Heteropolyacid ammonium salt catalyst and its preparation method

A heteropolyacid ammonium salt and catalyst technology, applied in the direction of physical/chemical process catalysts, chemical instruments and methods, organic compounds/hydrides/coordination complex catalysts, etc., can solve the problem of selectivity and activity decline, and equipment requirements are very high High and low temperature problems such as poor activity, to achieve the effect of reducing interaction, reducing excessive reaction, and concentrated distribution of acidic components

Active Publication Date: 2021-08-06
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] At present, the catalyst used for methanol dehydration is generally Al 2 o 3 Or molecular sieves, among which the commonly used molecular sieves include aluminum phosphate, HZSM-5, HY, SAPO, etc., and they all have their own shortcomings: for example, although alumina has high stability, the reaction temperature is high, and the requirements for reaction equipment are very high, resulting in cost High; molecular sieve catalysts have strong acidity and low initial temperature, but they also have the disadvantages of many by-products, easy carbon deposition, and easy deactivation
The above-mentioned catalysts have high catalytic activity and selectivity in the reaction, and the optimal load of silicotungstic acid is 10wt%~16wt%. Under normal pressure, when used to treat pure methanol raw materials, its selectivity is high, but Its low-temperature activity is not good, and when it is used as a methanol raw material containing water, its stability is not good, and the selectivity and activity also decrease.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] (1) Preparation of catalyst:

[0041] 87.3g alumina carrier (pore volume 0.70mL / g, specific surface area 300m 2 / g, spherical shape, particle diameter 0.4mm~0.6mm) was added to 200mL cyclohexane solution containing 12.2g dodecyltrimethoxysilane, reacted at 50℃ for 3.0h, and dried at 70℃ for 8h to obtain the catalyst Precursor A; then added to 200mL of 5# diesel oil, filtered after soaking for 30min, the obtained material was placed in a low-temperature reaction bath at 0°C, and then 150mL of an aqueous solution containing 43.7g of citric acid was added, and after soaking for 30min, the solution was poured out. Then add 150mL ammonium carbonate solution with a mass fraction of 30% for immersion for 5min, pour out the solution, then add 100mL aqueous solution containing 8.3g phosphotungstic acid and 10.2g ferric nitrate, immerse for 30min and filter, and put the obtained solid in a relative vacuum At -0.1MPa, dry at 110°C for 8.0h, and then calcined at 500°C for 3.0h to ...

Embodiment 2

[0047] (1) Preparation of catalyst:

[0048] 77.9g alumina carrier (pore volume 0.70mL / g, specific surface area 300m 2 / g, spherical shape, particle diameter 0.4mm~0.6mm) was added to 200mL cyclohexane solution containing 22.2g hexadecyltrimethoxysilane, reacted at 50°C for 3.0h, dried at 70°C for 8h to obtain the catalyst Precursor A; then added to 200mL of 0# diesel oil, soaked for 30min and then filtered, the obtained material was placed in a low-temperature reaction bath at -10°C, and then 150mL of an aqueous solution containing 77.9g of citric acid was added, and after soaking for 30min, the solution was poured out , then add 150mL ammonium carbonate solution with a mass fraction of 30% for immersion for 5min, pour out the solution, then add 100mL aqueous solution containing 15.6g phosphotungstic acid and 15.3g ferric nitrate, filter after immersion for 30min, and put the obtained solid in a relative vacuum At -0.1MPa, dry at 110°C for 8.0h, and then calcined at 470°C fo...

Embodiment 3

[0054] (1) Preparation of catalyst:

[0055] 68.1g alumina carrier (pore volume 0.70mL / g, specific surface area 300m 2 / g, spherical shape, particle diameter 0.4mm~0.6mm) was added to 200mL cyclohexane solution containing 34.6g octadecyltrimethoxysilane, reacted at 50°C for 3.0h, dried at 70°C for 8h to obtain the catalyst Precursor A; then added to 200mL-10# diesel oil, filtered after soaking for 30min, the obtained material was placed in a low-temperature reaction bath at -20°C, and then 150mL of an aqueous solution containing 81.7g of citric acid was added, and after soaking for 30min, the solution was Pour it out, then add 150mL of ammonium carbonate solution with a mass fraction of 30% and soak for 5min, pour out the solution, then add 100mL of an aqueous solution containing 22.4g of phosphotungstic acid and 20.4g of ferric nitrate, soak for 30min and then filter, and the obtained solid is in Under the relative vacuum degree of -0.1MPa, dry at 110°C for 8.0h, and then ca...

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Abstract

The invention discloses a heteropolyacid ammonium salt catalyst and a preparation method thereof. The catalyst comprises an active component, an auxiliary agent and a carrier. The active component is heteropolyacid ammonium salt, the auxiliary agent is Fe, and the carrier is a composite carrier of alumina and silicon dioxide. The catalyst of the invention has high low-temperature activity and selectivity, and is especially suitable for the reaction of dehydrating methanol raw materials with high water content to produce dimethyl ether.

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 methanol dehydration to produce dimethyl ether and a preparation method thereof. Background technique [0002] Dimethyl ether (Dimethy Ether, abbreviated as DME) is a colorless, non-toxic gas at normal temperature and pressure, which can be compressed into a liquid. Dimethyl ether is an important organic chemical raw material and chemical intermediate, which can be used in aerosols, refrigerants, alkylating agents, pharmaceuticals, cosmetics, fuels and other industries. [0003] Dimethyl ether was first produced by rectification of by-products in high-pressure methanol production, and soon developed into two processes of methanol dehydration and direct synthesis of synthesis gas. The liquid-phase method of methanol dehydration to produce dimethyl ether, the reaction is carried out i...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/18B01J27/188B01J27/24C07C41/09C07C43/04B01J35/10
Inventor 金浩朱慧红葛海龙孟兆会杨光孙素华杨涛
Owner CHINA PETROLEUM & CHEM CORP
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