US20100111826A1 - Set-Up for Production of Hydrogen Gas By Thermo-Chemical Decomposition of Water Using Steel Plant Slag and Waste Materials - Google Patents

Set-Up for Production of Hydrogen Gas By Thermo-Chemical Decomposition of Water Using Steel Plant Slag and Waste Materials Download PDF

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Publication number
US20100111826A1
US20100111826A1 US11/922,955 US92295506A US2010111826A1 US 20100111826 A1 US20100111826 A1 US 20100111826A1 US 92295506 A US92295506 A US 92295506A US 2010111826 A1 US2010111826 A1 US 2010111826A1
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US
United States
Prior art keywords
water
slag
gas
hydrogen
hydrogen gas
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Abandoned
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US11/922,955
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English (en)
Inventor
Debashish Bhattacharjee
Tridibesh Mukharjee
Vilas Tathavadkar
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Tata Steel Ltd
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Tata Steel Ltd
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Assigned to TATA STEEL LIMITED reassignment TATA STEEL LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BHATTACHARJEE, DEBASHISH, MUKHARJEE, TRIDIBESH, TATHAVADKAR, VILAS
Publication of US20100111826A1 publication Critical patent/US20100111826A1/en
Abandoned legal-status Critical Current

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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
    • 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
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • 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
    • 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
    • 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
    • C01B3/12—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 water vapour with carbon monoxide
    • C01B3/14—Handling of heat and steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/04—Cyclic processes, e.g. alternate blast and run
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/57—Gasification using molten salts or metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
    • C10J2300/1615—Stripping
    • 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
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • This invention relates to a novel method of generating hydrogen gas from water.
  • Hydrogen is emerging as the favorite alternative to fossil fuels.
  • hydrogen is primarily used as a feedstock, intermediate chemical, or, on a much smaller scale, a specialty chemical.
  • Only a small portion of the hydrogen produced today is used as an energy carrier, mostly by the Aerospace industries. Automotive industries are developing new models that run on either hydrogen based internal combustion engines (ICEs), or gasoline-fuel cell cars.
  • ICEs hydrogen based internal combustion engines
  • most of the commercial hydrogen production processes are not considered as renewable as these technologies merely shift the source of pollution from a distributed one (like cars, households for example) to a more concentrated source like a hydrogen producing plants or thermal power plants.
  • the United States hydrogen industry alone currently produces nine million tons of hydrogen per year for use in chemicals production, petroleum refining, metals treating, and electrical applications.
  • the technologies for the utilization of hydrogen as a fuel are at a more advanced stage today than the technologies for the efficient production of hydrogen from renewable resources like solar energy, wind, tidal energy or geo-thermal energy.
  • renewable resources like solar energy, wind, tidal energy or geo-thermal energy.
  • the National Hydrogen Energy Road map of Government of India has also given prominence on development of advanced production techniques and application of technologies based on hydrogen fuel.
  • the primary by-product of this process is oxygen.
  • Steam-methane reforming process is also used widely for the hydrogen production. In this catalytic process natural gas or other light hydrocarbons are reacted with steam to produce a mixture of hydrogen and carbon dioxide. The high-purity hydrogen is then separated from the product mixture.
  • This method is the most energy-efficient commercialized technology currently available, and is most cost-effective when applied to large, constant loads.
  • Partial oxidation of fossil fuels in large gasifiers is another method of thermal hydrogen production. It involves the reaction of a fuel with a limited supply of oxygen to produce a hydrogen mixture, which is then purified. Partial oxidation can be applied to a wide range of hydrocarbon feedstock, including natural gas, heavy oils, solid biomass, and coal.
  • thermo-chemical water-splitting using nuclear and solar heat thermo-chemical water-splitting using nuclear and solar heat
  • photolytic (solar) processes using solid state techniques photo-electrochemical, electrolysis
  • fossil fuel hydrogen production with carbon sequestration and biological techniques (algae and bacteria).
  • An object of this invention is to propose a novel method of producing hydrogen gas from water.
  • Another object of this invention is to propose a novel method of producing hydrogen gas from water in presence of carbonaceous waste material and catalytic fluxes.
  • Further object of this invention is to propose a novel method of producing hydrogen gas from water wherein molten slag is used for the thermo-chemical decomposition of water.
  • Still further object of this invention is to propose a novel method of producing hydrogen gas from water which is simple and cost effective.
  • FIG. 1 a shows the Effect of water addition on the concentration of FeO and Fe 2 O 3 in the slag and formation of H 2 gas, based on results of computation of Water-Slag phase equilibria at 1873 K.
  • FIG. 1 b relates to a plot of enthalpy of water-slag system verses water addition, based on results of computation of Water-Slag phase equilibria at 1873 K. (b).
  • FIG. 2 shows the effect of water addition on the concentration of FeO and Fe 2 O 3 in the slag and formation of H 2 , CO and CO 2 gases computed using FACT-sage programme.
  • FIG. 3 shows the experimental set-up for hydrogen production.
  • FIG. 4 shows the line diagram and schematic of the set-up for hydrogen production in the slag pit at plant level.
  • A is amount of water added in the system
  • x is amount of C available in the flux
  • y is FeO in the slag and z formation of CO 2 by reaction between CO and water.
  • slag not only provides sensible heat for endothermic water decomposition reaction but also arrest the reverse reactions between hydrogen and oxygen gas.
  • the Fe and lower oxides of Fe in the slag react with oxygen gas in the product gas mix and form Fe 2 O 3 and thereby reduce the thermodynamic activity of oxygen.
  • Different types of wastes which can act as a deoxidizer, can be used as a flux to improve the production of hydrogen gas.
  • the sensible heat of molten slag can be used for the thermo-chemical decomposition of water.
  • slag acts as heat sources and some of the deoxidizing constituents (Fe, FeO) in the slag also take part in the decomposition reaction (1) by reacting with nascent oxygen via reaction (2):
  • the exothermic oxidation reaction provides additional energy required for reaction (1) and also reduces the oxygen partial pressure of the system and thereby enhances the rate of formation of hydrogen gas.
  • the phase equilibria data was computed for reaction between 100 g LD slag with water at 1600 C. The amount of water varied from 0 to 100 ml to study the effect of water to slag ratio on hydrogen gas generation. The results of computation are presented in FIGS. 1 a and b.
  • the FIG. 1 a shows effect of water addition on the formation of hydrogen gas and changes in the concentration of FeO and Fe 2 O 3 in the slag.
  • the enthalpy of the system at different water addition is shown in FIG.
  • the carbonaceous and other plant wastes materials such as coal fines, coke breeze, etc. can be used as deoxidizer which will enhance formation of hydrogen by thermo-chemical decomposition of water.
  • the reactions between water and carbon are:
  • Phase equilibrium data of 100 gin slag and ⁇ A>ml water and 10 gm carbon was computed for 1873 K temperature and results of computation are shown in FIG. 2 .
  • the results computation revealed that the addition of excess water than stoichiometric requirement for carbon reaction enhances the production of hydrogen gas.
  • the innovative devices (laboratory and plant) have been designed and fabricated for production of hydrogen gas using the steel plant slag as a heat source.
  • the device designed can effectively harvest the product gas with >35% hydrogen using waste heat from slag.
  • the condenser ( 6 ) and gas collection ( 11 ) tanks were first evacuated using vacuum pump ( 13 ), for removal of residual air and generation of negative pressure for flow of gas in the tanks.
  • the system was isolated from surrounding by closing valves ( 6 , 12 ) before experiment.
  • the granulated slag from LD steel plant was melted in the induction furnace and superheated to ⁇ 1650-1700 C.
  • the molten slag was poured in the pre-heated graphite crucible ( 1 ).
  • the reaction hood ( 2 ) was then kept on the crucible.
  • the controlled amount of water was sprayed on molten slag surface through water line ( 3 ).
  • the product gases were formed by reactions between water, deoxidizers in the slag, and carbon from the crucible, as discussed in above sections.
  • the product gas of the reactions was collected from the hood ( 2 ) via steel tube ( 4 ) connected to the tank. During experiment, the product gas samples were collected from the sample port ( 5 ) for chemical analysis.
  • the product gas was passed through condenser tank ( 7 ) by opening gas valve ( 6 ).
  • the condenser tank ( 7 ) was cooled by water stored in the outer tank ( 8 ).
  • the products gas after removal/stripping of the steam was then collected in the gas collection tank ( 11 ) by opening the gas flow control valves ( 9 , 10 ).
  • the gas samples from condenser tank and gas collection tank were collected by connecting the gas sampler to the valves ( 9 ) and ( 12 ) respectively.
  • the condensed water from the condenser tank ( 7 ) was removed by opening the valve ( 14 ) connected at the bottom of the condenser tank ( 7 ).
  • the product gases were formed by reactions between water-slag-flux as described earlier.
  • the gas blower ( 22 ) was switched ON and valve ( 19 ) was opened to remove the air and steam from the gas pipe line, once product gas with steam started coming out from the exhaust pipe of the blower ( 22 ), the valve ( 19 ) was closed and valve ( 6 ) was opened slowly.
  • the product gas samples were collected by opening valve ( 5 ) and by connecting gas sampler.
  • gas pressure in the tank reached +800 mm (compound gauge ( 15 ) the gas valve ( 6 ) was closed and gas valve ( 19 ) was opened.
  • reaction hood ( 2 ) was moved up samples were collected from condenser ( 7 ) and collection ( 11 ) tanks using samples ports connected to valves ( 17 and 18 ). After sample collection the set-up was evacuated as described before for next experiment. Explosive diaphragms were provided on both collection and condenser tanks to protect the system from any explosion as product gas contained >30% hydrogen and ⁇ 10% CO gases which are explosive and inflammable.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Processing Of Solid Wastes (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
US11/922,955 2006-04-28 2006-06-13 Set-Up for Production of Hydrogen Gas By Thermo-Chemical Decomposition of Water Using Steel Plant Slag and Waste Materials Abandoned US20100111826A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IN387/KOL/06 2006-04-28
IN387KO2006 2006-04-28
PCT/IN2006/000198 WO2007125537A1 (en) 2006-04-28 2006-06-13 Set - up for production of hydrogen gas by thermo- chemical decomposition of water using steel plant slag and waste materials

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US13/415,894 Active US9346675B2 (en) 2006-04-28 2012-03-09 Set-up for production of hydrogen gas by thermo-chemical decomposition of water using steel plant slag and waste materials

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US (3) US20100111826A1 (zh)
EP (1) EP2013139A4 (zh)
JP (1) JP5017362B2 (zh)
KR (1) KR101298052B1 (zh)
CN (1) CN101203455A (zh)
BR (1) BRPI0612895B1 (zh)
CA (1) CA2622171C (zh)
MX (1) MX2007016201A (zh)
RU (1) RU2415071C2 (zh)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110027133A1 (en) * 2006-04-28 2011-02-03 Tata Steel Limited Set-Up For Production Of Hydrogen Gas By Thermo-Chemical Decomposition Of Water Using Steel Plant Slag And Waste Materials
CN103894199A (zh) * 2014-04-04 2014-07-02 哈尔滨工程大学 用作光解水制氧的石墨烯修饰的多孔氧化铁纳米片及制备方法
US20160039669A1 (en) * 2013-03-29 2016-02-11 Centre National De La Recherche Scientifique (Cnrs) Method for Producing High-Purity Hydrogen Gas
US9567215B2 (en) 2005-09-30 2017-02-14 Tata Steel Limited Method for producing hydrogen and/or other gases from steel plant wastes and waste heat
US10899610B2 (en) 2013-03-29 2021-01-26 Centre National De La Recherche Scientifique Method for producing high-purity hydrogen gas and/or nanomagnetite

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IT1400139B1 (it) * 2010-05-20 2013-05-17 Asiu S P A Un procedimento per la produzione di idrogeno, per il sequestro di anidride carbonica e per la produzione di materiali da costruzione a partire da scorie e/o ceneri industriali.
CN105056857A (zh) * 2015-08-21 2015-11-18 黄文鹏 一种螺杆合成挤出原料生产线
CN108467012A (zh) * 2018-05-07 2018-08-31 浙江高成绿能科技有限公司 一种可快速持续产氢的化学制氢系统
CN111943136A (zh) * 2020-07-29 2020-11-17 浙江工业大学 一种直接利用生活垃圾焚烧炉渣制氢的方法
CN113023672B (zh) * 2021-04-28 2022-11-25 北京中电企发能源科技有限公司 一种炼钢转炉铸余渣余热制氢的系统和方法

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