WO2015092547A2 - Methods for removing contaminants from exhaust gases - Google Patents
Methods for removing contaminants from exhaust gases Download PDFInfo
- Publication number
- WO2015092547A2 WO2015092547A2 PCT/IB2014/003168 IB2014003168W WO2015092547A2 WO 2015092547 A2 WO2015092547 A2 WO 2015092547A2 IB 2014003168 W IB2014003168 W IB 2014003168W WO 2015092547 A2 WO2015092547 A2 WO 2015092547A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas stream
- nitrogen oxides
- scrubber
- flue gas
- contacting
- Prior art date
Links
- 239000007789 gas Substances 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000000356 contaminant Substances 0.000 title claims abstract description 42
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 285
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000005201 scrubbing Methods 0.000 claims abstract description 46
- 239000013535 sea water Substances 0.000 claims abstract description 44
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052815 sulfur oxide Inorganic materials 0.000 claims abstract description 29
- 239000003595 mist Substances 0.000 claims abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 66
- 239000003546 flue gas Substances 0.000 claims description 66
- 239000002253 acid Substances 0.000 claims description 26
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 11
- 229910052753 mercury Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012717 electrostatic precipitator Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 5
- 239000003337 fertilizer Substances 0.000 claims description 4
- -1 particulates Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 25
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 25
- 150000002823 nitrates Chemical class 0.000 abstract description 8
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 229910002651 NO3 Inorganic materials 0.000 description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002609 medium Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 239000012736 aqueous medium Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005200 wet scrubbing Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012719 wet electrostatic precipitator Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000009420 retrofitting Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
Definitions
- the invention provides for methods for removing contaminants selected from the group consisting of nitrogen oxides, sulfur oxides, particulates, heavy metals and acid gases from gas streams. More particularly, the invention provides for the removal of contaminants from gas streams arising from engines and other combustion devices on board ships and on land where seawater is used for scrubbing of the combustion gas streams.
- the invention can also treat exhaust gas streams from chemical, metallurgical, partial and full combustion processes by the removal of
- contaminants such as nitrogen oxide, sulfur oxides, hydrochloric acid and particulate materials when co-scrubbing of nitrogen oxides would generate nitrates that are objectionable by-products.
- Nitric oxide is the major component of nitrogen oxides In combustion processes. Nitric oxide is almost insoluble in water so aqueous scrubbing removes negligible amounts of nitric oxide from nitrogen oxide streams. Coal, solid fuels, heavy oils and other carbon feed stocks when combusted form exhaust gas streams that contain particulate matter and other objectionable contaminants such as heavy metals like mercury which may or may not be effectively scrubbed by aqueous scrubbing operations.
- ozone-based processes as described in US Pat Nos.
- 8,849,132 and 7,303,735 uses the chemistry of nitrogen oxide reaction with ozone to form higher oxides of nitrogen, especially the pentavalent form or higher, These oxides are very soluble in water and are easily removed by wet scrubbing.
- the stoichiometric amount of ozone required to convert one mole of nitrogen oxides in the form of NO to the pentavalent form is about 1.5 moles of ozone. This number is reduced to 0.5 moles of ozone if the nitrogen oxides are in the form of NO2.
- seawater When seawater is used as a scrubbing medium, it is used in a once through mode due to its limited alkalinity. This generates a large quantity of liquid discharge from the wet scrubber. When ozone is added for nitrogen oxides removal, the purge stream will contain nitrates which will require treatment before discharge back to the sea.
- the invention is able to overcome the problems that earlier methods have experienced. Contamination of scrubber purge with nitrate is mitigated so that a large quantity of seawater can be used in a once through scrubbing medium that can be safely discharged without additional treatments. A separate scrubber for nitrogen oxides removal is also not necessary thereby minimizing capital investment in retrofitting acid gas (suifur oxides, hydrochloric acid, etc.) or particulate scrubbing equipment with nitrogen oxides control.
- a method for removing contaminants from a gas stream comprising the steps: a) Feeding the gas stream containing the contaminants into a scrubber; b) Contacting the gas stream with a scrubbing solution; c) Contacting the gas stream with ozone, wherein nitrogen oxides are oxidized; d) Contacting the gas stream containing the oxidized nitrogen oxides with a device selected from the group consisting of a droplet separator and a
- a method for removing contaminants from a gas stream comprising the steps: a) Feeding the gas stream containing the contaminants into a scrubber; b) Contacting the gas stream with a scrubbing solution; c) Contacting the gas stream with ozone, wherein nitrogen oxides are oxidized; and d) Contacting the gas stream containing the oxidized nitrogen oxides with a device selected from the group consisting of a droplet separator and a
- a method for removing contaminants selected from the group consisting of nitrogen oxides, sulfur oxides, particulates, acid gases and mercury from a flue gas stream comprising the steps: a) Feeding the flue gas stream into a scrubber; b) Contacting the flue gas stream with a sea water scrubbing solution; c) Contacting the flue gas stream with ozone wherein the nitrogen oxides are oxidized; d) Contacting the flue gas stream containing the oxidized nitrogen oxides with a device selected from the group consisting of a droplet separator and a
- the gas stream that is treated is typically a flue gas stream from a combustion or chemical process.
- these flue gas streams are from onboard ship processes or from operations that are near the ocean where seawater is plentiful.
- These flue gas streams typically contain contaminants selected from the group consisting of particulates, sulfur oxides, nitrogen oxides, acid gases and heavy metals such as mercury.
- the contaminants, particularly the sulfur oxides and the nitrogen oxides will react when contacted with the ozone. These reactions will also produce byproducts such as nitrates and nitric acid which may be recovered for additional operational uses or they may be treated and disposed of in preferably an environmentally responsible manner.
- the scrubber is typically selected from the group consisting of spray type, venturi type, rod, packed bed and plate column scrubbers.
- the scrubber employed in the methods of the invention should be of sufficient size to allow for the ozone to mix with the gas stream and remain in contact with the contaminants for a sufficient enough time to oxidize the contaminants.
- the ozone will be added in an amount of greater stoichiometry than the amount of nitrogen oxides present in the gas stream and will remain in contact with the gas stream for a time sufficient to allow oxidation of the nitrogen oxides to occur.
- the gas stream containing the oxidized nitrogen oxides will contact a droplet separator where nitric acid that is present in the treated gas stream will condense and can be captured in the liquid state.
- the scrubber may further include a device selected from the group consisting of a cooling coil, a mist eliminator and an electro static precipitator (ESP). These devices can be used to help condense certain of the reaction products of the reaction between the contaminants and the ozone that will be present in the gas stream as it rises through the scrubber. These condensed reaction products can be recovered and recycled or treated for disposal.
- the seawater is preferably fed to the scrubber through a system of one or more distributors so that the seawater more freely contacts that gas stream containing the contaminants to be treated. The seawater may be fed
- the device where the oxidized nitrogen oxides will contact is selected from a droplet separator and a condensing surface having sufficient surface area to dissolve, condense, absorb and remove nitrogen oxides.
- the droplets from the surface are recovered and they can be drained, neutralized and collected for uses such as a fertilizer.
- the scrubber assembly may be two or more scrubbers in fluid communication with each other.
- the gas stream from the first scrubber is fed to the second scrubber after removing the oxidized nitrogen oxides as described above.
- the gas stream is contacted with a scrubbing solution, thereby removing particulates, sulfur oxides, acid gases and mercury from the gas stream and recovering the gas stream.
- the scrubbing solution that may be employed in this second scrubber may be sea water and the scrubber design, like the first scrubber may be on a once through basis or by recycling the sea water content.
- the second scrubber may also have a device selected from the group consisting of a droplet separator and a condensing device to collect droplets after the gas stream has been contacted with the scrubbing solution.
- Fig, 1 is a schematic of a scrubber incorporating ozone addition to the flue gas stream.
- Fig. 2 is a schematic of another scrubber showing the addition of seawater and ozone and nitrate/nitric acid purge recovery.
- Fig. 3 is a schematic of a scrubber that contains a droplet separator incorporating ozone addition to the flue gas stream.
- Flue gas is quenched and scrubbed by seawater in a wet scrubbing device which could be a standard spray type, venturi type, rod, packed bed, plate column or other scrubber commonly used in industrial operations for acid gas and particuiate clean up.
- Wet scrubbers such as EDV scrubber by Belco
- Ozone is then added to the scrubbed gas stream.
- the oxidation of the nitrogen oxides is accomplished by mixing ozone with the scrubbed gas stream and providing adequate reaction time as described in US Pat Nos. 7,303,735 and 7,788,995. Proper oxidation of the nitrogen oxides in the presence of moisture will result in the formation of nitric acid which is miscible with water.
- the flue gas containing the oxidized nitrogen oxides is then subjected to a droplet separator to lower the carry-over mist or to a controlled cooling on the condensing surface.
- the droplets in the separator and/or on the condensing surface provide adequate surface area to dissolve, condense, absorb and remove nitrogen oxides.
- the droplets are collected to form a small aqueous stream in the droplet separator/condenser and removed and if required neutralized and handled for safe discharge or by product use.
- the flue gas stream to be treated contains nitrogen oxides.
- the nitrogen oxides are oxidized. If ail the nitrogen oxides are in the form of nitric oxide, stoichiometric amounts of ozone required to convert the nitric oxide to dinitrogen pentoxide is 1.5 moles of ozone per mole of nitrogen oxide. For every mole of NO2, only 0.5 moles of ozone are required. Accordingly, a range of about 0.5 to 1.5 moles of ozone per mole of nitrogen oxides can be added to the flue gas stream to be treated.
- the nitrogen oxide oxidation to dinitrogen pentoxide involves many reactions but for sake of brevity these reactions can be simplified as follows:
- reaction (1 ) is an order of magnitude faster compared to reaction (2).
- Reactions (1), (2), and (3) are somewhat consecutive reactions.
- N0 2 has finite solubility so unless the reaction is brought forward to form oxides higher than N0 2 removal of nitrogen oxides in a wet scrubber is limited.
- it is essential to mix ozone well and provide the necessary reaction time while minimizing back mixing.
- the ozone for example can be introduced in the gas phase by a distributor which uniformly distributes ozone in the entire cross section of the flue gas flow.
- the flow path can be selected for mixing oxygen where the gas flow is turbulent.
- the velocity of the ozone containing gas stream's injection info the flue gas can be maintained at least two times and preferably three times or more than the flow velocity of the flue gas stream.
- Modern tools such as Computational Fluid Dynamic (CFD) modeling can be employed to ensure through mixing of ozone in the flue gas stream in minimum time.
- CFD Computational Fluid Dynamic
- Conicai or diverging nozzles in the distributor can quickly disperse ozone into the cross section of the flowing flue gas stream.
- Ozone can be mixed with large quantities of a diluent gas and introduced into the distributor for mixing with the gas stream containing the nitrogen oxides.
- the ozone too may be introduced in a co-current or counter-current direction,
- the nitrogen oxides When oxidized, the nitrogen oxides are transformed into their pentavalent form.
- the gas stream exiting the nitrogen oxides treatment zone is saturated with vapor.
- the dinitrogen pentoxide will react with the moisture in the gas phase forming nitric acid in the gas phase:
- HNO 3 (g) being soluble in all proportions with liquid water will instantaneously dissolve in the condensing or coalescing water droplets.
- FIG. 1 a scrubber assembly is shown. Flue gas which contains contaminants selected from the group consisting of particulates, sulfur oxides, nitrogen oxides and acid gases is fed through line 1 into scrubber assembly 10. The flue gas containing the contaminants will rise through the scrubber assembly 10 first contacting seawater which is first fed through line 3 into a cooling coil or mist eliminator A, The seawater will exit the cooling coil or mist eliminator A through line 5 and be fed down to join with the flue gas as it enters the scrubber assembly 10 through line 1. Line 6 will redirect the seawater through a number of distributors C so that the flue gas will contact the seawater and be quenched by this contact.
- Flue gas which contains contaminants selected from the group consisting of particulates, sulfur oxides, nitrogen oxides and acid gases is fed through line 1 into scrubber assembly 10.
- the flue gas containing the contaminants will rise through the scrubber assembly 10 first contacting seawater which is first fed through line 3 into a cooling coil or mist eliminator A, The seawater will exit the cooling coil or mis
- the flue gas which has been moistened by the seawater will continue to rise through the scrubber assembly 10 and will contact ozone that is fed through line 2 into the scrubber assembly 10.
- the ozone will have sufficient space based on the size of the scrubber assembly 10 to react with the nitrogen oxides and sulfur oxides present in the flue gas stream. This will allow for the requisite contact time during which the ozone and nitrogen oxides and sulfur oxides will react.
- Part of the reaction product will be nitric acid which will condense or coalesce on a tray device D and will be removed from the scrubber assembly 10 through line 9 for neutralization and either reused as may be allowed or disposed of in an environmentally friendly manner.
- the treated gas stream will continue to rise through the scrubber assembly 10 and will exit as exhaust through line 4.
- the seawater which is used as the scrubbing medium in the scrubber assembly 10 can be used as a once through or recycled depending upon the operators preferences.
- the used scrubbing agent is captured at the bottom of the scrubbing assembly 10 and can be withdrawn through line 7 with the aid of a pump B and purged from the scrubber assembly 10 through line 8.
- the ozone adding device is a separate device from the scrubbing assembly.
- scrubbing assembly 20 is attached to a droplet separator F.
- ozone is injected through line 13. Flue gas is fed through line 1 1 and will rise through the scrubber assembly 20 where it will contact the seawater fed through line 12 to a distribution assembly E.
- the moist scrubbed flue gas will exit scrubber assembly 20 and enter droplet separator F.
- the flue gas will contact the ozone where the nitrogen oxides and sulfur oxides present in the flue gas stream will oxidize and their reaction products of nitrates and nitric acid will be collected and purged through line 15.
- This stream can be treated and neutralized and either used or disposed of in an environmentally friendly manner.
- the treated flue gas stream will exit the droplet separator F through line 14 and be evacuated to the atmosphere.
- the seawater that is employed as the scrubbing medium can be used in a once through manner or be recycled and used for several cycles of treating the flue gas.
- the used seawater will leave the bottom of the scrubber assembly 20 through line 18 and is assisted in its removal through line 17 by pump G.
- a wet electro static precipitator can be employed instead of a cooling coil or mist elimination device at the top of the scrubbing assembly shown in figures 1 and 2.
- the wet ESP condenses the nitric
- Sulfur oxides and acid gas scrubbing are accomplished by quenching or wetting zones of the wet ESP and a small section downstream between the wetting zone and the charged plates is an oxidizer for nitrogen oxides.
- the seawater used in the wetting zone removes sulfur oxides,
- FIG. 3 shows a scrubber assembly that is similar in scope to the one described in Figure 1 with the inclusion of a droplet separator present above the reaction zone where ozone will be added to the flue gas stream to be treated.
- the scrubber 30 is an aqueous scrubber which can use water or seawater depending upon where the scrubber is located and economics of using the type of water as a scrubbing medium.
- the flue gas containing contaminants to be treated is fed through line 31 into the scrubber 30.
- the flue gas will typically be from combustion and chemical processes.
- the scrubber 30 can be a standard spray, venturi, rod, packed bed, plate column scrubber used for acid gas and particulate clean up as routinely used in air pollution control measures and technologies.
- Proprietary scrubbers such as the EDV scrubber by Belco or Dynawave scrubber by MECS may also be employed in the treatment methods of the present invention,
- the flue gas containing the contaminants will rise in the scrubber 30 through a first scrubbing unit I where some acid gases and particulates that are present in the flue gas stream will be removed.
- the flue gas stream will also be quenched.
- the flue gas stream still contains nitrogen oxides and possibly sulfur oxides will rise through scrubber 30 where it will contact ozone which is injected through line 38.
- the ozone will be allowed to contact the flue gas stream for a sufficient time to allow for the oxidation of the nitrogen oxides present in the flue gas stream.
- the flue gas stream which now contains the oxidized nitrogen oxides will then contact the droplet separator J where droplets will dissolve and
- the collected droplets will form a small aqueous stream which is recovered and removed from the scrubber 30, typically as dilute nitric acid through line 37. Depending upon its desired end use, this stream through line 37 can be collected and can be treated and neutralized for use in other operations or discharged in an environmentally friendly manner.
- the flue gas stream will next be subjected to scrubbing for sulfur oxides at scrubber unit K. This can be performed with seawater in a once through mode or with other aqueous scrubbing media in recycle mode. Since the nitrogen oxides and their oxidation products have been removed by the droplet separator, there is no interference from these components in the sulfur oxides removal scrubber. Any excess ozone would also be effectively removed as it will react to form sulphites or other alkali which can be removed by the scrubber medium. Some of the liquid is aqueous scrubber medium is collected and directed through line 39 to the volume of liquid collected at the bottom of scrubber 30. The thus treated flue gas stream may be treated one more time with an optional second droplet separator L which will coalesce/condense any remaining acids in the flue gas stream for removal there from. The treated flue gas stream will exit scrubber 30 through line 40 to the atmosphere.
- the invention can employ using an aqueous medium instead of sea water in the wet scrubber with once through or
- Spray may be projected to the wails of the scrubbers as is done in the EDV scrubbers.
- fvlercury or other heavy metals when present in the flue gas are oxidized along with the nitrogen oxides and can also be removed on the condensing/coalescing surfaces along with the nitric acid/nitrate,
- dry adsorbents in a fiuidized form or in a fixed bed can be used downstream of the wet scrubber to adsorb moisture and oxidized nitrogen oxides/nitric acid.
- the invention oxidizes nitrogen oxides with the addition of ozone downstream of a wet scrubbing stage thereby separating nitrogen oxides removal products such as nitric acid and/or nitrates from the scrubbing of other
- the scrubbing is preferably performed with seawater such as those industrial installations on sea coasts and aboard ships in a once through mode in the scrubber and where nitrate discharge is to be avoided.
- the invention effectively scrubs sulfur oxides, hydrochloric acid and other gases using seawater.
- ESPs wet electrostatic precipitators
- the method of the invention eliminates contamination of nitrate/nitric acid in the particulate scrubber or the wet scrubber for acid gas removal but also removes the need for a separate scrubbing device for nitrogen oxides removal and minimizes purge stream containing nitrate/nitric acid that could be neutralized and disposed of in an environmentally responsible manner.
- the small stream of liquid that is collected in the droplet separation device or the cooler/condenser with nitric acid can be neutralized, processed and disposed of in an environmentally safe manner or sold/used as a by-product.
- the invention is not limited to purely sea water scrubbing but could be employed in conjunction with any industrial wet scrubber meant for particulate and/or acid gas scrubbing.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14853140.3A EP3083015A2 (en) | 2013-12-16 | 2014-12-12 | Methods for removing contaminants from exhaust gases |
CA2932697A CA2932697A1 (en) | 2013-12-16 | 2014-12-12 | Methods for removing contaminants from exhaust gases |
CN201480068536.5A CN105980035A (en) | 2013-12-16 | 2014-12-12 | Method for removing contaminants from exhaust gases |
AU2014369342A AU2014369342A1 (en) | 2013-12-16 | 2014-12-12 | Methods for removing contaminants from exhaust gases |
KR1020167019106A KR20160098448A (en) | 2013-12-16 | 2014-12-12 | Methods for removing contaminants from exhaust gases |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361916386P | 2013-12-16 | 2013-12-16 | |
US61/916,386 | 2013-12-16 | ||
EP14179009.7A EP2883593A1 (en) | 2013-12-16 | 2014-07-29 | Method for removing contaminants from exhaust gases |
EP14179009.7 | 2014-07-29 | ||
US14/567,262 US9533256B2 (en) | 2013-12-16 | 2014-12-11 | Methods for removing contaminants from exhaust gases |
US14/567,262 | 2014-12-11 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2015092547A2 true WO2015092547A2 (en) | 2015-06-25 |
WO2015092547A3 WO2015092547A3 (en) | 2015-09-24 |
Family
ID=52814144
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2014/003168 WO2015092547A2 (en) | 2013-12-16 | 2014-12-12 | Methods for removing contaminants from exhaust gases |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2015092547A2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018222035A1 (en) | 2017-05-30 | 2018-12-06 | Koninklijke De Vries Scheepsbouw B.V. | Process and apparatus for reducing nox emissions |
CN110898594A (en) * | 2019-12-11 | 2020-03-24 | 曾旭炜 | Flue gas of chemical plant exhaust chimney takes off white equipment |
US11118492B1 (en) | 2020-04-27 | 2021-09-14 | Stec Technology, Inc. | Reactive cyclic induction system and method for reducing pollutants in marine diesel exhaust |
WO2021222151A1 (en) * | 2020-04-27 | 2021-11-04 | Stec Technology, Inc. | Reactive cyclic induction system and method for reducing pollutants in marine diesel exhaust |
WO2023066770A1 (en) * | 2021-10-19 | 2023-04-27 | Daphne Technology SA | Pollutant removal apparatus and method |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106196355B (en) * | 2016-08-03 | 2019-06-28 | 南华大学 | Utilize the energy-saving type air conditioner case and purification method of condensation Water warfare air |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5206002A (en) | 1991-08-29 | 1993-04-27 | Cannon Boiler Works, Inc. | Process for removing nox and sox from exhaust gas |
US6162409A (en) | 1999-03-15 | 2000-12-19 | Arthur P. Skelley | Process for removing Nox and Sox from exhaust gas |
US6649132B1 (en) | 2002-07-23 | 2003-11-18 | The Boc Group, Inc. | Process for the removal of impurities from gas streams |
US7303735B2 (en) | 2003-10-17 | 2007-12-04 | The Boc Group, Inc. | Process for the removal of contaminants from gas streams |
US7766995B2 (en) | 2006-05-01 | 2010-08-03 | Linde Llc | Ozone production processes and its use in industrial processes |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5985223A (en) * | 1998-06-02 | 1999-11-16 | The Boc Group, Inc. | Removal of NOx and SOx emissions form pickling lines for metal treatment |
EP2659947A1 (en) * | 2012-04-30 | 2013-11-06 | Linde Aktiengesellschaft | Method and apparatus for removing contaminants from exhaust gases |
US8734741B1 (en) * | 2012-04-30 | 2014-05-27 | Linde Aktiengesellschaft | Methods for removing contaminants from exhaust gases |
HUE033923T2 (en) * | 2012-10-15 | 2018-01-29 | Linde Ag | Method for removing contaminants from exhaust gases by adding ozone |
-
2014
- 2014-12-12 WO PCT/IB2014/003168 patent/WO2015092547A2/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5206002A (en) | 1991-08-29 | 1993-04-27 | Cannon Boiler Works, Inc. | Process for removing nox and sox from exhaust gas |
US6162409A (en) | 1999-03-15 | 2000-12-19 | Arthur P. Skelley | Process for removing Nox and Sox from exhaust gas |
US6649132B1 (en) | 2002-07-23 | 2003-11-18 | The Boc Group, Inc. | Process for the removal of impurities from gas streams |
US7303735B2 (en) | 2003-10-17 | 2007-12-04 | The Boc Group, Inc. | Process for the removal of contaminants from gas streams |
US7766995B2 (en) | 2006-05-01 | 2010-08-03 | Linde Llc | Ozone production processes and its use in industrial processes |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018222035A1 (en) | 2017-05-30 | 2018-12-06 | Koninklijke De Vries Scheepsbouw B.V. | Process and apparatus for reducing nox emissions |
NL2018994B1 (en) * | 2017-05-30 | 2018-12-07 | Koninklijke De Vries Scheepsbouw B V | Process and apparatus for reducing NOx emissions |
US11060431B2 (en) | 2017-05-30 | 2021-07-13 | Koninklijke De Vries Scheepsbouw B.V. | Process and apparatus for reducing NOx emissions |
CN110898594A (en) * | 2019-12-11 | 2020-03-24 | 曾旭炜 | Flue gas of chemical plant exhaust chimney takes off white equipment |
US11118492B1 (en) | 2020-04-27 | 2021-09-14 | Stec Technology, Inc. | Reactive cyclic induction system and method for reducing pollutants in marine diesel exhaust |
WO2021222151A1 (en) * | 2020-04-27 | 2021-11-04 | Stec Technology, Inc. | Reactive cyclic induction system and method for reducing pollutants in marine diesel exhaust |
WO2023066770A1 (en) * | 2021-10-19 | 2023-04-27 | Daphne Technology SA | Pollutant removal apparatus and method |
Also Published As
Publication number | Publication date |
---|---|
WO2015092547A3 (en) | 2015-09-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9533256B2 (en) | Methods for removing contaminants from exhaust gases | |
US8734741B1 (en) | Methods for removing contaminants from exhaust gases | |
EP2659947A1 (en) | Method and apparatus for removing contaminants from exhaust gases | |
EP2719440B1 (en) | Method for removing contaminants from exhaust gases by adding ozone | |
WO2015092547A2 (en) | Methods for removing contaminants from exhaust gases | |
US7303735B2 (en) | Process for the removal of contaminants from gas streams | |
US9440188B2 (en) | Method for removing contaminants from exhaust gases | |
US6605263B2 (en) | Sulfur dioxide removal using ammonia | |
AU2007290817B2 (en) | Wet gas scrubbing process | |
EP3012011A1 (en) | Method and apparatus for partial removal of contaminants from process gas stream | |
KR19990014503A (en) | Facilities and methods for dust removal and desulfurization of flue gas during steel production and bunker seed oil combustion |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14853140 Country of ref document: EP Kind code of ref document: A2 |
|
ENP | Entry into the national phase |
Ref document number: 2932697 Country of ref document: CA |
|
ENP | Entry into the national phase |
Ref document number: 2014369342 Country of ref document: AU Date of ref document: 20141212 Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112016013345 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 20167019106 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2016126186 Country of ref document: RU Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2014853140 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014853140 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 112016013345 Country of ref document: BR Kind code of ref document: A2 Effective date: 20160609 |