CN106553996A - A kind of coupling of methanation dry reforming production CO, H2Method and device - Google Patents
A kind of coupling of methanation dry reforming production CO, H2Method and device Download PDFInfo
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- CN106553996A CN106553996A CN201510639569.7A CN201510639569A CN106553996A CN 106553996 A CN106553996 A CN 106553996A CN 201510639569 A CN201510639569 A CN 201510639569A CN 106553996 A CN106553996 A CN 106553996A
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- 238000002407 reforming Methods 0.000 title claims abstract description 22
- 230000008878 coupling Effects 0.000 title claims abstract description 21
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
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- 239000010949 copper Substances 0.000 claims description 10
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- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 239000003034 coal gas Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003345 natural gas Substances 0.000 claims description 5
- 238000009628 steelmaking Methods 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 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
- 239000003643 water by type Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000013589 supplement Substances 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 229910001868 water Inorganic materials 0.000 description 27
- 229960004424 carbon dioxide Drugs 0.000 description 14
- 239000001569 carbon dioxide Substances 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 9
- -1 natural gas Chemical class 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000008246 gaseous mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
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- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
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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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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the preparation field of synthesis gas, and in particular to a kind of coupling of methanation dry reforming production CO, H2Method and device.The described coupling of methanation dry reforming production CO, H2Method comprise the following steps：(1) thick desulfurization；(2) separate；(3) fine de-sulfur；(4) methanation；(5) convert.The present invention has H in Product Process gas2, CO contents it is high, process is simple, energy consumption are low, it is not necessary to arrange producing steam equipment, the features such as reaction system should not supplement vapor.
Description
Technical field
The invention belongs to the preparation field of synthesis gas, and in particular to a kind of coupling of methanation dry reforming production CO, H2Method and
Device.
Background technology
Hydrogen, carbon monoxide are important chemical resources, of many uses, and the method for producing them at present is numerous, such as hydrocarbon vapours
Conversion (reformation), sulphur-resistant conversion, hydrocarbon vapours cracking, partial oxidation process etc..
Industrialized hydrocarbon steam conversion H at present2, CO synthesis gas processes have that operating flexibility is little, energy consumption is big, equipment is huge
The shortcomings of big complicated and operating cost costliness.H is produced by sulphur-resistant conversion as raw material with coal, petroleum coke2, CO synthesis gas work
Skill, equipment investment are high, and technological process is complicated.Hydrocarbon vapours cracking is generally employed to produce the alkene resource such as ethene, propylene, H2、
CO is its byproduct.Partial oxidation process, with gaseous hydrocarbons such as natural gas, oven gas as raw material, needs allocate one in process gas into
Quantitative O2, the investment of air separation plant is huge, and air separation plant lacks the achievement of operation steady in a long-term.
Carbon dioxide is to cause greenhouse effects, the one of the main reasons for causing global climate to deteriorate.Limit being emitted on for carbon dioxide
The development of modern industry and World Economics will be affected largely.Therefore how effectively utilizing carbon dioxide, to cause the world each
The extensive concern of state.
The content of the invention
In order to reduce CO2 emissions, utilize carbon dioxide as industrial chemicals；Meanwhile, to overcome above-mentioned process
Shortcoming, the present invention provides that a kind of equipment investment is moderate, and flow process is relatively easy, by the methanation of carbon monoxide, hydrogenation of carbon dioxide,
Methanation dry reforming coupling production CO, H of the reaction coupling such as methane carbon dioxide reformation2Method and device, which has product
H in process gas2, CO contents it is high, process is simple, energy consumption are low, it is not necessary to arrange producing steam equipment, and reaction system should not be supplemented
The features such as vapor.
A kind of coupling of methanation dry reforming production CO, H2Method, which comprises the following steps：
(1) thick desulfurization：One or two Jing eliminating waters in ironmaking, the coal gas produced in steelmaking process, the reduction tail gas after conversion,
Dedusting and thick desulfurization process；
Eliminating water, dedusting can adopt industrial common technique, the thick sulfur removal technology for adopting to be industrial common thick desulfurization work at present
Skill, such as ammonia process, Benfield method, low-temp methanol wash method etc., the sulphur compound Jing after thick desulfurization in process gas be reduced to 20ppm with
Under.
(2) separate：Process gas after thick desulfurization are partly into burning line, used as the fuel of reburner, most techniques
Gas enters centrifugal station, and here completes logistics separation；
(3) fine de-sulfur：Hydrogen in high methane gas and logistics is mixed into the hydrogenation reactor of fine de-sulfur workshop section, the thing after hydrogenation
Expect and from CO, CO of centrifugal station2Mix the first desulfurizer and the second desulfurizer by connecting and complete fine de-sulfur；
High methane gas is exchanged heat with flue gas in the heat exchanging segment of reburner with the hydrogen mixed gas in logistics, by the reaction of hydrogenation catalyst
Temperature is raised.
One or more in natural gas, shale gas, casing-head gas and oven gas of the high methane gas, in hydrogenation reactor
Saturated hydrogenation and hydrodesulfurization are completed, sulphur compound hydrogenation is become into hydrogen sulfide.
The hydrogenation reactor epimere uses nickel molybdenum or cobalt Mo-Ni catalyst, and hypomere uses cobaltmolybdate catalyst, to improve hydrogenation precision.
First desulfurizer uses Zinc oxide desulfurizer, the second desulfurizer to use combination loading, epimere to load Zinc oxide desulfurizer,
Hypomere loads copper-based whole level desulfurizing agent；By copper-based ultimate desulfurizing agent, the sulfur content in gaseous mixture B is reduced to into below 20ppb.
(4) methanation：Material after fine de-sulfur enters methanator；
The methanation reaction based on CO is carried out in methanator, has a small amount of CO2Also assist in methanation reaction.Methane
Process gas after change, component are CH4、CO、CO2、H2、H2O.To reduce the formation of carbonyl nickel, optimization methaneization reaction
The entrance feeding temperature of device is 295-300 DEG C；To control reaction depth, methanator is preferably shell and tube reactor, in pipe
Ni-based methanation catalyst is filled with, it is heat-conducting medium that pipe is outer, such as conduction oil, water, steam etc., and heat of reaction is taken away, from
And control reactor outlet temperature and be less than 550 DEG C, preferred control range is 520-550 DEG C, in case high concentration CO is in high-temperature region
There is more CO and is disproportionated charcoal in domain.
(5) convert：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.
The reaction carried out in reburner is extremely complex, mainly has following reaction：
CH4+CO2=2CO+2H2 (1)
CH4+H2O=CO+3H2 (2)
CO+H2O=CO2+H2 (3)
It is main reaction wherein to react (1).Be also accompanied by numerous side reactions in addition, 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 always to account for logistics mole
The 88-91% of amount.
Reburner is L-type stove or inverted L shape stove, and during using L-type stove, feeding manner is upper entering and lower leaving, provides heat for reaction
Flame is burnt under combustion chamber draft effect vertically downward；During using inverted L shape stove, feeding manner is bottom in and top out, is provided for reaction
The flame of heat 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 less than 520 DEG C, but can affect heat exchanging segment
Design, wastes the heat recovery ability of heat exchanging segment, uneconomical so as to cause.
Conversion heater outlet temperature, relevant with the concrete needs of owner, usual process gas are used as metallurgical reduction gas, it is desirable to
(H2+CO)/(H2+CO+CH4+CO2+H2O) >=90%, this requires that conversion outlet temperature is high as far as possible, and 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 stove
The restriction of tube material, outlet temperature answer≤980 DEG C, in case boiler tube service life is too short, if there is the more preferable stove of resistance to elevated temperatures in future
Tube material occurs, then preferably adopt it, and improve outlet temperature as far as possible, with fully by CH4、CO2It is converted into effective gas
(H2、CO)。
Step (5) is converted the process gas of outlet as metallurgical reduction gas, is not lowered the temperature, is introduced directly into blast furnace；Smelt iron, made steel
Reduction tail gas after the coal gas that produces in journey, conversion returns thick desulfurization workshop section.
One kind realizes the described coupling of methanation dry reforming production CO, H2The device of method, which includes the thick desulfurization dress being sequentially connected
Put, separator, hydrogenation reactor, the first desulfurizer, the second desulfurizer, methanator and reburner, and thick desulfurization
Device is also connected with the burning line of reburner, and separator is also connected with the first desulfurizer.
Preferably, described device also includes the blast furnace being connected with conversion outlet of still, and blast furnace is also connected with thick desulfurizer
Connect.
It is of the present invention with rich in methane, carbon monoxide, carbon dioxide hydrocarbon raw material carry out the methanation of carbon monoxide, two
Carbonoxide hydrogenation, the principle explanation of methane and carbon dioxide reformation coupling technique and the technique effect for obtaining：
The catalyst of methane and carbon dioxide dry reforming reaction also in conceptual phase, lacks ripe catalyst application at present.As
Metallurgical reduction gas are general to require (H2+CO)/(H2+CO+CH4+CO2+H2O) >=90%, the feelings of more water are allocated in reaction system
Under condition (as hydrocarbon steam conversion is reacted), it is unable to reach this process gas and requires.Therefore only try to reduce as far as possible
H2O/CH4Ratio.Blast furnace top discharge coal gas, conversion after reduction tail gas also have a large amount of CO, H2, being recycled to utilize is
Relatively inexpensive means.It is found by experiment that when reburner inlet process temperature degree is higher, such as temperature is higher than 450 DEG C, if not
Through methanation workshop section, and fine desulfurizing technology gas is introduced into reburner directly, then very fierce methane can occur on transforming agent
Change reaction, reaction is initially leading by CO, and the reaction bed temperature of porch can rise rapidly and more than 600 DEG C, at 580 DEG C
More than temperature substantially can observe there is CO2Hydrogenation reaction, the reaction be strong exothermal reaction, so as to cause reaction bed temperature after
Continuous to rise, in the case, the CO not reacted in time can produce a large amount of disproportionation charcoals, blocking pipeline.And the present invention is by one
Carbonoxide methanation, hydrogenation of carbon dioxide, methane and carbon dioxide these reactions of reforming are coupled together, using methanation reaction,
On the one hand the CO contents in fine desulfurizing technology gas are reduced, one side methanation reaction generates a small amount of water.So as to avoid
The CO disproportionation charcoals of reburner entrance, and the water generated by the reaction of this portion of methaneization helps transforming agent to disappear charcoal, by reburner
The reaction of generation is changed into methane and carbon dioxide steam reaction, reduces the difficulty of methane carbon dioxide reformation, overcomes existing urging
The easily coking technical barrier in methane and carbon dioxide dry reforming course of reaction of agent；So that not needing volume on whole reaction process
Outer supplementary vapor, it is not required that the useless pot of steam is set, equipment investment is saved.
Description of the drawings
Fig. 1 is methanation dry reforming coupling production CO, H described in the embodiment of the present invention 12Process chart.
Fig. 2 is methanation dry reforming coupling production CO, H described in the embodiment of the present invention 22Process chart.
Specific embodiment
Below in conjunction with accompanying drawing, the invention will be further described：
Embodiment 1
As shown in figure 1, the reduction tail gas after the coal gas produced in ironmaking, steelmaking process, conversion is through eliminating water, dedusting, it is thick de-
After sulphur, the sulphur compound in process gas is reduced to into below 20ppm, contained humidity is the saturation water under operation temperature.
Process gas after thick desulfurization are partly into burning line, used as the fuel of reburner；Most process gas are entered and are separated
Workshop section, here complete logistics separation.Unstripped gas (the hydro carbons gas rich in methane such as natural gas, shale gas, casing-head gas, oven gas
Body) the hydrogenation reactor entrance of fine de-sulfur workshop section is mixed into the hydrogen in logistics, the saturated hydrogenation and sulfuration for carrying out alkene is closed
The hydrogenation of thing；CO, CO in logistics2Then be directly entered the desulfurizer of fine de-sulfur workshop section, so as not to hydrogenation reactor occur CO,
CO2Methanation reaction.
Raw material and CO, the CO from centrifugal station after hydrogenation2Mix the first desulfurizer and the second desulfurizer by connecting and complete essence
Desulfurization.
Zinc oxide desulfurizer is used in the first desulfurizer；Combination loading, epimere is used to load Zinc oxide desulfurizer in the second desulfurizer,
Copper-based whole level desulfurizing agent is loaded in hypomere.By copper-based ultimate desulfurizing agent, the sulfur content in gaseous mixture is reduced to into below 20ppb.
Unstripped gas after desulfurization, pressure 0.4MPa, flow 20000Nm3(component is /h：CO 22%, H240.5%, CO217.5%,
Methane 20%, only contains saturation water) methanator is entered, here carries out the methanation reaction based on CO, has a small amount of
CO2Also assist in methanation reaction.Process gas after methanation, pressure 0.35MPa, flow 15000Nm3/ h, component are CH4
42.8%th, CO 6.8%, CO229.2%th, H210.8%th, H2O 10.3%.To reduce the formation of carbonyl nickel, methanator
Entrance feeding temperature control at 295 DEG C；To control reaction depth, methanator is preferably shell and tube reactor, in pipe
Ni-based methanation catalyst KLJ-101 is filled with, it is heat-conducting medium that pipe is outer, and heat of reaction is taken away, controls reactor outlet temperature
520 DEG C of degree.
Process gas after methanation into reburner, are urged using described in CN102380394A after the intensification of reburner heat exchanging segment
Agent, convert inlet pressure 0.33MPa, 580 DEG C of temperature, outlet pressure 0.20MPa, 980 DEG C of temperature, obtain with CO,
H2Based on 26800Nm3(component is /h gaseous mixtures：CH42.1%, CO 42%, H255.5%, balance of CO2And H2O),
Gas component meets (H2+CO)/(H2+CO+CH4+CO2+H2O) >=90% requirement, can be used for blast furnace.
In above-mentioned course of reaction, the catalyst for using is the product of research institute of sinopec asphalt in Shenli Refinery exploitation, wherein, institute
State copper-based ultimate desulfurizing agent to be obtained 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.Will
1593.0g Na2CO3It is configured to 10L solution Bs.Solution A is warmed up to into 85 DEG C, solution B is warmed up to 80 DEG C.By solution B
It is placed in reactor, turn on agitator, ultrasonic wave, ultrasonic frequency is 50KHz, sound intensity 0.5W/cm2, mixing speed control
In 0.30rad/s.Solution A is added drop-wise in solution B with 85 minutes, neutralization precipitation, rate of addition is 125mL/min.
After completion of dropwise addition, it is 50KHz, sound intensity 1W/cm in ultrasonic frequency2Under, stirring 30 minutes is maintained, is measured with Accurate pH
The pH value of slurries is 9.Slurries static aging 2h under 80 DEG C of temperature conditionss.Slurries are washed using filter washing equipment
Wash, using 80 DEG C of deionized water cyclic washings, filter cake it is scrubbed to 0.1% concentration diphenylamines sulphate reagent titration for it is colourless when, recognize
To have reached washing terminal.After filter cake is dried 24h at 120 DEG C, roaster is sent into, 650 DEG C are heated to, carry out the de- of 4h
Water and decomposition, constant temperature 4h obtain semi-finished product.500g semi-finished product are taken, adds 15g graphite, ball milling after 15 minutes, to cross 120
Mesh sieve.The material after sieving is taken, 80g H are added2O, is well mixed, and rolls, granulation, crosses 20 mesh sieves.Take the thing after sieving
Material, it is compressing with forming machine.
Embodiment 2
As shown in Fig. 2 the reduction tail gas after the coal gas produced in ironmaking, steelmaking process, conversion is through eliminating water, dedusting, it is thick de-
After sulphur, the sulphur compound in process gas is reduced to into below 20ppm, contained humidity is the saturation water under operation temperature.
Process gas after thick desulfurization are partly into burning line, used as the fuel of reburner；Most process gas are entered and are separated
Workshop section, here complete logistics separation.Unstripped gas (the hydro carbons gas rich in methane such as natural gas, shale gas, casing-head gas, oven gas
Body) the hydrogenation reactor entrance of fine de-sulfur workshop section is mixed into the hydrogen in logistics, the saturated hydrogenation and sulfuration for carrying out alkene is closed
The hydrogenation of thing；CO, CO in logistics2Then be directly entered the desulfurizer of fine de-sulfur workshop section, so as not to hydrogenation reactor occur CO,
CO2Methanation reaction.
Raw material and CO, the CO from centrifugal station after hydrogenation2Mix the first desulfurizer and the second desulfurizer by connecting and complete essence
Desulfurization.
Zinc oxide desulfurizer is used in the first desulfurizer；Combination loading, epimere is used to load Zinc oxide desulfurizer in the second desulfurizer,
Copper-based whole level desulfurizing agent is loaded in hypomere.By copper-based ultimate desulfurizing agent, the sulfur content in gaseous mixture is reduced to into below 20ppb.
Unstripped gas after desulfurization, pressure 0.4MPa, flow 20000Nm3(component is /h：CO 22%, H240.5%, CO217.5%,
Methane 20%, only contains saturation water) methanator is entered, here carries out the methanation reaction based on CO, has a small amount of
CO2Also assist in methanation reaction.Process gas after methanation, pressure 0.35MPa, flow 15600Nm3/ h, component are CH4
39.7%th, CO 10.1%, CO226.5%th, H213.7%th, H2O 10%.To reduce the formation of carbonyl nickel, methanator
Entrance feeding temperature control at 300 DEG C；To control reaction depth, methanator is preferably shell and tube reactor, in pipe
Ni-based methanation catalyst KLJ-101 is filled with, it is heat-conducting medium that pipe is outer, and heat of reaction is taken away, controls reactor outlet temperature
550 DEG C of degree.
After process gas after methanation are without the intensification of reburner heat exchanging segment, reburner is directly entered, using CN102380394A
The catalyst, convert inlet pressure 0.33MPa, 520 DEG C of temperature, outlet pressure 0.20MPa, 800 DEG C of temperature, obtain with
CO、H2Based on 25000m3(component is /h gaseous mixtures：CH45.9%, CO 40.7%, H251.5%, balance of CO2
And H2O), gas component meets (H2+CO)/(H2+CO+CH4+CO2+H2O) >=90% requirement, can be used for blast furnace.
In above-mentioned course of reaction, the catalyst for using is the product of research institute of sinopec asphalt in Shenli Refinery exploitation, wherein, institute
State copper-based ultimate desulfurizing agent preparation method same as Example 1, therefore repeat no more.
Claims (10)
1. a kind of methanation dry reforming coupling produces CO, H2Method, it is characterised in that comprise the following steps：
(1) thick desulfurization：One or two Jing eliminating waters, dedusting and thick desulfurization process in ironmaking, the coal gas produced in steelmaking process, the reduction tail gas after conversion；
(2) separate：Process gas after thick desulfurization are partly into burning line, and used as the fuel of reburner, most process gas enter centrifugal station, and here completes logistics separation；
(3) fine de-sulfur：Hydrogen in high methane gas and logistics is mixed into the hydrogenation reactor of fine de-sulfur workshop section, the material and CO, the CO from centrifugal station after hydrogenation2Mix the first desulfurizer and the second desulfurizer by connecting and complete fine de-sulfur；
(4) methanation：Material after fine de-sulfur enters methanator；
(5) convert：Process gas after methanation can heat up with or without reburner heat exchanging segment, and into reburner, conversion outlet is obtained containing CO, H2Process gas.
2. the coupling of methanation dry reforming produces CO, H according to claim 12Method, it is characterised in that one or more in natural gas, shale gas, casing-head gas and the oven gas of the high methane gas.
3. the coupling of methanation dry reforming produces CO, H according to claim 12Method, it is characterised in that in step (3), hydrogenation reactor epimere uses nickel molybdenum or cobalt Mo-Ni catalyst, hypomere to use cobaltmolybdate catalyst.
4. the coupling of methanation dry reforming produces CO, H according to claim 12Method, it is characterised in that the first desulfurizer described in step (3) uses Zinc oxide desulfurizer, and the second desulfurizer uses combination loading, epimere filling Zinc oxide desulfurizer, hypomere to load copper-based whole level desulfurizing agent.
5. the coupling of methanation dry reforming produces CO, H according to claim 12Method, it is characterised in that in step (4), methanator is shell and tube reactor, the Ni-based methanation catalyst of filling in pipe, and it is heat-conducting medium that pipe is outer, and its entrance feeding temperature is 295-300 DEG C, and outlet temperature is 520-550 DEG C.
6. the coupling of methanation dry reforming produces CO, H according to claim 12Method, it is characterised in that 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 the flame for providing heat for reaction is burnt vertically downward in the case where combustion chamber draft is acted on；During using inverted L shape stove, feeding manner is bottom in and top out, and the flame for providing heat for reaction burns upwards.
7. the coupling of methanation dry reforming produces CO, H according to claim 12Method, it is characterised in that reburner inlet temperature be 520～580 DEG C, outlet temperature be more than 850 DEG C.
8. the coupling of methanation dry reforming produces CO, H according to claim 12Method, it is characterised in that using step (5) convert outlet process gas as metallurgical reduction gas, do not lower the temperature, be introduced directly into blast furnace；Ironmaking, the coal gas produced in steelmaking process, the reduction tail gas after conversion return thick desulfurization workshop section.
9. one kind realizes methanation dry reforming coupling production CO, H described in claim 1-8 any one2The device of method, it is characterized in that, including the thick desulfurizer, separator, hydrogenation reactor, the first desulfurizer, the second desulfurizer, methanator and the reburner that are sequentially connected, and thick desulfurizer is also connected with the burning line of reburner, separator is also connected with the first desulfurizer.
10. the coupling of methanation dry reforming produces CO, H according to claim 92Device, it is characterised in that also include and convert the blast furnace that is connected of outlet of still, and blast furnace is also connected with thick desulfurizer.
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