CN117685697A - System and process for preparing green low-carbon methanol and co-producing LNG (liquefied Natural gas) from coke oven gas - Google Patents
System and process for preparing green low-carbon methanol and co-producing LNG (liquefied Natural gas) from coke oven gas Download PDFInfo
- Publication number
- CN117685697A CN117685697A CN202311849026.9A CN202311849026A CN117685697A CN 117685697 A CN117685697 A CN 117685697A CN 202311849026 A CN202311849026 A CN 202311849026A CN 117685697 A CN117685697 A CN 117685697A
- Authority
- CN
- China
- Prior art keywords
- gas
- methanol
- coke oven
- tower
- carbon
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 338
- 239000000571 coke Substances 0.000 title claims abstract description 89
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 239000007789 gas Substances 0.000 title claims description 243
- 239000003949 liquefied natural gas Substances 0.000 title description 45
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 58
- 238000000926 separation method Methods 0.000 claims abstract description 51
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 48
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 33
- 230000023556 desulfurization Effects 0.000 claims abstract description 33
- 238000009833 condensation Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000005494 condensation Effects 0.000 claims abstract description 27
- 238000000746 purification Methods 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000006481 deamination reaction Methods 0.000 claims abstract description 15
- 239000012716 precipitator Substances 0.000 claims abstract description 15
- 230000009615 deamination Effects 0.000 claims abstract description 14
- 230000006835 compression Effects 0.000 claims abstract description 13
- 238000007906 compression Methods 0.000 claims abstract description 13
- 238000005261 decarburization Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 22
- 238000011084 recovery Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 238000010926 purge Methods 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 11
- 230000001502 supplementing effect Effects 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 239000003034 coal gas Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000003595 mist Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000003009 desulfurizing effect Effects 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000003245 coal Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- QOTAEASRCGCJDN-UHFFFAOYSA-N [C].CO Chemical compound [C].CO QOTAEASRCGCJDN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B43/00—Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B31/00—Compressor arrangements
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Power Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a green low-carbon methanol co-production LNG system and a process for preparing green low-carbon methanol co-production LNG from coke oven gas. The system for preparing green low-carbon methanol and co-producing LNG by using coke oven gas comprises a coke oven gas primary purification device, a coke oven gas deep purification device, a liquefied separation and co-production LNG device and a methanol preparation device, wherein the coke oven gas primary purification device comprises a gas-liquid separator, an electric tar precipitator and a desulfurization, deamination and debenzolization device; the coke oven gas deep purification device comprises a first purifier, a fine desulfurization tower and a decarburization device; the liquefied separation co-production LNG device comprises a second purifier and a cryogenic liquefied separation tower; the methanol preparation device comprises a compression device, a methanol synthesis tower, a condensation separator, a flash evaporator and a methanol rectifying tower. The green low-carbon methanol co-production LNG system prepared from the coke oven gas solves the energy consumption problem in the conversion process in the traditional process of preparing methanol from the coke oven gas, reduces byproducts of methanol synthesis, reduces production energy consumption, and improves the raw material utilization rate.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of coke oven gas, in particular to a system and a process for preparing green low-carbon methanol and co-producing LNG (Liquefied Natural Gas ) from coke oven gas.
Background
Coal energy is an important component of energy structures in China, and plays a vital role in ensuring energy supply safety in China. The coal chemical industry is used as a powerful means for realizing the efficient utilization of coal resources, and is directly related to national energy strategy development planning. The traditional technology for preparing methanol from coke oven gas converts methane in the coke oven gas into carbon monoxide as a carbon source for methanol synthesis, has large energy loss in the conversion process, high hydrogen content in purge gas and low raw material utilization rate, and does not meet the relevant requirements of national 'double carbon' policy and target.
In view of this, there is a need for low carbonization research and modification of the process for producing methanol from coke oven gas in the coal chemical industry.
Disclosure of Invention
The invention mainly aims to provide a green low-carbon methanol co-production LNG system and a process for preparing green low-carbon methanol co-production LNG from coke oven gas, and aims to realize comprehensive utilization of the coke oven gas and improve the utilization rate of raw materials.
In order to achieve the aim, the invention provides a green low-carbon methanol co-production LNG system prepared from coke oven gas, which comprises a coke oven gas primary purification device, a coke oven gas deep purification device, a liquefaction separation co-production LNG device and a methanol preparation device which are connected in sequence,
the coke oven gas primary purification device comprises a gas-liquid separator, an electric tar precipitator and a desulfurization, deamination and debenzolization device which are sequentially communicated;
the coke oven gas deep purification device comprises a first purifier, a fine desulfurization tower and a decarburization device which are sequentially communicated;
the liquefied separation co-production LNG device comprises a second purifier and a cryogenic liquefied separation tower which is communicated with the second purifier, wherein a first outlet of the cryogenic liquefied separation tower is an LNG product outlet, and a second outlet of the cryogenic liquefied separation tower is a hydrogen-rich outlet;
the methanol preparation device comprises a compression device, a methanol synthesis tower, a condensation separator, a flash evaporator and a methanol rectifying tower which are sequentially arranged, wherein the compression device is communicated with a second outlet of the cryogenic liquefaction separation tower.
Preferably, a primary cooler is arranged between the gas-liquid separator and the electric tar precipitator, and a blower and a pre-cooling tower are arranged between the electric tar precipitator and the desulfurization, deamination and debenzolization device.
Preferably, the desulfurization, deamination and debenzolization device comprises a desulfurization tower, a deamination tower, a final cooling tower and a debenzolization tower which are sequentially arranged.
Preferably, the coke oven gas deep purification device further comprises a gas buffer tank and a compressor, wherein the gas buffer tank and the compressor are sequentially arranged at the inlet side of the first purifier, the gas buffer tank is communicated with the outlet of the benzene removal tower, and the compressor is communicated with the inlet of the first purifier.
Preferably, the compression device comprises a carbon supplementing compressor, a mixed gas compressor and a synthetic gas compressor which are sequentially arranged, wherein an inlet of the carbon supplementing compressor is communicated with an outlet of the decarburization device, an outlet of the carbon supplementing compressor is communicated with an inlet of the mixed gas compressor, a second outlet of the cryogenic liquefaction separation tower is communicated with an inlet of the mixed gas compressor, and an outlet of the mixed gas compressor is communicated with an inlet of the synthetic gas compressor.
Preferably, the liquefied separation and co-production LNG device further comprises a hydrogen recovery device, wherein an inlet of the hydrogen recovery device is communicated with a gas outlet of the condensation separator, a liquid outlet of the condensation separator is communicated with an inlet of the flash evaporator, and an outlet of the hydrogen recovery device is communicated with an inlet of the mixed gas compressor; and a synthesis gas preheater is also arranged between the synthesis gas compressor and the methanol synthesis tower.
Preferably, the first outlet of the second purifier is communicated with the inlet of the gas mixture compressor, the second outlet of the second purifier is communicated with the inlet of the cryogenic liquefaction separation, the first outlet of the second purifier flows out of the gas mixture compressor into a carbon-rich gas, and the second outlet of the second purifier flows out of the gas mixture compressor into a gas mixture compressor 4 And H 2 。
The invention further provides a green low-carbon methanol co-production LNG process prepared from coke oven gas, which comprises the following steps of:
removing most of tar and ammonia water from coke oven gas through a gas-liquid separator, cooling in a primary cooler, further washing to remove oil and naphthalene, removing tar mist drops in an electrical tar precipitator, and sequentially desulfurizing, deaminizing and debenzolizing to obtain primary clean gas;
the primary clean gas passes through a first purifier, the contents of tar, naphthalene and benzene in the gas are reduced through temperature swing adsorption, and then the gas is sent into a fine desulfurization tower for desulfurization and is sent into a decarburization device for decarburization;
the decarbonized clean gas is firstly dried by a second purifier to further remove CO and CO 2 Then sending the LNG to a cryogenic liquefaction separation device to obtain LNG products;
externally captured CO 2 With CO from decarbonizing apparatus 2 And after the carbon-rich gas analyzed and regenerated by the second purifier is mixed and pressurized, the carbon-rich gas and the hydrogen-rich gas obtained by the cryogenic liquefaction separation device are compressed in the compression device, the compressed gas is sent into the methanol synthesis device, the high-temperature crude methanol gas generated by the synthesis reaction enters the condensation separator for condensation and gas-liquid separation, the separated crude methanol is decompressed and then enters the flash evaporator, and the flashed crude methanol is sent into the methanol rectification device for purification, and water and by-product fusel are separated, so that a methanol product is obtained.
Preferably, when the primary clean gas passes through the first purifier, tar, naphthalene and benzene contents in the gas are respectively removed to 1mg/Nm through temperature swing adsorption 3 、1mg/Nm 3 、10mg/Nm 3 The following are set forth; when the desulfurization is carried out in the fine desulfurization tower, the total sulfur in the coal gas is removed to be below 0.15 ppm; when decarbonizing is carried out in the decarbonizer, CO in the gas is removed 2 Removing to below 45 ppm.
Preferably, when the condensation separator is used for condensation and gas-liquid separation, most of the separated uncondensed gas is used as recycle gas to be sent into the synthesis gas compressor to be mixed with each path of fresh raw gas and then to be sent into the methanol synthesis tower again, and a small part of the extracted purge gas is sent into the hydrogen recovery device to recover hydrogen, and the crude methanol separated by the condensation separator is decompressed to 0.6MPa and then is sent into the flash evaporator.
The green low-carbon methanol co-production LNG system prepared from the coke oven gas has the following beneficial effects:
1. the system can realize H in coke oven gas 2 、CH 4 And efficient staged utilization of CO, capturing CO outside the utilization 2 The LNG is co-produced while the green low-carbon methanol is produced;
2. compared with the traditional technology for preparing methanol from coke oven gas, the technology uses CO 2 And H 2 The synthesis reaction is mainly due to CO 2 Compared with the method that CO is relatively inert, the reaction exotherm is less, byproducts (hetero alcohol) of the synthesis reaction are less, and the purity of the methanol product is high;
3. the system can capture CO externally 2 H separated from coke oven gas for carbon source 2 The methanol is synthesized, so that a coke oven gas conversion device and an air separation oxygen generation device are not required, and the production energy consumption is greatly reduced;
4. the system can be used for controlling the production load of the coke oven, namely H 2 Yield-regulated external capture of CO 2 Control of H/C of synthesis gas to realize H 2 Solves the problem of a great amount of H in the residual purge gas in the prior art 2 Is a problem of (2);
5. the tail gas of the methanol synthesis purge gas recovered by the hydrogen recovery device can be used as fuel for heating the coke oven, so that the consumption of the return gas is reduced;
6. the system can utilize CO trapped in external industrial tail gas 2 As synthesis raw material gas, directly realize CO 2 Is reduced in emissions.
Drawings
FIG. 1 is a schematic diagram of a primary purification device of coke oven gas in a system for preparing green low-carbon methanol and co-producing LNG from coke oven gas;
FIG. 2 is a schematic structural view of a coke oven gas deep purification device in the coke oven gas green low-carbon methanol co-production LNG system;
FIG. 3 is a schematic structural diagram of a liquefaction separation LNG co-production device in the coke oven gas green low-carbon methanol co-production LNG system;
FIG. 4 is a schematic structural view of a methanol production device in the coke oven gas green low-carbon methanol co-production LNG system;
fig. 5 is a schematic flow chart of the process for preparing green low-carbon methanol and co-producing LNG from coke oven gas.
In the figure, a 1-gas-liquid separator, a 2-primary cooler, a 3-electric tar precipitator, a 4-blower, a 5-pre-cooling tower, a 6-desulfurizing tower, a 7-deamination tower, an 8-final cooling tower, a 9-debenzolization tower, a 10-gas buffer tank, an 11-compressor, a 12-first purifier, a 13-fine desulfurizing tower, a 14-decarbonizer, a 15-second purifier, a 16-cryogenic liquefaction separation tower, a 17-carbon supplementing compressor, an 18-mixed gas compressor, a 19-synthetic gas compressor, a 20-synthetic gas preheater, a 21-methanol synthesis tower, a 22-condensation separator, a 23-flash evaporator, a 24-methanol rectifying tower and a 25-hydrogen recovery device.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
It should be noted that, in the description of the present invention, the terms "transverse", "longitudinal", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
The invention provides a green low-carbon methanol co-production LNG system prepared from coke oven gas.
In the preferred embodiment, referring to fig. 1 to 4, a system for preparing green low-carbon methanol and co-producing LNG from coke oven gas comprises a coke oven gas primary purification device, a coke oven gas deep purification device, a liquefaction separation and co-production LNG device and a methanol preparation device which are sequentially connected, wherein,
the coke oven gas primary purification device comprises a gas-liquid separator 1, an electric tar precipitator 3 and a desulfurization, deamination and debenzolization device which are sequentially communicated;
the coke oven gas deep purification device comprises a first purifier 12, a fine desulfurization tower 13 and a decarburization device 14 which are sequentially communicated;
the liquefied separation co-production LNG device comprises a second purifier 15 and a cryogenic liquefied separation tower 16 communicated with the second purifier, wherein a first outlet of the cryogenic liquefied separation tower 16 is an LNG product outlet, and a second outlet of the cryogenic liquefied separation tower 16 is a hydrogen-rich outlet;
the methanol production device comprises a compression device, a methanol synthesis tower 21, a condensation separator 22, a flash evaporator 23 and a methanol rectifying tower 24 which are sequentially arranged, wherein the compression device is communicated with a second outlet of the cryogenic liquefaction separation tower 16.
The decarbonizer 14 may be a PSA (Pressure Swing Adsorption ) decarbonizer. The first purifier 12 is a TSA purifier and the second purifier 15 is a combination purifier of a PSA purifier and a TSA purifier.
Further, a primary cooler 2 (thus carrying out preliminary cooling on the coal gas) is arranged between the gas-liquid separator 1 and the electric tar precipitator 3, and a blower 4 (pressurizing the coal gas through the blower 4) and a precooling tower 5 (cooling the coal gas by the precooling tower 5) are arranged between the electric tar precipitator 3 and the desulfurization, deamination and debenzolization device.
Specifically, in this embodiment, the desulfurization, deamination and debenzolization apparatus includes a desulfurization tower 6, a deamination tower 7, a final cooling tower 8 and a debenzolization tower 9 which are sequentially arranged.
The coke oven gas deep purification device further comprises a gas buffer tank 10 and a compressor 11, wherein the gas buffer tank 10 and the compressor 11 are sequentially arranged on the inlet side of the first purifier 12, the gas buffer tank 10 is communicated with the outlet of the debenzolization tower 9, and the compressor 11 is communicated with the inlet of the first purifier 12. In addition, the outlet of the debenzolization tower 9 is also communicated with the coke oven, so that part of the primary clean gas flowing out of the debenzolization tower 9 can be returned to the coke oven to be used as heating gas, and the rest of the primary clean gas is completely sent to a subsequent process to be used as a production raw material.
Specifically, the compression device comprises a carbon supplementing compressor 17, a gas mixture compressor 18 and a synthesis gas compressor 19 which are sequentially arranged, wherein an inlet of the carbon supplementing compressor 17 is communicated with an outlet of the decarburization device 14, an outlet of the carbon supplementing compressor 17 is communicated with an inlet of the gas mixture compressor 18, a second outlet of the cryogenic liquefaction separation tower 16 is communicated with an inlet of the gas mixture compressor 18, and an outlet of the gas mixture compressor 18 is communicated with an inlet of the synthesis gas compressor 19. Carbon-rich gas outlet of the second purifier 15And also communicates with the inlet of the mixture compressor 18. The second purifier 15 is provided with two outlets, one for discharging the carbon-rich gas and the other for discharging the CH 4 And H 2 。
Further, the liquefied separation co-production LNG plant further includes a hydrogen recovery device 25 (PSA hydrogen recovery device may be used), an inlet of the hydrogen recovery device 25 is connected to a gas outlet of the condensation separator 22, a liquid outlet of the condensation separator 22 is connected to an inlet of the flash evaporator 23, and an outlet of the hydrogen recovery device 25 is connected to an inlet of the gas mixture compressor 18; a synthesis gas preheater 20 is also provided between the synthesis gas compressor 19 and the methanol synthesis column 21.
The first outlet of the second purifier 15 is communicated with the inlet of the gas mixture compressor 18, the second outlet of the second purifier 15 is communicated with the inlet of the cryogenic liquefaction separation, the first outlet of the second purifier 15 flows out of the gas mixture to be rich in carbon, and the second outlet of the second purifier 15 flows out of the gas mixture to be CH 4 And H 2 。
Referring to fig. 5, the working process of the device for preparing green low-carbon methanol and co-producing LNG from coke oven gas is as follows:
1. primary purification procedure of coke oven gas: the method is used for purifying the raw gas, removing most of tar, naphthalene, ammonia, hydrogen sulfide, hydrogen cyanide, benzene and other impurities in the raw gas to obtain primary purified gas, and comprises the following specific processes: raw gas containing a large amount of tar and ammonia water generated by a coke oven is firstly removed by a gas-liquid separator 1, then is sent into a primary cooler 2 for cooling and cooling, is further washed for degreasing and naphthalene removal, is sent into an electrical tar precipitator 3 for removing tiny tar mist drops, is pressurized by a blower 4, and is sequentially subjected to precooling and cooling, HPF wet desulfurization and NH removal 3 And finally cooling and debenzolizing to obtain the primary clean gas. And returning part of the primary clean gas to the coke oven as heating gas, and feeding the rest of the primary clean gas to a subsequent process as a production raw material.
2. Deep purification procedure of coke oven gas: the method is used for compressing and deeply purifying the coal gas, and removing tar, naphthalene, benzene, total sulfur, carbon dioxide and other impurities in the primary purified coal gas to the trace level required by the subsequent process, and the specific process is as follows: the primary clean gas is stored in a gas buffer tank 10 for enteringBuffering, compressing to 0.6MPa, introducing into the first purifier 12, and removing tar, naphthalene and benzene to 1mg/Nm by temperature swing adsorption 3 、1mg/Nm 3 、10mg/Nm 3 Then the gas is sent to a fine desulfurization tower 13 (a molecular sieve fine desulfurization device can be adopted) to remove the total sulfur in the gas to below 0.15ppm, and then sent to a decarbonizer 14 to remove CO in the gas 2 The liquefied natural gas is separated to be less than 45ppm so as to meet the requirement of cryogenic liquefaction and separation for extracting LNG. CO separated by the decarbonizer 14 2 The carbon removal unit is fed to a carbon make-up compressor 17.
3. Liquefaction separation co-production LNG process: the method is used for drying and component liquefaction separation of clean gas to produce LNG products, and comprises the following specific processes: the decarbonized clean gas is firstly dried by a second purifier 15 to further remove CO and CO 2 The impurity components are then sent to cryogenic liquefaction separation column 16 to produce LNG product; the hydrogen-rich gas (mainly H) 2 ) Sending the regenerated gas into a PSA/TSA combined adsorption device for adsorbent regeneration, sending the regenerated gas into a methanol preparation device for mixing with other methanol synthesis gas, and analyzing and regenerating carbon-rich gas (mainly CO and CO) by a second purifier 15 2 ) Is sent to a carbon supplementing compressor 17 of the methanol preparation device.
4. Green low carbon methanol process: the method is used for synthesizing methanol, rectifying and purifying, recycling purge gas and the like, and comprises the following specific processes: externally captured CO 2 With CO from decarbonizer 14 2 The carbon-rich gas after the analysis and regeneration by the second purifier 15 is mixed and pressurized to 0.5MPa, and then the mixture is mixed with the hydrogen-rich gas and the H of the hydrogen recovery device 25 in the previous step 2 Mixed and compressed to 2.5MPa, sent to a mixed gas compressor 18, mixed and pressurized with recycle gas from a methanol synthesis tower 21 to 7.8MPa, and sent to the methanol synthesis tower 21. After the synthesis gas is preheated to 220 ℃, the synthesis gas is sent into a methanol synthesis tower 21, high-temperature crude methanol gas generated by the synthesis reaction is subjected to waste heat recovery and heat exchange with raw material synthesis gas at the inlet of a synthesis device, and then enters a condensation separator 22 for condensation and gas-liquid separation, most of the separated uncondensed gas is sent into a synthesis gas compressor 19 as recycle gas to be mixed with each path of fresh raw material gas, and then enters the methanol synthesis tower 21 again, and a small part of purge gas is pumped out for deliveryInto the hydrogen recovery device 25 to recover H 2 The separated crude methanol is decompressed to 0.6MPa and then enters a flash evaporator 23, the flashed crude methanol is sent into a methanol rectifying tower 24 for purification, and water and by-product fusel are separated to obtain a methanol product. Wherein, the H recovered by the hydrogen recovery device 25 2 The tail gas of the P methanol rectifying tower 24 and the non-condensable gas of the condensation separator 22 are sent to the first purifier 12 as adsorbent regenerated gas and then sent back to the coke oven heating system to replace part of heating fuel gas.
The green low-carbon methanol co-production LNG system prepared from the coke oven gas has the following beneficial effects:
1. the system can realize H in coke oven gas 2 、CH 4 And efficient staged utilization of CO, capturing CO outside the utilization 2 The LNG is co-produced while the green low-carbon methanol is produced;
2. compared with the traditional technology for preparing methanol from coke oven gas, the technology uses CO 2 And H 2 The synthesis reaction is mainly due to CO 2 Compared with the method that CO is relatively inert, the reaction exotherm is less, byproducts (hetero alcohol) of the synthesis reaction are less, and the purity of the methanol product is high;
3. the system can capture CO externally 2 H separated from coke oven gas for carbon source 2 The methanol is synthesized, so that a coke oven gas conversion device and an air separation oxygen generation device are not required, and the production energy consumption is greatly reduced;
4. the system can be used for controlling the production load of the coke oven, namely H 2 Yield-regulated external capture of CO 2 Control of H/C of synthesis gas to realize H 2 Solves the problem of a great amount of H in the residual purge gas in the prior art 2 Is a problem of (2);
5. the tail gas of the methanol synthesis purge gas recovered by the hydrogen recovery device 25 can be used as fuel for heating the coke oven, so that the consumption of the return gas is reduced;
6. the system can utilize CO trapped in external industrial tail gas 2 As synthesis raw material gas, directly realize CO 2 Is reduced in emissions.
The invention provides a technology for preparing green low-carbon methanol and LNG (liquefied Natural gas) by using coke oven gas.
Referring to fig. 5, in the preferred embodiment, a process for preparing green low-carbon methanol and LNG from coke oven gas includes the following steps:
step S10, after removing most of tar and ammonia water from coke oven gas through a gas-liquid separator 1, sending the coke oven gas into a primary cooler 2 for cooling, further washing for degreasing and naphthalene removal, sending the coke oven gas into an electrical tar precipitator 3 for removing tar mist drops, and sequentially carrying out desulfurization, deamination and debenzolization to obtain primary clean gas;
step S20, the primary clean gas passes through a first purifier 12, the contents of tar, naphthalene and benzene in the gas are reduced through temperature swing adsorption, and then the gas is sent to a fine desulfurization tower 13 for desulfurization and sent to a decarburization device 14 for decarburization;
step S30, the decarbonized clean gas is firstly dried by a second purifier 15 to further remove CO and CO 2 Then sending the LNG to a cryogenic liquefaction separation device to obtain LNG products;
step S40, capturing CO from outside 2 With CO from decarbonizing apparatus 2 And the second purifier 15 analyzes the regenerated carbon-rich gas, mixes and pressurizes to 0.5MPa, compresses the carbon-rich gas and the hydrogen-rich gas obtained by the cryogenic liquefaction separation device in the compression device, sends the compressed gas into the methanol synthesis device, and sends high-temperature crude methanol gas generated by the synthesis reaction into the condensation separator 22 for condensation and gas-liquid separation, and the separated crude methanol is decompressed and then enters the flash evaporator, and the flashed crude methanol is sent into the methanol rectification device for purification, and water and by-product fusel are separated, thus obtaining a methanol product.
Specifically, in step S20, when the primary clean gas passes through the first purifier 12, the tar, naphthalene and benzene contents in the gas are removed to 1mg/Nm respectively by temperature swing adsorption 3 、1mg/Nm 3 、10mg/Nm 3 The following are set forth; when the fine desulfurization tower 13 is used for desulfurization, the total sulfur in the coal gas is removed to be below 0.15 ppm; when decarbonizing is performed in the decarbonizer 14, CO in the gas is removed 2 Removing to below 45 ppm.
Specifically, in step S40, when the condensation separator 22 condenses and separates gas from liquid, most of the separated uncondensed gas is sent to the synthesis gas compressor 19 as recycle gas, mixed with each fresh feed gas, and then sent to the methanol synthesis tower 21 again, a small part of purge gas is withdrawn and sent to the hydrogen recovery device 25 to recover hydrogen, and crude methanol separated by the condensation separator 22 is depressurized to 0.6MPa and then sent to the flash evaporator 23.
The process for preparing green low-carbon methanol and co-producing LNG from coke oven gas has the following beneficial effects:
1. the process can realize H in coke oven gas 2 、CH 4 And efficient staged utilization of CO, capturing CO outside the utilization 2 The LNG is co-produced while the green low-carbon methanol is produced;
2. compared with the traditional technology for preparing methanol from coke oven gas, the technology uses CO 2 And H 2 The synthesis reaction is mainly due to CO 2 Compared with the method that CO is relatively inert, the reaction exotherm is less, byproducts (hetero alcohol) of the synthesis reaction are less, and the purity of the methanol product is high;
3. the process externally captures CO 2 Is H separated from carbon source and coke oven gas 2 The methanol is synthesized without arranging a coke oven gas conversion device and an air separation oxygen generation device, so that the production energy consumption is greatly reduced;
4. the process can be based on the coke oven production load, namely H 2 Yield-regulated external capture of CO 2 Control of H/C of synthesis gas to realize H 2 Solves the problem of a great amount of H in the residual purge gas in the prior art 2 Is a problem of (2);
5. the tail gas of the methanol synthesis purge gas after PSA hydrogen recovery can be used as fuel for heating a coke oven, so that the consumption of return gas is reduced;
6. the process can utilize CO trapped in external industrial tail gas 2 As synthesis raw material gas, directly realize CO 2 Is reduced in emissions.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the invention, but is intended to cover all equivalent structures modifications, direct or indirect application in other related arts, which are included in the scope of the present invention.
Claims (10)
1. The system for preparing green low-carbon methanol and co-producing LNG from coke oven gas is characterized by comprising a coke oven gas primary purification device, a coke oven gas deep purification device, a liquefaction separation and co-production LNG device and a methanol preparation device which are connected in sequence,
the coke oven gas primary purification device comprises a gas-liquid separator, an electric tar precipitator and a desulfurization, deamination and debenzolization device which are sequentially communicated;
the coke oven gas deep purification device comprises a first purifier, a fine desulfurization tower and a decarburization device which are sequentially communicated;
the liquefied separation co-production LNG device comprises a second purifier and a cryogenic liquefied separation tower which is communicated with the second purifier, wherein a first outlet of the cryogenic liquefied separation tower is an LNG product outlet, and a second outlet of the cryogenic liquefied separation tower is a hydrogen-rich outlet;
the methanol preparation device comprises a compression device, a methanol synthesis tower, a condensation separator, a flash evaporator and a methanol rectifying tower which are sequentially arranged, wherein the compression device is communicated with a second outlet of the cryogenic liquefaction separation tower.
2. The system for producing green low-carbon methanol and co-producing LNG from coke oven gas according to claim 1, wherein a primary cooler is arranged between the gas-liquid separator and the electric tar precipitator, and a blower and a pre-cooling tower are arranged between the electric tar precipitator and the desulfurization, deamination and debenzolization device.
3. The system for producing green low-carbon methanol and co-producing LNG from coke oven gas according to claim 2, wherein the desulfurization, deamination and debenzolization device comprises a desulfurization tower, a deamination tower, a final cooling tower and a debenzolization tower which are sequentially arranged.
4. The system for producing green low-carbon methanol and co-producing LNG from coke oven gas according to claim 3, wherein the coke oven gas deep purification device further comprises a gas buffer tank and a compressor, wherein the gas buffer tank and the compressor are sequentially arranged at the inlet side of the first purifier, the gas buffer tank is communicated with the outlet of the debenzolization tower, and the compressor is communicated with the inlet of the first purifier.
5. The system for producing green low-carbon methanol and LNG from coke oven gas according to any one of claims 1 to 4, wherein the compression device comprises a carbon supplementing compressor, a gas mixture compressor and a synthesis gas compressor which are sequentially arranged, wherein an inlet of the carbon supplementing compressor is communicated with an outlet of the decarbonizer, an outlet of the carbon supplementing compressor is communicated with an inlet of the gas mixture compressor, a second outlet of the cryogenic liquefaction separation tower is communicated with an inlet of the gas mixture compressor, and an outlet of the gas mixture compressor is communicated with an inlet of the synthesis gas compressor.
6. The system for producing green low-carbon methanol and co-producing LNG from coke oven gas according to claim 5, wherein the liquefied separation and co-production LNG device further comprises a hydrogen recovery device, an inlet of the hydrogen recovery device is communicated with a gas outlet of a condensation separator, a liquid outlet of the condensation separator is communicated with an inlet of a flash evaporator, and an outlet of the hydrogen recovery device is communicated with an inlet of a gas mixture compressor; and a synthesis gas preheater is also arranged between the synthesis gas compressor and the methanol synthesis tower.
7. The system for producing green low-carbon methanol and co-producing LNG from coke oven gas as claimed in claim 5, wherein the first outlet of the second purifier is communicated with the inlet of the gas mixture compressor, the second outlet of the second purifier is communicated with the inlet of the cryogenic liquefaction separation, the first outlet of the second purifier flows out of the gas mixture to be rich in carbon, and the second outlet of the second purifier flows out of the gas mixture to be CH 4 And H 2 。
8. The green low-carbon methanol co-production LNG process by using coke oven gas is characterized by comprising the following steps of:
removing most of tar and ammonia water from coke oven gas through a gas-liquid separator, cooling in a primary cooler, further washing to remove oil and naphthalene, removing tar mist drops in an electrical tar precipitator, and sequentially desulfurizing, deaminizing and debenzolizing to obtain primary clean gas;
the primary clean gas passes through a first purifier, the contents of tar, naphthalene and benzene in the gas are reduced through temperature swing adsorption, and then the gas is sent into a fine desulfurization tower for desulfurization and is sent into a decarburization device for decarburization;
the decarbonized clean gas is firstly dried by a second purifier to further remove CO and CO 2 Then sending the LNG to a cryogenic liquefaction separation device to obtain LNG products;
externally captured CO 2 With CO from decarbonizing apparatus 2 And after the carbon-rich gas analyzed and regenerated by the second purifier is mixed and pressurized, the carbon-rich gas and the hydrogen-rich gas obtained by the cryogenic liquefaction separation device are compressed in the compression device, the compressed gas is sent into the methanol synthesis device, the high-temperature crude methanol gas generated by the synthesis reaction enters the condensation separator for condensation and gas-liquid separation, the separated crude methanol is decompressed and then enters the flash evaporator, and the flashed crude methanol is sent into the methanol rectification device for purification, and water and by-product fusel are separated, so that a methanol product is obtained.
9. The process for preparing green low-carbon methanol and co-producing LNG from coke oven gas as claimed in claim 8, wherein the tar, naphthalene and benzene contents in the primary purified gas are removed to 1mg/Nm respectively by temperature swing adsorption when the primary purified gas passes through the first purifier 3 、1mg/Nm 3 、10mg/Nm 3 The following are set forth; when the desulfurization is carried out in the fine desulfurization tower, the total sulfur in the coal gas is removed to be below 0.15 ppm; when decarbonizing is carried out in the decarbonizer, CO in the gas is removed 2 Removing to below 45 ppm.
10. The process for producing green low-carbon methanol and LNG from coke oven gas according to claim 8, wherein when the condensation separator performs condensation and gas-liquid separation, most of the separated uncondensed gas is fed as recycle gas into the synthesis gas compressor to be mixed with each path of fresh feed gas and then fed into the methanol synthesis tower again, a small part of the purge gas is extracted and fed into the hydrogen recovery device to recover hydrogen, and the crude methanol separated by the condensation separator is depressurized to 0.6MPa and then fed into the flash evaporator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311849026.9A CN117685697A (en) | 2023-12-29 | 2023-12-29 | System and process for preparing green low-carbon methanol and co-producing LNG (liquefied Natural gas) from coke oven gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311849026.9A CN117685697A (en) | 2023-12-29 | 2023-12-29 | System and process for preparing green low-carbon methanol and co-producing LNG (liquefied Natural gas) from coke oven gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117685697A true CN117685697A (en) | 2024-03-12 |
Family
ID=90137094
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311849026.9A Pending CN117685697A (en) | 2023-12-29 | 2023-12-29 | System and process for preparing green low-carbon methanol and co-producing LNG (liquefied Natural gas) from coke oven gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117685697A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118479957A (en) * | 2024-07-12 | 2024-08-13 | 浙江吉利控股集团有限公司 | A methanol preparation process and preparation system |
-
2023
- 2023-12-29 CN CN202311849026.9A patent/CN117685697A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118479957A (en) * | 2024-07-12 | 2024-08-13 | 浙江吉利控股集团有限公司 | A methanol preparation process and preparation system |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2597920C2 (en) | Method for production of ammonia | |
| US20090214902A1 (en) | Adsorptive Bulk Separation for Upgrading Gas Streams | |
| US12084347B2 (en) | Process and plant for producing hydrogen and for separating carbon dioxide from synthesis gas | |
| CN110127613B (en) | An efficient and advanced coke oven gas hydrogen production process | |
| CN112897464B (en) | Process for producing hydrogen and coproducing LNG (liquefied natural gas) by using raw gas with methanation | |
| CN114149837B (en) | Process for preparing liquefied natural gas and co-producing liquid ammonia or hydrogen by coke oven gas with conversion decarburization | |
| CN217459345U (en) | Device for producing low-carbon methanol by using coke oven gas | |
| CN101343580A (en) | Method for preparing methanol synthesis gas with oven gas and blast furnace gas | |
| CN114409503A (en) | Process for preparing BDO and co-producing liquid ammonia by using coke oven gas | |
| CN117685697A (en) | System and process for preparing green low-carbon methanol and co-producing LNG (liquefied Natural gas) from coke oven gas | |
| CN102924228B (en) | Method for producing methanol from semi-coke furnace tail gas | |
| CN101607859B (en) | Process employing coke-oven gas for production of methane | |
| CN105683086B (en) | For the Joint Production pig iron and the organic chemistry product based on synthesis gas method | |
| CN112678773A (en) | Process for producing hydrogen and coproducing LNG (liquefied Natural gas) by using raw gas | |
| US12109527B2 (en) | Process and apparatus for the separation of two gaseous streams each containing carbon monoxide, hydrogen and at least one acid gas | |
| CN107399737B (en) | Preparation method of high-pressure gas-phase carbon dioxide for high-pressure pulverized coal gasification | |
| CN107311173B (en) | Preparation method of high-pressure gas-phase carbon dioxide for pulverized coal gasification unit | |
| CN114736719A (en) | Device and method for producing ethylene glycol and co-producing LNG and dimethyl carbonate | |
| CN209052640U (en) | It is a kind of to utilize coke-stove gas synthesis of methanol with joint production LNG, richness H2Device | |
| CN108034464B (en) | Method for preparing liquefied natural gas from semi-coke tail gas | |
| RU2088518C1 (en) | Method of producing hydrogen from hydrocarbon gas | |
| CN110669542A (en) | Method and device for preparing Fischer-Tropsch wax by using coke oven gas | |
| CN116789519A (en) | A green low-carbon methanol production process | |
| CN113666386B (en) | Method for synthesizing ammonia from coke oven gas | |
| CN210560263U (en) | Device for preparing Fischer-Tropsch wax by utilizing coke oven gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |