CN104709876B - The process of synthesis gas is prepared using zero carbon or negative carbon emission system - Google Patents
The process of synthesis gas is prepared using zero carbon or negative carbon emission system Download PDFInfo
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Abstract
The invention discloses a kind of process that synthesis gas is prepared using zero carbon or negative carbon emission system, including step：1）After first raw material desulfurization, water vapour is incorporated, boosts and heats up, reacted, obtain the first conversion gas and export；First conversion gas of output is mixed with pure oxygen, is reacted again into secondary reformer, is obtained the second conversion gas and is exported from secondary reformer；2）It after second raw material desulfurization, boosts and heats up, by itself and pure oxygen and carbon dioxide mix, reforming reaction occurs, obtain third conversion gas and exported from reforming reactor；3）After second conversion gas recycling heat, by it, conversion gas mix with third, formation crude synthesis gas, the crude synthesis gas by or not by decarbonization device after, as subsequent synthesis gas.The present invention reduces greenhouse gas emission, improves carbon efficiencies, realizes that the carbon resource of energy chemistry product recycles, and the hydrogen-carbon ratio of synthesis gas is made to reach the desired proportions of downstream processing requirements and realize zero carbon of total system or negative carbon emission.
Description
Technical field
The present invention relates to a kind of processes for preparing synthesis gas, and zero carbon or negative carbon emission system are utilized more particularly to a kind of
Controlling for synthesis gas process.
Background technology
It 2005, for the trend that national weather constantly warms, in order to make the mankind from the threat of weather acute variation, issues
Cloth reduces the Kyoto Protocol of CO2 emission, therefore the reduction of CO2 emission and efficiently uses as critical class
Topic.Synthesis gas is prepared as the extensive chemical utilization of carbon dioxide through high-temperature catalytic conversion using carbon dioxide as carbon oxygen resource
Important channel.Reforming reaction is carried out using two kinds of greenhouse gases of methane and carbon dioxide and prepares synthesis gas, can not only be realized low
The direct emission reduction of carbon dioxide under carbon scene also achieves Resources of Carbon Dioxide and the carbon cycle of scale, improves the energy and turns
The carbon efficiencies of change process.
At present, synthesis gas H/C ≈ 0.6-1 are prepared using reforming carbon dioxide-methane reaction, cannot be used directly for methanol conjunction
Into or Fischer-tropsch process.In order to obtain the synthesis gas of suitable hydrogen-carbon ratio, in methane-carbon dioxide/methane-steam reforming technique
On the basis of, it is proposed that method of methane and carbon dioxide mixed reforming technique, methane and high carbon raw material Joint Production synthesis gas etc..
" method that methyl methanol syngas is produced using gaseous hydrocarbon and coal as raw material " of China Patent No. 200410042446.7 is public
It opens：Respectively using gaseous hydrocarbon and coal as waste methyl methanol syngas, it is mixed in proportion, makes methanol feedstock gas obtained by mixing
Hydrogen-carbon ratio value：（H2-CO2）/（CO+CO2）=2.0-2.1 removes methanol-fueled CLC process synthesizing methanol after compression.The technique coal system is closed
Into gas part shift step containing CO, process generates a large amount of CO2, reduce system carbon utilisation rate.
" preparation of synthesis gas " of publication number CN101223103A using with low H/C than several mineral products（Coal, lignite,
Mud coal, pitch and tar sand）Any or combination be the first source, high H/C than several gases（Natural gas, associated gas and
Coal bed methane）For the second source, Fiscber-Tropscb synthesis gas is prepared by the method for partial oxidation and self-heating recapitalization/steam reformation respectively.So
And the technique can not realize the efficient utilization of carbon dioxide, it is thus impossible to carry out the emission reduction of greenhouse gases and energy chemistry product
Carbon resource recycles.
China Patent No. 200710177471.X's " utilizes the Poly-generation energy side of coal gasification sensible heat in a manner of methane reforming
The characteristics of method and system " is also mentioned using gasification gas richness carbon and reforming reaction gas hydrogen-rich, will according to the production of chemical products
It asks and mixes the two by different proportion, remove the shift process in traditional coal base chemical products production process from, however, the technique is same
Sample can not realize the efficient utilization of carbon dioxide.
Publication number CN102307835A patents " are synthesized using the synthesis gas produced by natural gas and carbon dioxide mixed reforming
The method of methanol " discloses：By using catalyst（Ni/Ce/MgAlOx or Ni/Ce-Zr/MgAlOx）And it can keep
CO、CO2And H2Estimated rate [H2/（2CO+3CO2）=0.85-1.15] process conditions, from the steam carbon dioxide weight of methane
Whole acquisition synthesis gas, wherein natural gas steam reform carry out synchronous with methane carbon dioxide reformation.However, process system control is multiple
It is miscellaneous.
Therefore, exist in existing synthesis gas preparation process to reach suitable hydrogen-carbon ratio and use CO transformationreations production
Raw great amount of carbon dioxide can not realize that Resources of Carbon Dioxide utilizes or the reaction of single reforming carbon dioxide-methane prepares synthesis
Gas hydrogen-carbon ratio is relatively low, cannot be used directly for methanol-fueled CLC or the defects of Fischer-tropsch process, and carbon utilization can be improved by needing to develop one kind
Efficiency can realize the synthesis gas preparation method of the recycling of greenhouse gases again.
Invention content
The technical problem to be solved in the present invention is to provide a kind of works that synthesis gas is prepared using zero carbon or negative carbon emission system
Process.This method is a kind of to be steamed using methane rich unstripped gas and by single reforming carbon dioxide-methane technique and methane-water
The coupling of vapour reforming process passes through methane-steam to prepare the method that can be directly used for methanol-fueled CLC or Fischer-tropsch process synthesis gas
Reform the low hydrogen-carbon ratio conversion gas that the conversion of high hydrogen-carbon ratio gas and methane-carbon dioxide self-heating recapitalization route that route generates generates with
Certain ratio mixing, obtains the high-quality synthesis gas for being suitable for downstream methanol or fischer-tropsch synthesis process.The features of the present invention exists
It is zero carbon or negative carbon emission system in entire synthesis gas preparation system, improves carbon utilization ratio simultaneously and realize carbon dioxide
Recycling；The ratio of gas and high hydrogen-carbon ratio conversion gas can be converted by adjusting low hydrogen-carbon ratio, obtains and is suitable for downstream work
The synthesis gas of skill difference hydrogen-carbon ratio requirement.
In order to solve the above technical problems, the technique side that zero carbon of utilization or negative carbon emission system of the present invention prepare synthesis gas
Method includes the following steps：
1）After the first raw material desulfurization rich in methane, water vapour is incorporated, 3~5MPa is boosted to and is warming up to 400~700
DEG C, methane-steam reforming reaction is carried out into primary reformer, the first conversion gas is obtained and is exported from primary reformer；
After the first conversion gas exported from primary reformer is mixed with pure oxygen, reacted again into secondary reformer（Carry out methane
With the deep conversion of water vapour）, obtain the second conversion gas and exported from secondary reformer；
2）After the second raw material desulfurization rich in methane, boost to normal pressure~5MPa and be warming up to 400~700 DEG C, by it
After pure oxygen and carbon dioxide mix, reforming reaction occurs into methane-carbon dioxide autothermal reforming reaction device, obtains third
It converts gas and is exported from methane-carbon dioxide autothermal reforming reaction device；
3）After second conversion gas recycling heat, it with the third conversion gas after recycling heat is mixed, forms crude synthesis gas,
The crude synthesis gas by or not by being used for the decarbonization device of carbon dioxide recovery after, it is made to meet certain hydrogen-carbon ratio, as
Subsequent synthesis gas.Since hydrogen-carbon ratio needed for follow-up synthesis gas is different, gas can be converted with third by adjusting the second conversion gas
Mixing ratio reaches.
The step 1）In, the first unstripped gas rich in methane includes：Gas rich in methane and it is rich in methane simultaneously
With the gas of carbon dioxide, wherein, methane molar content >=10% of the first unstripped gas；Such as the unstripped gas rich in methane includes：My god
In right gas, oven gas, casing-head gas, refinery gas, coal bed gas, shale gas, biogas, methanol-fueled CLC periodic off-gases, F- T synthesis periodic off-gases
It is one or more；The sulfur content of the first unstripped gas rich in methane after desulfurization should be less than according to downstream process demand
100ppm；Temperature after the first raw material desulfurization rich in methane is 350~370 DEG C.
Step 1）In, the condition for being incorporated water vapour is：Water vapor pressure 4MPa, temperature are 370 DEG C.
Step 1）In, the mixing molar ratio of the first unstripped gas and water vapour rich in methane is H2O/CH4=2~5, preferably
3~3.5；Primary reformer, secondary reformer operating pressure be 3~5MPa；
The outlet temperature of primary reformer is 700~920 DEG C, preferably 700~750 DEG C；The outlet methane mole of primary reformer contains
Measure is 12~15%.
Step 1）In, the mixing molar ratio of the first conversion gas and pure oxygen is O2/CH4=0.3~0.6, preferably 0.4~0.5；Two
The outlet temperature of section stove is 950~1050 DEG C, preferably 950~990 DEG C；The outlet methane molar content of secondary reformer is within 1%
（I.e.≤1%）, second converts the H in gas2The molar ratio of/CO is 3~5.
The step 2）In, the second unstripped gas rich in methane includes：Gas rich in methane and it is rich in methane simultaneously
With the gas of carbon dioxide, wherein, methane molar content >=10% of the second unstripped gas rich in methane；Such as it is rich in the original of methane
Material gas bag includes：Natural gas, oven gas, casing-head gas, refinery gas, coal bed gas, shale gas, biogas, methanol-fueled CLC periodic off-gases, Fischer-Tropsch close
Into one or more in periodic off-gases；The sulfur content of the second unstripped gas rich in methane after desulfurization should according to downstream process demand
Less than 100ppm；Temperature after the second raw material desulfurization rich in methane is 350~370 DEG C.
Step 2）In, after the second raw material desulfurization that will be enriched in methane, preferably boost to 3.5~4.5MPa；Rich in methane
The second unstripped gas and oxygen molar ratio be O2/CH4=0.1~0.8, preferably 0.6；The second unstripped gas and two rich in methane
The molar ratio of carbonoxide is CH4/CO2=0.5~3, preferably 1~1.5；It is interior in methane-carbon dioxide autothermal reforming reaction device
Agent bed operating temperature is 700~1250 DEG C, preferably 1000~1100 DEG C；Methane-carbon dioxide autothermal reforming reaction device
It is within 1% to export methane molar content（I.e.≤1%）；H in third conversion gas2The molar ratio of/CO is 0.5~1.
Above-mentioned zero carbon or negative carbon emission system are prepared in the process of synthesis gas, and variety classes unstripped gas is due to phosphorus content
Or hydrogen content is different, the synthesis gas type preferably prepared is also different, such as the first unstripped gas rich in methane and rich in methane
Second unstripped gas is higher for methane content（Methane molar content >=60%）Unstripped gas（Including：Natural gas, coal bed gas, oil field
Gas, refinery gas, shale gas and biogas）When, step 3）In synthesis gas（Subsequent synthesis gas）Preferably F- T synthesis gas；It is rich in
First unstripped gas of methane and the second unstripped gas rich in methane are higher for hydrogen content（Hydrogen molar content >=50%）Raw material
Gas（Including：Oven gas, methanol-fueled CLC periodic off-gases and Fischer-Tropsch periodic off-gases）When, step 3）In synthesis gas（Subsequent synthesis gas）It is excellent
It is selected as methyl methanol syngas.
In addition, above-mentioned zero carbon or negative carbon emission system are prepared in the process of synthesis gas, when the first original rich in methane
When expecting gas and the second unstripped gas rich in the methane unstripped gas higher for methane content, i.e. step 3）In synthesis gas be preferably expense
When holding in the palm synthesis gas, step 3）Concrete operations be：After second conversion gas carries out heat recovery, temperature is down to 40~160 DEG C, by it
Gas is converted with the third that the temperature after heat exchange is 40~160 DEG C to mix, and forms crude synthesis gas, which passes through decarbonization device
Afterwards, it is made to meet certain hydrogen-carbon ratio, as subsequent synthesis gas.Two needed for methane-carbon dioxide autothermal reforming reaction device
Raw material of carbon oxide gas can be provided all by the carbon dioxide of decarbonization device recycling, at this point, the method for the present invention is to be arranged using zero carbon
Place system prepares synthesis gas.
Above-mentioned zero carbon or negative carbon emission system are prepared in the process of synthesis gas, when the first unstripped gas rich in methane and
When the second unstripped gas rich in methane is hydrogen content higher unstripped gas, i.e. step 3）In synthesis gas be preferably methanol-fueled CLC
During gas, step 3）Concrete operations be：After second conversion gas carries out heat recovery, temperature is down to 40~160 DEG C, by itself and heat exchange
The third that temperature afterwards is 40~160 DEG C converts gas mixing, forms crude synthesis gas, the crude synthesis gas is not by decarbonization device, directly
It connects as subsequent synthesis gas, i.e., above-mentioned zero carbon or negative carbon emission system are prepared in the process of synthesis gas, can be free of decarburization
Device, cancels carbon dioxide recycle compression set, and carbon dioxide is all provided by the external world（Namely for methane-carbon dioxide self-heating recapitalization
CO 2 raw material gas needed for reactor is all provided by the external world）, at this point, the method for the present invention is to utilize negative carbon emission system system
Standby synthesis gas.
The heat recovery of the third conversion gas of the methane mentioned in above-mentioned steps-carbon dioxide autothermal reforming reaction, can lead to
Preheating is crossed into the unstripped gas or oxygen of reforming reactor（Oxygen-containing air）Or carbon dioxide, the flow of oxygen of system is reduced, is dropped
Low system operation cost.
Innovation of the present invention is：1）Pass through methane-steam reforming route and methane-carbon dioxide self-heating recapitalization road
Line is coupled, and is improved uniline production synthesis gas hydrogen-carbon ratio and is difficult to meet the techniques such as downstream methanol synthesis, F- T synthesis
Requirement；2）The present invention realizes the reformation that need not supplement carbon dioxide and methane under conditions of vapor, passes through supplemental oxygen
The heat of reaction is provided；3）The present invention is using the carbon dioxide that decarbonization device recycles as the original of methane-carbon dioxide self-heating recapitalization
Expect gas, realize zero carbon of system or negative carbon emission, improve system carbon utilization ratio.
Therefore, from the energy, environmental, combining with green, low-carbon, environmental protection industry requirement, the present invention has following excellent
Point：
1）By methane-carbon dioxide reforming process, at the same realize carbon dioxide, two kinds of methane " greenhouse gases "
It efficiently utilizes, both reduces greenhouse gas emission, improve system carbon efficiencies, and obtain valuable resource, realize the energy
The carbon resource of chemicals recycles.
2）Based on the unstripped gas for being rich in methane, by methane-steam reforming and methane-carbon dioxide self-heating recapitalization two
Route separately carries out, and then, couples manufacture with methane-CO 2 reformation two lines using methane-steam reforming and closes
Into gas, therefore, the conversion gas ratio of its production can be adjusted flexibly according to requirement of the downstream process to synthesis gas, to reach best hydrogen
Carbon ratio simplifies process system control condition, you can to make full use of the H having more than needed in steam reformation2In CO 2 reformation
CO more than needed, so as to which the hydrogen-carbon ratio for making synthesis gas reaches the desired proportions of downstream processing requirements.
3）This technique prepares synthesis gas, eliminates the shift process in prepared by conventional syngas, reduces or eliminate decarburization
Device, the carbon dioxide of decarburization recycling can realize the zero of total system as the unstripped gas of methane-carbon dioxide reforming process
Carbon or negative carbon emission.Therefore, which is zero carbon emission or negative carbon emission system.
Description of the drawings
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings：
Fig. 1 is the process flow chart of the present invention.
Specific embodiment
The present invention is described in further detail with case study on implementation below in conjunction with the accompanying drawings, it should be noted that due to being rich in
The gaseous hydrocarbon type of methane is more, and different hydrocarbons gas forms different, methane-water vapour two process transform process route form
Various, following embodiment is merely illustrative of the technical solution of the present invention and unrestricted, and those skilled in the art can be to this
The technical solution of invention is modified or replaced equivalently, and without departing from the spirit and scope of technical solution of the present invention, it should all
Cover in the technological right claimed range of the present invention.
Flow chart in embodiment 1-2 can be as shown in Figure 1.
Embodiment 1
The fine de-sulfur natural gas that flow is 182.64kmol/hr, pressure 4.2MPa, temperature are 360 DEG C（Sulfur content<
1ppm）, it is divided into two strands through current divider, one flow is 100kmol/hr, removes methane-steam reforming（First unstripped gas）, separately
One removes CH4 production device（Second unstripped gas）.
First unstripped gas and the middle pressure steam that flow is 300kmol/hr, pressure 4MPa, temperature are 370 DEG C（Water vapour）
After mixing, temperature rises to 600 DEG C after exchanging heat into external-heat primary reformer convection section, and reforming reaction occurs into primary reformer, obtains
First conversion gas.Wherein, the operating pressure of primary reformer is 4MPa, and outlet temperature is 708 DEG C, and the molar content of residual methane is
12.5%。
In secondary reformer with the first conversion gas combustion reaction and portion occur for the pure oxygen from space division, flow 39kmol/hr
Divide oxidation reaction, methane is made further to convert, obtains the second conversion gas.The operating pressure of secondary reformer is 4MPa, goes out secondary reformer
Second conversion temperature degree is 974 DEG C, and the molar content of methane remnants is 0.4%, and mole composition in the second conversion gas is：H2：
41.1%CO：9.9%CO2：6.5%CH4：0.4%, remaining is moisture and inert gas, after waste heat boiler recycles heat, then through more
Temperature is down to 40 DEG C after grade heat exchange, after being mixed from the third of CH4 production device conversion gas, into decarburization
Device.
The flow of second unstripped gas is 82.64kmol/hr, temperature is 360 DEG C, pressure 4.2MPa, through integrated heat exchanger
It is preheated to 600 DEG C.Pure oxygen flow from space division is 48.4kmol/hr, pressure 4MPa, temperature are 40 DEG C, through integrated heat exchange
After device is preheated to 400 DEG C, into methane-carbon dioxide autothermal reforming reaction device, reactor operating pressure 4MPa.From decarburization
The carbon dioxide flow of device is 70.25kmol/hr, temperature is 25 DEG C, pressure 0.3MPa, is compressed to through recycle compressor
After 4.2MPa, it is preheated to 500 DEG C and enters reforming reactor.Reactor outlet temperature（Methane-carbon dioxide autothermal reforming reaction device
In interior agent bed operating temperature）It it is 1009 DEG C, a mole composition for the third conversion gas after reaction is：H2：32.4%CO：
36.6%CO2：12%CH4：1%（I.e. the molar content of residual methane is 1%）, remaining is moisture and inert gas, through integrated heat exchanger
Temperature is down to 858 DEG C after preheating material gas, heat is recycled, then temperature is down to 40 DEG C after multi-stage heat exchanger through waste heat boiler, with first
Second conversion gas mixing of alkane-steam reformation route.
The recovery rate of CO 2 of decarbonization device is 93.5%, the carbon dioxide molar content in net synthesis gas<1%, recycling
Carbon dioxide supercharging after into methane-carbon dioxide reforming device make unstripped gas, the purified gas for going out decarbonization device is Fischer-Tropsch
Synthesis gas, flow 524.5kmol/hr, pressure 3.3MPa, temperature are 40 DEG C, and a mole composition for main component is：H2：
65.2%CO：32.6%CO2：0.9%CH4：1.11%.
Embodiment 2
The fine de-sulfur oven gas that flow is 157.09kmol/hr, pressure 3.8MPa, temperature are 358 DEG C（Sulfur content<
1ppm）, hydrogen molar content is 58%, and methane molar content is 28.7%, is divided into two strands through current divider, one flow is
100kmol/hr, methane-steam reformation is removed（First unstripped gas）, another stock removes methane-carbon dioxide reforming device（Second raw material
Gas）.
With flow it is 85kmol/hr, pressure 4MPa, temperature since the methane content in the first unstripped gas is relatively low
After 370 DEG C of medium pressure steam mixing, temperature rises to 600 DEG C after the heat exchange of external-heat primary reformer convection section, into primary reformer
Reforming reaction occurs, obtains the first conversion gas.Wherein, primary reformer operating pressure is 4MPa, and outlet temperature is 750 DEG C.Remaining first
The molar content of alkane is 12.8%.
Pure oxygen from space division, flow 14.5kmol/hr, in secondary reformer with first conversion gas occur combustion reaction and
Partial oxidation reaction makes methane further convert, and obtains the second conversion gas.The operating pressure of secondary reformer is 4MPa, goes out secondary reformer
The second conversion temperature degree be 970 DEG C, the molar content of methane remnants is 1%, and flow 237.3kmol/hr, second converts gas
In a mole composition be：H2：48.6%CO：10.2%CO2：4.6%CH4：1%, remaining is moisture and inert gas, through waste heat boiler
After recycling heat, then temperature is down to 40 DEG C after multi-stage heat exchanger, is converted with the third from CH4 production device
Gas mixes.
Second raw gas flow is 57.09kmol/hr, temperature is 358 DEG C, pressure 3.8MPa, pre- through integrated heat exchanger
Heat is to 600 DEG C.Pure oxygen flow from space division is 11.42kmol/hr, pressure 4MPa, temperature are 40 DEG C, through integrated heat exchanger
After being preheated to 410 DEG C, into methane-carbon dioxide autothermal reforming reaction device, reactor operating pressure 4MPa.What the external world provided
Carbon dioxide flow is 13.7kmol/hr, after compressed preheating temperature be 508 DEG C, pressure 4.2MPa, with the second unstripped gas,
Oxygen enters reforming reactor and autothermal reforming reaction occurs together, obtains third conversion gas.Reactor outlet temperature（Methane-two
Interior agent bed operating temperature in carbonoxide autothermal reforming reaction device）It it is 1093 DEG C, a mole composition for third conversion gas is H2：
46.1%CO：28.5%CO2：5.3%CH4：0.6%, remaining is moisture and inert gas, and temperature is down to after integrated heat exchanger exchanges heat
913 DEG C, heat is recycled through waste heat boiler, then temperature is down to 40 DEG C after multi-stage heat exchanger, the with methane-steam reforming route
Two conversion gas mixing.Mixed crude synthesis gas is after dehydration, flow 241.1kmol/hr, pressure 3.6MPa, temperature
It it is 40 DEG C, a mole composition for main component is：H2：67.3%CO：22.1%CO2：6.8%CH4：1.2%,（H2-CO2）/（CO+CO2）=
2.1, it can be directly used for methanol synthesizing process.
Unstripped gas is done using oven gas and prepares methyl methanol syngas, eliminates decarbonization device, eliminates carbon dioxide recycle pressure
Contracting machine reduces system engineering money and operating cost, and the carbon dioxide needed for technique is provided by the external world, and whole system is that negative carbon is arranged
It puts.
Claims (10)
1. a kind of process that synthesis gas is prepared using zero carbon or negative carbon emission system, which is characterized in that include the following steps：
1) after the first raw material desulfurization rich in methane, water vapour is incorporated, 3~5MPa is boosted to and is warming up to 400~700 DEG C,
Methane-steam reforming reaction is carried out into primary reformer, obtain the first conversion gas and is exported from primary reformer；
After the first conversion gas exported from primary reformer is mixed with pure oxygen, reacted again into secondary reformer, obtain the second conversion gas
And it is exported from secondary reformer；
2) after the second raw material desulfurization rich in methane, boost to normal pressure~5MPa and be warming up to 400~700 DEG C, by its with it is pure
After oxygen and carbon dioxide mix, reforming reaction occurs into methane-carbon dioxide autothermal reforming reaction device, obtains third conversion
Gas is simultaneously exported from methane-carbon dioxide autothermal reforming reaction device；
3) after the second conversion gas recycling heat, it with the third conversion gas after recycling heat is mixed, forms crude synthesis gas, this is thick
Synthesis gas by or not by being used for the decarbonization device of carbon dioxide recovery after, as subsequent synthesis gas.
2. the method as described in claim 1, it is characterised in that：In the step 1), the first unstripped gas rich in methane includes：
Gas rich in methane and the simultaneously gas rich in methane and carbon dioxide, wherein, the methane molar content of the first unstripped gas
>=10%；
The sulfur content of the first unstripped gas rich in methane after desulfurization should be less than 100ppm according to downstream process demand；Rich in methane
The first raw material desulfurization after temperature be 350~370 DEG C；
In step 1), the condition for being incorporated water vapour is：Water vapor pressure 4MPa, temperature are 370 DEG C；
In step 1), the mixing molar ratio of the first unstripped gas and water vapour rich in methane is H2O/CH4=2~5；Primary reformer, two
The operating pressure of section stove is 3~5MPa；The outlet temperature of primary reformer is 700~920 DEG C；The outlet methane molar content of primary reformer
It is 12~15%；
In step 1), the mixing molar ratio of the first conversion gas and pure oxygen is O2/CH4=0.3~0.6；The outlet temperature of secondary reformer is
950~1050 DEG C；The outlet methane molar content of secondary reformer is the H in the second conversion gas within 1%2The molar ratio of/CO is 3
~5.
3. method as claimed in claim 2, it is characterised in that：In the step 1), the unstripped gas rich in methane includes：Naturally
In gas, oven gas, casing-head gas, refinery gas, coal bed gas, shale gas, biogas, methanol-fueled CLC periodic off-gases, F- T synthesis periodic off-gases
It is one or more；
In step 1), the mixing molar ratio of the first unstripped gas and water vapour rich in methane is H2O/CH4=3~3.5；Primary reformer
Outlet temperature be 700~750 DEG C；
In step 1), the mixing molar ratio of the first conversion gas and pure oxygen is O2/CH4=0.4~0.5；The outlet temperature of secondary reformer is
950~990 DEG C.
4. the method as described in claim 1, it is characterised in that：In the step 2), the second unstripped gas rich in methane includes：
Gas rich in methane and the simultaneously gas rich in methane and carbon dioxide, wherein, the first of the second unstripped gas rich in methane
Alkane molar content >=10%；
The sulfur content of the second unstripped gas rich in methane after desulfurization should be less than 100ppm according to downstream process demand；Rich in methane
The second raw material desulfurization after temperature be 350~370 DEG C；
In step 2), after the second raw material desulfurization that will be enriched in methane, 3.5~4.5MPa is boosted to.
5. method as claimed in claim 4, it is characterised in that：In the step 2), the unstripped gas rich in methane includes：Naturally
In gas, oven gas, casing-head gas, refinery gas, coal bed gas, shale gas, biogas, methanol-fueled CLC periodic off-gases, F- T synthesis periodic off-gases
It is one or more；
The molar ratio of the second unstripped gas and pure oxygen rich in methane is O2/CH4=0.1~0.8；
The molar ratio of the second unstripped gas and carbon dioxide rich in methane is CH4/CO2=0.5~3；
Catalyst bed operating temperature in methane-carbon dioxide autothermal reforming reaction device is 700~1250 DEG C；Methane-dioxy
The outlet methane molar content for changing carbon autothermal reforming reaction device is within 1%；H in third conversion gas2The molar ratio of/CO is
0.5~1.
6. method as claimed in claim 5, it is characterised in that：In the step 2), the second unstripped gas rich in methane and pure
The molar ratio of oxygen is O2/CH4=0.6；
The molar ratio of the second unstripped gas and carbon dioxide rich in methane is CH4/CO2=1~1.5；
Catalyst bed operating temperature in methane-carbon dioxide autothermal reforming reaction device is 1000~1100 DEG C.
7. the method as described in claim 1, it is characterised in that：First unstripped gas rich in methane and rich in methane
When two unstripped gas are the unstripped gas of methane molar content >=60%, the subsequent synthesis gas in step 3) is F- T synthesis gas；
When the first unstripped gas rich in methane and the second unstripped gas rich in methane are the unstripped gas of hydrogen molar content >=50%,
Subsequent synthesis gas in step 3) is methyl methanol syngas.
8. the method for claim 7, it is characterised in that：The unstripped gas of methane molar content >=60% includes：My god
Right gas, coal bed gas, casing-head gas, refinery gas, shale gas or biogas；
The unstripped gas of hydrogen molar content >=50% includes：Oven gas, methanol-fueled CLC periodic off-gases or Fischer-Tropsch periodic off-gases.
9. the method for claim 7, it is characterised in that：The process is to prepare to synthesize using zero carbon emission system
During the process of gas, the subsequent synthesis gas in step 3) is F- T synthesis gas, and the concrete operations of step 3) are：Second conversion
After gas carries out heat recovery, temperature is down to 40~160 DEG C, itself and third of the temperature after heat exchange for 40~160 DEG C are converted gas
Mixing forms crude synthesis gas, after the crude synthesis gas is by decarbonization device, as subsequent synthesis gas；Methane-carbon dioxide self-heating
CO 2 raw material gas needed for reforming reactor is all provided by the carbon dioxide of decarbonization device recycling；
The process is the subsequent synthesis in step 3) when preparing the process of synthesis gas using negative carbon emission system
Gas is methyl methanol syngas, and the concrete operations of step 3) are：After second conversion gas carries out heat recovery, temperature is down to 40~160 DEG C,
It is converted gas with the third that the temperature after heat exchange is 40~160 DEG C to mix, forms crude synthesis gas, the crude synthesis gas is not by de-
Carbon device, directly as subsequent synthesis gas；And methane-CO 2 raw material gas needed for carbon dioxide autothermal reforming reaction device
All provided by the external world.
10. the method as described in claim 1, it is characterised in that：In the step 3), the heat recovery of third conversion gas is logical
Preheating is crossed into the unstripped gas or pure oxygen or carbon dioxide of methane-carbon dioxide autothermal reforming reaction device, reduces the oxygen of system
Dosage.
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| CN106553996B (en) * | 2015-09-30 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of methanation dry reforming coupling production CO, H2Method and device |
| CN106553995B (en) * | 2015-09-30 | 2019-05-28 | 中国石油化工股份有限公司 | Natural gas and carbon dioxide dry reforming process for preparing synthetic gas |
| CN108315523B (en) * | 2018-01-26 | 2020-01-07 | 中国科学院上海高等研究院 | Method and system for producing direct reduced iron by autothermal reforming of carbon dioxide-methane |
| CN109135796B (en) * | 2018-07-27 | 2020-08-04 | 北京嘉岳能源科技开发有限公司 | Method for preparing oil product by using methane as raw material |
| CN109181800B (en) * | 2018-10-22 | 2024-02-20 | 广东索特能源科技有限公司 | Coupling device for decarbonizing and reforming methane and decarbonizing and reforming system for methane |
| CN110357039B (en) * | 2019-08-12 | 2021-04-02 | 中国科学院工程热物理研究所 | Biogas and solar complementary synthesis gas preparation system and method |
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