US3912502A - Method of preparing reducing gas - Google Patents

Method of preparing reducing gas Download PDF

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Publication number
US3912502A
US3912502A US432245A US43224574A US3912502A US 3912502 A US3912502 A US 3912502A US 432245 A US432245 A US 432245A US 43224574 A US43224574 A US 43224574A US 3912502 A US3912502 A US 3912502A
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United States
Prior art keywords
gas
reducing
hydrocarbon
furnace
heat
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Expired - Lifetime
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US432245A
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English (en)
Inventor
Tsuneo Miyashita
Toshio Nayuki
Kazuo Sano
Takeo Yamada
Shoichiro Ohzeki
Hiroaki Nishio
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JFE Engineering Corp
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Nippon Kokan Ltd
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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
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • 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

Definitions

  • ABSTRACT Reducing gas containing CO and H as the major ingredients is prepared by partially oxidizing a hydrocarbon oil with oxygen or oxygen rich air to produce an intermediate gas containing CO and H 0 and converting CO2 and H 0 into CO and H2 by means of a gaseous hydrocarbon such as coke oven gas or natural gas by using the heat generated by the partial oxidation.
  • Furnace top gas exhausted from a reducing furnace may be added to the partially oxidizing zone.
  • This invention relates to a method of preparing reducing gas and more particularly to a method of preparing at high efficiencies reducing gas containing at least less than 7 of CO and H and only a little quantity of free carbon by partially oxidizing a hydrocarbon while incorporating thereto oxygen or oxygen rich air.
  • the invention also relates to a method for preparing at an extremely low cost reducing gas of the character described above by utilizing as the main raw material furnace top gas exhausted from-the top of a reducing furnace, for example a blast furnace and containing CO and H 0.
  • a hydrocarbon oil or a hydrocarbon gas is merely heat decomposed by the heat accumulated in a heat exchanger so that it is necessary to accumulate heat in the heat exchanger by suitable means.
  • the composition of the resulting reducing gas and the content of soot contained therein are determined solely depending upon the quantity of heat accumulated. Moreover, the operation is troublesome, and the composition and the temperature of the reducing gas are not always constant at the start and the end in the making of the gas. It is difficult to adjust the composition.
  • This invention is suitable to reform a hydrocarbon by using CO and H 0 in a furnace top gas with partial oxidation of the oil, as the abovementioned two steps.
  • it is not necessary to maintain a paricular ratio of oxygen to the raw material hydrocarbon as in the prior art partial oxidation process thereby enabling a desired partial oxidation reaction with a higher oxygen ratio in a wide range, with the result that the operation is greatly simplified and the formation of soot is greatly decreased.
  • the quantities of CO and H 0 generated increase proportionally with the oxygen and the quantity of heat generated by the partial oxidation reaction also increases.
  • the quality of the intermediate gas can be improved by the second step in which a gaseous hydrocarbon is incorporated and the resulting mixture is pyrolyzed. More particularly, in the second step, CO and H 0 produced in the first step are converted into CO and H which are advantageous for the reducing gas. Moreover, the heat generated in the first step is advantageously and reversibly used for the heat of pyrolysis. With these two steps, even if the composition of the intermediate gas resulting from the first step is not constant it is possible to adjust or improve the composition by the second step thereby making it possible to produce reducing gases of any desired composition or characteristic. Thus it is always possible to assure stable operation and to reduce the quantity of soot. Moreover, it is not necessary to prepare any source of heat necessary for the pyrolysis and improvement of the quality of the reducing gas.
  • Another object of this invention is to obtain reducing gas at a low cost.
  • the method of this invention is easy to carry out and since it is not necessary to install any independent source of heat for the pyrolysis it is possible to greatly reduce the cost of manufacturing the reducing gas.
  • exhaust gas exhausted from a reducing furnace such as a blast furnace and containing appropriate quantities of CO and H 0 is used as the principal raw material. It is possible to reduce the cost of manufacturing reducing gas by at least more than 30 than the prior art methods described above. Usually, it is possible to reduce the cost by even more.
  • FIGURE is a diagrammatic representation for explaining the process steps of the method of this invention.
  • a gas manufacturing furnace 10 In the furnace 10 are installed oxy-fuel burners 5 and 6 to atomize a hydrocarbon oil. Oxgen or oxygen rich air is admixed with the atomized hydrocarbon oil at a ratio in a range described above to effect a partial oxidation combustion or the first process step to form hydrocarbon gas which is mixed with the furnace top gas to act as the modifying gas.
  • hydrocarbon gas such as coke oven gas 11 HQ 45 55 %,CH,,35 -45% ,CO:3-6%,CmHn:2-4%) is admixed with said gas mixture in a reformer thereby effecting the pyrolysis of the second process step.
  • reducing gas of the desired quality is produced from a hydrocarbon oil without forming soot by supplementing by itself the heat required for the pyrolysis and by adjusting the atmosphere at the time of switching.
  • the resulting reducing gas is admitted into the blast furnace 1 via a conduit 12.
  • the gas is blown into the furnace through an inlet part 13 provided above the tuyers not shown.
  • the reducing gas manufacturing furnace of this invention is combined with the blast furnace l to effect partial oxidation of the top gas exhausted from the blast furnace and the resulting reducing gas is blown into and circulated through the blast furnace.
  • This arrangement reduces not only the quantity of the discarded gas but also the heat loss, thereby assuring efficient operations both in the blast furnace l and the reducing gas manufacturing furnace l0. 1
  • CmHn represents heavy oil, for example, and corresponds to a value of about 0.95 to 0.97 Nm /Kg/(C) as in the prior art method.
  • the value a amounts to from 2 to 6 by volume based on the total quantity of the gas produced, [2 equals to -45 d equals to l8-60%, and e equals to from 4 to 18
  • the value a represents the quantity of heat generated and in the partial oxidation process is used to increase the temperature of the resulting reducing gas.
  • the value of a should correspond to about 0.95 to 0.97 Nm /Kg/(C).
  • the CO and H 0 components formed in a reducing furnace are decomposed by the hydrocarbon gas Cm'Hn as shown by the following equation V
  • the reaction process according to equation V to form reducing gas consisting essentially of C0 H is endothermic so that it is necessary to supplement a heat quantity q.
  • the invention is characterized in that a hydrocarbon oil is partially burnt according to equation I with a value ofa selected in a range not to form as far as possible soot and to form gas containing excess a quantities of CO and H 0. Thereafter an excess quantity of a gaseous hydrocarbon CmHn is added to the gas for converting the CO and H 0 into CO and H and a portion of the heat q, generated by the reaction of equation I is used reversibly as the heat for converting CO and H 0 into CO and H In other words, chemical reactions expressed by the following equation l) and Vl proceed in parallel.
  • the furnace top gas 2 exhausted from reducing furnace l or blast furnace has a composition of l8-22 of CO 2-50 of H and 8-57 of N for example.
  • the gas is admitted into the reducing gas manufacturing furnace l0 equipped with oxyfuel burners 5 and 6.
  • the gas is then partially burnt by selecting a ratio O /oil of 1.30 Nm/Kg/(C), for example, to produce intermediate containing higher contents of CO; and H 0 than the conventional method.
  • the intermediate gas thus produced is then caused to react in the re- CO and H O H
  • the resulting reducing gas generally has a composition of 2-4 of CO 30-40 of CO, 18-60 of H and 4-36 of N all in volume percent, and can be directly blown into the reducing furnace l.
  • the hydrocarbon oil is partially oxidized by the oxy-fuel burners 5 and 6 in the furnace l0 and the CO and H 0 components contained in the resulting intermediate gas are pyrolyzed and converted in into CO and H in the reformer 8 by a gaseous hydrocarbon such as coke oven gas or natural gas.
  • a gaseous hydrocarbon such as coke oven gas or natural gas.
  • the value of O contained in the oxyfuel used to partially oxidize the hydrocarbon oil should be in a range of from 1.00 to 3.00 Nm lKg/(C).
  • composition of the blast furnace gas utilized in these examples was: CO 18 CO, 23 H 2 and N 57 and the composition of the heavy oil was C, 90.5%; Specific Gravity 20(A.P.l.), Pour Point 6 C.
  • the coke oven gas had a composition of CH 30 CmHn, 3 CO, 6 and H 55 Control Control Ex. 1 Ex. 2 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7
  • the quantity of soot formed is below 2.0g/Nm Test was also made wherein the value of O in O- /(C in oil) was selected to be higher than 3.00.
  • the quantity of- CO generated in the first step was from 8 to 20% and that of H was from 16 to 40
  • the invention provides a novel method of preparing reducing gas without regard to the ratio of oxygen to fuel which is the most important factor in the method of manufacturing reducing gas by partial oxidation process, thus making it possible to produce valuable reducing gas by selectingthe ration of higher than unity and to greatly decrease the quantity of soot formed.
  • the intermediate gas is converted by a gaseous hydrocarbon to obtain reducing gas having excellent composition and characteristic and can be advantageously used in such reducing furnaces as a blast furnace.
  • the partial oxidation reaction which is inherently an endothermic reaction is caused to proceed in parallel with the conversion of the furnace top gas by hydrocarbon gas thus making it possible to use furnace top gas as the main raw material.
  • the heat of reaction is efficiently utilized to control the composition and temperature of the reducing gas formed so that it is possible to prepare valuable reducing gas at an extremely low cost.
  • a method of preparing reducing gas comprising the steps of I partially oxidizing a hydrocarbon with oxygen or oxygen-rich air to form an intermediate gaseous product containing CO and H 0, wherein heat is generated, the quantity of oxygen being from 1 to 3 Nm/Kg of carbon contained in said hydrocarbon, and pyrolyzing said intermediate gaseous product and a gaseous hydrocarbon with said heat whereby said CO and H 0 are converted into a reducing gas containing CO and 2.
  • said hydrocarbon is a hydrocarbon oil and said gaseous hydrocarbon is coke oven gas or natural gas.
  • a method of preparing reducing gas comprising the steps of atomizing and partially oxidizing a hydrocarbon oil with oxygen or oxygenrich air, wherein heat is generated, the quantity of oxygen being froml to 3 Nm/Kg of carbon contained in said hydrocarbon oil, admixing the resulting gas with a furnace top gas exhausted from a reducing furnace to form an intermediate gas containing CO and H 0 and incorporating a coke oven gas or a natural gas with said intermediate gas and pyrolying the resulting mixture with said heat, whereby said CO and H 0 are converted into a reducing gas containing CO and H 4.
  • the method according to claim 3 wherein said reducing gas is blown into said reducing furnace.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Industrial Gases (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US432245A 1973-01-16 1974-01-10 Method of preparing reducing gas Expired - Lifetime US3912502A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP48007243A JPS4994592A (de) 1973-01-16 1973-01-16

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US3912502A true US3912502A (en) 1975-10-14

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US (1) US3912502A (de)
JP (1) JPS4994592A (de)
BE (1) BE809668A (de)
BR (1) BR7400243D0 (de)
CA (1) CA1012355A (de)
DE (1) DE2401991B2 (de)
FR (1) FR2221398B1 (de)
GB (1) GB1457793A (de)
IT (1) IT1003351B (de)
LU (1) LU69180A1 (de)
NL (1) NL7400290A (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4381938A (en) * 1980-06-12 1983-05-03 Claflin H Bruce Multi-purpose zone controlled blast furnace and method of producing hot metal, gases and slags
US4631182A (en) * 1984-02-01 1986-12-23 Haldor Topsoe A/S Process for preparation of a reducing gas
US5714132A (en) * 1993-09-07 1998-02-03 The Boc Group, Inc. Production of hydrogen and carbon monoxide from oxyfuel furnace off-gas
US20100313711A1 (en) * 2008-02-15 2010-12-16 Siemens Vai Metals Tech Gmbh Method for the melting of pig iron with the recirculation of blast furnace gas and with the addition of hydrocarbons
WO2011081432A2 (ko) * 2009-12-29 2011-07-07 재단법인 포항산업과학연구원 이산화탄소를 이용한 코크스 오븐 가스의 증량방법

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1021774B (it) * 1974-10-11 1978-02-20 Centro Speriment Metallurg Processo per la preparazione di gas riducenti
GB2153383B (en) * 1984-02-01 1988-05-18 Haldor Topsoe As Preparing reducing gas
US5078788A (en) * 1989-12-22 1992-01-07 C.V.G. Siderurgica Del Orinoco, C.A. Method for the direct reduction of iron
CA2100811C (en) * 1992-08-19 1999-01-19 Akhilesh Kapoor Hydrogen and carbon monoxide production by partial oxidation of hydrocarbon feed
DE19853836C2 (de) * 1998-11-21 2002-02-21 Internat Briquettes Holding Ca Verfahren zur Direktreduktion von Oxiden
DE19955892C2 (de) * 1999-11-20 2002-04-25 Daimler Chrysler Ag Vorrichtung zur Reformierung eines Kohlenwasserstoffs mit langkettigen Kohlenwasserstoffanteilen
US7837928B2 (en) 2007-01-16 2010-11-23 U.S. Steel Canada Inc. Apparatus and method for injection of fluid hydrocarbons into a blast furnace

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3536455A (en) * 1959-02-24 1970-10-27 Huettenwerk Oberhausen Ag Plant for the production of metallurgical reducing gas
US3813229A (en) * 1970-09-03 1974-05-28 Snam Progetti Process for the production of a reducing gas for blast furnace

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3536455A (en) * 1959-02-24 1970-10-27 Huettenwerk Oberhausen Ag Plant for the production of metallurgical reducing gas
US3813229A (en) * 1970-09-03 1974-05-28 Snam Progetti Process for the production of a reducing gas for blast furnace

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4381938A (en) * 1980-06-12 1983-05-03 Claflin H Bruce Multi-purpose zone controlled blast furnace and method of producing hot metal, gases and slags
US4631182A (en) * 1984-02-01 1986-12-23 Haldor Topsoe A/S Process for preparation of a reducing gas
US5714132A (en) * 1993-09-07 1998-02-03 The Boc Group, Inc. Production of hydrogen and carbon monoxide from oxyfuel furnace off-gas
US20100313711A1 (en) * 2008-02-15 2010-12-16 Siemens Vai Metals Tech Gmbh Method for the melting of pig iron with the recirculation of blast furnace gas and with the addition of hydrocarbons
US8287620B2 (en) 2008-02-15 2012-10-16 Siemens Vai Metals Technologies Gmbh Method for the melting of pig iron with the recirculation of blast furnace gas and with the addition of hydrocarbons
RU2496884C2 (ru) * 2008-02-15 2013-10-27 Сименс Фаи Металз Текнолоджиз Гмбх Способ выплавки чугуна с возвратом колошникового газа при добавлении углеводородов
WO2011081432A2 (ko) * 2009-12-29 2011-07-07 재단법인 포항산업과학연구원 이산화탄소를 이용한 코크스 오븐 가스의 증량방법
WO2011081432A3 (ko) * 2009-12-29 2011-11-24 재단법인 포항산업과학연구원 이산화탄소를 이용한 코크스 오븐 가스의 증량방법
US20120305381A1 (en) * 2009-12-29 2012-12-06 Research Institute Of Industrial Science & Technology Method for increasing amount of coke oven gas by using carbon dioxide
US9255224B2 (en) * 2009-12-29 2016-02-09 Research Institute Of Industrial Science & Technology Method for increasing amount of coke oven gas by using carbon dioxide

Also Published As

Publication number Publication date
BR7400243D0 (pt) 1974-08-22
BE809668A (nl) 1974-05-02
FR2221398B1 (de) 1978-11-10
JPS4994592A (de) 1974-09-07
IT1003351B (it) 1976-06-10
AU6458174A (en) 1975-07-17
FR2221398A1 (de) 1974-10-11
LU69180A1 (de) 1974-04-08
DE2401991A1 (de) 1974-07-25
GB1457793A (en) 1976-12-08
DE2401991B2 (de) 1980-01-10
NL7400290A (de) 1974-07-18
CA1012355A (en) 1977-06-21

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