WO2022049769A1 - Appareil d'épuration d'ammoniac de type humide et installation de production d'engrais comprenant ledit appareil d'épuration d'ammoniac de type humide - Google Patents
Appareil d'épuration d'ammoniac de type humide et installation de production d'engrais comprenant ledit appareil d'épuration d'ammoniac de type humide Download PDFInfo
- Publication number
- WO2022049769A1 WO2022049769A1 PCT/JP2020/033783 JP2020033783W WO2022049769A1 WO 2022049769 A1 WO2022049769 A1 WO 2022049769A1 JP 2020033783 W JP2020033783 W JP 2020033783W WO 2022049769 A1 WO2022049769 A1 WO 2022049769A1
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- WO
- WIPO (PCT)
- Prior art keywords
- ammonia
- fine bubble
- carbon dioxide
- bubble generator
- absorption liquid
- Prior art date
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 384
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 192
- 238000004140 cleaning Methods 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 75
- 239000003337 fertilizer Substances 0.000 title claims description 38
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 242
- 239000007788 liquid Substances 0.000 claims abstract description 177
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 120
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 120
- 238000010521 absorption reaction Methods 0.000 claims abstract description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 68
- 239000004202 carbamide Substances 0.000 claims description 68
- 239000002250 absorbent Substances 0.000 claims description 23
- 230000002745 absorbent Effects 0.000 claims description 23
- 239000012528 membrane Substances 0.000 claims description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 17
- 238000005469 granulation Methods 0.000 claims description 16
- 230000003179 granulation Effects 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002407 reforming Methods 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 104
- 239000000428 dust Substances 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- -1 ammonium ions Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003398 denaturant Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002211 methanization Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Images
Classifications
-
- 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
- B01D53/14—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 absorption
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Definitions
- the present disclosure relates to a wet ammonia cleaning device and a fertilizer manufacturing plant equipped with this wet ammonia cleaning device.
- a fertilizer production plant that produces fertilizer using methane-containing gas such as natural gas has an ammonia production unit that produces ammonia from methane-containing gas and a urea production unit that produces a urea solution by reacting ammonia with carbon dioxide. , Equipped with a urea granulation unit that produces granular solid urea from a urea solution. In the urea granulation unit, a basic gas containing urea dust such as solid urea powder and ammonia is generated.
- Patent Document 1 describes a wet ammonia cleaning device in which urea dust is removed by gas-liquid contact between water and a basic gas, and ammonia is removed by gas-liquid contact between an absorption liquid containing carbon dioxide and a basic gas. Are listed.
- At least one embodiment of the present disclosure is an object of providing a wet ammonia cleaning device capable of improving the treatment efficiency of a basic gas and a fertilizer production plant equipped with the wet ammonia cleaning device.
- the wet ammonia cleaning device is a wet ammonia cleaning device that treats a basic gas containing carbon dioxide, and is a gas-liquid contact between an absorbing liquid containing carbon dioxide and the basic gas.
- Ammonia scrubber to be generated and a fine bubble generator for producing the absorption liquid from carbon dioxide and water are provided, and the fine bubble generator is at least a first fine bubble generator for producing the first absorption liquid from carbon dioxide and water.
- a second fine bubble generator that produces the absorption liquid from carbon dioxide and the first absorption liquid.
- the wet ammonia cleaning device of the present disclosure when carbon dioxide is absorbed by one fine bubble generator by absorbing carbon dioxide in at least each of the first fine bubble generator and the second fine bubble generator. As compared with this, the carbon dioxide concentration of the absorbing liquid can be increased, so that the processing efficiency of the basic gas can be improved.
- the wet ammonia cleaning device of the present disclosure treats, for example, a basic gas containing ammonia generated from a fertilizer production plant. Specifically, the wet ammonia cleaning device removes ammonia from the basic gas by bringing the basic gas containing ammonia into gas-liquid contact with the absorbing liquid.
- the basic gas targeted in the present disclosure is not limited to that generated from a fertilizer production plant, and the basic gas containing ammonia is targeted regardless of where it is generated.
- the wet ammonia cleaning device 10 includes an ammonia scrubber 11 and a fine bubble generator 12 for producing an absorption liquid supplied to the ammonia scrubber 11. ..
- the ammonia scrubber 11 has a housing 13 having an internal space 13a through which a basic gas flows, and an absorbing liquid circulation line 14 for extracting the absorbing liquid stored in the housing 13 and returning it to the gas phase in the housing 13.
- a pump 15 provided in the absorption liquid circulation line 14.
- the absorption liquid extraction line 22 is branched from the absorption liquid circulation line 14 on the downstream side of the pump 15 in the direction in which the absorption liquid flows through the absorption liquid circulation line 14.
- a pipe 17 for supplying the basic gas to the internal space 13a is connected between the top and bottom of the housing 13 to allow the basic gas in gas-liquid contact with the absorption liquid to flow out from the internal space 13a.
- the exhaust line 18 is connected to the top of the housing 13.
- the internal space 13a is provided with a nozzle 16 for sprinkling make-up water in the internal space 13a and a nozzle 20 for sprinkling the absorbing liquid in the internal space 13a.
- a make-up water supply pipe 19 for supplying make-up water to the nozzle 16 is connected to the nozzle 16, and the nozzle 20 is provided at the downstream end of the absorption liquid circulation line 14.
- the nozzle 20 may be configured to inject the absorbing liquid toward the tray 21 (for example, composed of a perforated plate) installed in the internal space 13a.
- the number of trays 21 may be one or any number of two or more.
- the nozzle 16 is drawn so as to be located above the nozzle 20 and the tray 21, but the present invention is not limited to this form.
- the nozzle 16 may be configured to be located between the nozzle 20 and the tray 21, or may be configured to be located below the tray 21.
- the nozzle 20 is provided at a position above the tray 21 and at a position between trays adjacent to each other in the vertical direction when two or more trays 21 are provided, but the present invention is limited to this form.
- the nozzle 20 may be provided only at a position above the tray 21.
- the fine bubble generator 12 includes a first fine bubble generator 12a and a second fine bubble generator 12b arranged in series with each other.
- the first fine bubble generator 12a and the second fine bubble generator 12b are provided on the absorption liquid circulation line 14 on the downstream side of the pump 15, and the second fine bubble generator 12b is more than the first fine bubble generator 12a. It is provided on the downstream side.
- the configuration of the first fine bubble generator 12a and the second fine bubble generator 12b is not particularly limited, and carbon dioxide and water (or water in the absorbing liquid) supplied via the carbon dioxide supply line 118 are not particularly limited. Any device can be used as long as it can produce an absorbent liquid from (including), but a fine bubble generator that generates carbon dioxide bubbles of 100 micrometers or less is preferable.
- an ejector method, a cavitation method, a swirling flow method, a pressure melting method, or the like can be used.
- a more preferable configuration for the fine bubble generator 12 is to use a fine bubble generator that generates carbon dioxide bubbles of 1 to 100 micrometers as the first fine bubble generator 12a and 50 to several as the second fine bubble generator 12b. It is configured to use a fine bubble generator that generates 100 (for example, 500) nanometers of carbon dioxide bubbles.
- an ejector type device is adopted as the first fine bubble generator 12a in order to generate carbon dioxide bubbles within the above range. 2
- a pressure melting type device can be adopted as the fine bubble generator 12b.
- the basic gas flowing through the pipe 17 flows into the housing 13 (internal space 13a) of the ammonia scrubber 11.
- the basic gas flows upward, it is contained in the basic gas by flowing through the absorption liquid circulation line 14 by the pump 15 and making gas-liquid contact with the absorption liquid injected from the nozzle 20.
- Ammonia is absorbed by the absorption liquid and the ammonia is removed from the basic gas.
- the basic gas from which ammonia has been removed flows out of the internal space 13a via the exhaust line 18 and is exhausted.
- the absorption liquid retained in the internal space 13a the absorbed ammonia is present in the liquid in the form of at least one of ammonia molecules and ammonium ions.
- the absorbent liquid is manufactured by the fine bubble generator 12. Specifically, a part of the absorbing liquid staying in the internal space 13a is extracted from the internal space 13a by the pump 15 and circulated through the absorbing liquid circulation line 14, and the water in the absorbing liquid in the first fine bubble generator 12a.
- the first absorption liquid is produced by blowing carbon dioxide into the first absorption liquid, and then carbon dioxide is blown into the first absorption liquid in the second fine bubble generator 12b to produce the absorption liquid.
- the fine bubble generator 12 includes two devices, that is, a first fine bubble generator 12a and a second fine bubble generator 12b. Therefore, by absorbing carbon dioxide in each of these, the carbon dioxide concentration of the absorbing liquid can be increased as compared with the case where carbon dioxide is absorbed by one fine bubble generator.
- the first fine bubble generator 12a is an ejector type device and the second fine bubble generator 12b is a pressure dissolution type device
- carbon dioxide is dissolved in water by the first fine bubble generator 12a
- the fine bubble generator 12b supplies carbon dioxide to the first absorbing liquid as fine bubbles (fine bubbles).
- the absorbed liquid and the basic gas having a carbon dioxide partial pressure lower than the equilibrium carbon dioxide partial pressure are brought into gas-liquid contact, so that carbon dioxide in the absorbed liquid is contained.
- the fine bubble 200 As a result, it is possible to suppress a decrease in the concentration of carbon dioxide in the absorption liquid. Since the smaller the diameter of the fine bubble 200, the lower the speed at which the fine bubble 200 floats in the absorbing liquid, the residence time of the fine bubble 200 in the liquid becomes longer, and the fine bubble 200 is less likely to be released to the basic gas side. Further, as the diameter of the fine bubble 200 is smaller, the internal pressure of the fine bubble 200 is increased, so that the dissolution rate in the absorbing liquid is also improved.
- the concentration of ammonia in the absorption liquid staying in the internal space 13a increases, so the ammonia removal rate decreases, and eventually ammonia. Cannot be removed. Therefore, while a part of the absorption liquid flowing through the absorption liquid circulation line 14 is extracted through the absorption liquid extraction line 22, make-up water is injected from the nozzle 16 into the internal space 13a. As a result, the concentration of ammonia in the absorbing liquid staying in the internal space 13a decreases, so that the decrease in the ammonia removal rate can be suppressed.
- both the first fine bubble generator 12a and the second fine bubble generator 12b are provided on the absorbing liquid circulation line 14, but the embodiment is not limited to this.
- the second fine bubble generator 12b is provided in the absorption liquid circulation line 14, and the first absorption liquid produced by the first fine bubble generator 12a is configured to be supplied to the second fine bubble generator 12b. You can also.
- the absorption liquid produced by the fine bubble generator 12 is absorbed in the absorption liquid circulation line 14.
- the concentration of carbon dioxide in the absorption liquid supplied to the internal space 13a is higher than that in the case of supplying to the internal space 13a or the configuration for supplying the internal space 13a. This is because there is a limit to the amount of carbon dioxide that can be supplied to the circulating flow rate of the absorbent liquid in the fine bubble generator 12, so it is better to provide the fine bubble generator 12 on the line where the flow rate of the absorbent liquid is as large as possible. This is because the supply amount of carbon dioxide increases and the amount of carbon dioxide in the absorption liquid also increases. As a result, the processing efficiency of the basic gas can be improved.
- the fine bubble generator 12 includes two fine bubble generators, that is, a first fine bubble generator 12a and a second fine bubble generator 12b, but the present invention is not limited to the two. It may be equipped with one or more fine bubble generators. Even in this case, it is preferable that at least two fine bubble generators are arranged in series with each other, and it is further preferable that all the fine bubble generators are arranged in series with each other.
- the wet ammonia cleaning device according to the second embodiment is obtained by adding a membrane separation device for removing ammonia from the absorbent liquid flowing through the absorbent liquid circulation line 14 to the first embodiment.
- a membrane separation device for removing ammonia from the absorbent liquid flowing through the absorbent liquid circulation line 14 to the first embodiment.
- the absorption liquid circulation line 14 is provided with the first fine bubble generator 12a and the second fine bubble generator 12b. ..
- the absorption liquid circulation line 14 is provided with a membrane separation device 30 for removing ammonia from the absorption liquid between the pump 15 and the first fine bubble generator 12a.
- the configuration of the membrane separation device 30 is not particularly limited, and for example, a membrane separation device provided with a reverse osmosis membrane (RO membrane) can be used.
- RO membrane reverse osmosis membrane
- the absorbent liquid circulation line 14 may be provided with a tank 31 in which make-up water is stored between the membrane separation device 30 and the first fine bubble generator 12a.
- Other configurations are the same as those of the first embodiment except that the absorption liquid extraction line 22 (see FIG. 1) is not provided.
- a part of the absorbing liquid staying in the internal space 13a is extracted from the internal space 13a by the pump 15 and circulates in the absorbing liquid circulation line 14.
- the absorption liquid flows into the membrane separation device 30, only water passes through the separation membrane (for example, RO membrane) provided in the membrane separation device 30, and at least one of ammonia molecules, ammonium ions, carbonate ions, etc. that dissolves in the absorption liquid. Since the part cannot pass through the separation membrane, the absorption liquid flows out from the membrane separation device 30 in a state where the concentrations of ammonia and carbon dioxide dissolved in the absorption liquid are lowered. Ammonia molecules or concentrates of ammonium ions, carbonate ions, etc.
- the separation membrane that could not pass through the separation membrane are supplied to, for example, a stripper (not shown), and carbon dioxide and ammonia can be recovered and reused in the stripper. If the concentration of these molecules or ions is high, the concentrate can be reused as it is in the urea production process of the fertilizer production plant.
- the absorption liquid flowing out of the membrane separation device 30 flows into the tank 31, then flows into the fine bubble generator 12 from the tank 31, and carbon dioxide is blown into the water in the absorption liquid in the first fine bubble generator 12a. 1 Absorption liquid is produced, and then carbon dioxide is blown into the first absorption liquid in the second fine bubble generator 12b to produce the absorption liquid.
- the operation after this is the same as that of the first embodiment.
- the concentrations of ammonia and carbon dioxide in the absorbing liquid flowing into the fine bubble generator 12 are lower than those in the first embodiment. Therefore, the dissolution of carbon dioxide in the fine bubble generator 12 is promoted, and the carbon dioxide / ammonia ratio in the absorbing liquid becomes large.
- the larger this ratio in the absorption liquid is, the more the removal of ammonia from the basic gas by the gas-liquid contact between the absorption liquid and the basic gas is promoted, so that the treatment efficiency of the basic gas is higher than that in the first embodiment. Can be improved.
- the wet ammonia cleaning device according to the third embodiment is obtained by adding a cooling device for cooling the basic gas to the first or second embodiment before the basic gas flows into the ammonia scrubber 11.
- a cooling device for cooling the basic gas
- the third embodiment will be described with a configuration in which a cooling device is added to the configuration of the first embodiment, but the third embodiment may be configured by adding a cooling device to the configuration of the second embodiment. ..
- the same reference numerals as those of the constituent requirements of the first embodiment are designated by the same reference numerals, and detailed description thereof will be omitted.
- the pipe 17 has a cooling device 40, for example, heat exchange between a cooling medium and a basic gas flowing through the pipe 17.
- a vessel is provided in the absorption liquid circulation line 14.
- the cooling device 41 for example, the cooling medium and the absorption liquid flowing through the absorption liquid circulation line 14 exchange heat between the pump 15 and the first fine bubble generator 12a.
- a heat exchanger may be provided in the absorption liquid circulation line 14.
- any fluid can be used as the cooling medium flowing through each of the cooling devices 40 and 41, for example, ammonia produced by an ammonia production unit which is a component of a fertilizer production plant equipped with a wet ammonia cleaning device 10. Can be used. Other configurations are the same as those in the first embodiment.
- the basic gas is cooled by the cooling device 40 before the basic gas is supplied to the ammonia scrubber 11.
- the operation of removing ammonia from the basic gas in the ammonia scrubber 11 is the same as that of the first embodiment.
- the cooling device 41 When the cooling device 41 is provided in the absorbing liquid circulation line 14, the absorbing liquid is cooled in the cooling device 41 before flowing into the fine bubble generator 12.
- the solubility of carbon dioxide increases as the temperature of water decreases, so that the concentration of carbon dioxide in the absorbing liquid can be increased as compared with the case where the absorbing liquid is not cooled before flowing into the fine bubble generator 12.
- the temperature of the absorbed liquid in the ammonia scrubber 11 rises due to the gas-liquid contact between the basic gas and the absorbed liquid in the ammonia scrubber 11 as compared with the first embodiment. Is suppressed. Therefore, since the absorbing liquid having a high concentration of carbon dioxide comes into gas-liquid contact with the basic gas, the processing efficiency of the basic gas can be improved as compared with the first embodiment.
- the fourth embodiment of the present disclosure will be described.
- the wet ammonia cleaning device according to any one of the first to third embodiments is provided in the fertilizer production plant.
- the fourth embodiment will be described with the configuration in which the wet ammonia cleaning device 10 of the first embodiment is provided in the fertilizer production plant, but the wet ammonia cleaning device 10 of the second or third embodiment is provided in the fertilizer production plant.
- Form 4 may be configured.
- the same reference numerals as those of the constituent requirements of the first embodiment are designated by the same reference numerals, and detailed description thereof will be omitted.
- the fertilizer production plant 100 produces a urea solution by reacting ammonia and carbon dioxide with an ammonia production unit 5 that produces ammonia using a raw material gas such as a natural gas containing methane. It is provided with a urea production unit 70 for producing urea, a urea granulation unit 60 for producing granular solid urea from a urea solution, and a wet ammonia cleaning device 10 for treating basic gas generated from the urea granulation unit 60. ..
- the fertilizer production plant 100 includes a reformer 1 that reforms the raw material gas, a modifier 2 that modifies carbon monoxide and steam in the gas supplied from the reformer 1, and a gas flowing out from the reformer 2.
- a carbon dioxide recovery device 3 for recovering carbon dioxide and a steaming device 4 for converting carbon dioxide and carbon monoxide in the gas flowing out from the carbon dioxide recovery device 3 into methane, respectively, may be further provided.
- the methanizer 4 and the ammonia production unit 5 are connected.
- the urea production unit 70 includes a compressor 71 and a urea production apparatus 72.
- the compressor 71 and the urea production apparatus 72 are connected to each other via a pipe 121.
- the carbon dioxide recovery device 3 and the compressor 71 are connected to each other via a pipe 122.
- the ammonia supply line 123 is provided so that the ammonia produced by the ammonia production unit 5 is supplied to the pipe 121, and the ammonia supply line 123 is provided with a compressor 76 for boosting the ammonia.
- the carbon dioxide supply line 118 branches from the upstream side of the position where the ammonia supply line 123 joins in the pipe 121, and the carbon dioxide supply line 118 is the first fine bubble generator 12a and the second fine bubble generator 12b (FIG. 1). See) connected to each.
- the wet ammonia cleaning device 10 removes ammonia from the dust scrubber 51 that removes solid components such as urea dust from the basic gas generated from the urea granulation unit 60 and the basic gas from which the solid components have been removed from the dust scrubber 51. It is equipped with an ammonia scrubber 11.
- the urea granulation unit 60 and the dust scrubber 51 are connected via a basic gas flow line 111.
- the dust scrubber 51 and the ammonia scrubber 11 are connected to each other via a pipe 17.
- the other end of the make-up water supply pipe 19 to which one end is connected to the nozzle 16 (see FIG. 1) provided in the ammonia scrubber 11 is the compressor 71 or the pipe 6 connecting the reformer 1 and the modifier 2. It is connected to at least one of them.
- the make-up water water supply pipe 19 is connected to the compressor 71
- the drain generated in the compressor 71 is drained from the compressor 71 via the make-up water water supply pipe 19 so that the make-up water can be drained.
- the water supply pipe 19 is connected to the pipe 6, the condensate contained in the gas flowing out from the reforming device 1 is drained from the pipe 6.
- the raw material gas is reformed by air and steam in the reformer 1 to become a gas containing at least hydrogen and carbon dioxide. Since the reformer 1 also takes in air, the gas discharged from the reformer 1 and supplied to the modifier 2 in the subsequent stage also includes components derived from air. Specifically, the gas discharged from the reformer 1 also includes nitrogen and the like. This gas also contains carbon monoxide, which is converted into carbon dioxide and hydrogen by a chemical reaction with water in the modifier 2 in the subsequent stage.
- the carbon dioxide recovery device 3 downstream of the denaturant 2 can suppress the introduction of carbon dioxide into the ammonia production unit 5 and suppress the influence on the ammonia production catalyst. ..
- the recovery of carbon dioxide in the carbon dioxide recovery device 3 can be performed, for example, by bringing an alkaline aqueous solution into contact with the gas.
- the recovered carbon dioxide is separated from the alkaline aqueous solution by heating the alkaline aqueous solution or the like, and then supplied to the fine bubble generator 12 (see FIG. 1) of the urea production unit 70 and the wet ammonia cleaning device 10.
- Carbon monoxide and carbon monoxide are each converted to methane.
- the introduction of carbon oxide into the ammonia production unit 5 is suppressed. This makes it possible to suppress the influence of carbon oxide on the ammonia production catalyst.
- the gas flowing out of the methanizer 4 and flowing into the ammonia production unit 5 contains hydrogen and nitrogen, and contains methane as an impurity.
- a chemical reaction represented by the following chemical formula (1) occurs, and ammonia is produced.
- the generated ammonia sequentially flows through the ammonia supply line 123 and the pipe 121 by the compressor 76 and flows into the urea production apparatus 72 of the urea production unit 70. Further, the carbon dioxide recovered by the carbon dioxide recovery device 3 flows out from the carbon dioxide recovery device 3, flows through the pipe 122, is boosted by the compressor 71, and flows into the urea production apparatus 72 through the pipe 121. ..
- urea (urea solution) is produced from carbon dioxide and ammonia by a chemical reaction represented by the following chemical formula (2). 2NH 3 + CO 2 ⁇ (NH 2 ) 2 CO + H 2 O ⁇ ⁇ ⁇ (2)
- the urea solution produced by the urea production unit 70 flows into the urea granulation unit 60.
- the urea supplied from the urea production unit 70 is granulated.
- Granular urea obtained by granulation of urea is shipped and used as fertilizer.
- urea granulation unit 60 a basic gas containing urea dust, which is a powder of solid urea, and ammonia is generated during the granulation of urea.
- the basic gas flows through the basic gas flow line 111 and flows into the wet ammonia cleaning device 10.
- urea dust is removed from the basic gas by the gas-liquid contact between the cleaning water and the basic gas in the dust scrubber 51.
- the basic gas from which the urea dust has been removed flows into the ammonia scrubber 11 via the pipe 17.
- ammonia scrubber 11 ammonia is removed from the basic gas by the same operation as that described in the first embodiment.
- the basic gas from which ammonia has been removed is exhausted through the exhaust line 18.
- At least one of the condensates contained in the drain generated in the compressor 71 or the gas flowing out from the reformer 1 is supplied to the ammonia scrubber 11 as make-up water via the make-up water supply pipe 19. .
- the drain and condensate are carbonated water in which carbon dioxide is dissolved, carbonated water is supplied to the ammonia scrubber 11 as make-up water.
- carbonated water is supplied to the ammonia scrubber 11 as make-up water.
- not only carbonated water as an absorption liquid but also carbonated water as make-up water can absorb ammonia, so that treatment of basic gas is performed as compared with the case of supplying water containing no carbon dioxide as make-up water. Efficiency can be improved.
- carbonated water is used as the make-up water supplied to the ammonia scrubber 11 as the condensate contained in the drain generated in the compressor 71 or the gas flowing out from the reforming device 1, but the present invention is limited to this embodiment. is not it.
- An apparatus for producing carbonated water as make-up water may be provided in the fertilizer production plant 100.
- Such a device can be a device for extracting a part of carbon dioxide flowing through the carbon dioxide supply line 118 and dissolving it in water, and the configuration of this device is a filling type filled with a filler such as Raschig ring. It is possible to adopt an absorption tower, a plate-type absorption tower, an absorption tower in which the plate can be cooled in the plate-type absorption tower, and the like.
- carbonated water generated or produced at an arbitrary location in the fertilizer production plant 100 is used as make-up water, but instead of or in combination with this form, carbonated water is generated as a first fine bubble. It may be supplied to at least one of the device 12a and the second fine bubble generator 12b.
- the pipe branched from the make-up water supply pipe 19 has a configuration in which carbonated water is connected to at least one of the first fine bubble generator 12a and the second fine bubble generator 12b.
- the wet ammonia cleaning device 10 is provided with two fine bubble generators and may be further provided with three or more fine bubble generators, but the present invention is not limited to this embodiment. As long as it is a fine bubble generator capable of producing carbonated water having a sufficient carbon dioxide concentration, the wet ammonia cleaning device 10 may be configured to include one fine bubble generator provided in the absorption liquid circulation line 14.
- the wet ammonia cleaning device is A wet ammonia cleaning device (10) that treats a basic gas containing ammonia.
- Ammonia scrubber (11) that brings carbon dioxide-containing absorption liquid into gas-liquid contact with basic gas,
- a fine bubble generator (12) for producing the absorbent liquid from carbon dioxide and water is provided.
- the fine bubble generator (12) is at least A first fine bubble generator (12a) that produces a first absorbent liquid from carbon dioxide and water, and It includes carbon dioxide and a second fine bubble generator (12b) for producing the absorption liquid from the first absorption liquid.
- the wet ammonia cleaning device of the present disclosure when carbon dioxide is absorbed by one fine bubble generator by absorbing carbon dioxide in at least each of the first fine bubble generator and the second fine bubble generator. As compared with this, the carbon dioxide concentration of the absorbing liquid can be increased, so that the processing efficiency of the basic gas can be improved.
- the wet ammonia cleaning device according to another aspect is the wet ammonia cleaning device according to [1].
- the fine bubble generator (12) generates carbon dioxide bubbles of 100 micrometers or less.
- carbon dioxide bubbles of 100 micrometers or less are supplied to the water and the first absorbing liquid, so that the dissolution of carbon dioxide can be promoted.
- the wet ammonia cleaning device is the wet ammonia cleaning device of [2].
- the first fine bubble generator (12a) is an ejector type fine bubble generator
- the second fine bubble generator (12b) is a pressure melting type fine bubble generator.
- carbon dioxide is dissolved in water by the first fine bubble generator, and carbon dioxide is supplied to the first absorbing liquid as fine bubbles (fine bubbles) by the second fine bubble generator. ..
- the absorbed liquid and the basic gas having a lower carbon dioxide partial pressure than the equilibrium carbon dioxide partial pressure come into gas-liquid contact, so that the carbon dioxide in the absorbed liquid is released to the basic gas side.
- the fine bubble supplements the amount corresponding to the emitted carbon dioxide and the carbon dioxide dissociated in the absorption liquid. As a result, it is possible to suppress a decrease in the concentration of carbon dioxide in the absorption liquid, so that the treatment efficiency of the basic gas can be improved.
- the wet ammonia cleaning device is the wet ammonia cleaning device according to any one of [1] to [3].
- the ammonia scrubber (11) is provided with an absorbent liquid circulation line (14) for extracting the absorbent liquid stored therein and returning it to the gas phase in the ammonia scrubber (11).
- the fine bubble generator (12) is provided in the absorbent liquid circulation line (14).
- the gas of the ammonia scrubber is compared with the case of supplying the absorbent liquid produced by the fine bubble generator to the absorbent liquid circulation line or the case of supplying the absorbent liquid stored inside the ammonia scrubber. Since the concentration of carbon dioxide in the absorption liquid supplied in the phase is increased, the treatment efficiency of the basic gas can be improved.
- the wet ammonia cleaning device is the wet ammonia cleaning device according to [4].
- a membrane separation device (30) for removing ammonia from the absorbent liquid flowing through the absorbent liquid circulation line (14) is further provided.
- the membrane separation device is provided in the absorption liquid circulation line so as to be located upstream of the fine bubble generator in the flow direction of the absorption liquid.
- the wet ammonia cleaning device is the wet ammonia cleaning device according to any one of [1] to [5].
- a cooling device (40) for cooling the basic gas before the basic gas flows into the ammonia scrubber (11) is further provided.
- the fertilizer production plant is A fertilizer production plant (100) for producing fertilizer from a raw material gas containing methane.
- An ammonia production unit (5) that produces ammonia from the raw material gas
- a urea production unit (70) that produces a urea solution by reacting ammonia with carbon dioxide, and the like.
- a urea granulation unit (60) for producing granular solid urea from the urea solution, and a urea granulation unit (60).
- the wet ammonia cleaning device (10) according to any one of [1] to [6] for treating the basic gas generated from the urea granulation unit (60) is provided.
- the carbonated water generated in the fertilizer production plant (100) is configured to be supplied in the gas phase in the ammonia scrubber (11) or to the fine bubble generator (12).
- the fertilizer production plant of the present disclosure by supplying carbonated water to the ammonia scrubber as make-up water supplied to the ammonia scrubber, not only the carbonated water as the absorption liquid but also the carbonated water as the make-up water is ammonia. Can be absorbed, so that the treatment efficiency of basic gas can be improved as compared with the case of supplying water containing no carbon dioxide as make-up water.
- the fertilizer production plant is the fertilizer production plant of [7].
- the urea production unit (70) is The urea production apparatus (72) for producing the urea solution, and The urea production apparatus (72) is provided with a compressor (71) for supplying carbon dioxide. The carbonated water is a drain generated by the compressor (71).
- the fertilizer production plant is the fertilizer production plant of [7] or [8].
- a reformer (1) for reforming the raw material gas with air and steam before the raw material gas flows into the ammonia production unit (5) is further provided.
- the carbonated water is a condensate contained in the gas flowing out from the reformer (1).
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- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
L'invention concerne un appareil d'épuration d'ammoniac de type humide permettant de traiter un gaz basique contenant de l'ammoniac, l'appareil comprenant : un épurateur d'ammoniac qui provoque un contact gaz-liquide entre le gaz basique et un liquide d'absorption contenant du dioxyde de carbone ; et des dispositifs de génération de bulles fines permettant de produire le liquide d'absorption à partir de dioxyde de carbone et d'eau, les dispositifs de génération de bulles fines comprenant au moins un premier dispositif de génération de bulles fines permettant de produire un premier liquide d'absorption à partir de dioxyde de carbone et d'eau et un second dispositif de génération de bulles fines permettant de produire un liquide d'absorption à partir de dioxyde de carbone et du premier liquide d'absorption.
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PCT/JP2020/033783 WO2022049769A1 (fr) | 2020-09-07 | 2020-09-07 | Appareil d'épuration d'ammoniac de type humide et installation de production d'engrais comprenant ledit appareil d'épuration d'ammoniac de type humide |
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PCT/JP2020/033783 WO2022049769A1 (fr) | 2020-09-07 | 2020-09-07 | Appareil d'épuration d'ammoniac de type humide et installation de production d'engrais comprenant ledit appareil d'épuration d'ammoniac de type humide |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01168322A (ja) * | 1987-12-22 | 1989-07-03 | Nippon Sangyo Gijutsu Kk | 多段式微細気泡発生装置 |
WO2009016998A1 (fr) * | 2007-07-31 | 2009-02-05 | Meiji University | Procédé de traitement d'aliment et appareil de traitement d'aliment |
JP2009101269A (ja) * | 2007-10-22 | 2009-05-14 | Sharp Corp | 悪臭処理方法、悪臭処理システムおよび飼育システム |
WO2019234816A1 (fr) * | 2018-06-05 | 2019-12-12 | 三菱重工エンジニアリング株式会社 | Usine de production d'engrais et procédé de production d'engrais |
-
2020
- 2020-09-07 WO PCT/JP2020/033783 patent/WO2022049769A1/fr active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01168322A (ja) * | 1987-12-22 | 1989-07-03 | Nippon Sangyo Gijutsu Kk | 多段式微細気泡発生装置 |
WO2009016998A1 (fr) * | 2007-07-31 | 2009-02-05 | Meiji University | Procédé de traitement d'aliment et appareil de traitement d'aliment |
JP2009101269A (ja) * | 2007-10-22 | 2009-05-14 | Sharp Corp | 悪臭処理方法、悪臭処理システムおよび飼育システム |
WO2019234816A1 (fr) * | 2018-06-05 | 2019-12-12 | 三菱重工エンジニアリング株式会社 | Usine de production d'engrais et procédé de production d'engrais |
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