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Method for preparing ZSM-11 molecular sieve catalyst for dimethyl ether and benzene alkylation reaction

A technology of ZSM-11 and benzene alkylation, which is applied in the direction of molecular sieve catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problems affecting the yield and selectivity of alkane aromatization, and achieve the reduction of benzene content , high yield, and the effect of increasing the octane number

Active Publication Date: 2018-04-27
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in the process of alkane aromatization, hydrogen seriously affects the yield and selectivity of alkane aromatization, so the gas phase products of methanol and dimethyl ether aromatization are directly put into the aromatization reaction of low-carbon hydrocarbons for aromatization The process of the reaction is not the optimal process

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] 2.24g Al in a stainless steel synthesis kettle 2 (SO 4 ) 3 18H 2 O was dissolved in 20ml of water, and 39.07g of silica sol, 1.72g of NaOH, 1.20g of TBABr, 3.40g of CTAB (99.0wt%, the same below) were sequentially added and mixed evenly under the condition of stirring, and the remaining water was added according to the metering ratio, Get a molar ratio of 12Na 2 O:1.8Al 2 o 3 :90SiO2 2 :2TBABr:5CTAB:3600H 2 A mixed sample of O, then the mixed sample was synthesized at a crystallization temperature of 160°C and a rotation speed of 70rpm for 16h, then lowered to room temperature, washed to neutrality, dried, and roasted at 550°C for 6h, followed by 0.8mol / L The ammonium nitrate solution was exchanged three times at 85°C (1 hour / time), washed three times with water (1 hour / time), dried at 110°C for 10 hours, and calcined at 510°C for 4 hours to prepare the catalyst Cat-B, which was detected by XRF. Na 2 O is less than 0.05 wt%.

Embodiment 2

[0034] 1.88g Al in a stainless steel synthesis kettle 2 (SO 4 ) 3 18H 2 O and 0.05g of alumina were dissolved in 20ml of water, and 23.45g of silica sol, 4.37g of silica gel (91.5wt%), 1.75g ​​of NaOH, 1.20g of TBABr, and 1.70g of CTAB were added in turn and mixed evenly under stirring conditions, and the remaining of water is added to obtain a molar ratio of 12Na 2 O:1.8Al 2 o 3 :90SiO2 2 :2TBABr:0.25CTAB:3600H 2 A mixed sample of O, then the mixed sample was synthesized at a crystallization temperature of 150°C and a rotation speed of 100rpm for 24h, then lowered to room temperature, washed to neutrality, dried, and roasted at 450°C for 8h, followed by 0.5mol / L The ammonium nitrate solution was exchanged at 90°C for three times (1 hour / time), washed with water three times (1 hour / time), dried at 130°C for 5h, and calcined at 580°C for 2h to prepare the catalyst Cat-C, which was detected by XRF. Na 2 O is less than 0.05 wt%.

Embodiment 3

[0036] In a stainless steel synthesis kettle, 1.17g Al 2 (SO 4 ) 3 18H 2 O and 0.03g of alumina were dissolved in 20ml of water, and 23.45g of silica sol, 4.71g of white carbon black (85.0wt%, the same below), 1.99g of NaOH, 1.35g of TBABr, and 7.66g of CTAB were sequentially added and mixed under stirring conditions Evenly, add the remaining water according to the metering ratio to obtain a molar ratio of 12Na 2 O:1.0Al 2 o 3 :80SiO2 2 :2TBABr:10CTAB:3600H 2 A mixed sample of O, then the mixed sample was synthesized at a crystallization temperature of 180°C and a rotation speed of 80rpm for 12h, then lowered to room temperature, washed to neutrality, dried, and roasted at 550°C for 8h, followed by 0.9mol / L The ammonium nitrate solution was exchanged three times at 85°C (1 hour / time), washed three times with water (1 hour / time), dried at 95°C for 11 hours, and calcined at 550°C for 6 hours to prepare the catalyst Cat-D, which was detected by XRF. Na 2 O is less than 0...

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Abstract

The invention provides a method for preparing a ZSM-11 molecular sieve catalyst for the dimethyl ether and benzene alkylation reaction. The method comprises uniformly mixing water, an aluminum source,a silicon source, NaOH, TBABr and CTAB in a synthesis kettle according to a molar ratio of Na2O: Al2O3: SiO2: TBABr: CTAB: H2O of 12: 1-1.8: 80-120: 2: 0.25-10: 3600, carrying out synthesis at a crystallization temperature of 150 to 180 DEG C at a rotation number of 60-100rpm for 12-24h, cooling the product to the room temperature, carrying out washing until pH of 7, carrying out drying and calcination, carrying out exchange through an ammonium nitrate solution with the concentration of 0.5 to 1.0mol / L at 70-90 DEG C, carrying out drying and then carrying out calcination to obtain the H-typemolecular sieve catalyst. Through combined action of TBABr and CTAB, the ZSM-11 molecular sieve catalyst is prepared. Compared with the conventional ZSM-11 molecular sieve catalyst prepared only fromTBABr, the ZSM-11 molecular sieve catalyst can further improve the dimethyl ether and benzene conversion rate.

Description

technical field [0001] The invention belongs to the field of molecular sieve catalysts, in particular to a method for preparing a ZSM-11 molecular sieve catalyst used in the alkylation reaction of dimethyl ether and benzene. Background technique [0002] Aromatics are an important basic raw material of petrochemical industry. Among the total of about 8 million known organic compounds, aromatics account for about 30%. The use of natural gas (mainly composed of methane) or petroleum refinery dry gas (mainly containing methane, ethane, ethylene) and petroleum liquefied gas or methanol (dimethyl ether) for anaerobic aromatization to prepare aromatics is currently a popular topic in academia and industry. popular research topic. [0003] In the patent CN1880288A of Shanxi Coal Chemical Institute, methanol and dimethyl ether are used as raw materials, and modified ZSM-5 is used as a catalyst to convert methanol and dimethyl ether into aromatic hydrocarbon-based products. After co...

Claims

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Application Information

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IPC IPC(8): C01B39/36B01J29/40C07C2/86C07C15/02
Inventor 辛文杰刘惠徐龙伢刘盛林
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI