Method for preparing styrene by coupling reaction of methanol dehydrogenation without oxygen and toluene side chain alkylation

A coupling reaction and alkylation technology, applied in the field of catalysis, can solve problems such as low selectivity and low conversion rate, and achieve the effects of increasing yield, solving low conversion rate and improving methanol utilization

Active Publication Date: 2019-06-07
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] According to one aspect of the present invention, a method for preparing styrene by the coupling reaction of anaerobic dehydrogenation of methanol and side chain alkylation of toluene is provided, which can effectively improve the conversi

Method used

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  • Method for preparing styrene by coupling reaction of methanol dehydrogenation without oxygen and toluene side chain alkylation
  • Method for preparing styrene by coupling reaction of methanol dehydrogenation without oxygen and toluene side chain alkylation
  • Method for preparing styrene by coupling reaction of methanol dehydrogenation without oxygen and toluene side chain alkylation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0071] Embodiment 1: the preparation of basic molecular sieve

[0072] The molecular sieves used in the examples were purchased commercially.

[0073] Preparation of X-type and Y-type molecular sieves modified by alkali metal ions:

[0074] Take 20g of NaX or NaY molecular sieves, and use 0.2-0.6mol / L potassium nitrate, rubidium nitrate, cesium nitrate and other precursor solutions to ion-exchange the molecular sieves respectively. When the solid-liquid ratio is 10:1, exchange at 80°C for 4 hours, and suction filter , washed and dried, the solid obtained was roasted in a muffle furnace at 550°C for 6 hours, and then the process was repeated twice to obtain alkali metal type X and Y molecular sieves, and the samples were respectively numbered H-1 # ~H-6 # .

[0075] The obtained sample number, precursor solution type and concentration, and ion exchange degree are shown in Table 1. Adopt XRF elemental analyzer (Axios 2.4KW type of PANAbalytical company) to carry out elementa...

Embodiment 2

[0079] Embodiment 2: the preparation of dehydrogenation catalyst

[0080] Preparation of the alkali metal refractory salt: the alkali metal refractory salt is at least one selected from sodium carbonate, sodium borate, sodium molybdate and sodium metaaluminate. First, the alkali metal refractory salt is ground, then dried at 110°C and calcined at 550°C for 6h. Obtain alkali metal refractory salt, sample number is DE-1 # ~DE-6 # .

[0081] The obtained sample number, alkali metal refractory salt type and mixing ratio are shown in Table 2. Wherein the mixing ratio is calculated according to the mass of alkali metal refractory salt.

[0082] Sample serial number

Alkali metal refractory salt types

The mixing ratio

DE-1 #

Sodium carbonate

--

DE-2 #

sodium borate

--

DE-3 #

Sodium molybdate

--

DE-4 #

Sodium Carbonate + Sodium Borate

1:2

DE-5 #

Sodium Carbonate + Sodium Molybdate

1:1 ...

Embodiment 3

[0097] Embodiment 3: the preparation of bifunctional catalyst

[0098] The basic molecular sieve H-1 prepared by embodiment 1 # ~H-6 # At least one of and the dehydrogenation catalyst DE-1 obtained in embodiment 2 # ~DE-24 # At least one of them is mixed, shaped, crushed, and sieved to 20-40 meshes, and the obtained bifunctional catalyst is numbered CAT-1 # ~CAT-40 # . of which CAT-1 # ~CAT-20 # The basic molecular sieve and the dehydrogenation catalyst were ball milled on a ball mill for 10h (CAT-1 # ~CAT-5 # ), 15h (CAT-6 # ~CAT-15 # ), 20h (CAT-16 # ~CAT-20 # ), after mixing evenly, then molding; CAT-21 # ~CAT-40 #After the basic molecular sieve and the dehydrogenation catalyst are mixed evenly, they are ball milled on a ball mill for 10 hours (CAT-21 # ~CAT-25 # ), 15h (CAT-26 # ~CAT-35 # ), 20h (CAT-36 # ~CAT-40 # ) for molding.

[0099] Table 5 shows the relationship between the number of the obtained bifunctional catalyst and the type and mass ratio...

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Abstract

The invention discloses a method for preparing styrene by a coupling reaction of methanol dehydrogenation without oxygen and toluene side chain alkylation. In the method, a raw material gas containingtoluene and methanol is introduced into a reactor and contacted with a bifunctional catalyst, firstly methanol is subjected to a dehydrogenation reaction without oxygen to produce formaldehyde, and then the obtained formaldehyde and toluene is subjected to a side chain alkylation reaction to produce styrene. By the mutual coupling of the two reactions in the method, the toluene conversion, the methanol utilization and the styrene yield can be improved.

Description

technical field [0001] The invention relates to a method for preparing styrene through the coupling reaction of methanol anaerobic dehydrogenation and toluene side chain alkylation, which belongs to the field of catalysis. Background technique [0002] As an important monomer of polymers, styrene is mainly used in the production of polystyrene (PS), acrylonitrile-butadiene resin (ABS), expanded polystyrene (EPS), styrene-butadiene rubber ( SBR) and other chemical products. The traditional styrene production technology is the ethylbenzene dehydrogenation method, which mainly obtains the target product styrene through Friedel-Craft reaction and catalytic dehydrogenation reaction. This method has the disadvantages of long process route, large equipment investment, many side reactions, high energy consumption, A series of problems such as over-reliance on oil resources. Therefore, the new styrene production process has received widespread attention. [0003] In 1967, Japanese...

Claims

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Application Information

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IPC IPC(8): C07C15/46C07C2/86B01J29/08B01J29/16B01J29/14B01J29/12B01J29/80B01J37/30B01J37/08B01J37/03B01J37/02
Inventor 许磊韩乔李沛东徐力袁扬扬
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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