CN111389453B - 一种液相转化高浓度木质素为环烷烃的方法 - Google Patents
一种液相转化高浓度木质素为环烷烃的方法 Download PDFInfo
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Abstract
本申请公开了一种液相转化高浓度木质素为环烷烃的方法，在浆态床反应器中，加入木质素、溶剂和双组分催化剂，在氢气中反应得到环烷烃。其中，第一催化剂的金属中心为Ni；第二催化剂的金属中心为Ru、Pd、Pt、Co、Re中的一种或多种。其优点表现在：木质素来源非常广泛，成本低廉。本申请利用多相多功能耦合催化，反应后的产物与催化剂易于分离，且催化剂可循环。且木质素的转化率接近100％，环烷烃液体质量收率达到40‑50wt％，环烷烃的选择性达到90‑95％，有较高的原子经济性。本申请所能处理的木质素浓度可高达180g/L，有利于发展木质素的大规模工业化利用。
Description
技术领域
本申请涉及木质素生物质资源利用技术领域，尤其是涉及一种液相转化高浓度木质素为环烷烃的方法。
背景技术
木质素广泛存在于自然界的植物中，也是自然界中唯一含有苯环结构的可再生资源。高效转化木质素为环烷烃是木质素利用的有效途径之一，但由于木质素独特的三维高分子结构导致其结构异常稳固及解聚生成的酚类单元易聚合等特点，使得木质素在催化转化过程中效率低、容易积炭且转化浓度低，这些问题限制了工业规模的木质素的转化利用。
目前已经报道了一些一步法催化转化木质素为环烷烃的方法。比如中国专利CN102876349A利用Ni/HBEA催化剂转化酶解木质素为碳链C5-C10的烃类，其中木质素处理浓度为40g/L。中国专利CN 105441106A利用固体酸和贵金属催化转化木质素为碳链C6-C18的长链烷烃，其中木质素处理浓度为3.3g/L。与之类似的是，中国专利CN 101885978A利用液体酸和金属双功能催化剂加氢脱氧木质素为烷烃燃料，其中木质素处理浓度为4.0g/L。中国专利CN 110052276A开发了1％Ni-2％ReOX/CeO2催化剂来转化玉米秸秆木质素为液体烷烃燃料，其中木质素处理浓度为10g/L。此外，中国专利CN 109776259A开发了一种金属/金属氧化物双功能催化剂催化转化原生生物质为环烷烃和多元醇，其中生物质处理浓度为5g/L。值得注意的是，这些催化反应过程处理的木质素或生物质浓度都不超过40g/L，这严重制约其进一步的工业放大应用。而制约木质素处理浓度提高的一大原因是木质素解聚生成酚类与酚类化合物加氢脱氧生成烷烃反应速率的匹配性难以控制，且木质素的吸附和解聚速度都很慢而且木质素的转化浓度很低，造成大量结焦的产生而使催化剂快速失活和反应终止。
发明内容
为了解决木质素转化浓度低且结焦严重问题，本发明提供了一种高效解聚高浓度木质素为环烷烃的方法。
本申请采用下述技术方案：
一种环烷烃的制备方法，所述制备方法为：在浆态床反应器中，加入木质素、溶剂和双组分催化剂，在氢气中反应得到环烷烃。
进一步地，所述双组分催化剂由第一催化剂和第二催化剂组成：第一催化剂为负载型金属催化剂，金属中心为Ni；第二催化剂为负载型金属催化剂，金属中心为Ru、Pd、Pt、Co、Re中的一种或多种。
进一步地，所述第一催化剂的载体为氧化硅、氧化钛、氧化铝、无定型硅铝、分子筛、氧化锆、活性炭中的一种或者多种，所述第二催化剂的载体为氧化硅、氧化钛、羟基磷灰石、氧化铝、无定型硅铝、分子筛中的一种或者多种。
进一步地，所述双组分催化剂由质量比例为1:1-1:10的第一催化剂和第二催化剂物理混合而得。
进一步地，第一催化剂的金属中心的含量为0.1％-40％，第二催化剂的金属中心的含量为0.1％-5％。
进一步地，所述木质素为酶解木质素、碱木质素、磺化木质素、有机溶剂型木质素中的一种或多种。
进一步地，所述木质素的浓度为50-180g/L。
进一步地，双组分催化剂和木质素的质量比例为1:1-1:100。
进一步地，所述溶剂为烷烃，包括C6-C16的直链烷烃或环烷烃。
进一步地，反应温度为150-300℃，氢气压力为1-6MPa，反应时间为1-20小时。
本申请采用的上述至少一个技术方案能够达到以下有益效果：
本申请所用的木质素来自于可再生的生物质资源或者工业生产废弃物，来源非常广泛，成本低廉。本申请利用多相多功能耦合催化，反应后的产物与催化剂易于分离，且催化剂可循环。且木质素的转化率接近100％，环烷烃液体质量收率接近40-50wt％(接近理论收率)，环烷烃的选择性达到90-95％，有较高的原子经济性。本申请所能处理的木质素浓度可高达180g/L，是目前所知的最高转化浓度，有利于发展木质素的大规模工业化利用。
附图说明
图1为转化不同浓度木质素得到的GC图谱。其中，(a)50g/L,(b)100g/L,(c)150g/L,(d)180g/L。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚，下面将结合本申请具体实施例对本申请技术方案进行清楚、完整地描述。显然，所描述的实施例仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
实施例1-7
Ru/SiO2，Pd/SiO2，Pt/SiO2，Pt/Al2O3，Pt/HZSM-5，Pt/MgO和Pt/HAP通过离子交换法制备，方法如下：称取1g载体(SiO2，Al2O3，HZSM-5，MgO，HAP)以此为投料基准，用移液枪吸取5％金属(Ru，Pd，Pt)担载量的溶液于烧瓶中并用蒸馏水稀释至100mL，在搅拌下将载体加入烧瓶中，并将悬浮液在80℃下回流8h，冷却后抽滤分离固体，用去离子水洗涤至中性。接着将样品在60℃下干燥过夜。将催化剂在350℃空气气氛中煅烧4h，并在350℃氢气气氛中还原4h，得到第一组分催化剂。
Ni/ASA通过沉积沉淀法制备，方法如下：称取10.0g的六水合硝酸镍硝酸镍溶解于250mL去离子水中配成盐溶液，将250mL盐溶液分成两部分，一方面将2g无定型硅铝(ASA)载体加入其中的200mL溶液中，在搅拌的条件下使用油浴加热到70℃，另一方面称取6.0g的尿素加入到余下的50mL溶液中，将所得溶液用滴液漏斗缓慢地滴入到上述加热到70℃的200mL混合溶液中，等滴加结束后，在搅拌的条件下将混合溶液加热到90℃并且维持10小时。反应结束后，冷却到室温，抽滤并用去离子水洗至中性后，在100℃烘箱中干燥过夜。最后将催化剂在450℃空气气氛中煅烧4h，随后在450℃的氢气气氛中还原4h，得到第二组分催化剂。
分别称取4.0g酶解木质素，1.0g第一组分催化剂、1.0g第二组分催化剂(Ni/ASA)和80mL十二烷加入到300mL Parr反应釜中。反应前，先用氮气洗气三次，再用氢气洗气三次，最后充入6MPa氢气，然后在反应搅拌速率为每分钟600转的条件下将反应釜加热至300℃，反应14小时。等待反应釜冷却，释放氢气，将反应后的溶液过滤，用气相色谱质谱联用仪检测液相产物，检测结果显示木质素转化率为85wt％，环烷烃收率为13-48wt％。结果如表1所示。
实施例8-10
分别称取8.0g、12.0g和14.4g酶解木质素，对用质量比例的第一组分催化剂(Pt/HAP)和第二组分催化剂(Ni/ASA)和80mL十二烷加入到300mL Parr反应釜中。反应前，先用氮气洗气三次，再用氢气洗气三次，最后充入3MPa氢气，然后在反应搅拌速率为每分钟600转的条件下将反应釜加热至300℃，反应16小时。等待反应釜冷却，释放氢气，将反应后的溶液过滤，用气相色谱质谱联用仪检测液相产物，检测结果显示木质素转化率为90-93％，环烷烃选择性为42-47％。结果如表1所示。
表1：不同催化剂组合转化不同浓度酶解木质素为环烷烃
实施例11-14
分别称取12.0g不同种类木质素，3.0g第一组分催化剂(Pt/HAP)和3.0g第二组分催化剂(Ni/ASA)和80mL十二烷加入到300mL Parr反应釜中，其中木质素浓度为150g/L。反应前，先用氮气洗气三次，再用氢气洗气三次，最后充入3MPa氢气，然后在反应搅拌速率为每分钟600转的条件下将反应釜加热至300℃，反应8小时。等待反应釜冷却，释放氢气，将反应后的溶液过滤，用气相色谱质谱联用仪检测液相产物，检测结果显示木质素转化率为90-95wt％，环烷烃收率为40-50wt％。结果如表2所示。
表2：转化不同木质素为环烷烃
以上所述仅为本申请的实施例而已，并不用于限制本申请。对于本领域技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原理之内所作的任何修改、等同替换、改进等，均应包含在本申请的权利要求范围之内。
Claims (8)
1.一种转化木质素为环烷烃的双组分催化剂，其特征在于，所述双组分催化剂由第一催化剂和第二催化剂组成：第一催化剂为负载型金属催化剂，金属中心为Ni、载体为无定型硅铝；第二催化剂为负载型金属催化剂，金属中心为Pt、载体为羟基磷灰石，所述双组分催化剂由质量比例为1:1-1:10的第一催化剂和第二催化剂物理混合而得。
2.如权利要求1所述的双组分催化剂，其特征在于，第一催化剂的金属中心的含量为0.1％-40％，第二催化剂的金属中心的含量为0.1％-5％。
3.一种环烷烃的制备方法，其特征在于，所述制备方法为：在浆态床反应器中，加入木质素、溶剂和权利要求1或2任一项所述的双组分催化剂，在氢气中反应得到环烷烃。
4.如权利要求3所述的制备方法，其特征在于，所述木质素为酶解木质素、碱木质素、磺化木质素、有机溶剂型木质素中的一种或多种。
5.如权利要求3所述的制备方法，其特征在于，所述木质素的浓度为50-180g/L。
6.如权利要求3所述的制备方法，其特征在于，双组分催化剂和木质素的质量比例为1:1-1:100。
7.如权利要求3所述的制备方法，其特征在于，所述溶剂为C6-C16的直链烷烃或环烷烃。
8.如权利要求3所述的制备方法，其特征在于，反应温度为150-300℃，氢气压力为1-6MPa，反应时间为1-20小时。
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