CN116217371A - 一种葡萄糖经mof材料催化转化制乳酸酯的方法 - Google Patents
一种葡萄糖经mof材料催化转化制乳酸酯的方法 Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 32
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 29
- 239000008103 glucose Substances 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 21
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000013110 organic ligand Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 claims description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 abstract description 2
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 34
- 239000004310 lactic acid Substances 0.000 description 17
- 235000014655 lactic acid Nutrition 0.000 description 17
- 239000012621 metal-organic framework Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 239000013173 zeolitic imidazolate framework-9 Substances 0.000 description 2
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- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
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- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000003903 lactic acid esters Chemical class 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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Abstract
一种葡萄糖经MOF材料催化转化制乳酸酯的方法，采用高压反应釜系统，MOF材料作为催化剂，醇类作为溶剂，温度为423～503K，充入1～2MPa N2，反应时间为2h的条件下将葡萄糖催化转化为乳酸酯；本发明具有装置简单、催化剂合成简便、目标产物乳酸酯的收率高等优点。
Description
技术领域
本发明涉及多相催化法制备乳酸领域，尤其涉及一种葡萄糖经MOF材料催化转化制乳酸酯的方法。
背景技术
有机酸在人们的生活及化工工业中有着非常广泛的利用，尤其是乳酸，其消耗量是仅次于柠檬酸的有机酸，在农业、工业、医学、食品等方面都有较大量的应用。从原子经济学角度考虑，以纤维素或其水解产物葡萄糖为原料制备乳酸是一条非常理想的路线，不仅具有高的原子利用率，也能减少化石能源的使用。目前工业上乳酸的生产主要是以葡萄糖为原料经过生物发酵法来进行，但生物发酵法的时空收率较低，而且由于要调节微生物生存所需要的pH，会消耗大量的无机盐，另外，生物发酵法生产的乳酸在分离提纯方面也比较复杂。因此，发展高效的、易分离的化学催化方法来从生物质生产乳酸具有重要意义。
目前基于化学催化法制备生物质基乳酸及其衍生酯类，以纤维素或葡萄糖制备乳酸首先需要在酸或碱的条件下使葡萄糖异构成果糖，再经由酸或碱催化发生反羟醛缩合反应致使C3-C4键发生断裂而生成甘油醛和甘油酮，之后发生异构、脱水等过程而生成乳酸，其中，如何打破葡萄糖与果糖的异构平衡而减少葡萄糖的反羟醛缩合反应是提高乳酸收率的关键。虽然均相催化的收率较高，能够达到80％以上，但是其产物的分离是制约其作为工业应用的最大困难，此外，强碱NaOH会对反应设备有一定的腐蚀，Pb2+本身也对环境具有一定的危害作用。因此，将均相催化多相化并获得高收率的乳酸或其酯类衍生物是非常值得研究的。
发明内容
本发明的目的在于解决现有技术中的上述问题，提供一种葡萄糖经MOF材料催化转化制乳酸酯的方法，具有装置简单、催化剂合成简便、目标产物乳酸酯的收率高等优点。
为达到上述目的，本发明采用如下技术方案：
一种葡萄糖经MOF材料催化转化制乳酸酯的方法，采用高压反应釜系统，MOF材料作为催化剂，醇类作为溶剂，温度为423～503K，充入1～2MPa N2，反应时间为2h的条件下将葡萄糖催化转化为乳酸酯；反应产物采用液相色谱进行定量检测。
所述的MOF材料采用水热法或溶剂热法合成。
所述MOF材料金属中心为Zn、Co、In或Al。
所述MOF材料有机配体为对苯二甲酸、均苯三甲酸、均苯四甲酸、苯并咪唑、2,6-萘二羧酸或1,4,5,8-萘四羧酸。
所述醇类为甲醇、乙醇、正丙醇、正丁醇中的一种或几种。
相对于现有技术，本发明技术方案取得的有益效果是：
本发明采用酸性合适的MOF材料作为催化剂，有效地催化葡萄糖及三碳糖的异构以及果糖的反羟醛缩合反应；本发明采用醇类作为反应溶剂，有效地避免了乳酸在水溶液中的副反应，收率显著提高；本发明装置简单、催化剂合成简便，并且催化剂可回收重复利用，具有工业化生产的潜力。
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚、明白，以下结合实施例，对本发明做进一步详细说明。
金属有机框架化合物(MOF)是一类新型无机有机杂化材料，其由金属离子和有机配体自组装而成，其结构具有诸多特征，如比表面积大、孔隙率高、金属含量高、后处理方法多。
本发明中，葡萄糖催化转化为乳酸的反应路径如下：
实施例1
制备MOF-5(Zn)：称取2.4g Zn(NO3)2·6H2O以及0.66g对苯二甲酸(BDC)使之均匀的溶解在80ml N,N-二甲基甲酰胺(DMF)中，待溶液澄清后，在大力搅拌下逐滴加入4.4ml的三乙胺(TEA)，之后在室温下继续搅拌1h，所得悬浮液离心以分离液体，固体产物分散到100ml DMF中，室温搅拌8h，重复上述洗涤操作6次，将DMF洗涤后的固体产物再分散到60ml三氯甲烷中，室温搅拌8h，重复6次以完全交换掉客体分子DMF，最后，离心分离，所得固体于333K真空干燥箱中干燥12h。
在反应器中称取MOF-5(Zn)0.1g，葡萄糖0.1g，溶剂甲醇20ml，充入1MPa N2于463K反应条件下反应2h。
反应结束后经液相色谱检测，葡萄糖转化率>99％，乳酸收率为33.3％。
实施例2
制备MIL-120(Al)：称取12.8g Al(NO3)3·9H2O以及2.0g均苯四甲酸(PMA)溶解于80ml的去离子水中，搅拌并逐滴加入13.6ml 4mol L-1的NaOH溶液，继续搅拌30min后将其转移到200ml的聚四氟乙烯内衬中，于483K烘箱中加热反应24h，所得悬浮液过滤并用乙醇和水多次洗涤，固体产物置于333K烘箱中过夜干燥。
在反应器中称取MIL-120(Al)0.1g，葡萄糖0.1g，溶剂甲醇20ml，充入1MPa N2于463K反应条件下反应2h。
反应结束后经液相色谱检测，葡萄糖转化率>99％，乳酸收率为43.4％。
实施例3
制备ZIF-9(Co)：称取2.1g Co(NO3)2·6H2O和0.6g苯并咪唑溶解于180ml DMF中，搅拌成均一溶液后密封，所得溶液置于烘箱中，采用程序升温的方法从室温升至403K并反应48h，升温速率为5K min-1，反应结束，所得溶液过滤并用DMF多次洗涤，固体产物置于333K烘箱中过夜干燥。
在反应器中称取ZIF-9(Co)0.1g，葡萄糖0.1g，溶剂甲醇20ml，充入1MPa N2于463K反应条件下反应2h。
反应结束后经液相色谱检测，葡萄糖转化率>99％，乳酸收率为32.1％。
实施例4
在反应器中称取实施例2中制备的MIL-120(Al)0.1g，葡萄糖0.01g，溶剂甲醇20ml，充入1MPa N2于463K反应条件下反应2h。
反应结束后经液相色谱检测，葡萄糖转化率>99％，乳酸收率为69.1％。
Claims (4)
1.一种葡萄糖经MOF材料催化转化制乳酸酯的方法，其特征在于：采用高压反应釜，MOF材料作为催化剂，醇类作为溶剂，温度为423～503K，充入1～2MPa N2，将葡萄糖催化转化为乳酸酯，所述MOF材料的金属中心为Zn、Co、In或Al。
2.如权利要求1所述的一种葡萄糖经MOF材料催化转化制乳酸酯的方法，其特征在于：所述MOF材料采用水热法或溶剂热法合成。
3.如权利要求1所述的一种葡萄糖经MOF材料催化转化制乳酸酯的方法，其特征在于：所述MOF材料的有机配体为对苯二甲酸、均苯三甲酸、均苯四甲酸、苯并咪唑、2,6-萘二羧酸或1,4,5,8-萘四羧酸。
4.如权利要求1所述的一种葡萄糖经MOF材料催化转化制乳酸酯的方法，其特征在于：所述醇类为甲醇、乙醇、正丙醇、正丁醇中的一种或几种。
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