CN102229520B - 一种由醋酸气相加氢制备乙醇的方法 - Google Patents

一种由醋酸气相加氢制备乙醇的方法 Download PDF

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CN102229520B
CN102229520B CN2011101038021A CN201110103802A CN102229520B CN 102229520 B CN102229520 B CN 102229520B CN 2011101038021 A CN2011101038021 A CN 2011101038021A CN 201110103802 A CN201110103802 A CN 201110103802A CN 102229520 B CN102229520 B CN 102229520B
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宋勤华
邵守言
胡宗贵
代松涛
朱桂生
丁云杰
严丽
王涛
马立新
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Jiangsu Sopo Chemical Co.,Ltd.
Dalian Institute of Chemical Physics of CAS
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Abstract

一种醋酸气相加氢制备乙醇的方法，反应体系由醋酸、氢气和催化剂组成；反应温度为120～300℃，反应压力为1.0～20.0MPa，醋酸液体空速为0.5～10.5h-1，H2/醋酸＝1～250(摩尔比)；催化剂是以活性炭为载体，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；醋酸和氢气在催化剂的作用下可高活性、高选择性地转化为乙醇。

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一种由醋酸气相加氢制备乙醇的方法
技术领域
本发明涉及一种醋酸气相加氢制备乙醇的方法，具体地是由一种用于以醋酸为原料气相加氢生成乙醇的方法。
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。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。而我国人口众多，耕地面积不足，总的来说粮食不充裕，石油资源也相对不足，煤炭资源相对丰富。因此，研究开发如何从煤炭资源出发经合成气生产乙醇来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。
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，红薯等原料供应紧张，价格上涨，不少厂家已陷入″无米之炊″的窘境，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、环境污染严重的一个行业。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，可将醋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。USP 4,804,791，USP4,990,655和USP 5,061,671公开了活性炭负载的Pd-Re基催化剂用于醋酸和丙酸加氢制乙醇和丙醇的专利。USP 4,985,572报道了用于醋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报道了适用于醋酸气相加氢乙醇的石墨负载Co基催化剂专利。目前的这些方法普遍存在反应压力高、选择性差的缺点。
发明内容
本发明的目的是提供一种由醋酸气相加氢制备乙醇的方法，以醋酸、氢气为原料在气固两相固定床反应条件下制备乙醇。
本发明的技术方案为：一种由醋酸气相加氢制备乙醇的方法，按照摩尔比H2/醋酸＝1～250的比例使醋酸、氢气和催化剂在100～300℃、1.0～20.0MPa的反应压力下、醋酸液体空速为0.5～10.5h-1的条件下进行反应得到的产物中乙醇的含量≥95％wt；
所述的催化剂是以载体负载活性组分和助活性组分，其中活性组分为W、Mo中的一种或两种，活性组分的负载量为催化剂总重量的0.1-30.0％；助活性组分为Pd、Re、Pt、Rh或Ru中的一种或几种，助活性组分的负载量为催化剂总重量的0.1～10.0％。
反应压力为2.0～15.0MPa。
反应温度为120～280℃。
醋酸液液体空速为1.0～10.0h-1。
摩尔比H2/醋酸＝5～200。
所述的催化剂采用常规的沉淀法、浸渍法、水热合成法或上述方法的结合制备，所述载体选用活性炭、石墨或多壁纳米碳管中的任意一种。
催化剂在使用前用H2原位还原法进行活化。
所述反应在固定床反应器或浆态床反应器内进行。
有益效果：可以显著降低反应压力和能耗，提高在气相条件下醋酸和氢为原料制备为乙醇的选择性。
具体实施方式
本发明提供了一种以醋酸和氢气为原料在固定床反应器或浆态床反应器中制备乙醇的方法，其中优选固定床反应器。反应体系由醋酸、氢气和催化剂组成。在上述体系中醋酸和氢气在一定的温度和压力下与催化剂接触一定时间后高活性、高选择性地转化为乙醇。本发明可以直接将醋酸液体泵入到混合器中与H2混合，进入预热器中，预热后进入到固定床反应器中或采用浆态床反应器。
本发明的催化剂在使用之前可以采用常规的氢气原位还原法进行活化。按常规条件：GHSV＝1000h-1，常压，300℃，还原时间5小时即可。
本发明的具体的反应条件为：反应温度为100～300℃，较佳的反应温度为130～250℃；反应压力为1.0～20.0MPa，较佳的反应压力为7.0～16.0MPa；H2/醋酸的摩尔比为1～250，较佳的摩尔比为10～160，醋酸液体空速为0.1～15.0h-1，较佳的液体空速为0.3～5.0h-1。
所述催化剂是以活性炭、石墨或多壁纳米碳管中的任一为载体，负载的活性组分可为W或Mo中的一种或两种，活性组分的负载量为催化剂总重量的0.1-30.0％；助活性组分为Pd、Re、Pt、Rh或Ru等贵金属中的一种或几种。助活性组分的重量为催化剂总重量的0.1～10.0％。载体可以是活性炭。催化剂可以采用本领域所熟悉的常规催化剂制备方法如：沉淀法、浸渍法、水热合成法或上述方法结合使用。
所述原料采用常规的工业醋酸即可，若为脱碘精制醋酸则碘含量为小于10ppb，或普通醋酸碘含量为小于40ppb。氢气为常规的普氢或纯氢，总硫含量不大于0.1ppm，氧含量不大于1ppm，最后得到的主产品为乙醇，乙醇的质量占产物总质量的95％以上。
下面通过具体实施例对本发明做进一步说明。
实施例1
采用的催化剂为W-Re-Ru/杏核炭。催化剂重量组成为：W＝10.0％，Re＝5％，Ru＝2％，其余为载体活性炭。载体采用商品杏核炭，并通过常规浸渍法将催化剂活性组分W和助剂Re和Ru担载在载体活性炭(活性炭的颗粒度为20～40目)上。7.0克(10ml左右)催化剂在反应之前经过氢气活化，活化条件为：GHSV＝1000h-1，常压，300℃，还原时间5小时。选用固定床反应器。反应温度为250℃，氢气压力为10.0MPa，H2/醋酸(精制醋酸)摩尔比为15醋酸液体空速为1.0h-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色谱柱，FID检测器。戊醇为内标进行定量分析。
实施例2
采用醋酸液体空速为0.5h-1，其它条件与实施例1相同。
实施例3
采用醋酸液体空速为1.9h-1，其它条件与实施例1相同。
实施例4
采用醋酸液体空速为1.3h-1和Mo-Re-Ru/杏核炭以外，其它条件与实施例1相同。
实施例5
采用醋酸液体空速为2.8h-1，其它条件与实施例1相同。
实施例6
采用反应温度为230℃，其它条件与实施例1相同。
实施例7
采用反应温度为270℃，其它条件与实施例1相同。
实施例8
采用氢气压力为7.0Mpa，其它条件与实施例1相同。
实施例9
采用氢气压力为9.0Mpa，其它条件与实施例1相同。
实施例10
采用氢气压力为12.0Mpa，其它条件与实施例1相同。
实施例11
采用H2/醋酸摩尔比为10，其它条件与实施例1相同。
实施例12
采用H2/醋酸摩尔比为50，其它条件与实施例1相同。
实施例13
采用H2/醋酸摩尔比为80，其它条件与实施例1相同
实施例14
采用H2/醋酸摩尔比为100，其它条件与实施例1相同
实施例15
采用200毫升搅拌式浆态床，16.0克催化剂的颗粒度为150-200目和120ml醋酸泵入200ml浆态床高压釜反应器，再充入H2至压力为10.0MPa，其它条件与实施例1相同。
实施例16
采用普通醋酸作为原料，其它条件与实施例1相同。
本发明的醋酸和氢气为原料在气固两相反应条件条件下加氢制备乙醇反应评价结果总结在表1中。
表1：醋酸气相加氢转化为乙醇的条件优化评价结果
Figure BDA0000057238180000051
Figure BDA0000057238180000061

Claims (5)

1.一种由醋酸气相加氢制备乙醇的方法，其特征在于，按照摩尔比H2/醋酸＝1～250的比例使醋酸、氢气和催化剂在120～280℃、2.0～15.0MPa的反应压力下、醋酸液体空速为0.5～10.5h-1的条件下进行反应得到的产物中乙醇的含量≥95%wt；
所述的催化剂由W，Re，Ru和杏核炭活性炭组成，其重量组成为：W=10.0%，Re=5%，Ru=2%，其余为载体杏核炭活性炭。
2.根据权利要求1所述的由醋酸气相加氢制备乙醇的方法，其特征在于，醋酸液液体空速为1.0～10.0h-1。
3.根据权利要求1所述的由醋酸气相加氢制备乙醇的方法，其特征在于，摩尔比H2/醋酸=5～200。
4.根据权利要求1所述的由醋酸气相加氢制备乙醇的方法，其特征在于，催化剂在使用前用H2原位还原法进行活化。
5.根据权利要求1所述的由醋酸气相加氢制备乙醇的方法，其特征在于，所述反应在固定床反应器或浆态床反应器内进行。
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