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Heteropolyacid ammonium salt catalyst and preparation method thereof

A heteropolyacid ammonium salt and catalyst technology, applied in catalysts, carbon compound catalysts, chemical instruments and methods, etc., can solve problems such as poor stability and decreased catalyst activity, and achieve good stability, high low-temperature activity, and high selectivity. good effect

Active Publication Date: 2017-07-14
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The above-mentioned catalysts show high catalytic activity and selectivity when using high-concentration ethanol as a raw material, but when using low-concentration ethanol as a raw material, the catalyst activity decreases significantly, and the stability is not good

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0047] (1) Preparation of carrier:

[0048] Weigh 145.8g of cetyltrimethylammonium bromide and 205g of citric acid to form a mixed solution, add 302mL tetraethyl orthosilicate to the mixed solution, stir for 2 h, and then stir at 70°C until coagulation gel, the gel was aged at 40°C for 12 h, then dried at 110°C for 8 h to produce spherical silica with a particle size of 0.4 mm, and calcined at 580°C for 3 h to obtain a silica carrier, in which hexadecyl The molar ratio of trimethylammonium bromide to silicon oxide is 0.3, and the molar ratio of citric acid to silicon oxide is 0.8. The nature of the carrier is: the specific surface area is 525 m 2 / g, the pore volume is 0.64 mL / g, and the average pore diameter is 4.9 nm.

[0049] Add the prepared spherical silicon oxide with a particle size of 0.4mm into the ball rolling machine, start the ball rolling machine, and evenly sprinkle amorphous silica-alumina dry powder (calculated on a dry basis, with a silicon oxide content of ...

Embodiment 2

[0057] (1) Preparation of carrier:

[0058] Weigh 200g of cetyltrimethylammonium bromide and 105.7g of citric acid to make a mixed solution, add 250mL tetraethyl orthosilicate into the mixed solution, stir for 2 h, and then stir at 70°C until coagulation gel, the gel was aged at 40°C for 12 h, then dried at 110°C for 8 h to produce spherical silica with a particle size of 0.3 mm, and calcined at 600°C for 3 h to obtain a silica carrier, in which hexadecyl The molar ratio of trimethylammonium bromide to silicon oxide is 0.5, and the molar ratio of citric acid to silicon oxide is 0.5. The nature of the carrier is: the specific surface area is 570 m 2 / g, the pore volume is 0.72 mL / g, and the average pore diameter is 5.1 nm.

[0059] Add the prepared spherical silicon oxide with a particle size of 0.3mm into the ball rolling machine, start the ball rolling machine, and evenly sprinkle amorphous silicon-aluminum dry powder (calculated on a dry basis, with a silicon oxide content...

Embodiment 3

[0065] (1) Preparation of carrier:

[0066] Weigh 316g of cetyltrimethylammonium bromide and 62.4g of citric acid to form a mixed solution, add 246mL tetraethyl orthosilicate into the mixed solution, stir for 2 h, and then stir at 70°C until coagulation gel, aged at 40°C for 12 h, then dried at 110°C for 8 h to produce spherical silica with a particle size of 0.2 mm, and calcined at 650°C for 3 h to obtain a silica carrier, in which hexadecyl The molar ratio of trimethylammonium bromide to silicon oxide is 0.8, and the molar ratio of citric acid to silicon oxide is 0.3. The nature of the carrier is: the specific surface area is 630 m 2 / g, the pore volume is 0.81 mL / g, and the average pore diameter is 5.1 nm.

[0067] Add the prepared spherical silicon oxide with a particle size of 0.2mm into the ball rolling machine, start the ball rolling machine, and evenly sprinkle amorphous silica-alumina dry powder (on a dry basis, with a silicon oxide content of 40wt%) into the machin...

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Abstract

The present invention discloses a heteropolyacid ammonium salt catalyst and a preparation method thereof. The catalyst comprises an active component, auxiliary agents and a carrier, wherein the active component is a heteropolyacid ammonium salt, the auxiliary agents are nickel oxide and ferric oxide, and the carrier is amorphous silicon-aluminum coated silica. The catalyst of the present invention has advantages of high low-temperature activity, high selectivity, high carbon deposition resistance and improved stability, and is particularly suitable for the ethylene preparation reaction through dehydration by using the low-concentration ethanol aqueous solution as the raw material.

Description

technical field [0001] The invention relates to a heteropolyacid ammonium salt catalyst and a preparation method thereof, in particular to a loaded heteropolyacid ammonium salt catalyst used for ethanol dehydration to produce ethylene and a preparation method thereof. Background technique [0002] Ethylene is a basic organic chemical raw material and a leading product in the petrochemical industry. About 75% of chemical products are prepared from ethylene. Therefore, ethylene production has become an important indicator to measure the development level of a country's petrochemical industry. Traditional ethylene is mainly produced through the distillation and cracking of light petroleum, which relies heavily on petroleum resources. With the increasingly tense international energy situation and the depletion of oil resources, it is imperative to develop new renewable alternative energy sources. [0003] Recently, the dehydration of ethanol, especially renewable bioethanol, to...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/18B01J27/188B01J21/08C07C1/24C07C11/04
CPCC07C1/24B01J21/08B01J27/188C07C2527/188C07C2531/18B01J35/60C07C11/04Y02P20/52
Inventor 金浩孙素华朱慧红杨光
Owner CHINA PETROLEUM & CHEM CORP
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