Oxalic ester hydrogenated copper silicon catalyst and preparation method thereof

A technology of catalyst and oxalate, which is applied in molecular sieve catalysts, chemical instruments and methods, preparation of hydroxyl compounds, etc., to achieve the effects of easy large-scale production, high dispersion of copper, and simple preparation process

Inactive Publication Date: 2011-06-15
XIAMEN UNIV
4 Cites 8 Cited by

AI-Extracted Technical Summary

Problems solved by technology

In addition, there are literatures (Chem.Eur.J.2007, 13, 6502-6507; Appl.Catal.A 2000, 202: 179-182) that hydrogen overflow can o...
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Abstract

The invention discloses an oxalic ester hydrogenated copper silicon catalyst and a preparation method thereof, and relates to a catalyst used in preparation of ethylene glycol by using oxalic ester hydrogenation. The invention provides the silicon-aluminum molecular sieve promoted oxalic ester hydrogenated copper silicon catalyst with environmental friendliness, high activity and high thermal stability for synthesizing the ethylene glycol by oxalic ester hydrogenation and a preparation method thereof. The catalyst comprises copper, silicon dioxide and silicon-aluminum molecular sieve, the composition of the catalyst is expressed as x%Cu/SiO2-y% silicon-aluminum molecular sieve, in the formula, x% expresses the mass percentage of the copper in the catalyst, and y% expresses the mass percentage of the silicon-aluminum molecular sieve in the catalyst. The catalyst comprises the following components in percentage by mass: 5 to 60 percent of Cu, 0.5 to 30 percent of silicon-aluminum molecular sieve, and the balance of SiO2. The preparation method comprises the following steps of: preparing a catalyst precursor, and reducing the catalyst precursor under hydrogen-containing atmosphere toobtain the oxalic ester hydrogenated copper silicon catalyst.

Application Domain

Molecular sieve catalystsOrganic compound preparation +2

Technology Topic

Molecular sieveAluminium +7

Image

  • Oxalic ester hydrogenated copper silicon catalyst and preparation method thereof
  • Oxalic ester hydrogenated copper silicon catalyst and preparation method thereof

Examples

  • Experimental program(9)
  • Comparison scheme(2)

Example Embodiment

[0022] Example 1
[0023] Weigh 6.84g copper nitrate trihydrate, dissolve it in 100mL deionized water, add 28wt% ammonia solution dropwise under stirring until the precipitation disappears, and obtain a transparent dark blue solution, which is transferred to the glass containing 0.06g HX molecular sieve In the container, under strong mechanical stirring, slowly drop 10.35g of 40wt% silica sol and 20ml of 20wt% urea aqueous solution at a rate of about 1ml/min. The temperature is raised to 60°C and stirred at a rate of 500r/min for 8h. After cooling, After the precipitate was washed to neutrality, it was dried at 120°C for 12 hours, placed in a muffle furnace at a heating rate of 4°C/min to 350°C, and calcined for 2 hours to obtain a catalyst precursor. Tablets are sieved to obtain 40-60 mesh particles, and the catalyst is put into the reactor. 2 /Ar atmosphere, heat up at 2℃/min to 350℃ and reduce for 4h to obtain 30%Cu/SiO 2 -1% HX catalyst, ICP-MS quantitative analysis results show that the copper content is 27.6wt%; after nitrogen static adsorption test, the specific surface area is 409.0m 2 /g, the pore volume is 1.19ml/g, and the average pore diameter is 8.4nm.
[0024] The catalyst loading amount for the evaluation of catalytic activity is 0.1g. After heating to 200°C at 2°C/min under a 30ml/min high-purity hydrogen purge atmosphere, adjust the high-pressure back pressure valve until the reaction system pressure is constant at 3 MPa, and control it with a mass flow controller The high-purity hydrogen flow rate is 58.8ml/min, and the high-pressure constant-flow pump is used to input the methanol solution of dimethyl oxalate with a concentration of 0.02g/mL into the reactor. The liquid flow rate is 0.25ml/min. At this time, the mass space velocity of dimethyl oxalate is 3.0h -1 , The hydrogen ester molar ratio is 80; the reaction product is collected with a gas-liquid separator, and the sample is taken at 0.5h intervals for quantitative analysis on the gas chromatography. The activity data is basically stable after the reaction for 2h. The dimethyl oxalate is calculated according to the ratio of each component in the product The conversion rate and the selectivity of various products. The catalyst activity evaluation results are shown in Table 1.
[0025] The thermal stability of the catalyst was investigated under the following conditions: the catalyst loading amount was 0.1g, the reaction temperature was 200℃, the pressure was 3MPa, the hydrogen ester molar ratio was 80, the concentration of the methanol solution of dimethyl oxalate was 0.02g/mL, and the mass space velocity of dimethyl oxalate was 2.0h -1 After 4 hours of reaction, the steady-state activity data is obtained, and the mass space-time yield A of ethylene glycol is calculated. Keep the conditions of reaction pressure, hydrogen ester ratio, space velocity and other conditions, and increase the temperature to 350°C at a rate of 5°C/min. After 24 hours After the temperature is lowered back to 200°C, the ethylene glycol mass space-time yield B is calculated after the catalytic activity is stable; the B/A ratio is used as a parameter to measure the thermal stability of the catalyst. The results of thermal stability investigation are shown in Table 2.

Example Embodiment

[0026] Example 2
[0027] Weigh 6.84g copper nitrate trihydrate, dissolve it in 100mL deionized water, add dropwise 28wt% ammonia solution under stirring until the blue precipitate disappears, transfer it into a glass container containing 0.16g HY molecular sieve, and stir it under strong mechanical stirring. Under the state, slowly drop 10.20g of 40wt% silicate and 30ml of 20wt% urea aqueous solution at a speed of about 1ml/min. The water bath is heated to 70℃ and stirred at 400r/min for 8h. After cooling, the precipitate After suction filtration and washing to neutrality, drying at 120°C for 12h, placing it in a muffle furnace at a heating rate of 4°C/min to 450°C, calcining for 4h to obtain a catalyst precursor. Tablets are sieved to obtain 40-60 mesh particles, and the catalyst is put into the reactor. 2 /Ar atmosphere, heating up at 1℃/min to 320℃ and reducing for 4h to obtain 30%Cu/SiO 2 -3% HY catalyst, ICP-MS analysis results show that the copper content is 29.1wt%; after nitrogen static adsorption test, the specific surface area is 382.3m 2 /g, the pore volume is 1.02ml/g, and the average pore diameter is 7.4nm.
[0028] The activity evaluation and thermal stability of the catalyst are the same as in Example 1, and the results are shown in Table 1 and Table 2.

Example Embodiment

[0029] Example 3
[0030] Weigh 6.59g of copper acetate monohydrate, dissolve it in 120mL of deionized water, add dropwise 28wt% aqueous ammonia solution under stirring until the blue precipitate disappears, and transfer it into a 0.3g H-type ZSM-5 molecular sieve (silica to aluminum ratio of 38 ) In a glass container under strong mechanical stirring, slowly drop 9.47g of 40wt% silica sol and 30ml of 20wt% urea aqueous solution at a rate of about 1ml/min. The water bath is heated to 70°C at a rate of 400r/min After stirring for 6 hours, after cooling, the precipitate was suction filtered and washed to neutrality, dried at 120°C for 12 hours, placed in a muffle furnace at a heating rate of 4°C/min to 450°C, and calcined for 4 hours to obtain a catalyst precursor. Tablets are sieved to obtain 40-60 mesh particles, and the catalyst is put into the reactor. 2 /Ar atmosphere, heating up at 1℃/min to 320℃ and reducing for 4h, 35%Cu/SiO is obtained 2 -5% HZSM-5 catalyst, ICP-MS analysis results show that the copper content is 32.7wt%; after nitrogen static adsorption test, the specific surface area is 438.0m 2 /g, the pore volume is 1.11ml/g, and the average pore diameter is 8.5nm.
[0031] The activity evaluation and thermal stability of the catalyst are the same as in Example 1, and the results are shown in Table 1 and Table 2.
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Description & Claims & Application Information

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