▎ 摘　　要

NOVELTY - Manufacture of oligo-layer carbon-protected metal-based catalyst involves (i) grinding a metal precursor and a carbon-containing organic material evenly with a mortar in nitrogen glove box to form the precursor of the bulk metal catalyst, and adding the carrier to the precursor of the bulk metal catalyst, while dripping the liquid reagent, mixing and stirring, and aging, centrifuging and washing to obtain a dry powder as the precursor of the solid-supported metal catalyst, (ii) preparing the metal-based catalyst by performing two-step method of thermal decomposition-reaction atmosphere treatment or a one-step reduction treatment method, by treating the precursor of the bulk metal catalyst or the precursor of the solid-supported metal catalyst with hot atmosphere, so that the surface carbon carrier is partially thermally decomposed or methanated on the surface of the metal particles. The molar ratio of carbon-containing organic material to metal ions in the metal precursor is 0.5-100. USE - Manufacture of oligo-layer carbon-protected metal-based catalyst used for carbonylation of ethylene oxide (claimed). ADVANTAGE - The method enables simple manufacture of oligo-layer carbon-protected metal-based catalyst with easy separation and recovery. The raw material ethylene oxide can be recovered from industrial waste gas, which reduces costs while reducing environmental pollution. The conversion rate of epoxide is 92.6% or more, and the selectivity of methyl 3-hydroxypropionate is 98.6% or more. DETAILED DESCRIPTION - Manufacture of oligo-layer carbon-protected metal-based catalyst involves (i) grinding a metal precursor and a carbon-containing organic material evenly with a mortar in nitrogen glove box to form the precursor of the bulk metal catalyst, and adding the carrier to the precursor of the bulk metal catalyst, while dripping the liquid reagent, mixing and stirring for 1-10 minutes, and aging for 0.5-72 hours, centrifuging and washing to obtain a dry powder as the precursor of the solid-supported metal catalyst, (ii) preparing the metal-based catalyst by performing two-step method of thermal decomposition-reaction atmosphere treatment or a one-step reduction treatment method, by treating the precursor of the bulk metal catalyst or the precursor of the solid-supported metal catalyst with hot atmosphere, so that the surface carbon carrier is partially thermally decomposed or methanated on the surface of the metal particles to form the metal-based catalyst with oligo-layer carbon protection. When using the two-step method of thermal decomposition-reactive atmosphere treatment, the precursor is treated in nitrogen, air or oxygen/argon atmosphere for 2-10 hours in the temperature range of 20-1000 degrees C, and carbon monoxide, carbon monoxide/oxygen or hydrogen sulfide/oxygen/argon at 20-450 degrees C for 2-72 hours to obtain metal-based catalyst. When the one-step method is used, the metal-based catalyst is obtained by treating the precursors at temperature range of 20-1000 degrees C under hydrogen/argon atmosphere for 2-10 hours. When preparing the solid-supported metal catalyst, carbon material is used as the carrier or silicon oxide is used as the structural framework, and silicon oxide is further removed as a template, and after the heat treatment, it is etched by hydrofluoric acid at 30-90 degrees C for 0.5-12 hours, washed and dried to obtain metal-based catalyst protected by oligo-layer carbon. The prepared metal-based catalyst is a bulk metal catalyst or a solid-supported metal catalyst. An INDEPENDENT CLAIM is included for use of the metal-based catalyst protected by oligo-layer carbon shell in the carbonylation of ethylene oxide. The carbonylation of ethylene oxide is performed by conveying ethylene oxide to a continuous stirred tank reactor containing catalyst powder through a liquid transport pump and a solvent, in which the mole ratio of ethylene oxide in the solvent is 0.1-20 mol%, entering 0.1-15 MPa carbon monoxide, and realizing the hydrogen esterification reaction of ethylene oxide in the temperature of room temperature to 150 degrees C, after the reaction, cooling the sample by a cooler and entering the gas-liquid separator to recover carbon monoxide gas, entering the liquid-solid mixture into the rectification tower, and using different distillation temperatures in the top of the tower to obtain 1,1-dimethoxyethane, ethylene oxide and methanol, and recovering ethylene oxide and methanol, and obtaining methyl 3-hydroxypropionate and catalyst residues at the bottom of the tower, separating liquid-solid phase by filtration to obtain high-purity methyl 3-hydroxypropionate, and recovering catalyst residues.