CN110844944A - 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 - Google Patents
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 Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000001301 oxygen Substances 0.000 title claims abstract description 118
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 117
- 239000007789 gas Substances 0.000 title claims abstract description 111
- 229910020647 Co-O Inorganic materials 0.000 title claims abstract description 50
- 229910020704 Co—O Inorganic materials 0.000 title claims abstract description 50
- 239000001257 hydrogen Substances 0.000 title claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000126 substance Substances 0.000 title claims abstract description 26
- 238000002407 reforming Methods 0.000 title claims abstract description 22
- 229910003168 MnCo2O4 Inorganic materials 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 17
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 17
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 229910018663 Mn O Inorganic materials 0.000 claims description 3
- 229910003176 Mn-O Inorganic materials 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 16
- 239000001569 carbon dioxide Substances 0.000 abstract description 6
- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- 238000000629 steam reforming Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 8
- 208000012839 conversion disease Diseases 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000004088 simulation Methods 0.000 description 6
- 239000003034 coal gas Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/061—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of metal oxides with water
- C01B3/063—Cyclic methods
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
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 nitrate2‑MnCo2O4Oxygen carrier, CeO2‑MnCo2O4The 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 CeO2‑MnCo2O4In 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 CeO2‑MnCo2O4And H2(ii) a Purifying the tail gas to obtain pure H2. The invention can realize the high-efficiency utilization of blast furnace gas combustible resources.
Description
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.
Example 1: the preparation method of the Ce-Mn-Co-O oxygen carrier comprises the following specific steps:
(1) uniformly mixing manganese nitrate and cobalt nitrate to obtain a mixed salt, wherein the molar ratio of the manganese nitrate to the cobalt nitrate is 1: 2;
(2) adding the mixed salt obtained in the step (1) into deionized water, wherein the solid-to-liquid ratio cm of the mixed salt to the deionized water3The volume ratio mL is 1:1, ultrasonic treatment is carried out for 2h under the condition of stirring at room temperature, solid-liquid separation and solid vacuum drying are carried out, and then the obtained product is roasted for 6h at the temperature of 300 ℃ 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 3h at room temperature under stirring, carrying out solid-liquid separation, drying the solid, and roasting for 5h at 400 ℃ to obtain CeO2-MnCo2O4An oxygen carrier; wherein 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%;
the application of the Ce-Mn-Co-O oxygen carrier in the chemical looping reforming hydrogen production of blast furnace gas:
(1) heating blast furnace gas to 800 ℃;
(2) introducing the heated blast furnace gas into oxygen carrier CeO2-MnCo2O4In the method, gas conversion is carried out at the temperature of 800 ℃ to obtain oxygen loss carrier and CO2(ii) a Wherein blast furnace gas and oxygen carrier CeO2-MnCo2O4The gas-solid ratio L: g of (1: 5) and oxygen carrier CeO2-MnCo2O4The granularity is 30-50 meshes;
(3) then introducing the water vapor into an oxygen loss carrier, and carrying out water vapor reforming at the temperature of 800 ℃ to obtain an oxygen carrier CeO2-MnCo2O4And H2(ii) a Wherein steam is oxidized in the steam oxidation stageThe flow rate is 1 g/min;
(4) purifying the tail gas to obtain pure H2；
The gas shift reaction conditions and the reaction results are shown in table 1 and table 2;
TABLE 1 blast furnace gas flow, temperature and composition simulation at the blast furnace gas conversion reaction stage
The hydrogen preparation mainly occurs in the stage of hydrogen preparation by steam reforming, and the analysis shows that the generated H2The purity reaches more than 97 percent, and the recovery degree of the oxygen carrier is 97 percent; thus, the recycling of the oxygen carrier can be realized by alternately carrying out the blast furnace gas conversion and the steam reforming operation.
Example 2: the preparation method of the Ce-Mn-Co-O oxygen carrier comprises the following specific steps:
(1) uniformly mixing manganese nitrate and cobalt nitrate to obtain a mixed salt, wherein the molar ratio of the manganese nitrate to the cobalt nitrate is 1: 2;
(2) adding the mixed salt obtained in the step (1) into deionized water, wherein the solid-to-liquid ratio cm of the mixed salt to the deionized water3The volume ratio mL is 1:1, ultrasonic treatment is carried out for 3h under the conditions of room temperature and stirring, solid-liquid separation and solid vacuum drying are carried out, and then the obtained product is roasted for 3h at the temperature of 300 ℃ to obtain a Mn-Mn-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 3h at room temperature under stirring, carrying out solid-liquid separation, drying the solid, and roasting at 900 ℃ for 6h to obtain CeO2-MnCo2O4An oxygen carrier; wherein 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%;
the application of the Ce-Mn-Co-O oxygen carrier in the chemical looping reforming hydrogen production of blast furnace gas:
(1) heating blast furnace gas to 870 ℃;
(2) will addIntroducing hot blast furnace gas into oxygen carrier CeO2-MnCo2O4In the process, gas conversion is carried out at the temperature of 870 ℃ to obtain oxygen loss carrier and CO2And H2O; wherein blast furnace gas and oxygen carrier CeO2-MnCo2O4The gas-solid ratio L: g of (1: 3), oxygen carrier CeO2-MnCo2O4The granularity is 30-50 meshes;
(3) then introducing the water vapor into an oxygen loss carrier, and carrying out water vapor reforming at the temperature of 800 ℃ to obtain an oxygen carrier CeO2-MnCo2O4And H2(ii) a Wherein the steam flow in the steam oxidation stage is 1 g/min;
(4) purifying the tail gas to obtain pure H2；
The gas shift reaction conditions and the reaction results are shown in table 3 and table 4;
TABLE 3 blast furnace gas flow, temperature and composition simulation at the blast furnace gas conversion reaction stage
The hydrogen preparation mainly occurs in the stage of hydrogen preparation by steam reforming, and the analysis shows that the generated H2The purity reaches more than 95 percent, and the recovery degree of the oxygen carrier is 95 percent; thus, the recycling of the oxygen carrier can be realized by alternately carrying out the blast furnace gas conversion and the steam reforming operation.
Example 3: the preparation method of the Ce-Mn-Co-O oxygen carrier comprises the following specific steps:
(1) uniformly mixing manganese nitrate and cobalt nitrate to obtain a mixed salt, wherein the molar ratio of the manganese nitrate to the cobalt nitrate is 1: 2;
(2) adding the mixed salt obtained in the step (1) into deionized water, wherein the solid-to-liquid ratio cm of the mixed salt to the deionized water3The volume ratio mL is 1:1, ultrasonic treatment is carried out for 2h under the conditions of room temperature and stirring, solid-liquid separation and solid vacuum drying are carried out, and then the obtained product is roasted for 2h at the temperature of 500 ℃ to obtain a Mn-Co-O oxygen-carrying precursor;
(3) adding the Mn-Co-O oxygen-carrying precursor obtained in the step (2) and cerium nitrate into deionized water, and placing the mixture in a chamberUltrasonic treating for 2h under the condition of warm and stirring, separating solid from liquid, drying the solid, and roasting for 12h at the temperature of 900 ℃ to obtain CeO2-MnCo2O4An oxygen carrier; wherein 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 10%;
the application of the Ce-Mn-Co-O oxygen carrier in the chemical looping reforming hydrogen production of blast furnace gas:
(1) heating blast furnace gas to 900 ℃;
(2) introducing the heated blast furnace gas into oxygen carrier CeO2-MnCo2O4In the middle, the coal gas conversion is carried out at the temperature of 900 ℃ to obtain oxygen loss carrier and CO2(ii) a Wherein blast furnace gas and oxygen carrier CeO2-MnCo2O4The gas-solid ratio L: g of (1: 2) and oxygen carrier CeO2-MnCo2O4The granularity is 30-50 meshes;
(3) then introducing the water vapor into an oxygen loss carrier, and carrying out water vapor reforming at the temperature of 800 ℃ to obtain an oxygen carrier CeO2-MnCo2O4And H2(ii) a Wherein the steam flow in the steam oxidation stage is 1 g/min;
(4) purifying the tail gas to obtain pure H2；
The gas shift reaction conditions and the reaction results are shown in table 5 and table 6;
TABLE 5 blast furnace gas flow, temperature and composition simulation at the blast furnace gas conversion reaction stage
The hydrogen preparation mainly occurs in the stage of hydrogen preparation by steam reforming, and the analysis shows that the generated H2The purity reaches 92 percent, and the recovery degree of the oxygen carrier is 98 percent; thus, the recycling of the oxygen carrier can be realized by alternately carrying out the blast furnace gas conversion and the steam reforming operation.
Example 4: the preparation method of the Ce-Mn-Co-O oxygen carrier comprises the following specific steps:
(1) uniformly mixing manganese nitrate and cobalt nitrate to obtain a mixed salt, wherein the molar ratio of the manganese nitrate to the cobalt nitrate is 1: 2;
(2) adding the mixed salt obtained in the step (1) into deionized water, wherein the solid-to-liquid ratio cm of the mixed salt to the deionized water3The volume ratio mL is 1:1, ultrasonic treatment is carried out for 4 hours at room temperature under the stirring condition, solid-liquid separation and solid vacuum drying are carried out, and then the obtained product is roasted for 6 hours at the temperature of 500 ℃ 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 5h at room temperature under stirring, carrying out solid-liquid separation, drying the solid, and roasting at 860 ℃ for 12h to obtain CeO2-MnCo2O4An oxygen carrier; wherein 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%;
the application of the Ce-Mn-Co-O oxygen carrier in the chemical looping reforming hydrogen production of blast furnace gas:
(1) heating blast furnace gas to 860 ℃;
(2) introducing the heated blast furnace gas into oxygen carrier CeO2-MnCo2O4In the middle, the coal gas conversion is carried out at the temperature of 860 ℃ to obtain oxygen loss carrier and CO2(ii) a Wherein blast furnace gas and oxygen carrier CeO2-MnCo2O4The gas-solid ratio L: g of (1) and oxygen carrier CeO2-MnCo2O4The granularity is 30-50 meshes;
(3) then introducing the water vapor into an oxygen loss carrier, and carrying out water vapor reforming at the temperature of 860 ℃ to obtain an oxygen carrier CeO2-MnCo2O4And H2(ii) a Wherein the steam flow in the steam oxidation stage is 1 g/min;
(4) purifying the tail gas to obtain pure H2；
The gas shift reaction conditions and the reaction results are shown in table 7 and table 8;
TABLE 7 blast furnace gas flow, temperature and composition simulation at the blast furnace gas conversion reaction stage
The hydrogen preparation mainly occurs in the stage of hydrogen preparation by steam reforming, and the analysis shows that the generated H2The purity reaches more than 93 percent, and the recovery degree of the oxygen carrier is 93 percent; thus, the recycling of the oxygen carrier can be realized by alternately carrying out the blast furnace gas conversion and the steam reforming operation.
Example 5: the preparation method of the Ce-Mn-Co-O oxygen carrier comprises the following specific steps:
(1) uniformly mixing manganese nitrate and cobalt nitrate to obtain a mixed salt, wherein the molar ratio of the manganese nitrate to the cobalt nitrate is 1: 2;
(2) adding the mixed salt obtained in the step (1) into deionized water, wherein the solid-to-liquid ratio cm of the mixed salt to the deionized water3The volume ratio mL is 1:1, ultrasonic treatment is carried out for 2h under the conditions of room temperature and stirring, solid-liquid separation and solid vacuum drying are carried out, and then the obtained product is roasted for 2h at the temperature of 300 ℃ 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 2h at room temperature under stirring, carrying out solid-liquid separation, drying the solid, and roasting at 800 ℃ for 10h to obtain CeO2-MnCo2O4An oxygen carrier; wherein 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 15%;
the application of the Ce-Mn-Co-O oxygen carrier in the chemical looping reforming hydrogen production of blast furnace gas:
(1) heating blast furnace gas to 700 ℃;
(2) introducing the heated blast furnace gas into oxygen carrier CeO2-MnCo2O4In the method, gas conversion is carried out at the temperature of 700 ℃ to obtain oxygen loss carrier and CO2(ii) a Wherein blast furnace gas and oxygen carrier CeO2-MnCo2O4The gas-solid ratio L: g of (1: 4) and oxygen carrier CeO2-MnCo2O4The granularity is 30-50 meshes；
(3) Then introducing the water vapor into an oxygen loss carrier, and carrying out water vapor reforming at the temperature of 700 ℃ to obtain an oxygen carrier CeO2-MnCo2O4And H2(ii) a Wherein the steam flow in the steam oxidation stage is 1 g/min;
(4) purifying the tail gas to obtain pure H2；
The gas shift reaction conditions and the reaction results are shown in table 9 and table 10;
TABLE 9 blast furnace gas flow, temperature and composition simulation at the blast furnace gas conversion reaction stage
The hydrogen preparation mainly occurs in the stage of hydrogen preparation by steam reforming, and the analysis shows that the generated H2The purity reaches more than 96 percent, and the recovery degree of the oxygen carrier is 91 percent; thus, the recycling of the oxygen carrier can be realized by alternately carrying out the blast furnace gas conversion and the steam reforming operation.
Example 6: the preparation method of the Ce-Mn-Co-O oxygen carrier comprises the following specific steps:
(1) uniformly mixing manganese nitrate and cobalt nitrate to obtain a mixed salt, wherein the molar ratio of the manganese nitrate to the cobalt nitrate is 1: 2;
(2) adding the mixed salt obtained in the step (1) into deionized water, wherein the solid-to-liquid ratio cm of the mixed salt to the deionized water3The volume ratio mL is 1:1, ultrasonic treatment is carried out for 3 hours at room temperature under the stirring condition, solid-liquid separation and solid vacuum drying are carried out, and then the obtained product is roasted for 6 hours at the temperature of 400 ℃ 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 3h at room temperature under stirring, carrying out solid-liquid separation, drying the solid, and roasting at 800 ℃ for 12h to obtain CeO2-MnCo2O4An oxygen carrier; wherein 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 carrier2Has a mass fraction of5%；
The application of the Ce-Mn-Co-O oxygen carrier in the chemical looping reforming hydrogen production of blast furnace gas:
(1) heating blast furnace gas to 750 ℃;
(2) introducing the heated blast furnace gas into oxygen carrier CeO2-MnCo2O4In the middle, the coal gas conversion is carried out at the temperature of 750 ℃ to obtain oxygen loss carrier and CO2(ii) a Wherein blast furnace gas and oxygen carrier CeO2-MnCo2O4The gas-solid ratio L: g of (1: 5) and oxygen carrier CeO2-MnCo2O4The granularity is 30-50 meshes;
(3) then introducing the steam into an oxygen loss carrier, and carrying out steam reforming at the temperature of 750 ℃ to obtain an oxygen carrier CeO2-MnCo2O4And H2(ii) a Wherein the steam flow in the steam oxidation stage is 1 g/min;
(4) purifying the tail gas to obtain pure H2；
The gas shift reaction conditions and the reaction results are shown in table 9 and table 10;
TABLE 9 blast furnace gas flow, temperature and composition simulation at the blast furnace gas conversion reaction stage
The hydrogen preparation mainly occurs in the stage of hydrogen preparation by steam reforming, and the analysis shows that the generated H2The purity reaches more than 98 percent, and the recovery degree of the oxygen carrier is 92 percent; thus, the recycling of the oxygen carrier can be realized by alternately carrying out the blast furnace gas conversion and the steam reforming operation.
The present invention is not limited to the above-described embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (6)
- 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).
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101066534A (en) * | 2007-04-13 | 2007-11-07 | 中国科学院山西煤炭化学研究所 | Composite CeO2-CoOx oxide carrier and its prepn process |
| CN102092683A (en) * | 2011-01-06 | 2011-06-15 | 昆明理工大学 | Oxygen carrier for preparing synthesis gas by catalytic partial oxidation of methane |
| CN102862952A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Application and preparation of composite oxide oxygen carrier in chemical looping circulation hydrogen production |
| CN104941620A (en) * | 2015-05-28 | 2015-09-30 | 昆明理工大学 | Method for preparing oxygen carrier by using vanadium-titanium magnetite, and applications of oxygen carrier |
| CN105170158A (en) * | 2015-07-22 | 2015-12-23 | 重庆工商大学 | CoMn composite oxide catalyst for eliminating benzene-serial volatile organic compounds in air and preparation method for therefor |
| WO2017111614A1 (en) * | 2015-12-22 | 2017-06-29 | Institutt For Energiteknikk | Sustainable oxygen carriers for chemical looping combustion with oxygen uncoupling and methods for their manufacture |
| CN107804824A (en) * | 2017-11-09 | 2018-03-16 | 东南大学 | A kind of compound calcium iron oxygen carrier and its hydrogen production of chemical chain cooperate with CO2Capture method |
| CN108002449A (en) * | 2017-12-07 | 2018-05-08 | 中国石油大学胜利学院 | A kind of MnCo2O4The preparation method of spinelle type composite oxides |
-
2019
- 2019-11-29 CN CN201911199104.9A patent/CN110844944A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101066534A (en) * | 2007-04-13 | 2007-11-07 | 中国科学院山西煤炭化学研究所 | Composite CeO2-CoOx oxide carrier and its prepn process |
| CN102092683A (en) * | 2011-01-06 | 2011-06-15 | 昆明理工大学 | Oxygen carrier for preparing synthesis gas by catalytic partial oxidation of methane |
| CN102862952A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Application and preparation of composite oxide oxygen carrier in chemical looping circulation hydrogen production |
| CN104941620A (en) * | 2015-05-28 | 2015-09-30 | 昆明理工大学 | Method for preparing oxygen carrier by using vanadium-titanium magnetite, and applications of oxygen carrier |
| CN105170158A (en) * | 2015-07-22 | 2015-12-23 | 重庆工商大学 | CoMn composite oxide catalyst for eliminating benzene-serial volatile organic compounds in air and preparation method for therefor |
| WO2017111614A1 (en) * | 2015-12-22 | 2017-06-29 | Institutt For Energiteknikk | Sustainable oxygen carriers for chemical looping combustion with oxygen uncoupling and methods for their manufacture |
| CN107804824A (en) * | 2017-11-09 | 2018-03-16 | 东南大学 | A kind of compound calcium iron oxygen carrier and its hydrogen production of chemical chain cooperate with CO2Capture method |
| CN108002449A (en) * | 2017-12-07 | 2018-05-08 | 中国石油大学胜利学院 | A kind of MnCo2O4The preparation method of spinelle type composite oxides |
Non-Patent Citations (4)
| Title |
|---|
| BYEONG SUB KWAK ET AL.: ""Reduction and oxidation performance evaluation of manganese-based iron, cobalt, nickel, and copper bimetallic oxide oxygen carriers for chemical-looping combustion"", 《APPLIED THERMAL ENGINEERING》 * |
| YANE ZHENG ET AL.: ""Designed oxygen carriers from macroporous LaFeO3 supported CeO2 for chemical-looping reforming of methane"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| 岳雷: "《钢铁企业燃气工程设计手册》", 31 March 2015, 冶金工业出版社 * |
| 杨春丽 等: "《让智慧成长-基于STEAM理念的创客课程》", 30 April 2018, 宁波出版社 * |
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