Catalyst for preparing 1,2-propylene glycol by glycerol hydrogenation and use thereof

A catalyst and hydrogen preparation technology, applied in the direction of metal/metal oxide/metal hydroxide catalyst, physical/chemical process catalyst, elimination of hydroxyl group, etc., can solve the problem of high reaction temperature, affecting production unit consumption, and no catalyst preparation methods, etc.

Active Publication Date: 2008-08-13
SHANGHAI HUAYI NEW MATERIAL
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the patent uses gaseous glycerin and a very high ratio of hydrogen to glycerin, which leads to high energy consumption and greatly increases the operating cost of the device. In addition, due to the high boiling point of glycerin, its gasification will inevitably lead to coking of part of glycerin, which will affect production. Unit consumption
[0007] Chinese patent CN200710043082.8 discloses a method for preparing 1,2-propanediol with a ternary composite oxide catalyst for hydrogenation of glycerol, but this method does not describe the preparation method of the catalyst, and adopts a smaller ratio of hydrogen to glycerin (3:1 ~ 15:1), so that the reaction temperature is high, the heat of reaction cannot be removed quickly, resulting in an increase in by-products, which will shorten the service life of the catalyst
[0008] In view of the problems of high reaction pressure, high operating cost, and short catalyst life in the glycerol hydrogenation process in the above patent, the present invention adopts a trickle bed liquid-phase catalytic reaction process, using highly active Cu-Zr-A as a catalyst, with a raw material concentration of High, low hydrogen pressure, moderate molar ratio of hydrogen to glycerol, low reaction temperature, high selectivity and long life

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Add 178.1g of zirconium oxychloride, 39.0g of ammonium molybdate, 15.2g of copper nitrate, and 2.0g of polyethylene glycol into 1000ml of water in sequence, and add 30% by weight of ammonia water dropwise at 70°C with continuous stirring until the pH value reaches 7.0 , to obtain a slurry. After the slurry was dried at 120°C, it was calcined at 500°C to obtain a catalyst precursor. Cu accounts for 4% by weight of the catalyst precursor, and A / Zr (atomic ratio) is 0.4 (catalyst composition is shown in Table 1).

[0019] The catalytic reaction adopts a trickle bed reactor with a catalyst loading of 7.5g, and both ends are filled with quartz sand. Before the catalyst is used, at 260°C, 2.0MPa and 500h in space velocity -1 Under the conditions of hydrogen reduction treatment 8h. The glycerol solution with a concentration of 60% by weight is preheated at 150°C and enters the reactor for hydrogenation reaction. The reaction conditions are: hydrogen pressure 6.0MPa, tempera...

Embodiment 2-6

[0021] The preparation of the catalyst is the same as in Example 1, except that the weight percentage of Cu in the catalyst precursor is different. The catalyst components are shown in Table 1, and the hydrogenation reaction conditions and results are shown in Table 2.

Embodiment 7-11

[0023] The preparation of the catalyst is the same as in Example 3, except that A / Zr (atomic ratio) is different. The catalyst components are shown in Table 1, and the hydrogenation reaction conditions and results are shown in Table 2.

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PUM

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Abstract

The present invention provides a catalyst for preparing 1, 2-trimethylene glycol using glycerol and hydrogen, and its application. The catalyst precursors are prepared by coprecipitation method or immersion method, the constitute of non-oxygen element is Cu-Zr-A, A is one selected from titanium, tungsten or molybdenum, Cu is 4-40% by weight percentage composition of the catalyst precursors, A/Zr ratio is 0.1-10; the catalyst being reduction activation in hydrogen stream under 200-450 Celsius before being used. The catalyst shows excellent catalyzing effect in the preparing course of the 1, 2-trimethylene glycol using glycerol and hydrogen, and lower hydrogen pressure, reacting temperature, high selectivity and life.

Description

technical field [0001] The invention relates to a catalyst for preparing 1,2-propanediol by hydrogenation of glycerin, a preparation method of the catalyst and its application in hydrogenation reaction of glycerin. Background technique [0002] The shortage of oil resources in the world has further increased the price of oil, and many countries are actively looking for alternatives to oil. Biodiesel is a clean and renewable energy. It is a liquid made from oil crops such as soybeans and rapeseeds, oil-bearing forest fruits such as oil palm and pistachio, engineering microalgae and other oil-bearing aquatic plants, animal fats, and waste cooking oil. Fuel is a high-quality petroleum diesel substitute. However, the rapidly rising investment in biodiesel has resulted in a surplus of by-product glycerin in the production process. About 100 grams of glycerol is produced for every 1000 grams of biodiesel produced. Therefore, finding new ways to utilize these glycerols has attrac...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/885B01J23/888B01J23/72C07C31/20C07C29/60
Inventor 焦昆张春雷宁春利刘汉勇张猛
Owner SHANGHAI HUAYI NEW MATERIAL
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