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CN-122006716-A - Coke oven gas dry reforming catalyst and preparation method thereof

CN122006716ACN 122006716 ACN122006716 ACN 122006716ACN-122006716-A

Abstract

The invention discloses a coke oven gas dry reforming catalyst and a preparation method thereof, and belongs to the field of ferrous metallurgy. The preparation method comprises the steps of roasting aluminum-magnesium hydrotalcite, adding the roasted aluminum-magnesium hydrotalcite into an acid solution for pickling treatment, filtering, washing to be neutral, drying, carrying out first grinding and drying again to obtain a catalyst carrier, adding the catalyst carrier into a nickel salt water solution, carrying out impregnation under the stirring condition, obtaining a suspension after the impregnation is finished, standing, heating and drying the suspension to obtain a semi-finished product, and roasting, carrying out second grinding, tabletting, screening and activating the semi-finished product to obtain the coke oven gas dry reforming catalyst. The catalyst provided by the invention can show higher activity and stability in a dry reforming reaction of coke oven gas.

Inventors

  • WEI BAOYONG
  • DU XIONGWEI
  • SU HAILAN

Assignees

  • 北京京诚泽宇能源环保工程技术有限公司
  • 中冶京诚工程技术有限公司

Dates

Publication Date
20260512
Application Date
20251229

Claims (10)

  1. 1. The preparation method of the coke oven gas dry reforming catalyst comprises the following steps: (1) Roasting aluminum-magnesium hydrotalcite, adding the roasted aluminum-magnesium hydrotalcite into an acid solution for pickling treatment, and filtering, washing to be neutral, drying, carrying out first grinding and drying again to obtain a catalyst carrier; (2) Adding the catalyst carrier into nickel salt water solution, soaking under stirring, and obtaining a suspension after soaking; (3) And standing the suspension, heating the suspension under stirring to evaporate the liquid in the suspension to obtain a semi-dry material, drying the semi-dry material to obtain a semi-finished product, and roasting, second grinding, tabletting, screening and activating the semi-finished product to obtain the coke oven gas dry reforming catalyst.
  2. 2. The method for preparing a coke oven gas dry reforming catalyst according to claim 1, wherein in the step (1), the roasting temperature of the aluminum-magnesium hydrotalcite is 700-1000 ℃ and the roasting time is 4-6 hours.
  3. 3. The method for preparing a dry reforming catalyst of coke oven gas according to claim 1, wherein in step (1), the acid solution comprises one or more of hydrochloric acid solution, nitric acid solution and sulfuric acid solution; And/or, in the step (1), the concentration of the acid solution is 0.1mol/L to 1.0mol/L; and/or in the step (1), the concentration of the acid solution is 0.5 mol/L-0.8 mol/L.
  4. 4. The method for preparing a coke oven gas dry reforming catalyst according to claim 1, wherein in the step (1), the temperature of the acid washing treatment is 30-60 ℃, the acid washing treatment is performed under stirring, and the time of the acid washing treatment is 2-8 hours; and/or in the step (1), the temperature of the acid washing treatment is 40-50 ℃, the acid washing treatment is carried out under the stirring condition, and the time of the acid washing treatment is 3-5 hours; and/or, in the step (1), the first grinding is grinding to 80-200 meshes.
  5. 5. The method for preparing a dry reforming catalyst of coke oven gas according to claim 1, wherein in step (2), the nickel salt in the aqueous nickel salt solution comprises one or more of nickel nitrate, nickel sulfate and nickel acetate; And/or in the step (2), the molar concentration of nickel salt in the nickel salt aqueous solution is 0.05mol/L to 0.2mol/L; And/or, in the step (2), the ratio of the catalyst carrier to the nickel salt aqueous solution is such that the mass fraction of Ni in the coke oven gas dry reforming catalyst is 1.0wt.% to 15.0wt.%; and/or in the step (2), the ratio of the catalyst carrier to the nickel salt water solution is such that the mass fraction of Ni in the coke oven gas dry reforming catalyst is 5.0wt.% to 10.0wt.%.
  6. 6. The method for preparing a coke oven gas dry reforming catalyst according to claim 1, wherein in the step (2), the impregnation temperature is 40 ℃ to 60 ℃ and the time is 2h to 12h; And/or in the step (2), the soaking temperature is 40-45 ℃ and the soaking time is 4-12 hours.
  7. 7. The method for preparing a coke oven gas dry reforming catalyst according to claim 1, wherein in the step (3), the standing temperature is normal temperature and the time is 6-12 hours; And/or, in the step (3), the heating temperature is 60-80 ℃; and/or in the step (3), the roasting temperature of the semi-finished product is 700-1000 ℃ and the time is 4-8 hours; And/or, in step (3), the second grinding is grinding to 200 mesh or more; and/or in the step (3), screening is carried out to 40-60 meshes.
  8. 8. The method for preparing a coke oven gas dry reforming catalyst according to claim 1, wherein in the step (3), the activating condition comprises activating in a mixed gas flow of hydrogen and nitrogen at 700-1000 ℃ for 4-8 hours.
  9. 9. A coke oven gas dry reforming catalyst prepared by the method for preparing a coke oven gas dry reforming catalyst according to any one of claims 1-8, the coke oven gas dry reforming catalyst comprising an active component comprising Ni and a catalyst support.
  10. 10. The coke oven gas dry reforming catalyst of claim 9, wherein the mass fraction of Ni in the coke oven gas dry reforming catalyst is 1.0wt.% to 15.0wt.%; And/or the mass fraction of Ni in the coke oven gas dry reforming catalyst is 5.0wt.% to 10.0wt.%.

Description

Coke oven gas dry reforming catalyst and preparation method thereof Technical Field The invention relates to a dry reforming catalyst for coke oven gas and a preparation method thereof, belonging to the field of ferrous metallurgy. Background Hydrogen is an ideal clean energy source, and the combustion product is only H 2 O, which has no pollution to the environment and is called as 'the final energy source in 21 st century'. A large amount of coke oven gas exists in the steel coking combined enterprises, the direct combustion and utilization mode is single, and the environment pollution is easy to cause. Coke oven gas mainly comprises combustible components such as hydrogen, methane, carbon monoxide, carbon dioxide, unsaturated hydrocarbon and the like. The coke oven gas is scientifically and reasonably utilized, so that the potential of coal resources can be fully utilized, and important raw material resources can be provided for the steel industry and the chemical industry. At present, the industry is mature, the coke oven gas is recycled through Pressure Swing Adsorption (PSA) hydrogen production, and the hydrogen with the purity of 99.999% can be obtained through the process. In addition to hydrogen, coke oven gas contains more energy-containing components such as methane. If the energy-containing components in the coke oven gas are converted into hydrogen through dry reforming, the hydrogen quantity can be further improved, the carbon dioxide emission can be reduced, the energy conversion function of the iron and steel enterprises can be fully exerted, and conditions are created for the ecological transformation of the iron and steel enterprises and the integration into the circular economy society. In the reaction of preparing the synthesis gas by methane dry reforming, the catalyst which takes noble metals such as Pt, pd, rh, ru and the like as active components generally has good catalytic performance, but the cost of the catalyst is too high due to the high price of the noble metals, so that the large-scale industrialized application is hindered. Researchers have therefore focused on dry methane reforming catalysts on non-noble metal catalysts, such as Co, ni, cu, fe, etc., where Ni-based catalysts have relatively high catalytic activity, stability, and are favored by many researchers. However, compared with noble metals, ni-based catalysts have serious carbon deposition and rapid deactivation. The preparation method of the catalyst of Ni-Mo@ZrO 2 -MgO is adopted by the Jiang Hongtao subject group of Zhejiang industrial university by a template-dipping method, and the reaction effect of the catalyst on methane dry reforming is explored in a fixed bed reactor. When the reaction temperature is 650 ℃, the conversion rate of methane and carbon dioxide can reach about 90%, and the catalyst shows better catalytic activity. However, the conversion of the raw material gas was slightly lowered with the increase of the reaction time. The research group of Huadong university Tian Chengcheng uses nickel salt, magnesium acetate tetrahydrate, calcium acetate monohydrate and ethylenediamine tetraacetic acid as raw materials, and the catalyst Ni-NC is prepared by mixing and calcining the ball-milled product and melamine at high temperature. The dry reforming performance of methane of the catalyst obtained above is examined in a fixed bed reactor with continuous flow at 750 ℃, and the result shows that the activity of the Ni-NC catalyst is still higher after the reaction is continuously operated for 1000 hours, the conversion rate of carbon dioxide reaches 77.9%, and the conversion rate of methane reaches 92.1%. Dry reforming hydrogen production from coke oven gas differs from dry reforming hydrogen production from methane mainly because coke oven gas contains a large amount of H 2 in addition to CH 4. It was found that the activity of the reforming catalyst gradually decreases or is completely deactivated as the catalytic reaction proceeds under a high temperature, strong reducing atmosphere. This is mainly due to the low heat of vaporization of nickel metal relative to some noble metal catalysts, which can occur as a result of sintering in a continuous high temperature reaction with concomitant loss of metal, which can lead to a decrease in the specific surface area and content of active components, and thus a decrease in catalyst activity. Therefore, the improvement of the stability of the catalyst in a reaction system for dry reforming hydrogen production of coke oven gas becomes extremely critical. CN117282442a discloses a catalyst for preparing synthetic gas by reforming coke oven gas and a preparation method thereof. The catalyst takes MgAl 2O4 or ZnCr 2O4 as a carrier, takes Mg or Ca element as an auxiliary agent, and takes metal Ni and metal Ru or Ir as active centers. The metal Ru or Ir is presented in a partial oxidation state RuO x or IrO x in the reaction process by carrying out high-temperature CO 2