Catalyst for preparing H2 by direct cracking of methanol, and preparation method and application of catalyst

A catalyst and methanol technology, which is applied in the field of hydrogen production from methanol, can solve the problems affecting the economic cost and competitiveness of hydrogen production, side reactions, etc., and achieve the effects of high stability, high selectivity and high activity

Pending Publication Date: 2020-05-19
SICHUAN TECHAIRS
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] Third, the hydrogen-containing methane cracking synthesis gas produced by methanol anaerobic catalytic direct cracking reaction also involves H 2 Purified H with relatively small adsorption separation coefficients with CO 2 It will also directly affect the economic cost and competitiveness of hydrogen production
These methods will generate more side reactions, and the by-product CO will be further transformed into CO 2

Method used

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  • Catalyst for preparing H2 by direct cracking of methanol, and preparation method and application of catalyst
  • Catalyst for preparing H2 by direct cracking of methanol, and preparation method and application of catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Such as figure 1 As shown, a direct cleavage of methanol to produce H 2 Catalyst and its application, copper cobalt bimetallic catalyst preparation precursor is copper nitrate (Cu(NO 3 ) 2 ) and cobalt nitrate (Co(NO 3 ) 2 ) mixed solution, the co-catalyst precursor is lanthanum nitrate series (La(NO 3 ) 3 ) and modified enhancer as potassium nitrate (KNO 3 ) mixed solution, the carrier is pretreated multi-layered carbon nanotubes (CNTs), the matrix is ​​magnesium oxide (MgO), and the active component copper containing 20-25% (w / w, below similar), 10% to 15% cobalt, 3% to 5% lanthanum containing catalyst promoter, 3% to 5% potassium promoter, and the rest is a solid catalyst containing CNTs and MgO mixed carrier, and methanol anaerobic Catalytic direct cracking to produce hydrogen (H 2 ) and methanol anaerobic catalytic thermal cracking reaction of by-product carbon monoxide (CO):

[0033] (1) The raw material is industrial methanol (liquid), after gasification...

Embodiment 2

[0038] The pretreatment of the multilayer carbon nanotube CNTs described in Example 1 is to add about 1 to 2 g of commercially available CNTs carriers with a specification of 10 nm into a total volume of about 230 to 260 mL of nitric acid with a mass concentration of 30% and about 70% In the mixed solution of nitric acid with mass concentration, heat to 110-120°C, stir evenly, and azeotropically reflux at 110-120°C for 6-8 hours, cool to ambient temperature, vacuum filter, and wash with deionized water for two After three times to neutrality, the resulting filter cake is dried at 120°C for 1-2 hours, ground into 10-20nm powder, mixed with 1-1.5g of MgO powder, roasted and cooled under nitrogen flow at 630-660°C A mixed carrier of CNTs and MgO is formed to support active components Cu, Co, cocatalyst La, and promoter K.

Embodiment 3

[0040] On the basis of Embodiment 1 and 2, the preparation of MgO in the mixed carrier is that about 5~7g oxalic acid (H 2 C 2 o 4 ) and 7~9g magnesium acetate (Mg(CH 3 COO) 3 ) were dissolved in 200-240mL and 50-70mL deionized water respectively, and the magnesium acetate solution was poured into the oxalic acid solution and stirred for about 3-5 hours to produce a precipitate, which was taken out and washed continuously with deionized water for 2-3 hours. Once again, dry at 70-80°C for 1-2 hours, then grind it into powder, and bake it at 650-700°C and nitrogen flow for 3-4 hours. / h, at 120-140°C / 2h in the late stage of heating up, take it out after being purged with nitrogen and cooled to ambient temperature, and mix with the treated CNTs to form a catalyst carrier.

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Abstract

The invention discloses a catalyst for preparing H2 through direct cracking of methanol and application of the catalyst. According to the composition of the catalyst, a precursor for preparing the copper-cobalt bimetallic catalyst is a mixed solution of copper nitrate and cobalt nitrate; ae cocatalyst precursor is a mixed solution of lanthanide nitrate and potassium nitrate; a carrier is a mixtureof pretreated multilayer carbon nanotubes and magnesium oxide. The catalyst comprises 20-30% (w / w) of copper serving as an active component, 10-20% (w / w) of cobalt serving as another active component, 1-10% (w / w) of lanthanum serving as a co-catalytic component and 1-5% (w / w)of potassium serving as an accelerant, with the balance being the mixed carrier composed of the carbon nanotubes and magnesium oxide; and the catalyst is prepared through an alcohol heating-roasting method. According to the invention, methanol is directly cracked to prepare hydrogen, the conversion rate of methanol exceeds 95%, and the selectivity of H2 and CO exceeds 95%.

Description

technical field [0001] The invention belongs to methanol as raw material to prepare hydrogen (H 2 ) technical field, specifically, is a kind of direct cracking of methanol to prepare H 2 catalysts and their applications. Background technique [0002] The existing methanol hydrogen production technology is relatively common and mature, mainly using methanol and water vapor as raw materials, at 250-280°C and under certain pressure conditions, and under the action of a copper-containing catalyst, the reaction of methanol cracking conversion is carried out to obtain hydrogen containing 70% hydrogen 2 with 30% CO 2 The reformed gas, and through the conventional pressure swing adsorption (PSA) technology to obtain the final H 2 Products have been widely used at home and abroad. However, the hydrogen production process of methanol water vapor conversion requires a certain external heat source to provide heat for its reaction, and a large amount of greenhouse gas CO is produced ...

Claims

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Application Information

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IPC IPC(8): B01J23/83B01J23/889B01J37/18C01B3/22C01B3/50
CPCB01J23/83B01J23/8892B01J37/18C01B3/22C01B3/50C01B2203/0277C01B2203/1223C01B2203/1082C01B2203/1076C01B2203/1052C01B2203/1094C01B2203/042
Inventor 钟雨明汪兰海陈运唐金财蔡跃明蒋强
Owner SICHUAN TECHAIRS
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