阅读说明：本技术 Ce-Mn-Co-O氧载体的制备方法及在高炉煤气化学链重整制氢中的应用 (Preparation method of Ce-Mn-Co-O oxygen carrier and application of Ce-Mn-Co-O oxygen carrier in chemical looping reforming hydrogen production of blast furnace gas ) 是由 李孔斋 卢春强 徐瑞东 王�华 魏永刚 赵滟楠 于 2019-11-29 设计创作，主要内容包括：本发明涉及Ce-Mn-Co-O氧载体的制备方法及在高炉气化学链重整制氢中的应用,属于能源化工技术领域。本发明利用硝酸钴、硝酸锰和硝酸铈制备出CeO<Sub>2</Sub>-MnCo<Sub>2</Sub>O<Sub>4</Sub>氧载体,CeO<Sub>2</Sub>-MnCo<Sub>2</Sub>O<Sub>4</Sub>氧载体用于高炉煤气化学链重整制氢,将高炉煤气加热至温度为800~900℃,将加热的高炉煤气通入载氧体CeO<Sub>2</Sub>-MnCo<Sub>2</Sub>O<Sub>4</Sub>中,在温度800~900℃下进行高炉煤气转化得到失氧载体和二氧化碳；再将水蒸气通入失氧载体中进行水蒸气重整得到载氧体CeO<Sub>2</Sub>-MnCo<Sub>2</Sub>O<Sub>4</Sub>和H<Sub>2</Sub>；尾气净化处理即得纯净H<Sub>2</Sub>。本发明可实现高炉煤气可燃资源的高效利用。(The invention relates to a preparation method of a Ce-Mn-Co-O oxygen carrier and application thereof in hydrogen production by chemical looping reforming of blast furnace gas, belonging to the technical field of energy chemical industry. The invention prepares CeO by utilizing cobalt nitrate, manganese nitrate and cerium nitrate 2 ‑MnCo 2 O 4 Oxygen carrier, CeO 2 ‑MnCo 2 O 4 The oxygen carrier is used for the chemical looping reforming of blast furnace gas to prepare hydrogen, the blast furnace gas is heated to 800-900 ℃, and the heated blast furnace gas is introduced into oxygen carrier CeO 2 ‑MnCo 2 O 4 In the method, blast furnace gas is converted at the temperature of 800-900 ℃ to obtain an oxygen loss carrier and carbon dioxide; then introducing the water vapor into an oxygen loss carrier to carry out waterSteam reforming to obtain oxygen carrier CeO 2 ‑MnCo 2 O 4 And H 2 (ii) a Purifying the tail gas to obtain pure H 2 . The invention can realize the high-efficiency utilization of blast furnace gas combustible resources.)

The preparation method of the Ce-Mn-Co-O oxygen carrier is characterized by comprising the following specific steps:

(1) uniformly mixing manganese nitrate and cobalt nitrate to obtain mixed salt;

(2) adding the mixed salt obtained in the step (1) into deionized water, carrying out ultrasonic treatment for 2-5 h at room temperature under stirring, carrying out solid-liquid separation, carrying out vacuum drying on the solid, and roasting at 300-500 ℃ for 2-6 h to obtain a Mn-Co-O oxygen-carrying precursor;

(3) adding the Mn-Co-O oxygen-carrying precursor in the step (2) and cerium nitrate into deionized water, carrying out ultrasonic treatment for 2-5 h at room temperature under stirring conditions, carrying out solid-liquid separation, drying the solid, and roasting at 800-900 ℃ for 6-12 h to obtain CeO₂-MnCo₂O₄An oxygen carrier.

2. The method for preparing the Ce-Mn-Co-O oxygen carrier according to claim 1, characterized in that: the molar ratio of the manganese nitrate to the cobalt nitrate in the step (1) is 1: 2.

3. The method for preparing the Ce-Mn-Co-O oxygen carrier according to claim 1, characterized in that: the solid-to-liquid ratio cm of the mixed salt and the deionized water in the step (2)³mL is 1: 1.

4. The method for preparing the Ce-Mn-Co-O oxygen carrier according to claim 1, characterized in that: and (3) the solid-to-liquid ratio cm of the Mn-Co-O oxygen-loaded precursor to the deionized water³mL is 1: 1; CeO (CeO)₂-MnCo₂O₄CeO in oxygen carrier₂The mass fraction of (A) is 5-15%.

5. The application of the Ce-Mn-Co-O oxygen carrier prepared by the method for preparing the Ce-Mn-Co-O oxygen carrier according to any one of claims 1 to 4 in the chemical looping reforming hydrogen production of blast furnace gas is characterized in that:

(1) heating blast furnace gas to 700-900 ℃;

(2) introducing the heated blast furnace gas into oxygen carrier CeO₂-MnCo₂O₄In the method, gas conversion is carried out at the temperature of 700-900 ℃ to obtain oxygen loss carrier and CO₂；

(3) Then introducing water vapor into an oxygen loss carrier, and carrying out water treatment at the temperature of 700-900 DEG CSteam reforming to obtain oxygen carrier CeO₂-MnCo₂O₄And H₂；

(4) Purifying the tail gas to obtain pure H₂。

6. The application of the Ce-Mn-Mn-O oxygen carrier in the chemical looping reforming hydrogen production of blast furnace gas according to claim 5, wherein the Ce-Mn-Mn-O oxygen carrier is characterized in that: blast furnace gas and oxygen carrier CeO₂-MnCo₂O₄The gas-solid ratio L g is 1 (2-5).

Technical Field

The invention relates to a preparation method of a Ce-Mn-Co-O oxygen carrier and application thereof in chemical looping reforming hydrogen production of blast furnace gas, belonging to the technical field of energy chemical industry.

Background

Blast furnace gas is a byproduct generated in the iron-making process, and the main components of the blast furnace gas are CO and CO₂、N₂And a small amount of H₂、CH₄And the like. The composition of blast furnace gas and the quality of the fuel and pig iron used by the blast furnace are related to the smelting process. The molten iron is discharged at the bottom of the furnace at regular time, and simultaneously, a large amount of residual CO which is not available for reaction exists in furnace gas of the blast furnace. In practice, the treatment of blast furnace gas is difficult due to various factors, resulting in a large energy loss and air pollution. CO in blast furnace gas₂、N₂The mixed gas is not involved in combustion reaction, and absorbs a large amount of heat during combustion, so that the ignition point of blast furnace gas is higher, and the temperature of the mixed gas is far higher than the ignition point, so that stable combustion can be ensured. The gas discharged by the blast furnace is large, so that the temperature rising rate of the mixed gas is slow, the temperature is not high, and the combustion stability is not good.

The hydrogen production method mainly comprises the steps of hydrogen production by water electrolysis, hydrogen production by coal, hydrogen production by biomass and hydrogen production by steam conversion reaction of synthesis gas, and most of the existing hydrogen production methods have the conditions of harsh reaction conditions, high energy consumption, difficult realization of industrial production and the like, and are difficult to economically meet the rapidly-increased hydrogen energy market demand. The preparation of hydrogen needs to consume a large amount of energy, but the hydrogen production efficiency is very low at present, and a large-scale cheap hydrogen production method needs to be found urgently in order to adapt to the exhaustion of global warming energy.

Disclosure of Invention

The invention provides a preparation method of Ce-Mn-Co-O oxygen carrier and application thereof in the chemical looping reforming hydrogen production of blast furnace gas aiming at the resource utilization problem of the blast furnace gas, and the invention utilizes the chemical looping combustion method of the blast furnace gas from the angle of chemical looping combustion to comprehensively utilize the residual available combustible gas and the waste heat in the blast furnace gas, collects carbon dioxide and simultaneously generates clean energy hydrogen, thereby effectively overcoming the traditional chemical looping steam reforming method, and utilizing the gas to carry out the chemical looping hydrogen production, reducing energy consumption and rapidly reactingQuickly can realize CO₂The method has the characteristics of trapping, hydrogen production and the like, most of heat required by the reaction is supplied by the mixed gas, the reaction process can be continuous, the comprehensive utilization efficiency of energy is higher, and the efficient clean utilization of energy resources can be realized.

A preparation method of a Ce-Mn-Co-O oxygen carrier comprises the following specific steps:

(1) uniformly mixing manganese nitrate and cobalt nitrate to obtain mixed salt;

(2) adding the mixed salt obtained in the step (1) into deionized water, carrying out ultrasonic treatment for 2-5 h at room temperature under stirring, carrying out solid-liquid separation, carrying out vacuum drying on the solid, and roasting at 300-500 ℃ for 2-6 h to obtain a Mn-Co-O oxygen-carrying precursor;

(3) adding the Mn-Co-O oxygen-carrying precursor in the step (2) and cerium nitrate into deionized water, carrying out ultrasonic treatment for 2-5 h at room temperature under stirring conditions, carrying out solid-liquid separation, drying the solid, and roasting at 800-900 ℃ for 6-12 h to obtain CeO₂-MnCo₂O₄An oxygen carrier.

The molar ratio of the manganese nitrate to the cobalt nitrate in the step (1) is 1: 2.

The solid-to-liquid ratio cm of the mixed salt and the deionized water in the step (2)³mL is 1: 1.

The solid-to-liquid ratio cm of the Mn-Co-O oxygen-loaded precursor to the deionized water in the step (3)³mL is 1: 1; CeO (CeO)₂-MnCo₂O₄CeO in oxygen carrier₂The mass fraction of (A) is 5-15%.

The application of the Ce-Mn-Co-O oxygen carrier in the chemical looping reforming hydrogen production of blast furnace gas comprises the following steps:

(1) heating blast furnace gas to 700-900 ℃;

(2) introducing the heated blast furnace gas into oxygen carrier CeO₂-MnCo₂O₄In the method, gas conversion is carried out at the temperature of 700-900 ℃ to obtain oxygen loss carrier and CO₂；

(3) Then introducing the steam into an oxygen loss carrier, and carrying out steam reforming at the temperature of 700-900 ℃ to obtain an oxygen carrier CeO₂-MnCo₂O₄And H₂；

(4) Purifying the tail gas to obtain pure H₂。

The blast furnace gas is the tail gas after the reaction of the high-temperature reaction equipment, the temperature of the tail gas is within the range of 700-900 ℃ under the condition of normal operation of the blast furnace, and the heat of the blast furnace gas serving as a main heat source can not completely meet the energy required by the reaction of gas chemical-looping hydrogen production, so that the auxiliary heating device can be used for increasing the reaction temperature;

further, the blast furnace gas and oxygen carrier CeO₂-MnCo₂O₄The gas-solid ratio L g is 1 (2-5).

The blast furnace gas contains carbon monoxide and carbon dioxide, and the CeO is carried by oxygen₂-MnCo₂O₄Selectively utilizes the residual CO energy to completely convert the carbon monoxide into the carbon dioxide.

The gas-liquid separation treatment of the reacted gas can achieve the separation of water vapor and hydrogen through the condensation pipe, and H is finally obtained₂The steel can be used as fuel or chemical raw materials by collection and compression, and can also be supplied to a blast furnace to be used as a reducing component for steel smelting.

The invention has the beneficial effects that:

(1) the invention utilizes the chemical looping combustion method of the blast furnace gas from the angle of chemical looping combustion to comprehensively utilize the residual available combustible gas and the waste heat in the blast furnace gas, collects the carbon dioxide and simultaneously generates the clean energy hydrogen, effectively overcomes the defects of the traditional chemical looping steam reforming method, has the advantages of reducing energy consumption and rapid reaction when the coal gas is used for chemical looping hydrogen production, and can realize CO₂The method has the characteristics of trapping, hydrogen production and the like, most of heat required by the reaction is supplied by the mixed gas, the reaction process can be continuous, the comprehensive utilization efficiency of energy is higher, and the efficient clean utilization of energy resources can be realized;

(2) the invention utilizes combustible components and waste heat in blast furnace gas as resources, reduces environmental pollution, realizes capture of carbon dioxide and prepares clean energy hydrogen which is friendly to environment.

Detailed Description

The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.