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Toluene and methanol and/or dimethyl ether alkylation reaction catalyst and preparation method thereof

A technology of dimethyl ether alkanes and catalysts, which is applied in the field of catalysts for the alkylation reaction of toluene and methanol or/and dimethyl ether and its preparation, can solve the problems of weak acid center strength and reduced toluene conversion rate, and reduce light The generation of hydrocarbons, the improvement of toluene conversion rate, and the effect of inhibiting the disproportionation reaction of toluene

Active Publication Date: 2016-07-20
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Although high-selectivity p-xylene products can be obtained from the above-mentioned alkylation reaction products of toluene and methanol, the modification process of the catalyst greatly weakens the strength of the acid centers on the inner and outer surfaces of the catalyst, thus reducing the conversion rate of the raw material toluene

Method used

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  • Toluene and methanol and/or dimethyl ether alkylation reaction catalyst and preparation method thereof
  • Toluene and methanol and/or dimethyl ether alkylation reaction catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Catalyst preparation

[0040] (1) 200gHZSM-5 zeolite molecular sieve (SiO 2 / Al 2 o 3 =100) (Nankai University Catalyst Factory) was added into 300 g concentration of 8% phosphoric acid aqueous solution, soaked at normal temperature for about 6 hours. Then the solid sample was centrifuged, dried in an air atmosphere at 120°C for 12 hours, and calcined in an air atmosphere at 550°C for 4 hours.

[0041] (2) Add the impregnated phosphorus sample in step (1) into 300 g of lanthanum nitrate aqueous solution with a concentration of 8 wt%, and immerse at room temperature for about 6 hours. Then the solid sample was centrifuged, dried in an air atmosphere at 120°C for 12 hours, and calcined in an air atmosphere at 550°C for 4 hours.

[0042] (3) Cool the roasted sample in step (2) to 150° C. and then move it into a desiccator to continue cooling to room temperature. Move the sample down to room temperature into a desiccator filled with deionized water at the bottom, and the...

Embodiment 2

[0046] Catalyst preparation

[0047] (3) 200gHZSM-5 zeolite molecular sieve (SiO 2 / Al 2 o 3 =150) (Nankai University Catalyst Factory) was added into 300 g concentration of 5% phosphoric acid aqueous solution, soaked at normal temperature for about 6 hours. Then the solid sample was centrifuged, dried in an air atmosphere at 120°C for 24 hours, and calcined in an air atmosphere at 550°C for 8 hours.

[0048] (4) Add the impregnated phosphorus sample in step (1) into 300 g of 5 wt % lanthanum nitrate aqueous solution, and immerse at room temperature for about 6 hours. Then the solid sample was centrifuged, dried in an air atmosphere at 120°C for 24 hours, and calcined in an air atmosphere at 550°C for 6 hours.

[0049] (6) Cool the roasted sample in step (2) to 150° C. and then move it into a desiccator to continue cooling to room temperature. Move the sample down to room temperature into a desiccator filled with deionized water at the bottom, and then put the desiccator ...

Embodiment 3

[0053] Response evaluation

[0054] The catalysts HCTM-01 and HCTM-02 prepared in Examples 1 and 2 were pressed into tablets, crushed and sieved to 40-60 meshes. 10 g of catalysts were loaded into the reactor respectively, treated in a nitrogen atmosphere at 550°C for 1 hour, and then cooled to a reaction temperature of 480°C. Pump toluene and methanol into the reactor through the feed pump to contact with the catalyst for reaction, the mass space velocity of toluene feed is 2h -1 , the feed molecular ratio of toluene to methanol was 2 / 1, and the reaction products were analyzed online by gas chromatography, and the composition of non-aqueous products was shown in Table 1.

[0055] Table 1

[0056] catalyst

[0057] *wt%, product mass distribution.

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Abstract

The invention provides a toluene and methanol and / or dimethyl ether alkylation reaction catalyst and a preparation method thereof. The outer surface acid site of the catalyst is passivated through modification, and the inner surface acid site of the catalyst is retained. The preparation method of the catalyst comprises the following steps: a hydrogen-type molecular sieve with an MFI topological structure is subjected to element modification, such that the acid site is modified; the sample is dried and roasted, and is subjected to pre-absorption in saturated water vapor; the sample is then subjected to absorption in saturated ethanol vapor; the sample is impregnated in a siloxane-based agent, such that the siloxane-based agent is only absorbed on the outer surface of the molecular sieve; and drying and roasting are carried out, such that a high-activity selective catalyst is obtained. When the catalyst is applied in a toluene and methanol and / or dimethyl ether alkylation reaction, toluene conversion ate can be effectively improved, and the generation of light hydrocarbon components can be reduced.

Description

technical field [0001] The invention belongs to the field of chemistry and chemical engineering, and particularly provides a catalyst for the alkylation reaction of toluene and methanol or / and dimethyl ether and a preparation method thereof. Background technique [0002] Paraxylene (PX) is an important basic chemical raw material. At present, p-xylene is mainly obtained through aromatics complex. Because the content of p-xylene in the three isomers is controlled by thermodynamics, p-xylene only accounts for about 23% in the xylene isomers, especially the difference between the boiling points of the three isomers of xylene is very small, and the usual Distillation technology cannot obtain high-purity p-xylene, but an expensive adsorption separation process must be used. Therefore, in the entire PX production process, the amount of material circulation is large, the equipment is huge, and the operating cost is high. P-xylene is mainly used to produce polyester. With the rap...

Claims

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Application Information

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IPC IPC(8): B01J29/40C07C15/08C07C2/86
CPCY02P20/52
Inventor 许磊王莹利张洁黄治华
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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