A kind of nickel-phyllosilicate structure catalyst and preparation method thereof

Abstract

The invention relates to a nickel-phyllosilicate structure catalyst and a preparation method thereof. The catalyst has low-temperature and low-pressure catalytic hydrogenation activity, high selectivity and high stability. The catalyst comprises active metal Ni, auxiliary agent X and carrier, and the mass percentage of said active metal Ni, auxiliary agent X and carrier is metal Ni 5%-40%, auxiliary agent X 0.01%-15%, and the balance is carrier; The additive X is any one of Ce, Mg or Mo, and the carrier is a metal phyllosilicate composed of the above metals and additives. The preparation steps are: (1) making the active component nickel precursor and the auxiliary agent X precursor in proportion to make a mixed aqueous solution of metal salt; (2) making the degassed SiO 2 The airgel is dispersed in the metal salt mixed aqueous solution; (3) to SiO 2 Add urea to the mixed aqueous solution of airgel-Ni-X metal salt, heat up, reflux and stir; (4) centrifuge, wash, dry and roast the obtained precipitate to obtain the Ni-X-Phy catalyst precursor; (5) before the catalyst The Ni@X‑phy catalyst was obtained through reduction treatment.

Description

technical field [0001] The invention relates to a nickel-phyllosilicate structure catalyst and a preparation method thereof, which belongs to the low-temperature and low-pressure hydrogenation for the preparation of coal-based 1,4-butynediol and direct hydrogenation to 1,4-butanediol in one step catalyst. Background technique [0002] Hydrogenation of 1,4-butynediol (BYD) is the main method for the industrial production of 1,4-butanediol (BDO). As an important organic synthesis and fine chemical raw material, BDO's downstream products are widely used in many fields such as chemical industry, medicine, textile, automobile and daily chemical industry. But since 1,4-butynediol (OH-CH 2 -C≡C-CH 2 -OH) itself is rich in a variety of unsaturated groups, and its hydrogenation process not only involves C≡C bonds, but also involves side reactions such as C-OH bond isomerization. So far, research on catalysts for this reaction system is limited to noble metals (Pd, Pt, etc.) and R...

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Problems solved by technology

[0003] The industrial development of noble metal catalysts is limited due to high production costs and limited reserves

The Raney nickel catalyst also has problems of environmental pollution and safety risks due to its high metal content.

In the reported work, the supported Ni-based catalyst has the advantages of low cost and easy availability (CN 108097254 A), but this material also cannot achieve a good BYD direct reaction due to the problems of low activity, poor selectivity and easy deactivation. The effect of hydrogenation to prepare BDO

The reason is that in the hydrogenation process of 1,4-butynediol, it is first hydrogenated to form a transition state of 1,4-butenediol, which is very prone to C=C double bond and C- Structural isomerization of OH bonds and conversion to 2-hydroxytetrahydrofuran by-product, thereby reducing product selectivity (S.Tanielyan et al.Org.Process Res.Dev.2017,21,327-335)

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