CN104818065B - A kind of adiabatic cooling type methanation synthesizing methane method - Google Patents
A kind of adiabatic cooling type methanation synthesizing methane method Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 238000001816 cooling Methods 0.000 title claims abstract description 117
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 166
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 160
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 38
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 36
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000012495 reaction gas Substances 0.000 claims description 49
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000005804 alkylation reaction Methods 0.000 claims description 13
- 230000029936 alkylation Effects 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 208000027418 Wounds and injury Diseases 0.000 abstract description 2
- 230000006378 damage Effects 0.000 abstract description 2
- 208000014674 injury Diseases 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229960004424 carbon dioxide Drugs 0.000 description 17
- 230000002631 hypothermal effect Effects 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 235000019628 coolness Nutrition 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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Abstract
The invention discloses a kind of adiabatic cooling type methanation synthesizing methane method, belong to chemical field synthetic natural gas technology, method includes arranging saturator and hot-water tower, a large amount of steam condenser heats contained by high-temperature gas after methanation reaction are reclaimed with hot-water tower, then the heat that hot-water tower is reclaimed is evaporated the water in entrance unstripped gas with saturator, increase and enter moisture content in methanator unstripped gas, control methanation equilibrium temperature simultaneously suppresses side reaction to occur.Methanator is adiabatic cooling type reactor.When carbon monoxide in unstripped gas and carbon dioxide volumetric concentration summation >=12%; arrange circulator to be recycled back into gas after methanation reaction; control methanation adiabatic reaction equilibrium temperature; guard catalyst does not receive high temperature injury; two tandem adiabatic cooling type reactors are set simultaneously; and unstripped gas is divided into two parts, respectively enter two adiabatic cooling type reactors.The present invention is high in order to solve the problems, such as isothermal methanation high energy consumption, adiabatic methanation investment.
Description
Technical field
The invention belongs to chemical field synthetic natural gas technology.
Background technology
Methanation synthesizing methane technique mainly has the adiabatic methanation synthesizing methane technique with circulation and without circulation at present
Isothermal methanation synthesizing methane technique.
Using the isothermal methanation synthesizing methane technique without circulation, as methanation reaction speed is fast, focus temperature is reacted
Degree will be close to equilibrium temperature, and for the higher unstripped gas of carbon monoxide and carbon dioxide content, methanation hot(test)-spot temperature will very
, now easily analysis carbon reaction and cause methanation catalyst to fail, although a large amount of steam can be directly added in unstripped gas in height there is
Methanation hot(test)-spot temperature is controlled to dilute in unstripped gas carbon monoxide and gas concentration lwevel, a large amount of due to needing to be directly added into
Steam, energy consumption are high；For the relatively low unstripped gas of carbon monoxide and carbon dioxide content, as isothermal reaction moves heat, cause first
Alkanisation hot(test)-spot temperature is not high, and methanation reaction speed reduces with temperature and reduces, and catalyst efficiency will reduce.
The adiabatic methanation synthesizing methane technique circulated using band, after reacting, methane gas is returned one in dilution unstripped gas
Carbonoxide and gas concentration lwevel controlling methanation hot(test)-spot temperature, as after adiabatic reaction, temperature is higher, after reaction in gas
Carbon monoxide and carbon dioxide balance concentration are also higher, for the higher unstripped gas of carbon monoxide and carbon dioxide content, in order to
Control methanation hot(test)-spot temperature, needs to increase internal circulating load and increase adiabatic methanation reactor quantity, while will also increase recovery
The related facility of adiabatic methanation reaction gas heat of high temperature, causes to invest larger, and energy consumption is also of a relatively high.
Content of the invention
It is an object of the invention to：It is based on problem above, it is proposed that adiabatic cooling type methanation synthesizing methane technique, so as to
Solve the problems, such as that isothermal methanation high energy consumption, adiabatic methanation investment are high.
The object of the invention is realized by following technical proposals：
Saturator and hot-water tower are set, and low level heat contained by methanation reaction gas are reclaimed with hot-water tower, then will with saturator
The heat that hot-water tower is reclaimed enters water evaporation in unstripped gas, increases moisture content in unstripped gas, is lowered into methanation reaction
Carbon monoxide and gas concentration lwevel in the unstripped gas of device, control methanation temperature simultaneously suppress side reaction to occur, and protect methanation
Catalyst, methanator are adiabatic cooling type reactor, and in adiabatic cooling type reactor, unstripped gas is first passed through and do not changed
The methanation catalyst bed of heat carries out methanation adiabatic reaction, makes reaction quickly reach balance, exchanges heat subsequently into there is water
Methanation catalyst bed, cooling simultaneously carry out further methanation reaction simultaneously, and heat of reaction produces steam by water and takes away.
In such scheme, the adiabatic cooling type reaction process synthesizing methane with saturator, hot-water tower is adopted：Returned with hot-water tower
A large amount of steam condenser heats contained by high-temperature gas after methanation reaction are received, the heat that hot-water tower is reclaimed is made water with saturator then
Evaporate in unstripped gas, replacement prior art is directly added into a large amount of steam come the mode for diluting, and energy consumption declines to a great extent；Add and steam
Vapour combines adiabatic cooling type reactor, effective control methanation hot(test)-spot temperature, and reduces methanation side reaction, and extending catalyst makes
Use the life-span.
Hot-water tower is all returned to after the condensed water heat exchange condensed out by cooling after hot-water tower, in hot-water tower
It is dissolved in the gas such as methane parsing in condensed water to return in methane gas, the water that methanation is generated finally is arranged from hot-water tower bottom
Remove, methane is reduced with water is generated and exclude loss.
In such scheme, after hot-water tower both plays recovery methanation reaction, a large amount of steam condenser heats contained by high-temperature gas are made
With, while and play recovery methane effect, kill two birds with one stone.
More specifically, adiabatic cooling type methanation synthesizing methane method of the present invention, step include：Saturator and heat are set
Water tower, unstripped gas exchange heat through the 3rd heat exchanger and the methanation reaction gas for going out the hot-water tower after heating up, and enter the saturator
After middle increase moisture content, entrance First Heat Exchanger is exchanged heat with the methanation reaction gas for going out methanator after heating up and enters institute
Stating methanator carries out methanation reaction, and the methanator is adiabatic cooling type reactor, in adiabatic cooling type
In reactor, unstripped gas first passes through the methanation catalyst bed not exchanged heat and carries out methanation adiabatic reaction, and reaction reaches balance
Enter back into the methanation catalyst bed of cooling heat transferring afterwards, further methanation reaction, reaction heat is carried out simultaneously in heat exchange cooling
Amount produces steam by heat-exchanging water and takes away；Go out the methanation reaction gas of methanator through First Heat Exchanger heat exchange cooling
Afterwards, go successively to the second heat exchanger with go out the hot-water tower hot water exchange heat cooling after enter the hot-water tower, go out the hot water
The methanation reaction gas of tower exchanges heat through the 3rd heat exchanger, and temperature is entered after being down to normal temperature after sending after separator separates free water
Continuous technique；The hot water for going out the hot-water tower bottom of towe is divided into two-way, after heating up through second heat exchanger heat exchange all the way, enters described
Saturator is evaporated to water vapour, after tetra- heat exchangers of another Lu Jing are lowered the temperature with the free water heat exchange that isolates from the separator
Discharge；After going out the hot water of the saturator and heating up through the 4th heat exchanger heat exchange, free water returns the hot-water tower,
The gas parsing being dissolved in hot-water tower in condensed water is returned to out in the methanation reaction gas of hot-water tower.
In order to control methanation adiabatic reaction equilibrium temperature, guard catalyst does not receive high temperature injury, when in entrance unstripped gas
Arrange circulator to return a gas circulation part after methanation reaction when carbon monoxide and carbon dioxide volumetric concentration summation >=12%
Return methanator and mix reduction carbon monoxide and gas concentration lwevel with unstripped gas, while arranging two tandem adiabatic coolings
Unstripped gas is divided into two parts by type reactor, respectively enters two adiabatic cooling type reactors, reduces the total gas of recycle compressor
Amount.Carbon monoxide and carbon dioxide volumetric concentration summation in unstripped gas<When 12%, then methane gas circulation or outer after need not reacting
Plus steam is being lowered into carbon monoxide and gas concentration lwevel in the unstripped gas of methanator.
More specifically, in the present invention program, when carbon monoxide in unstripped gas and carbon dioxide volumetric concentration summation >=12%
When, while arranging first and second adiabatic cooling type methanator of two tandems, unstripped gas is divided into two parts, a part
The saturator, another part and the methane for going out the first adiabatic cooling type methanator is entered with circulating air after mixing
The second adiabatic cooling type methanator is entered after changing reaction gas mixing and proceeds methanation reaction, go out described second
The methanation reaction gas of adiabatic cooling type methanator enters the First Heat Exchanger heat exchange cooling；Go out the 3rd heat exchange
The methanation reaction gas of device is divided into two-way after the heat exchange cooling of the 5th heat exchanger, returns the described 5th as the circulating air all the way
Heat exchanger heat exchange is mixed into saturator with the unstripped gas after heating up, and another road enters after the separator separates free water and send
Subsequent technique.When carbon monoxide in unstripped gas and carbon dioxide volumetric concentration summation<When 12%, it is not necessary to which after reaction, methane gas are followed
Ring is being lowered in the unstripped gas of methanator between carbon monoxide and gas concentration lwevel, and saturator, hot-water tower
Adiabatic cooling type methanator only 1.
Also containing a small amount of carbon monoxide and carbon dioxide in methane gas after refrigerated separation, when methane gas needs to produce
During LNG product, then a methanator is set wherein remaining carbon monoxide and carbon dioxide reaction are fallen, after making reaction
Carbon dioxide in methane gas meets the requirement of cryogenic liquefying.A hydrogen rich gas part for cryogenic liquefying returns to methanation system.
The remaining carbon monoxide and the methanator of carbon dioxide of reacting is also that adiabatic cooling type methanation is anti-
Answer device.
More specifically, in the present invention program, when methane gas needs to produce LNG product, methanation reaction gas is through institute
State after separator separates free water, entering the 3rd adiabatic cooling type methanator through heat exchanger after heating up, to carry out methanation anti-
Should, go out the methanation reaction gas of the 3rd adiabatic cooling type methanator, separate after free water as LNG through another separator
Product pneumatic transmission successor company, and the free water that isolates returns the hot-water tower after heating up through the 4th heat exchanger heat exchange.
LNG is produced to the high feed gas containing carbon monoxide synthesizing methane of low pressure, and band is first adopted under raw gas pressure≤1.2MPa
Then synthesizing methane air pressure be reduced to >=more than 2.0MPa by saturator, the adiabatic cooling type reaction process synthesizing methane of hot-water tower,
Wherein remaining carbon monoxide and carbon dioxide reaction are fallen by a methanator again, made after reaction in methane gas
Carbon dioxide meets the requirement of cryogenic liquefying.A hydrogen rich gas part for cryogenic liquefying returns to methanation system.
The high feed gas containing carbon monoxide of the low pressure is that finger pressure≤1.2MPa, carbon monoxide and carbon dioxide volumetric concentration are total
With >=12% unstripped gas.The remaining carbon monoxide and the methanator of carbon dioxide of reacting is also adiabatic cooling type
Methanator.
When unstripped gas synthesizing methane produces SNG, while arranging first and second adiabatic cooling type methanation reaction of two tandems
Unstripped gas is divided into two parts by device, is partly into the saturator, another part with go out the first adiabatic cooling type methane
The second adiabatic cooling type methanator is entered after the methanation reaction gas mixing for changing reactor and proceeds methanation
Reaction, the methanation reaction gas for going out the second adiabatic cooling type methanator enter the First Heat Exchanger heat exchange drop
Temperature, methanation reaction gas are separated after free water as SNG product pneumatic transmission subsequent techniques through the separator.
Beneficial effects of the present invention：
（One）, by the low level of methanation reaction heat for unstripped gas humidification, be lowered into the carbon monoxide and two of reactor
Oxidation concentration of carbon, effective control methanation hot(test)-spot temperature, and methanation side reaction is reduced, extend catalyst service life.
（Two）, combine to increase moisture content in unstripped gas using hot-water tower and saturator, controlling reaction temperature simultaneously suppresses
Side reaction occurs, and without additional steam, saves energy consumption, while ensureing catalyst life.
（Three）, LNG is produced to the high feed gas containing carbon monoxide synthesizing methane of low pressure, synthesizing methane, makes follow-up first under low pressure
Alkane gas compression volume is greatly reduced, and saves gas compression work(.
（Four）, methanation generate water through hot-water tower higher temperature strip, by the gases such as methane dissolve in water return be
System, reduces the component such as contained methane in the water of exclusion methanation system, improves methane recovery.
（Five）, for each link for needing to rise gentle cooling, carry out sufficient heat exchange, capacity usage ratio is high.
Description of the drawings
Fig. 1 is the high feed gas containing carbon monoxide adiabatic cooling type methanation synthesizing methane LNG of low pressure in the inventive method
Schematic flow sheet, and the high feed gas containing carbon monoxide adiabatic cooling type methanation synthesizing methane LNG stream of low pressure as embodiment 1
Journey schematic diagram；
Fig. 2 is the pressure feed gas adiabatic cooling type methanation synthesizing methane LNG stream journey schematic diagram in the inventive method,
And the pressure feed gas adiabatic cooling type methanation synthesizing methane LNG stream journey schematic diagram as embodiment 2；
Fig. 3 is the high feed gas containing carbon monoxide adiabatic cooling type methanation synthesizing methane LNG of middle pressure in the inventive method
Schematic flow sheet, and the high feed gas containing carbon monoxide adiabatic cooling type methanation synthesizing methane LNG stream of middle pressure as embodiment 3
Journey schematic diagram；
Fig. 4 is the middle pressure unstripped gas adiabatic cooling type methanation synthesizing methane LNG stream journey schematic diagram in the inventive method,
And the middle pressure unstripped gas adiabatic cooling type methanation synthesizing methane LNG stream journey schematic diagram as embodiment 4；
Fig. 5 is the adiabatic cooling type methanation synthesizing methane SNG schematic flow sheets in the inventive method, and as enforcement
The adiabatic cooling type methanation synthesizing methane SNG schematic flow sheets of example 5；
In Fig. 1,2,3,4,5, in figure, each digital number is only used for marked differential, does not represent order arrangement, and wherein R1-3 is
Adiabatic cooling type methanator（The first to three）, V1-4 is separator（First to fourth）, T1 is saturator, and T2 is hot water
Tower, E1-9 are heat exchanger（The first to nine）, C1 is recycle compressor, and C2 is supercharger, and P1-2 is water pump, and 0 is raw material tracheae
Road, 1-39 are pipeline.
Specific embodiment
Following non-limiting examples are used for the present invention to be described.
Embodiment 1：
The high feed gas containing carbon monoxide adiabatic cooling type methanation synthesizing methane techniqueflow of the low pressure of the present embodiment is as follows：
Flow process is as shown in Figure 1.The present embodiment unstripped gas be the high CO gas of low pressure, raw gas pressure for～
0.93MPa (G), temperature are normal temperature, and flow is～51000 Nm3/ h, gas mainly consist of CO:20%、CO2：3%、H2:74%、
CH4:1.4%, enter heat exchanger E3 and exchange heat with hot-water tower exit gas, unstripped gas is heated to～110 DEG C, is then divided into two
Point：～40% unstripped gas is mixed with equal flow circulating air after heating, CO after mixing:～10%, CO2：～2%, H2:~
45.7%、CH4:～38.5%, saturator T1 is entered, from saturator T1 out unstripped gas temperature～129 DEG C, water content～
26.5%, heat exchanger E1 and the second adiabatic cooling type methanator R2 out reaction gas heat exchange is entered, unstripped gas is heated to
～250 DEG C of first adiabatic cooling type methanator R1 of entrance, adiabatic reaction hot(test)-spot temperature～509 DEG C, hypothermic response export
Temperature～350 DEG C；～60% unstripped gas with from the first adiabatic cooling type methanator R1, out reaction gas mixes, after mixing
Temperature～275 DEG C, enter the second adiabatic cooling type methanator R2, adiabatic reaction hot(test)-spot temperature～531 DEG C, hypothermic response
Outlet temperature～350 DEG C, reaction methane gas contain CO:～0.01%, CO2：～0.96%, H2:～10%, CH4:～43.6%.First
With water needed for second adiabatic cooling type methanator R1, R2 coolings from same drum.
From the second adiabatic cooling type methanator R2 out reaction gas through heat exchanger E1 and E2, temperature is down to respectively
260 DEG C and 170 DEG C, subsequently into hot-water tower T2, from hot-water tower T2 out methane gas temperature～128 DEG C, then respectively through changing
Hot device E3, E5, E6 heat exchange, temperature are down to～60 DEG C, are then divided into two parts：～20400 Nm3/ h methane gas are through circulation pressure
Contracting machine C1 boostings enter heat exchanger E5 and are heated to～113 DEG C, then mix with unstripped gas；Remainder methane gas are through heat exchanger
E7 is cooled to normal temperature and enters separator V2.
Separate free water after methane gas be compressed to～2.0MPa (G) through compressor C2, subsequently into heat exchanger E8 with from
The out reaction gas heat exchange of front three alkylation reactors R3, is heated to～250 DEG C of entrance front three alkylation reactors R3, reflects
Mouthful temperature～317 DEG C, from the 3rd adiabatic cooling type methanator R3 out reaction gas through heat exchanger E8 and E9, temperature drops
To normal temperature, subsequently into separator V3, after separating free water, methane product gas contains CO:Micro-, CO2：＜ 20ppm, H2:～12%,
CH4:～84.6%, then send subsequent technique.
Converge entrance heat exchange after the pressurization of water pump P 2 with the water from separator V3 out from separator V2 free waters out
Device E4, be warmed to～114 DEG C enter into hot-water tower T2, from hot-water tower T2 bottom of towe out hot water temperature～144 DEG C, flow～
137 m3/ h, is divided into two：～126 m3/ h through water pump P 1 pressurization after enter saturator T1, saturator T1 out hot water temperature～
73 DEG C, flow～115 m3/ h, returns to hot-water tower T2；～11 m3/ h hot water enter heat exchanger E4 cool to～75 DEG C send first
Alkanisation system.
Embodiment 2：
The pressure feed gas adiabatic cooling type methanation synthesizing methane LNG stream journey of the present embodiment is as follows：
Flow process is as shown in Figure 2.The present embodiment unstripped gas is pressure feed gas, and raw gas pressure is～0.93MPa (G), warm
Spend for normal temperature, flow is～60000 Nm3/ h, gas mainly consist of CO:8.6%、CO2：3%、H2:60%、CH4:24%, enter
Heat exchanger E3 is exchanged heat with hot-water tower T2 exit gas, and unstripped gas is heated to～113 DEG C, subsequently into saturator T1, from saturation
Tower T1 out unstripped gas temperature～123 DEG C, water content～22% enter heat exchanger E1 and adiabatic cooling type methanator R1
Out reaction gas heat exchange, unstripped gas are heated to～250 DEG C of entrance adiabatic cooling type methanator R1, adiabatic reaction focus
Temperature～553 DEG C, hypothermic response outlet temperature～350 DEG C, reaction methane gas contain CO:Micro-, CO2：～0.1%, H2:～22%,
CH4:～34%.Needed for adiabatic cooling type methanator R1 coolings, water is from drum.
From adiabatic cooling type methanator R1 out reaction gas through heat exchanger E1 and E2, temperature is down to 215 respectively
DEG C and 170 DEG C, subsequently into hot-water tower T2, from hot-water tower T2 out methane gas temperature～123 DEG C, then respectively through heat exchanger
E3, E5, E6 exchange heat, and temperature is down to normal temperature and enters separator V2.
Separate free water after methane gas be compressed to～2.1MPa (G) through compressor C2, subsequently into heat exchanger E7 with from
The out reaction gas heat exchange of front three alkylation reactors R3, is heated to～300 DEG C of entrance front three alkylation reactors R3, reflects
Mouthful temperature～309 DEG C, from the 3rd adiabatic cooling type methanator R3 out reaction gas through heat exchanger E7 and E8, temperature drops
To normal temperature, subsequently into separator V3, after separating free water, methane product gas contains CO:Micro-, CO2：＜ 20ppm, H2:～36%,
CH4:～57%, then send subsequent technique.
Converge entrance heat exchange after the pressurization of water pump P 2 with the water from separator V3 out from separator V2 free waters out
Device E4, be warmed to～114 DEG C enter into hot-water tower T2, from hot-water tower T2 bottom of towe out hot water temperature～144 DEG C, flow～
133 m3/ h, is divided into two：～126 m3/ h through water pump P 1 pressurization after enter saturator T1, saturator T1 out hot water temperature～
73 DEG C, flow～113 m3/ h, returns to hot-water tower T2；～7 m3/ h hot water enter heat exchanger E4 cool to～74 DEG C send first
Alkanisation system.
Embodiment 3：
The high feed gas containing carbon monoxide adiabatic cooling type methanation synthesizing methane LNG stream journey of the middle pressure of the present embodiment is as follows：
Flow process is as shown in Figure 3.The present embodiment unstripped gas is that the high CO gas of middle pressure, raw gas pressure are～2.0MPa
(G), temperature is normal temperature, and flow is～51000 Nm3/ h, gas mainly consist of CO:20%、CO2：3%、H2:74%、CH4:
1.4%, enter heat exchanger E3 and exchange heat with hot-water tower T2 exit gas, unstripped gas is heated to～142 DEG C, is then divided into two parts：
～45% unstripped gas is mixed with equal flow circulating air after heating, CO after mixing:～10%, CO2：～2.1%, H2:～45%,
CH4:～40%, saturator T1 is entered, from saturator T1 out unstripped gas temperature～148 DEG C, water content～22%, heat exchanger is entered
E1 and the second adiabatic cooling type methanator R2 out reaction gas heat exchange, unstripped gas are heated to～250 DEG C of entrance first
Adiabatic cooling type methanator R1, adiabatic reaction hot(test)-spot temperature～553 DEG C, hypothermic response outlet temperature～350 DEG C；~
55% unstripped gas with from the first adiabatic cooling type methanator R1, out reaction gas mixes, enter by temperature～280 DEG C after mixing
Enter the second adiabatic cooling type methanator R2, adiabatic reaction hot(test)-spot temperature～553 DEG C, hypothermic response outlet temperature～350
DEG C, reaction methane gas contain CO:Micro-, CO2：～0.77%, H2:～8.4%, CH4:～48%.First and second adiabatic cooling type methane
Change water needed for reactor R1, R2 cooling from same drum.
From the second adiabatic cooling type methanator R2 out reaction gas through heat exchanger E1 and E2, temperature is down to respectively
270 DEG C and 170 DEG C, subsequently into hot-water tower T2, from hot-water tower T2 out methane gas temperature～153 DEG C, then respectively through changing
Hot device E3, E5, E6 heat exchange, temperature are down to～60 DEG C, are then divided into two parts：～23000 Nm3/ h methane gas are through circulation pressure
Contracting machine C1 boostings enter heat exchanger E5 and are heated to～133 DEG C, then mix with unstripped gas；Remainder methane gas are through heat exchanger
E7 is cooled to normal temperature and enters separator V2.
After separating free water, methane gas enter heat exchanger E8 and from front three alkylation reactors R3, out reaction gas exchanges heat, quilt
～250 DEG C of entrance front three alkylation reactors R3 are heated to, outlet temperature～302 DEG C is reacted, from front three alkylation reactors R3
Out through heat exchanger E8 and E9, temperature is down to normal temperature to reaction gas, subsequently into separator V3, separates methane product after free water
Gas contains CO:Micro-, CO2：＜ 20ppm, H2:～9.5%, CH4:～87%, then send subsequent technique.
Heat exchanger E4 is entered from separator V2 and V3 free water out after the pressurization of water pump P 2, be warmed to～141 DEG C
Hot-water tower is entered into, from hot-water tower bottom of towe out hot water temperature～171 DEG C, flow～101 m3/ h, is divided into two：～90 m3/h
Saturator T1, saturator T1 out hot water temperature～104 DEG C, flow～79 m is entered through water pump P 1 after pressurizeing3/ h, returns to heat
Water tower T2；～11 m3/ h hot water enter heat exchanger E4 cool to～76 DEG C send methanation system.
Embodiment 4：
The middle pressure unstripped gas adiabatic cooling type methanation synthesizing methane LNG stream journey of the present embodiment is as follows：
Flow process is as shown in Figure 4.The present embodiment unstripped gas is middle pressure unstripped gas, and raw gas pressure is～2.0MPa (G), temperature
For normal temperature, flow is～60000 Nm3/ h, gas mainly consist of CO:5.8%、CO2：2%、H2:62%、CH4:26%, entrance is changed
Hot device E3 is exchanged heat with hot-water tower T2 exit gas, and unstripped gas is heated to～119 DEG C, subsequently into saturator T1, from saturator
T1 out unstripped gas temperature～146 DEG C, water content～21% enter heat exchanger E1 and adiabatic cooling type methanator R1 and go out
Carry out reaction gas heat exchange, unstripped gas is heated to～250 DEG C of entrance adiabatic cooling type methanator R1, adiabatic reaction focus temperature
～557 DEG C of degree, hypothermic response outlet temperature～350 DEG C, reaction methane gas contain CO:Micro-, CO2：～0.02%, H2:～33%, CH4:
～30.2%.Needed for adiabatic cooling type methanator R1 coolings, water is from drum.
From adiabatic cooling type methanator R1 out reaction gas through heat exchanger E1 and E2, temperature is down to 243 respectively
DEG C and 170 DEG C, subsequently into hot-water tower T2, from hot-water tower T2 out methane gas temperature～129 DEG C, then respectively through heat exchanger
E3, E5, E6 exchange heat, and temperature is down to normal temperature and enters separator V2.
After separating free water, methane gas enter heat exchanger E7 and from front three alkylation reactors R3, out reaction gas exchanges heat, quilt
～300 DEG C of entrance front three alkylation reactors R3 are heated to, outlet temperature～302 DEG C is reacted, from the 3rd adiabatic cooling type methane
Change reactor R3 out reaction gas through heat exchanger E7 and E8, temperature is down to normal temperature, subsequently into separator V3, separate free water
Methane product gas contains CO afterwards:Micro-, CO2：＜ 20ppm, H2:～50%, CH4:～45%.Send subsequent technique.
Heat exchanger E4 is entered from separator V2 and V3 free water out after the pressurization of water pump P 2, be warmed to～133 DEG C
Hot-water tower T2 is entered into, from hot-water tower T2 bottom of towe out hot water temperature～163 DEG C, flow～131 m3/ h, is divided into two：~
126 m3/ h enters saturator T1, saturator T1 out hot water temperature～73 DEG C, flow～113 m after the pressurization of water pump P 13/ h,
Return to hot-water tower T2；～5 m3/ h hot water enter heat exchanger E4 cool to～75 DEG C send methanation system.
Embodiment 5：
The middle pressure unstripped gas adiabatic cooling type methanation synthesizing methane SNG flow processs of the present embodiment are as follows：
Flow process is as shown in Figure 5.The present embodiment unstripped gas is middle pressure unstripped gas, and raw gas pressure is～2.0MPa (G), temperature
For normal temperature, flow is～60000 Nm3/ h, gas mainly consist of CO:8.6%、CO2：3%、H2:60%, enter heat exchanger E3 with
Hot-water tower T2 exit gas exchanges heat, and unstripped gas is heated to～133 DEG C, is then divided into two parts：～40% unstripped gas enters full
With tower T1, from saturator T1 out unstripped gas temperature～157 DEG C, water content～28%, heat exchanger E1 and the second adiabatic cooling is entered
Type methanator R2 out reaction gas heat exchange, unstripped gas are heated to～250 DEG C of first adiabatic cooling type methanations of entrance
Reactor R1, adiabatic reaction hot(test)-spot temperature～556 DEG C, hypothermic response outlet temperature～400 DEG C；～60% unstripped gas with from first
Adiabatic cooling type methanator R1 out reaction gas mixing, temperature～260 DEG C after mixing enter the second adiabatic cooling type first
Alkylation reactors R2, adiabatic reaction hot(test)-spot temperature～541 DEG C, hypothermic response outlet temperature～350 DEG C, reaction methane gas contain CO:
Micro-, CO2：～0.02%, CH4:～39%.First and second adiabatic cooling type methanator R1, R2 cooling needed for water from
Same drum.
From the second adiabatic cooling type methanator R2 out reaction gas through heat exchanger E1 and E2, temperature is down to respectively
301 DEG C and 170 DEG C, subsequently into hot-water tower T2, from hot-water tower T2 out methane gas temperature～143 DEG C, then respectively through changing
Hot device E3, E5, E6 heat exchange, temperature are down to normal temperature and enter separator V2, separate methane product pneumatic transmission subsequent technique after free water.
Heat exchanger E4 is entered from separator V2 free waters out after the pressurization of water pump P 2, be warmed to～132 DEG C of entrance
Hot-water tower T2 is arrived, from hot-water tower T2 bottom of towe out hot water temperature～162 DEG C, flow～115m3/ h, is divided into two：～108 m3/h
Saturator T1, saturator T1 out hot water temperature～123 DEG C, flow～100 m is entered through water pump P 1 after pressurizeing3/ h, returns to
Hot-water tower T2；～7 m3/ h hot water enter heat exchanger E4 cool to～73 DEG C send methanation system.
Presently preferred embodiments of the present invention is the foregoing is only, not in order to limit the present invention, all in essence of the invention
Any modification, equivalent and improvement that is made within god and principle etc., should be included within the scope of the present invention.
Claims (6)
1. a kind of adiabatic cooling type methanation synthesizing methane method, it is characterised in that step includes：Saturator and hot-water tower are set,
Unstripped gas exchanges heat through the 3rd heat exchanger and the methanation reaction gas for going out the hot-water tower after heating up, and entering in the saturator increases
After moisture content, entrance First Heat Exchanger is exchanged heat with the methanation reaction gas for going out methanator after heating up and enters the methane
Changing reactor carries out methanation reaction, and the methanator is adiabatic cooling type reactor, in adiabatic cooling type reactor
Middle unstripped gas first passes through the methanation catalyst bed not exchanged heat and carries out methanation adiabatic reaction, and reaction is entered after reaching balance again
Entering the methanation catalyst bed of cooling heat transferring, further methanation reaction simultaneously being carried out in heat exchange cooling, heat of reaction is by changing
Hot water produces steam and takes away；After going out the methanation reaction gas of methanator through First Heat Exchanger heat exchange cooling, continue
Enter the second heat exchanger with go out the hot-water tower hot water exchange heat cooling after enter the hot-water tower, go out the methane of the hot-water tower
Change reaction gas to exchange heat through the 3rd heat exchanger, temperature is entered after separator separates free water after being down to normal temperature and send subsequent technique；
The hot water for going out the hot-water tower bottom of towe is divided into two-way, after heating up through second heat exchanger heat exchange all the way, enters the saturator
Water vapour is evaporated to, is discharged after tetra- heat exchangers of another Lu Jing and the free water heat exchange cooling that isolates from the separator；
After going out the hot water of the saturator and heating up through the 4th heat exchanger heat exchange, free water returns the hot-water tower, in hot-water tower
In the gas parsing that is dissolved in condensed water return to out in the methanation reaction gas of hot-water tower.
2. adiabatic cooling type methanation synthesizing methane method as claimed in claim 1, it is characterised in that step includes：Work as raw material
Carbon monoxide and during carbon dioxide volumetric concentration summation >=12% in gas, while arrange first and second adiabatic cooling type of two tandems
Unstripped gas is divided into two parts by methanator, and a part enters the saturator with circulating air after mixing, another part and
The second adiabatic cooling type first is entered after the methanation reaction gas mixing for going out the first adiabatic cooling type methanator
Alkylation reactors proceed methanation reaction, and the methanation reaction gas for going out the second adiabatic cooling type methanator enters
Enter the First Heat Exchanger heat exchange cooling；After going out the methanation reaction gas of the 3rd heat exchanger through the heat exchange cooling of the 5th heat exchanger
Be divided into two-way, be mixed into the unstripped gas full after the 5th heat exchanger heat exchange intensification being returned as the circulating air all the way
And tower, another road enters after the separator separates free water and send subsequent technique.
3. adiabatic cooling type methanation synthesizing methane method as claimed in claim 1 or 2, it is characterised in that step includes：When
When methane gas needs to produce LNG product, methanation reaction gas is separated through the separator after free water, after heating up through heat exchanger
Entering the 3rd adiabatic cooling type methanator carries out methanation reaction, goes out the first of the 3rd adiabatic cooling type methanator
Alkylation reaction gas, separates through another separator as LNG product pneumatic transmission subsequent technique after free water, and the free water warp that isolates
The 4th heat exchanger heat exchange returns the hot-water tower after heating up.
4. adiabatic cooling type methanation synthesizing methane method as claimed in claim 3, it is characterised in that step includes：To low pressure
High feed gas containing carbon monoxide synthesizing methane produces LNG, first using with saturator, hot-water tower under raw gas pressure≤1.2MPa
Then synthesizing methane air pressure be reduced to >=2.0MPa by adiabatic cooling type reaction process synthesizing methane, then anti-by a methanation
Device is answered to fall wherein remaining carbon monoxide and carbon dioxide reaction, the carbon dioxide after making reaction in methane gas meets cryogenic liquid
The requirement of change；The high feed gas containing carbon monoxide of the low pressure is finger pressure≤1.2MPa, carbon monoxide and carbon dioxide volumetric concentration
The unstripped gas of summation >=12%.
5. adiabatic cooling type methanation synthesizing methane method as claimed in claim 1, it is characterised in that step includes：Work as raw material
Carbon monoxide and carbon dioxide volumetric concentration summation in gas<When 12%, it is not necessary to which after reaction, methane gas circulate to be lowered into methane
Change the adiabatic cooling type methane between carbon monoxide and gas concentration lwevel, and saturator, hot-water tower in the unstripped gas of reactor
Change reactor only 1.
6. adiabatic cooling type methanation synthesizing methane method as claimed in claim 1, it is characterised in that step includes：Unstripped gas
When synthesizing methane produces SNG, while first and second adiabatic cooling type methanator of two tandems is set, by unstripped gas point
For two parts, the saturator, another part and the first for going out the first adiabatic cooling type methanator is partly into
Enter the second adiabatic cooling type methanator and proceed methanation reaction after the mixing of alkylation reaction gas, go out described the
The methanation reaction gas of two adiabatic cooling type methanators enters the First Heat Exchanger heat exchange cooling, methanation reaction gas
Separate after free water as SNG product pneumatic transmission subsequent techniques through the separator.
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| CN106565395B (en) * | 2016-10-26 | 2019-12-17 | 中石化宁波工程有限公司 | Methanation process |
| CN115364807B (en) * | 2022-08-25 | 2024-10-11 | 北京航天试验技术研究所 | Sabatier reactor and method for hydromethanation of Mars surface carbon dioxide |
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| WO2010004300A1 (en) * | 2008-07-11 | 2010-01-14 | Johnson Matthey Plc | Apparatus & process for treating offshore natural gas |
| CN101880559A (en) * | 2010-06-18 | 2010-11-10 | 大唐国际化工技术研究院有限公司 | A method and device for producing synthetic natural gas |
| CN102886230A (en) * | 2012-10-08 | 2013-01-23 | 中国石油化工集团公司 | CO (carbon monoxide) conversion process adopting tandem isothermal furnaces of saturation tower |
| CN102888252A (en) * | 2012-10-08 | 2013-01-23 | 中国石油化工集团公司 | Saturation tower/isothermal furnace series/heat isolation furnace CO transformation technology |
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| WO2010004300A1 (en) * | 2008-07-11 | 2010-01-14 | Johnson Matthey Plc | Apparatus & process for treating offshore natural gas |
| CN101880559A (en) * | 2010-06-18 | 2010-11-10 | 大唐国际化工技术研究院有限公司 | A method and device for producing synthetic natural gas |
| CN102886230A (en) * | 2012-10-08 | 2013-01-23 | 中国石油化工集团公司 | CO (carbon monoxide) conversion process adopting tandem isothermal furnaces of saturation tower |
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