CN105623762B - A kind of method that natural gas is produced in carbon dioxide segmentation methanation - Google Patents
A kind of method that natural gas is produced in carbon dioxide segmentation methanation Download PDFInfo
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- CN105623762B CN105623762B CN201610037828.3A CN201610037828A CN105623762B CN 105623762 B CN105623762 B CN 105623762B CN 201610037828 A CN201610037828 A CN 201610037828A CN 105623762 B CN105623762 B CN 105623762B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
Abstract
The invention discloses the method that natural gas is produced in a kind of segmentation methanation of carbon dioxide.1) and 3) or 2) and 3) the described method includes following step：1) by H2It is divided at least 3 strands to be separately input into the methanator of 3 series connection, then by CO2It is divided at least 3 strands and is separately input into 3 methanators and carries out methanation reaction；2) by CO2It is divided at least 3 strands to be separately input into the methanator of 3 series connection, then by H2It is divided at least 3 strands and is separately input into 3 methanators and carries out methanation reaction；3) input of working off one's feeling vent one's spleen of the methanator carries out methanation reaction into the methanator of at least 2 series connection, and the methanator is worked off one's feeling vent one's spleen as gas product.Product (the CH that the reactant and upper level acted on by reaction controlling reacts4And H2O temperature control measure) is used as, avoids adding the influence that vapor control temperature balances methanation reaction in conventional methanation technique.
Description
Technical field
The present invention relates to the method that natural gas is produced in a kind of segmentation methanation of carbon dioxide, belong to methanation field.
Background technology
Carbon dioxide is one of arch-criminal of global warming.Because carbon dioxide has the function that insulation, it can gradually make the earth
Surface temperature raises.Nearly 100 years, Global Temperature raised 0.6 DEG C, goes down after this manner, it is contemplated that to mid-21st Century, Global Temperature will
1.5~4.5 DEG C of rise.As the sea-level rise caused by greenhouse effects, huge shadow can be also produced to the living environment of the mankind
Ring.The ice cube of the two poles of the earth ocean is also by whole thawings.All these changes are tantamount to extinction for wild animal.By
In May, 2013, the gas concentration lwevel in earth atmosphere is more than 400ppm (400/1000000ths).Between 2000 to 2009 years
Concentration growth rate be annual 2.0ppm, and accelerate year by year.280ppm concentration before current concentration ratio industrialization is much higher,
And human factor is the main reason for causing gas concentration lwevel to steeply rise.In the carbon dioxide discharged, 57% enters greatly
Gas-bearing formation, remaining then enters ocean, causes Ocean acidification.China, which surmounted the U.S. in 2006, becomes the maximum carbon emission in the whole world
State, 7.2 tons of the carbon dioxide of discharge per capita of 2013, more than 6.8 tons of European Union, carbon emission accounts for 28% that the whole world is always discharged,
Summation through more than European Union's (14%) and the U.S. (10%).The Chinese government pays much attention to carbon emission problem, it is desirable to strong carbon
Emission control target, strives realizing and arrives the year two thousand twenty, and on the basis of 2005, the intensity of CO2 emission declines 40% and arrives
45% upper limit target.
Carbon dioxide is also a kind of valuable carbon resource in itself, and it is the world today how Resources of Carbon Dioxide to be utilized
Important subject, this patent be using the means of chemical synthesis carbon dioxide under catalyst action, suitable
Generation substitutes gas product under temperature, pressure, and greenhouse gases are changed into the energy, are turned waste into wealth.Process needs substantial amounts of hydrogen
Gas, and the source of hydrogen can be contemplated and utilize the hydrogen such as power generation in superfluous electric power or solar power generation, wind.Solar hydrogen making
Possible approaches include solar power generation and water electrolysis hydrogen production, solar energy high-temperature heat collection decomposes water, reforming biomass hydrogen preparation, photoproduction
Thing hydrogen manufacturing, photocatalysis hydrogen production etc., have wide prospects for commercial application, but hydrogen production efficiency is relatively low at present, apart from large-scale industry
Solve the problems, such as that energy transformation ratio is low using still needing.Comparatively speaking, wind-power electricity generation and water electrolysis hydrogen production technology are very ripe.I
The grid-connected bottleneck of the land wind-powered electricity generation of state, which causes, largely abandons wind, abandons wind and has become the outstanding problem for restricting wind energy development.According to
Chinese energy office counts, and first half of the year wind-powered electricity generation in 2015 abandons 17,500,000,000 kilowatt hour of wind-powered electricity generation amount, increases by 10,100,000,000 kilowatt hours on year-on-year basis；Averagely abandon
Wind rate 15.2%, rises 6.8 percentage points on year-on-year basis；Abandon wind ration the power supply be concentrated mainly on illiteracy western (abandoning wind rate 20%), wind rate (is abandoned in Gansu
31%), the area such as Xinjiang (abandoning wind rate 28.82%), Jilin (abandoning wind rate 43%).Exemplified by abandoning the higher Xinjiang of wind rate, it is produced
Industry develop based on the fossil energies such as coal, and in hydrogen energy-storage system electrolysis water have to the unstability power output of wind turbine it is very strong
Adaptability, can be used to solve wind-powered electricity generation overstock problem, and reduces pollution, reduces energy consumption.Although the cost of water electrolysis hydrogen production gas is higher,
And economy is also obvious poor if building wind park and being used for water electrolysis hydrogen production, but it is come hydrogen manufacturing using the wind of abandoning wasted originally
Economical.The water of electrolysis water can be that factory reaches necessarily required waste water after treatment, also be provided newly for sewage disposal
Thinking.If using abandon wind power generation it is necessary to have certain scale wind-powered electricity generation and H2Storage and handling facility, by the load for adjusting decarburization
To adjust total carbon, to adapt to the actual conditions of available wind-powered electricity generation.
Superfluous electric power storage difficulty is big, it is therefore desirable to a kind of method that can be realized electric energy and be converted into chemical energy is provided,
Be conducive to store and utilize, while solve the problems, such as carbon emission.
Chinese patent CN103107588A discloses a kind of non-grid connected wind power device for producing hydrogen, including wind turbine, device for producing hydrogen and
Control device, storage battery etc., are conducive to make full use of wind-force, non-environmental-pollution, resource utilization is high, can be easily lasting
Hydrogen is produced, and need to only use less storage battery to can be achieved, reaches and has saved cost.Chinese patent CN101976853A
Disclose a kind of wind power hydrogen production regulation and control grid-connected system, including wind power generation plant, hydrogen generator, hydrogen storage and Hydrogen Energy
Power generator, using the memory technology of hydrogen energy source, can effectively solve wind power-generating grid-connected, particularly large-scale wind generating is grid-connected
Problem.Chinese patent CN204342750U discloses the structure of a kind of electrolytic hydrogen production and producing synthesis gas from coal preparing natural gas, including standby
Coal unit, standby coal unit are connected with gasification furnace, and the outlet of gasification furnace raw gas is connected with the first absorption tower entrance, and the first absorption tower goes out
The main line of mouth is washed unit with low-temp methanol by converter unit connection all the way and is connected, and by-pass is connected with power plant all the way, and electric energy is direct
Water electrolysis hydrogen production unit is supplied, alleviates the produce load of conversion section in conventional natural gas from coal technique, improves carbon utilization
Rate.At present, still without the correlation technique available for large carbon dioxide methanation.
The content of the invention
The object of the present invention is to provide the method that natural gas is produced in a kind of segmentation methanation of carbon dioxide, the present invention can be used for
The carbon resource hydrogenation of high concentration carbon dioxide is produced replacement natural gas.
The method that natural gas is produced in carbon dioxide provided by the present invention segmentation methanation, including it is following 1) and 3) or 2) and
3) step：
1) by H2It is divided at least 3 strands to be separately input into the methanator of 3 series connection, then by CO2It is divided at least 3
Stock, which is separately input into 3 methanators, carries out methanation reaction；
2) by CO2It is divided at least 3 strands to be separately input into the methanator of 3 series connection, then by H2It is divided at least 3
Stock, which is separately input into 3 methanators, carries out methanation reaction；
3) input of working off one's feeling vent one's spleen of the methanator carries out methanation into the methanator of at least 2 series connection
Reaction, the methanator are worked off one's feeling vent one's spleen as gas product.
The present invention innovatively utilizes the reactant (H being initially passed through of a part of non-reaction controlling2And CO2) and reaction generation
Produce product (working off one's feeling vent one's spleen for each methanator) are diluted, and are come using the reactant of reaction controlling as temperature control means
Reaction depth is controlled, deep reaction area is used for deep reaction CO2And H2, to meet the quality requirements of product.The present invention can produce
High-quality substitutes natural gas.
In above-mentioned method, the H2From electric power hydrogen manufacturing, solar hydrogen making or wind power hydrogen production.
In above-mentioned method, by the way of water electrolysis hydrogen production；
The water electrolysis hydrogen production uses coal gasification waste water, before use, handling in a conventional manner coal gasification waste water.
In the methods of the invention, the H2It is both reactant and diluent；H2Purity >=96%, hydrogen sulfide content ＜
20ppb, O2Content ＜ 0.1%；
The CO2Purity requirement 10%-100%, hydrogen sulfide content ＜ 20ppb, such as the CO of purity 100%2。
Therefore, the present invention can make full use of solar energy or abandon wind, obtain hydrogen resources；Fully CO2Recycling,
Reduce CO2Discharge；Whole reaction process is divided into segmentation reaction zone (step 1) or step 2) by the method for the present invention) and deep reaction
Area's (step 3)), segmentation reaction zone is by controlling the concentration of reactant to carry out segmentation progressively methanation reaction.
In above-mentioned method, in step 1) and step 2), by the H2With the CO2It is defeated after being both heated to 250~320 DEG C
Enter into the methanator.
In above-mentioned method, in step 1) and step 2), the temperature of the methanation reaction can be 250 DEG C~670 DEG C.
Pressure in the methanator can be 1~5MPa.
In above-mentioned method, in step 3), the temperature of the methanation reaction can be 230 DEG C~250 DEG C；
Pressure in the methanator can be 1~5MPa；
Step 3) is as in deep reaction area, by being segmented (step 1) or step 2) in reaction zone) after unreacted it is complete
CO2With H2Generation deep reaction.
In above-mentioned method, in step 1),
In methanator described in First, the H2With the CO2Molar ratio can be 30~4：1, concretely
18.6：1, gas therein comes from the H each led into2And CO2, hydrogen is in excessive state；
In second methanator, the H2With the CO2Molar ratio be 30~4：1, concretely
14.7：1, gas therein comes from the H each led into2And CO2With the product exported from methanator described in First
Gas, wherein the product gas from methanator outlet described in First is to the gas in second methanator
Concentration plays certain diluting effect, and hydrogen is in excessive state；
In 3rd methanator, the H2With the CO2Molar ratio be 30~4：1, concretely
10.7：1, gas therein comes from the H each led into2And CO2With the product from second methanator outlet
Gas, wherein the product gas from second methanator outlet is to the gas in the 3rd methanator
Concentration plays certain diluting effect, and hydrogen is in excessive state, but hydrogen-carbon ratio gradually reduces.
In step 2),
In methanator described in First, the H2With the CO2Molar ratio can be 0.5~6：1, concretely
1：1, gas therein comes from the H each led into2And CO2, CO2In excessive state；
In second methanator, the H2With the CO2Molar ratio be 0.5~6：1, concretely
1.4：1, gas therein comes from the H each led into2And CO2With the product exported from methanator described in First
Gas, wherein the product gas from methanator outlet described in First is to the gas in second methanator
Concentration plays certain diluting effect, CO2Still in excessive state；
In 3rd methanator, the H2With the CO2Molar ratio be 0.5~6：1, concretely
2.9：1, gas therein comes from the H each led into2And CO2With the product from second methanator outlet
Gas, wherein the product gas from second methanator outlet is to the gas in the 3rd methanator
Concentration plays certain diluting effect, CO2In excessive state, but hydrogen-carbon ratio steps up.
The present invention is by controlling CO2Input quantity, Discrete control reaction depth, carries out substantial amounts of methanation reaction, previous
The CH of a methane reactor generation4And H2Diluents of the O as next reactor.
In specific one embodiment, in step 1), the H2Can be 0.65 according to volume ratio：0.30：0.05 is divided into
Three strands are separately input into the methanator；
The CO2Can be 0.14 according to volume ratio：0.22：0.24：0.40, which is divided into four strands, is separately input into the methanation
Reactor.
In another specific embodiment, in step 2), the CO2Can be 0.6 according to volume ratio：0.3：0.1 is divided into
Three strands are separately input into the methanator；
The H2Can be 0.15 according to volume ratio：0.23：0.23：0.39 is divided into four strands, and to be separately input into the methanation anti-
Answer in device.
In the method for the present invention, unstripped gas is divided into the purpose that at least 3 stocks do not input and is primarily used for avoiding reactor mistake
Greatly, balanced each reactor load.
In the method for the present invention, each methanator outlet high-temperature technology gas can connect waste heat boiler and drum, by-product
The vapor of high-quality, if it is desired, also can by-product high-quality superheated vapour.
In carbon dioxide segmentation methanation process of the present invention, the fixed bed methanation catalyst of the methanation reaction can be adopted
With catalyst commonly used in the art, the carbon dioxide methanation catalyst as disclosed in Chinese patent CN102091629A.
Compared with prior art, the present invention has the advantages that：
1st, the segmentation methanation of carbon dioxide, can realize the utilization to large CO_2 Resource, reduce carbon emission；
2nd, superfluous electric power storage difficulty is big, can realize that electric energy is converted into chemical energy by the present invention, be conducive to store
And utilization；
If the 3rd, using solar hydrogen making, abandon wind power hydrogen production, inexhaustible, nexhaustible cleaning solar energy is converted into
Chemical energy is stored in synthetic natural gas product, realizes green circulation economy, and solution abandons wind-electricity integration difficulty and causes energy waste
Problem；
4th, water electrolysis hydrogen production can use the waste water for meeting that electrolysis requires after processing, realize the processing of sewage and the circulation of water
Utilize；
5th, it is used as the diluent of unstripped gas by reactant itself, avoiding needs circulation to compress in conventional methanation technique
Product gas is introduced into diluting reaction thing concentration in unstripped gas by machine, eliminates compressor, saves the power consumption of dynamic equipment；
6th, the product (CH that the reactant and upper level acted on by reaction controlling reacts4And H2O temperature control measure) is used as,
Avoid adding the influence that vapor control temperature balances methanation reaction in conventional methanation technique；
7th, the present invention can utilize the principle by-product high-quality water vapour or mistake of methanation reaction process release amount of heat
Hot steam；
8th, can realize to H in product gas2、CO2The accuracy controlling of content, realizes the control to product quality, obtains Gao Pin
Matter synthetic natural gas product.
Brief description of the drawings
Fig. 1 is to be of the invention to excessive H2CO is mended in middle segmentation2The process flow chart of preparing natural gas by methanation.
Fig. 2 is to be of the invention to excessive CO2H is mended in middle segmentation2The process flow chart of preparing natural gas by methanation.
Each mark is as follows in figure：
1- the first adiabatic methanation reactors, 2- the second adiabatic methanation reactors, the 3rd adiabatic methanation reactors of 3-,
The 4th adiabatic methanation reactors of 4-, the adiabatic methanators of 5- the 5th, the 6th adiabatic methanation reactors of 6-, 7- gas-liquids point
From device, the hot methanator of 8- four-line poems with seven characters to a line.
Being segmented reaction zone includes the first adiabatic methanation reactor, the second adiabatic methanation reactor, the 3rd adiabatic methane
Change reactor, the 4th adiabatic methanation reactor；Deep reaction area includes the 5th adiabatic methanator, the 6th adiabatic methane
Change reactor, the hot methanator of four-line poem with seven characters to a line.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples, is commercially available unless otherwise specified.
Embodiment 1,
The methanation of unstripped gas is carried out according to technological process shown in Fig. 1.
Unstripped gas (H2) pressure is 3.0MPa, 40000kmol/h, purity ＞ 99% and total sulfur is less than 0.1ppm.
Above-mentioned raw materials gas (H2) according to 0.65：0.30：0.05 volume ratio, is divided into three strands and respectively enters main methanation device
The first adiabatic methanation reactor 1, the second adiabatic methanation reactor 2 and the 3rd adiabatic methanation reactor 3, each reactor
Inlet temperature is controlled at 250 DEG C, and by methanation reaction, methanator outlet temperatures at different levels are 630 DEG C, each stage reactor
Reaction pressure be 2.8MPa~3.0MPa.
Unstripped gas (CO2) pressure is 3.0MPa, 10000kmol/h, purity ＞ 99% and total sulfur is less than 0.1ppm.
Above-mentioned raw materials gas (CO2) according to 0.14:0.22:0.24:0.40 volume ratio, is divided into four strands and respectively enters main methane
Disguise the first adiabatic methanation reactor 1 put, the second adiabatic methanation reactor 2, the 3rd adiabatic methanation reactor 3 and the
Four adiabatic methanation reactors 4.
First adiabatic methanation reactor inlet process gas H2With CO2Molar ratio be 18.6：1, hydrogen is in excessive shape
State；Second adiabatic methanation reactor inlet process gas H2With CO2Molar ratio be 14.7：1, it is anti-from the first adiabatic methanation
The product gas that device exports is answered to play certain diluting effect, hydrogen is in excessive state；3rd adiabatic methanation reactor inlet
Process gas H2With CO2Molar ratio be 10.7：1, the product gas from the second adiabatic methanation reactor outlet plays certain dilute
Effect is released, hydrogen is in excessive state, but hydrogen-carbon ratio gradually reduces；4th adiabatic methanation reactor inlet process gas H2With CO2
Molar ratio be 4.0：1, hydrogen-carbon ratio further reduces and in the molar ratio that can be reacted completely；Deep reaction device is each afterwards
The inlet process gas H of reactor2With CO2Molar ratio maintain essentially in 4.0：1.
According to methanation reaction principle, per 1molCO2Reaction needs 4molH2, generate 1mol methane and 2mol water.Segmentation is anti-
Answer in each reactor in area, CO2Relative amount is few, is the reactant of reaction controlling, by controlling CO2Amount controlling reaction temperature
And reaction depth.Waste heat boiler and drum can be connected by being segmented the high-temperature technology gas of each reactor outlet of reaction zone, and by-product is high
The vapor of quality, if it is desired, also can by-product high-quality superheated vapour.
Include the 5th adiabatic methanator 5, the 6th adiabatic methanation reactor 6 and four-line poem with seven characters to a line heat in deep reaction area
Methanator 8.In deep reaction device, the complete CO of unreacted after being segmented reaction zone2With H2Generation deep reaction, the 5th
The inlet temperature control of 5 and the 6th adiabatic methanation reactor 6 of adiabatic methanation reactor is 250 DEG C, the 5th adiabatic methanation
About 580 DEG C of 5 outlet process gas of reactor, about 450 DEG C of 6 outlet process gas of the 6th adiabatic methanation reactor.Last fixation
Bed reactor inlet temperature is controllable to 230 DEG C to deepen reaction, improves CH in outlet process gas4Content.It is wherein second from the bottom
Platform reactor outlet process gas is cooled to 40~80 DEG C by heat exchange, the water of reaction generation is gone out by gas-liquid separator separates, most
Latter reactor outlet process gas (380 DEG C) is cooled to 40~80 DEG C by heat exchange, goes out reaction by gas-liquid separator separates
The water of generation is final products.
Process gas (can be the carbon dioxide disclosed in CN102091629A in insulation fix bed methanation catalysts at different levels
Methanation catalyst, is specially product prepared by embodiment 1) the lower generation methanation reaction of effect.
CH in product gas (butt)4Volume content is 95%, H2Molar concentration ＜ 2%, CO2Molar concentration ＜ 2%.
Embodiment 2,
Unstripped gas (CO2) pressure is 3.0MPa, 10000kmol/h, purity ＞ 99% and total sulfur is less than 0.1ppm.
Above-mentioned raw materials gas (CO2) according to 0.6:0.3:0.1 volume ratio, is divided into three strands and respectively enters main methanation device
First adiabatic methanation reactor 1, the second adiabatic methanation reactor 2 and 3 each reactor of the 3rd adiabatic methanation reactor enter
Mouth temperature control is at 250 DEG C, and by methanation reaction, methanator outlet temperatures at different levels are 630 DEG C, each stage reactor
Reaction pressure is 2.8MPa~3.0MPa.
Unstripped gas (H2) pressure is 3.0MPa, 40000kmol/h, purity ＞ 99% and total sulfur is less than 0.1ppm.
Above-mentioned raw materials gas (H2) according to 0.15:0.23:0.23:0.39 volume ratio, is divided into four strands and respectively enters main methane
Disguise the first adiabatic methanation reactor 1 put, the second adiabatic methanation reactor 2, the 3rd adiabatic methanation reactor 3, the
Four adiabatic methanation reactors 4.
First adiabatic methanation reactor inlet process gas H2With CO2Molar ratio be 1：1, CO2In excessive state；The
Two adiabatic methanation reactor inlet process gas H2With CO2Molar ratio be 1.4：1, go out from the first adiabatic methanation reactor
The product gas of mouth plays certain diluting effect, CO2Still in excessive state；3rd adiabatic methanation reactor inlet process gas
H2With CO2Molar ratio be 2.9：1, the product gas from the second adiabatic methanation reactor outlet plays certain diluting effect,
CO2In excessive state, but hydrogen-carbon ratio steps up；4th adiabatic methanation reactor inlet process gas H2With CO2Molar ratio
For 4.0：1, hydrogen-carbon ratio further improves and in the molar ratio that can be reacted completely；Each reactor of deep reaction device afterwards
Inlet process gas H2With CO2Molar ratio maintain essentially in 4.0：1.
According to methanation reaction principle, per 1molCO2Reaction needs 4molH2, generate 1mol methane and 2mol water.Segmentation is anti-
Answer in each reactor in area, H2Relative amount is few, is the reactant of reaction controlling, by controlling H2Amount controlling reaction temperature and
Reaction depth.Waste heat boiler and drum, by-product Gao Pin can be connected by being segmented the high-temperature technology gas of each reactor outlet of reaction zone
The vapor of matter, if it is desired, also can by-product high-quality superheated vapour.
Include the 5th adiabatic methanator 5, the 6th adiabatic methanation reactor 6 and four-line poem with seven characters to a line heat in deep reaction area
Methanator 8.In deep reaction device, the complete CO of unreacted after being segmented reaction zone2With H2Generation deep reaction, the 5th
The control of the inlet temperature of adiabatic methanation reactor and the 6th adiabatic methanation reactor is 250 DEG C, and the 5th adiabatic methanation is anti-
Answer about 580 DEG C of device outlet process gas, the 6th about 450 DEG C of adiabatic methanation reactor outlet process gas.Last fixed bed is anti-
Answer device inlet temperature to be controllable to 230 DEG C to deepen reaction, improve CH in outlet process gas4Content.Wherein second from the bottom anti-
Answer device outlet process gas to be cooled to 40~80 DEG C by heat exchange, the water of reaction generation is gone out by gas-liquid separator separates, last
Platform reactor outlet process gas (380 DEG C) is cooled to 40~80 DEG C by heat exchange, and going out reaction by gas-liquid separator separates generates
Water be final products.
Process gas (can be the carbon dioxide disclosed in CN102091629A in insulation fix bed methanation catalysts at different levels
Methanation catalyst, is specially product prepared by embodiment 1) the lower generation methanation reaction of effect.
CH in product gas (butt)4Volume content is 95%, H2Molar concentration ＜ 2%, CO2Molar concentration ＜ 2%.
Claims (9)
1) and 3) or 2) and 3) 1. the method that natural gas is produced in a kind of segmentation methanation of carbon dioxide, including following step：
1) by H2It is divided at least 3 strands to be separately input into the methanator of 3 series connection, then by CO2It is divided at least 3 stocks
Do not input and carry out methanation reaction into 3 methanators；
2) by CO2It is divided at least 3 strands to be separately input into the methanator of 3 series connection, then by H2It is divided at least 3 stocks
Do not input and carry out methanation reaction into 3 methanators；
3) it is anti-to carry out methanation into the methanator of at least 2 series connection for the input of working off one's feeling vent one's spleen of the methanator
Should, the methanator is worked off one's feeling vent one's spleen as gas product.
2. according to the method described in claim 1, it is characterized in that：The H2From electric power hydrogen manufacturing, solar hydrogen making or wind-powered electricity generation
Hydrogen manufacturing.
3. according to the method described in claim 2, it is characterized in that：By the way of water electrolysis hydrogen production；
The water electrolysis hydrogen production uses coal gasification waste water.
4. method according to any one of claim 1-3, it is characterised in that：In step 1) and step 2), by the H2With
The CO2Input is into the methanator after being both heated to 250~320 DEG C.
5. method according to any one of claim 1-3, it is characterised in that：In step 1) and step 2), the methane
The temperature for changing reaction is 250 DEG C~670 DEG C；
Pressure in the methanator is 1~5MPa.
6. method according to any one of claim 1-3, it is characterised in that：In step 3), the methanation reaction
Temperature is 230 DEG C~250 DEG C；
Pressure in the methanator is 1~5MPa.
7. method according to any one of claim 1-3, it is characterised in that：In step 1),
In methanator described in First, the H2With the CO2Molar ratio be 30~4：1；
In second methanator, the H2With the CO2Molar ratio be 30~4：1；
In 3rd methanator, the H2With the CO2Molar ratio be 30~4：1；
In step 2),
In methanator described in First, the H2With the CO2Molar ratio be 0.5~6：1；
In second methanator, the H2With the CO2Molar ratio be 0.5~6：1；
In 3rd methanator, the H2With the CO2Molar ratio be 0.5~6：1.
8. method according to any one of claim 1-3, it is characterised in that：In step 1), the H2It is according to volume ratio
0.65：0.30：0.05, which is divided into three strands, is separately input into the methanator；
The CO2It is 0.14 according to volume ratio：0.22：0.24：0.40, which is divided into four strands, is separately input into the methanator.
9. method according to any one of claim 1-3, it is characterised in that：In step 2), the CO2According to volume ratio
For 0.6：0.3：0.1, which is divided into three strands, is separately input into the methanator；
The H2It is 0.15 according to volume ratio：0.23：0.23：0.39, which is divided into four strands, is separately input into the methanator.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2060686A (en) * | 1979-10-22 | 1981-05-07 | Conoco Inc | Concurrent shift-methanation process |
| CN104845689A (en) * | 2014-02-18 | 2015-08-19 | 中国石油化工股份有限公司 | Technology for preparing synthetic natural gas through methanation of coal-based synthetic gas |
| WO2015159044A1 (en) * | 2014-04-16 | 2015-10-22 | Johnson Matthey Public Limited Company | Process |
-
2016
- 2016-01-20 CN CN201610037828.3A patent/CN105623762B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2060686A (en) * | 1979-10-22 | 1981-05-07 | Conoco Inc | Concurrent shift-methanation process |
| CN104845689A (en) * | 2014-02-18 | 2015-08-19 | 中国石油化工股份有限公司 | Technology for preparing synthetic natural gas through methanation of coal-based synthetic gas |
| WO2015159044A1 (en) * | 2014-04-16 | 2015-10-22 | Johnson Matthey Public Limited Company | Process |
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