CN116789080A - Improved process for preparing ammonia and LNG from coke oven gas - Google Patents
Improved process for preparing ammonia and LNG from coke oven gas Download PDFInfo
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- CN116789080A CN116789080A CN202310012153.7A CN202310012153A CN116789080A CN 116789080 A CN116789080 A CN 116789080A CN 202310012153 A CN202310012153 A CN 202310012153A CN 116789080 A CN116789080 A CN 116789080A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000000571 coke Substances 0.000 title claims abstract description 26
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 109
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 125000001741 organic sulfur group Chemical group 0.000 claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000000746 purification Methods 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 238000010521 absorption reaction Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 claims abstract description 7
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- WINTXHPCODMMRI-UHFFFAOYSA-N benzene naphthalene Chemical compound C1=CC=CC=C1.C1=CC=CC=C1.C1=CC=CC2=CC=CC=C21 WINTXHPCODMMRI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001784 detoxification Methods 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract description 9
- 239000003949 liquefied natural gas Substances 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0415—Purification by absorption in liquids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0435—Catalytic purification
- C01B2203/044—Selective oxidation of carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Industrial Gases (AREA)
Abstract
The invention discloses an improved method for co-producing LNG and synthetic ammonia by coke oven gas, which comprises the steps of compressing the coke oven gas to 0.8-2.5MPa, removing tar and benzene naphthalene, sending the coke oven gas to a conversion tower which is set up by combining low-temperature sulfur-resistant and medium-temperature organic sulfur hydrolysis catalysts, converting 5-8% of carbon monoxide in the coke oven gas to be lower than 0.8% and converting 200-1000ppm of organic sulfur to 99% of hydrogen sulfide in the conversion, enabling the gas to pass through a heat exchanger for heating a heat source for Fischer-Tropsch purification, cooling to 30-40 ℃ after cooling, and sending the gas to 1ppm of hydrogen sulfide in a first-stage absorption tower; the residual organic sulfur in the gas is 2-10ppm, then the gas is sent to a low-temperature organic sulfur conversion tower to convert 99 percent of organic sulfur into hydrogen sulfide, the residual organic sulfur in the gas is 0.02-0.1ppm, the residual organic sulfur in the gas is sent to a second-stage absorption tower of hydrogen sulfide to less than 0.9ppm, the total sulfur is removed to be less than 1ppm, the total sulfur in the gas is sent to MDEA to remove carbon dioxide to 1000-2000 ppm, the gas is sent to a heat exchanger to be heated, the gas is sent to a deoxidization and detoxification tower, and then the gas is sent to a Fischer-Tropsch purification tower to reduce the total concentration of carbon monoxide and carbon dioxide to be less than 10ppm, and the gas is called purified gas; the purified gas is sent to a liquid nitrogen washing device to manufacture LNG, and the demethanized synthetic gas and the supplementary 99.99% nitrogen (50 ppm oxygen) are prepared into hydrogen-nitrogen ratio 3:1 sending the liquid ammonia to the ammonia synthesis process after normal temperature refined deoxidization.
Description
Technical Field
The invention relates to the technical field of energy utilization and environmental protection, in particular to a method and a device for preparing ammonia from coke oven gas and recycling LNG.
Background
The technology for preparing ammonia and LNG from coke oven gas generally adopts compression, tar removal and C removal 3 + Compressing to above 2.5MPa, removing hydrogen sulfide at high temperature, hydroconverting at high temperature, removing hydrogen sulfide at high temperature again, removing total sulfur to below 0.1ppm, cooling to normal temperature, removing carbon dioxide to below 30ppm by MDEA, washing with liquid nitrogen to prepare LNG, and obtaining the mixed hydrogen-nitrogen ratio of 3:1, the carbon monoxide in the synthesis gas is below 3ppm and the hydrocarbon is below 1ppm, and ammonia is fed to synthesize and manufacture liquid ammonia. The byproduct liquid nitrogen washing tail gas of the liquid nitrogen washing process contains 5-20% of carbon monoxide and 80-95% of nitrogen.
CN202111272968 discloses a process for preparing liquefied natural gas and co-producing liquid ammonia or hydrogen from coke oven gas with transformation decarburization. In the process, coke oven gas is subjected to compression purification, hydrodesulfurization, conversion, decarburization, methanation, cryogenic separation and other process units, liquid after cryogenic separation is an LNG product, and the gas can be used as a hydrogen-nitrogen raw material of a downstream ammonia synthesis device to produce a liquid ammonia product after reheating or used as a raw material of a PSA hydrogen extraction device to produce pure hydrogen. Coke oven gas contains 5-10% carbon monoxide, and removal of carbon monoxide during liquid nitrogen scrubbing produces liquid nitrogen scrubbed tail gas that is typically used only for combustion to produce a heat source.
In CN110041969A, a method and a device for recycling liquid nitrogen washing tail gas are provided, and the liquid nitrogen washing tail gas is subjected to pressure boosting and water cooling in sequence to obtain pretreatment liquid nitrogen washing tail gas. The pretreatment liquid nitrogen washing tail gas is subjected to carbon monoxide adsorption to obtain carbon monoxide gas, and then the carbon monoxide gas is mixed with first water vapor for high-temperature conversion to obtain high-temperature conversion gas; mixing the high-temperature conversion gas with second water vapor to perform medium-low temperature conversion to obtain medium-low temperature conversion gas; and cooling and decarbonizing the medium-low temperature shift gas in sequence to obtain the synthesis gas. Wherein the production cost is high and the equipment cost is high by using the noble metal catalyst.
The invention converts carbon monoxide in the coke oven gas into hydrogen, which is beneficial to reducing the tail gas of liquid nitrogen washing, simultaneously reduces the energy consumption of the carbon monoxide purifying process, and converts the carbon monoxide in the coke oven gas into hydrogen to be combined with the desulfurizing process, thereby the energy is used in a conjugation way, and the energy consumption is reduced, thus becoming our inventive idea.
Disclosure of Invention
The invention adopts the following technical scheme: compressing the coke oven gas to 0.8-2.5MPa, removing tar and benzene naphthalene, sending the coke oven gas to a conversion tower which is arranged to work in combination with a low-temperature sulfur-resistant and medium-temperature organic sulfur hydrolysis catalyst, converting 5-8% carbon monoxide in the coke oven gas to be lower than 0.8% through conversion reaction, converting 200-1000ppm organic sulfur to 99% hydrogen sulfide, and sending the gas to a heat source for Fischer-Tropsch purification through a heat exchanger, cooling to 30-40 ℃ after cooling, and sending the gas to 1ppm of hydrogen sulfide to a first-stage absorption tower; the residual organic sulfur in the gas is 2-10ppm, then the gas is sent to a low-temperature organic sulfur conversion tower to convert 99 percent of organic sulfur into hydrogen sulfide, the residual organic sulfur in the gas is 0.02-0.1ppm, the residual organic sulfur in the gas is sent to a second-stage absorption tower of hydrogen sulfide to be less than 0.9ppm, the total sulfur is removed to be less than 1ppm, the total sulfur in the gas is sent to MDEA to remove carbon dioxide to be 1000-2000 ppm, the gas is sent to a heat exchanger to be heated, the gas is sent to a deoxidizing and detoxication tower, and then the gas is sent to a Fischer-Tropsch purification tower to reduce the total concentration of carbon monoxide and carbon dioxide to be less than 8ppm, thus the gas is called purified gas; the purified gas is sent to a liquid nitrogen washing device to manufacture LNG, and the demethanized synthetic gas and the supplementary 99.99% nitrogen (50 ppm oxygen) are prepared into hydrogen-nitrogen ratio 3:1 sending the liquid ammonia to the ammonia synthesis process after normal temperature refined deoxidization.
The innovation point of the invention is that: 1. in general, considering the characteristic of high organic sulfur content of coke oven gas, medium-temperature hydrolysis is generally adopted to realize quick hydrolysis and desulfurization, the organic sulfur can reach lower concentration by low reaction speed, while high Wen Qingjie organic sulfur is a common means, and has high speed and deep conversion of organic sulfur, so that most of organic sulfur is converted by adopting a high-temperature hydrogenolysis mode, and in order to avoid cold and hot problems, the removal of hydrogen sulfide by adopting high-temperature zinc oxide is a necessary means, but the price of zinc oxide is high, and therefore, the disposable investment and replacement cost are high. In addition, the heating process usually adopts a coke oven gas combustion heating method, and the energy consumption is high. If the method of simultaneous working of the conversion and the deep hydrolysis desulfurization machine is adopted, the method has the energy-saving effect of removing a large amount of organic sulfur. The conversion of 8% of carbon monoxide into hydrogen by a conversion method has large investment and poor economic benefit, and the technicians in the field can not use the method to remove organic sulfur and convert the organic sulfur together at the same time, so that the economic benefit is improved and the energy utilization efficiency is improved. 2. The high-concentration carbon monoxide and carbon dioxide blast furnace gas adopts methanation purification technology, has the characteristics that steam generation can not be used in the device, a large amount of carbon monoxide and carbon dioxide are converted to consume a large amount of hydrogen, the economy is poor, and the low-concentration carbon monoxide and carbon dioxide can be converted into methane and high-carbon hydrocarbon by adopting Fischer-Tropsch purification technology, so that the device has the characteristics of low reaction heat and low steam generation, and has obvious advantages in the device. 3. The heat of the conversion desulfurization of the coke oven gas is used for Fischer-Tropsch purification and preheating, so that the cooling water consumption in the conversion process is reduced, and the heating energy consumption of Fischer-Tropsch purification is saved. 4. The total concentration of carbon monoxide and carbon dioxide after Fischer-Tropsch purification is lower than 8ppm. The liquid nitrogen washing tail gas of the common process can only be used as fuel due to the high carbon monoxide, and the liquid nitrogen washing tail gas can be directly pressurized to be used as synthesis gas.
Detailed Description
Example 1 certain Coke oven gas contains H 2 62% ,CO 8% ,CO 2 3%, CH 4 25% ,C 2 + 1% N 2 1 percent, 450ppm of organic sulfur is compressed to 0.9MPa, tar and benzene naphthalene are removed, then the organic sulfur is sent to a conversion tower for conversion reaction, carbon monoxide is converted to 0.7 percent, 99 percent of the organic sulfur is converted to hydrogen sulfide, and the gas passes through a heat exchanger and is used as a heating source for Fischer-Tropsch purification, and is cooled to 34 ℃ after being cooled, and then is sent to a first stage absorption tower of hydrogen sulfide to 1ppm; the residual organic sulfur in the gas is 6ppm, the residual organic sulfur in the gas is 0.05ppm, the total sulfur is removed to be less than 1ppm, the total sulfur is removed to be 1400ppm by MDEA, the residual organic sulfur is heated by a heat exchanger, the residual organic sulfur is sent to a deoxidization detoxification tower, and the residual organic sulfur in the gas is sent to a Fischer-Tropsch purification tower, wherein the total concentration of carbon monoxide and carbon dioxide is reduced to 6ppm and is called as purified gas; the purified gas is sent to a liquid nitrogen washing device to manufacture LNG, and the demethanized synthetic gas and the supplementary 99.99% nitrogen (50 ppm oxygen) are prepared into hydrogen-nitrogen ratio 3:1 sending the liquid ammonia to the ammonia synthesis after normal temperature refined deoxidization and dehydration.
Example 2 certain Coke oven gas contains H 2 52% ,CO 6% ,CO 2 5%, CH 4 35% ,C 2 + 0.8% N 2 1.2 percent, the organic sulfur is compressed to 1.5MPa at 600ppm, and tar and benzene are removedAfter naphthalene, sending the mixture to a shift tower for a shift reaction, converting carbon monoxide to 0.5%, converting 99% of organic sulfur to hydrogen sulfide, passing the gas through a heat exchanger for a heating source for Fischer-Tropsch purification, cooling to 38 ℃ after cooling, and sending the gas to a first stage absorption tower of hydrogen sulfide to 1ppm; the residual organic sulfur in the gas is 9ppm, the residual organic sulfur in the gas is 0.09ppm, the total sulfur is removed to be less than 1ppm, the total sulfur is removed to be 1900ppm by MDEA, the residual organic sulfur is heated by a heat exchanger, the residual organic sulfur is sent to a deoxidization detoxification tower, and the residual organic sulfur in the gas is sent to a Fischer-Tropsch purification tower, wherein the total concentration of carbon monoxide and carbon dioxide is reduced to 2ppm and is called as purified gas; the purified gas is sent to a liquid nitrogen washing device to manufacture LNG, and the demethanized synthetic gas and the supplementary 99.99% nitrogen (50 ppm oxygen) are prepared into hydrogen-nitrogen ratio 3:1 sending the liquid ammonia to the ammonia synthesis after normal temperature refined deoxidization and dehydration.
Example 3 certain Coke oven gas contains H 2 58% ,CO5% ,CO 2 4%, CH 4 31.2% ,C 2 + 1% N 2 0.8 percent, 450ppm of organic sulfur is compressed to 0.9MPa, after tar and benzene naphthalene are removed, the organic sulfur is sent to a conversion tower for conversion reaction, 900ppm of organic sulfur is 99 percent converted into hydrogen sulfide, gas passes through a heat exchanger and is used as a heating source for Fischer-Tropsch purification, and the gas is cooled to 31 ℃ after being cooled and is sent to a first stage absorption tower of hydrogen sulfide to 1ppm; the residual organic sulfur in the gas is 3ppm, the residual organic sulfur in the gas is 0.03ppm, the total sulfur is removed to be less than 1ppm, the total sulfur is removed to be 1100ppm by MDEA, the residual organic sulfur is heated by a heat exchanger, the residual organic sulfur is sent to a deoxidization detoxification tower, and the residual organic sulfur in the gas is sent to a Fischer-Tropsch purification tower, wherein the total concentration of carbon monoxide and carbon dioxide is reduced to 8ppm and is called as purified gas; the purified gas is sent to a liquid nitrogen washing device to manufacture LNG, and the demethanized synthetic gas and the supplementary 99.99% nitrogen (50 ppm oxygen) are prepared into hydrogen-nitrogen ratio 3:1 sending the liquid ammonia to the ammonia synthesis after normal temperature refined deoxidization and dehydration.
Claims (2)
1. An improved method for co-producing LNG and synthetic ammonia from coke oven gas is characterized in that the coke oven gas is compressed to 0.8-2.5MPa, tar and benzene naphthalene are removed, then the coke oven gas is sent to a conversion tower which is set up to work in combination with a low-temperature sulfur-resistant and medium-temperature organic sulfur hydrolysis catalyst, 5-8% of carbon monoxide in the coke oven gas is converted to be lower than 0.8%, 200-1000ppm of organic sulfur is 99% converted into hydrogen sulfide, the gas passes through a heat exchanger and is used as a heating source for Fischer-Tropsch purification, and is cooled to 30-40 ℃ after being cooled, and then the hydrogen sulfide is sent to a first-stage absorption tower to 1ppm; the residual organic sulfur in the gas is 2-10ppm, then the gas is sent to a low-temperature organic sulfur conversion tower to convert 99 percent of organic sulfur into hydrogen sulfide, the residual organic sulfur in the gas is 0.02-0.1ppm, the residual organic sulfur in the gas is sent to a second-stage absorption tower of hydrogen sulfide to less than 0.9ppm, the total sulfur is removed to be less than 1ppm, the total sulfur in the gas is sent to MDEA to remove carbon dioxide to 1000-2000 ppm, the gas is sent to a heat exchanger to be heated, the gas is sent to a deoxidization and detoxification tower, and then the gas is sent to a Fischer-Tropsch purification tower to reduce the total concentration of carbon monoxide and carbon dioxide to be less than 8ppm, and the gas is called purified gas; the purified gas is sent to a liquid nitrogen washing device to manufacture LNG, and the demethanized synthetic gas and the supplementary 99.99% nitrogen (50 ppm oxygen) are prepared into hydrogen-nitrogen ratio 3:1 sending the liquid ammonia to the ammonia synthesis process after normal temperature refined deoxidization.
2. The first stage hydrogen sulfide absorber of claim 1 employing iron oxide, activated carbon or other low temperature inexpensive adsorbent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310012153.7A CN116789080A (en) | 2023-01-05 | 2023-01-05 | Improved process for preparing ammonia and LNG from coke oven gas |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310012153.7A CN116789080A (en) | 2023-01-05 | 2023-01-05 | Improved process for preparing ammonia and LNG from coke oven gas |
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| CN116789080A true CN116789080A (en) | 2023-09-22 |
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