CN103881780A - Process of preparing liquefied natural gas by supplementing carbon dioxide with coke-oven gas - Google Patents
Process of preparing liquefied natural gas by supplementing carbon dioxide with coke-oven gas Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical engineering and specifically discloses a novel process of preparing liquefied natural gas. The process comprises the steps as follows: purifying and pre-purifying a CO2-rich gas to obtain the CO2 gas with content over 95%, mixing the gas with a hydrogen-rich gas, carrying out deep hydrodesulfurization to obtain a gas mixture rich in CO2 and H2 with total sulfur less than 0.05ppm; pre-treating, compressing and purifying a cove-oven gas, carrying out multi-stage external-circulation heat-insulation methanation with the gas mixture rich in CO2 and H2, carrying out molecular sieve deep dehydration, and finally carrying out copious-cooling, separating and liquefying to obtain the liquefied natural gas, the hydrogen-rich gas and a nitrogen-rich gas, wherein the hydrogen-rich gas is returned to an inlet of a material gas compressor for being recycled, and the hydrogen-rich gas is applied as a tail gas for being returned to a coking unit and used as a fuel. In the process, utilization rate of CO, CO2 and H2 is high, so that yield of the liquefied natural gas is improved, and product unit consumption is low; and meanwhile, a waste gas can be utilized to purify and sufficiently utilize carbon dioxide.
Description
Technical field
The invention belongs to chemical technology field, relate to containing CO, CO
2and H
2mixed gas produce the technique of natural gas liquids, the technique that is specially a kind of coke(oven)gas and supplements carbonic acid gas preparing liquefied natural gas.
Background technology
In recent years, Sweet natural gas receives much concern as clean energy.Current global Natural Gas Consumption Using is up to annual 2.32 trillion Nm
3, account for 24.3% of world's primary energy source total demand.China economy growth momentum continuously and healthily is still continuing, but for ensureing that economic energy source and power is but extremely in short supply.Under the situation successively raising at International Petroleum Price, the energy dilemma of China seems more serious.The energy structure of China is take coal as main, and oil, Sweet natural gas only account for very little ratio, well below world average level.Expect the year two thousand twenty, China's natural gas output is expected to reach 1850 billion cubic meters, and demand reaches 2000 billion cubic meters, and insufficiency of supply-demand reaches 750 billion cubic meters.Along with the continuous growth of national energy demand, Imported Natural Gas, by optimizing Chinese energy structure, effectively solves the dual problem of the energy safety of supply, ecological environmental protection.
Coke(oven)gas composition is comparatively complicated, mainly contains CH
4, CO, CO
2, H
2, CnHm etc., and H
2volume fraction be generally 54%～61%, CO and CO
2volume fraction and be generally 8%～12%, can make CO and CO by methanation reaction
2be converted into methanation, that is:
CO+3H
2→CH
4+H
2O
CO
2+4H
2→CH
4+2H
2O
But due to CO+CO in coke(oven)gas
2content is lower, and hydrogen content is relatively high, still contains the hydrogen that exceedes 20% after coke(oven)gas direct methanation in high methane gas, causes the great wasting of resources.In stack gas, limestone kiln tail gas and blast furnace gas, contain a large amount of CO simultaneously
2also effectively do not utilize.
Mend the technique of carbonic acid gas preparing liquefied natural gas by coke(oven)gas, not only can make the CO in hydrogen excessive in coke(oven)gas and other tail gas
2be fully used, improve methane production, make the hydrogen-rich gas of low temperature separation process liquefaction turn back to front end continuation reaction simultaneously, increasing H
2when utilization, also without decarbonization process, not only having reduced investment and energy consumption, is also to reduce carbon emission, improves a kind of new solution of resource utilization.
Summary of the invention
The object of this invention is to provide H in a kind of coke(oven)gas
2utilization ratio is high, CO
2the technique that gas purification degree is high, output is large, invest less coke(oven)gas supplements carbonic acid gas preparing liquefied natural gas.
In order to realize foregoing invention object, the technical solution used in the present invention is as follows:
Coke(oven)gas supplements a technique for carbonic acid gas preparing liquefied natural gas, comprises that following technological process (referring to Fig. 1) is: first will be rich in CO
2gas (such as stack gas, lime-kiln gas, blast furnace gas etc.) purify and preliminary cleaning, obtain CO
2content (vol%) is greater than more than 95% CO
2gas, then this gas mixes with hydrogen-rich gas, then carries out deep hydrodesulfurizationof purification, obtains the CO that is rich in that total sulfur content is less than 0.05ppm
2and H
2mixed gas.Coke(oven)gas removes tar, naphthalene etc. through pre-treatment, and recompression is carried out hydrogenating desulfurization purification after 1.5～6.0MPa, removes the toxic substance such as sulphur, chlorine.Pre-treatment and the tar content purifying in rear coke(oven)gas are less than 0.1ppm, and sulphur content is less than 20ppb, and cl content is less than 5ppb.Enter one-level methanator, one-level methanator exit gas, hydrogen-rich gas and supplementary CO through the coke(oven)gas purifying after qualified
2gas enters secondary methanator, and from utilizing waste heat boiler to reclaim heat, the second methanator exit gas extracts portion gas as recycle gas, supplement successively more multistage adiabatic methanation reaction, obtain high methane gas, then utilize molecular sieve to carry out deep dehydration to high methane gas, finally enter low temperature separation process liquefying plant and carry out low temperature separation process liquefaction, obtain natural gas liquids, hydrogen-rich gas and nitrogen-rich gas, wherein natural gas liquids is as product.Supplement CO
2(vol%) content is more than or equal to 95% CO
2the amount of substance of gas be coke(oven)gas amount of substance 4～7.5%.Supplementing multistage adiabatic methanation reaction is 2 grades of methanators, 3 grades of methanators or 4 grades of methanation reaction reactors; Preferably 2 grades of methanators or 3 grades of methanators.
Be rich in CO
2gas be stack gas, lime-kiln gas and blast furnace gas.
Coke(oven)gas through pre-treatment, compression and purification enters one-level methanator, is rich in CO
2and H
2mixed gas all enter secondary methanator, and extract portion gas as circulation gas from the second methanator outlet, this circulation gas only enters the first methanator simultaneously.Bring circulation gas into one-level methanation adiabatic reactor by steam injector or recycle gas compressor, and circulation gas is 0.5～2:1 with the amount of substance ratio that enters one-level adiabatic methanation gas reactor, circulation gas temperature is 60 ℃～130 ℃.
In methanation process, the temperature in that enters each methanator is 230 ℃～350 ℃, and pressure is 1.5～6MP
a, the volume space velocity calculating take dry gas in described firsts and seconds reactor is as 8000h
-1～30000h
-1, and the volume space velocity calculating take dry gas in last methanator is as 2000h
-1～5000h
-1.
Low temperature separation process liquefaction operation utilizes rectifying tower to make methane rich oxidizing gases be divided into three strands, first strand is natural gas liquids, second strand is nitrogen-rich gas, the 3rd strand is hydrogen-rich gas, and extract part hydrogen-rich gas and return to front end continuation utilization, 2～10% of the amount of substance that the amount of substance of hydrogen-rich gas is coke(oven)gas.
Positively effect of the present invention shows: CO, CO
2and H
2utilization ratio is high, has improved liquefied natural gas (LNG)-throughput, and unit consumption of product is low, can utilize waste gas carry out purifying carbon dioxide and make full use of simultaneously, has reached bi-directional energy-saving reduction of discharging.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment example:
Below in conjunction with embodiment, the present invention is described in further detail.But this should be interpreted as to the above-mentioned subject area of the present invention only limits to following embodiment.
Embodiment 1
The present embodiment schematic flow sheet is shown in Fig. 1.
Coke(oven)gas forms in table 1, and flow is 100000Nm
3/ h, supplements CO
2the composition of gas is in table 2, and flow is 4000Nm
3/ h.
Table 1 coke(oven)gas butt composition (vol%)
| Title | H 2 | CO | CO 2 | N 2 | CH 4 | C nH m | O 2 |
| Content/% | 59.5 | 6.0 | 2.5 | 4.5 | 24.5 | 2.5 | 0.5 |
Table 2 supplements CO
2butt composition (vol%)
| Title | CO 2 | N 2 |
| Content/% | 95 | 5 |
(1) CO
2purify and purify
First will be rich in CO
2blast furnace gas purify and preliminary cleaning, obtain CO
2the CO of content～95%
2gas, then this part CO
2gas with mix from the hydrogen-rich gas of low temperature separation process liquefaction unit, then hydrogenating desulfurization purifies, and CO
2the flow of gas is 4% of coke(oven)gas flow.
Be coke(oven)gas from the hydrogen-rich gas flow of low temperature separation process liquefying plant 2%, the flow of hydrogen-rich gas is 2000Nm
3/ h, its composition (vol%) is: H
290.82, CH
44.04, N
25.14.
(2) compression and purifying: mixed gas mixture first passes through pre-treatment, then by centrifugal (or back and forth) formula compressor boost extremely～enter clean unit after 1.5MPa.
Pre-treatment adopts Temp .-changing adsorption and dry method hydrogenating desulfurization technical combinations to carry out pre-treatment and purification, removes the toxic substances such as tar in coke(oven)gas, naphthalene, sulphur, chlorine, and wherein tar content is less than 0.1ppm, and sulphur content is less than 20ppb, and cl content is less than 5ppb.To meet the requirement to unstripped gas of follow-up methanation operation.
(3) methanation unit:
Enter one-level methanator, one-level methanator exit gas and hydrogen-rich gas and supplementary CO through the coke(oven)gas purifying after qualified
2gas enters secondary methanator, and extracts portion gas as recycle gas from the second methanator exit gas utilizes waste heat boiler to reclaim heat.This recycle gas is brought circulation gas into first methanation adiabatic reactor by steam injector, and circulation gas is 2:1 with the ratio of amount of substance of the gas that enters the first adiabatic methanation reactor.One-level alkylation reactors and with secondary methanator in dry gas calculate volume space velocity be 8000h
-1, and temperature in is respectively 280 ℃ and 350 ℃, and the volume space velocity that in front three alkylation reactors, dry gas calculates is 5000h
-1, temperature in is 230 ℃.
Butt composition (vol%) after methanation is: H
223.87, CH
468.28, N
27.84, CO
2≤ 50ppm.High methane gas tolerance after methanation is 61223Nm
3/ h, and at this by-product 3.8MP
a～10.0MP
ahigher-grade steam.
(4) low temperature separation process liquefaction
(a) drying and dehydrating
The high methane gas obtaining after methanation utilizes molecular sieve to carry out deep dehydration, makes the H in high methane gas
2o content is less than 1ppm.Drying and dehydrating adopts three tower molecular sieve dehydration schemes.High methane gas by under the water adsorption in gas, makes gas be able to deep dehydration under siccative effect.Under state at a dehydration tower for dehydration, another dehydration tower is in regenerative process, and whole dewatering unit is closed flow process.
(b) high methane gas low temperature separation process liquefaction
High methane gas after drying and dehydrating enters low temperature separation process liquefying plant, and low temperature separation process liquefying plant adopts the low temperature separation process liquefaction process with rectifying.Under the effect of rectifying tower rectifying, high methane gas is separated into natural gas liquids, hydrogen-rich gas and nitrogen-rich gas.
In the present embodiment, natural gas liquids LNG output is 41324Nm
3/ h, and the composition of natural gas liquids LNG (vol%) is: CH
499.14, N
20.86.
Embodiment 2:
The present embodiment process flow diagram is shown in Fig. 1.
Coke(oven)gas forms in table 1, and tolerance is 100000Nm
3/ h, supplements CO
2the composition of gas is in table 2, and tolerance is 7500Nm
3/ h.
Table 1 coke(oven)gas composition (vol%)
| Title | H 2 | CO | CO 2 | N 2 | CH 4 | C nH m | O 2 |
| Content/% | 59.5 | 6.0 | 2.5 | 4.5 | 24.5 | 2.5 | 0.5 |
Table 2 supplements CO
2composition (vol%)
| Title | CO 2 | N 2 |
| Content/% | 98.5 | 1.5 |
(1) CO
2purify and purify
First will be rich in CO
2blast furnace gas purify and purify, obtain CO
2the CO of content～98.5%
2gas, then this part CO
2gas with mix from the hydrogen-rich gas of low temperature separation process liquefaction unit, then hydrogenating desulfurization purifies, and CO
2the flow of gas is 7.5% of coke(oven)gas flow.
Be coke(oven)gas from the hydrogen-rich gas flow of low temperature separation process liquefying plant 5%, the flow of hydrogen-rich gas is 5000Nm
3/ h, its composition (vol%) is: H
287.31, CH
44.41, N
28.28.
(2) compression and purifying: mixed gas mixture first passes through pre-treatment, then by centrifugal (or back and forth) formula compressor boost extremely～enter clean unit after 3.5MPa.
Pre-treatment adopts Temp .-changing adsorption and dry method hydrogenating desulfurization technical combinations to carry out pre-treatment and purification, removes the toxic substances such as tar in gas mixture, naphthalene, sulphur, chlorine, and wherein tar content is less than 0.1ppm, and sulphur content is less than 20ppb, and cl content is less than 5ppb.To meet the requirement to unstripped gas of follow-up methanation operation.
(3) methanation operation:
Enter one-level methanator, one-level methanator exit gas, hydrogen-rich gas and supplementary CO through the coke(oven)gas purifying after qualified
2gas enters secondary methanator, and extracts portion gas as recycle gas from the second methanator exit gas utilizes waste heat boiler to reclaim heat.This recycle gas is brought circulation gas into first methanation adiabatic reactor by steam injector, and circulation gas is 0.5:1 with the ratio of amount of substance of the gas that enters the first adiabatic methanation reactor.The first methanator and with the second methanator in dry gas calculate volume space velocity be 30000h
-1, and temperature in is respectively 300 ℃ and 310 ℃; The volume space velocity that in front three alkylation reactors, dry gas calculates is 10000h
-1, and temperature in is 260 ℃; The volume space velocity that in tetramethyl alkylation reactors, dry gas calculates is 3000h
-1, and temperature in is 240 ℃.
Butt composition (vol%) after methanation is: H
25.29, CH
485.27, N
29.44, CO
2≤ 50ppm.High methane gas tolerance after methanation is 53234Nm
3/ h, and at this by-product 3.8MPa～10.0MPa higher-grade steam.
(4) low temperature separation process liquefaction
(a) drying and dehydrating
The high methane gas obtaining after methanation utilizes molecular sieve to carry out deep dehydration, makes the H in high methane gas
2o content is less than 1ppm.Drying and dehydrating adopts three tower molecular sieve dehydration schemes.High methane gas by under the water adsorption in gas, makes gas be able to deep dehydration under siccative effect.Under state at a dehydration tower for dehydration, another dehydration tower is in regenerative process, and whole dewatering unit is closed flow process.
(b) high methane gas low temperature separation process liquefaction
High methane gas after drying and dehydrating enters low temperature separation process liquefying plant, and low temperature separation process liquefying plant adopts the low temperature separation process liquefaction process with rectifying.Under the effect of rectifying tower rectifying, high methane gas is separated into natural gas liquids, hydrogen-rich gas and nitrogen-rich gas.
In the present embodiment, natural gas liquids LNG output is 44871Nm
3/ h, and the composition of natural gas liquids LNG (vol%) is: CH
499.14, N
20.86.
Embodiment 3
The present embodiment schematic flow sheet is shown in Fig. 1.
Coke(oven)gas forms in table 1, and tolerance is 100000Nm
3/ h, supplements CO
2the composition of gas is in table 2, and tolerance is 5300Nm
3/ h.
Table 1 coke(oven)gas composition (vol%)
| Title | H 2 | CO | CO 2 | N 2 | CH 4 | C nH m | O 2 |
| Content/% | 59.5 | 6.0 | 2.5 | 4.5 | 24.5 | 2.5 | 0.5 |
Table 2 supplements CO
2composition (vol%)
| Title | CO 2 | N 2 |
| Content/% | 98.5 | 1.5 |
(1) CO
2purify and purify
First will be rich in CO
2blast furnace gas purify and purify, obtain CO
2the CO of content～98.5%
2gas, then this part CO
2gas with mix from the hydrogen-rich gas of low temperature separation process liquefaction unit, then hydrogenating desulfurization purifies, and CO
2the flow of gas is 5.3% of coke(oven)gas flow.
Be coke(oven)gas from the hydrogen-rich gas flow of low temperature separation process liquefying plant 10%, the flow of hydrogen-rich gas is 10000Nm
3/ h, its composition (vol%) is: H
290.82, CH
44.04, N
25.14.
(2) compression and purifying: mixed gas mixture first passes through pre-treatment, then by centrifugal (or back and forth) formula compressor boost extremely～enter clean unit after 6MPa.
Pre-treatment adopts Temp .-changing adsorption and dry method hydrogenating desulfurization technical combinations to carry out pre-treatment and purification, removes the toxic substances such as tar in gas mixture, naphthalene, sulphur, chlorine, and wherein tar content is less than 0.1ppm, and sulphur content is less than 20ppb, and cl content is less than 5ppb.To meet the requirement to unstripped gas of follow-up methanation operation.
(3) methanation operation:
Enter one-level methanator, one-level methanator exit gas, hydrogen-rich gas and supplementary CO through the coke(oven)gas purifying after qualified
2gas enters secondary methanator, and extracts portion gas as recycle gas from the second methanator exit gas utilizes waste heat boiler to reclaim heat.This recycle gas is brought circulation gas into first methanation adiabatic reactor by steam injector, and circulation gas is 1.5:1 with the ratio of amount of substance of the gas that enters the first adiabatic methanation reactor.The first methanator and with the second methanator in dry gas calculate volume space velocity be 10000h
-1, and temperature in is respectively 280 ℃ and 290 ℃, and the volume space velocity that in front three alkylation reactors, dry gas calculates is 4000h
-1, and temperature in is 250 ℃.
Gas butt composition (vol%) after methanation is: H
225.11, CH
467.00, N
27.89, CO
2≤ 50ppm.High methane gas tolerance after methanation is 64518Nm
3/ h, and at this by-product 3.8MPa～10.0MPa higher-grade steam.
(4) low temperature separation process liquefaction
(a) drying and dehydrating
The high methane gas obtaining after methanation utilizes molecular sieve to carry out deep dehydration, makes the H in high methane gas
2o content is less than 1ppm.Drying and dehydrating adopts three tower molecular sieve dehydration schemes.High methane gas by under the water adsorption in gas, makes gas be able to deep dehydration under siccative effect.Under state at a dehydration tower for dehydration, another dehydration tower is in regenerative process, and whole dewatering unit is closed flow process.
(b) high methane gas low temperature separation process liquefaction
High methane gas after drying and dehydrating enters low temperature separation process liquefying plant, and low temperature separation process liquefying plant adopts the low temperature separation process liquefaction process with rectifying.Under the effect of rectifying tower rectifying, high methane gas is separated into natural gas liquids, hydrogen-rich gas and nitrogen-rich gas.
In the present embodiment, natural gas liquids LNG output is 42728Nm
3/ h, and the composition of natural gas liquids LNG (vol%) is: CH
499.14, N
20.86.
Embodiment 4
The present embodiment schematic flow sheet is shown in Fig. 1.
Coke(oven)gas forms in table 1, and tolerance is 100000Nm
3/ h, supplements CO
2the butt of gas forms in table 2, and tolerance is 6000Nm
3/ h.
Table 1 coke(oven)gas composition (vol%)
| Title | H 2 | CO | CO 2 | N 2 | CH 4 | C nH m | O 2 |
| Content/% | 59.5 | 6.0 | 2.5 | 4.5 | 24.5 | 2.5 | 0.5 |
Table 2 supplements CO
2composition (vol%)
| Title | CO 2 | N 2 |
| Content/% | 98.5 | 1.5 |
(1) CO
2purify and purify
First will be rich in CO
2gas purify and purify, obtain CO
2the CO of content～98.5%
2gas, then this part CO
2gas with mix from the hydrogen-rich gas of low temperature separation process liquefaction unit, then hydrogenating desulfurization purifies, and CO
2the flow of gas is 6.0% of coke(oven)gas flow.
Be coke(oven)gas from the hydrogen-rich gas flow of low temperature separation process liquefying plant 4%, the flow of hydrogen-rich gas is 4000Nm
3/ h, its composition (vol%) is: H
287.31, CH
44.41, N
28.28.
(2) compression and purifying: mixed gas mixture first passes through pre-treatment, then by centrifugal (or back and forth) formula compressor boost extremely～enter clean unit after 5MPa.
Pre-treatment adopts Temp .-changing adsorption and dry method hydrogenating desulfurization technical combinations to carry out pre-treatment and purification, removes the toxic substances such as tar in gas mixture, naphthalene, sulphur, chlorine, and wherein tar content is less than 0.1ppm, and sulphur content is less than 20ppb, and cl content is less than 5ppb.To meet the requirement to unstripped gas of follow-up methanation operation.
(3) methanation operation:
Enter one-level methanator, one-level methanator exit gas, hydrogen-rich gas and supplementary CO through the coke(oven)gas purifying after qualified
2gas enters secondary methanator, and extracts portion gas as recycle gas from secondary methanator exit gas utilizes waste heat boiler to reclaim heat.This recycle gas is brought circulation gas into one-level alkanisation adiabatic reactor by steam injector, and circulation gas is 0.8:1 with the ratio of amount of substance of the gas that enters one-level adiabatic methanation reactor.The first methanator and with the second methanator in dry gas calculate volume space velocity be 20000h
-1, and temperature in is respectively 290 ℃ and 340 ℃; The volume space velocity that in front three alkylation reactors, dry gas calculates is 15000h
-1, and temperature in is 310 ℃, the volume space velocity that in tetramethyl alkylation reactors, dry gas calculates is 13000h
-1, and temperature in is 280 ℃.The volume space velocity that in the 5th methanator, dry gas calculates is 2000h
-1, and temperature in is 250 ℃.
Gas butt composition (vol%) after methanation is: H
213.85, CH
477.47, N
28.68, CO
2≤ 50ppm.High methane gas tolerance after methanation is 56688Nm
3/ h, and at this by-product 3.8MPa～10.0MPa higher-grade steam.
(4) low temperature separation process liquefaction
(a) drying and dehydrating
The high methane gas obtaining after methanation utilizes molecular sieve to carry out deep dehydration, makes the H in high methane gas
2o content is less than 1ppm.Drying and dehydrating adopts three tower molecular sieve dehydration schemes.High methane gas by under the water adsorption in gas, makes gas be able to deep dehydration under siccative effect.Under state at a dehydration tower for dehydration, another two dehydration towers are in regenerative process, and whole dewatering unit is closed flow process.
(b) high methane gas low temperature separation process liquefaction
High methane gas after drying and dehydrating enters low temperature separation process liquefying plant, and low temperature separation process liquefying plant adopts the low temperature separation process liquefaction process with rectifying.Under the effect of rectifying tower rectifying, high methane gas is separated into natural gas liquids, hydrogen-rich gas and nitrogen-rich gas.
In the present embodiment, natural gas liquids LNG output is 43410Nm
3/ h, and the composition of natural gas liquids LNG (vol%) is: CH
499.14, N
20.86.
Claims (8)
1. coke(oven)gas supplements a technique for carbonic acid gas preparing liquefied natural gas, it is characterized in that comprising following technological process: first will be rich in CO
2gas purify and preliminary cleaning, obtain CO
2(vol%) content is more than or equal to 95% CO
2gas, then this gas carries out deep hydrodesulfurizationof after mixing with hydrogen-rich gas, obtains the CO that is rich in that total sulfur content is less than 0.05ppm
2and H
2mixed gas; Meanwhile, enter one-level methanator through the coke(oven)gas of pre-treatment, compression and purification, the gas of one-level methanator outlet again with the above-mentioned CO that is rich in
2and H
2mixed gas enter secondary methanator after mixing, then carry out successively multistage adiabatic methanation reaction, obtain high methane gas; Then utilize molecular sieve to carry out deep dehydration to high methane gas, make H in high methane gas
2o content is less than 1ppm, and finally the high methane gas after dehydration enters low temperature separation process liquefaction operation and separates liquefaction, obtains natural gas liquids, hydrogen-rich gas and nitrogen-rich gas, and wherein natural gas liquids is as product.
2. coke(oven)gas according to claim 1 supplements the technique of carbonic acid gas preparing liquefied natural gas, it is characterized in that: the described CO that is rich in
2gas be stack gas, lime-kiln gas and blast furnace gas.
3. coke(oven)gas according to claim 1 supplements the technique of carbonic acid gas preparing liquefied natural gas, it is characterized in that: supplement CO
2(vol%) be more than or equal to 95% CO
2the amount of substance of gas be coke(oven)gas amount of substance 4～7.5%.
4. coke(oven)gas according to claim 1 supplements the technique of carbonic acid gas preparing liquefied natural gas, it is characterized in that: described supplementary multistage adiabatic methanation reaction is 2 grades, 3 grades or 4 grades.
5. coke(oven)gas according to claim 1 supplements the technique of carbonic acid gas preparing liquefied natural gas, it is characterized in that: the coke(oven)gas through pre-treatment, compression and purification enters one-level methanator, is rich in CO
2and H
2mixed gas all enter secondary methanator, and extract portion gas as circulation gas from the second methanator outlet, this circulation gas only enters the first methanator simultaneously.
6. coke(oven)gas according to claim 5 supplements the technique of carbonic acid gas preparing liquefied natural gas, it is characterized in that: bring circulation gas into one-level alkanisation adiabatic reactor by steam injector or recycle gas compressor, and circulation gas is 0.5～2:1 with the amount of substance ratio that enters one-level adiabatic methanation gas reactor, and circulation gas temperature is 60 ℃～130 ℃.
7. coke(oven)gas according to claim 1 supplements the technique of carbonic acid gas preparing liquefied natural gas, it is characterized in that: in methanation process, the temperature in that enters each methanator is 230 ℃ ~ 350 ℃, pressure is 1.5 ~ 6 MPa, and the volume space velocity calculating take dry gas in described firsts and seconds reactor is as 8000 h
-1～30000h
-1, and the volume space velocity calculating take dry gas in last methanator is as 2000 h
-1～5000 h
-1.
8. coke(oven)gas according to claim 1 supplements the technique of carbonic acid gas preparing liquefied natural gas, it is characterized in that: low temperature separation process liquefaction operation utilizes rectifying tower to make methane rich oxidizing gases be divided into three strands, first strand is natural gas liquids, second strand is nitrogen-rich gas, the 3rd strand is hydrogen-rich gas, and extract part hydrogen-rich gas and return to front end, the hydrogen-rich gas returning amount of substance be 2～10% of coke(oven)gas amount of substance.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132055A (en) * | 2015-08-05 | 2015-12-09 | 西南化工研究设计院有限公司 | Technology using coke oven gas and methanol to prepare synthetic natural gas (SNG) |
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| CN113061475A (en) * | 2021-03-10 | 2021-07-02 | 广西大学 | Liquefaction process method and device for separating carbon dioxide from critical biogas by adjusting concentration of carbon dioxide |
| CN113061475B (en) * | 2021-03-10 | 2024-05-31 | 广西大学 | Liquefaction process method and device capable of adjusting carbon dioxide concentration and separating carbon dioxide from critical methane |
| CN114105142A (en) * | 2021-11-22 | 2022-03-01 | 西南化工研究设计院有限公司 | Method for producing liquid carbon dioxide from carbon dioxide-rich gas |
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