Selective Hydrogenation of 2-Butyne-1,4-diol to 1,4-Butanediol Over Particulate Raney® Nickel Catalysts

Abstract

The current study describes the results on the selective hydrogenation of the 2-butyne-1,4-diol to 1,4-butanediol over Raney Ò nickel catalysts both in batch and in CSTR mode. The detailed kinetic analysis of the reaction in batch mode revealed the existence of three characteristic regions. In the first region, A, the starting 2-butyne-1,4-diol produces primarily cis-2-butene-1,4-diol.In the second region, B, the dominant species is cis-2-butene-1,4-diol, which is either hydrogenated to 1,4-butanediol or isomerizes to trans-2-butene-1,4-diol. In the third region, C, the accumulated 4-hydroxybutanal is slowly hydrogenated to 1,4-butanediol. When the same reaction was carried out in a CSTR mode, the only products detected initially are the 1,4-butanediol and n-butanol. The first by-product detected immediately after the end of the first stage is the linear hemiacetal between the 4-hydroxybutanal with 1,4-butanediol. This species has been used as convenient tracer for determining the length of the selective region of the catalyst performance.

Bimetallic Synergy Effects of Phyllosilicate‐Derived NiCu@SiO2 Catalysts for 1,4‐Butynediol Direct Hydrogenation to 1,4‐Butanediol

“…[8,47] In order to prove this deduction, we also made an investigation on the product distribution by changing the H 2 pressures for 3 h batch reaction. As the reaction duration prolonged, the yields of by-products were first slightly increasing and then decreasing since some of the byproducts may also be reversibly hydrogenated to BDO.…”

“…As the reaction duration prolonged, the yields of by-products were first slightly increasing and then decreasing since some of the byproducts may also be reversibly hydrogenated to BDO. [8,47] In order to prove this deduction, we also made an investigation on the product distribution by changing the H 2 pressures for 3 h batch reaction. Data listed in Table S5 proved that HTHF can be suppressed or re-hydrogenated to BDO under a more intense hydrogenation condition.…”

“…[3] By far, the most important BDO production method in industry is 1,4-butynediol (BYD) hydrogenation, and based on this reaction system, noble metals (Pd, Pt etc.) [4][5][6][7] and Raney Ni catalysts [1,8] have been widely used.…”

High-Performance Chlorine-Doped Cu2O Catalysts for the Ethynylation of Formaldehyde

“…In general, the formation of polyacetylene is due to two factors: (1) metallic Cu catalyzes the polymerization of acetylene and (2) the acidic center favors the formation of polyacetylene [20]. According to the XRD and XAES results of used samples, metallic Cu was observed in Cu2O-NO3, but only a small amount of metallic Cu existed in Cu2O-Cl (2). This metallic Cu may be responsible for promoting the formation of polyacetylene, which covered the surface of the catalyst, resulting in its deactivation.…”

“…Catalytic ethynylation of formaldehyde is an important initial process for mass production of high-value intermediates, such as 1,4-butynediol (BD), propynol (PO), and downstream chemicals, such as 1,4-butanediol (BDO), 3-butene-1-alcohol (BTO), tetrahydrofuran (THF), poly (tetramethylene ether) glycol (PTMEG), γ-butyrolactone (GBL), polybutylene succinate (PBS), and polybutylene terephthalate (PBT). These compounds are in high demand in various industries, such as pharmaceutical, textile, military, electrical/electronics, automotive manufacturing, and others [1][2][3][4][5][6][7][8].…”