Process for producing ruthenium base catalyst for producing cyclohexene with benzene selective hydrogenation

A technology for selective hydrogenation and ruthenium catalyst is applied in the field of novel preparation of ruthenium-based catalysts, and can solve the problems of large usage amount, large ruthenium powder catalyst particles and high catalyst cost

Inactive Publication Date: 2008-07-16
FUDAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the large particle size and low dispersion of the ruthenium powder catalyst, its usage is large and the cost of the catalyst is high.

Method used

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  • Process for producing ruthenium base catalyst for producing cyclohexene with benzene selective hydrogenation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] Example 1: Preparation of Ru / HMS catalyst

[0017] The preparation of the catalyst adopts the preparation method of a cyclohexane / water mixed solvent system. Disperse 1g HMS into 30mL cyclohexane solution, add RuCl dropwise to the above suspension under stirring 3 Aqueous solution (containing Ru 0.01g, 0.04g, 0.08g, 0.12g, 0.16g), after dripping, continue to stir for 10min, filter and dry. The reduction treatment of the catalyst is carried out in a tube furnace. Put the dried catalyst into the tube furnace and pass H 2 / Ar reduction, the gas flow rate is 50mL / min, the reduction temperature is 200-500℃, and the reduction time is 240min.

[0018] The preparation methods of MCM-41 and SBA-15 supported catalysts are similar to those of HMS supported catalysts, which are denoted as Ru / MCM-41 and Ru / SBA-15, respectively.

Embodiment 2

[0019] Example 2: Preparation of Ru-Fe / SBA-15 catalyst

[0020] The preparation of the catalyst adopts the preparation method of a cyclohexane / water mixed solvent system. Will RuCl 3 (Containing Ru 0.12g) and FeCl 3 (The atomic ratio of Fe to Ru is 1:10, 2:10, and 3:10 respectively) mixed aqueous solution was added dropwise to the suspension of 1g SBA-15 and 30mL cyclohexane to prepare the precursor of the catalyst, The reduction treatment conditions were the same as in Example 1.

[0021] The Sn and Ba modified catalysts were prepared by the same method as above. The tin salt and barium salt are respectively pre-dissolved in the mixed solution. The atomic ratios of Sn and Ru are 1:10, 2:10, and 3:10, respectively, and the atomic ratios of Ba and Ru are 1:10, 2:10, and 3:10, 5:10, 10:10, and the catalysts are denoted as Ru-Sn / SBA-15 and Ru-Ba / SBA-15, respectively.

Embodiment 3

[0022] Example 3: Preparation of Ru-Ba / MCM-41 catalyst

[0023] The preparation of the catalyst adopts the preparation method of a cyclohexane / water mixed solvent system. Will RuCl 3 (Containing Ru 0.04g) and Ba(NO3) 2 (The atomic ratio of Ba to Ru is 1:10, 2:10, and 3:10 respectively) mixed aqueous solution was added dropwise to the suspension of 1g MCM-41 and 30mL cyclohexane to prepare the precursor of the catalyst, The reduction treatment conditions were the same as in Example 1.

[0024] The HMS-supported catalyst adopts the same preparation method as described above, wherein the content of Ru in the catalyst is 0.08 g, and the catalyst is denoted as Ru-Ba / HMS.

[0025] Benzene selective hydrogenation activity evaluation example 1: Ru / HMS catalyst

[0026] The amount of catalyst is 1 unit, benzene 50 mL, water 100 mL, reaction temperature 150°C, hydrogen pressure 4.0 MPa, stirring rate 1000 rpm, and the results of selective hydrogenation are shown in Table 1.

[0027] Benzene...

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Abstract

The invention pertains to chemical engineering field, in particular to a preparation method of a Ru-based catalyst, the catalyst has uniform load and high catalytic efficiency and is used for preparing cyclohexene from benzene through selectively hydrogenation reaction. A precursor of the catalyst is prepared through a cyclohexene/ water component solvent system, and then reduced by a mixing gas of H2 or Ar to prepare the catalyst, and the catalyst consists of ruthenium, a dressing agent and a mesoporous silicon dioxide carrier L, amongst which the active component is ruthenium metal, the dressing agent is a metal oxide, and the precursor is selected from the nitrate or chloride of metal elements in IIA main group, VIII group and IVA main group in the element periodic table; ruthenium and the dressing agent are uniformly carried on the carrier L through the preparation method of the invention. When being used in preparing cyclohexene from benzene through selectively hydrogenation reaction, and compared with the catalyst used for the selectively hydrogenation of industrial benzene, the catalyst has the advantages that: lower the ruthenium consumption, higher selectively hydrogenation activity and selectivity for benzene.

Description

Technical field [0001] The invention belongs to the technical field of chemical industry, and is a novel preparation method of a ruthenium-based catalyst used for selective hydrogenation of benzene to produce cyclohexene. Background technique [0002] Cyclohexene has a lively double bond. As an important organic chemical raw material, it is widely used in the production of medicines, pesticides, agrochemicals, feed additives, polyester and other fine chemical products. In particular, cyclohexene can be directly oxidized to prepare the intermediate cyclohexanone and adipic acid used in a large amount in the synthesis of polyamide fibers, thereby greatly shortening the production route of ε-caprolactam and adipic acid. Because the traditional methods for producing cyclohexene such as cyclohexanol dehydration method, halogenated cyclohexane dehydrohalogenation method and Birch reduction method have the disadvantages of complex production process, low yield and high cost, so that cyc...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/03C07C13/20C07C5/10
CPCY02P20/52
Inventor 乔明华卜娟范康年
Owner FUDAN UNIV
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