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Catalyst for synthesizing methyl formate by selective oxidation of methanol and preparation method thereof

A catalyst and oxide technology, applied in the field of composite catalyst and its preparation, can solve the problems of low catalyst efficiency, low activity, low methanol selectivity, etc., and achieve the effects of long service life, high activity and simple synthesis process

Active Publication Date: 2011-03-16
PEKING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Catalysts for the selective oxidation of methanol mainly include V 2 o 5 / TiO 2 、MoO 3 / SnO 2 and ReO x / CeO 2 , but the efficiency of these catalysts is low, showing that the conversion rate of the reactant methanol or the selectivity of the target product methyl formate is not high, and the highest yield of methyl formate is only about 60%, and because the activity of the reaction is very low, The reaction generally needs to be carried out at a higher temperature

Method used

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  • Catalyst for synthesizing methyl formate by selective oxidation of methanol and preparation method thereof
  • Catalyst for synthesizing methyl formate by selective oxidation of methanol and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Embodiment 1, impregnation method prepares TiO 2 Supported Pt catalyst (Pt / TiO 2 )

[0027] Precursor Pt(NH 3 ) 4 (NO 3 ) 2 2mL of aqueous solution, wherein the mass percentage of Pt is 5%, containing 0.100g Pt;

[0028] Add 4 g of TiO to the above solution 2 Carrier (manufacturer: Alfa Aesar); stirred at 20°C for 1h, dried at 120°C, put into a muffle furnace and roasted at 400°C for 2h to obtain 2 Pt catalyst (Pt / TiO 2 ).

[0029] Characterized by plasma emission spectrometry (ICP), the actual loading mass percentage of Pt is 5.2%, which is consistent with the theoretical loading (5.0%).

Embodiment 2

[0030] Embodiment 2, impregnation method prepares WO 3 Modified γ-Al 2 o 3 Supported (monolayer dispersed) Pt catalyst (Pt / WO 3 -Al 2 o 3 )

[0031] (1) Preparation of WO 3 Modified γ-Al 2 o 3 carrier

[0032] Formulation Modifier WO 3 The precursor of [NH 4 ] 6 W 7 o 24 ·6H 2 Aqueous solution of O: weigh 1.268g [NH 4 ] 6 W 7 o 24 ·6H 2 O dissolved in 2ml of water, WO 3The molar concentration is 2.33mol / L, and the amount of total substance is 4.66×10 -3 mol.

[0033] Add 4 g of γ-Al to the above solution 2 o 3 Carrier (manufacturer: CONDEA); stirred at 40°C for 2h, dried at 120°C, put into a muffle furnace and roasted at 400°C for 4h to obtain WO 3 Modified γ-Al 2 o 3 Carrier (WO 3 -Al 2 o 3 ).

[0034] (2) Preparation of WO 3 Modified γ-Al 2 o 3 Supported Pt catalyst

[0035] Precursor Pt(NH 3 ) 4 (NO 3 ) 2 2mL of aqueous solution, wherein the mass percentage of Pt is 1%, containing 0.020g of Pt;

[0036] Add 4 g of the above WO to the a...

Embodiment 3

[0038] Embodiment 3, coprecipitation method prepares Al 2 o 3 Supported Pt catalyst (Pt / Al 2 o 3 )

[0039] Precursor of active ingredient Pt and oxide Al 2 o 3 The preparation of the mixed solution of the soluble metal salt: 30gAl(NO 3 ) 3 9H 2 O was dissolved in 150mL water, and then mixed with 10mL H 2 PtCl 6 ·6H 2 O aqueous solution is mixed; wherein the mass percentage of Pt is 0.38%, containing 0.038g Pt; the mass concentration of Al is 1.20%, converted into Al 2 o 3 The mass of 4.08g.

[0040] Preparation of NaOH aqueous solution: 40g NaOH was dissolved in 100mL water to obtain solution B, whose mass percentage was 28.6%.

[0041] At the same time, the above-mentioned mixed solution and NaOH aqueous solution were added dropwise into 100mL water in a co-current dropwise manner, during which the rate of addition of the two was adjusted to control the pH value to 8-9, then stirred and aged at 70°C for 4h, suction filtered and dissolved. Wash until Cl-free in ...

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Abstract

The invention discloses a catalyst for synthesizing methyl formate by selective oxidation of methanol and a preparation method thereof. The catalyst is composed of active ingredients and a carrier, wherein the active ingredients account for 0.1%-10% of the catalyst by mass percent and comprise Au, Pd or Pt; and the carrier is an oxide A or B, the oxide A is any one of Al2O3, TiO2, ZrO2 and CeO2, and the oxide B is the oxide obtained by modifying the oxide A with a modifier WO3, MoO3, ZnO, MgO or NiO. The invention provides a preparation method of the catalyst. The preparation process is simple, the contents of the used noble metals are less, the used noble metals have high activity, and the method is suitable for the current common industrial production conditions and has good applicationprospects. The catalyst can be used for producing methyl formate by efficiently transforming methanol.

Description

technical field [0001] The invention relates to a composite catalyst in the chemical field and a preparation method thereof, in particular to a catalyst for efficiently selectively oxidizing methanol to synthesize methyl formate and a preparation method thereof. Background technique [0002] As an important platform molecule in C1 chemistry, methyl formate has broad application prospects. Starting from methyl formate, important chemicals such as formic acid, acetic acid and dimethyl carbonate can be synthesized, and methyl formate can be used as a gasoline additive to replace methyl tert-butyl ether. At present, methyl formate is mainly obtained by dehydrogenation of methanol on CuO catalyst and carbonylation under liquid caustic conditions. The former has problems such as high reaction temperature, high operating cost, and the conversion is limited by thermodynamic equilibrium; the latter is greatly restricted due to environmental pollution. In contrast, methanol selectiv...

Claims

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Application Information

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IPC IPC(8): B01J23/42B01J23/652B01J23/66C07C69/06C07C67/40
Inventor 刘海超黄华
Owner PEKING UNIV
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