A nickel-chromium-manganese mesoporous composite oxide catalyst for hydrogen production by autothermal reforming of acetic acid

A composite oxide, nickel-chromium-manganese mesoporous technology, applied in the direction of metal/metal oxide/metal hydroxide catalyst, physical/chemical process catalyst, catalyst activation/preparation, etc., can solve the problem of catalyst structure instability, active group Solve problems such as easy oxidation and reduced catalyst activity, and achieve the effects of inhibiting acetic acid dehydration and ketonization reactions, improving activity and stability, and improving oxidation resistance

CN109225250BActive Publication Date: 2019-10-25CHENGDU UNIVERSITY OF TECHNOLOGY
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Publication Date
2019-10-25

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Abstract

The invention relates to a nickel, chromium and manganese mesoporous compound oxide catalyst for acetic acid self-heating hydrogen production by reforming. In order to solve the problems that existingcatalysts are oxidized, sintered and deposited in carbon in the process of acetic acid self-heating by reforming, the invention provides a novel catalyst which is stable in structure, sintering-resistant, carbon deposition-resistant and oxidiation-resistant. The catalyst is as shown in a formula by mole: (NiO)a(MnO)b(CrO1.5)c, wherein a is 0.12-0.18, b is 0.7-0.33 and c is 0.14-0.5. The catalystis prepared by means of a coprecipitation method, and the Ni-Cr-Mn-O mesoporous compound oxide catalyst which is stable and contains spinels such as NiMn2O4, NiCr2O4 and Mn3O4 is obtained after sintering. The reducing property of active components and the stability of the catalyst are improved. In the process of acetic acid self-heating by reforming, generation of byproducts such as methane and acetone is inhibited, and the hydrogen yield is improved.
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Description

technical field

[0001] The invention relates to a nickel-chromium-manganese mesoporous composite oxide catalyst for hydrogen production by autothermal reforming of acetic acid and a preparation method thereof, belonging to the field of hydrogen production by autothermal reforming of acetic acid. Background technique

[0002] As a secondary energy source, hydrogen energy has the advantages of good thermal conductivity, wide source of raw materials, high calorific value, good combustion performance, non-toxicity, multiple utilization forms, and high utilization rate. It is a clean energy with great development potential. At present, about 95% of hydrogen is produced from fossil fuels such as natural gas and coal. However, using fossil raw materials to produce hydrogen will bring CO 2 One of the solutions is to use clean renewable resources to produce hydrogen in large quantities and at low cost.

[0003] Biomass is a renewable resource that converts solar energy into chemica...

Examples

Embodiment 1

[0034] Weigh 4.781g of Cr(NO 3 ) 3 9H 2 O, 10.151g of Mn(NO 3 ) 2 (50wt%) and 2.372g of Ni(NO 3 ) 2 .6H 2 O, add 94.3ml of deionized water to make solution #1. Weigh 9.348g of NaOH and 1.548g of Na 2 CO 3 , adding 250ml of deionized water to prepare solution #2, the follow-up steps are the same as those in reference example 1, and a solution with a typical structure as attached is obtained. figure 1 shown containing NiMn 2 o 4 and NiCr 2 o 4 and Mn 3 o 4 and other spinel structures, such as attached figure 2 The molar composition of the mesoporous structure shown is (NiO) 0.17 (MnO) 0.58 (CrO 1.5 ) 0.25 The composite oxide CDUT-NM3C catalyst; The weight composition of this catalyst is: nickel oxide (NiO) content is 15.2%, manganese oxide (MnO) is 61.7%, chromium oxide (CrO 1.5 ) is 23.1%.

[0035] The catalyst CDUT-NM3C is tested by the autothermal reforming activity of acetic acid. When the reaction conditions are normal pressure, space velocity 30000ml / ...

Embodiment 2

[0037] Weigh 6.567g of Cr (NO 3 ) 3 9H 2 O, 8.810g of Mn(NO 3 ) 2 (50wt%) and 2.386g of Ni(NO 3 ) 2 .6H 2 O, add 96.3ml of deionized water to make solution #1. Weigh 9.452g of NaOH and 1.565g of NaOH 2 CO 3 , adding 250ml of deionized water to prepare solution #2, the follow-up steps are the same as those in reference example 1, and a solution with a typical structure as attached is obtained. figure 1 The crystal structure shown contains NiMn 2 o 4 and NiCr 2 o 4 and Mn 3 o 4 such as spinel, such as attached figure 2 (NiO) with mesoporous structure shown 0.17 (MnO) 0.50 (CrO 1.5 ) 0.33 Composite oxide CDUT-NM2C catalyst. The weight composition of this catalyst is: nickel oxide (NiO) is 15.3%, manganese oxide (MnO) is 53.5%, chromium oxide (CrO 1.5 ) is 31.2%.

[0038] The catalyst CDUT-NM3C was tested for activity of acetic acid autothermal reforming, the reaction conditions were normal pressure, space velocity 30000ml / (g-catalyst h), reaction temperatur...