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Heteropolyacid ammonium salt type catalyst and preparation method thereof

A heteropolyacid ammonium salt and catalyst technology, which is applied in the direction of catalysts, carbon compound catalysts, heterogeneous catalyst chemical elements, etc., can solve the problems of catalyst activity decline and poor stability, and achieve high low temperature activity and good stability , good selective 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

[0045] (1) Preparation of carrier:

[0046] 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 room temperature for 12 h, then dried at 110 °C for 8 h, pressed and calcined at 580 °C for 3 h to obtain a silica carrier, in which hexadecyltrimethylammonium bromide and silica The molar ratio of citric acid to silicon oxide is 0.3, and the molar ratio of citric acid to silicon oxide is 0.8. Dissolve 31.1 g of nickel nitrate and 3.6 g of boric acid in deionized water, add to 75 g of silica carrier, stir at 70 °C until the solution evaporates to dryness, dry the obtained solid at 110 °C for 8.0 h, and then calcinate at 400 °C for 3.0 h, the prepared catalyst support containing nickel and boron, its properties are: the specific surface area is 495 m 2 / g, the pore volume is 0.61 mL / g, and the average p...

Embodiment 2

[0054] (1) Preparation of carrier:

[0055] 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 room temperature for 12 h, then dried at 110 °C for 8 h, pressed and calcined at 600 °C for 3 h to obtain a silica carrier, in which hexadecyltrimethylammonium bromide and silica The molar ratio of citric acid to silicon oxide is 0.5, and the molar ratio of citric acid to silica is 0.5. Dissolve 38.9 g of nickel nitrate and 5.3 g of boric acid in deionized water, add to 67 g of silica carrier, stir at 70 °C until the solution is evaporated to dryness, dry the obtained solid at 110 °C for 8.0 h, and then calcinate at 400 °C for 3.0 h, the prepared catalyst support containing nickel and boron, its properties are: the specific surface area is 515 m 2 / g, the pore volume is 0.65 mL / g, and the average por...

Embodiment 3

[0061] (1) Preparation of carrier:

[0062] 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, the gel was aged at room temperature for 12 h, then dried at 110 °C for 8 h, pressed and calcined at 650 °C for 3 h to obtain a silica carrier, in which hexadecyltrimethylammonium bromide and silica The molar ratio of citric acid to silicon oxide is 0.8, and the molar ratio of citric acid to silicon oxide is 0.3. Dissolve 46.7 g of nickel nitrate and 7.1 g of boric acid in deionized water, add to 59 g of silica carrier, stir at 70 °C until the solution evaporates to dryness, dry the obtained solid at 110 °C for 8.0 h, and then calcinate at 400 °C for 3.0 h, the prepared catalyst support containing nickel and boron, its properties are: the specific surface area is 540 m 2 / g, the pore volume is 0.69mL / g, and the average p...

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Abstract

The present invention discloses a heteropolyacid ammonium salt type catalyst and a preparation method thereof. The catalyst comprises an active component and an auxiliary agent-containing carrier, wherein the active component is a heteropolyacid ammonium salt, the carrier is silicon oxide containing auxiliary agents such as nickel and boron, the heteropolyacid ammonium salt content is 3-35% by adopting the weight of the catalyst as the reference, and the auxiliary agents comprise (calculated as the oxide) 3-18% of nickel oxide, 1-6% of boron oxide and 41-93% of silicon oxide. According to the present invention, the catalyst is particularly suitable for the ethylene preparation reaction through dehydration by using the low-concentration ethanol aqueous solution as the raw material, and has advantages of high low-temperature activity, high selectivity, high carbon deposition resistance and good stability.

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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IPC IPC(8): B01J31/16B01J23/755B01J35/10B01J27/188B01J27/19C07C1/24C07C11/04
CPCC07C1/24B01J23/002B01J23/755B01J27/188B01J27/19C07C2527/188C07C2527/19B01J2523/00B01J35/617B01J35/635B01J35/647B01J35/615B01J2523/305B01J2523/41B01J2523/847C07C11/04Y02P20/52
Inventor 金浩孙素华朱慧红杨光
Owner CHINA PETROLEUM & CHEM CORP
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