CN104031710B - A kind of technique utilizing oven gas to produce liquefied natural gas - Google Patents
A kind of technique utilizing oven gas to produce liquefied natural gas Download PDFInfo
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Abstract
The invention discloses a kind of technique utilizing oven gas to produce liquefied natural gas, belonging to liquefied natural gas (LNG) production field, this processing step includes raw material mixing, just compression, pretreatment, purification, recompression, methanation, dry demercuration, cryogenic liquefying separation, LNG tank and liquefied natural gas entrucking。The present invention utilize oven gas produce liquefied natural gas technique compared to the prior art, qualified liquefied natural gas product can be produced with oven gas, liquefied natural gas can conveniently carry out transporting and utilizing, improve oven gas added value；Effectively reduce production cost, improve economic benefit, reduce environmental pollution。
Description
Technical field
The present invention relates to liquefied natural gas (LNG) production field, specifically a kind of technique utilizing oven gas to produce liquefied natural gas。
Background technology
China is coke production state the biggest in the world, annual side-product oven gas about 400～60,000,000,000 Nm produced3/ year。In typical case's oven gas composition, H254～59%(volume fraction, lower same), CH421～25%, CO5～8%, CO21.9～2.3%, CmHn1.6～2.0%, N22～6%, O20.3～0.7%, and containing impurity such as tar, benzene, naphthalene, ammonia, Blausure (German), hydrogen sulfide, organic sulfurs。Effective ingredient in oven gas is more, but impurity is also many, is used for producing methanol, dimethyl ether, hydrogen, ammonia and life coal gas after current major part oven gas is purified, and part is directly diffused。
Liquefied natural gas is called for short LNG, is mainly composed of methane, encourages the clean energy resource developed for country, is widely used in: gas, motor vehicle fuel, low temperature cold source。Domestic LNG demand is vigorous, and currently mainly source is pipe natural gas, external imported L NG, and China region is vast, and above-mentioned source can not meet far away the market demand for LNG。
Utilize the oven gas that the domestic coke-oven plant run discharges to produce LNG, transported by tank car, it is possible to meet the various user demand to LNG, significantly developing LNG market。The comprehensive utilization of resource can be realized, clean energy resource, energy-saving and emission-reduction can be provided for market again。
At present, have patent disclosure oven gas and produce the correlation technique of liquefied natural gas, example: CN1952082A utilizes pressure swing adsorption method that the oven gas separation after compression, again condensation are produced LNG, the disclosure patent proposes the methane gas contained in oven gas simply by physical change, it does not have make full use of CO, CO in oven gas2And H2So that it is occur methanation reaction to produce methane, cause the waste of resource；CN101709237A utilizes membrance separation that the oven gas after methanation is isolated the hydrogen not reacted completely to then pass through condensation production liquefied natural gas again, and the patent methane production of the disclosure is relatively low；CN101100622A, CN101921641A are that preprocessed, desulfurization, methanation, PSA produce synthetic natural gas, and the natural gas of above-mentioned two patent disclosure is not through liquefaction, and natural gas volume is big, transport difficult, and logistics cost is high。
Summary of the invention
The technical assignment of the present invention is to provide a kind of technique utilizing oven gas to produce liquefied natural gas。
The technical assignment of the present invention realizes in the following manner, and this processing step includes raw material mixing, just compression, pretreatment, purification, recompression, methanation, dry demercuration, cryogenic liquefying separation, LNG tank and liquefied natural gas entrucking,
Processing step is specific as follows:
1) raw material mixing: mixed material gas bag draws together the oven gas, high methane gas and the liquefied natural gas that come coke-oven plant, the boil-off gas Homogeneous phase mixing of oven gas, high methane gas and LNG tank that coke-oven plant is come；
2) just compression: the helical-lobe compressor that entered to spray water by above-mentioned mixed material pneumatic transmission carries out two stages of compression, makes the pressure of mixed material gas be boosted to 0.9MpaG by 30KpaG；
3) pretreatment: just the mixed material gas after compression is by Temp .-changing adsorption imurity-removal tar, benzene, naphthalene, ammonia and Blausure (German)；
4) purify: by the hydrogen sulfide in above-mentioned pretreated mixed material gas oxidized ferrum adsorbing and removing mixed material gas, mixed material gas organic sulfur in ferrum molybdenum and nickel molybdenum hydrogenation and zinc oxide adsorption elimination mixed material gas, the mass content of sulfur in mixed material gas is reduced to 0.1ppm；
5) recompression: the unstripped gas after purification enters centrifugal compressor, carries out two sections of compressions, by 0.65MpaG, the pressure of unstripped gas is boosted to 4.0-5.0MpaG, the temperature 137 DEG C of unstripped gas outlet；
6) methanation: the unstripped gas after recompression enters sulfur protective pot, carries out level Four methanation reaction, by CO, CO2It is converted into methane, makes CO, CO2Mass content less than 50ppm；
7) dry demercuration: the synthetic natural gas from methanation utilizes Temp .-changing adsorption dehydration to-70 DEG C of dew points, removes the mercury metal in synthetic natural gas by sulfur loading active carbon；
8) cryogenic liquefying separates: synthetic natural gas is introduced ice chest, pre-cooling plate-fin heat exchanger is pre-chilled to-50～-55 DEG C, then after heavy hydrocarbon knockout drum separates, 1:9 is divided into two parts by volume, major part gas enters cryogenic plate fin heat exchanger and continues cooling liquefaction, isolate the hydrogen not liquefied and a small amount of nitrogen by dehydrogenation tank, cryogenic liquid is then sent into denitrification column after decompression and is carried out denitrogenation processing, obtains product liquefied natural gas after denitrogenation；Small portion of gas through decompression and with the low temperature periodic off-gases heat exchange of denitrogenation tower top after enter at the bottom of denitrification column as stripping gas；
9) LNG tank: above-mentioned liquefied natural gas is delivered to LNG tank, due to fluid column and Pressure Drop, causes that charging liquefied natural gas contains a large amount of flashed vapour, and flashed vapour enters tank top boil-off gas space, sends together with storage tank boil-off gas；
10) liquefied natural gas entrucking: the liquefied natural gas come from LNG tank pressurizes through the outer liquefied natural gas cylinder band pump of tank, delivers to jack works, utilizes the liquefied natural gas entrucking arm with boil-off gas return-air arm to carry out liquefied natural gas entrucking。
The carbon dioxide gas that described raw material mixing link is come possibly together with chemical plant。
Described pretreatment link, Temp .-changing adsorption use purging gas come from pretreated mixed material gas, consumption is the 1/10 of mixed material air volume, this purging gas through electric tar, wash benzene naphthalene process Hou Hui coke-oven plant do fuel gas。
Reaction heat produced by described methanation link is introduced in middle pressure, the useless pot of low pressure and uses, and presses through vapours and low-pressure saturated steam in generation。
The stripping gas of described cryogenic liquefying separation link, through pressure-variable adsorption separate nitrogen therein, hydrogen, afterwards by blower fan be pressurized to 40kPaG deliver to raw material mixing, isolated nitrogen, hydrogen tail gas reduce phlegm and internal heat fire from；The boil-off gas that LNG tank flashed vapour, liquefied natural gas entrucking produce, after air temperature type recuperator re-heat, is pressurized to 40kPaG by blower fan and delivers to raw material mixing。
The present invention utilize oven gas produce liquefied natural gas technique compared to the prior art, qualified liquefied natural gas product can be produced with oven gas, liquefied natural gas can conveniently carry out transporting and utilizing, improve oven gas added value；Effectively reduce production cost, improve economic benefit, reduce environmental pollution。
Detailed description of the invention
Embodiment 1:
Boil-off gas Homogeneous phase mixing by oven gas from coke-oven plant under 30KpaG, high methane gas that cryogenic liquefying separates and LNG tank；Send into water spray helical-lobe compressor and carry out two stages of compression, make the pressure of mixed material gas be boosted to 0.9MpaG by 30KpaG；Then pass through Temp .-changing adsorption imurity-removal tar, benzene, naphthalene, ammonia and Blausure (German)；Temp .-changing adsorption use purging gas come from pretreated mixed material gas, consumption is the 1/10 of mixed material air volume, this purging gas through electric tar, wash benzene naphthalene process Hou Hui coke-oven plant do fuel gas。
The mass content of sulfur in mixed material gas, then through the hydrogen sulfide in ferrum oxide adsorbing and removing mixed material gas, mixed material gas organic sulfur in ferrum molybdenum and nickel molybdenum hydrogenation and zinc oxide adsorption elimination mixed material gas, is reduced to 0.1ppm by mixed material gas；Unstripped gas after purification enters centrifugal compressor, carries out two sections of compressions, by 0.65MpaG, the pressure of unstripped gas is boosted to 4.0-5.0MpaG, the temperature 137 DEG C of unstripped gas outlet；Reaction heat produced by methanation is introduced in middle pressure, the useless pot of low pressure and uses, and presses through vapours and low-pressure saturated steam in generation。
Unstripped gas enters sulfur protective pot afterwards, carries out level Four methanation reaction, by CO, CO2It is converted into methane, makes CO, CO2Mass content less than 50ppm；Then utilize Temp .-changing adsorption dehydration to-70 DEG C of dew points, remove the mercury metal in synthetic natural gas by sulfur loading active carbon；Synthetic natural gas is introduced ice chest, pre-cooling plate-fin heat exchanger is pre-chilled to-50～-55 DEG C, then after heavy hydrocarbon knockout drum separates, 1:9 is divided into two parts by volume, major part gas enters cryogenic plate fin heat exchanger and continues cooling liquefaction, isolate the hydrogen not liquefied and a small amount of nitrogen by dehydrogenation tank, cryogenic liquid is then sent into denitrification column after decompression and is carried out denitrogenation processing, obtains product liquefied natural gas after denitrogenation。Above-mentioned liquefied natural gas being delivered to LNG tank, due to fluid column and Pressure Drop, causes that charging liquefied natural gas contains a large amount of flashed vapour, flashed vapour enters tank top boil-off gas space, sends together with storage tank boil-off gas；The liquefied natural gas come from LNG tank pressurizes through the outer liquefied natural gas cylinder band pump of tank, delivers to jack works, utilizes the liquefied natural gas entrucking arm with boil-off gas return-air arm to carry out liquefied natural gas entrucking。
Small portion of gas through decompression and with the low temperature periodic off-gases heat exchange of denitrogenation tower top after enter at the bottom of denitrification column as stripping gas using-145 DEG C, this stripping gas separates nitrogen therein, hydrogen through pressure-variable adsorption, afterwards by blower fan be pressurized to 40kPaG deliver to raw material mixing, isolated nitrogen, hydrogen tail gas reduce phlegm and internal heat fire from；The boil-off gas that LNG tank flashed vapour, liquefied natural gas entrucking produce, after air temperature type recuperator re-heat, is pressurized to 40kPaG by blower fan and delivers to raw material mixing。
Embodiment 2:
By oven gas from coke-oven plant under 30KpaG, high methane gas that cryogenic liquefying separates, LNG tank boil-off gas, from the about 2692Nm in chemical plant3/ h is containing CO285%(V/V%) waste gas, Homogeneous phase mixing；Send into water spray helical-lobe compressor and carry out two stages of compression, make the pressure of mixed material gas be boosted to 0.9MpaG by 30KpaG；Then pass through Temp .-changing adsorption imurity-removal tar, benzene, naphthalene, ammonia and Blausure (German)；Temp .-changing adsorption use purging gas come from pretreated mixed material gas, consumption is the 1/10 of mixed material air volume, this purging gas through electric tar, wash benzene naphthalene process Hou Hui coke-oven plant do fuel gas。
The mass content of sulfur in mixed material gas, then through the hydrogen sulfide in ferrum oxide adsorbing and removing mixed material gas, mixed material gas organic sulfur in ferrum molybdenum and nickel molybdenum hydrogenation and zinc oxide adsorption elimination mixed material gas, is reduced to 0.1ppm by mixed material gas；Unstripped gas after purification enters centrifugal compressor, carries out two sections of compressions, by 0.65MpaG, the pressure of unstripped gas is boosted to 4.0-5.0MpaG, the temperature 137 DEG C of unstripped gas outlet；Reaction heat produced by methanation is introduced in middle pressure, the useless pot of low pressure and uses, and presses through vapours and low-pressure saturated steam in generation。
Unstripped gas enters sulfur protective pot afterwards, carries out level Four methanation reaction, by CO, CO2It is converted into methane, makes CO, CO2Mass content less than 50ppm；Then utilize Temp .-changing adsorption dehydration to-70 DEG C of dew points, remove the mercury metal in synthetic natural gas by sulfur loading active carbon；Synthetic natural gas is introduced ice chest, pre-cooling plate-fin heat exchanger is pre-chilled to-50～-55 DEG C, then after heavy hydrocarbon knockout drum separates, 1:9 is divided into two parts by volume, major part gas enters cryogenic plate fin heat exchanger and continues cooling liquefaction, isolate the hydrogen not liquefied and a small amount of nitrogen by dehydrogenation tank, cryogenic liquid is then sent into denitrification column after decompression and is carried out denitrogenation processing, obtains product liquefied natural gas after denitrogenation。Above-mentioned liquefied natural gas being delivered to LNG tank, due to fluid column and Pressure Drop, causes that charging liquefied natural gas contains a large amount of flashed vapour, flashed vapour enters tank top boil-off gas space, sends together with storage tank boil-off gas；The liquefied natural gas come from LNG tank pressurizes through the outer liquefied natural gas cylinder band pump of tank, delivers to jack works, utilizes the liquefied natural gas entrucking arm with boil-off gas return-air arm to carry out liquefied natural gas entrucking。
Small portion of gas through decompression and with the low temperature periodic off-gases heat exchange of denitrogenation tower top after enter at the bottom of denitrification column as stripping gas using-145 DEG C, this stripping gas separates nitrogen therein, hydrogen through pressure-variable adsorption, afterwards by blower fan be pressurized to 40kPaG deliver to raw material mixing, isolated nitrogen, hydrogen tail gas reduce phlegm and internal heat fire from；The boil-off gas that LNG tank flashed vapour, liquefied natural gas entrucking produce, after air temperature type recuperator re-heat, is pressurized to 40kPaG by blower fan and delivers to raw material mixing。
Claims (3)
1. one kind utilizes the technique that oven gas produces liquefied natural gas, it is characterized in that, this processing step includes raw material mixing, just compression, pretreatment, purification, recompression, methanation, dry demercuration, cryogenic liquefying separation, LNG tank and liquefied natural gas entrucking
Processing step is specific as follows:
1) raw material mixing: mixed material gas bag draws together the oven gas, high methane gas and the liquefied natural gas that come coke-oven plant, the boil-off gas Homogeneous phase mixing of oven gas, high methane gas and LNG tank that coke-oven plant is come；
2) just compression: the helical-lobe compressor that entered to spray water by above-mentioned mixed material pneumatic transmission carries out two stages of compression, makes the pressure of mixed material gas be boosted to 0.9MpaG by 30KpaG；
3) pretreatment: just the mixed material gas after compression is by Temp .-changing adsorption imurity-removal tar, benzene, naphthalene, ammonia and Blausure (German)；
4) purify: by the hydrogen sulfide in above-mentioned pretreated mixed material gas oxidized ferrum adsorbing and removing mixed material gas, mixed material gas organic sulfur in ferrum molybdenum and nickel molybdenum hydrogenation and zinc oxide adsorption elimination mixed material gas, the mass content of sulfur in mixed material gas is reduced to 0.1ppm；
5) recompression: the unstripped gas after purification enters centrifugal compressor, carries out two sections of compressions, by 0.65MpaG, the pressure of unstripped gas is boosted to 4.0-5.0MpaG, the outlet temperature of unstripped gas 137 DEG C；
6) methanation: the unstripped gas after recompression enters sulfur protective pot, carries out level Four methanation reaction, by CO, CO2It is converted into methane, makes CO, CO2Mass content less than 50ppm；
7) dry demercuration: the synthetic natural gas from methanation utilizes Temp .-changing adsorption dehydration to-70 DEG C of dew points, removes the mercury metal in synthetic natural gas by sulfur loading active carbon；
8) cryogenic liquefying separates: synthetic natural gas is introduced ice chest, pre-cooling plate-fin heat exchanger is pre-chilled to-50～-55 DEG C, then after heavy hydrocarbon knockout drum separates, 1:9 is divided into two parts by volume, major part gas enters cryogenic plate fin heat exchanger and continues cooling liquefaction, isolate the hydrogen not liquefied and a small amount of nitrogen by dehydrogenation tank, cryogenic liquid is then sent into denitrification column after decompression and is carried out denitrogenation processing, obtains product liquefied natural gas after denitrogenation；Small portion of gas through decompression and with the low temperature periodic off-gases heat exchange of denitrogenation tower top after enter at the bottom of denitrification column as stripping gas；
9) LNG tank: above-mentioned liquefied natural gas is delivered to LNG tank, due to fluid column and Pressure Drop, causes that charging liquefied natural gas contains a large amount of flashed vapour, and flashed vapour enters tank top boil-off gas space, sends together with storage tank boil-off gas；
10) liquefied natural gas entrucking: the liquefied natural gas come from LNG tank pressurizes through the outer liquefied natural gas cylinder band pump of tank, delivers to jack works, utilizes the liquefied natural gas entrucking arm with boil-off gas return-air arm to carry out liquefied natural gas entrucking；
The carbon dioxide gas that described raw material mixing link is come possibly together with chemical plant；
The stripping gas of described cryogenic liquefying separation link, through pressure-variable adsorption separate nitrogen therein, hydrogen, afterwards by blower fan be pressurized to 40kPaG deliver to raw material mixing, isolated nitrogen, hydrogen tail gas reduce phlegm and internal heat fire from；The boil-off gas that LNG tank flashed vapour, liquefied natural gas entrucking produce, after air temperature type recuperator re-heat, is pressurized to 40kPaG by blower fan and delivers to raw material mixing。
2. a kind of technique utilizing oven gas to produce liquefied natural gas according to claim 1, it is characterized in that, described pretreatment link, the purging gas that Temp .-changing adsorption uses comes from pretreated mixed material gas, consumption is the 1/10 of mixed material air volume, this purging gas through electric tar, wash benzene naphthalene process Hou Hui coke-oven plant do fuel gas。
3. a kind of technique utilizing oven gas to produce liquefied natural gas according to claim 1, it is characterised in that reaction heat produced by described methanation link is introduced in middle pressure, the useless pot of low pressure and uses, and presses through vapours and low-pressure saturated steam in generation。
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| CN104557390B (en) * | 2015-02-12 | 2016-08-17 | 鹤壁宝发能源科技股份有限公司 | A kind of method utilizing methanol purge gas coproduction synthesizing liquid methane |
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| CN106433826A (en) * | 2016-08-18 | 2017-02-22 | 北京三聚环保新材料股份有限公司 | Method and device for preparing liquefied natural gas through replacement of coke-oven gas by gas |
| CN109282572A (en) * | 2017-07-21 | 2019-01-29 | 通用电气公司 | The system and method for flashed vapour are handled in production liquefied natural gas |
| US10960349B2 (en) | 2017-12-04 | 2021-03-30 | Cri, Ehf | System for separating gas |
| CN111410171B (en) * | 2020-03-31 | 2021-03-02 | 中国华能集团清洁能源技术研究院有限公司 | Coal gasification synthesis gas mercury removal agent and preparation method thereof |
| WO2022153214A1 (en) | 2021-01-15 | 2022-07-21 | Cri, Ehf | Methanol synthesis reactor |
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Address after: 100010 Beijing City, Dongcheng District Chaoyangmen No. 25 North Street CNOOC building Co-patentee after: China National Offshore Oil Corporation Patentee after: China Offshore Oil Group Co., Ltd. Co-patentee after: CNOOC Petrochemical Engineering Co Ltd Address before: 100010 Beijing City, Dongcheng District Chaoyangmen North Street, No. 25 building, Chinese CNOOC Offshore Oil Corporation, the Ministry of science and technology Co-patentee before: China National Offshore Oil Corporation Patentee before: China National Offshore Oil Corporation Co-patentee before: China National Offshore Oil Shandong Chemical Engineering Co., Ltd. |