CN107128876A - The manufacture device and its manufacture method of forming gas containing carbon monoxide and hydrogen - Google Patents
The manufacture device and its manufacture method of forming gas containing carbon monoxide and hydrogen Download PDFInfo
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- CN107128876A CN107128876A CN201710533431.8A CN201710533431A CN107128876A CN 107128876 A CN107128876 A CN 107128876A CN 201710533431 A CN201710533431 A CN 201710533431A CN 107128876 A CN107128876 A CN 107128876A
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- 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
- C01B3/38—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 catalysts
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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- 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
- C01B3/48—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 followed by reaction of water vapour with carbon monoxide
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- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
- C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- C01B2203/1258—Pre-treatment of the feed
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- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses a kind of manufacture device of the forming gas containing carbon monoxide and hydrogen.The manufacture device of the forming gas containing carbon monoxide and hydrogen of the present invention includes：First pretreatment unit of the ironmaking by-product gas containing methane；Second pretreatment unit of the ironmaking by-product gas containing carbon dioxide for separating and setting with first pretreatment unit；Steam raising plant, the mixed gas that its ironmaking by-product gas containing carbon dioxide for being used to handle to the ironmaking by-product gas containing methane handled through first pretreatment unit and through second pretreatment unit is mixed supplies steam；And conversion reaction device, it receives the mixed gas containing the steam being supplied to and is allowed to convert, so that the mixed gas to be converted into the reducing gas containing carbon monoxide and hydrogen.
Description
The application is the entitled " manufacture of the forming gas containing carbon monoxide and hydrogen that August in 2012 is submitted on the 27th
The divisional application of 201280043420.7 applications for a patent for invention of device and its manufacture method ".
Technical field
The present invention relates to a kind of manufacture device of forming gas, more specifically, it is related to one kind and utilizes iron-smelting process gas
Manufacture the device of the forming gas containing carbon monoxide and hydrogen.
Background technology
At present, depend on blast furnace iron-making process in the technique of comprehensive iron-smelter manufacture molten iron, and it is most of will be from
The CO gases produced in coal are used as the reducing agent of iron ore.
In addition, can be produced comprising CH in comprehensive iron-smelting process4/CO/H2Various by-product gases, wherein most use
Produce the heater of steel products, produce power plant etc. of electric power, used by-product gas is to include a large amount of CO2Waste gas shape
Formula is discharged from iron-smelter.
Therefore, molten iron making processes, the heating technique of production steel products and offer necessity at present in comprehensive iron-smelter
Substantial amounts of CO is produced in the iron-smelter electrification technique of electric power2.For example, will be produced about during one ton of steel products is produced
2.18 tons of carbon dioxide (CO2)。
At present, in order to reduce the CO produced in iron-smelting process2Although making great efforts to improve is included in reduction molten iron production
Process efficiency including reducing agent ratio, but the process efficiency of the synthesis iron-smelting process based on blast furnace has been reached the limit values,
Therefore it is difficult further to reduce CO2。
The content of the invention
The invention problem to be solved
The present invention is proposed to solve the above problems, and the purpose is to provide a kind of synthesis containing carbon monoxide and hydrogen
The manufacture device of gas, the manufacture device makes the carbon dioxide produced in comprehensive iron-smelting process be reacted with methane, so that
Manufacture contains carbon monoxide (CO) and hydrogen (H2) forming gas.
The method for solving problem
In order to reach the purpose, the utilization iron-smelting process gas of the preferred embodiment of the invention containing carbon monoxide and
The manufacture device of the forming gas of hydrogen, including：First pretreatment unit of the ironmaking by-product gas containing methane；With described
Second pretreatment unit of the ironmaking by-product gas containing carbon dioxide that one pretreatment unit is separated and set；Steam generation is filled
Put, it is used for the ironmaking by-product gas containing methane handled through first pretreatment unit and through the described second pre- place
Steam is supplied in the mixed gas that the ironmaking by-product gas containing carbon dioxide of reason device processing is mixed；And conversion
(reforming) reaction unit, it is received simultaneously is allowed to convert containing the mixed gas of the steam being supplied to, so that by institute
State mixed gas and be converted into the gas containing carbon monoxide and hydrogen.
It is a feature of the present invention that the ironmaking by-product gas containing methane is coke-stove gas (COG, COKE OVEN
GAS)。
It is a feature of the present invention that the ironmaking by-product gas containing carbon dioxide is selected from blast furnace waste gas, FINEX works
Reduction on Fluidized Bed furnace exhaust, the waste gas of iron-smelter generating equipment, the furnace exhaust and coke oven heating for producing steel products of skill
At least one of furnace exhaust.
It is a feature of the present invention that the ironmaking by-product gas containing carbon dioxide is further included from the conversion instead
Answer the waste gas discharged in device.
It is a feature of the present invention that being obtained in the waste gas that the steam raising plant is discharged from the conversion reaction device
Thermal source is supplied.
First pretreatment unit includes：First storage chamber, it is used to store the ironmaking by-product containing methane
Gas；And purifier, it is used to refine the ironmaking by-product gas containing methane discharged from first storage chamber.
First pretreatment unit further comprises：Liquefied natural gas (LNG) is blown into pipeline, its be used for further to from
Methane is supplied in the ironmaking by-product gas containing methane discharged in first storage chamber；And desulfurizer, it is used for
Sulphur removal is gone from the liquefied natural gas.
Second pretreatment unit includes：Second storage chamber, it is used to store the ironmaking containing carbon dioxide
By-product gas；Purifier, it is used to refine the ironmaking manufacture gas containing carbon dioxide discharged from second storage chamber
Body.
Second pretreatment unit further comprises carbon dioxide separation device, the carbon dioxide separation device be used for from
By some or all middle separation carbon dioxide of the ironmaking by-product gas containing carbon dioxide described in refining.
It is a feature of the present invention that in the waste gas that the carbon dioxide separation device is discharged from the conversion reaction device
To thermal source supply.
The manufacture device of the forming gas containing carbon monoxide and hydrogen of the present invention further comprises increasing apparatus, the liter
Pressure device be used to making the ironmaking by-product gas containing methane and the ironmaking by-product gas mixing containing carbon dioxide and
Into mixed gas boost to the operating pressure of the reduction of iron ore device.
The manufacture device of the forming gas containing carbon monoxide and hydrogen of the present invention further comprises heat riser, the liter
Warm device is used to make the heating of the mixed gas after boosting be adapted to the reaction temperature in the conversion reaction device.
It is a feature of the present invention that obtaining thermal source confession in the waste gas that the heat riser is discharged from the conversion reaction device
Give.
The manufacture device of the forming gas containing carbon monoxide and hydrogen further comprises Hydrogen production device, the hydrogen
Gas manufacture device is used for the reduction containing carbon monoxide manufactured by converting mixed gas in the conversion reaction device
Some or all manufacture hydrogen of gas.
The Hydrogen production device further comprises：Water-gas shift, it, which is used to increasing, described contains an oxidation
The hydrogen content of the reducing gas of carbon；And hydrogen separation device, it is used to contain carbon monoxide described in hydrogen from adding
Reducing gas in separate hydrogen.
The Hydrogen production device further comprises heat reclamation device, and the heat reclamation device is used to cool down the institute by conversion
State the reducing gas containing carbon monoxide.
It is a feature of the present invention that the water-gas shift obtains steam supply from the steam raising plant.
It is a feature of the present invention that a part of hydrogen separated by the hydrogen separation device by described with being converted instead
Answer the mixing of the reducing gas containing carbon monoxide and hydrogen that device is converted.
It is a feature of the present invention that the waste gas containing carbon dioxide discharged from the hydrogen separation device contains with described
The ironmaking by-product gas for having carbon dioxide is mixed.
In the manufacture device of the forming gas containing carbon monoxide and hydrogen, to the conversion reaction unit feeding
The mixed gas in methane, the mol ratio of carbon dioxide and steam meet 0≤H2O/CO2≤5、0.1≤(H2O+CO2)/
CH4≤5。
The reduction of iron ore system of one embodiment of the invention can will pass through the forming gas manufacture device system
The forming gas containing carbon monoxide and hydrogen made is supplied to reduction of iron ore device with reducing iron ore.
The reduction of iron ore device is the fluidisation of blast furnace (blast furnace) or FINEX (melting and reducing) technique
Reduction furnace.
In order to reach the purpose, the synthesis gas containing carbon monoxide and hydrogen of another preferred embodiment of the invention
The manufacture method of body, comprises the following steps：Pre-process the ironmaking by-product gas containing methane；Pre-process the refining containing carbon dioxide
Iron by-product gas；Mixing is by the ironmaking by-product gas containing methane of pretreatment and the ironmaking by-product containing carbon dioxide
Gas makes the mixed gas boost to predetermined pressure to be formed after mixed gas；Make the mixed gas liter after boosting
Temperature is to predetermined temperature；And the mixed gas after will heat up is supplied to conversion reaction device and turns the mixed gas
Turn to the reducing gas containing carbon monoxide and hydrogen.
The step of ironmaking by-product gas of the pretreatment containing methane, comprises the following steps：Refine the ironmaking containing methane
By-product gas；And to by mixed liquefied natural gas (LNG) in the ironmaking by-product gas containing methane described in refining.
It is a feature of the present invention that the ironmaking by-product gas containing methane is coke-stove gas (COG, COKE OVEN
GAS)。
The step of pretreatment ironmaking by-product gas containing carbon dioxide, comprises the following steps：Refining contains titanium dioxide
The ironmaking by-product gas of carbon；And from by a part for the ironmaking by-product gas containing carbon dioxide described in refining or entirely
Carbon dioxide is separated in portion.
It is a feature of the present invention that the ironmaking by-product gas containing carbon dioxide is selected from blast furnace waste gas, FINEX works
Reduction on Fluidized Bed furnace exhaust, the waste gas of iron-smelter generating equipment, the furnace exhaust and coke oven heating for producing steel products of skill
At least one of furnace exhaust.
It is a feature of the present invention that the ironmaking by-product gas containing carbon dioxide is further included from the conversion instead
Answer the waste gas discharged in device.
The manufacture method of the forming gas containing carbon monoxide and hydrogen further comprises to described mixed after heating
The step of closing gas supply steam.
The manufacture method of the forming gas containing carbon monoxide and hydrogen further comprise as converting after described in contain
The step of having part or all of manufacture hydrogen of reducing gas of carbon monoxide.
Moreover, the hydrogen comprises the following steps the step of manufacture：The cooling reducing gas containing carbon monoxide；It is right
The reducing gas containing carbon monoxide after cooling carries out Water gas shift/WGS；And from by being gone back described in Water gas shift/WGS
Hydrogen is separated in raw-gas.
It is a feature of the present invention that by the hydrogen produced with conversion after the gas mixing.
The iron ore reduction process of one embodiment of the invention can contain one by what is manufactured by the manufacture method
The forming gas of carbonoxide and hydrogen is to reduction of iron ore unit feeding with reducing iron ore.
It is a feature of the present invention that the reduction of iron ore device is blast furnace or the Reduction on Fluidized Bed stove of FINEX techniques.
The effect of invention
By the present invention, the carbon dioxide produced in comprehensive iron-smelting process is set to be reacted and be manufactured containing one with methane
Carbonoxide (CO) and hydrogen (H2) forming gas, and reuse in the reduction of iron ore the forming gas or in diformazan
The forming gas is used in the manufacture of base ether (DME) etc., so as to which the amount of the carbon dioxide produced in iron-smelter is greatly decreased.
Brief description of the drawings
Fig. 1 be represent one embodiment of the invention utilization iron-smelting process gas containing carbon monoxide and hydrogen
The flow chart of forming gas manufacture device.
Fig. 2 is the manufacturing process of the forming gas containing carbon monoxide and hydrogen of the utilization iron-smelting process gas of the present invention
Figure.
Fig. 3 be represent another embodiment of the present invention utilization iron-smelting process gas containing carbon monoxide and hydrogen
The flow chart of forming gas manufacture device.
Embodiment
Referring to the drawings and be described in detail embodiment it can be clearly understood that advantages of the present invention and feature and realize should
The method of advantage and feature.But the invention is not limited in embodiment disclosed below, it can be realized by many different forms,
The present embodiment is intended merely to intactly disclose the present invention, and intactly informs this to those skilled in the art
Invention scope and propose, the present invention should be defined by the scope of claim.In specification in the whole text, identical accompanying drawing mark
Note represents identical structural element.
Below, carbon monoxide and hydrogen are contained referring to the drawings the utilization iron-smelting process gas to the preferred embodiment of the invention
The manufacture device of the forming gas of gas is described in detail.It should be noted that in explanation process of the present invention, when thinking to phase
When the detailed description of pass known function or structure may not protrude idea of the invention, description is omitted.
Fig. 1 be represent one embodiment of the invention utilization iron-smelting process gas containing carbon monoxide and hydrogen
The flow chart of forming gas manufacture device.
The synthesis containing carbon monoxide and hydrogen of the utilization iron-smelting process gas of the preferred embodiment of the present invention
The manufacture device of gas includes：First pretreatment unit 10 of the ironmaking by-product gas containing methane；Refining containing carbon dioxide
Second pretreatment unit 20 of iron by-product gas；Steam raising plant 30, it is to handling through first pretreatment unit 10
Ironmaking by-product gas containing methane and the ironmaking manufacture gas containing carbon dioxide handled through second pretreatment unit 20
The mixed gas supply steam of body；Conversion reaction device 40, carries out conversion to the mixed gas for having supplied steam and is allowed to turn
Turn to the reducing gas containing carbon monoxide；And reduction of iron ore device 50, it utilizes the reduction for including the carbon monoxide
Gas reduction iron ore.
First pretreatment unit 10 includes：First storage chamber 13, it is used to store the ironmaking containing methane
By-product gas；And purifier 15, it is used to refine the ironmaking pair containing methane discharged from first storage chamber 13
Aerogenesis body.The ironmaking by-product gas containing methane directly can also pass through appendix without first storage chamber 13
Road is supplied.
Moreover, first pretreatment unit 10 can further comprise：Liquefied natural gas (LNG) is blown into pipeline 17, and it is used
In further supplying methane into the ironmaking by-product gas containing methane discharged from first storage chamber 13；And desulfurization
Device 19, for going sulphur removal from the liquefied natural gas.
What the ironmaking by-product gas containing methane was produced included in comprehensive iron-smelting process contains a large amount of methane (CH4)
By-product gas, such as coke-stove gas (COG；COKE OVEN GAS).Coke-stove gas also includes hydrogen, an oxygen in addition to methane
Change carbon, carbon dioxide, nitrogen and tar (tar) etc..
Tar, sulphur, ash containing the catalyst poisoning that can make in following conversion reaction devices 40 in this by-product gas
Dirt etc., therefore the material is removed by appropriate purifier 15.
For the refining of by-product gas, dry dust-collecting, wet type dust, cyclone, H can be used2S is controlled and BTX is controlled etc.
Method.
In addition, the yield in order to increase the reducing gas that the ironmaking by-product gas containing methane is converted and manufactured
With reducibility gas (CO, H in reducing gas2) ratio, can be further by the gas (example containing methane being externally supplied
Such as by liquefied natural gas) mixed with the ironmaking by-product gas containing methane by refining.
The mixed proportion of by-product gas as the liquefied natural gas (LNG) being externally supplied and containing methane, can basis
The supply/demand of the by-product gas produced in iron-smelter and the supply/demand of liquefied natural gas and determine.It is thus also possible to
The situation that the ratio that there is a situation where iron-smelter by-product gas is 100% or the liquefied natural gas that is externally supplied is 100%.
When supplying liquefied natural gas, it can further increase desulfurizer 19 and be included in removing in liquefied natural gas
Sulphur.
Second pretreatment unit 20 includes：Second storage chamber 23, it is used to store described containing carbon dioxide
Smelt iron by-product gas；And purifier 25, its be used to refining from second storage chamber 23 discharge containing carbon dioxide
Smelt iron by-product gas.The ironmaking by-product gas containing carbon dioxide can not be stored and direct in the second storage chamber 23
Supplied by pipeline (pipe).
The ironmaking by-product gas containing carbon dioxide can be included in the blast furnace waste gas produced in comprehensive iron-smelting process
(blast furnace offgas), the Reduction on Fluidized Bed furnace exhaust of FINEX techniques, the waste gas of iron-smelter generating equipment, production steel
The furnace exhaust and coke oven heating furnace exhaust of iron product, and comprising substantial amounts of carbon dioxide in these waste gas.
The ironmaking by-product gas containing carbon dioxide is removed by appropriate refinery practice makes conversion reaction device 40
Tar, sulphur and the dust of catalyst poisoning etc..
Moreover, when existing in the by-product gas containing carbon dioxide by refining, substantial amounts of to be not involved in reduction of iron ore anti-
During the inert gases such as the nitrogen answered, the reducibility gas in the reducing gas converted by following conversion reaction devices 40 can be reduced
(CO、H2) concentration, and conversion reaction device 40 can consume excessive heat, therefore can be by being inhaled based on absorption process, transformation
Attached (PSA；Pressure Swing Adsorption) method or diaphragm process etc. carbon dioxide separation device 27 from it is described by essence
After some or all middle separation carbon dioxide of the ironmaking by-product gas containing carbon dioxide of refining, then with containing dioxy
The by-product gas for changing carbon is mixed, so as to reduce the concentration of inert gas.
In addition, when utilizing the absorption process for being used as absorbing liquid with amine, ammonia etc. to separate carbon dioxide, the regeneration of absorbing liquid needs
Heat, and supplied in the high-temp waste gas that these heats can be produced by appropriate heat exchange from conversion reaction device 40.
Can be in mixing by the ironmaking by-product gas containing methane described in refining and the ironmaking by-product containing carbon dioxide
After gas formation mixed gas, the fluidisation of blast furnace (blast furnace) or FINEX techniques is boosted to also using compressor
The operating pressure 3-10Bar of the reduction of iron ore such as former stove device 50.
The mixed gas after boosting is set to be warming up in following conversion reaction devices 40 by heater and heat exchanger
600-1000 DEG C of reaction temperature.Now, some or all of the heat needed for temperature-rise period can be handed over by appropriate heat
Change and supplied in the high-temp waste gas produced from conversion reaction device 40.
In addition, the gaseous mixture of the ironmaking by-product gas containing methane and the ironmaking by-product gas containing carbon dioxide can be made
After body boosts and heated up, some vapor (steam) generated by steam generator is mixed.If by steam with containing methane and
The mixed gas mixing of carbon dioxide, then can reduce carbon (carbon) in conversion reaction device 40 and be deposited over catalyst layer
Phenomenon, and the growing amount of hydrogen can be increased in conversion reaction.
Heat needed for generation in steam it is some or all, can be by appropriate heat exchange from anti-in conversion
The high-temp waste gas produced in device 40 is answered to be supplied.
As for the mol ratio of the methane, carbon dioxide and steam supplied to conversion reaction device 40, when for H2O/CO2Shi You
More than 0 and less than 5 is elected as, when for (H2O+CO2)/CH4When be preferably more than 0.1 and less than 5.
Wherein, why it is defined as above ratio (the i.e. H of steam and carbon dioxide2O/CO2) the reasons why it is as follows：From titanium dioxide
Carbon (CO2) reuse from the aspect of when, steam (H is not supplied2O carbon dioxide (CO) and is only used2) trigger methane and carbon dioxide
Reaction it is most favourable.That is, preferably H2O/CO2=0.
If however, only using CH4/CO2Initiation reaction, then can produce serious Carbon deposition phenomenon, so that meeting on catalyst layer
Operation to reactor brings harmful effect, therefore in order to prevent Carbon deposition from preferably adding moisture.
If moreover, by H2O/CO2Ratio lifted to less than 5, then the Carbon deposition of catalyst layer can be substantially prevented from, if but super
5 are crossed, then Carbon deposition can be caused to prevent effect from reaching saturation state.
In addition, on (H2O+CO2)/CH4Ratio, in general with methane (CH4) reaction steam (H2) and carbon dioxide O
(CO2) ratio it is higher, methane (CH4) conversion ratio it is higher.But, if steam (H2) and carbon dioxide (CO O2) relative to
Methane (CH4) ratio it is too high, then process efficiency and operating cost excessively increase, therefore (H2O+CO2)/CH4Ratio be preferably
More than 0.1 and less than 5.
Main conversion reaction in conversion reaction device 40 is shown below.
CH4+CO2→2CO+2H2····(1)
CH4+H2O→CO+3H2····(2)
The carbon dioxide produced in iron-smelter by above-mentioned reaction equation (1) can be regenerated as carbon monoxide, and being capable of conduct
Reducing gas is reclaimed and reused, therefore, it is possible to which the carbon dioxide produced in iron-smelter is greatly decreased.
The conversion reaction of above-mentioned reaction equation (1) and (2) is that the heat needed for the endothermic reaction, therefore reaction can be in reactor
External jacket is supplied by the burning of fuel.The high-temp waste gas now produced can be discharged to the outside of reactor and as steaming
Heat needed for vapour generator, the heating of mixed gas and the separation of carbon dioxide is used.
Fixed bed (fixed bed) or fluidized-bed reactor can be used in the conversion reaction device 40.Fixed bed reactors
The state configuration of inside reactor is filled in reforming catalyst, and as fluidized-bed reactor, catalyst is in fluidized reactor
Conversion reaction is carried out during internal flow.
The material of platinum or nickel series can be used in catalyst in the conversion reaction device.
The reducing gas of the conversion produced in conversion reaction device 40 keep 3-10Barg pressure and 600-1000 DEG C
Temperature, therefore can just be used as the reducing gas of blast furnace and Reduction on Fluidized Bed stove without extra device.
Hydrogen production device 80 can further comprise：For increasing the hydrogen in the reducing gas containing carbon monoxide
The water-gas shift 83 of content；And for dividing from the reducing gas containing carbon monoxide described in hydrogen is added
From the hydrogen separation device 85 of hydrogen.
More particularly, a part for the reducing gas after conversion can be cooled to after 200-450 DEG C by heat reclamation device 81,
Utilize water-gas shift (WGSR；Water Gas Shift Reactor) 83 increase reducing gas in hydrogen content,
Then hydrogen is isolated by the hydrogen separation device 85 based on pressure-variable adsorption (PSA) method or diaphragm process etc..
The steam generated in the steam generator, which can be fed into water-gas shift 83 and increase hydrogen, to be contained
Amount.
In water-gas shift 83, such as formulas below (3), the carbon monoxide in reducing gas is carried out with steam
React and generate hydrogen and carbon dioxide.
CO+H2O→H2+CO2····(3)
Separated hydrogen is available for being given to the hydrogen market of outside or mixes to increase also with the reducing gas after conversion
Hydrogen content in raw-gas.
When in the Reduction on Fluidized Bed stove in blast furnace or FINEX techniques using a large amount of reducing gas containing hydrogen, due to logical
The reduction rate of iron ore can be improved by crossing hydrogen, therefore, it is possible to improve the speed of production of molten iron and reduced iron.
Now, the waste gas containing carbon dioxide produced in hydrogen separation device 85 can be with the ironmaking pair containing carbon dioxide
Produce gas mixing and be used to generate the reducing gas converted.
Fig. 2 is the forming gas manufacturing process containing carbon monoxide and hydrogen of the utilization iron-smelting process gas of the present invention
Figure.
The synthesis containing carbon monoxide and hydrogen of the utilization iron-smelting process gas of the preferred embodiment of the present invention
The manufacture method of gas comprises the following steps：Pre-process the ironmaking by-product gas containing methane；Pretreatment contains carbon dioxide
Smelt iron by-product gas；Mixing is by the ironmaking by-product gas containing methane of pretreatment and the ironmaking pair containing carbon dioxide
Aerogenesis body and formed after mixed gas, the mixed gas is boosted to predetermined pressure；Make the mixed gas after boosting
It is warming up to predetermined temperature；And supply the mixed gas after heating to conversion reaction device 40 and make the mixed gas
It is converted into the gas containing carbon monoxide and hydrogen.
It is a feature of the present invention that including following step described in the pretreatment the step of ironmaking by-product gas containing methane
Suddenly：Refine the ironmaking by-product gas containing methane；And mixed in the ironmaking by-product gas containing methane by refining
Close liquefied natural gas (LNG).
Now, it is a feature of the present invention that the ironmaking by-product gas containing methane is coke-stove gas (COG, COKE
OVEN GAS)。
It is a feature of the present invention that the step of ironmaking by-product gas of the pretreatment containing carbon dioxide includes following step
Suddenly：Refine the ironmaking by-product gas containing carbon dioxide；And the ironmaking by-product containing carbon dioxide refined from the process
Some or all middle separation carbon dioxide of gas.
It is a feature of the present invention that the ironmaking by-product gas containing carbon dioxide is selected from blast furnace waste gas, FINEX works
Reduction on Fluidized Bed furnace exhaust, the waste gas of iron-smelter generating equipment, the furnace exhaust and coke oven heating for producing steel products of skill
At least one of furnace exhaust.
The ironmaking by-product gas containing carbon dioxide is further useless comprising what is discharged from the conversion reaction device
Gas.
The manufacture method of the forming gas containing carbon monoxide and hydrogen further comprises to mixed after the heating
The step of closing gas supply steam.
Moreover, the manufacture method of the forming gas containing carbon monoxide and hydrogen further comprises as described in converting
The step of part or all of manufacture hydrogen of reducing gas containing carbon monoxide.
The hydrogen manufacturing process comprises the following steps：The cooling reducing gas containing carbon monoxide；By cooling
The reducing gas containing carbon monoxide is converted to reducing gas by Water gas shift/WGS；And turn from by Water gas shift/WGS
Hydrogen is separated in the reducing gas changed.
The forming gas (syngas) containing carbon monoxide and hydrogen can be used as reducing gas for reduction of iron ore
Stone or manufacture dimethyl ether (DME).
Fig. 3 be represent another embodiment of the present invention by using iron-smelting process gas produced contain an oxidation
The forming gas of carbon and hydrogen carrys out the flow chart of the reduction of iron ore system of reducing iron ore.
The restoring method of the iron ore of one embodiment of the invention by by the manufacture method of the forming gas come
The forming gas containing carbon monoxide and hydrogen of manufacture is supplied to reduction of iron ore device, so as to reducing iron ore.
Moreover, it is a feature of the present invention that the reduction of iron ore device is blast furnace or the Reduction on Fluidized Bed of FINEX techniques
Stove.
Embodiments of the invention have been illustrated with reference to above-mentioned, but can in those skilled in the art
This hair can also be implemented in other specific ways in the case where not changing the technological thought and essential features of the present invention by understanding
It is bright.
Therefore, above-described embodiment is schematical explanation in every respect, and should not be construed as limited explanation.This hair
Bright protection domain is defined by claims, is unable to be determined by above-mentioned detailed description.The scope of the present invention should be solved
It is interpreted as including derived all being changed or deformation form by the implication and scope of claims and its equivalents institute.
Claims (22)
1. a kind of manufacture device of the forming gas containing carbon monoxide and hydrogen, including：
First pretreatment unit of the ironmaking by-product gas containing methane；
Second pretreatment of the ironmaking by-product gas containing carbon dioxide for separating and setting with first pretreatment unit is filled
Put；
Steam raising plant, its be used for the ironmaking by-product gas containing methane handled through first pretreatment unit and
Supplied in the mixed gas that the ironmaking by-product gas containing carbon dioxide handled through second pretreatment unit is mixed
Steam；And
Conversion reaction device, it receives the mixed gas containing the steam being supplied to and is allowed to convert, so that will be described
Mixed gas is converted into the gas containing carbon monoxide and hydrogen,
Second pretreatment unit includes：
Second storage chamber, for storing the ironmaking by-product gas containing carbon dioxide；
Purifier, for refining the ironmaking by-product gas containing carbon dioxide discharged from second storage chamber；And
Carbon dioxide separation device, for from by refining described in containing carbon dioxide ironmaking by-product gas a part or
Carbon dioxide is separated in person's whole,
In the waste gas that the steam raising plant and the carbon dioxide separation device are discharged from the conversion reaction device respectively
Thermal source supply is obtained,
And the manufacture device for being somebody's turn to do the forming gas containing carbon monoxide and hydrogen further comprises：
Hydrogen production device, it is used to contain an oxidation by what is converted mixed gas in the conversion reaction device and manufacture
Some or all manufacture hydrogen of the reducing gas of carbon,
The Hydrogen production device further comprises：
Water-gas shift, it is used to increase hydrogen content in the reducing gas containing carbon monoxide；And
Hydrogen separation device, it is used to from the reducing gas containing carbon monoxide described in hydrogen is added separate hydrogen,
The mol ratio of methane, carbon dioxide and steam into the mixed gas of the conversion reaction unit feeding meet with
Following formula (1) and (2),
0≤H2O/CO2≤5····(1)
0.1≤(H2O+CO2)/CH4≤ 5 (2),
A part of hydrogen isolated by the hydrogen separation device by conversion reaction device conversion with containing one
The reducing gas mixing of carbonoxide, and it is supplied to reduction of iron ore device.
2. the manufacture device of the forming gas according to claim 1 containing carbon monoxide and hydrogen, it is characterised in that
The ironmaking by-product gas containing methane is COG (coke-stove gas).
3. the manufacture device of the forming gas according to claim 1 containing carbon monoxide and hydrogen, it is characterised in that
The ironmaking by-product gas containing carbon dioxide is selected from blast furnace waste gas, the Reduction on Fluidized Bed furnace exhaust of FINEX techniques, refining
At least one of the waste gas of ironworks generating equipment, the furnace exhaust and coke oven heating furnace exhaust for producing steel products.
4. the manufacture device of the forming gas according to claim 3 containing carbon monoxide and hydrogen, it is characterised in that
The ironmaking by-product gas containing carbon dioxide further includes the waste gas discharged from the conversion reaction device.
5. the manufacture device of the forming gas according to claim 1 containing carbon monoxide and hydrogen, it is characterised in that
First pretreatment unit includes：
First storage chamber, it is used to store the ironmaking by-product gas containing methane；And
Purifier, it is used to refine the ironmaking by-product gas containing methane discharged from first storage chamber.
6. the manufacture device of the forming gas according to claim 5 containing carbon monoxide and hydrogen, wherein,
First pretreatment unit further comprises：
Liquefied natural gas is blown into pipeline, and it is used for further to the ironmaking pair containing methane discharged from first storage chamber
Aerogenesis body supplies methane；And
Desulfurizer, it is used to go sulphur removal from the liquefied natural gas.
7. the manufacture device of the forming gas according to claim 1 containing carbon monoxide and hydrogen, further comprises：
Increasing apparatus, it is used for the ironmaking by-product gas and the ironmaking manufacture gas containing carbon dioxide containing methane
The mixed gas that body is mixed boosts to the operating pressure of the reduction of iron ore device.
8. the manufacture device of the forming gas according to claim 7 containing carbon monoxide and hydrogen, further comprises：
Heat riser, it is used to make the mixed gas after boosting to heat up to be adapted to the reaction temperature in the conversion reaction device
Degree.
9. the manufacture device of the forming gas according to claim 8 containing carbon monoxide and hydrogen, wherein,
Thermal source supply is obtained in the waste gas that the heat riser is discharged from the conversion reaction device.
10. the manufacture device of the forming gas according to claim 1 containing carbon monoxide and hydrogen, wherein,
The Hydrogen production device further comprises：
Heat reclamation device, it is used to cool down the reducing gas containing carbon monoxide after conversion.
11. the manufacture device of the forming gas according to claim 1 containing carbon monoxide and hydrogen, wherein,
The water-gas shift obtains steam supply from the steam raising plant.
12. the manufacture device of the forming gas according to claim 1 containing carbon monoxide and hydrogen, wherein,
A part of hydrogen separated by the hydrogen separation device is discharged to outside, so as to be used as the use beyond reducing iron ore
Way is used.
13. the manufacture device of the forming gas according to claim 1 containing carbon monoxide and hydrogen, wherein,
The waste gas containing carbon dioxide and the ironmaking manufacture gas containing carbon dioxide discharged from the hydrogen separation device
Body is mixed.
14. a kind of reduction of iron ore system, it is characterised in that
To reduction of iron ore unit feeding by containing carbon monoxide and hydrogen according to any one of claim 1 to 13
The forming gas containing carbon monoxide and hydrogen of the manufacture device manufacture of the forming gas of gas is with reducing iron ore.
15. reduction of iron ore system according to claim 14, wherein,
The reduction of iron ore device is blast furnace or the Reduction on Fluidized Bed stove of FINEX techniques.
16. a kind of manufacture method of the forming gas containing carbon monoxide and hydrogen, comprises the following steps：
Pre-process the ironmaking by-product gas containing methane；
Pre-process the ironmaking by-product gas containing carbon dioxide；
The ironmaking by-product gas containing methane of the mixing by pretreatment and ironmaking by-product gas containing carbon dioxide with
Formed after mixed gas, the mixed gas is boosted to predetermined pressure；
The mixed gas after boosting is set to be warming up to predetermined temperature；
Steam is supplied to the mixed gas after the heating；And
The mixed gas after will heat up is supplied to conversion reaction device and the mixed gas is converted into containing an oxidation
The reducing gas of carbon,
The step of ironmaking by-product gas of the pretreatment containing carbon dioxide, comprises the following steps：
Refine the ironmaking by-product gas containing carbon dioxide；And
From some or all middle separation carbon dioxide of the ironmaking by-product gas containing carbon dioxide by the refining,
In the waste gas that the steam supplying step and the carbon dioxide separation step are discharged from the conversion reaction device respectively
Thermal source supply is obtained,
Methods described further comprises：
The step of part or all of manufacture hydrogen of reducing gas containing carbon monoxide described in after as converting,
Wherein described hydrogen manufacturing process comprises the following steps：
The cooling reducing gas containing carbon monoxide；
Water gas shift/WGS conversion is carried out to the reducing gas containing carbon monoxide described in after cooling；And
Hydrogen is separated from the reducing gas changed by Water gas shift/WGS,
The mol ratio of methane, carbon dioxide and steam into the mixed gas of the conversion reaction unit feeding meet with
Following formula (1), (2),
0≤H2O/CO2≤5····(1)
0.1≤(H2O+CO2)/CH4≤ 5 (2),
By it is separated go out a part of hydrogen mixed with the reducing gas containing carbon monoxide, and for reducing iron ore.
17. the manufacture method of the forming gas according to claim 16 containing carbon monoxide and hydrogen, wherein,
The step of ironmaking by-product gas of the pretreatment containing methane, comprises the following steps：
Refine the ironmaking by-product gas containing methane；And
The mixed liquefied natural gas in by the ironmaking by-product gas containing methane described in refining.
18. the manufacture method of the forming gas according to claim 17 containing carbon monoxide and hydrogen, wherein,
The ironmaking by-product gas containing methane is COG (coke-stove gas).
19. the manufacture method of the forming gas according to claim 16 containing carbon monoxide and hydrogen, wherein,
The ironmaking by-product gas containing carbon dioxide is selected from blast furnace waste gas, the Reduction on Fluidized Bed furnace exhaust of FINEX techniques, refining
At least one of the waste gas of ironworks generating equipment, the furnace exhaust and coke oven heating furnace exhaust for producing steel products.
20. the manufacture method of the forming gas according to claim 19 containing carbon monoxide and hydrogen, wherein,
The ironmaking by-product gas containing carbon dioxide is further comprising the waste gas discharged from the conversion reaction device.
21. a kind of iron ore reduction process, it is characterised in that
To reduction of iron ore unit feeding by according to any one of claim 16 to 20 containing carbon monoxide and
The forming gas containing carbon monoxide and hydrogen of the forming gas manufacture method manufacture of hydrogen is with reducing iron ore.
22. iron ore reduction process according to claim 21, wherein,
The reduction of iron ore device is blast furnace or the Reduction on Fluidized Bed stove of FINEX techniques.
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| KR1020110090306A KR101321072B1 (en) | 2011-09-06 | 2011-09-06 | Apparatus for manufacturing syngas containing co and h2 and method thereof |
| KR10-2011-0090306 | 2011-09-06 | ||
| CN201280043420.7A CN103781724A (en) | 2011-09-06 | 2012-08-27 | Apparatus for producing a synthetic gas including carbon monoxide and hydrogen, and method therefor |
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| CN201710533431.8A Pending CN107128876A (en) | 2011-09-06 | 2012-08-27 | The manufacture device and its manufacture method of forming gas containing carbon monoxide and hydrogen |
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| CN113582214A (en) * | 2021-09-06 | 2021-11-02 | 上海源晗能源技术有限公司 | Green low-carbon closed-loop metallurgy and carbon dioxide capture and utilization process |
| CN115427588A (en) * | 2020-04-27 | 2022-12-02 | 杰富意钢铁株式会社 | Steel-making equipment and method for manufacturing reduced iron |
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| KR102117403B1 (en) * | 2013-07-03 | 2020-06-02 | 재단법인 포항산업과학연구원 | Method of Coke Dry Quenching by using Coke Oven Gas and Recycle Method of Syngas |
| CN104807955B (en) * | 2014-01-24 | 2017-01-04 | 上海华林工业气体有限公司 | Improve and produce the method that the hydrogen of hydrogen and carbon monoxide device analyzes detection rates |
| CN104058368B (en) * | 2014-06-10 | 2015-09-23 | 中国五环工程有限公司 | A kind of hydrocarbonaceous tail gas reforming process and system |
| KR101626602B1 (en) * | 2014-12-05 | 2016-06-01 | 주식회사 포스코 | Method for compacting fine reduced irons, apparatus for compacting fine reduced irons, and apparatus for manufacturing molten iron comprising the same |
| KR101758521B1 (en) * | 2015-12-23 | 2017-07-17 | 주식회사 포스코 | Apparatus and Method of Recycling and Decomposition of Carbon Dioxide via Accumulated Energy of Hot Stove |
| CN106276795A (en) * | 2016-08-03 | 2017-01-04 | 西南化工研究设计院有限公司 | A kind of group technology utilizing coke-stove gas extraction metallurgy reducing gases |
| WO2018187213A1 (en) * | 2017-04-03 | 2018-10-11 | Qatar Foundation For Education, Science And Community Development | System and method for carbon and syngas production |
| KR101974562B1 (en) * | 2017-06-22 | 2019-05-02 | 주식회사 포스코 | Method for treating byproduct |
| KR102072506B1 (en) * | 2017-12-20 | 2020-02-03 | 재단법인 포항산업과학연구원 | The catalyst for direct synthesis of hydrocarbon and alcohol from syngas, the method of the same and the direct synthesis method of hydrocarbon and alcohol from syngas by using the same |
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| WO2013035998A2 (en) | 2013-03-14 |
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