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A bismuth-containing catalyst for selectively oxidizing glycerin to prepare glyceric acid and its preparation method

A technology of bismuth catalyst and glycerol oxidation, which is applied in the field of bismuth-containing catalysts and its preparation, can solve the problems of high cost, energy consumption, and material consumption, and achieve the effects of reduced reactivity, high conversion rate of glycerol, and mild reaction conditions

Active Publication Date: 2019-11-08
NANJING INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Moreover, the catalyst efficiency and stability need to be further improved to meet the requirements of industrial production, and the energy consumption and material consumption are still relatively serious.
higher cost

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Dissolve 0.2mol of bismuth chloride in 5L of absolute ethanol, and stir at room temperature for 0.5h to obtain ethanol solution of bismuth chloride. Then 3 mol of copper nitrate, 3 mol of nickel chloride and 3 mol of aluminum nitrate were dissolved in 6 L of deionized water, ie the polymetallic salt solution. Slowly add 5L bismuth chloride ethanol solution and 6L polymetallic salt solution into a certain amount of 12L 2mol / L ammonium carbonate solution within 1h, adjust the pH value to 9-11 with ammonia water, stir and age at 60°C for 8h, cool, Wash until neutral, filter under reduced pressure, and vacuum-dry at 60°C for 12 hours to obtain a bismuth-containing layered multimetal hydroxide catalyst. N 2 Calcining at lower temperature for 3 hours, the bismuth-containing layered metal composite oxide catalyst was obtained, the catalytic effect: the conversion rate of glycerol was 34.2%, and the selectivity of glyceric acid was 48.3%.

Embodiment 2

[0031] Dissolve 1 mol of bismuth nitrate in 10L of ethylene glycol, and stir at room temperature for 3 hours to obtain a bismuth nitrate ethylene glycol solution. Then 1.5 mol of ferric nitrate and 1.5 mol of cobalt nitrate were dissolved in 6 L of deionized water, ie the polymetallic salt solution. Slowly add 10L bismuth nitrate ethylene glycol solution and 6L polymetallic salt solution into a certain amount of 12L 2mol / L sodium carbonate solution within 1 hour, adjust the pH value to 9-11 with sodium hydroxide solution, stir and age at 30°C 24h, cooling, washing to neutral, vacuum filtration under reduced pressure, vacuum drying at 110°C for 8h to obtain a bismuth-containing layered multimetal hydroxide catalyst, and the bismuth-containing layered multimetal hydroxide catalyst in a heating furnace in N at 450°C 2 Calcining at lower temperature for 4 hours, the bismuth-containing layered metal composite oxide catalyst was obtained, the catalytic effect: the conversion rate o...

Embodiment 3

[0033] Dissolve 1.5 mol of bismuth chloride in 10L of absolute ethanol and glycerin (volume ratio 1:1), and stir at room temperature for 2 hours to obtain bismuth chloride ethanol-glycerol solution. Then 4.5 mol of copper chloride, 4.5 mol of zinc chloride and 1.5 mol of manganese nitrate were dissolved in 6 L of deionized water, that is, the polymetallic salt solution. Slowly add 10L bismuth chloride ethanol glycerin solution and 6L polymetallic salt solution into a certain amount of 6L 5mol / L sodium carbonate solution within 1 hour, adjust the pH value to 9-11 with potassium hydroxide solution, and stir and age at 45°C 18h, cooling, washing to neutral, suction filtration under reduced pressure, vacuum drying at 90°C for 10h to obtain a bismuth-containing layered multi-metal hydroxide catalyst, and the bismuth-containing layered multi-metal hydroxide catalyst in a heating furnace in N at 600°C 2 Calcined for 6 hours, the bismuth-containing layered metal composite oxide catal...

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Abstract

The invention discloses a bismuth-containing catalyst for preparation of glyceric acid through selective oxidation of glycerin and a preparation method of the catalyst. The bismuth-containing catalyst is characterized in that the catalyst takes bismuth as an active component and layered hydroxide or layered metal composite oxide as a carrier. The preparation method comprises steps as follows: a bismuth salt solution is prepared; a soluble metallic salt solution is prepared, the two solutions are slowly added to a certain quantity of soluble carbonate solutions for pH value adjustment, stirred at the constant temperature to be aged, cooled, washed to be neutral, subjected to suction filtration under reduced pressure and vacuum drying and then calcined, and the catalyst is obtained. The prepared catalyst is used for preparation of glyceric acid through selective oxidation of glycerin and has the characteristics of high glycerin conversion rate, good selectivity of the product, namely, glyceric acid, simple preparation method, good repeated use performance and low cost.

Description

technical field [0001] The invention relates to a bismuth-containing catalyst for selectively oxidizing glycerin to prepare glyceric acid and a preparation method thereof, belonging to the technical field of glycerin selective catalysts. Background technique [0002] There are three hydroxyl groups in the glycerol molecule. Theoretically, the catalytic oxidation of glycerin will generate a series of high value-added chemical products. The conventional production processes of these chemicals are mostly traditional chemical oxidation processes with high cost and serious pollution (such as potassium permanganate oxidation, nitric acid oxidation, and chromic acid oxidation) or low-yield fermentation processes. Their industrial applications and yields limited. The catalytic oxidation of glycerol is a complex process of multiple parallel reactions and series of reactions. Catalytic oxidation of the hydroxyl functional group on the primary carbon of glycerol can produce glycerald...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/843B01J23/86B01J23/889C07C51/235C07C59/10
CPCB01J23/002B01J23/8437B01J23/868B01J23/8892B01J2523/00C07C51/235B01J2523/17B01J2523/31B01J2523/54B01J2523/847B01J2523/842B01J2523/845B01J2523/27B01J2523/72B01J2523/55B01J2523/67B01J2523/15B01J2523/22B01J2523/25C07C59/10
Inventor 吴功德王晓丽黄江棱唐旭
Owner NANJING INST OF TECH
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