Catalyst used for preparing 1,3-propylene glycol through glycerin hydrogenolysis, preparation method thereof, and application thereof

A glycerol hydrogenolysis and catalyst technology, applied in metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, preparation of eliminating hydroxyl groups, etc., can solve the problem of inability to convert glycerol on a large scale, low product concentration, and product separation problems such as rising costs

Active Publication Date: 2012-10-17
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0010] At present, the biotransformation of glycerol to prepare 1,3-propanediol is affected by biological metabolism, and it is impossible to convert glycerol on a large scale, and the concentration of the obtained product is very low, resulting in an increase in the cost of product separation. Compared with biotransformation of glycerol, chemical synthesis is benefici...

Method used

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  • Catalyst used for preparing 1,3-propylene glycol through glycerin hydrogenolysis, preparation method thereof, and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Preparation of mesoporous tungsten oxide and ammonium metatungstate calcined tungsten oxide:

[0021] 0.5 g of P123 (EO 20 PO 70 EO 20 ) was dissolved in 5 g of n-propanol, and after P123 was completely dissolved, 1.78 g of tungsten precursor WCl was added 6 (P 123 : Solvent: WCl 6 The mass ratio is 0.5:4:1.78), stirred at room temperature for 4 hours, the obtained sol was coated on a glass plate, placed in an oven at 60°C for 5 days, and the obtained tungsten oxide precursor was calcined at 500°C for 1 hour to obtain mesoporous Tungsten oxide support, labeled M-WO 3 .

[0022] Calcinate ammonium metatungstate at 500°C in an air atmosphere for 4 hours, the heating rate is 1°C / min, and the air flow rate is 40ml / min to obtain tungsten oxide, which is marked as A-WO 3 .

[0023] Commercial tungsten oxide, labeled C-WO, was purchased from Aladdin reagents 3

[0024] The pore structure parameters of the obtained tungsten oxide are shown in Table 1.

[0025] ...

Embodiment 2

[0028] Preparation of Pt / WO by Impregnation Method 3 catalyst

[0029] Weigh 1.0g of the tungsten oxide carrier prepared in Example 1, immerse the tungsten oxide carrier in 0.5ml of aqueous solution containing 0.054g of chloroplatinic acid, let stand at 20°C for 12 hours, and then pass through 60°C and 120°C oven After drying for 6 hours, the catalyst was calcined in an air atmosphere. The specific process was as follows: from 20°C to 400°C at a rate of 10°C / min and maintained for 1 hour, the air flow rate was 40ml / min. The catalyzer after this calcining is carried out temperature-programmed reduction in hydrogen, and concrete reaction process is: rise to 300 ℃ and keep 1 hour by room temperature with 10 ℃ / min heating rate and keep 1 hour, and hydrogen flow rate is 60ml / min. The theoretical loading of platinum in the prepared catalyst is 2wt%, and the catalyst is marked as 2Pt / M-WO 3 (here M-WO 3 example).

Embodiment 3

[0031] Catalyst performance evaluation of glycerin catalytic conversion:

[0032] The catalytic reaction was carried out in a stainless steel autoclave made by Parr (100ml), and 1g of catalyst was weighed, and 40ml of glycerol was used as a 10wt% aqueous solution. Replace the air in the reactor with hydrogen three times, and then fill with 5.5MPa hydrogen. Heat up to 180 DEG C and react for 12 hours and then cool down. After the product is filtered or centrifuged, the pre-reaction and post-reaction liquids are diluted ten times with methanol and then analyzed by GC.

[0033] The calculation formulas of the conversion rate of glycerol and the selectivity of product are as follows respectively:

[0034] The conversion rate of glycerol (%) = (the number of moles of glycerol before the reaction - the number of moles of glycerol after the reaction) / the number of moles of glycerol before the reaction × 100%.

[0035]Selectivity of 1,3-propanediol or 1,2-propanediol (%)=(moles of...

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Abstract

The invention relates to a catalyst used for preparing 1,3-propylene glycol through glycerin hydrogenolysis, and specifically relates to a preparation method and an application of a mesoporous-tungsten oxide-supported platinum-based catalyst. According to the invention, mesoporous tungsten oxide is adopted as a carrier, and active components such as metal platinum or other noble metals are highly dispersed on the surface of the carrier, wherein the theoretical content of the active components accounts for 0.1-40% of the mass of the carrier. The catalyst is characterized by good selectivity and high activity. With the catalyst, high-selectivity preparation of 1,3-propylene glycol can be realized through glycerin hydrogenolysis under hydrothermal conditions comprising a temperature of 120-300 DEG C and a hydrogen pressure of 0.1-15MPa.

Description

technical field [0001] The invention relates to a catalyst for preparing 1,3-propanediol by hydrogenolysis of glycerol, a preparation method and application thereof, specifically, mesoporous tungsten oxide supports a noble metal active component, and the catalyst prepares 1,3-propanediol by hydrogenolysis of glycerin in the application. technical background [0002] With the rapid development of biodiesel, the by-product glycerol in the process of biodiesel production has a large surplus, and the conversion of glycerol to high-value chemicals has become a hot spot in industrial applications. Glycerol is an important raw material in chemical products and can be hydrogenolyzed Produce 1,3-propanediol, 1,2-propanediol, of which 1,3-propanediol is an industrial raw material (PTT) as a monomer of propylene terephthalate, and PTT is a kind of biodegradable polyester fiber , has strong stretchability, and has great potential for development in industries such as carpets and clothi...

Claims

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Application Information

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IPC IPC(8): B01J23/888B01J23/652C07C31/20C07C29/60
CPCC07C29/60C07C31/205
Inventor 王爱琴刘龙杰张艳华郑明远张涛
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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