CN114735651A - Oxygen carrier for chemical ring hydrogen production and preparation method and application thereof - Google Patents
Oxygen carrier for chemical ring hydrogen production and preparation method and application thereof Download PDFInfo
- Publication number
- CN114735651A CN114735651A CN202110018986.5A CN202110018986A CN114735651A CN 114735651 A CN114735651 A CN 114735651A CN 202110018986 A CN202110018986 A CN 202110018986A CN 114735651 A CN114735651 A CN 114735651A
- Authority
- CN
- China
- Prior art keywords
- source
- oxygen carrier
- ligand
- reaction
- hydrogen production
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000001301 oxygen Substances 0.000 title claims abstract description 88
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 88
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000001257 hydrogen Substances 0.000 title claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 239000000126 substance Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 18
- 239000013110 organic ligand Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 3
- 150000001298 alcohols Chemical class 0.000 claims abstract description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 3
- 150000001408 amides Chemical class 0.000 claims abstract description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims abstract description 3
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 3
- 150000002576 ketones Chemical class 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims description 45
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 42
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 42
- 239000011572 manganese Substances 0.000 claims description 41
- -1 inorganic acid salt Chemical class 0.000 claims description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 description 38
- 235000019441 ethanol Nutrition 0.000 description 29
- 238000010926 purge Methods 0.000 description 18
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 16
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 13
- 239000002131 composite material Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 9
- 239000012621 metal-organic framework Substances 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical group Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
-
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/344—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using non-catalytic solid particles
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an oxygen carrier for chemical looping hydrogen production, which comprises the following steps: (1) mixing an organic ligand and a solvent, wherein the organic ligand comprises one or more of a carboxyl ligand, a ligand containing hetero nitrogen, a carboxylic acid nitrogen-containing mixed ligand, a phosphoric acid ligand, a sulfonic acid ligand and a porphyrin ligand; the solvent comprises one or more of alcohols, ketones, amides, aromatic hydrocarbons, chlorinated hydrocarbons and low-carbon hydrocarbons, and preferably one or more of ethanol, acetone and N, N-dimethylformamide; (2) and (2) adding a Fe source, a Ti source and a Mn source into the material obtained in the step (1) for reaction, and drying and roasting the reacted material to obtain the oxygen carrier for chemical ring hydrogen production. The oxygen carrier is simple to synthesize, and has high porosity and dispersity and excellent hydrogen production performance.
Description
Technical Field
The invention relates to an oxygen carrier for chemical ring hydrogen production, a preparation method and application thereof, in particular to an oxygen carrier for high-activity stable chemical ring hydrogen production, a preparation method and application thereof.
Background
With the rapid development of the global hydrogen fuel cell automobile industry, hydrogen sources and hydrogen production technologies are receiving much attention. Currently, global industrial hydrogen is mainly from natural gas reforming process, but the process requires high temperature and high pressure, and complex hydrogen purification and CO are required2The separation process has high cost and energy consumption.
The chemical ring hydrogen production technology is a novel and environment-friendly green hydrogen production technology, and is a hydrogen production technology which utilizes oxygen atoms in an oxygen carrier to replace oxygen to oxidize fuel and produce hydrogen at the same time. Compared with the traditional natural gas hydrogen production technology, the advantages of the chemical ring hydrogen production mainly include (1) relatively simple device, no need of water-vapor conversion, and no need of hydrogen and CO2The purification and separation device has less investment and low energy consumption; (2) only one solid catalyst is needed, while the traditional steam reforming process needs 3 shift catalysts including steam reforming, high-temperature steam shift agent and low-temperature steam; (3) in the fuel reactor, the raw material is not in direct contact with oxygen, almost no NOx is generated, and the emission of pollutant gas is low.
In the chemical ring hydrogen production process, the oxygen carrier is used as an oxygen and heat carrier, and the physicochemical property of the oxygen carrier directly influences the raw material conversion rate, the hydrogen production efficiency and the energy transfer efficiency of the reaction, so that the oxygen carrier has an important position. The oxygen carrier is mainly divided into a single-active-component oxygen carrier and a multi-active-component oxygen carrier. The single-component oxygen carrier has poor thermal stability, low oxygen carrying rate and slow reaction rate in the reaction process.
The main method adopted at present is to compound single-component oxygen carriers, and the performance of the oxygen carrier is improved by utilizing the synergistic effect of different metals. CuFe is obtained by combustion synthesis method through Zhang Hei et al (fuel science and technology, 2019, 25 (3): 220-2O4The oxygen carrier shows higher hydrogen yield in the coal chemical looping gasification reaction at 750-950 ℃. However, the method has complex synthetic process and low oxygen carrier porosity. CN104694206A Synthesis of Fe-containing Material by sol-gel method2O3，Al2O3，NiO，K2CO3The composite oxygen carrier has better gasification efficiency in the process of preparing hydrogen by biomass chemical looping. Patent CN110055120A adopts mechanical mixing method to mix Fe2O3The composite oxygen carrier prepared by mixing the CuO and the inert oxygen carrier has the advantages of simple operation and low cost, but the sample has low porosity and poor uniformity and is easy to sinter in the reaction process.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a composite oxygen carrier for chemical looping hydrogen production and a preparation method and application thereof. The oxygen carrier is simple to synthesize, and has high porosity and dispersity and excellent hydrogen production performance.
A method for preparing an oxygen carrier for chemical looping hydrogen production, the method comprising the steps of:
(1) mixing an organic ligand and a solvent, wherein the organic ligand comprises one or more of a carboxyl ligand, a ligand containing hetero nitrogen, a carboxylic acid nitrogen-containing mixed ligand, a phosphoric acid ligand, a sulfonic acid ligand and a porphyrin ligand; the solvent comprises one or more of alcohols, ketones, amides, aromatic hydrocarbons, chlorinated hydrocarbons and low-carbon hydrocarbons, and preferably one or more of ethanol, acetone and N, N-dimethylformamide;
(2) and (2) adding a Fe source, a Ti source and a Mn source into the material obtained in the step (1) for reaction, and drying and roasting the reacted material to obtain the oxygen carrier for chemical looping hydrogen production.
In the method, the organic ligands in the step (1) are terephthalic acid and trimesic acid, and the molar ratio of the terephthalic acid to the trimesic acid is (1-9): 1, preferably (2-7): 1, more preferably (3-6): 1.
in the method, the solvent in the step (1) is N, N-dimethylformamide and ethanol, and the molar ratio of the N, N-dimethylformamide to the ethanol is (1-100): 1: preferably (5-80): 1, and more preferably (10-60): 1.
in the above method, the Fe source in step (2) includes at least one of an oxide, a hydroxide, an inorganic acid salt, an organic acid salt, and a chloride of Fe, and also includes hydrates of these compounds, in which water-soluble inorganic acid salts and chlorides of Fe are preferred, and nitrates and chlorides of Fe are more preferred.
In the above method, the Ti source in step (2) includes at least one of an oxide, a hydroxide, an inorganic acid salt, an organic acid salt, and an organic metal compound of Ti, and also includes a hydrate of these compounds, among which a chloride and a titanium alkoxide of Ti are preferable, and a titanium alkoxide is more preferable.
In the above method, the Mn source in step (2) includes at least one of an oxide, a hydroxide, an inorganic acid salt, and an organic acid salt of Mn, and also includes a hydrate of these compounds, in which a water-soluble inorganic acid salt of Mn is preferable, and a nitrate of Mn is more preferable.
In the method, the mass ratio of the Fe source, the Ti source and the Mn source in the step (2) calculated by Fe, Ti and Mn element oxides is (1-9) to (1-5) to 1, preferably (3-7) to (2-4) to 1.
In the method, the Fe source, the Ti source and the Mn source in the step (2) are added into the material in the step (1) sequentially or simultaneously for reaction.
In the above process, the reaction in the step (2) is preferably carried out under stirring.
In the above method, the reaction conditions of the Fe source, the Ti source, and the Mn source during the reaction are generally: total metals: total organic ligand: the molar ratio of the total solvent is 1: 0.2-10: 100-.
In the above method, the oxygen carrier may be formed into a suitable particle form, such as a strip, a sheet, a column, a sphere, a zigzag, etc., according to the techniques known in the art, if necessary. For example, the chemical ring hydrogen-producing oxygen carrier is mixed with a binder (preferably pseudo-boehmite) and kneaded to form the required product.
In the above method, the drying may be performed according to a method known in the art, and examples thereof include a spray drying method, a vacuum drying method, a hot oven drying method, and the like. The drying conditions include, for example, a drying temperature of 60 to 150 ℃, preferably 100 ℃ to 120 ℃, and a drying time of 4 to 48 hours, preferably 6 to 36 hours, and more preferably 8 to 24 hours.
In the method, the dried material is completely converted into the chemical ring hydrogen production oxygen carrier through roasting. Examples of the conditions for the calcination include a calcination temperature of 400-1300 ℃, preferably 600-1200 ℃, more preferably 700-1000 ℃, and a calcination time of 3-10 hours, preferably 4-8 hours. The calcination may be carried out in an oxygen-containing atmosphere (such as air), as required.
The chemical ring hydrogen production oxygen carrier prepared by the method has the weight content of ferric oxide of 30-90%, preferably 40-80% and further preferably 50-75% based on the weight of the oxygen carrier; the weight content of titanium oxide is 40 to 80%, preferably 30 to 60%, and more preferably 20 to 40%; the content of manganese oxide is 1 to 20% by weight, preferably 3 to 15% by weight, and more preferably 5 to 10% by weight.
The oxygen carrier is applied by adopting a fixed bed reactor, taking methane, CO or synthetic gas as raw materials, controlling the reaction temperature to be 500-1200 ℃, the reaction pressure to be 0.1-5 Mpa and the airspeed to be 50-1000 h-1(ii) a Reacting with an oxygen carrier in a reactor to generate a reduction reaction; switching N when feedstock conversion drops significantly2Purging is carried out; introducing water vapor to perform steam reaction with the reduced oxygen carrier, and condensing the product gas to obtain H2(ii) a Switching N2Purging is carried out; and introducing air to fully oxidize the oxygen carrier to complete a cycle reaction.
In the application of the oxygen carrier, the flow rate of the raw material gas is 100-500 ml/min, and the reaction time is 0.2-2 h.
In the application of the oxygen carrier, the distilled water has the water inflow of 0.1-1.0 ml/min, is vaporized into steam through the vaporizing chamber, and has the reaction time of 0.2-2 h.
Compared with the traditional oxygen carrier, the composite oxygen carrier provided by the invention has the advantages of higher porosity, better dispersion and higher reaction efficiency.
Detailed Description
A preparation method of an oxygen carrier for chemical ring hydrogen production comprises the following steps: adding a certain amount of terephthalic acid and trimesic acid into the mixed solution of N, N-dimethylformamide and ethanol for dissolving,then FeCl is added3Stirring and dissolving tetrabutyl titanate and manganese nitrate continuously; transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and putting the reaction kettle into a thermostat for reaction for a period of time at a certain temperature; and taking out the reactant, repeatedly washing with absolute ethyl alcohol, centrifuging and drying to obtain the multielement composite metal organic framework material, and roasting to obtain the target oxygen carrier.
The preparation method has the reaction temperature of 80-200 ℃, preferably 100-180 ℃, the reaction time of 4-72 hours, preferably 12-24 hours, and the rotation speed of 100-400 r/min.
In the above preparation method, the drying temperature is 60-150 ℃, preferably 100-120 ℃, and the drying time is 4-48 hours, preferably 6-36 hours, and more preferably 8-24 hours.
In the preparation method, the roasting condition is that the roasting temperature is 400-1300 ℃, preferably 600-1200 ℃, and more preferably 700-1000 ℃ in the air atmosphere; the roasting time is 1h-24h, preferably 4h-8 h.
In the method of the invention, the calculation formula of the methane conversion rate is as follows:
the calculation formula of the hydrogen production is as follows:
wherein FN2As a carrier gas N2Flow rate of SN2As a carrier gas N2Peak area of, SH2Is H2Peak area of (d), mOCIs the oxygen carrier mass.
Example 1
Weighing raw materials according to the molar ratio of total metal, organic ligand and solvent of 1: 4.8: 625, wherein the molar ratio of terephthalic acid to trimesic acid is 7: 1, the solvent is a mixture of N, N-dimethylformamide and ethanol, the mass fraction of the ethanol in the total solvent is 28%, the mass ratio of Fe source, Ti source and Mn source calculated by Fe, Ti and Mn element oxides is 6.2: 2.8: 1, and the Fe source is FeCl3The Ti source is titanium isopropoxide, and the Mn source is manganese nitrate.
Firstly, evenly mixing N, N-dimethylformamide and ethanol, then sequentially adding terephthalic acid and trimesic acid, stirring to dissolve, and then sequentially adding FeCl3Continuously stirring and dissolving titanium isopropoxide and manganese nitrate, transferring the mixed solution into a reaction kettle lined with polytetrafluoroethylene after complete dissolution, and reacting for 18.5 hours at 162 ℃ under a sealed condition; and after the reaction is finished, obtaining the multi-element composite metal organic framework material, taking out the reactant, repeatedly washing the reactant by using absolute ethyl alcohol, centrifuging the reactant, drying the reactant for 16 hours at the temperature of 110 ℃, and finally roasting the reactant for 6 hours at the temperature of 900 ℃ to obtain the target oxygen carrier.
The chemical ring hydrogen production reaction is carried out on a fixed bed reactor, methane is used as a raw material, the reaction temperature is 800 ℃, the reaction pressure is 0.1Mpa, and the airspeed is 800h-1(ii) a Reacting with an oxygen carrier in a reactor to generate a reduction reaction; switching N when feedstock conversion drops significantly2Purging is carried out; introducing water vapor to perform steam reaction with the reduced oxygen carrier, and condensing the product gas to obtain H2Analysis by gas chromatography; switching N2Purging is carried out; and introducing air to fully oxidize the oxygen carrier. The conversion rate of methane reaches 99.8 percent, and the single hydrogen yield is 65 ml/g.
Example 2
Weighing raw materials according to the molar ratio of total metal, organic ligand and solvent of 1: 3: 700, wherein the molar ratio of terephthalic acid to trimesic acid is 7: 1, the solvent is a mixture of N, N-dimethylformamide and ethanol, the mass fraction of the ethanol in the total solvent is 28%, the mass ratio of Fe source, Ti source and Mn source in terms of Fe, Ti and Mn element oxides is 6.2: 2.8: 1, and the Fe source is FeCl3The Ti source is titanium isopropoxide, and the Mn source is manganese nitrate.
Firstly, evenly mixing N, N-dimethylformamide and ethanol, then sequentially adding terephthalic acid and trimesic acid, stirring to dissolve, and then sequentially adding FeCl3Continuously stirring and dissolving titanium isopropoxide and manganese nitrate, transferring the mixed solution into a reaction kettle lined with polytetrafluoroethylene after complete dissolution, and reacting for 18.5 hours at 130 ℃ under a closed condition; reaction ofAnd (3) obtaining the multi-element composite metal organic framework material after the reaction is finished, taking out the reactant, repeatedly washing the reactant by using absolute ethyl alcohol, centrifuging the reactant, drying the reactant for 16h at the temperature of 110 ℃, and finally roasting the reactant for 6h at the temperature of 800 ℃ to obtain the target oxygen carrier.
The chemical ring hydrogen production reaction is carried out on a fixed bed reactor, methane is used as a raw material, the reaction temperature is 700 ℃, the reaction pressure is 0.1Mpa, and the airspeed is 800h-1(ii) a Reacting with an oxygen carrier in a reactor to generate a reduction reaction; switching N when feedstock conversion drops significantly2Purging is carried out; introducing water vapor to perform steam reaction with the reduced oxygen carrier, and condensing the product gas to obtain H2Analysis by gas chromatography; switching N2Purging is carried out; and introducing air to fully oxidize the oxygen carrier. The conversion rate of methane reaches 99.8 percent, and the single hydrogen yield is 77 ml/g.
Example 3
Weighing raw materials according to the molar ratio of total metal, organic ligand and solvent of 1: 4.2: 730, wherein the molar ratio of terephthalic acid to trimesic acid is 6.5: 1, the solvent is a mixture of N, N-dimethylformamide and ethanol, the mass fraction of the ethanol in the total solvent is 28%, the mass ratio of Fe source, Ti source and Mn source in terms of Fe, Ti and Mn element oxides is 5.8: 1.8: 1, and the Fe source is FeCl3The Ti source is tetrabutyl titanate, and the Mn source is manganese nitrate.
Firstly, evenly mixing N, N-dimethylformamide and ethanol, then sequentially adding terephthalic acid and trimesic acid, stirring to dissolve, and then sequentially adding FeCl3Stirring and dissolving tetrabutyl titanate and manganese nitrate continuously, transferring the mixed solution into a reaction kettle lined with polytetrafluoroethylene after the mixed solution is completely dissolved, and reacting for 24 hours at 120 ℃ under a closed condition; and after the reaction is finished, obtaining the multi-element composite metal organic framework material, taking out the reactant, repeatedly washing the reactant by using absolute ethyl alcohol, centrifuging the reactant, drying the reactant for 16 hours at the temperature of 110 ℃, and finally roasting the reactant for 6 hours at the temperature of 500 ℃ to obtain the target oxygen carrier.
The chemical ring hydrogen production reaction is carried out on a fixed bed reactor, CO is used as a raw material, the reaction temperature is 500 ℃, the reaction pressure is 0.12Mpa, and the space velocity is 1000h-1(ii) a Reacting with oxygen carrier in reactor to generate reduction reaction(ii) a Switching N when feedstock conversion drops significantly2Purging is carried out; introducing water vapor to carry out steam reaction with the reduced oxygen carrier, and condensing the product gas to obtain H2Analysis by gas chromatography; switching N2Purging is carried out; and introducing air to fully oxidize the oxygen carrier. The CO conversion rate reaches 99.8 percent, and the single hydrogen yield is 88 ml/g.
Example 4
Weighing raw materials according to the molar ratio of total metal to organic ligand to solvent of 1: 5.4: 680, wherein the molar ratio of terephthalic acid to trimesic acid is 5: 1, the solvent is a mixture of N, N-dimethylformamide and ethanol, the mass fraction of the ethanol in the total solvent is 30%, the mass ratio of Fe source, Ti source and Mn source counted by Fe, Ti and Mn element oxides is 5.8: 1.9: 1, the Fe source is ferric nitrate, the Ti source is titanium isopropoxide, and the Mn source is manganese nitrate.
Uniformly mixing N, N-dimethylformamide and ethanol, sequentially adding terephthalic acid and trimesic acid, stirring for dissolving, sequentially adding ferric nitrate, titanium isopropoxide and manganese nitrate, continuously stirring for dissolving, transferring the mixed solution into a reaction kettle lined with polytetrafluoroethylene after complete dissolution, and reacting for 24 hours at 120 ℃ under a closed condition; and after the reaction is finished, obtaining the multi-element composite metal organic framework material, taking out the reactant, repeatedly washing the reactant by using absolute ethyl alcohol, centrifuging the reactant, drying the reactant for 24 hours at the temperature of 110 ℃, and finally roasting the reactant for 6 hours at the temperature of 550 ℃ to obtain the target oxygen carrier.
The chemical ring hydrogen production reaction is carried out on a fixed bed reactor, CO is used as a raw material, the reaction temperature is 550 ℃, the reaction pressure is 0.1Mpa, and the space velocity is 1200h-1(ii) a Reacting with an oxygen carrier in a reactor to generate a reduction reaction; switching N when feedstock conversion drops significantly2Purging is carried out; introducing water vapor to perform steam reaction with the reduced oxygen carrier, and condensing the product gas to obtain H2Analysis by gas chromatography; switching N2Purging is carried out; and introducing air to fully oxidize the oxygen carrier. The CO conversion rate reaches 99.9 percent, and the single hydrogen yield is 84 ml/g.
Example 5
According to the molar ratio of total metal, organic ligand and solventWeighing raw materials according to the ratio of 1: 3.8: 750, wherein the molar ratio of terephthalic acid to trimesic acid is 6.6: 1, the solvent is a mixture of N, N-dimethylformamide and ethanol, the mass fraction of the ethanol in the total solvent is 32%, the mass ratio of Fe source, Ti source and Mn source in terms of Fe, Ti and Mn element oxides is 7.2: 1.6: 1, and the Fe source is FeCl3The Ti source is titanium isopropoxide, the Mn source is MnCl2。
Firstly, evenly mixing N, N-dimethylformamide and ethanol, then sequentially adding terephthalic acid and trimesic acid, stirring to dissolve, and then sequentially adding FeCl3Titanium isopropoxide, MnCl2Continuously stirring and dissolving, after the mixed solution is completely dissolved, transferring the mixed solution into a reaction kettle lined with polytetrafluoroethylene, and reacting for 24 hours at 125 ℃ under a closed condition; and after the reaction is finished, obtaining the multi-element composite metal organic framework material, taking out the reactant, repeatedly washing the reactant by using absolute ethyl alcohol, centrifuging the reactant, drying the reactant for 16 hours at the temperature of 110 ℃, and finally roasting the reactant for 4 hours at the temperature of 600 ℃ to obtain the target oxygen carrier.
The chemical ring hydrogen production reaction is carried out on a fixed bed reactor, CO is used as a raw material, the reaction temperature is 600 ℃, the reaction pressure is 0.3Mpa, and the space velocity is 2000h-1(ii) a Reacting with an oxygen carrier in a reactor to generate a reduction reaction; switching N when feedstock conversion drops significantly2Purging is carried out; introducing water vapor to perform steam reaction with the reduced oxygen carrier, and condensing the product gas to obtain H2Analysis by gas chromatography; switching N2Purging is carried out; and introducing air to fully oxidize the oxygen carrier. The CO conversion rate reaches 99.8 percent, and the single hydrogen yield is 60 ml/g.
Example 6
Weighing raw materials according to the molar ratio of total metal, organic ligand and solvent of 1: 4.3: 650, wherein the molar ratio of terephthalic acid to trimesic acid is 4.2: 1, the solvent is a mixture of N, N-dimethylformamide and ethanol, the mass fraction of the ethanol in the total solvent is 20%, the mass ratio of Fe source, Ti source and Mn source in terms of Fe, Ti and Mn element oxides is 6.5: 2.2: 1, and the Fe source is FeCl3The Ti source is tetrabutyl titanate, and the Mn source is manganese nitrate.
Firstly, N-dimethyl methylAmide and ethanol are mixed evenly, then terephthalic acid and trimesic acid are added in sequence and stirred to be dissolved, and FeCl is added in sequence3Stirring and dissolving tetrabutyl titanate and manganese nitrate continuously, transferring the mixed solution into a reaction kettle lined with polytetrafluoroethylene after the mixed solution is completely dissolved, and reacting for 24 hours at 125 ℃ under a closed condition; and after the reaction is finished, obtaining the multi-element composite metal organic framework material, taking out the reactant, repeatedly washing the reactant by using absolute ethyl alcohol, centrifuging the reactant, drying the reactant for 16 hours at the temperature of 110 ℃, and finally roasting the reactant for 4 hours at the temperature of 550 ℃ to obtain the target oxygen carrier.
The chemical ring hydrogen production reaction is carried out on a fixed bed reactor, synthesis gas is used as a raw material, the reaction temperature is 550 ℃, the reaction pressure is 0.1Mpa, and the space velocity is 2200h-1(ii) a Reacting with an oxygen carrier in a reactor to generate a reduction reaction; switching N when feedstock conversion drops significantly2Purging is carried out; introducing water vapor to perform steam reaction with the reduced oxygen carrier, and condensing the product gas to obtain H2Analysis by gas chromatography; switching N2Purging is carried out; and introducing air to fully oxidize the oxygen carrier. The CO conversion rate reaches 99.9 percent, and the single hydrogen yield is 70 ml/g.
Example 7
Weighing raw materials according to the molar ratio of total metal to organic ligand to solvent of 1: 3.9: 680, wherein the molar ratio of terephthalic acid to trimesic acid is 5.8: 1, the solvent is a mixture of N, N-dimethylformamide and ethanol, the mass fraction of the ethanol in the total solvent is 25%, the mass ratio of Fe source, Ti source and Mn source counted by Fe, Ti and Mn element oxides is 5.5: 1.2: 1, and the Fe source is FeCl3The Ti source is tetrabutyl titanate, and the Mn source is manganese nitrate.
Firstly, evenly mixing N, N-dimethylformamide and ethanol, then sequentially adding terephthalic acid and trimesic acid, stirring to dissolve, and then sequentially adding FeCl3Stirring and dissolving tetrabutyl titanate and manganese nitrate continuously, transferring the mixed solution into a reaction kettle lined with polytetrafluoroethylene after the mixed solution is completely dissolved, and reacting for 24 hours at 125 ℃ under a closed condition; obtaining the multi-element composite metal organic framework material after the reaction is finished, taking out the reactant, repeatedly washing the reactant by absolute ethyl alcohol,centrifuging, drying at 110 ℃ for 16h, and finally roasting at 600 ℃ for 6h to obtain the target oxygen carrier.
The chemical ring hydrogen production reaction is carried out on a fixed bed reactor, synthesis gas is used as a raw material, the reaction temperature is 600 ℃, the reaction pressure is 0.1Mpa, and the space velocity is 2200h-1(ii) a Reacting with an oxygen carrier in a reactor to generate a reduction reaction; switching N when feedstock conversion drops significantly2Purging is carried out; introducing water vapor to perform steam reaction with the reduced oxygen carrier, and condensing the product gas to obtain H2Analysis by gas chromatography; switching N2Purging is carried out; and introducing air to fully oxidize the oxygen carrier. The CO conversion rate reaches 99.9 percent, and the single hydrogen production is 100 ml/g.
Example 8
Weighing raw materials according to the molar ratio of total metal, organic ligand and solvent of 1: 5.1: 710, wherein the molar ratio of terephthalic acid to trimesic acid is 7.3: 1, the solvent is a mixture of N, N-dimethylformamide and ethanol, the mass fraction of the ethanol in the total solvent is 32%, the mass ratio of Fe source, Ti source and Mn source in terms of Fe, Ti and Mn element oxides is 6.5: 1.8: 1, and the Fe source is FeCl3The Ti source is tetrabutyl titanate, and the Mn source is manganese nitrate.
Firstly, evenly mixing N, N-dimethylformamide and ethanol, then sequentially adding terephthalic acid and trimesic acid, stirring to dissolve, and then sequentially adding FeCl3Stirring and dissolving tetrabutyl titanate and manganese nitrate continuously, transferring the mixed solution into a reaction kettle lined with polytetrafluoroethylene after the mixed solution is completely dissolved, and reacting for 24 hours at 125 ℃ under a closed condition; and after the reaction is finished, obtaining the multi-element composite metal organic framework material, taking out the reactant, repeatedly washing the reactant by using absolute ethyl alcohol, centrifuging the reactant, drying the reactant for 16 hours at the temperature of 110 ℃, and finally roasting the reactant for 4 hours at the temperature of 700 ℃ to obtain the target oxygen carrier.
The chemical ring hydrogen production reaction is carried out on a fixed bed reactor, methane is used as a raw material, the reaction temperature is 700 ℃, the reaction pressure is 0.1Mpa, and the space velocity is 2400h-1(ii) a Reacting with an oxygen carrier in a reactor to generate a reduction reaction; switching N when feedstock conversion drops significantly2Purging is carried out; introducing water vapor and reducing carrierCarrying out steam reaction on the oxygen, and condensing the product gas to obtain H2Analysis by gas chromatography; switching N2Purging is carried out; and introducing air to fully oxidize the oxygen carrier. The conversion rate of methane reaches 99.9 percent, and the single hydrogen yield is 77 ml/g.
Claims (15)
1. A preparation method of an oxygen carrier for chemical looping hydrogen production is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing an organic ligand and a solvent, wherein the organic ligand comprises one or more of a carboxyl ligand, a ligand containing hetero nitrogen, a carboxylic acid nitrogen-containing mixed ligand, a phosphoric acid ligand, a sulfonic acid ligand and a porphyrin ligand; the solvent comprises one or more of alcohols, ketones, amides, aromatic hydrocarbons, chlorinated hydrocarbons and low-carbon hydrocarbons, and preferably one or more of ethanol, acetone and N, N-dimethylformamide;
(2) and (2) adding a Fe source, a Ti source and a Mn source into the material obtained in the step (1) for reaction, and drying and roasting the reacted material to obtain the oxygen carrier for chemical ring hydrogen production.
2. The method of claim 1, wherein: in the step (1), the organic ligand is terephthalic acid and trimesic acid, and the molar ratio of the terephthalic acid to the trimesic acid is (1-9): 1, preferably (2-7): 1, more preferably (3-6): 1.
3. the method of claim 1, wherein: in the step (1), the solvent is N, N-dimethylformamide and ethanol, and the molar ratio of the N, N-dimethylformamide to the ethanol is (1-100): 1: preferably (5-80): 1, more preferably (10-60): 1.
4. the method of claim 1, wherein: in the step (2), the Fe source comprises at least one of Fe oxide, hydroxide, inorganic acid salt, organic acid salt and chloride.
5. The method of claim 1, wherein: in the step (2), the Ti source comprises at least one of Ti oxide, Ti hydroxide, Ti inorganic acid salt, Ti organic acid salt and Ti organic metal compound.
6. The method of claim 1, wherein: in the step (2), the Mn source comprises at least one of Mn oxide, Mn hydroxide, inorganic acid salt and organic acid salt.
7. The method of claim 1, wherein: in the step (2), the mass ratio of the Fe source, the Ti source and the Mn source in terms of Fe, Ti and Mn element oxides is (1-9) to (1-5) to 1, preferably (3-7) to (2-4) to 1.
8. The method of claim 1, wherein: and (3) adding the Fe source, the Ti source and the Mn source into the material obtained in the step (1) sequentially or simultaneously for reaction.
9. The method of claim 1, wherein: the reaction described in step (2) is carried out with stirring.
10. The method of claim 1, wherein: in the step (2), when the Fe source, the Ti source and the Mn source are subjected to the reaction, the reaction conditions are as follows: total metals: total organic ligand: the molar ratio of the total solvent is 1: 0.2-10: 100-.
11. The method of claim 1, wherein: the drying temperature in the step (2) is 60 to 150 ℃, preferably 100 ℃ to 120 ℃, and the drying time is 4 to 48 hours, preferably 6 to 36 hours, and more preferably 8 to 24 hours.
12. The method of claim 1, wherein: the calcination conditions in the step (2) are 400-1300 ℃, preferably 600-1200 ℃, more preferably 700-1000 ℃, and the calcination time is 3-10 hours, preferably 4-8 hours.
13. A chemical ring hydrogen production oxygen carrier prepared by any one of the methods of claims 1 to 12, characterized in that: the weight content of the ferric oxide in the oxygen carrier is 40-80% based on the weight of the oxygen carrier; the weight content of the titanium oxide is 30-60%; the weight content of the manganese oxide is 3-15%.
14. An oxygen carrier as claimed in claim 13, wherein: based on the weight of the oxygen carrier, the weight content of iron oxide in the oxygen carrier is 40-80%; the weight content of the titanium oxide is 30-60%; the weight content of manganese oxide is 3-15%.
15. Use of an oxygen carrier according to claim 13, characterized in that: a fixed bed reactor is adopted, methane, CO or synthesis gas is used as a raw material, the reaction temperature is 500-1200 ℃, the reaction pressure is 0.1-5 Mpa, and the airspeed is 50-1000 h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110018986.5A CN114735651B (en) | 2021-01-07 | 2021-01-07 | Oxygen carrier for chemical looping hydrogen production and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110018986.5A CN114735651B (en) | 2021-01-07 | 2021-01-07 | Oxygen carrier for chemical looping hydrogen production and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114735651A true CN114735651A (en) | 2022-07-12 |
| CN114735651B CN114735651B (en) | 2024-01-05 |
Family
ID=82274100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110018986.5A Active CN114735651B (en) | 2021-01-07 | 2021-01-07 | Oxygen carrier for chemical looping hydrogen production and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114735651B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186597A (en) * | 2007-12-20 | 2008-05-28 | 江南大学 | Method for preparing epoxy soybean acidified oil (C1-4) without protonic acid |
| KR20130035642A (en) * | 2011-09-30 | 2013-04-09 | 한국전력공사 | Oxygen carriers and manufacturing method thereof |
| CN106334552A (en) * | 2016-09-30 | 2017-01-18 | 上海理工大学 | MnOx catalyst, preparation method thereof and application thereof to prevention and control of environmental pollution |
| CN109772324A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of preparation method of O composite metallic oxide catalyst |
-
2021
- 2021-01-07 CN CN202110018986.5A patent/CN114735651B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186597A (en) * | 2007-12-20 | 2008-05-28 | 江南大学 | Method for preparing epoxy soybean acidified oil (C1-4) without protonic acid |
| KR20130035642A (en) * | 2011-09-30 | 2013-04-09 | 한국전력공사 | Oxygen carriers and manufacturing method thereof |
| CN106334552A (en) * | 2016-09-30 | 2017-01-18 | 上海理工大学 | MnOx catalyst, preparation method thereof and application thereof to prevention and control of environmental pollution |
| CN109772324A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of preparation method of O composite metallic oxide catalyst |
Non-Patent Citations (2)
| Title |
|---|
| LEI YU ET AL.: "Developing Oxygen Carriers for Chemical Looping Biomass Processing: Challenges and Opportunities" * |
| RAÚL PÉREZ-VEGA ET AL.: "Coal combustion via Chemical Looping assisted by Oxygen Uncoupling with a manganese‑iron mixed oxide doped with titanium" * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114735651B (en) | 2024-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Daza et al. | Carbon dioxide conversion by reverse water–gas shift chemical looping on perovskite-type oxides | |
| KR102184878B1 (en) | Manufacturing method for carbon monoxide by chemical looping combustion | |
| Tu et al. | Low temperature methanation of CO 2 over an amorphous cobalt-based catalyst | |
| WO2020160500A1 (en) | Metal-decorated barium calcium aluminum oxide catalyst for nh3 synthesis and cracking and methods of forming the same | |
| MX2010014351A (en) | Process for operating hts reactor. | |
| CN104014345B (en) | For the CuO-CeO of water gas shift reaction2Catalysts and its preparation method | |
| WO2021042874A1 (en) | Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof | |
| CN112811476B (en) | Nickel-doped brownmillerite type oxygen carrier and preparation method and application thereof | |
| WO2022141979A1 (en) | Nickel-iron composite oxygen carrier, preparation method therefor and use thereof | |
| CN114735651A (en) | Oxygen carrier for chemical ring hydrogen production and preparation method and application thereof | |
| CN112916030A (en) | Pt/alpha-MoC1-xPreparation method and application of water-vapor shift catalyst | |
| CN114195097B (en) | Method for preparing hydrogen by reforming, nano cuprous oxide-zinc oxide composite catalyst, preparation method thereof and cyclic regeneration method | |
| CN115626666A (en) | Tricalcium titanium ore type composite metal oxide oxygen carrier and preparation method and application thereof | |
| Liao et al. | Application of metal-BDC-derived catalyst on cordierite honeycomb ceramic support in a microreactor for hydrogen production | |
| CN109046364A (en) | A kind of preparation method and applications of Fe2O3 doping lanthana supported nickel based catalysts | |
| CN114797946A (en) | Load type Pt-based catalyst for preparing propylene by propane dehydrogenation | |
| CN113649014A (en) | Nickel-zinc-based catalyst and preparation method and application thereof | |
| CN114602449A (en) | ZnZrO2Surface solid solution catalyst and preparation method and application thereof | |
| CN114735645B (en) | Oxygen carrier and preparation method and application thereof | |
| JP7084378B2 (en) | Sulfur trioxide conversion method and hydrogen generation method | |
| CN114735648B (en) | Oxygen carrier for chemical looping hydrogen production and preparation method and application thereof | |
| CN114436337B (en) | Oxygen carrier for chemical looping hydrogen production and preparation method thereof | |
| CN110317233A (en) | Metallic nickel and Metallic Manganese Complex and the preparation method and application thereof | |
| TWI778890B (en) | Catalyst and method for selectively chemically reducing co to form co | |
| CN112916015B (en) | Strontium-zirconium perovskite type cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20231121 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant after: CHINA PETROLEUM & CHEMICAL Corp. Applicant after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant before: CHINA PETROLEUM & CHEMICAL Corp. Applicant before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |