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 PDF

Info

Publication number
CN103881780A
CN103881780A CN201410135509.7A CN201410135509A CN103881780A CN 103881780 A CN103881780 A CN 103881780A CN 201410135509 A CN201410135509 A CN 201410135509A CN 103881780 A CN103881780 A CN 103881780A
Authority
CN
China
Prior art keywords
gas
rich
coke
oven
methanator
Prior art date
Application number
CN201410135509.7A
Other languages
Chinese (zh)
Other versions
CN103881780B (en
Inventor
张新波
杨宽辉
马磊
谭建冬
Original Assignee
西南化工研究设计院有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 西南化工研究设计院有限公司 filed Critical 西南化工研究设计院有限公司
Priority to CN201410135509.7A priority Critical patent/CN103881780B/en
Publication of CN103881780A publication Critical patent/CN103881780A/en
Application granted granted Critical
Publication of CN103881780B publication Critical patent/CN103881780B/en

Links

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

A kind of coke(oven)gas supplements the technique of carbonic acid gas preparing liquefied natural gas

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.
CN201410135509.7A 2014-04-04 2014-04-04 A kind of coke(oven)gas supplements the technique of carbonic acid gas preparing liquefied natural gas CN103881780B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410135509.7A CN103881780B (en) 2014-04-04 2014-04-04 A kind of coke(oven)gas supplements the technique of carbonic acid gas preparing liquefied natural gas

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410135509.7A CN103881780B (en) 2014-04-04 2014-04-04 A kind of coke(oven)gas supplements the technique of carbonic acid gas preparing liquefied natural gas

Publications (2)

Publication Number Publication Date
CN103881780A true CN103881780A (en) 2014-06-25
CN103881780B CN103881780B (en) 2016-04-13

Family

ID=50950919

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410135509.7A CN103881780B (en) 2014-04-04 2014-04-04 A kind of coke(oven)gas supplements the technique of carbonic acid gas preparing liquefied natural gas

Country Status (1)

Country Link
CN (1) CN103881780B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
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)
CN105779047A (en) * 2016-04-22 2016-07-20 北京中科瑞奥能源科技股份有限公司 Technology and system for making flue gas into liquified natural gas
CN109609203A (en) * 2019-01-09 2019-04-12 中海石油气电集团有限责任公司 A kind of method of coal coproduction natural gas and hydrogen
CN110938481A (en) * 2019-11-26 2020-03-31 浙江天禄环境科技有限公司 LNG preparation process for quality-divided utilization of low-rank coal

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1019985C (en) * 1988-09-20 1993-03-03 伊得沃得·卡通·史特弗 Apparatus and method for reclaiming waste oil
CN1919985A (en) * 2006-09-13 2007-02-28 西南化工研究设计院 Method of preparing synthetic natural gas by coke oven gas
CN101100622A (en) * 2007-07-16 2008-01-09 张文慧 Method and device for synthesizing natural gas by using coke oven gas
CN101712897A (en) * 2009-11-19 2010-05-26 上海欧罗福企业（集团）有限公司 Method for realizing methanation of coke oven gas through carbon-replenishing hydrogen-returning process for synthetic natural gas
CN102021054A (en) * 2010-12-22 2011-04-20 西南化工研究设计院 New process for synthesizing natural gas by methanation of coke oven gas
CN102517108A (en) * 2011-12-15 2012-06-27 西南化工研究设计院 Technology for preparing liquefied natural gas and liquid ammonia by using coke oven gas

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1019985C (en) * 1988-09-20 1993-03-03 伊得沃得·卡通·史特弗 Apparatus and method for reclaiming waste oil
CN1919985A (en) * 2006-09-13 2007-02-28 西南化工研究设计院 Method of preparing synthetic natural gas by coke oven gas
CN101100622A (en) * 2007-07-16 2008-01-09 张文慧 Method and device for synthesizing natural gas by using coke oven gas
CN101712897A (en) * 2009-11-19 2010-05-26 上海欧罗福企业（集团）有限公司 Method for realizing methanation of coke oven gas through carbon-replenishing hydrogen-returning process for synthetic natural gas
CN102021054A (en) * 2010-12-22 2011-04-20 西南化工研究设计院 New process for synthesizing natural gas by methanation of coke oven gas
CN102517108A (en) * 2011-12-15 2012-06-27 西南化工研究设计院 Technology for preparing liquefied natural gas and liquid ammonia by using coke oven gas

Cited By (4)

* Cited by examiner, † Cited by third party
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)
CN105779047A (en) * 2016-04-22 2016-07-20 北京中科瑞奥能源科技股份有限公司 Technology and system for making flue gas into liquified natural gas
CN109609203A (en) * 2019-01-09 2019-04-12 中海石油气电集团有限责任公司 A kind of method of coal coproduction natural gas and hydrogen
CN110938481A (en) * 2019-11-26 2020-03-31 浙江天禄环境科技有限公司 LNG preparation process for quality-divided utilization of low-rank coal

Also Published As

Publication number Publication date
CN103881780B (en) 2016-04-13

Similar Documents

Publication Publication Date Title
CN100582201C (en) Combined system and process for producing electricity-substituted natural gas based on coal gasification and methanation
CN102115684B (en) Method for producing liquefied natural gas by using coke oven gas
CN101705128B (en) Adiabatic methanation process and device for preparing synthetic natural gas
CN101649232B (en) Synthesis process of natural gas employing methanation of coke oven gas
CN104945224B (en) A kind of methanol process
CN101597527B (en) Method for making synthetic natural gas by utilizing coke oven gas
CN104119975B (en) Coke-oven plant's combined production of methanol and the method for liquefied natural gas
CN100427443C (en) Method for simultaneously producing methanol, urea and artificial gas
CN103409187B (en) Methanation technology for preparing non-recycling gas of SNG or LNG from coke-oven gas
CN101245262B (en) Gas-steam combined cycle system and technique based on coal gasification and methanation
CA2879442A1 (en) Process for comprehensively utilizing low carbon emission fischer-tropsch synthesis tail gas
CN103160296B (en) Pyrolysis gasification coupling integrated poly-generation system and process for coal chemical industry
CN101289620A (en) Integration process of coke dry quenching co-production synthesis gas and downstream products thereof of methanol
CN102191086B (en) Integration device and method for coproducing carbon monoxide, methanol, hydrogen and refined synthetic gas in process of producing synthetic gas from coal
CN101508924B (en) Catalysis deoxidization process for coal bed gas of coal mine zone
CN101508922B (en) Methanation reaction process using oven gas to prepare substitute natural gas
FR2808223A1 (en) Purification of effluent containing carbon dioxide and hydrocarbons comprises gas/liquid separation and combustion to recover carbon dioxide and water for recycling
CN101550052B (en) Process for producing methanol and coproducing methane by using synthesis gas containing methane
CN104004547B (en) Coal gasification and coal coking co-supply and cogeneration system and method
CN201031677Y (en) Boiler flue gas pressurization absorption CO2 liquify pouring well oil production device
CN103242134A (en) Pyrolysis gasification and purification method of household garbage
CN101775319B (en) Method for producing synthetic natural gas SNG from coal and processing installation thereof
CN101538040A (en) Method for coproducing or singly producing food grade carbon dioxide and industrial grade carbon dioxide by utilizing industrial waste gas
CN101575540B (en) Method for producing liquefied natural gas and carbinol simultaneously
CN102329670B (en) Process for preparing synthesis gas from coke-oven gas

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
C14 Grant of patent or utility model