CN1066608A - Catalyst for hydrogenating reaction of diacetone alcohol - Google Patents

Catalyst for hydrogenating reaction of diacetone alcohol Download PDF

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CN1066608A
CN1066608A CN 91103161 CN91103161A CN1066608A CN 1066608 A CN1066608 A CN 1066608A CN 91103161 CN91103161 CN 91103161 CN 91103161 A CN91103161 A CN 91103161A CN 1066608 A CN1066608 A CN 1066608A
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ni
sio2
catalyst
toluene
diacetone alcohol
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CN 91103161
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Chinese (zh)
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CN1032574C (en )
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吴世华
赵维军
王序毗
张书芨
方延铨
黄唯平
杨树军
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南开大学
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132Preparation 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
    • C07C29/136Preparation 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
    • C07C29/143Preparation 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 ketones
    • C07C29/145Preparation 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 ketones with hydrogen or hydrogen-containing gases

Abstract

The present invention belongs to a nickeliferous SiOz catalyst. It uses the metal vaporization method to prepare the high-dispersion nickel (Ni) metal loaded catalyst Ni/SiO2 and uses the dipropyl keto-alcohol hydrogenation reaction to prepare methyl pentadiol-2.4, and the SiO2 carrier is immersed in the solvated (toluene) Ni atomic solution at -78 deg.C. As compared with the general immersion method, the made Ni/SiO2 catalyst has higher catalytic activity and selectivity.

Description

本发明属含镍的二氧化硅催化剂。 The present invention belongs to the nickel-containing silica catalyst.

甲基戊二醇-2,4是重要的化工原料,目前普遍采用Ranny镍作为催化剂由二丙酮醇加氢制备,Ranny镍催化剂的制备条件要求苛刻,成本比较高。 Methyl-2,4-pentanediol is an important chemical raw materials, now widely used as a catalyst a nickel Ranny diacetone alcohol was prepared by the hydrogenation, nickel catalyst preparation conditions Ranny demanding, relatively high cost. 近年来利用金属蒸气合成负载催化剂获得成功。 In recent years, a metal vapor synthesis using supported catalyst successful. 在催化剂制备过程中,由于金属原子反应器中产生的溶剂化金属原子作为中间体被浸渍在载体上,故称为溶剂化金属原子浸渍(SMAI)法,由此法制备的催化剂称为SMAI催化剂。 During the preparation of the catalyst, the solvent metal atoms because the metal atoms produced in the reactor is impregnated onto the support, it is known as the solvent metal atom impregnation (SMAI) method as an intermediate, referred to as catalyst thus prepared by catalyst SMAI . SMAI催化剂具有金属粒度小、分散度高、零价金属百分比高的特点,与普通浸渍(CI)法制备的催化剂相比,具有较高的催化活性和选择性。 SMAI metal catalyst has a particle size small, high dispersion, high percentage of zero-valent metal characteristics, compared with the conventional impregnation (CI) prepared by catalyst having high catalytic activity and selectivity.

本发明的目的在于提供一种SMAI Ni/SiO2催化剂用二丙酮醇的加氢反应,制备甲基戊二醇-2,4。 Object of the present invention is to provide a hydrogenation reaction of one SMAI Ni / SiO2 catalyst diacetone alcohol, Preparation of methyl-2,4-pentanediol.

本发明是在低温下将溶剂(甲苯)化镍(Ni)原子溶液浸渍SiO2载体,并在浸渍过程中剧烈搅拌,浸渍时间为6小时,浸渍后缓慢升至室温,真空脱去甲苯,使体系真空度达10-15乇,封管,制得的催化剂样品可直接用于表征和催化性能的测定。 The present invention is a solvent (toluene), nickel (Ni) atoms SiO2 support impregnated with a solution, and vigorously stirred at a low temperature during the impregnation process, the immersion time is 6 hours, slowly warmed to room temperature after impregnation, toluene was removed in vacuo, the system was a vacuum of 10-15 Torr, sealed tube, the catalyst sample may be prepared and used in assays to characterize the catalytic properties directly. Ni/SiO2催化剂中Ni的含量为0.5~20%。 The content of Ni / SiO2 catalyst of Ni is 0.5 to 20%.

本发明的实际效果可从表1给出的结果得以肯定。 The actual effect of the present invention can be sure from the results given in Table 1. 表1是SMAI和CI Ni/SiO2催化剂在二丙酮醇加氢反应中催化活性的比较。 Table 1 SMAI and CI Ni / SiO2 Catalyst Activity Comparison of diacetone alcohol in the hydrogenation reactions.

催化剂Ni含量(%) 催化剂二丙酮醇×OH∧OH用 量 转化率(%)选择性(%) The catalyst Ni content (%) of diacetone alcohol × OH∧OH catalyst with an amount of conversion (%) selectivity (%)

Ni/SiO2(SMAI) 8.4 0.09 54 37Ni/SiO2(CI) 8.4 0.09 39 25Ni/SiO2(SMAI) 4.1 0.18 68 34Ni/SiO2(CI) 4.1 0.18 56 23Ni/SiO2(SMAI) 2.54 0.30 95 50Ni/SiO2(CI) 2.54 0.30 64 31Ni/SiO2(SMAI) 0.63 1.20 86 13Ni/SiO2 (CI) 0.63 1.20 58 18 Ni / SiO2 (SMAI) 8.4 0.09 54 37Ni / SiO2 (CI) 8.4 0.09 39 25Ni / SiO2 (SMAI) 4.1 0.18 68 34Ni / SiO2 (CI) 4.1 0.18 56 23Ni / SiO2 (SMAI) 2.54 0.30 95 50Ni / SiO2 (CI ) 2.54 0.30 64 31Ni / SiO2 (SMAI) 0.63 1.20 86 13Ni / SiO2 (CI) 0.63 1.20 58 18

实施例1. Example 1.

SMAI法制备负载Ni催化剂的过程。 Preparation process SMAI supported Ni catalysts.

取金属Ni1.0克放入包Al2O3层的钨丝坩埚内,坩埚固定在两电极之间。 Take the metal Ni1.0 g Al2O3-layer packet into tungsten crucible, the crucible is fixed between the two electrodes. 体系抽真空至0.13Pa以下,用液氮冷却玻璃反应瓶至-196℃。 System was evacuated to 0.13Pa or less, a glass reaction flask was cooled with liquid nitrogen to -196 ℃. 引入少量甲苯后逐渐加大电流使金属蒸发,控制好金属蒸发速度和甲苯引入速度,使反应体系压力始终保持在0.13Pa左右,一小时左右之后,大约1克的Ni和130ml的甲苯被共凝聚在反应瓶内壁上。 After gradually increasing current to metal evaporation, metal evaporation rate and control the rate of introduction of toluene, the reaction system pressure is always maintained at 0.13Pa after introducing a small amount of toluene, about one hour, approximately one gram of Ni and 130ml toluene was co-coagulated in the walls of the reaction bottle. 共凝聚反应结束后,液氮浴换成干冰-丙酮浴。 After the co-condensation reaction, the liquid nitrogen bath replaced with a dry ice - acetone bath. 在-90℃左右共凝聚物融化落入反应瓶底。 At about -90 ℃ coagulating reaction bottle was melt falls. 用真空线把溶剂化金属Ni原子溶液转移到干冰-丙酮浴(-78℃)预先冷却好的载体SiO2上,剧烈搅拌6小时,缓慢升至室温;真空除甲苯至1.33×10-3Pa封管。 The vacuum line with the solvated solution was transferred to a metal Ni atom a dry ice - acetone bath (-78 deg.] C) pre-cooled on a good carrier of SiO2, with vigorous stirring for 6 hours and was slowly warmed to room temperature; the toluene was removed under vacuum to 1.33 × 10-3Pa sealed tube . 整个实验使用的装置如图1所示,图中1是甲苯,2是液氮,3是金属,4是溶剂化金属原子溶液,5是真空泵,6是电极和冷却水,7是干冰-丙酮浴,8是载体,9是玻璃反应瓶,10是坩埚。 The entire apparatus used for the experiment shown in FIG. 1, FIG. 1 is toluene, liquid nitrogen 2, 3 is a metal, a metal atom 4 is solvated solution, 5 is a vacuum pump, and the cooling water is an electrode 6, 7 is a dry ice - acetone bath, a carrier 8, 9 is a glass reaction flask, 10 crucible.

实施例2. Example 2.

二丙酮醇加氢活性的测定。 Determination of the hydrogenation activity of diacetone alcohol.

在160ml不锈钢反应釜中加入20ml二丙酮醇,于H2气流下加入0.30克实施例1制备的Ni/SiO2催化剂,用H2气冲洗三次后充入3MPa氢气,于140℃下搅拌反应5小时,产物用SP-501气相色谱仪分析,反应结果如下:催化剂 二丙酮醇 甲基戊二醇-2,4转化率(%) 选择性(%)2.54%Ni/SiO895 50参考文献1.KJKlabunde,J.Catal,54,254-268(1978). Added to the kettle 20ml diacetone alcohol in 160ml stainless steel reactor, 0.30 g Preparation Example 1 under H2 gas flow Ni / SiO2 catalyst was charged 3MPa hydrogen gas is washed three times with H2 gas, the reaction was stirred for 5 hours at 140 deg.] C, the product SP-501 by gas chromatography analysis, the reaction results were as follows: catalyst diacetone alcohol methyl-2,4-pentanediol conversion (%) selectivity (%) 2.54% Ni / SiO895 50 reference 1.KJKlabunde, J. Catal, 54,254-268 (1978).

2.USPatent,4292253(1981). 2.USPatent, 4292253 (1981).

Claims (5)

  1. 1.一种用于二丙酮醇加氢反应的催化剂Ni/SiO2,其特征在于在SiO2载体上载有高分散活性成分镍(Ni)。 Ni 1. The catalyst for the hydrogenation reaction of diacetone alcohol / SiO2, wherein the SiO2 carrier in a highly dispersed active ingredient containing a nickel (Ni).
  2. 2.按照权项1所说的催化剂Ni/SiO2的制备方法,其特征在于将溶剂化Ni原子溶液在-78℃温度下浸渍SiO2载体,剧烈搅拌6小时,缓慢升至室温,真空(10-5乇)脱去甲苯,封存即得。 2. The preparation process of claim 1 said catalyst Ni / SiO2, which is characterized in that Ni atoms solvate SiO2 support impregnated with a solution, vigorously stirred at a temperature of -78 ℃ 6 hours and slowly warmed to room temperature in vacuo (10- 5 torr) removing toluene, to obtain storage.
  3. 3.按照权项1所说的催化剂Ni/SiO2,其特征在于Ni的负载量为0.5~20%。 3. Claim 1 said catalyst Ni / SiO2, characterized in that the loading of Ni is 0.5 to 20%.
  4. 4.按照权项2所说的催化剂Ni/SiO2的制备方法,其特征在于所说的溶剂是甲苯。 4. The catalyst of Claim 2 of said Ni / SiO2 is prepared, wherein said solvent is toluene.
  5. 5.按照权项2所说的催化剂Ni/SiO2的制备方法,其特征在于溶剂化Ni原子溶液是在干冰-丙酮浴条件下浸渍SiO2载体。 5. The catalyst of Claim 2 of said Ni / SiO2 preparation, characterized in that the solvent is a solution of Ni atoms in a dry ice - acetone bath under impregnation conditions SiO2 support.
CN 91103161 1991-05-13 1991-05-13 Method for preparation of diacetol hydroreacting catalyst CN1032574C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1095691C (en) * 1999-09-29 2002-12-11 中国石油化工集团公司 Process for preparing carried catalyst for hydrogenation and demetalation
CN104549425B (en) * 2013-10-23 2017-05-17 中国石油化工股份有限公司 A two diacetone alcohol hydrogenation catalyst and its preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1095691C (en) * 1999-09-29 2002-12-11 中国石油化工集团公司 Process for preparing carried catalyst for hydrogenation and demetalation
CN104549425B (en) * 2013-10-23 2017-05-17 中国石油化工股份有限公司 A two diacetone alcohol hydrogenation catalyst and its preparation method and application

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