Catalyst for preparing propylene by disproportionation of ethylene and butane and preparation method of catalyst

A catalyst, butene technology, applied in physical/chemical process catalysts, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc., can solve problems such as large gaps, unindustrialization, and no industrialization reports , to achieve the effect of improving the utilization rate and improving the catalytic efficiency

Active Publication Date: 2013-09-04
NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

CN1403198A also studied the Mo / MCM-22 system, and found that adding Mg, K and other additives can improve the stability of the catalyst; Shanghai Petrochemical Research Institute has also carried out research and development of related olefin disproportionation technology, and its related patent CN101992119A uses MCM- 48 molecular sieve as carrier, WO 3 As the active component, the disproportionation reaction is carried out at 350 ° C, 3 MPa, and the molar ratio of ethylene / butene is 2. The conversion rate of butene can reach 78.2%, and the selectivity of butene to propylene can reach 98.0%. This technology not yet industrialized
Generally speaking, the technology of disproportionation of butene and ethylene to propylene in China is far behind that of foreign countries. Except for patent applications, there is no relevant industrialization report

Method used

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  • Catalyst for preparing propylene by disproportionation of ethylene and butane and preparation method of catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Weigh 19g specific surface area is 300m 2 / g SiO 2 , baked at 550 ° C for 4h. After dissolving 0.53g of zirconium nitrate in 20ml of water, impregnate the calcined silica for 2 hours, then place it in an oven at 100°C for 10 hours, and then bake it at 550°C for 4 hours in an air atmosphere to obtain SiO 2 -ZrO 2 Carrier, where ZrO 2 The mass fraction is 1%. Weigh 2.413g of ammonium tungstate, 0.324g of ammonium molybdate, and 0.016g of ammonium perrhenate according to the ratio of tungsten, molybdenum and rhenium oxides, heat and dissolve with 200ml of deionized water and impregnate them into SiO 2 -ZrO 2 Carrier, after impregnation for 5 hours, put it into an oven and dry it for 12 hours at 100°C. Prepare another 1mol / L nitric acid solution, impregnate the above-mentioned dried catalyst into the nitric acid solution, and wash it with a large amount of deionized water after soaking for 1 to 2 minutes, and wash it for 5 to 10 times. If it is 5-7, it is considered ...

Embodiment 2

[0029] Weigh 19g specific surface area is 400m 2 / g SiO 2 , roasted at 550°C for 4h, dissolved 0.53g of zirconium nitrate in 20ml of water, impregnated on the calcined silica for 2h, then put it in an oven at 100°C and dried for 10 hours, under air atmosphere, Calcined at 550°C for 4h to prepare SiO 2 -ZrO 2 Carrier, where ZrO 2 The mass fraction is 1%. Weigh ammonium tungstate, ammonium molybdate and ammonium perrhenate according to the ratio of oxides in Example 1, heat and dissolve with 200ml deionized water and impregnate them into SiO 2 -ZrO 2 Carrier, after impregnation for 5 hours, put it into an oven and dry it for 12 hours at 100°C. Prepare another 1mol / L nitric acid solution, impregnate the above-mentioned dried catalyst into the nitric acid solution, and wash it with a large amount of deionized water after soaking for 1 to 2 minutes, and wash it for 5 to 10 times. If it is 5-7, it is considered that the cleaning is complete, and then put it in an oven at 100°...

Embodiment 3

[0032] Weigh 19g specific surface area is 300m 2 / g SiO 2 , roasted at 550°C for 4h, dissolved 1.62g of zirconium nitrate in 20ml of water, impregnated on the calcined silica for 2h, then put it in an oven at 100°C and dried for 10 hours, under air atmosphere, 550 ℃ calcination for 4h to prepare SiO 2 -ZrO 2 Carrier, where ZrO 2 The mass fraction is 3%. Weigh 2.418g of ammonium tungstate, 0.331g of ammonium molybdate, and 0.017g of ammonium perrhenate according to the ratio of tungsten, molybdenum and rhenium oxides, heat and dissolve with 200ml of deionized water and impregnate them into SiO 2 -ZrO 2 Carrier, after impregnated for 5h, put it into 100℃ oven and dry for 12h. Prepare another 1mol / L nitric acid solution, impregnate the above-mentioned dried catalyst into the nitric acid solution, soak for 1 to 2 minutes, then quickly wash with a large amount of water for 5 to 10 times, and then put it in a 100°C oven for drying. Finally, the above prepared sample was place...

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Abstract

The invention discloses a catalyst for preparing propylene by disproportionation of ethylene and butane. The catalyst consists of 1-15% of active components and 85-99% of a carrier, wherein the active components comprise oxides of tungsten, molybdenum and rhenium; based on 100% of the total weight of the active components, the active components contain 80-100wt% of tungsten, 0-20wt% of molybdenum and 0-1wt% of rhenium; and the carrier is a zirconium oxide modified silicon dioxide carrier. The invention further discloses a preparation method of the catalyst. The preparation method comprises the following steps of: firstly, roasting a silicon dioxide carrier for 2-6 hours; then, dipping the roasted silicon dioxide carrier into a soluble zircon salt solution; subsequently, drying and roasting for 2-6 hours to obtain the zirconium oxide modified silicon dioxide carrier; then, dipping the zirconium oxide modified silicon dioxide carrier in a salt solution of tungsten, molybdenum and rhenium, and drying to obtain a carrier the surface of which is loaded by tungsten, molybdenum and rhenium; then, immobilizing the active components on the surface of the carrier through 0.1-6 M of an acidic precipitator, drying, and roasting for 2-6 hours so as to obtain the catalyst. The catalyst disclosed by the invention is high in catalytic efficiency and good in propylene selectivity.

Description

technical field [0001] The invention relates to the field of chemical synthesis, in particular to a catalyst for preparing propylene by disproportionation of olefins. Background technique [0002] Propylene is one of the important basic raw materials of petrochemical industry, and it is also the petrochemical product with the fastest demand in the world. In 2010, my country's total propylene production capacity was 10.5 million tons, while propylene consumption was 19.05 million tons, with a gap of 8.25 million tons. Although the production capacity of propylene is increasing year by year, it is still far below the actual demand for propylene, and the gap between supply and demand is widening year by year. It is urgent to develop new ways to increase propylene production. With the increasing scarcity of petroleum, there is little room to increase the production of propylene through petroleum, and the production of propylene can only be increased by other means. In addition...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/30C07C6/04C07C11/06
CPCY02P20/52
Inventor 周生虎刘欢于洪波
Owner NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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