CN106553996B - A kind of methanation dry reforming coupling production CO, H2Method and device - Google Patents
A kind of methanation dry reforming coupling production CO, H2Method and device Download PDFInfo
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- CN106553996B CN106553996B CN201510639569.7A CN201510639569A CN106553996B CN 106553996 B CN106553996 B CN 106553996B CN 201510639569 A CN201510639569 A CN 201510639569A CN 106553996 B CN106553996 B CN 106553996B
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- 238000002407 reforming Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
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- 239000003054 catalyst Substances 0.000 claims description 17
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 230000003009 desulfurizing effect Effects 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 239000003034 coal gas Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- 238000009628 steelmaking Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003345 natural gas Substances 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 229910017318 Mo—Ni Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims 2
- 238000005804 alkylation reaction Methods 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
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- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000013589 supplement Substances 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 description 37
- 239000001569 carbon dioxide Substances 0.000 description 13
- -1 ethylene, propylene Chemical group 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 8
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- 239000002002 slurry Substances 0.000 description 3
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- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention belongs to the preparation fields of synthesis gas, and in particular to a kind of methanation dry reforming coupling production CO, H2Method and device.Described methanation dry reforming coupling production CO, H2Method include the following steps：(1) thick desulfurization；(2) it detaches；(3) fine de-sulfur；(4) methanation；(5) it converts.The present invention has H in Product Process gas2, CO contents it is high, the features such as simple for process, low energy consumption, does not need to setting producing steam equipment, and reaction system not supplement vapor.
Description
Technical field
The invention belongs to the preparation fields of synthesis gas, and in particular to a kind of methanation dry reforming coupling production CO, H2Side
Method and device.
Background technology
Hydrogen, carbon monoxide are important chemical resource, widely used, and the method for producing them at present is numerous, such as hydro carbons
Steam conversion (reformation), sulphur-resistant conversion, hydrocarbon vapours cracking, partial oxidation process etc..
Current industrialized hydrocarbon steam conversion H2, there are operating flexibility is small, energy consumption is big, equipment for CO synthesis gas processes
The shortcomings of bulky complex and expensive operating cost.H is produced by sulphur-resistant conversion as raw material using coal, petroleum coke2, CO synthesis gas work
Skill, equipment investment is high, and technological process is complicated.Hydrocarbon vapours cracking is generally employed to produce the alkene resource such as ethylene, propylene, H2、 CO
Only its byproduct.Partial oxidation process using gaseous hydrocarbons such as natural gas, oven gas as raw material, needs to be incorporated in process gas certain
The O of amount2, the investment of air separation plant is huge, and the achievement that air separation plant shortage is run steadily in the long term.
Carbon dioxide is one of the main reason for causing greenhouse effects, global climate is caused to deteriorate.Limit carbon dioxide
The development that discharge will largely influence modern industry and world economy.Therefore carbon dioxide how is effectively utilized to cause
The extensive concerns of countries in the world.
Invention content
In order to reduce CO2 emissions, utilized carbon dioxide as industrial chemicals；Meanwhile to overcome above-mentioned technique
The shortcomings that method, a kind of equipment investment of present invention offer is moderate, and flow is relatively easy, by the methanation of carbon monoxide, carbon dioxide
Add the coupling production of methanation dry reforming CO, H that the reactions such as hydrogen, methane carbon dioxide reformation couple2Method and device, have
H in Product Process gas2, CO contents it is high, simple for process, low energy consumption, does not need to setting producing steam equipment, and reaction system not supplement
The features such as vapor.
A kind of methanation dry reforming coupling production CO, H2Method, include the following steps：
(1) thick desulfurization：One or both of reduction tail gas after ironmaking, the coal gas generated in steelmaking process, conversion warp
Water removal, dedusting and thick desulfurization process；
Water removal, dedusting can be used industrial common technique, and the thick sulfur removal technology used is industrially common thick at present
Sulfur removal technology, such as ammonia process, Benfield method, low-temp methanol wash method, and the sulphur compound after thick desulfurization in process gas is reduced to
Below 20ppm.
(2) it detaches：A process gas part after thick desulfurization enters burning line, as the fuel of reburner, the overwhelming majority
Process gas enters centrifugal station, completes logistics separation herein；
(3) fine de-sulfur：High methane gas is mixed into the hydrogenation reactor of fine de-sulfur workshop section with the hydrogen in logistics, after adding hydrogen
Material and CO, CO from centrifugal station2Mixing completes fine de-sulfur by the first desulfurizer connected and the second desulfurizer；
High methane gas exchanges heat with heat exchanging segment of the hydrogen mixed gas in logistics in reburner with flue gas, by hydrogenation catalyst
Reaction temperature raising.
The high methane gas is one or more in natural gas, shale gas, casing-head gas and oven gas, in hydrogenation reaction
Saturated hydrogenation and hydrodesulfurization are completed in device, sulphur compound is hydrogenated into as hydrogen sulfide.
The hydrogenation reactor epimere uses nickel molybdenum or cobalt Mo-Ni catalyst, and hypomere uses cobaltmolybdate catalyst, is added with improving
Hydrogen precision.
First desulfurizer uses Zinc oxide desulfurizer, and the second desulfurizer uses combination loading, epimere filling zinc oxide
Desulfurizing agent, the copper-based whole grade desulfurizing agent of hypomere filling；By copper-based ultimate desulfurizing agent, the sulfur content in gaseous mixture B is reduced to
Below 20ppb.
(4) methanation：Material after fine de-sulfur enters methanator；
The methanation reaction based on CO is carried out in methanator, there is a small amount of CO2Also assist in methanation reaction.First
Process gas after alkanisation, component CH4、CO、CO2、H2、H2O.To reduce the formation of carbonyl nickel, optimization methane reactor enters
Mouth feeding temperature is 295-300 DEG C；Reaction depth in order to control, methanator are preferably shell and tube reactor, manage interior load
There is Ni-based methanation catalyst, pipe is outside heat-conducting medium, such as conduction oil, water, steam, heat of reaction is taken away, so as to control
Reactor outlet temperature is no more than 550 DEG C, and preferably control range is 520-550 DEG C, in case high concentration CO occurs in high-temperature area
More CO is disproportionated charcoal.
(5) it converts：Process gas after methanation can heat up with or without reburner heat exchanging segment, into reburner, turn
Mouth is dissolved to obtain containing CO, H2Process gas.
The reaction carried out in reburner is extremely complex, mainly there is following reaction：
CH4+CO2=2CO+2H2 (1)
CH4+H2O=CO+3H2 (2)
CO+H2O=CO2+H2 (3)
Wherein reaction (1) is main reaction.In addition numerous side reactions are also accompanied by, it is known that have：
CO2+H2→CO+H2O (4)
CO2+4H2→CH4+2H2O (5)
2CH4→C2H2+3H2 (6)
C2H2→2C+H2 (7)
2CO→C+CO2 (8)
CH4→C+2H2 (9)
The component of conversion outlet process gas is CH4、CO、CO2、H2、H2O, wherein CO, H2It is total to account for logistics mole total amount
88-91%.
Reburner is L-type stove or inverted L shape stove, and during using L-type stove, feeding manner is upper entering and lower leaving, and heat is provided for reaction
Flame combustion chamber draft effect under burn vertically downward；During using inverted L shape stove, feeding manner is bottom in and top out, is carried for reaction
The flame of heating load burns upwards.The result of reaction is not interfered with using above-mentioned 2 kinds of type of furnaces.
Reburner inlet temperature preferred scope is 520~580 DEG C, and temperature is feasible, but can influence to exchange heat less than 520 DEG C
The design of section wastes the heat recovery ability of heat exchanging segment, so as to cause uneconomical.
Heater outlet temperature is converted, related with the specifically needs of owner, usual process gas is used as metallurgical reduction gas, it is desirable that
(H2+CO)/(H2+CO+CH4+CO2+H2O) >=90%, high as far as possible this requires converting outlet temperature, outlet temperature is higher,
H in process gas2, CO contents just can be higher, therefore convert outlet temperature preferably should be greater than 850 DEG C, it is contemplated that existing boiler tube
The limitation of material, outlet temperature should be≤980 DEG C, in case boiler tube service life is too short, if following have the better stove of high temperature resistance
Tube material occurs, then preferably using it, and outlet temperature is improved as far as possible, with fully by CH4、CO2It is converted into effective gas
(H2、CO)。
Using the process gas of step (5) conversion outlet as metallurgical reduction gas, do not cool down, be introduced directly into blast furnace；Ironmaking, steel-making
Reduction tail gas after the coal gas that generates in the process, conversion returns to thick desulfurization workshop section.
It is a kind of to realize described methanation dry reforming coupling production CO, H2The device of method, including sequentially connected thick de-
Sulphur device, separator, hydrogenation reactor, the first desulfurizer, the second desulfurizer, methanator and reburner, and it is thick de-
Sulphur device is also connected with the burning line of reburner, and separator is also connect with the first desulfurizer.
Preferably, described device further includes the blast furnace being connected with conversion outlet of still, and blast furnace is also filled with thick desulfurization
It puts and is connected.
It is of the present invention be rich in methane, carbon monoxide, carbon dioxide hydrocarbon raw material carry out carbon monoxide methane
Change, hydrogenation of carbon dioxide, methane and carbon dioxide reform the technique effect that the principle of coupling technique illustrates and obtains：
For the catalyst of methane and carbon dioxide dry reforming reaction at present also in conceptual phase, lacking ripe catalyst should
With.It is general to require (H as metallurgical reduction gas2+CO)/(H2+CO+CH4+CO2+H2O) >=90%, it is incorporated in reaction system more
In the case of water (such as hydrocarbon steam conversion reaction), it is unable to reach the requirement of this process gas.Therefore only try as far as possible
Reduce H2O/CH4Ratio.Blast furnace top discharge coal gas, conversion after reduction tail gas also have a large amount of CO, H2, it is recycled utilization
It is relatively inexpensive means.It is found by experiment that when reburner inlet process temperature degree is higher, if temperature is higher than 450 DEG C, if
Without methanation workshop section, and fine desulfurizing technology gas is directly introduced into reburner, then it is very fierce to occur on transforming agent
Methanation reaction, reaction is initially leading by CO, and the reaction bed temperature of inlet can rise rapidly and more than 600 DEG C,
More than 580 DEG C of temperature CO can be significantly observed2Hydrogenation reaction, which is strong exothermal reaction, so as to cause catalyst bed
Temperature continues to rise, and in the case, the CO not reacted in time can generate a large amount of disproportionation charcoals, blocking pipeline.It is and of the invention
The methanation of carbon monoxide, hydrogenation of carbon dioxide, methane and carbon dioxide are reformed these reactions to be coupled together, utilize methanation
Reaction, on the one hand reduces the CO contents in fine desulfurizing technology gas, and one side methanation reaction generates a small amount of water.So as to keep away
The CO disproportionation charcoals of reburner entrance are exempted from, and transforming agent have been helped to disappear charcoal by the water of this portion of methaneization reaction generation, will convert
The reaction occurred in stove is changed into methane and carbon dioxide steam reaction, reduces the difficulty of methane carbon dioxide reformation, overcomes
Existing catalyst technical barrier easily coking in methane and carbon dioxide dry reforming reaction process；So that on entire reaction process
It does not need to additionally supplement vapor, it is not required that setting steam gives up pot, saves equipment investment.
Description of the drawings
Fig. 1 is methanation dry reforming coupling production CO, H described in the embodiment of the present invention 12Process flow chart.
Fig. 2 is methanation dry reforming coupling production CO, H described in the embodiment of the present invention 22Process flow chart.
Specific embodiment
Below in conjunction with attached drawing, the invention will be further described：
Embodiment 1
As shown in Figure 1, the reduction tail gas after the coal gas generated in ironmaking, steelmaking process, conversion is by removing water, dedusting, slightly
After desulfurization, the sulphur compound in process gas is reduced to 20ppm hereinafter, contained humidity is the saturated water under operation temperature.
A process gas part after thick desulfurization enters burning line, the fuel as reburner；Most process gas into
Enter centrifugal station, complete logistics separation herein.(natural gas, shale gas, casing-head gas, oven gas etc. are rich in the hydrocarbon of methane to unstripped gas
Class gas) with the hydrogen in logistics be mixed into the hydrogenation reactor entrance of fine de-sulfur workshop section, carry out alkene saturated hydrogenation and
Sulphur compound adds hydrogen；CO, CO in logistics2The desulfurizer of fine de-sulfur workshop section is then directly entered, in order to avoid sent out in hydrogenation reactor
Raw CO, CO2Methanation reaction.
Add raw material and CO, CO from centrifugal station after hydrogen2The first desulfurizer and the second desulfurizer that mixing passes through series connection
Complete fine de-sulfur.
Zinc oxide desulfurizer is used in the first desulfurizer；Combination loading, epimere filling zinc oxide are used in the second desulfurizer
Desulfurizing agent, in the copper-based whole grade desulfurizing agent of hypomere filling.By copper-based ultimate desulfurizing agent, the sulfur content in gaseous mixture is reduced to
Below 20ppb.
Unstripped gas after desulfurization, pressure 0.4MPa, flow 20000Nm3(component is /h：CO 22%, H240.5%,
CO217.5%, methane 20% only contains saturated water) into methanator, the methanation carried out based on CO herein is anti-
Should, there is a small amount of CO2Also assist in methanation reaction.Process gas after methanation, pressure 0.35MPa, flow 15000Nm3/ h, component
For CH442.8%th, CO 6.8%, CO229.2%th, H210.8%th, H2O 10.3%.To reduce the formation of carbonyl nickel, methanation
The entrance feeding temperature of reactor is controlled at 295 DEG C；Reaction depth in order to control, methanator are preferably tubular reaction
Device, is filled with Ni-based methanation catalyst KLJ-101 in pipe, and pipe is outer for heat-conducting medium, and heat of reaction is taken away, controls reactor
520 DEG C of outlet temperature.
Process gas after methanation is after the heating of reburner heat exchanging segment, into reburner, using CN102380394A institutes
Catalyst is stated, converts inlet pressure 0.33MPa, 580 DEG C, outlet pressure 0.20MPa of temperature, 980 DEG C of temperature is obtained with CO, H2
Based on 26800Nm3(component is /h gaseous mixtures：CH42.1%, CO 42%, H255.5%, surplus CO2And H2O), gas group
Divide and meet (H2+CO)/(H2+CO+CH4+CO2+H2O requirement) >=90%, can be used for blast furnace.
In above-mentioned reaction process, the catalyst used is the product of research institute of sinopec asphalt in Shenli Refinery exploitation,
In, the copper-based ultimate desulfurizing agent is made by following step：1366.7g Cu (NO3)2·3H2O, 1644.8g Zn (NO3)2·
6H2O, 294.3g Al (NO3)3·9H2O, 55.1g Zr (NO3)4·5H2O is soluble in water, is configured to the mixed solution A of 10L.
By 1593.0g Na2CO3It is configured to 10L solution Bs.Solution A is warming up to 85 DEG C, solution B is warming up to 80 DEG C.Solution B is placed in
In reaction kettle, turn on agitator, ultrasonic wave, ultrasonic frequency 50KHz, sound intensity 0.5W/cm2, mixing speed, which controls, to exist
0.30rad/s.Solution A is added drop-wise in solution B with 85 minutes, neutralization precipitation, rate of addition 125mL/min.It is added dropwise
After, it is 50KHz, sound intensity 1W/cm in ultrasonic frequency2Under, stirring 30 minutes is maintained, with the pH value of Accurate pH measurement slurries
It is 9.Slurries static aging 2h under 80 DEG C of temperature condition.Slurries are washed using filter washing equipment, use 80 DEG C
Deionized water is washed repeatedly, filter cake it is washed to 0.1% concentration diphenylamines sulphate reagent titration for it is colourless when, it is believed that have reached
Wash terminal.Filter cake is sent into roaster, is heated to 650 DEG C, carries out the dehydration and decomposition of 4h, constant temperature after 120 DEG C of dryings for 24 hours
4h is to get to semi-finished product.500g semi-finished product are taken, add in 15g graphite, ball milling crosses 120 mesh sieve after 15 minutes.Take the object after sieving
Material adds in 80g H2O is uniformly mixed, rolls, and is granulated, and crosses 20 mesh sieve.The material after sieving is taken, with molding machine compression moulding.
Embodiment 2
As shown in Fig. 2, the reduction tail gas after the coal gas generated in ironmaking, steelmaking process, conversion is by removing water, dedusting, slightly
After desulfurization, the sulphur compound in process gas is reduced to 20ppm hereinafter, contained humidity is the saturated water under operation temperature.
A process gas part after thick desulfurization enters burning line, the fuel as reburner；Most process gas into
Enter centrifugal station, complete logistics separation herein.(natural gas, shale gas, casing-head gas, oven gas etc. are rich in the hydrocarbon of methane to unstripped gas
Class gas) with the hydrogen in logistics be mixed into the hydrogenation reactor entrance of fine de-sulfur workshop section, carry out alkene saturated hydrogenation and
Sulphur compound adds hydrogen；CO, CO in logistics2The desulfurizer of fine de-sulfur workshop section is then directly entered, in order to avoid sent out in hydrogenation reactor
Raw CO, CO2Methanation reaction.
Add raw material and CO, CO from centrifugal station after hydrogen2The first desulfurizer and the second desulfurizer that mixing passes through series connection
Complete fine de-sulfur.
Zinc oxide desulfurizer is used in the first desulfurizer；Combination loading, epimere filling zinc oxide are used in the second desulfurizer
Desulfurizing agent, in the copper-based whole grade desulfurizing agent of hypomere filling.By copper-based ultimate desulfurizing agent, the sulfur content in gaseous mixture is reduced to
Below 20ppb.
Unstripped gas after desulfurization, pressure 0.4MPa, flow 20000Nm3(component is /h：CO 22%, H240.5%,
CO217.5%, methane 20% only contains saturated water) into methanator, the methanation carried out based on CO herein is anti-
Should, there is a small amount of CO2Also assist in methanation reaction.Process gas after methanation, pressure 0.35MPa, flow 15600Nm3/ h, component
For CH439.7%th, CO 10.1%, CO226.5%th, H213.7%th, H2O 10%.To reduce the formation of carbonyl nickel, methanation is anti-
The entrance feeding temperature of device is answered to control at 300 DEG C；Reaction depth in order to control, methanator are preferably shell and tube reactor,
Ni-based methanation catalyst KLJ-101 is filled in pipe, outer pipe is heat-conducting medium, and heat of reaction is taken away, and control reactor goes out
550 DEG C of temperature of mouth.
After process gas after methanation heats up without reburner heat exchanging segment, reburner is directly entered, is used
Catalyst described in CN102380394A converts inlet pressure 0.33MPa, 520 DEG C, outlet pressure 0.20MPa of temperature, temperature 800
DEG C, it obtains with CO, H2Based on 25000m3(component is /h gaseous mixtures：CH45.9%, CO 40.7%, H251.5%, surplus is
CO2And H2O), gas component meets (H2+CO)/(H2+CO+CH4+CO2+H2O requirement) >=90%, can be used for blast furnace.
In above-mentioned reaction process, the catalyst used is the product of research institute of sinopec asphalt in Shenli Refinery exploitation,
In, the copper-based ultimate desulfurizing agent preparation method is same as Example 1, and so it will not be repeated.
Claims (10)
1. a kind of methanation dry reforming coupling production CO, H2Method, which is characterized in that include the following steps：
(1) thick desulfurization：One or both of reduction tail gas after ironmaking, the coal gas generated in steelmaking process, conversion through water removal,
Dedusting and thick desulfurization process；
(2) it detaches：A process gas part after thick desulfurization enters burning line, as the fuel of reburner, most techniques
Gas enters centrifugal station, completes logistics separation herein；
(3) fine de-sulfur：High methane gas is mixed into the hydrogenation reactor of fine de-sulfur workshop section with the hydrogen detached from centrifugal station,
Add the material after hydrogen and CO, CO from centrifugal station2Mixing completes essence by the first desulfurizer connected and the second desulfurizer
Desulfurization；
(4) methanation：Material after fine de-sulfur enters methanator；
(5) it converts：Process gas after methanation can heat up with or without reburner heat exchanging segment, into reburner, be converted to
Mouth is obtained containing CO, H2Process gas.
2. methanation dry reforming coupling production CO, H according to claim 12Method, which is characterized in that the high methane gas
It is one or more in natural gas, shale gas, casing-head gas and oven gas.
3. methanation dry reforming coupling production CO, H according to claim 12Method, which is characterized in that in step (3) plus
Hydrogen reactor epimere uses nickel molybdenum or cobalt Mo-Ni catalyst, and hypomere uses cobaltmolybdate catalyst.
4. methanation dry reforming coupling production CO, H according to claim 12Method, which is characterized in that institute in step (3)
The first desulfurizer is stated using Zinc oxide desulfurizer, the second desulfurizer uses combination loading, epimere filling Zinc oxide desulfurizer, hypomere
Load copper-based whole grade desulfurizing agent.
5. methanation dry reforming coupling production CO, H according to claim 12Method, which is characterized in that first in step (4)
Alkylation reactors are shell and tube reactor, manage in the Ni-based methanation catalyst of filling, pipe is outer for heat-conducting medium, and entrance is into material temperature
It is 295-300 DEG C to spend, and outlet temperature is 520-550 DEG C.
6. methanation dry reforming coupling production CO, H according to claim 12Method, which is characterized in that reburner is L-type
Stove or inverted L shape stove, during using L-type stove, feeding manner is upper entering and lower leaving, and the flame that heat is provided for reaction is acted in combustion chamber draft
Under burn vertically downward；During using inverted L shape stove, feeding manner is bottom in and top out, and the flame that heat is provided for reaction burns upwards.
7. methanation dry reforming coupling production CO, H according to claim 12Method, which is characterized in that reburner entrance temperature
It is 520~580 DEG C to spend, and outlet temperature is more than 850 DEG C.
8. methanation dry reforming coupling production CO, H according to claim 12Method, which is characterized in that by step (5) turn
The process gas of mouth is dissolved as metallurgical reduction gas, does not cool down, is introduced directly into blast furnace；Ironmaking, turns the coal gas generated in steelmaking process
Reduction tail gas after change returns to thick desulfurization workshop section.
9. a kind of methanation dry reforming coupling production CO, H described in realization claim 1-8 any one2The device of method, it is special
Sign is, including sequentially connected thick desulfurizer, separator, hydrogenation reactor, the first desulfurizer, the second desulfurizer, first
Alkylation reactors and reburner, and thick desulfurizer is also connected with the burning line of reburner, separator is also de- with first
Sulphur slot connects.
10. methanation dry reforming coupling production CO, H according to claim 92Device, which is characterized in that further include with turn
Change the blast furnace that outlet of still is connected, and blast furnace is also connected with thick desulfurizer.
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