CN116283842A - 一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法 - Google Patents
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法 Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 35
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
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- 239000012279 sodium borohydride Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 30
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- 238000002360 preparation method Methods 0.000 claims description 21
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- 239000004246 zinc acetate Substances 0.000 claims description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
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- 229960001668 cefuroxime Drugs 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 150000002240 furans Chemical class 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种糠醛选择性加氢合成四氢‑2‑呋喃甲醛的方法。首先在高压釜中依次加入钯基催化剂、糠醛和溶剂,混合均匀;然后调节高压釜温度为30~70℃,氢气压力为0.1~1MPa,反应时间0.5~8h,得到四氢‑2‑呋喃甲醛。本发明糠醛选择性加氢合成四氢‑2‑呋喃甲醛反应具有很好的催化效果,糠醛转化率可达到98.8%,目标产物四氢‑2‑呋喃甲醛的选择性最高可达91.2%。
Description
技术领域
本发明属于四氢-2-呋喃甲醛合成技术领域,具体涉及一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法。
背景技术
生物质是一种非常重要的可再生碳资源,以其用作原料可以制备许多有价值的化学品。其中,选择性加氢反应是实现生物质及其衍生物转化为有价值化合品的重要反应。然而,由于许多的生物质及其衍生物包含不止一种不饱和官能团,使其可控的选择性加氢到理想产物通常是一个巨大的挑战。
糠醛是一种非常重要的生物质平台化合物。糠醛分子中的C=O键及呋喃环上C=C键决定了加氢反应主要发生在C=O键及呋喃环上C=C键加氢。在热力学上,C=C键和C=O键的键能分别为615kJ/mol和715kJ/mol。因此,C=C键比C=O键更容易加氢。但是从糠醛的结构考虑,由于空间位阻的影响,C=O键相比于C=C键更容易接触到加氢活性金属表面,进而更有利于C=O键加氢,并且C=C键和C=O键形成共扼体系,使得C=O键加氢更为容易,因此在糠醛选择性加氢反应过程中,会发生C=C键和C=O键加氢的竞争反应。糠醛的C=O键和呋喃环上C=C键加氢的活化能分别为31.77kJ/mol和34.28kJ/mol。显然,糠醛的C=O键相比呋喃环上C=C键更容易加氢。因此,大多数研究者对糠醛选择性加氢反应的研究主要集中在实现其C=O键加氢,主要用于合成糠醇、2-甲基呋喃、环戊酮、呋喃、四氢糠醇、1,2-戊二醇、环戊醇和1,4-丁二醇。
四氢糠醛是生产呋喃类药物的重要中间体,如雷尼替丁、哌唑嗪、呋塞米和头孢呋辛,已广泛应用于制药行业。传统的四氢糠醛生产过程主要有两种方法:一是使用Rh(acac)CO2、HRh(CO)(PPh3)3或RhCl(CO)(PPh3)2作为催化剂催化二氢呋喃氢甲酰化反应合成四氢糠醛;二是2-呋喃锂与CO反应合成四氢糠醛。显然,这两种方法使用的原料环境不友好,而且生产过程较为复杂。使用生物质糠醛作为原料,通过选择性加氢反应制备四氢糠醛不仅符合绿色可持续发展的要求,而且反应较为简单。但是在常用的催化剂体系中,C=O键比呋喃环上的C=C键更容易加氢。因此,开发绿色高效的催化剂用于催化糠醛选择性加氢合成四氢-2-呋喃甲醛反应具有重要的学术价值和经济价值。
发明内容
本发明的目的在于提供一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法。
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)在高压釜中依次加入钯基催化剂、糠醛和溶剂,混合均匀;
(2)调节高压釜温度为30~70℃,氢气压力为0.1~1MPa,反应时间0.5~8h,得到四氢-2-呋喃甲醛。
所述钯基催化剂的加入量为糠醛质量的1~30%。
所述溶剂的加入量为糠醛质量的20~120倍。
所述的溶剂为乙醇或异丙醇。
步骤(1)中还加入占糠醛质量0.5~3%的助剂,所述助剂为AlCl3、FeCl3、硬脂酸锌或乙酸锌。
所述钯基催化剂为Pd/MgO、Pd/γ-Al2O3、Pd/ZrO2、Pd/α-Al2O3、Pd/ZSM-5、Pd/TiO2中的一种或几种。
所述钯基催化剂的制备方法如下:
(1)将0.01~0.04g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.01~0.04g的聚乙烯醇和0.01~0.04g的硼氢化钠先后加入到A液中;
(3)生成溶胶20-40min后,在剧烈搅拌下加入0.6~1.8g的载体,并将溶液用0.1mol·L-1H2SO4调至pH=1.5~3.5;
(4)0.5~2h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内70~90℃过夜,制成。
所述载体为MgO、γ-Al2O3、ZrO2、α-Al2O3、ZSM-5或TiO2。
本发明的有益效果:
(1)本发明所制备的负载型Pd/M(M=MgO、γ-Al2O3、ZrO2、α-Al2O3、ZSM-5和TiO2)催化剂具有制备过程简单、催化活性高、易于分离等优点。
(2)本发明所提供的工艺方法在合成四氢-2-呋喃甲醛的同时,也可以得到糠醇、四氢糠醇两种重要的有机化工产品。
(3)本发明提供的负载型Pd/M(M=MgO、γ-Al2O3、ZrO2、α-Al2O3、ZSM-5和TiO2)催化剂对生物平台分子糠醛选择性加氢合成四氢-2-呋喃甲醛反应具有很好的催化效果,糠醛转化率可达到98.8%,目标产物四氢-2-呋喃甲醛的选择性最高可达91.2%。
具体实施方式
为了便于理解本发明,下面将对本发明进行更全面的描述。但是,本发明可以以许多不同的形式来实现,并不限于本文所描述的实施例。相反地,提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
实施例1
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)向100mL高压釜中加入1.44g糠醛和0.34g的Pd/γ-Al2O3催化剂,50mL的异丙醇作溶剂;
(2)先用N2置换空气、而后用H2置换,在50℃的反应温度下,充入H2维持压力1MPa,机械搅拌90min;反应结束后对产液进行气相色谱分析,糠醛的转化率为56.8%,四氢-2-呋喃甲醛收率为43.2%。
所述Pd/γ-Al2O3催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入1.009g的γ-Al2O3载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
实施例2
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)向100mL高压釜中加入1.44g糠醛和0.34g的Pd/α-Al2O3催化剂,50mL的异丙醇作溶剂;
(2)先用N2置换空气、而后用H2置换,在30℃的反应温度下,充入H2维持压力0.6MPa,机械搅拌2h;反应结束后对产液进行气相色谱分析,糠醛的转化率为20.4%,四氢-2-呋喃甲醛收率为15.8%。
所述Pd/γ-Al2O3催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入1.009g的α-Al2O3载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
实施例3
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)向100mL高压釜中加入0.768g糠醛和0.2g的Pd/γ-Al2O3催化剂,50mL的乙醇作溶剂。
(2)先用N2置换空气、而后用H2置换,在70℃的反应温度下,充入H2维持压力0.1MPa,机械搅拌5h;反应结束后对产液进行气相色谱分析,糠醛的转化率为65.8%,四氢-2-呋喃甲醛收率为58.9%。
所述Pd/γ-Al2O3催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入1.009g的γ-Al2O3载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
实施例4
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)向100mL高压釜中加入1.44g糠醛和0.34g的Pd/γ-Al2O3催化剂,50mL的异丙醇作溶剂,0.02gFeCl3为助剂;
(2)先用N2置换空气、而后用H2置换,在50℃的反应温度下,充入H2维持压力0.1MPa,机械搅拌5h;反应结束后对产液进行气相色谱分析,糠醛的转化率为71.6%,四氢-2-呋喃甲醛收率为58.8%。
所述Pd/γ-Al2O3催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入1.009g的γ-Al2O3载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
实施例5
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)向100mL高压釜中加入1.44g糠醛和0.34g的Pd/MgO催化剂,50mL的异丙醇作溶剂;
(2)先用N2置换空气、而后用H2置换,在50℃的反应温度下,充入H2维持压力1MPa,机械搅拌90min;反应结束后对产液进行气相色谱分析,糠醛的转化率为48.8%,四氢-2-呋喃甲醛收率为39.8%。
所述Pd/MgO催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入0.872g的MgO载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
实施例6
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)向100mL高压釜中加入1.44g糠醛和0.34g的Pd/ZSM-5催化剂,50mL的异丙醇作溶剂;
(2)先用N2置换空气、而后用H2置换,在50℃的反应温度下,充入H2维持压力1MPa,机械搅拌90min;反应结束后对产液进行气相色谱分析,糠醛的转化率为49.9%,四氢-2-呋喃甲醛收率为41.2%。
所述Pd/ZSM-5催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入0.881g的ZSM-5载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
实施例7
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)向100mL高压釜中加入1.44g糠醛和0.34g的Pd/TiO2催化剂,50mL的异丙醇作溶剂;
(2)先用N2置换空气、而后用H2置换,在50℃的反应温度下,充入H2维持压力1MPa,机械搅拌90min;反应结束后对产液进行气相色谱分析,糠醛的转化率为43.3%,四氢-2-呋喃甲醛收率为31.5%。
所述Pd/TiO2催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入0.876g的TiO2载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
实施例8
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)向100mL高压釜中加入1.44g糠醛和0.34g的Pd/ZrO2催化剂,50mL的异丙醇作溶剂;
(2)先用N2置换空气、而后用H2置换,在50℃的反应温度下,充入H2维持压力1MPa,机械搅拌90min;反应结束后对产液进行气相色谱分析,糠醛的转化率为48.6%,四氢-2-呋喃甲醛收率为39.1%。
所述Pd/ZrO2催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入0.973g的ZrO2载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
实施例9
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)向100mL高压釜中加入1.44g糠醛和0.34g的Pd/γ-Al2O3催化剂,50mL的乙醇作溶剂,0.01g硬脂酸锌做助剂;
(2)先用N2置换空气、而后用H2置换,在70℃的反应温度下,充入H2维持压力0.2MPa,机械搅拌3h;反应结束后对产液进行气相色谱分析,糠醛的转化率为68.2%,四氢-2-呋喃甲醛收率为52.9%;
所述Pd/γ-Al2O3催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入1.009g的γ-Al2O3载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
实施例10
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)向100mL高压釜中加入1.44g糠醛和0.34g的Pd/γ-Al2O3催化剂,50mL的乙醇作溶剂,0.01g乙酸锌做助剂;
(2)先用N2置换空气、而后用H2置换,在70℃的反应温度下,充入H2维持压力0.2MPa,机械搅拌8h。反应结束后对产液进行气相色谱分析,糠醛的转化率为76.2%,四氢-2-呋喃甲醛收率为70.5%;
所述Pd/γ-Al2O3催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入1.009g的γ-Al2O3载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
实施例11
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)向100mL高压釜中加入1.44g糠醛和0.17gPd/γ-Al2O3催化剂和0.17gPd/ZSM-5催化剂,50mL的异丙醇作溶剂;
(2)先用N2置换空气、而后用H2置换,在50℃的反应温度下,充入H2维持压力1MPa,机械搅拌90min;反应结束后对产液进行气相色谱分析,糠醛的转化率为78.9%,四氢-2-呋喃甲醛收率为68.2%。
所述Pd/γ-Al2O3催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入1.009g的γ-Al2O3载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
所述Pd/ZSM-5催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入0.881g的ZSM-5载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
实施例12
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)向100mL高压釜中加入1.44g糠醛和0.17gPd/ZrO2催化剂和0.17gPd/MgO催化剂,50mL的异丙醇作溶剂;
(2)先用N2置换空气、而后用H2置换,在50℃的反应温度下,充入H2维持压力1MPa,机械搅拌90min;反应结束后对产液进行气相色谱分析,糠醛的转化率为81.1%,四氢-2-呋喃甲醛收率为73.2%。
所述Pd/ZrO2催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入0.973g的ZrO2载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
所述Pd/MgO催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入0.872g的MgO载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
实施例13
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)向100mL高压釜中加入1.44g糠醛和0.17gPd/γ-Al2O3催化剂和0.17gPd/ZSM-5催化剂,50mL的异丙醇作溶剂,0.01g乙酸锌做助剂;
(2)先用N2置换空气、而后用H2置换,在50℃的反应温度下,充入H2维持压力1MPa,机械搅拌90min;反应结束后对产液进行气相色谱分析,糠醛的转化率为92.7%,四氢-2-呋喃甲醛收率为81.2%。
所述Pd/γ-Al2O3催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入1.009g的γ-Al2O3载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
所述Pd/ZSM-5催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入0.881g的ZSM-5载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
实施例14
一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,按照如下步骤进行:
(1)向100mL高压釜中加入1.44g糠醛和0.17gPd/γ-Al2O3催化剂和0.17gPd/ZSM-5催化剂,50mL的异丙醇作溶剂,0.01g乙酸锌做助剂;
(2)先用N2置换空气、而后用H2置换,在70℃的反应温度下,充入H2维持压力1MPa,机械搅拌90min;反应结束后对产液进行气相色谱分析,糠醛的转化率为98.8%,四氢-2-呋喃甲醛收率为91.2%。
所述Pd/γ-Al2O3催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入1.009g的γ-Al2O3载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
所述Pd/ZSM-5催化剂的制备方法如下:
(1)将0.024g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.021g的聚乙烯醇和0.024g的硼氢化钠先后加入到A液中;
(3)生成溶胶30min后,在剧烈搅拌下加入0.881g的ZSM-5载体,并将溶液用0.1mol·L-1H2SO4调至pH=2;
(4)1h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内80℃过夜,制成。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (8)
1.一种糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,其特征在于,按照如下步骤进行:
(1)在高压釜中依次加入钯基催化剂、糠醛和溶剂,混合均匀;
(2)调节高压釜温度为30~70℃,氢气压力为0.1~1MPa,反应时间0.5~8h,得到四氢-2-呋喃甲醛。
2.根据权利要求1所述糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,其特征在于,所述钯基催化剂的加入量为糠醛质量的1~30%。
3.根据权利要求1所述糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,其特征在于,所述溶剂的加入量为糠醛质量的20~120倍。
4.根据权利要求1所述糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,其特征在于,所述的溶剂为乙醇或异丙醇。
5.根据权利要求1所述糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,其特征在于,步骤(1)中还加入占糠醛质量0.5~3%的助剂,所述助剂为AlCl3、FeCl3、硬脂酸锌或乙酸锌。
6.根据权利要求1所述糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,其特征在于,所述钯基催化剂为Pd/MgO、Pd/γ-Al2O3、Pd/ZrO2、Pd/α-Al2O3、Pd/ZSM-5、Pd/TiO2中的一种或几种。
7.根据权利要求1所述糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,其特征在于,所述钯基催化剂的制备方法如下:
(1)将0.01~0.04g的K2PdCl4添加到800mL水中充分搅拌,得到A液;
(2)称取0.01~0.04g的聚乙烯醇和0.01~0.04g的硼氢化钠先后加入到A液中;
(3)生成溶胶20-40min后,在剧烈搅拌下加入0.6~1.8g的载体,并将溶液用0.1mol·L-1H2SO4调至pH=1.5~3.5;
(4)0.5~2h后过滤并用蒸馏水洗涤催化剂,在真空干燥箱内70~90℃过夜,制成。
8.根据权利要求7所述糠醛选择性加氢合成四氢-2-呋喃甲醛的方法,其特征在于,所述载体为MgO、γ-Al2O3、ZrO2、α-Al2O3、ZSM-5或TiO2。
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