CN114410336B - 一种基于生物质乙酰丙酸直接制备长链烷烃的方法 - Google Patents

一种基于生物质乙酰丙酸直接制备长链烷烃的方法 Download PDF

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CN114410336B
CN114410336B CN202210120128.6A CN202210120128A CN114410336B CN 114410336 B CN114410336 B CN 114410336B CN 202210120128 A CN202210120128 A CN 202210120128A CN 114410336 B CN114410336 B CN 114410336B
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levulinic acid
metal oxide
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chain alkane
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赵新强
西茜
张一哲
安华良
王延吉
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Hebei University of Technology
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Abstract

本发明为一种基于生物质乙酰丙酸直接制备长链烷烃的方法。该方法包括以下步骤：在高压釜中加入固体酸负载金属氧化物催化剂、溶剂和原料乙酰丙酸，充入氢气后，180～260℃下反应5～12h，得到长链烷烃；所述的长链烷烃为含8～10个碳原子的饱和烷烃。本发明选择的催化剂具有高活性、选择性和稳定性的特点，工艺具有流程短、设备费用和操作费用低、环境友好等优点。

Description

一种基于生物质乙酰丙酸直接制备长链烷烃的方法
技术领域
本发明涉及绿色化学技术领域，具体为一种利用固体酸负载金属氧化物催化剂催化生物质乙酰丙酸直接制备可作为燃料组分长链烷烃的方法。
背景技术
燃料是支撑现代工业和人们日常生活的基础要素之一。面对化石燃料资源的日渐枯竭以及使用化石燃料所带来的全球气候变暖和环境污染问题，开发基于可再生资源和环境友好的燃料生产技术已成为国内外的研究热点。利用生物平台化合物为原料制备燃料是生物质化学利用的有效途径之一。
乙酰丙酸，又被称为4-氧代戊酸，在2004年的美国能源部生物质项目中被评为最有前景的12种生物平台分子之一。它可以由低品质或废弃的纤维素生物质，通过简单水解工艺直接转化生成，不需要复杂的预处理及转化途径，具有生产工艺简单、原料利用率高、生产成本低等优点。目前，对乙酰丙酸的应用研究主要集中在制备γ-戊内酯、二苯酚酸、δ-氨基乙酰丙酸、2-甲基四氢呋喃及乙酰丙酸酯等衍生物上，而以乙酰丙酸为原料制备生物燃料的研究相对较少。以乙酰丙酸为原料制备烃类生物燃料需经过两个反应过程：一是增长碳链以增加产物烃分子量，二是降低氧含量以增加产物烃能量密度。中科院过程工程研究所张锁江院士课题组(Green Chem,2014,16：3589～3595)通过乙酰丙酸先脱水生成当归内酯，当归内酯再经自由基反应得到二聚物和三聚物，最后加氢脱氧得到C6-C15的烷烃燃料。Blessing等(US20060135793A1,2006-06-22)在临氢状态下，采用酸性树脂(AmberlystCH-28)或分子筛(HZSM-5,Hβ)负载金属(Ni,Pd或Pt)的双功能催化剂催化乙酰丙酸的羟醛自缩合反应。在100-150℃和5-50bar的条件下，生成含有羰基的C10饱和脂肪二元羧酸，或具有一个羧基和一个内酯基团的C10化合物，或具有两个内酯基团的C10化合物，但原料乙酰丙酸的转化率仅为20％左右。
本发明采用固体酸负载金属氧化物为催化剂，催化乙酰丙酸羟醛自缩合延长碳链及缩合产物加氢脱氧的反应过程集成，实现基于生物质乙酰丙酸直接制备可作为燃料组分的长链烷烃。
发明内容
本发明的目的为针对当前技术的不足，提供一种基于生物质乙酰丙酸直接制备长链烷烃的方法。该方法使用固体酸负载金属氧化物为催化剂实现乙酰丙酸羟醛自缩合与缩合产物加氢脱氧的反应过程集成。本发明选择的催化剂具有高活性、选择性和稳定性的特点，工艺不仅具有工艺流程短、设备费用和操作费用低、环境友好等优点，而且设计制备的固体酸负载金属氧化物催化剂直接用于该反应过程，省去了催化剂的预还原等步骤。
本发明具体技术方案如下：
一种基于生物质乙酰丙酸直接制备长链烷烃的方法，该方法包括以下步骤：在高压釜中加入固体酸负载金属氧化物催化剂、溶剂和原料乙酰丙酸，充入氢气后，180～260℃下反应5～12h，得到长链烷烃；
其中催化剂的加入量为反应体系总质量的1～20％，氢气压力为2～6MPa。
所述的长链烷烃为含8～10个碳原子的饱和烷烃；
所述的溶剂为环己烷或二氯甲烷，其中溶剂与乙酰丙酸的质量比为1～6:1；
所述的固体酸负载金属氧化物催化剂，其组成包括金属氧化物、助剂和载体，其中，金属氧化物在催化剂中的质量分数为5～30％，助剂的质量分数为0～15％，其余为载体；所述的助剂质量分数为0时，是指不加入助剂。
所述的固体酸负载金属氧化物催化剂中的金属氧化物为下列金属氧化物中的两种或三种：CuO、Co3O4、PtO2、PdO、NiO、RuO2、Rh2O3或IrO2；
所述的固体酸负载金属氧化物催化剂中的助剂为：Ce、La、V、Mo、Re或W的氧化物；
所述的固体酸负载金属氧化物催化剂中的载体为固体酸，具体为：HZSM-5、NbOPO4、TiO2、ZrO2或Nb2O5；
本发明的有益效果如下：
1.本发明以生物平台分子乙酰丙酸为原料，经羟醛自缩合和加氢脱氧反应过程直接合成可作为生物燃料组分的长链烷烃，提供了一条基于乙酰丙酸原料合成生物燃料的新工艺，拓宽了生物质乙酰丙酸的应用领域。
2.本发明所提供的催化乙酰丙酸直接制备长链烷烃的固体酸负载金属氧化物催化剂，省去了催化剂的预还原步骤，简化了催化剂的制备流程，降低了操作费用。
3.采用固体酸负载金属氧化物催化剂催化乙酰丙酸直接制备长链烷烃，反应过程中催化剂上的金属氧化物逐渐被还原为金属位，从而强化反应按照先羟醛自缩合延长碳链再进行缩合产物加氢脱氧制备长链烷烃的顺序进行，进而获得较好的反应效果。乙酰丙酸的转化率可达100％，长链烷烃的选择性最高可达60％以上。
具体实施方式
本发明采用的催化乙酰丙酸直接制备长链烷烃的固体酸负载金属氧化物催化剂是公知材料，可以采用浸渍法制备：
以NiO-IrO2/ReO2-TiO2催化剂为例，其制备过程如下。首先，称取3.89g Ni(NO3)2·6H2O(以NiO质量计，负载量为10wt.％)和1.22g H2IrCl6·xH2O(以IrO2质量计，负载量为5wt.％)分别加入到50mL蒸馏水中。然后，将10g ReO2-TiO2(其中助剂ReO2的质量分数为8％)放入旋蒸瓶中，将溶解好的混合溶液倒入旋蒸瓶中，浸渍12h后于70℃旋蒸5h除去水分，将旋蒸好的固体放入干燥箱中于120℃干燥12h，然后在马弗炉中于450℃下焙烧2h，得到NiO-IrO2/ReO2-TiO2催化剂。
实施例其他涉及的催化剂照此制备。
实施例1
向100mL高压釜中加入5g乙酰丙酸、15g溶剂环己烷、以及NiO-IrO2/ReO2-TiO2催化剂3g，用N2置换空气，升温至230℃的反应温度下进行反应，充入5.0MPa H2，磁力搅拌9h。反应结束后对产液进行气相色谱分析，乙酰丙酸的转化率为100％，C5-C7饱和烷烃选择性为21.5％，C8-C10饱和烷烃选择性为61.3％。其中，C5-C7组分主要包括戊烷、己烷、3-甲基戊烷、甲基环戊烷、3-甲基己烷、4-甲基己烷、甲基环己烷等；C8-C10组分主要包括3-甲基庚烷、1,2-二甲基环己烷、3-甲基辛烷、4-甲基辛烷、2,4-二甲基庚烷、3,4-二甲基庚烷、壬烷、4-甲基壬烷、3,4二乙基己烷等。
实施例2
向100mL高压釜中加入5g乙酰丙酸、15g溶剂环己烷、以及NiO-RuO2/CeO2-TiO2催化剂3g，用N2置换空气，升温至240℃的反应温度下进行反应，充入6.0MPa H2，磁力搅拌6h。反应结束后对产液进行气相色谱分析，乙酰丙酸的转化率为100％，C5-C7饱和烷烃选择性为26.8％，C8-C10饱和烷烃选择性为56.2％。
实施例3
向100mL高压釜中加入5g乙酰丙酸、15g溶剂环己烷、以及RuO2-IrO2/La2O3-Nb2O5催化剂4g，用N2置换空气，升温至210℃的反应温度下进行反应，充入6.0MPa H2，磁力搅拌12h。反应结束后对产液进行气相色谱分析，乙酰丙酸的转化率为96.1％，C5-C7饱和烷烃选择性为19.1％，C8-C10饱和烷烃选择性为62.8％。
实施例4
向100mL高压釜中加入5g乙酰丙酸、15g溶剂环己烷、以及NiO-PdO/V2O5-ZrO2催化剂2g，用N2置换空气，升温至250℃的反应温度下进行反应，充入4.0MPa H2，磁力搅拌12h。反应结束后对产液进行气相色谱分析，乙酰丙酸的转化率为100％，C5-C7饱和烷烃选择性为23.1％，C8-C10饱和烷烃选择性为59.2％
实施例5
向100mL高压釜中加入5g乙酰丙酸、15g溶剂环己烷、以及NiO-PtO2/MoO3-HZSM-5催化剂2.5g，用N2置换空气，升温至260℃的反应温度下进行反应，充入3.0MPa H2，磁力搅拌8h。反应结束后对产液进行气相色谱分析，乙酰丙酸的转化率为98.8％，C5-C7饱和烷烃选择性为18.9％，C8-C10饱和烷烃选择性为58.1％。
实施例6
向100mL高压釜中加入5g乙酰丙酸、20g溶剂二氯甲烷、以及CuO-Rh2O3/CeO2-Nb2O5催化剂2.5g，用N2置换空气，升温至260℃的反应温度下进行反应，充入5.0MPa H2，磁力搅拌8h。反应结束后对产液进行气相色谱分析，乙酰丙酸的转化率为96.7％，C5-C7饱和烷烃选择性为26.6％，C8-C10饱和烷烃选择性为53.5％。
实施例7
向100mL高压釜中加入5g乙酰丙酸、20g溶剂环己烷、以及NiO-IrO2/NbOPO4催化剂3.75g，用N2置换空气，升温至250℃的反应温度下进行反应，充入5.0MPa H2，磁力搅拌10h。反应结束后对产液进行气相色谱分析，乙酰丙酸的转化率为100％，C5-C7饱和烷烃选择性为20.1％，C8-C10饱和烷烃选择性为63.6％。
实施例8
向100mL高压釜中加入10g乙酰丙酸、20g溶剂环己烷、以及IrO2-Co3O4/WO3-NbOPO4催化剂3g，用N2置换空气，升温至250℃的反应温度下进行反应，充入5.0MPa H2，磁力搅拌8h。反应结束后对产液进行气相色谱分析，乙酰丙酸的转化率为100％，C5-C7饱和烷烃选择性为22.6％，C8-C10饱和烷烃选择性为60.5％。
实施例9
向100mL高压釜中加入10g乙酰丙酸、20g溶剂二氯甲烷、以及RuO2-IrO2/ReO2-NbOPO4催化剂1.5g，用N2置换空气，升温至230℃的反应温度下进行反应，充入5.0MPa H2，磁力搅拌12h。反应结束后对产液进行气相色谱分析，乙酰丙酸的转化率为100％，C5-C7饱和烷烃选择性为17.8％，C8-C10饱和烷烃选择性为56.6％。
实施例10
向100mL高压釜中加入5g乙酰丙酸、20g溶剂环己烷、以及RuO2-NiO/ReO2-NbOPO4催化剂2.5g，用N2置换空气，升温至240℃的反应温度下进行反应，充入5.0MPa H2，磁力搅拌8h。反应结束后对产液进行气相色谱分析，乙酰丙酸的转化率为100％，C5-C7饱和烷烃选择性为16.8％，C8-C10饱和烷烃选择性为61.6％。将使用后的催化剂经乙醇洗涤、在120℃干燥6h，再于马弗炉中450℃焙烧2h后，重新用于催化生物质乙酰丙酸直接制备长链烷烃反应，催化剂使用五次后，其催化活性无明显变化。
由以上实施例可以看出，对于本发明提出的制备固体酸负载金属氧化物催化剂用于催化乙酰丙酸直接制备长链烷烃反应，催化剂表现出了较好的催化效果和重复使用性能，乙酰丙酸的转化率可达100％，长链烷烃的选择性最高可达60％以上。
以上所述仅为本发明的典型实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
本发明未尽事宜为公知技术。

Claims (1)

1.一种基于生物质乙酰丙酸直接制备长链烷烃的方法，其特征为该方法包括以下步骤：在高压釜中加入固体酸负载金属氧化物催化剂、溶剂和原料乙酰丙酸，充入氢气后，180~260 ℃下反应5~12 h，得到长链烷烃；
其中，催化剂的加入量为反应体系总质量的1~20%，溶剂与乙酰丙酸的质量比为1~6:1；氢气压力为2~6 MPa；
所述的固体酸负载金属氧化物催化剂，其组成包括金属氧化物、助剂和载体；金属氧化物在催化剂中的质量分数为5~30%，助剂的质量分数为0~15%，其余为载体；
所述的长链烷烃为含8~10个碳原子的饱和烷烃；
所述的溶剂为环己烷或二氯甲烷；
所述的固体酸负载金属氧化物催化剂中的金属氧化物为下列金属氧化物中的两种或三种：CuO、Co3O4、PtO2、PdO、NiO、RuO2、Rh2O3或IrO2；
所述的固体酸负载金属氧化物催化剂中的助剂为：Ce、La、V、Mo、Re或W的氧化物；
所述的固体酸负载金属氧化物催化剂中的载体为：HZSM-5、NbOPO4、TiO2、ZrO2或Nb2O5；
所述的方法以乙酰丙酸为原料，经羟醛自缩合和加氢脱氧反应过程直接合成得到长链烷烃。
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