CN111470973B - 一种利用生物质甘油催化氨化直接合成二元有机胺的方法 - Google Patents

一种利用生物质甘油催化氨化直接合成二元有机胺的方法 Download PDF

Info

Publication number
CN111470973B
CN111470973B CN202010452995.0A CN202010452995A CN111470973B CN 111470973 B CN111470973 B CN 111470973B CN 202010452995 A CN202010452995 A CN 202010452995A CN 111470973 B CN111470973 B CN 111470973B
Authority
CN
China
Prior art keywords
catalyst
metal
glycerol
alkali
solid acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010452995.0A
Other languages
English (en)
Other versions
CN111470973A (zh
Inventor
安华良
王瑞
郑广宗
赵新强
薛伟
王延吉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hebei University of Technology
Original Assignee
Hebei University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hebei University of Technology filed Critical Hebei University of Technology
Priority to CN202010452995.0A priority Critical patent/CN111470973B/zh
Publication of CN111470973A publication Critical patent/CN111470973A/zh
Application granted granted Critical
Publication of CN111470973B publication Critical patent/CN111470973B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/04—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/898—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with vanadium, tantalum, niobium or polonium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

本发明为一种利用生物质甘油催化氨化直接合成二元有机胺的方法。该方法包括以下步骤：在高压釜中加入固体催化剂、原料甘油和氨水，反应温度150～300℃，氢气压力为1～6MPa，密闭下反应8～24h，最后得到二元有机胺；所述的固体催化剂为金属‑固体酸(碱)催化剂，其组成包括金属和固体酸(碱)。本发明具有采用可再生原料、工艺流程短、反应过程清洁等优点，同时设计制备的金属‑固体酸(碱)具有高活性和选择性的特点。

Description

一种利用生物质甘油催化氨化直接合成二元有机胺的方法
技术领域
本发明涉及绿色化学技术领域，具体为一种利用生物质甘油经催化氨化直接合成二元有机胺的方法。
背景技术
在石油资源趋于枯竭和地球环境日益恶化的形势下，积极开发利用可再生资源已成为人类的必然选择。以生物质或生物基化学品为原料开发绿色化工过程生产化学品和清洁能源，将显著降低化石燃料的消耗和对环境的影响。2004年美国能源部制定了到2020年实现化学品10％来源于生物质及到2050年实现化学品50％来源于生物质的战略目标。2010年，Bozell等(Green Chemistry,2010,12(4):539-554)将Werpy和Petersen提出的12种生物平台分子修订为10种，仍然包括了甘油这种重要的生物平台化合物。甘油是酯交换法生产生物柴油过程中最主要的副产物，每生产9kg生物柴油就有1kg甘油粗品产生。近年来，生物柴油产业呈快速增长趋势，预计到2023年生物柴油产量将会达到4.0×103万吨，副产甘油的量也必将逐年增加。有效利用甘油既能促进生物柴油产业的健康发展，又能节约大量宝贵资源。因此，近年来如何有效利用甘油已成为国内外研究的热点。目前，利用生物质甘油制备高附加值化学品的研究包括通过选择性氧化合成甘油醛、甘油酸等，通过氢解合成1,2-丙二醇、1,3-丙二醇、正丙醇等，通过热解气化生产合成气、氢气、烷烃等，通过氯化和环化合成环氧氯丙烷，与尿素或碳酸二甲酯反应制备甘油碳酸酯，等。
1,2-丙二胺和乙二胺均为重要的化工原料和有机胺类精细化工产品。二者的工业生产方法分别为二氯丙烷法和二氯乙烷法，反应过程中会产生大量的无机盐，存在产品质量差、设备腐蚀严重和三废排放量大等问题。
本发明创新性地提出一种由生物质甘油直接制备二元胺(包括1,2-丙二胺和乙二胺)的绿色新工艺，具体为采用负载型金属催化剂，催化甘油和氨水发生氨化反应，直接合成1,2-丙二胺和乙二胺。
发明内容
本发明的目的为针对当前技术存在的不足，提供了一种利用生物质甘油催化氨化直接合成二元有机胺的方法。该方法采用金属-固体酸(碱)催化剂，提出了生物质甘油氨化直接合成二元有机胺的绿色新工艺。本发明具有采用可再生原料、工艺流程短、反应过程清洁等优点，同时设计制备的金属-固体酸(碱)具有高活性和选择性的特点。
本发明具体技术方案如下：
一种利用生物质甘油催化氨化直接合成二元有机胺的方法，该方法包括以下步骤：在高压釜中加入固体催化剂、原料甘油和氨水，反应温度150～300℃，氢气压力为1～6MPa，密闭下反应8～24h，最后得到二元有机胺；
其中，NH3与甘油的摩尔比为2～20:1，催化剂的加入量为原料甘油和氨水质量之和的5～25％；
所述的二元有机胺为1,2-丙二胺和乙二胺；
所述的固体催化剂为金属-固体酸(碱)催化剂，其组成为以下两种之一：
第一种，包括金属和固体酸(碱)，其中，金属在催化剂中的质量分数为3～30％，固体酸(碱)为70～97％；
或者，第二种，包括金属、固体酸(碱)和助剂，其中，金属在催化剂中的质量分数为3～30％，固体酸(碱)为65～95％；助剂占催化剂整体的质量分数为0.5～10％；所述的助剂为CeO2、La2O3、V2O5或Nb2O5；
所述的金属-固体酸(碱)催化剂中的金属为Cu、Ni、Co、Fe、Pt、Pd、Ru和Rh中的两种或三种；
所述的金属-固体酸(碱)催化剂中的固体酸或固体碱为：HY、HZSM-5、Hβ、Al2O3、MgO-Al2O3、MgO、TiO2、ZrO2或ZnO。
本发明的有益效果如下：
(1)1,2-丙二胺和乙二胺的工业生产方法分别为二氯丙烷法和二氯乙烷法，反应过程中会产生大量的无机盐，存在产品质量差、设备腐蚀严重和三废排放量大等问题。本发明提供的由金属-固体酸(碱)催化剂催化生物平台化合物甘油氨化直接合成二元有机胺的绿色新工艺。具有采用可再生原料、工艺流程短、反应过程清洁等优点。
(2)甘油是酯交换法生产生物柴油过程中最主要的副产物，每生产9kg生物柴油就有1kg甘油粗品产生。本发明提供了一种新的基于生物质甘油制备高附加值化学品工艺路线，拓宽了甘油化学利用的领域，有利于促进生物柴油产业的健康发展。甘油催化氨化制二元有机胺的主要副产物哌嗪类化合物(包括2,6-二甲基哌嗪、2-甲基哌嗪和2,5-二甲基哌嗪)同样具有重要的应用价值。
具体实施方式
本发明催化生物质甘油氨化合成1,2-丙二胺和乙二胺的金属-固体酸(碱)催化剂为公知材料。以下实施例1中的催化剂是通过采用浸渍法制备，但不限于此；
采用浸渍法制备金属-固体酸(碱)催化剂。以Co-Cu/γ-Al2O3的制备为例，过程描述如下：称取2.371g的Co(NO3)2·6H2O和0.354g的Cu(NO3)2配置成水溶液，将配好的溶液加入到装有3gγ-Al2O3的烧瓶中，老化12h后，先在旋转蒸发仪上于80℃旋蒸5h除水，再于120℃下干燥过夜；将干燥后的样品于500℃下焙烧4h，再于H2(20mL/min)和N2(80mL/min)的混合气氛下，450℃还原4h，从而制得Co-Cu/γ-Al2O3，催化剂中Co:Cu:γ-Al2O3的质量比为0.16:0.04:1。
实施例1
向100mL的高压反应釜中加入5.5g甘油、20.4g氨水(氨水中NH3的质量分数为25％)(甘油与NH3的摩尔比是1:5)、Co-Cu/γ-Al2O3催化剂2.6g(占反应原料质量之和的10％)及玻璃磁子，检查反应釜气密性，并用N2置换釜内空气；向高压釜中充入4.5MPa H2，开启加热和磁力搅拌，待温度升至190℃的反应温度后开始计时；反应15h，停止加热和搅拌，冷却至室温后，放残气开釜；在离心机中离心分离反应液和催化剂，用气相色谱仪对得到的产液进行定量分析。反应中除了生成乙二胺和1,2-丙二胺外，还会有部分哌嗪类化合物生成(包括2,6-二甲基哌嗪、2-甲基哌嗪和2,5-二甲基哌嗪)。反应结果为：甘油的转化率为60.5％，二元胺的选择性为75.2％，哌嗪类化合物的选择性为11.6％。
实施例2-12按照实施例1的操作步骤，甘油、氨水和催化剂的加入量分别为4.6g、20.4g和2.5g(甘油与NH3的摩尔比是1:6，催化剂占反应原料质量之和的10％)，催化剂的种类、反应条件及结果见汇总表。其中，实施例3-5和实施例11涉及催化剂中助剂Nb2O5、La2O3、CeO2和V2O5占催化剂整体的质量分数依次为0.5％、5％、5％和8％。
Figure BDA0002508331710000031
注：上表中金属负载量指金属在催化剂中的质量分数。
实施例13-19按照实施例1的操作步骤进行甘油催化氨化反应，反应条件为反应温度190℃、反应时间16h和氢气压力4MPa，甘油、氨水和催化剂的加入量、催化剂种类及反应结果见汇总表。其中，实施例16的催化剂Ru-Co-Fe/V2O5-TiO2中助剂V2O5占催化剂整体的质量分数为10％。
Figure BDA0002508331710000041
注：上表中金属负载量指金属在催化剂中的质量分数。
由以上实施例可以看出，对于本发明提出的由生物平台化合物甘油催化氨化直接合成二元有机胺这一新反应路线，金属-固体酸(碱)催化剂表现出了较好的催化效果，二元有机胺的选择性最高可以达到80％，同时还可以副产同样具有高附加值的哌嗪类化合物。
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)

1.一种利用生物质甘油催化氨化直接合成二元有机胺的方法，其特征为该方法包括以下步骤：在高压釜中加入固体催化剂、原料甘油和氨水，反应温度150～300℃，氢气压力为1～6MPa，密闭下反应8～24h，最后得到二元有机胺；所述的二元有机胺为1,2-丙二胺和乙二胺；
其中，NH3与甘油的摩尔比为2～20:1，催化剂的加入量为原料甘油和氨水质量之和的5～25%；
所述的固体催化剂为金属-固体酸（碱）催化剂，其组成为以下两种之一：
第一种，包括金属和固体酸（碱），其中，金属在催化剂中的质量分数为3～30%，固体酸（碱）为70～97%；
或者，第二种，包括金属、固体酸（碱）和助剂，其中，金属在催化剂中的质量分数为3～30%，固体酸（碱）为65～95%；助剂占催化剂整体的质量分数为0.5～10%；所述的助剂为CeO2、La2O3、V2O5或Nb2O5；
所述的金属-固体酸（碱）催化剂中的金属为Cu、Ni、Co、Fe、Pt、Pd、Ru和Rh中的两种或三种；
所述的金属-固体酸（碱）催化剂中的固体酸或固体碱为：HY、HZSM-5、Hβ、Al2O3、MgO-Al2O3、MgO、TiO2、ZrO2或ZnO。
CN202010452995.0A 2020-05-26 2020-05-26 一种利用生物质甘油催化氨化直接合成二元有机胺的方法 Active CN111470973B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010452995.0A CN111470973B (zh) 2020-05-26 2020-05-26 一种利用生物质甘油催化氨化直接合成二元有机胺的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010452995.0A CN111470973B (zh) 2020-05-26 2020-05-26 一种利用生物质甘油催化氨化直接合成二元有机胺的方法

Publications (2)

Publication Number Publication Date
CN111470973A CN111470973A (zh) 2020-07-31
CN111470973B true CN111470973B (zh) 2022-07-12

Family

ID=71760120

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010452995.0A Active CN111470973B (zh) 2020-05-26 2020-05-26 一种利用生物质甘油催化氨化直接合成二元有机胺的方法

Country Status (1)

Country Link
CN (1) CN111470973B (zh)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102151571A (zh) * 2011-02-18 2011-08-17 天津市凯瑞特科技有限公司 用于二氯乙烷法合成乙二胺的催化剂及其制备方法以及应用该催化剂合成乙二胺的方法
CN103819344A (zh) * 2013-12-18 2014-05-28 西安近代化学研究所 一种1，2-丙二胺的合成方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102151571A (zh) * 2011-02-18 2011-08-17 天津市凯瑞特科技有限公司 用于二氯乙烷法合成乙二胺的催化剂及其制备方法以及应用该催化剂合成乙二胺的方法
CN103819344A (zh) * 2013-12-18 2014-05-28 西安近代化学研究所 一种1，2-丙二胺的合成方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Catalytic H auto transfer amination of polyols to alkyl amines in one pot using supported Ru catalysts;Feng Du等;《Catalysis Today》;20180315;第302卷;第227-232页 *
乙二醇催化氨化合成乙二胺;张华良等;《应用化学》;20170531;第34卷(第5期);第557-562页 *

Also Published As

Publication number Publication date
CN111470973A (zh) 2020-07-31

Similar Documents

Publication Publication Date Title
RU2518371C1 (ru) Способ получения этиленгликоля из полиоксисоединений
Shang et al. CO 2 activation and fixation: highly efficient syntheses of hydroxy carbamates over Au/Fe 2 O 3
CN109453801B (zh) 用于富CO2胺溶液解吸的Fe2O3/ZrO2/SO42--分子筛复合型催化剂制备方法
CN109985626B (zh) 用于糠醛液相加氢制乙基糠基醚的方法及催化剂和催化剂的制备方法
CN111111675A (zh) 一种Ni-CeO2催化剂的制备方法
CN105597806A (zh) 一种加氢脱氧的钴催化剂及其制备方法
CN114289060A (zh) 一种负载型双金属催化剂及其制备方法和应用
CN107245065B (zh) 一种催化氢化乙酰丙酸乙酯制备戊内酯的方法
CN113976131B (zh) 一种多相催化剂以及由5-羟甲基糠醛制备2,5-呋喃二甲胺的方法
CN113528176B (zh) 一种生物质液体燃料的制备方法
CN111470973B (zh) 一种利用生物质甘油催化氨化直接合成二元有机胺的方法
CN104707646B (zh) 一种二甲醚氧化脱氢制备甲苯的催化剂及其制备方法和应用
CN109603837B (zh) 一种用于糠醛液相加氢的Cu/Ce/Co催化剂的制备方法
CN101781167A (zh) 二元醇和多元醇的合成方法
CN106916108A (zh) 一种吡唑离子液体及利用其催化合成环状碳酸酯的方法
CN112745267A (zh) 一种咪唑基离子液体及其应用
CN114805259A (zh) 一种耐失活镍基催化剂上糠醇选择性胺化制备糠胺的方法
Wang et al. A ternary composite oxides S 2 O 8 2−/ZrO 2–TiO 2–SiO 2 as an efficient solid super acid catalyst for depolymerization of lignin
CN110026191B (zh) 一种催化剂及甘油氢解制备1,3-丙二醇的方法
CN114410336A (zh) 一种基于生物质乙酰丙酸直接制备长链烷烃的方法
CN105435842B (zh) 一种均相催化剂及其在多羟基化合物氨化反应中的应用
CN107915594B (zh) 用于聚甲醛二甲醚的合成方法
WO2014024782A2 (ja) グリセリンからアクリル酸を製造するための触媒とその製造方法
CN114656442B (zh) 一种由5-羟甲基糠酸制备己内酯的方法
CN107915593B (zh) 用于合成聚甲醛二甲醚的方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant