CN106622368B - 一种脂肪酸酯加氢制备脂肪醇用的催化剂及其制法和应用 - Google Patents
一种脂肪酸酯加氢制备脂肪醇用的催化剂及其制法和应用 Download PDFInfo
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- CN106622368B CN106622368B CN201510738807.XA CN201510738807A CN106622368B CN 106622368 B CN106622368 B CN 106622368B CN 201510738807 A CN201510738807 A CN 201510738807A CN 106622368 B CN106622368 B CN 106622368B
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- sulfonic acid
- benzene sulfonic
- acid
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
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Abstract
本发明公开了一种脂肪酸酯加氢制备脂肪醇用的催化剂及其制法和应用。该催化剂为具有双功能催化活性位的核壳结构,以Pd或者Pt为核,以含有酸性位的多孔有机聚合物为壳。该催化剂能够高效的催化脂肪酸酯加氢制得脂肪醇,转化率可达95%以上。
Description
技术领域
本发明涉及化学化工领域,具体地说是一种脂肪酸酯加氢制备脂肪醇用的催化剂及其制法和应用。
背景技术
脂肪醇,特别是天然高级脂肪醇,是洗涤剂、表面活性剂、塑料增塑剂等精细化工产品的基础原料。由脂肪醇生产的精细化工产品有上千种之多,广泛用于化工、石油、冶金、纺织、机械、采矿、建筑、塑料、橡胶、皮革、造纸、交通运输、食品、医药卫生、日用化工以及农业等领域。
工业上生产脂肪醇主要有两条路线:一种是以烯烃为原料生产脂肪醇;另一种是以天然油脂为原料,天然油脂的主要成分为甘油三酸酯,其与甲醇发生酯交换,生成脂肪酸甲酯,再催化加氢得到脂肪醇。前者路线生产的脂肪醇价格偏高,而且合成的脂肪醇难降解;而后者路线生产的脂肪醇具有洗涤效果好、能够生物降解等特点。因而后者的合成路径具有更大的优势。
目前脂肪酸甲酯加氢的催化剂主要是Cu-Cr催化剂,反应的压力为16-30Mpa,温度为150-300℃,反应温度高,压力大。更重要的是Cr是一种有毒金属,目前已经被严格限制使用,开发新型的不含Cr的催化剂就成为一个重要的课题。
核壳型催化剂是一类新型的催化剂体系,其在诸多的反应中表现出了良好的反映效果。例如专利CN 102909007 A公布了一种二氧化硅包裹的核壳型催化剂,其在淀粉水解-加氢一步法生产山梨醇的反应中表现出了良好的催化效果。核壳型催化剂的壳层的性质对于催化反应的效果有着重要的影响。例如,文献Chem.Commun.2013,49,9591-9593中,核壳型催化剂壳层的疏水性对于催化反应的影响较大。因此,设计并制备具有特殊性质壳层的核壳型催化剂,并研究其催化效果,就成为了一个重要的课题。
多孔有机聚合物是近年来发展起来的一类新型的多孔材料,具有比表面大,比重低,合成简便等特点。其在催化方面取得了许多重要的进展,比如文献Chem.Eur.J.2012,18,6718–6723报道了一种碱性多孔有机聚合物,其在不对称耦合方面取得了良好的催化效果。但是关于多孔有机聚合物的认识还远远不足,探索其在其他催化方面中的依然十分紧迫。
发明内容
本发明旨在提供一种脂肪酸酯加氢制备脂肪醇的催化剂及其制备方法以及所述催化剂在脂肪酸酯加氢制备脂肪醇反应中的应用。相比于传统的负载型催化剂,本发明的催化剂具有稳定性好,抗烧结等性质;底物的普适性好,催化反应的转化率高,产物醇的选择性高。
本发明采用的技术方案为:
一种脂肪酸酯加氢制备脂肪醇用的催化剂,所述催化剂为一种核壳结构,以金属纳米颗粒Pd或Pt为核,以含有酸性位的多孔有机聚合物为壳。催化剂的粒径范围为50-250nm,壳层厚度为30-245nm,金属纳米颗粒的粒径范围5-20nm。所得的催化剂为粒径均一的核壳形貌,金属纳米颗粒位于球体中心,比表面积高,可达300m2/g以上。
所述含有酸性位的多孔有机聚合物为1,3,5-三溴苯或1,3,5-三碘苯与3,5-二乙炔基苯磺酸形成的聚合物(CMP)。
3,5-二乙炔基苯磺酸的结构式如下:
该催化剂为双功能催化活性位的核壳结构,以金属纳米颗粒核为加氢活性位,以酸性壳作为酯解聚活性位。
所述的催化剂按照以下方法制备:
1)将聚乙烯吡咯烷酮加入到氯铂酸或者氯化钯的水溶液中去,搅拌均匀,加入NaBH4水溶液还原后,搅拌均匀;
2)离心1)中所得的溶液,浓缩,将所得浓缩液加入到甲苯和三乙胺混合溶液中去,搅拌均匀;
3)加入1,3,5-三溴苯和3,5-二乙炔基苯磺酸,加入三苯基磷氯化钯和CuI作为聚合反应的催化剂,在剧烈搅拌的条件下,加热至80-120℃,优选为85-95℃,使1,3,5-三溴苯和3,5-二乙炔基苯磺酸在Pd和Pt颗粒的表面均匀聚合,聚合时间为12-48h,优选为22-26h,形成以金属纳米颗粒为核,多孔有机聚合物为壳的核壳材料的粗产品;
4)将得到的固体用乙醇为溶剂进行索氏提取,提取12-72h,优选为22-26h,得到以金属纳米颗粒为核,多孔有机聚合物为壳的核壳材料。
氯铂酸与氯化钯的水溶液的浓度,聚乙烯吡咯烷酮的质量以及硼氢化钠的水溶液的浓度和质量对于最终形成的Pt和Pd纳米颗粒的粒径,分散程度起着决定性的作用。而Pt和Pd纳米颗粒的粒径以及分散情况对于之后步骤中能否形成核壳结构有着重要的作用。所述氯铂酸或者氯化钯的水溶浓度为0.1–5wt%,优选为1.9-2.1wt%,加入的聚乙烯吡咯烷酮的量为氯铂酸或者氯化钯质量的1-4倍,优选为1.9-2.1倍,NaBH4水溶液的浓度为0.1–5wt%,优选为1.9-2.1wt%,加入NaBH4的总质量为氯铂酸或者氯化钯质量的10-100倍,优选为19-21倍。
其中甲苯和三乙胺混合溶液的量为浓缩液体积的1-100倍,优选为39-41倍,三乙胺在混合溶液中的质量比例为1-30wt%,优选为5-7%;
1,3,5-三溴苯和3,5-二乙炔基苯磺酸或1,3,5-三碘苯和3,5-二乙炔基苯磺酸总质量决定了最终形成的材料的形貌的状态,量过少则不能完成对所有的纳米颗粒的包裹,量过多则有的核壳结构中缺少纳米颗粒,加入的1,3,5-三溴苯和3,5-二乙炔基苯磺酸或1,3,5-三碘苯和3,5-二乙炔基苯磺酸总质量为氯铂酸或者氯化钯质量的1-30倍,优选为9-11倍。1,3,5-三溴苯与3,5-二乙炔基苯磺酸或1,3,5-三碘苯和3,5-二乙炔基苯磺酸对于形成多孔有机聚合物的结构有着重要的作用,二者的比例过高或者过低都不会形成多孔有机聚合物,1,3,5-三溴苯与3,5-二乙炔基苯磺酸或1,3,5-三碘苯和3,5-二乙炔基苯磺酸的质量比为1:1-1:1.5,优选为1:1,加入的三苯基磷氯化钯质量为1,3,5-三溴苯和3,5-二乙炔基苯磺酸或1,3,5-三碘苯和3,5-二乙炔基苯磺酸总质量1-5wt%,CuI的加入量为三苯基磷氯化钯质量为1,3,5-三溴苯和3,5-二乙炔基苯磺酸或1,3,5-三碘苯和3,5-二乙炔基苯磺酸总质量1-5wt%。
本发明所述催化剂在脂肪酸酯加氢制备脂肪醇反应中的应用。
所述反应温度为120-300℃,反应的压力为1.0-4.0MPa。
所述的脂肪酸酯为C1-C8脂肪酸与C1-C8脂肪醇形成的酯中的一种,脂肪酸酯具体为辛酸甲酯,辛酸乙酯,辛酸丙酯,辛酸丁酯,辛酸戊酯,辛酸己酯,辛酸庚酯,辛酸辛酯;庚酸甲酯,庚酸乙酯,庚酸丙酯,庚酸丁酯,庚酸戊酯,庚酸己酯,庚酸庚酯,庚酸辛酯;己酸甲酯,己酸乙酯,己酸丙酯,己酸丁酯,己酸戊酯,己酸己酯,己酸庚酯,己酸辛酯;戊酸甲酯,戊酸乙酯,戊酸丙酯,戊酸丁酯,戊酸戊酯,戊酸己酯,戊酸庚酯,戊酸辛酯;丁酸甲酯,丁酸乙酯,丁酸丙酯,丁酸丁酯,丁酸戊酯,丁酸己酯,丁酸庚酯,丁酸辛酯;丙酸甲酯,丙酸乙酯,丙酸丙酯,丙酸丁酯,丙酸戊酯,丙酸己酯,丙酸庚酯,丙酸辛酯;乙酸甲酯,乙酸乙酯,乙酸丙酯,乙酸丁酯,乙酸仲丁酯,乙酸戊酯,乙酸己酯,乙酸庚酯,乙酸辛酯。
本发明的优点:
相比于传统的负载型催化剂,本发明的催化剂的核壳结构使得催化剂的金属活性位具有稳定性好,抗烧结等性质;多孔有机聚合物的多孔性质保证了各种底物能够顺利的接触加氢位点,从而使得该催化剂的底物普适性较高。而该催化剂的酸性位与加氢活性位分别位于核壳结构中的核和壳的位置,二者位置的分离使得反应只能先进行加氢后进行解聚,从而避免了副反应,使得催化反应的转化率高,产物醇的选择性高。本发明将材料科学、纳米技术、催化剂工程结合起来,提出了制备催化剂的新思路,具有重要的应用价值,该催化剂能够高效的催化脂肪酸酯加氢制得脂肪醇,转化率可达95%以上。
附图说明
图1为实施例1中所得Pt@CMP的电镜图;
图2为实施例1中所得Pt@CMP的氮气吸附脱附等温曲线。
具体实施方式
下面结合附图实施例对本发明提供的方法进行详述,但不以任何形式限制本发明。
实施例1
将30mg聚乙烯吡咯烷酮加入到20g 0.1wt%氯铂酸水溶液中去,搅拌均匀,加入5g5wt%NaBH4水溶液,还原搅拌均匀。离心上述所得溶液,浓缩至0.5mL,将所得浓缩液加入到50mL甲苯/三乙胺(甲苯:三乙胺=8:1)混合溶液中去,搅拌均匀。
加入100mg 1,3,5-三溴苯和120mg 3,5-二乙炔基苯磺酸,加入10mg三苯基磷氯化钯和5mg CuI作为聚合反应的催化剂,在剧烈搅拌的条件下,加热至100℃,使1,3,5-三溴苯和3,5-二乙炔基苯磺酸在所得的Pt颗粒的表面均匀聚合,聚合时间为24h。将得到的固体用乙醇为溶剂进行索氏提取,提取48h。得到以Pt纳米颗粒为核,多孔有机聚合物为壳的核壳材料Pt@CMP。
实施例2
将60mg聚乙烯吡咯烷酮加入到20g 0.5wt%氯化钯水溶液中去,搅拌均匀,加入5g5wt%NaBH4水溶液,还原搅拌均匀。离心上述所得溶液,浓缩至1mL,将所得浓缩液加入到40mL甲苯/三乙胺(甲苯:三乙胺=4:1)混合溶液中去,搅拌均匀。
加入90mg 1,3,5-三溴苯和110mg 3,5-二乙炔基苯磺酸,加入8mg三苯基磷氯化钯和5mg CuI作为聚合反应的催化剂,在剧烈搅拌的条件下,加热至100℃,使1,3,5-三溴苯和3,5-二乙炔基苯磺酸在所得的Pd颗粒的表面均匀聚合,聚合时间为24h。将得到的固体用乙醇为溶剂进行索氏提取,提取24h。得到以Pt纳米颗粒为核,多孔有机聚合物为壳的核壳材料Pd@CMP。
实施例3
将40mg聚乙烯吡咯烷酮加入到20g 0.5wt%氯铂酸水溶液中去,搅拌均匀,加入10g 5wt%NaBH4水溶液,还原搅拌均匀。离心上述所得溶液,浓缩至0.5mL,将所得浓缩液加入到40mL甲苯/三乙胺(甲苯:三乙胺=4:1)混合溶液中去,搅拌均匀。
加入100mg 1,3,5-三碘苯和110mg 3,5-二乙炔基苯磺酸,加入8mg三苯基磷氯化钯和5mg CuI作为聚合反应的催化剂,在剧烈搅拌的条件下,加热至100℃,使1,3,5-三溴苯和3,5-二乙炔基苯磺酸在所得的Pt颗粒的表面均匀聚合,聚合时间为12h。将得到的固体用乙醇为溶剂进行索氏提取,提取12h。得到以Pt纳米颗粒为核,多孔有机聚合物为壳的核壳材料Pt@CMP。
催化剂加氢性能测试:
测试方法:
间歇釜式加氢反应装置:
将10mg催化剂加入到高压釜中,加入4mL酯类底物,密封,升温至相应的温度,充氢气至相应的压力,搅拌反应4h。反应过后用色谱内标法来确定反应的转化率和选择性。
相比于传统的负载型催化剂,本发明的催化剂酸性位与加氢活性位分别位于核壳结构中的核和壳的位置,二者位置的分离使得反应只能先进行加氢后进行解聚,从而避免了副反应,使得催化反应的转化率高,产物醇的选择性高。而核壳结构中的新型材料多孔有机聚合物的多孔性质保证了各种底物能够顺利的接触加氢位点,从而使得该催化剂的底物普适性较高。本发明的催化剂的核壳结构使得催化剂的金属活性位具有稳定性好,抗烧结等性质;本发明的催化剂将材料科学、纳米技术、催化剂工程结合起来,提出了制备催化剂的新思路,具有重要的应用价值,该催化剂能够高效的催化脂肪酸酯加氢制得脂肪醇。
Claims (9)
1.一种脂肪酸酯加氢制备脂肪醇用的催化剂,其特征在于:所述催化剂为一种核壳结构,以金属纳米颗粒Pd或Pt为核,以含有酸性位的多孔有机聚合物为壳;所述含有酸性位的多孔有机聚合物为1,3,5-三溴苯与3,5-二乙炔基苯磺酸形成的聚合物(CMP)或1,3,5-三碘苯与3,5-二乙炔基苯磺酸形成的聚合物(CMP)。
2.按照权利要求1所述的催化剂,其特征在于:催化剂的粒径为50-250 nm,壳层厚度为30-245 nm,金属纳米颗粒的粒径为5-20 nm。
3.按照权利要求1所述的催化剂,其特征在于:该催化剂为双功能催化活性位的核壳结构,以金属纳米颗粒核为加氢活性位,以酸性壳为酯解聚活性位。
4.按照权利要求1-3任一所述催化剂的制备方法,其特征在于:所述的催化剂按照以下方法制备:
1)将聚乙烯吡咯烷酮加入到氯铂酸水溶液或者氯化钯水溶液中去,加入NaBH4水溶液,对氯铂酸和氯化钯还原,搅拌均匀;
2)离心浓缩1)中所得的溶液,将所得的浓缩液加入到甲苯和三乙胺混合溶液中去,搅拌均匀;
3)加入1,3,5-三溴苯和3,5-二乙炔基苯磺酸或者1,3,5-三碘苯和3,5-二乙炔基苯磺酸,加入三苯基膦氯化钯和CuI作为聚合反应的催化剂,在剧烈搅拌的条件下,加热至80-120 ℃,使1,3,5-三溴苯和3,5-二乙炔基苯磺酸或者1,3,5-三碘苯和3,5-二乙炔基苯磺酸在Pd或Pt颗粒的表面均匀聚合,聚合时间为12-48 h,形成以金属纳米颗粒为核,多孔有机聚合物为壳的核壳材料的粗产品;
4)将得到的固体,用乙醇为溶剂进行索氏提取,提取12-72 h,得到以金属纳米颗粒为核,多孔有机聚合物为壳的核壳材料。
5.按照权利要求4所述的制备方法,其特征在于:所述氯铂酸水溶液或者氯化钯水溶液的浓度均为0.1–5 wt%,加入的聚乙烯吡咯烷酮的量为氯铂酸或者氯化钯质量的1-4倍,NaBH4水溶液的浓度为0.1–5 wt%,加入NaBH4水溶液的总质量为氯铂酸水溶液或者氯化钯水溶液质量的10-100倍。
6.按照权利要求5所述的制备方法,其特征在于:甲苯和三乙胺混合溶液的量为浓缩液体积的1-100倍,三乙胺在混合溶液中的质量比例为1-30 wt%;
加入的1,3,5-三溴苯和3,5-二乙炔基苯磺酸或者1,3,5-三碘苯和3,5-二乙炔基苯磺酸总质量为氯铂酸或者氯化钯质量的1-30倍,1,3,5-三溴苯与3,5-二乙炔基苯磺酸的质量比为1:1-1:1.5,加入的三苯基膦氯化钯质量为1,3,5-三溴苯和3,5-二乙炔基苯磺酸或者1,3,5-三碘苯和3,5-二乙炔基苯磺酸总质量1-5 wt%,CuI的加入量为1,3,5-三溴苯和3,5-二乙炔基苯磺酸或者1,3,5-三碘苯和3,5-二乙炔基苯磺酸总质量1-5 wt%。
7.一种权利要求1-3任一所述催化剂在脂肪酸酯加氢制备脂肪醇反应中的应用。
8.按照权利要求7所述的应用,其特征在于:所述反应温度为120-300 oC,反应的压力为1.0-4.0 MPa。
9.按照权利要求7所述的应用,其特征在于:所述的脂肪酸酯为C2-C8脂肪酸与C1-C8脂肪醇形成的酯中的一种。
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