CN104031710A - Process for producing liquefied natural gas by using coke-oven gas - Google Patents
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Abstract
The invention discloses a process for producing liquefied natural gas by using coke-oven gas, and belongs to the field of liquefied natural gas production. The process comprises the steps of raw material mixing, initial compression, pretreatment, purification, recompression, methanation, drying for mercury removal, cryogenic liquefying and separation, storage of liquefied natural gas, and truck loading of liquefied natural gas. Compared with the prior art, the process for producing liquefied natural gas by using coke-oven gas disclosed by the invention can produce qualified liquefied natural gas by using coke-oven gas, and the liquefied natural gas can be conveniently transported and utilized, thereby enhancing the added value of the coke oven gas; the production cost is effectively reduced, the economic benefit is improved, and the environment pollution is reduced.
Description
Technical field
The present invention relates to lng production field, specifically a kind of technique of utilizing coke(oven)gas to produce natural gas liquids.
Background technology
China is coke production the biggest in the world state, annual byproduct coke(oven)gas approximately 400～60,000,000,000 Nm that produce
3/ year.During typical case's coke(oven)gas forms, H
254～59%(volume fraction, lower same), CH
421～25%, CO 5～8%, CO
21.9～2.3%, C
mh
n1.6～2.0%, N
22～6%, O
20.3～0.7%, and contain the impurity such as tar, benzene, naphthalene, ammonia, prussic acid, hydrogen sulfide, organosulfur.Effective constituent in coke(oven)gas is more, but impurity is also many, and current most of coke(oven)gas is for the production of methyl alcohol, dme, hydrogen, ammonia and life coal gas after purifying, and part is directly diffused.
Natural gas liquids is called for short LNG, and main component is methane, and the clean energy for country encourages exploitation, is widely used in: gas, automobile fuel, low temperature cold source.Domestic LNG is in great demand, and main source is pipe natural gas, external imported L NG at present, and China region is vast, and above-mentioned source can not meet market far away for the demand of LNG.
Utilize the coke(oven)gas of the domestic coke-oven plant's discharge having moved to produce LNG, by tank car, transport, can meet the demand of various users to LNG, greatly open up LNG market.Can realize the comprehensive utilization of resource, again can be for market provides clean energy, energy-saving and emission-reduction.
At present, existing patent discloses the correlation technique that coke(oven)gas is produced natural gas liquids, example: CN195 2082A is that the coke(oven)gas after utilizing pressure swing adsorption process to compression is separated, LNG is produced in condensation again, the methane gas that the disclosure patent just proposes to contain in coke(oven)gas by physical change, does not make full use of CO in coke(oven)gas, CO
2and H
2, make it that methanation reaction occur and produce methane, cause the waste of resource; CN10170 9237 A utilize membrane sepn that the coke(oven)gas after methanation is isolated to the hydrogen not reacting completely then to pass through the production of condensation again natural gas liquids, and the patent methane production of the disclosure is lower; CN101100622 A, CN101921641A are through pre-treatment, desulfurization, methanation, PSA production synthetic natural gas, and above-mentioned two disclosed Sweet natural gases of patent are not through liquefaction, and Sweet natural gas volume is large, transportation difficulty, and logistics cost is high.
Summary of the invention
Technical assignment of the present invention is to provide a kind of technique of utilizing coke(oven)gas to produce natural gas liquids.
Technical assignment of the present invention is realized in the following manner, and this processing step comprises raw material mixing, just compression, pre-treatment, purification, recompression, methanation, dry demercuration, cryogenic liquefying separation, LNG tank and natural gas liquids entrucking,
Processing step is specific as follows:
1) raw material mixes: mixing raw material gas bag is drawn together coke(oven)gas, high methane gas and the natural gas liquids that coke-oven plant comes, and the boil-off gas of coke(oven)gas, high methane gas and the LNG tank that coke-oven plant is come is evenly mixed;
2) just compression: the above-mentioned mixing raw material pneumatic transmission spiral-lobe compressor that enters to spray water is carried out to two stages of compression, make the pressure of mixing raw material gas boost to 0.9MpaG by 30KpaG;
3) pre-treatment: just the mixing raw material gas after compression is by Temp .-changing adsorption imurity-removal tar, benzene, naphthalene, ammonia and prussic acid;
4) purify: the hydrogen sulfide by above-mentioned pretreated mixing raw material gas in ferric oxide adsorbing and removing mixing raw material gas, the organosulfur of mixing raw material gas in iron molybdenum and nickel molybdenum hydrogenation and zinc oxide adsorbing and removing mixing raw material gas, be reduced to 0.1ppm by the mass content of sulphur in mixing raw material gas;
5) recompression: the unstripped gas after purification enters centrifugal compressor, carries out two sections of compressions, and the pressure of unstripped gas is boosted to 4.0-5.0MpaG by 0.65 MpaG, 137 ℃ of the temperature of unstripped gas outlet;
6) methanation: the unstripped gas after recompression enters sulphur protective pot, carries out level Four methanation reaction, by CO, CO
2be converted into methane, make CO, CO
2mass content be less than 50ppm;
7) dry demercuration: utilize Temp .-changing adsorption dehydration to-70 ℃ of dew points from the synthetic natural gas of methanation, remove the mercury metal in synthetic natural gas by sulfur loading active carbon;
8) cryogenic liquefying is separated: synthetic natural gas is introduced to ice chest, in precooling plate-fin heat exchanger, be pre-chilled to-50～-55 ℃, then after the separation of heavy hydrocarbon separating tank, 1:9 is divided into two portions by volume, most of gas enters cryogenic plate fin heat exchanger and continues cooling liquefaction, hydrogen and a small amount of nitrogen of by dehydrogenation tank, isolating not liquefaction, cryogenic liquid is sent into denitrification column and is carried out denitrogenation processing after decompression, obtains product natural gas liquids after denitrogenation; Small portion gas through decompression and with the low temperature of denitrogenation tower top speed to exit enter denitrification column after heat exchange at the bottom of as stripping gas;
9) LNG tank: above-mentioned natural gas liquids is delivered to LNG tank, due to fluid column and Pressure Drop, cause charging natural gas liquids to contain a large amount of flashed vapours, flashed vapour enters tank top boil-off gas space, sends together with storage tank boil-off gas;
10) natural gas liquids entrucking: the natural gas liquids coming from LNG tank is the pressurization of natural gas liquids cylinder band pump outside tank, delivers to jack works, utilizes the natural gas liquids entrucking arm with boil-off gas return-air arm to carry out natural gas liquids entrucking.
Described raw material mixes link and also contains the carbon dioxide gas that chemical plant is come.
Described pre-treatment link, the sweep gas that Temp .-changing adsorption is used comes from pretreated mixing raw material gas, consumption is 1/10 of mixing raw material gas volume, this sweep gas through electric tar, wash benzene naphthalene and process Hou Hui coke-oven plant and do fuel gas.
The reaction heat that described methanation link produces is introduced in middle pressure, the useless pot of low pressure and uses, and presses superheated vapour and low-pressure saturated steam in generation.
The stripping gas of the separated link of described cryogenic liquefying, through pressure-variable adsorption separation nitrogen, hydrogen wherein, is pressurized to 40kPaG by blower fan afterwards and delivers to raw material and mix, isolated nitrogen, the hydrogen tail gas fiery distance of reducing phlegm and internal heat; The boil-off gas that LNG tank flashed vapour, natural gas liquids entrucking produce, after the re-heat of air temperature type recuperator, is pressurized to 40kPaG by blower fan and delivers to raw material and mix.
Of the present inventionly utilize technique that coke(oven)gas produces natural gas liquids compared to the prior art, can produce qualified liquefied natural gas product with coke(oven)gas, natural gas liquids can conveniently transport and utilize, and improves the added value of coke(oven)gas; Effectively reduce production cost, improved economic benefit, reduced environmental pollution.
Embodiment
Embodiment 1:
Coke(oven)gas, the high methane gas of cryogenic liquefying separation and the boil-off gas of LNG tank from coke-oven plant under 30KpaG evenly mixed; Send into water spray spiral-lobe compressor and carry out two stages of compression, make the pressure of mixing raw material gas boost to 0.9MpaG by 30KpaG; Then by Temp .-changing adsorption imurity-removal tar, benzene, naphthalene, ammonia and prussic acid; The sweep gas that Temp .-changing adsorption is used comes from pretreated mixing raw material gas, and consumption is 1/10 of mixing raw material gas volume, this sweep gas through electric tar, wash benzene naphthalene and process Hou Hui coke-oven plant and do fuel gas.
Mixing raw material gas is the hydrogen sulfide in ferric oxide adsorbing and removing mixing raw material gas, the organosulfur of mixing raw material gas in iron molybdenum and nickel molybdenum hydrogenation and zinc oxide adsorbing and removing mixing raw material gas again, and the mass content of sulphur in mixing raw material gas is reduced to 0.1ppm; Unstripped gas after purification enters centrifugal compressor, carries out two sections of compressions, and the pressure of unstripped gas is boosted to 4.0-5.0MpaG by 0.65 MpaG, 137 ℃ of the temperature of unstripped gas outlet; The reaction heat that methanation produces is introduced in middle pressure, the useless pot of low pressure and uses, and presses superheated vapour and low-pressure saturated steam in generation.
Unstripped gas enters sulphur protective pot afterwards, carries out level Four methanation reaction, by CO, CO
2be converted into methane, make CO, CO
2mass content be less than 50ppm; Then utilize Temp .-changing adsorption dehydration to-70 ℃ of dew points, by sulfur loading active carbon, remove the mercury metal in synthetic natural gas; Synthetic natural gas is introduced to ice chest, in precooling plate-fin heat exchanger, be pre-chilled to-50～-55 ℃, then after the separation of heavy hydrocarbon separating tank, 1:9 is divided into two portions by volume, most of gas enters cryogenic plate fin heat exchanger and continues cooling liquefaction, hydrogen and a small amount of nitrogen of by dehydrogenation tank, isolating not liquefaction, cryogenic liquid is sent into denitrification column and is carried out denitrogenation processing after decompression, obtains product natural gas liquids after denitrogenation.Above-mentioned natural gas liquids is delivered to LNG tank, due to fluid column and Pressure Drop, cause charging natural gas liquids to contain a large amount of flashed vapours, flashed vapour enters tank top boil-off gas space, sends together with storage tank boil-off gas; The natural gas liquids coming from LNG tank is the pressurization of natural gas liquids cylinder band pump outside tank, delivers to jack works, utilizes the natural gas liquids entrucking arm with boil-off gas return-air arm to carry out natural gas liquids entrucking.
Small portion gas through decompression and with the low temperature of denitrogenation tower top speed to exit using after heat exchange-145 ℃ enter denitrification column at the bottom of as stripping gas, this stripping gas is through pressure-variable adsorption separation nitrogen, hydrogen wherein, by blower fan, be pressurized to 40kPaG afterwards and deliver to raw material and mix, isolated nitrogen, the hydrogen tail gas fiery distance of reducing phlegm and internal heat; The boil-off gas that LNG tank flashed vapour, natural gas liquids entrucking produce, after the re-heat of air temperature type recuperator, is pressurized to 40kPaG by blower fan and delivers to raw material and mix.
Embodiment 2:
By under 30KpaG from the coke(oven)gas of coke-oven plant, the high methane gas of cryogenic liquefying separation, the boil-off gas of LNG tank, from the approximately 2692Nm in chemical plant
3/ h is containing CO
285%(V/V%) waste gas, evenly mixes; Send into water spray spiral-lobe compressor and carry out two stages of compression, make the pressure of mixing raw material gas boost to 0.9MpaG by 30KpaG; Then by Temp .-changing adsorption imurity-removal tar, benzene, naphthalene, ammonia and prussic acid; The sweep gas that Temp .-changing adsorption is used comes from pretreated mixing raw material gas, and consumption is 1/10 of mixing raw material gas volume, this sweep gas through electric tar, wash benzene naphthalene and process Hou Hui coke-oven plant and do fuel gas.
Mixing raw material gas is the hydrogen sulfide in ferric oxide adsorbing and removing mixing raw material gas, the organosulfur of mixing raw material gas in iron molybdenum and nickel molybdenum hydrogenation and zinc oxide adsorbing and removing mixing raw material gas again, and the mass content of sulphur in mixing raw material gas is reduced to 0.1ppm; Unstripped gas after purification enters centrifugal compressor, carries out two sections of compressions, and the pressure of unstripped gas is boosted to 4.0-5.0MpaG by 0.65 MpaG, 137 ℃ of the temperature of unstripped gas outlet; The reaction heat that methanation produces is introduced in middle pressure, the useless pot of low pressure and uses, and presses superheated vapour and low-pressure saturated steam in generation.
Unstripped gas enters sulphur protective pot afterwards, carries out level Four methanation reaction, by CO, CO
2be converted into methane, make CO, CO
2mass content be less than 50ppm; Then utilize Temp .-changing adsorption dehydration to-70 ℃ of dew points, by sulfur loading active carbon, remove the mercury metal in synthetic natural gas; Synthetic natural gas is introduced to ice chest, in precooling plate-fin heat exchanger, be pre-chilled to-50～-55 ℃, then after the separation of heavy hydrocarbon separating tank, 1:9 is divided into two portions by volume, most of gas enters cryogenic plate fin heat exchanger and continues cooling liquefaction, hydrogen and a small amount of nitrogen of by dehydrogenation tank, isolating not liquefaction, cryogenic liquid is sent into denitrification column and is carried out denitrogenation processing after decompression, obtains product natural gas liquids after denitrogenation.Above-mentioned natural gas liquids is delivered to LNG tank, due to fluid column and Pressure Drop, cause charging natural gas liquids to contain a large amount of flashed vapours, flashed vapour enters tank top boil-off gas space, sends together with storage tank boil-off gas; The natural gas liquids coming from LNG tank is the pressurization of natural gas liquids cylinder band pump outside tank, delivers to jack works, utilizes the natural gas liquids entrucking arm with boil-off gas return-air arm to carry out natural gas liquids entrucking.
Small portion gas through decompression and with the low temperature of denitrogenation tower top speed to exit using after heat exchange-145 ℃ enter denitrification column at the bottom of as stripping gas, this stripping gas is through pressure-variable adsorption separation nitrogen, hydrogen wherein, by blower fan, be pressurized to 40kPaG afterwards and deliver to raw material and mix, isolated nitrogen, the hydrogen tail gas fiery distance of reducing phlegm and internal heat; The boil-off gas that LNG tank flashed vapour, natural gas liquids entrucking produce, after the re-heat of air temperature type recuperator, is pressurized to 40kPaG by blower fan and delivers to raw material and mix.
Claims (5)
1. a technique of utilizing coke(oven)gas to produce natural gas liquids, it is characterized in that, this processing step comprises raw material mixing, just compression, pre-treatment, purification, recompression, methanation, dry demercuration, cryogenic liquefying separation, LNG tank and natural gas liquids entrucking
Processing step is specific as follows:
1) raw material mixes: mixing raw material gas bag is drawn together coke(oven)gas, high methane gas and the natural gas liquids that coke-oven plant comes, and the boil-off gas of coke(oven)gas, high methane gas and the LNG tank that coke-oven plant is come is evenly mixed;
2) just compression: the above-mentioned mixing raw material pneumatic transmission spiral-lobe compressor that enters to spray water is carried out to two stages of compression, make the pressure of mixing raw material gas boost to 0.9MpaG by 30KpaG;
3) pre-treatment: just the mixing raw material gas after compression is by Temp .-changing adsorption imurity-removal tar, benzene, naphthalene, ammonia and prussic acid;
4) purify: the hydrogen sulfide by above-mentioned pretreated mixing raw material gas in ferric oxide adsorbing and removing mixing raw material gas, the organosulfur of mixing raw material gas in iron molybdenum and nickel molybdenum hydrogenation and zinc oxide adsorbing and removing mixing raw material gas, be reduced to 0.1ppm by the mass content of sulphur in mixing raw material gas;
5) recompression: the unstripped gas after purification enters centrifugal compressor, carries out two sections of compressions, and the pressure of unstripped gas is boosted to 4.0-5.0MpaG by 0.65 MpaG, 137 ℃ of the temperature outs of unstripped gas;
6) methanation: the unstripped gas after recompression enters sulphur protective pot, carries out level Four methanation reaction, by CO, CO
2be converted into methane, make CO, CO
2mass content be less than 50ppm;
7) dry demercuration: utilize Temp .-changing adsorption dehydration to-70 ℃ of dew points from the synthetic natural gas of methanation, remove the mercury metal in synthetic natural gas by sulfur loading active carbon;
8) cryogenic liquefying is separated: synthetic natural gas is introduced to ice chest, in precooling plate-fin heat exchanger, be pre-chilled to-50～-55 ℃, then after the separation of heavy hydrocarbon separating tank, 1:9 is divided into two portions by volume, most of gas enters cryogenic plate fin heat exchanger and continues cooling liquefaction, hydrogen and a small amount of nitrogen of by dehydrogenation tank, isolating not liquefaction, cryogenic liquid is sent into denitrification column and is carried out denitrogenation processing after decompression, obtains product natural gas liquids after denitrogenation; Small portion gas through decompression and with the low temperature of denitrogenation tower top speed to exit enter denitrification column after heat exchange at the bottom of as stripping gas;
9) LNG tank: above-mentioned natural gas liquids is delivered to LNG tank, due to fluid column and Pressure Drop, cause charging natural gas liquids to contain a large amount of flashed vapours, flashed vapour enters tank top boil-off gas space, sends together with storage tank boil-off gas;
10) natural gas liquids entrucking: the natural gas liquids coming from LNG tank is the pressurization of natural gas liquids cylinder band pump outside tank, delivers to jack works, utilizes the natural gas liquids entrucking arm with boil-off gas return-air arm to carry out natural gas liquids entrucking.
2. a kind of technique of utilizing coke(oven)gas to produce natural gas liquids according to claim 1, is characterized in that, described raw material mixes link and also contains the carbon dioxide gas that chemical plant is come.
3. a kind of technique of utilizing coke(oven)gas to produce natural gas liquids according to claim 1, it is characterized in that, described pre-treatment link, the sweep gas that Temp .-changing adsorption is used comes from pretreated mixing raw material gas, consumption is 1/10 of mixing raw material gas volume, this sweep gas through electric tar, wash benzene naphthalene and process Hou Hui coke-oven plant and do fuel gas.
4. a kind of technique of utilizing coke(oven)gas to produce natural gas liquids according to claim 1, is characterized in that, the reaction heat that described methanation link produces is introduced in middle pressure, the useless pot of low pressure and uses, and presses superheated vapour and low-pressure saturated steam in generation.
5. a kind of technique of utilizing coke(oven)gas to produce natural gas liquids according to claim 1, it is characterized in that, the stripping gas of the described separated link of cryogenic liquefying, through pressure-variable adsorption separation nitrogen, hydrogen wherein, by blower fan, be pressurized to 40kPaG afterwards and deliver to raw material and mix, isolated nitrogen, the hydrogen tail gas fiery distance of reducing phlegm and internal heat; The boil-off gas that LNG tank flashed vapour, natural gas liquids entrucking produce, after the re-heat of air temperature type recuperator, is pressurized to 40kPaG by blower fan and delivers to raw material and mix.
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Cited By (8)
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| CN104557390A (en) * | 2015-02-12 | 2015-04-29 | 鹤壁宝发能源科技股份有限公司 | Method for coproducing and synthesizing liquid methane from methanol purge gas |
| CN104673415A (en) * | 2015-02-10 | 2015-06-03 | 中国海洋石油总公司 | Technology for improving yield of liquefied natural gas in process of preparing natural gas through methanation of coke-oven gas |
| CN105258452A (en) * | 2015-10-29 | 2016-01-20 | 中国科学院理化技术研究所 | Gas separation device and method of pyrolysis gas |
| 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 |
| CN111410171A (en) * | 2020-03-31 | 2020-07-14 | 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 |
| US11628399B2 (en) | 2017-12-04 | 2023-04-18 | Cri, Ehf | System for separating gas |
| US11738317B2 (en) | 2021-01-15 | 2023-08-29 | CRI, hf | Reactor for synthesizing methanol or other products |
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| CN104557390A (en) * | 2015-02-12 | 2015-04-29 | 鹤壁宝发能源科技股份有限公司 | Method for coproducing and synthesizing liquid methane from methanol purge gas |
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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 |
| US11628399B2 (en) | 2017-12-04 | 2023-04-18 | Cri, Ehf | System for separating gas |
| CN111410171A (en) * | 2020-03-31 | 2020-07-14 | 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 |
| 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 |
| US11738317B2 (en) | 2021-01-15 | 2023-08-29 | CRI, hf | Reactor for synthesizing methanol or other products |
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