合均匀,温度控制在30 ~40℃,甲醇与癸二酸二甲酯质量比为(0.2 ~5):1;
(2)将氢气与混合液送入装有三叶草形铜系催化剂的固定床反应器中反应,控制氢气与癸二酸二甲酯物质的量之比为(80 ~160):1,反应压力4 ~6MPa,反应温度190~205℃,体积空速(0.5~1 .2)h-1;
(3)反应结束后,反应液通过精馏后处理工艺,分离提纯癸二醇,气相色谱法分析癸 二醇的纯度,癸二酸二甲酯转化率为95 ~100%,癸二醇选择性为95~99%。
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CN202290060U (zh) * | 2011-10-17 | 2012-07-04 | 中国石油化工股份有限公司 | 一种三叶草形催化剂颗粒 |
CN103170349A (zh) * | 2011-12-23 | 2013-06-26 | 中国石油化工股份有限公司 | 一种混合碳四选择加氢的铜催化剂及其制备方法 |
CN104148086A (zh) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | 制备乙醇的催化剂及方法 |
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CN201061759Y (zh) * | 2007-04-04 | 2008-05-21 | 中国石油化工股份有限公司 | 一种三叶草形催化剂 |
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CN202290060U (zh) * | 2011-10-17 | 2012-07-04 | 中国石油化工股份有限公司 | 一种三叶草形催化剂颗粒 |
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