Supported Ni-based catalyst for DCPD (dicyclopentadiene) continuous hydrogenation and hydrogenating method

Abstract

The invention relates to a Ni-based catalyst for continuous hydrogenation of a DCPD fixed bed and a hydrogenating method for DCPD continuous hydrogenation to synthesize endo-tetrahydrodicyclopentadiene (endo-THDCPD), overcoming the problems of complex operation, low synthetic efficiency, rapid catalyst deactivation and difficulty in separation of the catalyst and a product for the existing intermittent synthetic reaction. The Ni-based catalyst is prepared from the following components by weight percentage: 5%-40% of NiO, 1-15% of CuO, 0.2%-5% of basic metallic oxide, 0.2%-5% of transition metallic oxide and the balance of a carrier gamma-Al2O3. The catalyst is prepared from a soluble salt solution of reactive metal and auxiliary metal by an impregnation method, and is subjected to drying, calcination and reduction for continuous hydrogenation reaction of a DCPD fixed bed. The Ni-based catalyst is prepared by a co-impregnation method, and also can be prepared by a substep impregnation method, the required reduction temperature is low, the reaction condition is mild, the one-step hydrogenation activity is high, the yield and the selectivity of the endo-THDCPD are high and the activity stability is good.

Description

technical field [0001] The invention relates to a Ni-based catalyst used for DCPD fixed-bed continuous hydrogenation and a hydrogenation method. Background technique [0002] The catalytic hydrogenation product of dicyclopentadiene (abbreviated as DCPD) bridged tetrahydrodicyclopentadiene (abbreviated as endo-THDCPD) is a high-density hydrocarbon fuel hanging tetrahydrodicyclopentadiene (abbreviated as exo- THDCPD, the important chemical intermediate of JP-10 fuel). [0003] The DCPD molecule has two carbon-carbon double bonds, and its hydrogenation reaction equation is as follows: [0004] [0005] Among them, the hydrogenation reaction heat of the 1 and 2 double bonds is -109.7kJ·mol -1 , the hydrogenation reaction heat of the 9, 10-position double bond is -139kJ·mol -1 , it can be seen that the 9 and 10 double bonds are more likely to undergo hydrogenation reactions than the 1 and 2 double bonds. Therefore, the intermediate product of DCPD hydrogenation is mainly 9...

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Problems solved by technology

Raney Ni and Pd / C catalysts are used, and the hydrogenation reaction generally needs to be carried out in a slurry bed reactor. The former is gradually deactivated due to the loss of catalyst pulverization during the hydrogenation process. Although the latter has high hydrogenation activity, the cost of the catalyst is relatively high. high

CN101215218B discloses the operating conditions of Raney Ni and Pd / C catalytic DCPD hydrogenation in a tank reactor, but the operation of the batch synthesis process is complicated, the fine powder catalyst is difficult to recycle, and the catalyst cannot be reused, which will inevitably increase its production cost

On the other hand, the weak acidity of the supported catalyst itself may cause side reactions such as carbon deposition, which can reduce the hydrogenation activity of the catalyst

In addition, for the supported Ni-based catalyst NiO / γ-Al commonly used in the fixed-bed process 2 o 3 , there are generally problems of high reduction temperature and low service temperature, how to effectively reduce the reduction temperature of the supported Ni-based catalyst while maintaining the hydrogenation activity is also a problem that needs to be considered

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