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Heteropolyacid ammonium salt catalyst and preparation method thereof

A heteropolyacid ammonium salt and catalyst technology, which is applied to catalysts, molecular sieve catalysts, carbon compound catalysts, etc., can solve problems such as poor stability and decreased catalyst activity, and achieve good stability, weakened acidity, and good selectivity 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

[0039] (1) Preparation of carrier:

[0040] The prepared particle diameter is 0.2mm spherical HZSM-5 molecular sieve (SiO 2 / Al 2 o 3 The molar ratio is 60) into the ball rolling machine, start the ball rolling machine, and evenly sprinkle amorphous silicon aluminum dry powder (on a dry basis, with a silicon oxide content of 20wt%) into the machine, and spray the mass concentration of 6% at the same time Aqueous aqueous solution of acetic acid, after sphere forming, the carrier was dried at room temperature for 12 h, and then calcined at 500 °C for 3 h to obtain HZSM-5 molecular sieve carrier coated with amorphous silicon-alumina, in which amorphous silicon-aluminum accounted for HZSM-5 molecular sieve 20% of the weight.

[0041] (2) Preparation of catalyst:

[0042] Weigh 75.7 g of the prepared carrier and add it to a mixed aqueous solution containing 27.4 g of nickel nitrate, 6.1 g of phosphoric acid and 1.1 g of ammonium metavanadate, stir at 70°C until the solution is ...

Embodiment 2

[0048] (1) Preparation of carrier:

[0049] The prepared particle size is 0.3mm spherical HZSM-5 molecular sieve (silicon-aluminum molar ratio is 100) is added in the ball rolling machine, start the ball rolling machine, and evenly sprinkle amorphous silicon-aluminum dry powder (on a dry basis) into the machine Calculated, the weight content of silicon oxide is 30%). At the same time, the acetic acid aqueous solution with a mass concentration of 6% is sprayed. After the ball is formed, the carrier is dried at 40°C for 12h, and then roasted at 500°C for 3h to obtain amorphous silicon-aluminum coating. The HZSM-5 molecular sieve carrier, in which amorphous silicon aluminum accounts for 30% of the weight of the HZSM-5 molecular sieve.

[0050] (2) Preparation of catalyst:

[0051] Weigh 65.6 g of the prepared carrier and add it to a mixed aqueous solution containing 38.3 g of nickel nitrate, 6.8 g of phosphoric acid and 2.1 g of ammonium metavanadate, stir at 70°C until the solu...

Embodiment 3

[0055] (1) Preparation of carrier:

[0056] The prepared 50g particle diameter is 0.4mm spherical HZSM-5 molecular sieve (SiO 2 / Al 2 o 3 The molar ratio is 150) into the ball rolling machine, start the ball rolling machine, and evenly sprinkle 20g of amorphous silicon-aluminum dry powder (on a dry basis, with a silicon oxide content of 40wt%) into the machine, and at the same time spray into the machine with a mass concentration of 6 % acetic acid aqueous solution, after the ball forming, the carrier was dried at 40°C for 12 h, and then calcined at 500°C for 3 h to obtain the HZSM-5 molecular sieve carrier coated with amorphous silica-alumina, in which amorphous silica-alumina accounted for HZSM- 5 40% of molecular sieve weight.

[0057] (2) Preparation of catalyst:

[0058] Weigh 56.2 g of the prepared carrier and add it to a mixed aqueous solution of 47.3 g of nickel nitrate, 7.4 g of phosphoric acid and 2.9 g of ammonium metavanadate, stir at 70°C until the solution is...

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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, phosphorus and vanadium, the carrier is an amorphous silicon-aluminum coated molecular sieve, the auxiliary agents comprise (calculated as the oxide) 3.0-10.0% of P2O5, 0.2-4.0% of V2O5 and 8-20% of NiO by adopting the weight of the carrier as the reference, the heteropolyacid ammonium salt content is 8-30% by adopting the weight of the catalyst as the reference, and the total content of the auxiliary agents and the carrier is 70-92% (calculated as the oxide). According to the present invention, the catalyst 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): B01J31/36C07C1/24C07C11/04
CPCY02P20/52B01J29/48B01J27/188B01J2229/186C07C1/24C07C2529/48C07C11/04
Inventor 金浩孙素华朱慧红杨光
Owner CHINA PETROLEUM & CHEM CORP
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