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Method for producing high-octane aromatic gasoline by alkylation of benzene and methanol

A high-octane, aromatic gasoline technology, applied in chemical instruments and methods, processing hydrocarbon oil, refining hydrocarbon oil, etc., can solve complex alkylation reaction process, low selectivity of methanol alkylation, and catalyst deactivation rate Fast and other problems, to achieve the effect of reducing the coking deactivation rate, long activity stability time, and long stable operation time

Inactive Publication Date: 2020-08-11
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The outstanding problems in these studies include fast catalyst deactivation rate; low selectivity of methanol alkylation; injection of inert gas nitrogen or hydrogenation gas hydrogen into the alkylation reaction system makes the alkylation reaction process complicated and energy-consuming

Method used

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  • Method for producing high-octane aromatic gasoline by alkylation of benzene and methanol
  • Method for producing high-octane aromatic gasoline by alkylation of benzene and methanol
  • Method for producing high-octane aromatic gasoline by alkylation of benzene and methanol

Examples

Experimental program
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Effect test

Embodiment 1

[0062] Embodiment 1: the preparation of extruded catalyst

[0063] Weigh 10g of SiO respectively 2 / Al 2 o 3 32 HZSM-5 molecular sieve raw powder, 55g gibbsite, 35g cerium nitrate hexahydrate, stir and mix the three for 15min to obtain a solid mixture; add 3g of squash powder to the solid mixture, stir and mix for 15min, then add 20g of deionized water, and stirred and mixed for 15min; then, while stirring, 106g of dilute nitric acid aqueous solution with a mass fraction of 5% was added dropwise, and the mixture was kneaded into a mud mass, which was formed and extruded by TBL-2 catalyst produced by Tianjin University Beiyang Chemical Experimental Equipment Co., Ltd. The equipment is extruded into strips; the strips are dried at 15°C for 10 hours, and then heated in a horse-boiler furnace at a heating rate of 10°C / min from 15°C to 540°C, and roasted at a constant temperature for 5 hours to obtain Ce 2 o 3 Mass fraction 21.43%, Al 2 o 3 The shaped HZSM-5 catalyst of mass ...

Embodiment 2

[0068] Example 2: Preparation of supported metal oxide modified catalyst

[0069] Add 2.0g of magnesium nitrate hexahydrate and 0.2g of citric acid to 20g of deionized water, stir and mix at 10°C for 5 minutes to obtain 22.2g of an impregnating solution with a molar ratio of citric acid penetrant to magnesium element of 0.12:1; 10g of HZSM-5(200) shaped catalyst was added to the impregnation solution, the mass ratio of liquid to solid was 2.22:1, stirred and impregnated at 10°C for 8h; dried at 60°C for 48h, and then placed in a The heating rate is ℃ / min, the temperature is programmed from 10 ℃ to 550 ℃, and the constant temperature is roasted for 4 hours to obtain a modified catalyst with a mass fraction of 3.14% MgO impregnated, which is marked as 3.14MgO / HZSM-5 (200).

[0070] Add 2.0g of magnesium nitrate hexahydrate, 0.5g of lanthanum cerium carbonate, and 0.2g of oxalic acid into 20g of deionized water, and stir and mix at 15°C for 15 minutes to obtain 22.7g of oxalic ac...

Embodiment 3

[0080] Embodiment 3: Evaluation of Catalyst Alkylation Catalytic Performance

[0081] Five shaped catalysts and 14 supported metal oxide modified catalysts were used to carry out the alkylation reaction of benzene and methanol under certain conditions, and the catalytic performance of each catalyst was evaluated. Put 4.0g of 20-40 mesh catalyst into the fixed bed reactor, under nitrogen pressure 2.0MPa, nitrogen flow rate 0.2m 3 / h, the temperature of 500 ° C activation conditions, the catalyst activation treatment for 2h. At a temperature of 480°C, a pressure of 0.2MPa, and a mass space velocity of 2.0h -1 , react under the reaction condition of 2:1 of raw material benzene and methanol molar ratio, obtain the benzene conversion rate (X B ), toluene selectivity (S T ), xylene selectivity (S X ), the selectivity of ethylbenzene+C9 aromatics (S E+C9 + ), methanol conversion (X M ), methanol alkylation selectivity (S AM ) The experimental results are listed in Table 1.

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Abstract

The invention provides a method for producing high-octane aromatic gasoline by alkylation of benzene and methanol, which comprises the following steps: inputting raw materials benzene and methanol into a fixed bed reactor, contacting with a modified HZSM-5 molecular sieve catalyst, and carrying out alkylation reaction to generate high-octane aromatic gasoline mainly containing toluene and xylene;the modified HZSM-5 molecular sieve catalyst with high catalytic performance is prepared by utilizing the dispersion effect of a penetrant and adopting a permeation impregnation method of a metal compound, so that a metal oxide tends to be uniformly loaded in molecular sieve pores, the surface acidity and the pore diameter are effectively regulated and controlled; the methanol alkylation selectivity reaches 98% or above, and the total selectivity of toluene and xylene is close to 100%; the methanol conversion rate reaches 100%, the benzene conversion rate is close to 40%, the activity stabilization time of the catalyst is longer than 2160 h, and the deactivated catalyst can be regenerated; inert gas or hydrogenated hydrogen does not need to be jointly fed into the reactor, the reaction technological process is simple, and energy consumption is low.

Description

technical field [0001] The invention relates to a method for producing high-octane aromatic gasoline by alkylation of benzene and methanol, in particular, the alkylation reaction of benzene and methanol is carried out by using a modified HZSM-5 catalyst loaded with metal oxides, and the production mainly contains toluene, di Toluene method for high-octane aromatic gasoline. Background technique [0002] At present, the proportion of catalytically cracked gasoline in my country's gasoline products is higher than 70%. The octane number of catalytically cracked gasoline is low, and it contains olefins, and a small amount of sulfur-containing and nitrogen-containing compounds, while catalytically reformed gasoline and other high-octane number The proportion of clean gasoline is small. Since the research octane number of aromatics such as toluene and xylene is greater than 100, the research octane number of gasoline rich in toluene and xylene aromatics can reach 137, and it is im...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G3/00C10G29/22B01J29/40
CPCB01J29/405B01J2229/186C10G3/44C10G3/54C10G29/205C10G29/22C10G2400/02C10G2400/30Y02P30/20
Inventor 任杰金辉
Owner ZHEJIANG UNIV OF TECH
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