WO2021129042A1 - 一种碳酸钙改性的炭材料负载纳米钯合金催化剂及其制备方法和应用 - Google Patents

一种碳酸钙改性的炭材料负载纳米钯合金催化剂及其制备方法和应用 Download PDF

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WO2021129042A1
WO2021129042A1 PCT/CN2020/120139 CN2020120139W WO2021129042A1 WO 2021129042 A1 WO2021129042 A1 WO 2021129042A1 CN 2020120139 W CN2020120139 W CN 2020120139W WO 2021129042 A1 WO2021129042 A1 WO 2021129042A1
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calcium carbonate
carbon material
palladium alloy
activated carbon
alloy catalyst
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PCT/CN2020/120139
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French (fr)
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吕国锋
张文城
王勇
朱传学
赵初秋
张生永
田金金
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上虞新和成生物化工有限公司
浙江新和成药业有限公司
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • 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
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
    • 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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

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  • the invention belongs to the technical field of catalysts, and specifically relates to a calcium carbonate-modified carbon material-loaded nano-palladium alloy catalyst and a preparation method thereof, and a calcium carbonate-modified carbon material-loaded nano-palladium alloy catalyst in C20 acetylenic alcohol (vitamin A is important) Intermediate) Application as a catalyst in the reaction of selective hydrogenation and reduction to C20 enol.
  • Vitamin A can protect eyesight, treat eye diseases, treat skin itching, dryness and other symptoms. It can also prevent skin scaling and promote development. It plays a very important role in the body's metabolism, development, and growth. In recent years, with the improvement of people's living conditions, the demand for vitamin A has increased year by year. The industrial production approach has become the main source of vitamin A. In the current industrial synthesis, the selective hydrogenation of C20 acetylenic alcohol is the most important reaction in the synthesis of vitamin A, and the main catalyst used is Lindela catalyst. However, the Lindela catalyst still exists with calcium carbonate and barium sulfate as the
  • Activated carbon is a cheap and easy-to-obtain, and has a good pore structure, abundant surface groups, and at the same time has good loading performance and reducibility, commonly used as a catalyst carrier material.
  • the palladium-based alloy catalyst prepared by using ordinary activated carbon materials instead of calcium carbonate and barium sulfate as the Lindera catalyst carrier is used for the reduction reaction of C20 acetylenic alcohol, and the selectivity of the product is poor.
  • activated carbon has a large specific area and high reaction activity, which makes it difficult to control the reaction and poor reaction selectivity. This is one of the difficulties faced by activated carbon as a carrier that cannot be used for selective hydrogenation.
  • the purpose of the present invention is to provide a highly active C20 acetylenic alcohol selective hydrogenation catalyst, in particular to a calcium carbonate modified carbon material loaded palladium nano-alloy catalyst and a preparation method thereof.
  • the preparation method uses cheap raw materials and a simple preparation method.
  • the carrier material with a more reasonable pore structure is prepared.
  • the small pores on the surface of the activated carbon are blocked by calcium carbonate precipitation, so that the palladium nano-alloy is uniformly dispersed on the outer layer of the activated carbon or adjacent to the outer layer. It has good catalytic performance in mesopores or macropores.
  • a preparation method of a calcium carbonate modified carbon material loaded nano-palladium alloy catalyst includes the following steps:
  • the activated carbon is one or more of coconut shell activated carbon, nut shell activated carbon, coal columnar activated carbon, powdered activated carbon, coal granular activated carbon, spherical activated carbon or coconut shell gold activated carbon;
  • the carbonate is potassium carbonate and/or sodium carbonate;
  • the acidic calcium salt solution is one or more of calcium acetate, calcium sulfate or calcium chloride and calcium nitrate, wherein the calcium ion concentration is 0.5 mmol/mL
  • the carbonate aqueous solution is prepared in situ from carbonate and water, and the water is distilled water, deionized water or purified water.
  • step (1) the mass ratio of carbonate to activated carbon is (1:3) to (5:1), preferably (0.78:1) to (0.95:1), more preferably 0.78:1 , 0.83:1, 0.90:1, 0.1:1, 0.95:1;
  • the mass ratio of the acidic calcium salt solution (measured by the acidic calcium salt) to activated carbon is (1:20) to (5:1), preferably It is (0.18:1) ⁇ (0.71:1), more preferably 0.71:1, 0.20:1, 0.18:1, 0.02:1;
  • the mass ratio of water to carbonate in the carbonate aqueous solution is ( 8:1) ⁇ (1:10).
  • step (1) the activated carbon is mixed with the carbonate aqueous solution and then the temperature is raised to 30-50°C, the heating rate is 1-10°C/min; the maintenance time is 10-240min; the dropping rate of the acidic calcium salt solution is 0.1- 2mL/min; After the addition of the acidic calcium salt solution, the temperature is raised to 50 ⁇ 70°C, the heating rate is 1 ⁇ 10°C/min; the maintenance time is 10 ⁇ 250min; the drying temperature is 50 ⁇ 80°C, and the drying time It is 6h ⁇ 24h.
  • the Pd precursor is one or more of PdCl 2 , H 2 PdCl 4 , Pd(NO 3 ) 2 or Pd(NH 3 ) 4 (NO 3 ) 2 ;
  • the chemical reagent It is one or more of sodium formate, formic acid, glucose or hydrazine hydrate;
  • the promoter is one or more of zinc nitrate, bismuth nitrate, acid liquid lead or copper nitrate.
  • step (2) the mass ratio of the Pd precursor and the activated carbon modified by calcium carbonate is (1:5) to (1:40).
  • the mass ratios of the Pd precursor to zinc nitrate, bismuth nitrate, acid solution lead, and copper nitrate are (1:0.02) ⁇ (1:0.35), (1:0.03) ⁇ (1:0.23), (1: 0.03) ⁇ (1:0.25), (1:0.05) ⁇ (1:0.4).
  • step (2) stirring time is 1 ⁇ 24h; reduction temperature is 60 ⁇ 100°C, heating rate is 1 ⁇ 10°C/min; maintenance time is 20 ⁇ 300min; poisoning temperature is 70 ⁇ 120°C, heating rate is 1 ⁇ 10°C /min; the maintenance time is 10-250min; the drying temperature is 50-80°C, and the drying time is 10h-24h.
  • the present invention further provides the application of the carbon material-loaded nano-palladium alloy catalyst modified by calcium carbonate as a catalyst in the selective hydrogenation and reduction of C20 alkynol (an important intermediate of vitamin A) to C20 enol.
  • the prepared calcium carbonate-modified carbon material supported nano-palladium alloy catalyst has excellent performance and good stability, and the specific performance is as follows:
  • the carrier material has a more reasonable pore structure, the loaded nano-palladium alloy is uniformly dispersed, more active sites are exposed, and the metal utilization rate is high.
  • the nano-palladium alloy is firmly adsorbed on the carrier, and it is not suitable for agglomeration or loss during the use process, and it can be repeatedly applied many times.
  • FIG. 1 Electron micrograph of activated carbon modified by calcium carbonate
  • the activated carbon modified by the calcium carbonate is used to support nano-palladium alloy catalyst, which is used for vitamin A important intermediate C20 acetylenic alcohol (3,6-dimethyl-8-(2,6,6-trimethyl-1-cyclohexyl) En-1-yl)-2,7-octadiene-4-yne-1,6-diol)) selective hydrogenation reaction.
  • the selectivity of -1-cyclohexen-1-yl)-2,7-octadiene-4-ene-1,6-diol is 93.7%.
  • Examples 2-6 are the same as Example 1, except for the mass ratio of carbonate to activated carbon; the mass ratio of acidic calcium salt solution to activated carbon; the specific conditions of these parameters for different calcium ion solutions are as follows:
  • the molar concentration of a is the same as in Example 1.
  • the above-mentioned activated carbon supported nano-palladium alloy catalyst is used for vitamin A important intermediate C20 acetylenic alcohol (3,6-dimethyl-8-(2,6,6-trimethyl-1-cyclohexen-1-yl) )-2,7-octadiene-4-yne-1,6-diol)) selective hydrogenation reaction.
  • the selectivity of -1-cyclohexen-1-yl)-2,7-octadiene-4-ene-1,6-diol is 58%.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

涉及一种碳酸钙改性的炭材料负载纳米钯合金催化剂及其制备方法，和碳酸钙改性的炭材料负载纳米钯合金催化剂在C20炔醇选择性加氢还原为C20烯醇的反应中作为催化剂的应用。一种碳酸钙改性的炭材料负载纳米钯合金催化剂的制备方法，包括以下步骤：(1)将活性炭与碳酸盐水溶液搅拌混合均匀后，加热保温，保温毕；缓慢滴加酸性钙盐溶液，加热保温，经后处理获得碳酸钙改性的炭材料；(2)将所述碳酸钙改性的炭材料浸渍于Pd前驱体溶液中后，依次经搅拌、加入化学试剂还原、加入助催化剂毒化处理、洗涤以及烘干，得到碳酸钙改性的炭载体负载纳米钯合金催化剂。

Description

一种碳酸钙改性的炭材料负载纳米钯合金催化剂及其制备方法和应用 技术领域
本发明属于催化剂技术领域，具体是涉及一种碳酸钙改性的炭材料负载纳米钯合金催化剂及其制备方法，和碳酸钙改性的炭材料负载纳米钯合金催化剂在C20炔醇(维生素A重要中间体)选择性加氢还原为C20烯醇的反应中作为催化剂的应用。
背景技术
维生素A可以保护视力，治疗眼部的疾病，治疗皮肤瘙痒，干燥等症状，还能够防止皮肤脱屑，以及促进发育的功效，在人体的新陈代谢、发育、成长过程中发挥着十分重要的作用。近年来随着人们生活条件的改善，对维生素A的需求量逐年增加。而工业生产的途径已成为维生素A的主要来源。目前工业合成中，C20炔醇选择性加氢反应是维生素A合成过程中最为重要的反应，使用的催化剂主要为林德拉催化剂。但是林德拉催化剂仍然存在以碳酸钙、硫酸钡作
为载体材料，机械强度差，水相稳定性差，使用过程钯流失严重等诸多问题，因此迫切开发一种更为稳定、高性能的C20炔醇选择性加氢反应催化剂。
活性炭是一种廉价易得，且具有良好的孔结构、丰富的表面基团，同时有良好的负载性能和还原性，常用做催化剂的载体材料。
使用普通活性炭材料代替碳酸钙、硫酸钡作为林德拉催化剂载体制备的钯基合金催化剂用于C20炔醇的还原反应，产物的选择性差。这是因为活性炭比面积大，反应活性高，导致反应较难控制，反应选择性差，这是活性炭作为载体无法用于选择性加氢所面临的难题之一。
发明内容
本发明的目的是提供一种高活性的C20炔醇选择性加氢反应催化剂，具体涉及一种碳酸钙改性的炭材料负载钯纳米合金催化剂及其制备方法。该制备方法应用的原料廉价，制备方法简单，制备得到具有更合理的孔结构载体材料，利用 碳酸钙沉淀堵住活性炭表面的小孔，使得钯纳米合金均匀分散在活性炭外层或临近外层的中孔或大孔中，具有良好的催化性能。
为实现上述发明目的，本发明提供以下技术方案：
一种碳酸钙改性的炭材料负载纳米钯合金催化剂的制备方法，包括以下步骤：
(1)将活性炭与碳酸盐水溶液搅拌混合均匀后，加热保温，保温毕；缓慢滴加酸性钙盐溶液，加热保温，经后处理获得碳酸钙改性的炭材料；
(2)将所述碳酸钙改性的炭材料浸渍于Pd前驱体溶液中后，依次经搅拌、加入化学试剂还原、加入助催化剂毒化处理、洗涤以及烘干，得到碳酸钙改性的炭载体负载纳米钯合金催化剂。
在步骤(1)中：所述活性炭为椰壳活性炭、果壳活性炭、煤质柱状活性炭、粉状活性炭、煤质颗粒活性炭、球形活性炭或椰壳黄金活性炭中的一种或多种；所述的碳酸盐为碳酸钾和/或碳酸钠；所述的酸性钙盐溶液为醋酸钙、硫酸钙或氯化钙以及硝酸钙中的一种或多种，其中钙离子浓度为0.5mmol/mL；所述的碳酸盐水溶液由碳酸盐和水原位配制得到，所述的水为蒸馏水、去离子水或纯净水。
在步骤(1)中：所述碳酸盐与活性炭的质量比为(1:3)～(5:1)，优选为(0.78：1)～(0.95:1)，进一步优选为0.78：1、0.83：1、0.90：1、0.1：1、0.95：1；所述的酸性钙盐溶液(以酸性钙盐计量)与活性炭的质量比为(1:20)～(5:1)，优选为(0.18:1)～(0.71:1)，进一步优选为0.71：1、0.20：1、0.18：1、0.02：1；所述的碳酸盐水溶液中水与碳酸盐的质量比为(8:1)～(1:10)。
步骤(1)中：所述活性炭与碳酸盐水溶液混合后升温至30～50℃，升温速度1～10℃/min；维持时间10～240min；所述酸性钙盐溶液的滴加速度为0.1～2mL/min；所述滴加完酸性钙盐溶液后升温至50～70℃，升温速度1～10℃/min；维持时间10～250min；所述烘干温度为50～80℃，烘干时间为6h～24h。
步骤(2)中：所述Pd前驱体为PdCl 2、H 2PdCl 4、Pd(NO 3) 2或Pd(NH 3) 4(NO 3) 2中的一种或多种；所述化学试剂为甲酸钠、甲酸、葡萄糖或水合肼中的一种或多种；所述助催化剂为硝酸锌、硝酸铋、酸液铅或硝酸铜中的一种或多种。
步骤(2)中：所述Pd前驱体与碳酸钙改性的活性炭材料质量比为(1:5)～(1:40)。
所述Pd前驱体与硝酸锌、硝酸铋、酸液铅、硝酸铜的质量比分别为(1:0.02)～(1:0.35)、(1:0.03)～(1:0.23)、(1:0.03)～(1:0.25)、(1:0.05)～(1:0.4)。
步骤(2)中：搅拌时间为1～24h；还原温度为60～100℃，升温速度1～10℃/min；维持时间20～300min；毒化温度为70～120℃，升温速度1～10℃/min；维持时间10～250min；所述烘干温度为50～80℃，烘干时间为10h～24h。
本发明还提供了上述制备方法制备得到碳酸钙改性的炭材料负载纳米钯合金催化剂。
本发明还进一步提供了上述碳酸钙改性的炭材料负载纳米钯合金催化剂在C20炔醇(维生素A重要中间体)选择性加氢还原为C20烯醇的反应中作为催化剂的应用。
具体地，所述维生素A合成工艺中C20炔醇选择性加氢反应为：
Figure PCTCN2020120139-appb-000001
本发明具有的有益效果表现为：
该制备方法以碳酸钙沉淀在活性炭表面上堵住活性炭表面上的微孔，制备出孔结构更加合理的活性炭材料，并将其作为载体可使得钯负载在活性炭的外层或临近外层的中孔或大孔中，从而暴露出更多的Pd活性位点催化剂。该制备方法应用的原料廉价，制备方法简单，原料来源非常广泛，环境友好，具有很大的工业应用前景。
制备得到的碳酸钙改性的炭材料负载纳米钯合金催化剂性能优异、稳定性好，具体表现在：
(1)载体材料具有更合理的孔结构，负载的纳米钯合金均匀分散，更多的活性位点暴露，金属利用率高。
(2)纳米钯合金在载体上吸附牢固，使用过程不宜团聚、流失，可重复套 用多次。
(3)催化活性高、选择性好。
附图说明
图1碳酸钙改性的活性炭电镜图；
图2活性炭电镜图。
具体实施方式
为使本发明目的、技术方案及优点更加清楚明白，下面通过具体的实施例和对照例对本方案的技术方案做进一步的说明。
实施例1
称取活性炭(电镜图结果如图2所示)1.8g，碳酸钾1.4g，蒸馏水50mL，混合后开搅拌升温至40℃，滴加16mL 80mg/mL醋酸钙溶液，滴加速度控制在4～5滴每秒。滴毕后升温至60℃保温30min，水洗4次，抽滤干燥，得到碳酸钙改性的活性炭材料，电镜图结果如图1所示。
称取1g碳酸钙改性的活性炭材料，加入60mL蒸馏水搅拌，缓慢滴加1mL 70mg/mL氯化钯溶液，40℃搅拌10h。滴加5mL浓度为10％的甲酸钠溶液，85℃搅拌1h。滴加5mL 23.5mg/mL醋酸铅，90℃搅拌0.5h。用蒸馏水水洗6次，将制备好的催化剂转移到真空干燥箱中60℃干燥12h，即得到碳酸钙改性的活性炭负载的纳米钯合金催化剂。
采用上述碳酸钙改性的活性炭负载纳米钯合金催化剂，用于维生素A重要中间体C20炔醇(3,6-二甲基-8-(2,6,6-三甲基-1-环己烯-1-基)-2,7-辛二烯-4-炔-1,6-二醇))选择性加氢反应。具体反应条件为：Pd/3,6-二甲基-8-(2,6,6-三甲基-1-环己烯-1-基)-2,7-辛二烯-4-炔-1,6-二醇＝22.3mol％，二氯甲烷9mL；氢气0.04MPa；反应时间3h；3,6-二甲基-8-(2,6,6-三甲基-1-环己烯-1-基)-2,7-辛二烯-4-炔-1,6-二醇转化率100％，3,6-二甲基-8-(2,6,6-三甲基-1-环己烯-1-基)-2,7-辛二烯-4-烯-1,6-二醇选择性93.7％。
实施例2-6其他均与实施例1相同，除了碳酸盐与活性炭的质量比；酸性钙盐溶液与活性炭的质量比；不同钙离子溶液，这些参数的具体情况如下表：
Figure PCTCN2020120139-appb-000002
Figure PCTCN2020120139-appb-000003
a摩尔浓度与实施例1相同。
对照例1
称取1g活性炭材料，加入60mL蒸馏水搅拌，缓慢滴加1mL 70mg/mL氯化钯溶液，40℃搅拌10h。滴加5mL浓度为10％的甲酸钠溶液，85℃搅拌1h。滴加5mL 23.5mg/mL醋酸铅℃搅拌0.5h。用蒸馏水水洗6次，将催化剂转移到真空干燥箱中60℃干燥12h，即可得到活性炭负载的纳米钯合金催化剂。
采用上述活性炭负载纳米钯合金催化剂，用于维生素A重要中间体C20炔醇(3,6-二甲基-8-(2,6,6-三甲基-1-环己烯-1-基)-2,7-辛二烯-4-炔-1,6-二醇))选择性加氢反应。具体反应条件为：Pd/3,6-二甲基-8-(2,6,6-三甲基-1-环己烯-1-基)-2,7-辛二烯-4-炔-1,6-二醇＝22.3mol％，二氯甲烷9mL；氢气0.04MPa；反应时间3h；3,6-二甲基-8-(2,6,6-三甲基-1-环己烯-1-基)-2,7-辛二烯-4-炔-1,6-二醇转化率80％，3,6-二甲基-8-(2,6,6-三甲基-1-环己烯-1-基)-2,7-辛二烯-4-烯-1,6-二醇选择性58％。
上述实施例仅用于解释说明本发明的发明构思，而非对本发明权利保护的限定，凡利用此构思对本发明进行非实质性的改动，均应落入本发明的保护范围。

Claims (10)

  1. 一种碳酸钙改性的炭材料负载纳米钯合金催化剂的制备方法，其特征在于，包括以下步骤：
    (1)将活性炭与碳酸盐水溶液搅拌混合均匀后，加热保温，保温毕；缓慢滴加酸性钙盐溶液，加热保温，经后处理获得碳酸钙改性的炭材料；
    (2)将所述碳酸钙改性的炭材料浸渍于Pd前驱体溶液中后，依次经搅拌、加入化学试剂还原、加入助催化剂毒化处理、洗涤以及烘干，得到碳酸钙改性的炭载体负载纳米钯合金催化剂。
  2. 如权利要求1所述的碳酸钙改性的炭材料负载纳米钯合金催化剂的制备方法，其特征在于，在步骤(1)中：所述活性炭为椰壳活性炭、果壳活性炭、煤质柱状活性炭、粉状活性炭、煤质颗粒活性炭、球形活性炭或椰壳黄金活性炭中的一种或多种；所述的碳酸盐为碳酸钾和/或碳酸钠；所述的酸性钙盐溶液为醋酸钙、氯化钙以及硝酸钙中的一种或多种，其中钙离子浓度为0.5mmol/mL；所述的水为蒸馏水、去离子水或纯净水。
  3. 如权利要求1或2所述的碳酸钙改性的炭材料负载纳米钯合金催化剂的制备方法，其特征在于，在步骤(1)中：所述碳酸盐与活性炭的质量比为(1:3)～(5:1)；所述的酸性钙盐溶液与活性炭的质量比为(1:20)～(5:1)；所述的碳酸盐水溶液中水与碳酸盐的质量比为(8:1)～(1:10)。
  4. 如权利要求1所述的碳酸钙改性的炭材料负载纳米钯合金催化剂的制备方法，其特征在于，步骤(1)中：所述活性炭与碳酸盐水溶液混合后升温至30～50℃，升温速度1～10℃/min；维持时间10～240min；所述酸性钙盐溶液的滴加速度为0.1～2mL/min；所述滴加完酸性钙盐溶液后升温至50～70℃，升温速度1～10℃/min；维持时间10～250min；所述烘干温度为50～80℃，烘干时间为6h～24h。
  5. 如权利要求1所述的碳酸钙改性的炭材料负载纳米钯合金催化剂的制备方法，其特征在于，步骤(2)中：所述Pd前驱体为PdCl 2、H 2PdCl 4、Pd(NO 3) 2或Pd(NH 3) 4(NO 3) 2中的一种或多种；所述化学试剂为甲酸钠、甲酸、葡萄糖或水合肼中的一种或多种；所述助催化剂为硝酸锌、硝酸铋、酸液铅或硝酸铜中的一种或多种。
  6. 如权利要求1或5所述的碳酸钙改性的炭材料负载纳米钯合金催化剂的制备 方法，其特征在于，步骤(2)中：所述Pd前驱体与碳酸钙改性的活性炭材料质量比为(1:5)～(1:40)。
  7. 如权利要求5所述的碳酸钙改性的炭材料负载纳米钯合金催化剂的制备方法，其特征在于：所述Pd前驱体与硝酸锌、硝酸铋、酸液铅、硝酸铜的质量比分别为(1:0.02)～(1:0.35)、(1:0.03)～(1:0.23)、(1:0.03)～(1:0.25)、(1:0.05)～(1:0.4)。
  8. 如权利要求1所述的碳酸钙改性的炭材料负载纳米钯合金催化剂的制备方法，其特征在于，步骤(2)中：搅拌时间为1～24h；还原温度为60～100℃，升温速度1～10℃/min；维持时间20～300min；毒化温度为70～120℃，升温速度1～10℃/min；维持时间10～250min；所述烘干温度为50～80℃，烘干时间为10h～24h。
  9. 一种如权利要求1～8任一项所述的制备方法制备得到碳酸钙改性的炭材料负载纳米钯合金催化剂。
  10. 一种如权利要求9所述的碳酸钙改性的炭材料负载纳米钯合金催化剂在C20炔醇选择性加氢还原为C20烯醇的反应中作为催化剂的应用。
PCT/CN2020/120139 2019-12-26 2020-10-10 一种碳酸钙改性的炭材料负载纳米钯合金催化剂及其制备方法和应用 WO2021129042A1 (zh)

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