CN102228831A - 一种乙酸气相加氢制取乙醇的催化剂 - Google Patents
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Abstract
一种乙酸气相加氢制取乙醇的催化剂。按本发明提供的乙酸气相加氢制取乙醇的催化剂,催化剂由主活性组分、助剂和载体三部分组成。主活性组分为过渡金属W和或Mo中一种或二种。助剂是Pd、Re、Pt、Rh和Ru等贵金属中一种或几种。载体选用活性炭或石墨或多壁纳米碳管。在固定床反应器中,在一定的温度,氢气压力和本催化剂的作用下,乙酸可高活性、高选择性地转化以乙醇为主要产物的产品。
Description
技术领域
本发明涉及一种乙酸气相加氢制取乙醇的催化剂,主要涉及一种用于气相反应条件下乙酸和氢气反应转化为以乙醇为主要产物的催化剂。
背景技术
乙醇是重要的溶剂和化工原料,还是理想的高辛烷值无污染的车用燃料及其添加剂。巴西多年来一直使用乙醇作汽车燃料或燃料添加剂,近年来我国在多个省份实施了乙醇汽油的推广工作,效果是明显的。随着环境质量要求的提高,发展醇燃料和在汽油中添加醇或醚已成为改善汽车燃料的主要出路。我国人口众多,而耕地面积不足,总的来说粮食不充裕,而且石油资源相对不足,而煤炭资源相对丰富。因此,研究开发从煤炭资源出发经合成气生产乙醇的技术替代传统的粮食发酵路线,对减少我国粮食的工业消耗和缓解石油资源紧缺的矛盾,提高人民生活水平和发展国民经济具有重要的战略意义。
巴西多年来一直使用乙醇作汽车燃料或燃料添加剂,近年来我国在多个省份实施了乙醇汽油的推广工作,效果是明显的。随着环境质量要求的提高,发展醇燃料和在汽油中添加醇或醚已成为改善汽车燃料的主要出路。乙醇的工业生产方法以粮食发酵法为主,粮食发酵法每生产一吨乙醇需耗用3.2吨玉米。目前看来,乙醇是为数不多的在金融危机前后价格坚挺甚至上涨的化学品之一,市场形势,仍然是货紧价高。而且从目前粮食价格上涨幅度大大超过乙醇价格上涨幅度的现状来看,后市乙醇价格仍有较大上涨空间。近年来,我国旱涝灾害频频发生,使生产乙醇的玉米,红薯等供应紧张,价格上涨,不少厂家已形成″无米之炊″,山东、河南,安徽等地的万吨级以上乙醇生产厂减产或停产,所以有专家明确指出乙醇生产的实际问题是原料(粮食)的货紧价高。不仅如此,酒精行业还是我国环境排放有机污染物最高、污染环境严重的一个行业,酒精废水的污染是食品与发酵工业最严重的污染源之一。我国人口众多,而耕地面积不足,当前中国的粮食需求仍然存在0.25~0.35亿吨的缺口。同时我国石油资源相对不足,乙烯紧缺,而煤炭资源相对丰富。因此,研究开发从煤炭资源出发经合成气生产乙醇的工艺技术,既可以节约粮食,又可以充分利用我国丰富的煤炭资源,还可以为我国乙醇生产开辟新的技术途径,解决环保问题,可以说是具有政治、经济、环保三重重要意义。
USP 4,398,039和USP4,443,639分别公开了两种Ru基催化剂,该类催化剂适用于羧酸加氢制相应碳数醇的专利。USP 4,517,391报导了Co-Cu-Mn-Mo沉淀型催化剂,可将乙酸气相加氢转化为乙醇,乙醇得率大于97%。USP 4,777,303和USP 4,826,795揭示了Pd-W(Mo)基催化剂,用于C2-C12碳数羧酸加氢生成相应碳数的醇的过程。USP4,804,791,USP 4,990,655和USP 5,061,671公开了活性炭负载的Pd-Re基催化剂用于乙酸和丙酸加氢制乙醇和丙醇的专利。USP4,985,572报道了用于乙酸和羧酸加氢制相应的醇类的Pd-Re-Ag/HSAG催化剂的专利。USP 5,149,680公开了负载Pd-Re-W(或Mo)催化剂用于羧酸加氢制醇类的专利。USP 7,608,744报道了适用于乙酸气相加氢乙醇的石墨负载Co基催化剂专利。
发明内容
本发明的目的在于提供一种乙酸气相加氢制取乙醇的催化剂,本发明的催化剂可以显著降低能耗,提高乙酸和氢气可转化为乙醇的选择性,同时,可以采用普通乙酸作为原料。
本发明的技术方案为:一种乙酸气相加氢制取乙醇的催化剂,该催化剂由主活性组分、助剂和载体三部分组成,载体为活性炭、石墨或多壁纳米碳管中的任意一种,所述的主活性组分的重量为催化剂重量的0.1~30.0%,助剂的重量为催化剂重量的0.1~10.0%,余量为载体;
主活性组分为金属W或Mo中的任意一种或二种;
助剂是Pd、Re、Pt、Rh或Ru中的一种或几种。
所述活性炭的比表面积为200~1100m2/g,平均孔径为1~100nm;所述石墨的比表面积为50~400m2/g,平均孔径为5~50nm;所述多壁纳米碳管的比表面积为10~300m2/g,平均孔径为5~30nm。
沉淀法、浸渍法、水热合成法中的一种制备,或几种相结合制备。
使用前于以下条件中进行还原活化:压力为1.0MPa,温度为100~500℃,空速为500~5000h-1。
有益效果:
本发明的催化剂可有效提高乙酸和氢气转化为乙醇的选择性,最终产物中乙醇的质量占95%以上。同时,可以采用普通乙酸作为原料,可以显著降低能耗。
具体实施方式
下面详细阐述本发明的内容。
本发明的催化剂是用于乙酸和氢气反应转化为以乙醇为主要产物的反应中,在固定床反应器中乙酸与氢气在气相条件和本催化剂作用下,可高活性、高选择性地转化为以乙醇为主产物的产品。本发明的反应体系中,可采用常规的乙酸与氢气反应的条件制备以乙醇为主要产物的产品,优选反应条件是直接将乙酸溶液泵入到预热器中与H2混合后预热至250℃后进入到固定床反应器中。本发明的反应可以采用常规的固定床反应器,也可以采用浆态床反应器,其中优选固定床反应器。
一种乙酸气相加氢制取乙醇的催化剂,该催化剂由主活性组分、助剂和载体三部分组成,载体为活性炭、石墨或多壁纳米碳管中的任意一种,所述的主活性组分的重量为催化剂重量的0.1~30.0%,最佳重量含量为0.5~15.0%;助剂的重量为催化剂重量的0.1~10.0%,最佳的含量为0.5~8.0%;余量为载体;
主活性组分为金属W或Mo中的任意一种或二种;
助剂是Pd、Re、Pt、Rh或Ru中的一种或几种。
所述活性炭的比表面积为200~1100m2/g,平均孔径为1~100nm,最佳的比表面积为活性炭的比表面积为400~1000m2/g,平均孔径为4~80nm;优选杏核炭或椰壳炭;
所述石墨的比表面积为50~400m2/g,平均孔径为5~50nm,最佳的比表面积为110~300m2/g,最佳孔径为6~45nm;
所述多壁纳米碳管的比表面积为10~300m2/g,平均孔径为5~30nm;最佳的比表面积为12~250m2/g,最佳孔径为8~25nm。
沉淀法、浸渍法、水热合成法中的一种制备,或几种相结合制备。
本发明的催化剂在使用之前可以通过一定条件下的氢气处理进行活化。条件为:压力为1.0MPa,温度为100~500℃,空速为500~5000h-1。用氢气活化催化剂的较佳条件为:GHSV=1000h-1,常压,300℃,还原时间5小时。
下面通过具体实施例对本发明做进一步说明。
以下皆为质量百分比。
实施例1
实施例1的催化剂为10%Mo-5%Re-1.0%Ru/杏核炭。采用常规的浸渍法进行制备:取8.40克杏核炭(20-40目),使用前经3%wt的硝酸浸泡煮沸4小时,蒸馏水洗至pH=7.0左右,120℃烘干6小时,配置15ml含有1.8971克(NH4)2Mo2O4.4H2O,0.7203克NH4ReO4和0.1996克RuCl3.3H2O的水溶液,自然晾干,120℃烘箱烘干4小时。使用前在300℃氢气中(常压,1000h-1)还原活化5小时。
实施例2
实施例2的催化剂10%W-5.0%Re-1.0%Ru/杏核炭。除了配置15ml含有1.5443克(NH4)2WO4水溶液外,其余的制备步骤与实施例1相同。
实施例3
实施例3的催化剂10%W-5.0%Re-1.0%Ru/椰壳炭。除了称取8.40克椰壳炭外,其余的制备步骤与实施例2相同。
实施例4
实施例4的催化剂10%W-5.0%Re-1.0%Pt/杏核炭。除了配置15ml含有0.3237克H2PtCl6.6H2O水溶液外,其余的制备步骤与实施例2相同。
实施例5
实施例5的催化剂10%W-5.0%Re-1.0%Pd/杏核炭。除了配置15ml含有0.4993克PdCl2.2H2O水溶液外,其余的制备步骤与实施例2相同。
实施例6
实施例6的催化剂10%W-5.0%Re-1.0%Rh/杏核炭。除了配置15ml含有0.3905克RhCl3.3H2O水溶液外,其余的制备步骤与实施例2相同。
实施例7
实施例7的催化剂10%W-5.0%Re-1.0%Ru/石墨炭。除了称取8.40克石墨炭外,其余的制备步骤与实施例2相同。
实施例8
实施例8的催化剂10%W-5.0%Re-1.0%Ru/多壁纳米碳管炭。除了称取8.40克多壁纳米碳管炭外,其余的制备步骤与实施例2相同。
实施例9
实施例9的催化剂10.0%W-1.0%Re/杏核炭。除了称取8.9克椰壳炭和配置15ml含有0.1441克NH4ReO4水溶液外,其余的制备步骤与实施例2相同。
实施例10
实施例10的催化剂10.0%W-5.0%Re/杏核炭,除了称取8.50克杏核炭和配置15ml含有0.5310克NH4ReO4水溶液外,其余的制备步骤与实施例9相同。
实施例11
实施例11的催化剂10.0%Mo-5.0%Re/杏核炭,除了配置15ml含有和1.8971克(NH4)2Mo2O4.4H2O水溶液外,其余的制备步骤与实施例10相同。
实施例12
实施例12的催化剂10.0%W-1.0%Ru/杏核炭,除了配置15ml含有0.1996克RuCl3.3H2O水溶液外,其余的制备步骤与实施例9相同。
上述方法制备的催化剂选用固定床反应器,催化剂装量为10ml。在反应温度为250℃,氢气压力为8.0MPa,H2/乙酸=15~20(摩尔比),乙酸液体空速为1.0~1.3h-1,反应时间为50h,取样分析。气相流出物采用气相色谱进行分析,Porapark Q填充柱,TCD检测器;液体产物样品采用气相色谱分析,FFAP毛细管色谱柱,FID检测器。戊醇为内标进行定量分析。
反应结果总结在表1中。
表1:乙酸气相加氢转化为乙醇的条件优化评价结果
由上表可以清楚的看出本发明的催化剂可以有效的提高乙酸和氢气转化为乙醇的选择性。
实施例13
催化剂为为10%Mo-5%W-5%Re-1.0%Ru/杏核炭。采用常规的沉淀法进行制备。
实施例14
催化剂为为0.1%Mo-5%W-0.5%Re-1.0%Ru/杏核炭。采用常规的水热合成法进行制备。
Claims (4)
1.一种乙酸气相加氢制取乙醇的催化剂,该催化剂由主活性组分、助剂和载体三部分组成,载体为活性炭、石墨或多壁纳米碳管中的任意一种,其特征在于,所述的主活性组分的重量为催化剂重量的0.1~30.0%,助剂的重量为催化剂重量的0.1~10.0%,余量为载体;
主活性组分为金属W或Mo中的任意一种或二种;
助剂是Pd、Re、Pt、Rh或Ru中的一种或几种。
2.根据权利要求1所述的乙酸气相加氢制取乙醇的催化剂,其特征在于,所述活性炭的比表面积为200~1100m2/g,平均孔径为1~100nm;所述石墨的比表面积为50~400m2/g,平均孔径为5~50nm;所述多壁纳米碳管的比表面积为10~300m2/g,平均孔径为5~30nm。
3.根据权利要求1所述的乙酸气相加氢制取乙醇的催化剂,其特征在于,沉淀法、浸渍法、水热合成法中的一种制备,或几种相结合制备。
4.根据权利要求1-3中任一项所述的乙酸气相加氢制取乙醇的催化剂,其特征在于,使用前于以下条件中进行还原活化:压力为1.0MPa,温度为100~500℃,空速为500~5000h-1。
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US9050585B2 (en) | 2012-02-10 | 2015-06-09 | Celanese International Corporation | Chemisorption of ethyl acetate during hydrogenation of acetic acid to ethanol |
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CN108126696A (zh) * | 2018-01-26 | 2018-06-08 | 东北石油大学 | 一种乙醇合成乙酸催化剂及制备方法和乙酸制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN86102452A (zh) * | 1985-04-13 | 1986-12-03 | Bp化学有限公司 | 通过羧酸加氢制备醇 |
CN1609089A (zh) * | 2004-06-24 | 2005-04-27 | 复旦大学 | 一种甲基丁二酸的催化合成方法 |
CN101199930A (zh) * | 2006-12-14 | 2008-06-18 | 马波 | 一种高碳多元醇加氢裂解催化剂,其制备方法和应用 |
-
2011
- 2011-04-25 CN CN2011101047637A patent/CN102228831A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN86102452A (zh) * | 1985-04-13 | 1986-12-03 | Bp化学有限公司 | 通过羧酸加氢制备醇 |
CN1609089A (zh) * | 2004-06-24 | 2005-04-27 | 复旦大学 | 一种甲基丁二酸的催化合成方法 |
CN101199930A (zh) * | 2006-12-14 | 2008-06-18 | 马波 | 一种高碳多元醇加氢裂解催化剂,其制备方法和应用 |
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