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CN-121972171-A - Bimetallic catalyst for catalyzing epoxide

CN121972171ACN 121972171 ACN121972171 ACN 121972171ACN-121972171-A

Abstract

The invention relates to the technical field of bimetallic catalysts, in particular to a bimetallic catalyst for catalyzing epoxide, which comprises the following raw materials: activated carbon, titanium tetrachloride, cobalt nitrate, cerium nitrate, glacial acetic acid and deionized water; the components and the proportion are as follows: the ratio of the active carbon is 80 parts; the proportion of the titanium tetrachloride is 4 parts; the cobalt nitrate ratio is 6 parts; the proportion of the cerium nitrate is 10 parts; the glacial acetic acid ratio is 20mL; the deionized water ratio is 50mL, and the glacial acetic acid and the deionized water are added additionally and not accounting for the total amount; the method also comprises the following steps: step one: deep pretreatment of an active carbon carrier; step two: preparing an active component solution; step three: breaking sol agglomerates; step four: aging and drying; step five: roasting and activating; step six: shaping and sieving; the invention aims to solve the problems in the existing materials through bimetal collaborative design, carrier structure regulation and control, load process innovation and roasting system optimization.

Inventors

  • ZHANG XUEYAN
  • LI JUN

Assignees

  • 南京工业大学

Dates

Publication Date
20260505
Application Date
20250902

Claims (7)

  1. 1. A bimetallic catalyst for catalyzing epoxide comprises the following components of active carbon, titanium tetrachloride, cobalt nitrate, cerium nitrate, glacial acetic acid and deionized water; the components and the proportions are that the active carbon proportion is 80 parts, the titanium tetrachloride proportion is 4 parts, the cobalt nitrate proportion is 6 parts, the cerium nitrate proportion is 10 parts, the glacial acetic acid proportion is 20mL, the deionized water proportion is 50mL, and the glacial acetic acid and the deionized water are added additionally and are not added in total; The method also comprises the following steps: step one, deeply preprocessing an active carbon carrier; step two, preparing an active component solution; breaking sol agglomerates; Aging and drying; step five, roasting and activating; And step six, molding and screening.
  2. 2. The bimetallic catalyst for catalyzing epoxide according to claim 1, wherein the advanced pretreatment of the activated carbon carrier comprises the steps of taking 80 parts of activated carbon, adding 10% hydrochloric acid solution (liquid-solid ratio is 5:1), placing in a constant-temperature water bath, stirring for 2h at 60 ℃, removing ash, repeatedly washing with deionized water until filtrate pH=6.5-7.0, ensuring no chloride ion residue, transferring to a blast drying box, setting 110 ℃ and air volume of 80m 3 /h, drying for 6h, and cooling to room temperature for standby.
  3. 3. The bimetallic catalyst for catalyzing epoxides according to claim 1, wherein the preparation of the active component solution comprises the steps of taking 4.0 parts of TiCl 4 in a fume hood, slowly dripping 20mL of glacial acetic acid, simultaneously stirring at a low speed by a magnetic stirrer to form a light yellow titanium sol, taking 6.0 parts of cobalt nitrate and 10.0 parts of cerium nitrate in 30mL of deionized water, stirring for 10min to complete dissolution to form a red-blue mixed nitrate solution, slowly pouring the nitrate solution into the titanium sol, and continuing stirring for 20min to obtain a uniform dark brown mixed sol.
  4. 4. A bimetallic catalyst for catalyzing epoxides according to claim 1, wherein breaking up sol agglomerates comprises the steps of adding 80.0 parts of pretreated activated carbon to the mixed sol, transferring to a high speed disperser, setting a rotation speed of 2000r/min for 30min, and observing every 10min during shutdown to ensure that the sol uniformly coats the surface of the activated carbon.
  5. 5. The bimetallic catalyst for catalyzing epoxide according to claim 1, wherein the aging and drying comprises the steps of transferring the loaded material to a vacuum drying oven, vacuumizing for 30min under the condition of room temperature, -0.05MPa, removing bubbles, heating to 70 ℃ and the vacuum degree-0.08 MPa, drying for 10h to obtain black xerogel, taking out, standing for 4h in a dryer, and balancing moisture.
  6. 6. A bimetallic catalyst for catalyzing epoxides according to claim 1, wherein the calcination activation comprises the steps of placing the xerogel in a box furnace, programming the xerogel to heat up at room temperature from room temperature to 100 ℃, keeping the temperature for 1h, continuing to heat up from 100 ℃ to 300 ℃, keeping the temperature for 2h, then heating up from 300 ℃ to 600 ℃ and keeping the temperature for 5 min, forming a Ti-O-Co-Ce composite active structure, and naturally cooling to room temperature.
  7. 7. A bimetallic catalyst for catalyzing epoxides according to claim 1, wherein the shaping and sieving comprises the steps of tabletting the calcined catalyst with a tablet press under a pressure of 10MPa for 30s, crushing into granules, sieving with a 20-40 mesh sieve, and removing fines and large pieces to obtain the final catalyst.

Description

Bimetallic catalyst for catalyzing epoxide Technical Field The invention relates to the technical field of bimetallic catalysts, in particular to a bimetallic catalyst for catalyzing epoxide. Background The bimetallic catalyst is a material for improving the catalytic performance by introducing two metal active components such as Ti-Co, zn-Al, fe-Mn and the like in the synthesis, ring opening or conversion process of epoxide and utilizing the synergistic effect among metals, such as electron transfer, active site complementation, valence state circulation coordination and the like. The existing single-metal or traditional bimetallic catalyst lacks an effective synergistic effect, the activity and the selectivity are difficult to be compatible, the single-Ti catalyst has weak oxidizing capability, the single-Co catalyst is easy to excessively oxidize, the traditional bimetallic catalyst is only physically mixed and has no chemical bond combination, the dispersion of active components is poor, the traditional impregnation or precipitation method is easy to form agglomerate particles with the particle size of more than 100nm, the exposure of effective sites is insufficient, the carrier is not deeply pretreated, ash residues are more, micropores are easy to collapse, and the mass transfer and adsorption capability are weak. Disclosure of Invention The invention aims to provide a bimetallic catalyst for catalyzing epoxide, which aims to solve the problems in the prior materials through bimetallic collaborative design, carrier structure regulation, load process innovation and roasting system optimization. The bimetal catalyst for catalyzing epoxide comprises the following components of 80 parts of active carbon, 4 parts of titanium tetrachloride, 6 parts of cobalt nitrate, 10 parts of cerium nitrate, 20mL of glacial acetic acid and 50mL of deionized water, wherein the glacial acetic acid and the deionized water are additionally added and the total amount is not counted; The method also comprises the following steps: step one, deeply preprocessing an active carbon carrier; step two, preparing an active component solution; breaking sol agglomerates; Aging and drying; step five, roasting and activating; And step six, molding and screening. Preferably, the advanced pretreatment of the activated carbon carrier comprises the following steps of taking 80 parts of activated carbon, adding 10% hydrochloric acid solution (liquid-solid ratio is 5:1), placing in a constant-temperature water bath kettle, stirring for 2 hours at 60 ℃, removing ash, repeatedly washing with deionized water until the pH value of filtrate is=6.5-7.0, ensuring no chloride ion residue, transferring to a blast drying box, setting 110 ℃ and air volume of 80m 3/h, drying for 6 hours, and cooling to room temperature for standby. Preferably, the preparation of the active component solution comprises the following steps of taking 4.0 parts of TiCl 4 in a fume hood, slowly dripping 20mL of glacial acetic acid, simultaneously stirring at a low speed by a magnetic stirrer to form light yellow titanium sol, taking 6.0 parts of cobalt nitrate and 10.0 parts of cerium nitrate in addition, dissolving in 30mL of deionized water, stirring for 10min till complete dissolution to form a red-blue mixed nitrate solution, slowly pouring the nitrate solution into the titanium sol, and continuously stirring for 20min to obtain uniform dark brown mixed sol. Preferably, the breaking of the sol agglomerates comprises the steps of adding 80.0 parts of pretreated activated carbon into the mixed sol, transferring to a high-speed dispersing machine, setting the rotating speed to 2000r/min and the dispersing time to 30min, and stopping for observation every 10min during the period to ensure that the sol uniformly coats the surface of the activated carbon. Preferably, the ageing and drying comprises the steps of transferring the loaded material to a vacuum drying oven, vacuumizing for 30min at room temperature and minus 0.05MPa, removing bubbles, heating to 70 ℃ and the vacuum degree of minus 0.08MPa, drying for 10h to obtain black xerogel, taking out, standing in a dryer for 4h, and balancing moisture. Preferably, the roasting activation comprises the steps of placing xerogel into a box-type furnace, programming the temperature at room temperature, heating from room temperature to 100 ℃, keeping the temperature for 1h, continuously heating from 100 to 300 ℃ at a heating rate of 5 ℃ per min, keeping the temperature for 2h, heating from 300 to 600 ℃ at a heating rate of 5 ℃ per min, keeping the temperature for 3h, forming a Ti-O-Co-Ce composite active structure, and naturally cooling to room temperature. Preferably, the forming and screening comprises the steps of tabletting the roasted catalyst by a tabletting machine under the pressure of 10MPa for 30s, crushing the catalyst into particles, sieving the particles by a 20-40-mesh sieve, and removing fine powder and large blocks to