WO2011122925A1 - Proceso de eliminación de gases ácidos del aire y gases de combustión de quemadores y motores de combustión interna mediante una absorción con solución de hidróxido de sodio y proceso de obtención de carbonato de sodio para acreditar bonos de carbono - Google Patents
Proceso de eliminación de gases ácidos del aire y gases de combustión de quemadores y motores de combustión interna mediante una absorción con solución de hidróxido de sodio y proceso de obtención de carbonato de sodio para acreditar bonos de carbono Download PDFInfo
- Publication number
- WO2011122925A1 WO2011122925A1 PCT/MX2010/000149 MX2010000149W WO2011122925A1 WO 2011122925 A1 WO2011122925 A1 WO 2011122925A1 MX 2010000149 W MX2010000149 W MX 2010000149W WO 2011122925 A1 WO2011122925 A1 WO 2011122925A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gases
- solution
- absorption
- sodium
- air
- Prior art date
Links
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 title claims abstract description 105
- 239000007789 gas Substances 0.000 title claims abstract description 65
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 46
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000008569 process Effects 0.000 title claims abstract description 33
- 229910000029 sodium carbonate Inorganic materials 0.000 title claims abstract description 33
- 239000000567 combustion gas Substances 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 title claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000006096 absorbing agent Substances 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 35
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 14
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 13
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007921 spray Substances 0.000 claims abstract description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000006227 byproduct Substances 0.000 claims abstract description 7
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims abstract description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 5
- 239000002803 fossil fuel Substances 0.000 claims abstract description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 4
- 235000010269 sulphur dioxide Nutrition 0.000 claims abstract description 4
- 239000003546 flue gas Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 6
- 239000004571 lime Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 5
- 229910001626 barium chloride Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- 230000002706 hydrostatic effect Effects 0.000 claims description 3
- 239000008267 milk Substances 0.000 claims description 3
- 210000004080 milk Anatomy 0.000 claims description 3
- 235000013336 milk Nutrition 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 241001579016 Nanoa Species 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- 230000002745 absorbent Effects 0.000 claims 1
- 239000002250 absorbent Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 230000003134 recirculating effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 3
- 235000010288 sodium nitrite Nutrition 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 2
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 2
- 239000012080 ambient air Substances 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- 239000004291 sulphur dioxide Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000005431 greenhouse gas Substances 0.000 description 7
- 238000009434 installation Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- 239000010962 carbon steel Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- -1 diesel Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 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
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- 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
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- 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
- B01D53/60—Simultaneously removing sulfur oxides and 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
- B01D53/62—Carbon 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
- B01D53/73—After-treatment of removed components
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- 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
Definitions
- the present invention relates in general to the reduction of greenhouse gases (GHG), such as acid gases: carbon dioxide (CO2), sulfur dioxide (SO2), and nitrogen dioxide (NO2), these last two not declared within the GHG; and in particular with the accreditation of carbon credits according to the Kyoto Protocol, through a chemical process that can produce calcium carbonate or sodium carbonate for commercialization; For the latter, the process is carried out in an industrial installation of minimum economic size.
- GHG greenhouse gases
- CO2 carbon dioxide
- SO2 sulfur dioxide
- NO2 nitrogen dioxide
- the carbon bond transaction — a carbon bond represents the right to emit a ton of carbon dioxide — allows mitigating the generation of greenhouse gases, benefiting companies that do not emit or decrease the emission and making the They emit more than allowed.
- any An organization that captures CO2 (or any greenhouse gas) is entitled to carbon credits and is likely to receive the corresponding economic incentive.
- the capture of CO2 from the air and combustion gases by means of an absorption with NaOH solution produces sodium carbonate in solution, which can be concentrated and crystallized for commercialization or to treat the sodium carbonate solution with lime slurry to obtain Calcium carbonate and commercialize it, regenerating in this case sodium hydroxide. It is important that in sodium carbonate applications this salt is not decomposed by returning CO2 to the atmosphere, in order to be able to credit carbon bonds.
- the equipment for carrying out the process of eliminating acidic gases from the atmosphere and combustion gases is a horizontal absorber in which the gases run (in the horizontal direction) along the equipment and receive, perpendicularly, in shower form and at the sides, at 90 or with respect to the vertical, through dispersion nozzles, the alkaline solution that dissolves and reacts with the solute the acid gases, producing the following reactions:
- Carbon dioxide concentrations handled in the process varied from 0.44% for urban atmospheric air, up to 16% in flue gases using natural gas as fuel.
- Sulfur dioxide concentrations varied from 60 ppm to 0.2% (2000 ppm) and nitrogen dioxide levels from 20 to 69 ppm.
- Two horizontal spray absorption equipment were used to test the effectiveness of the 30 cm internal diameter process made in austenitic steel in 50 cm attachable sections, in order to study the mechanism of acid gas absorption.
- the other absorber of 60 cm in diameter and sections of 75 cm in length.
- Each of the sections of the absorbers have three series of nozzles separated 10 cm, for the 30 cm diameter and 15 cm apart for the equipment with 60 cm diameter, one series at the top and the other two at each side at 90 o , making a total of 15 nozzles per section.
- the gaseous flows through the absorber must have global average speeds between 3 and 7 m / sec, since less than 3 m / sec the efficiency of the equipment is reduced and greater than 7 m / sec requires more pressure to make passing the gas and the entrainment of the liquid increases making it difficult to separate with the baffles that are installed in the chimney.
- the flux density of the absorption liquid can vary from 1.0 to 3.3 Kg / m 2 sec. Of course there would be no major problem if the liquid flow density were less than 1.0 kg / m 2 sec as long as it absorbed the acid gases contained in the gas flow. Using higher fluid flow densities at 3.3 Kg / m 2 sec runs the risk of flooding the equipment and also having unnecessary and expensive pumping equipment.
- the acid gas uptake process is complemented by regenerating sodium hydroxide for reuse with lime milk for sodium carbonate, and with ammonium hydroxide for sodium nitrate, oxidizing sodium nitrite to nitrate with an oxidizing agent .
- Sodium sulphite must previously be oxidized to sulfate by an oxidizing agent, treated with barium chloride to form barium sulfate that precipitates and sodium chloride that remains in solution. The reactions are as follows:
- the calcium carbonate that forms when washed and dried is impalpable passes the 325 mesh of the Taylor series and can be used for the manufacture of Mexican handicraft figures.
- Barium sulfate that is formed has application in the pharmaceutical industry and ammonium nitrate is a fertilizer.
- the complete process for the capture of acidic gases from the atmosphere or combustion gases, in order to accredit carbon bonds is outlined in the Flowchart of Figure No. i.
- the liquid that will be used to wash the gases will be a 2 N sodium hydroxide solution (80 g / l), with an operating liquid flow density between 2.7 and 3.4 ⁇ , which are the values of optimal industrial operation.
- the gas flow to be treated is 10,000 m 3 / h giving a global average speed, both for atmospheric air and for flue gases, between 3 and 7 m / sec.
- the temperature of the gases and the absorber solution will be 22 ° C, even if the flue gases enter the absorber hot, in a very short time they will take the temperature of the absorber solution.
- the pressure of the gases at the inlet of the absorber shall be 20 mm of gauge Hg.
- the absorber is connected, at one end to the atmospheric air or to the outlet of the flue gases, and on the other to the atmosphere for the exit of the washed gases;
- the atmospheric pressure is considered to be the place where the equipment is installed.
- the equipment for carrying out the process of capturing carbon dioxide from the atmosphere and combustion gases, and producing sodium carbonate comprises:
- a horizontal absorber through which the gases run (in the horizontal direction) along the equipment and receive perpendicularly, in the form of a shower at the top and sides, forming an angle of 90 or with respect to the vertical, through dispersion nozzles, the alkaline solution that dissolves and reacts with acid solutes, particularly CO2;
- the chemical reaction that takes place is as follows:
- the industrial absorber consists of seven modules of one meter in length, attachable and removable as required, and 0.85 m inside diameter, made of austenitic steel.
- the dispersion nozzles are distributed 20 cm from each other, both at the top and at the sides, so that each module of one meter has 15 nozzles, the size of which is V inch. These nozzles "spray" the liquid into small droplets, which increase the area of mass transfer, producing the absorption of CO2 to be captured.
- the absorbing solution of 80 g NaOH / lt (that is 2 N) has a flow of 50 m 3 / h to absorb CO2 which gives a flow density of 3.22 Kg / m 2 sec for when the gas flow be air and 3.26 Kg / m 2 sec for when they are flue gases; values within those recommended industrially for the flux density of the absorption liquid.
- the gas flow of 10,000 m 3 / h has a gas flow density of 4.5 Kg / m 2 sec, for air, with a CO2 concentration of 0.044%; and 4-8 Kg / m 2 sec for flue gases, considering a concentration of -COa of 16%.
- the solution is then transferred to a heat exchanger and basket crystallizer in order to crystallize this by-product, which is washed with water and dried with hot air and then ground to the desired commercial particle size.
- the remaining liquid is sent to the NaOH solution feed tank.
- FIG. 2 A diagram of the horizontal absorber is shown in Figure No. 2 with three assembled sections of one meter in length each section and 0.85 m inside diameter, representing the dispersion nozzles: 5 at the top separated 20 cm from each other and two rows, also of 5 nozzles each with the same separation, at 90 or with respect to the vertical.
- the channel for the outlet of the absorption liquid with a height of 30 cm that serves as a hydraulic seal is also shown.
- Figure No. 3 Three diagrams are shown in Figure No. 3: Figure No. 3 (a) section of the straight section of the absorber of 0.85 m inside diameter and the outlet channel of the absorption liquid with a height of 30 cm that serves as a seal hydraulic; Figure No. 3 (b) Straight cross section of a section of the absorber one meter long, showing the rows of dispersion nozzles of the absorption liquid separated 20 cm from each other, a row at the top and two more on each side of the first one forming an angle of 90 or with respect to the vertical, with the same number of nozzles and of equal separation, the channel for the exit of the absorption liquid with a height of 30 cm is also shown as a hydraulic seal; and Figure No. 3 (c) an isometric view of a section of the absorber with the markings for the liquid dispersion nozzles of absorption and the channel for its exit, with the same dimensions indicated in Figures 3 (a) and 3 (b).
- Figure 4 shows the exhaust duct of the clean gases of the absorber: Figure 4 (a) section of the straight section of the gas outlet to the chimney of 0.85 m inside diameter; Figure 4 (b) straight cross section of three sections of one meter in length each, of the horizontal absorber and duct of one meter in length for the exit of the clean gases towards the chimney with its retention screens of the absorption liquid which is dragged by the gases when leaving the absorber, the outlet channel of the absorption liquid with a height of 30 cm of hydraulic seal is also shown; and Figure 4 (c) isometric view of three sections of the absorber of one meter in length each section and the outlet duct of one meter in length with its screens to retain the absorption liquid carried by the exhaust gases towards the chimney, also The 30 cm high channel for the hydraulic seal and the rows of nozzles are indicated in the absorber sections, five for each section separated 20 cm from each other, for dispersion of the absorption liquid at the inlet of the absorber; Each section of the absorber has three rows with five nozzles each, the
- Two horizontal unpacked spray absorbers described above 30 and 60 cm in diameter and in sections of 50 cm for the first and 75 cm for the second with 15 nozzles each section. These equipments are manufactured in austenitic steel.
- a centrifugal fan to handle gases from 800 to 3000 m 3 / h A pump of an HP for handling the absorption liquid.
- a pump of 0.5 HP for the return of the regenerated absorption liquid A pump of 0.5 HP for the return of the regenerated absorption liquid.
- a chimney to expel the clean gases of acid gases with baffles to stop the liquid that drags the gas to the outlet of the absorber.
- Horizontal absorber of 83 cm of internal diameter and seven sections of one meter in length with 15 nozzles of E-01 dispersion per section and a channel with 30 cm of seal
- the installation in its minimum economic size, as shown in the present invention, is highly cost effective for treating combustion gases, with an internal rate of return of the order of 60% and an equilibrium point of 13%. Not so for the treatment of atmospheric air where a subsidy is required to carry out the capture of carbon dioxide.
- the breakeven point indicates the production capacity such that the benefits from product sales and accreditation of carbon credits equal the sum of fixed and variable costs, that is, after this value there are gains and below it there are losses.
- the absorber comprises:
- Each section has three series of nozzles, one at the top and the other two on each side of the first, forming an angle of 90 o ; Each nozzle is separated 20 cm from each other, making a total of 15 nozzles per section.
- the process for obtaining sodium carbonate from the capture of carbon dioxide from the air and combustion gases by absorption with a solution of partner hydroxide, in a horizontal spray absorber allows the equipment, with this position , handle higher speeds for gaseous flow and not require large equipment since a vertical absorber handles global gas speeds up to 1 m / sec; while the same horizontal team can handle global gas speeds up to 7 m / sec.
- the process contributes to the reduction of the greenhouse effect by reducing the content of carbon dioxide in the air and in the combustion gases of burners and internal combustion engines that use fossil fuels.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/637,937 US20130115151A1 (en) | 2010-03-29 | 2010-12-09 | Process for the removal of acid gases from the air and from combustion gases from burners and internal combustion engines by means of absorption with sodium hydroxide solution and process for obtaining sodium carbonate in order to acquire carbon credits |
CN2010800671129A CN102946976A (zh) | 2010-03-29 | 2010-12-09 | 借助于利用氢氧化钠溶液吸收用于从空气和从来自燃烧器和内燃机的燃烧气体中除去酸性气体的方法以及用于获得碳酸钠以便获得碳信用的方法 |
EP10849082.2A EP2554244A4 (en) | 2010-03-29 | 2010-12-09 | METHOD FOR REMOVING ACIDIC AIR GASES AND COMBUSTION GAS FROM BURNERS AND INTERNAL COMBUSTION ENGINES BY ABSORPTION WITH SOLUTION OF SODIUM HYDROXIDE AND PROCESS FOR OBTAINING SODIUM CARBONATE FOR DELIVERING CARBON CREDITS |
AU2010349824A AU2010349824A1 (en) | 2010-03-29 | 2010-12-09 | Process for the removal of acid gases from the air and from combustion gases from burners and internal combustion engines by means of absorption with sodium hydroxide solution and process for obtaining sodium carbonate in order to acquire carbon credits |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2010003472A MX2010003472A (es) | 2010-03-29 | 2010-03-29 | Bonos de carbono por via quimica. |
MXMX/A/2010/003472 | 2010-03-29 | ||
MXMX/A/2010/010186 | 2010-09-20 | ||
MX2010010186A MX345914B (es) | 2010-09-20 | 2010-09-20 | Proceso de obtención de carbonato de sodio a partir de la captura de dióxido de carbono del aire y de gases de combustión mediante una absorción con solución de hidróxido de sodio para acreditar bonos de carbono. |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011122925A1 true WO2011122925A1 (es) | 2011-10-06 |
Family
ID=44712422
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/MX2010/000149 WO2011122925A1 (es) | 2010-03-29 | 2010-12-09 | Proceso de eliminación de gases ácidos del aire y gases de combustión de quemadores y motores de combustión interna mediante una absorción con solución de hidróxido de sodio y proceso de obtención de carbonato de sodio para acreditar bonos de carbono |
Country Status (6)
Country | Link |
---|---|
US (1) | US20130115151A1 (es) |
EP (1) | EP2554244A4 (es) |
CN (1) | CN102946976A (es) |
AU (1) | AU2010349824A1 (es) |
CL (1) | CL2012002736A1 (es) |
WO (1) | WO2011122925A1 (es) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013157912A1 (es) * | 2012-04-19 | 2013-10-24 | Miklos Ilkovics Roberto Tomas | Eliminación de sulfuro de hidrógeno y dióxido de carbono del gas natural mediante una absorción con solución de hidróxido de sodio y posterior tratamiento con hidróxido de amonio y oxidación para producir sulfato y carbonato de amonio |
CN104437049A (zh) * | 2014-11-12 | 2015-03-25 | 贵州开磷(集团)有限责任公司 | 一种耦合共生双碱烟气脱硫方法 |
WO2020124184A1 (pt) * | 2018-12-20 | 2020-06-25 | Universidade Federal De Minas Gerais | Processo de captura de co2 e processo de regeneração contínua de solvente |
US11484831B1 (en) * | 2021-08-18 | 2022-11-01 | Eric Phillips | Direct air capture system removing carbon dioxide |
CN115557476A (zh) * | 2022-09-20 | 2023-01-03 | 成都德美工程技术有限公司 | 二氧化氮制备装置及制备方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10508191B2 (en) * | 2015-08-31 | 2019-12-17 | Mitsubushi Gas Chemical Company, Inc. | Flame-retardant polycarbonate resin composition, sheet and film each using same, and method for producing said sheet or film |
CN108854495A (zh) * | 2018-07-19 | 2018-11-23 | 华电电力科学研究院有限公司 | 一种燃气分布式能源站多种污染物脱除的系统及其工作方法 |
CN115159555B (zh) * | 2022-08-01 | 2023-12-22 | 华中科技大学 | 一种固废焚烧烟气的处理方法和系统 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3532595A (en) * | 1965-06-02 | 1970-10-06 | Mo Och Domsjoe Ab | Method for producing high-grade hot water by means of combustion gases from sulphite or sulphate cellulose processes and apparatus for carrying out the method |
US4369167A (en) * | 1972-03-24 | 1983-01-18 | Weir Jr Alexander | Process for treating stack gases |
US4690697A (en) * | 1986-02-20 | 1987-09-01 | Schwartz Arthur G | Long residence pollution control system |
EP1201290A1 (en) * | 1999-07-19 | 2002-05-02 | Ebara Corporation | Apparatus and method for cleaning acidic gas |
US20090104098A1 (en) * | 2007-10-19 | 2009-04-23 | Uday Singh | Method and apparatus for the removal of carbon dioxide from a gas stream |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB755548A (en) * | 1953-02-17 | 1956-08-22 | Jean Luc Berry | Improvements relating to distillation apparatus |
US3522000A (en) * | 1967-09-06 | 1970-07-28 | Chillum Sheet Metal Inc | Method and apparatus for cooling and purifying gaseous products of combustion |
AT333782B (de) * | 1973-10-05 | 1976-12-10 | Ind Chemie Thoma Gmbh & Co Kg | Verfahren zur umsetzung von alkalisulfit |
US6214097B1 (en) * | 1994-11-08 | 2001-04-10 | Marsulex Environmental Technologies, Llc | Flue gas scrubbing apparatus |
US6001152A (en) * | 1997-05-29 | 1999-12-14 | Sinha; Rabindra K. | Flue gas conditioning for the removal of particulates, hazardous substances, NOx, and SOx |
CN2452604Y (zh) * | 2000-11-27 | 2001-10-10 | 唐念华 | 消烟除尘脱硫净化装置 |
US6759022B2 (en) * | 2002-06-05 | 2004-07-06 | Marsulex Environmental Technologies | Flue gas desulfurization process and apparatus for removing nitrogen oxides |
US7947239B2 (en) * | 2004-05-04 | 2011-05-24 | The Trustees Of Columbia University In The City Of New York | Carbon dioxide capture and mitigation of carbon dioxide emissions |
US7727374B2 (en) * | 2004-09-23 | 2010-06-01 | Skyonic Corporation | Removing carbon dioxide from waste streams through co-generation of carbonate and/or bicarbonate minerals |
CN101068610A (zh) * | 2004-09-23 | 2007-11-07 | 乔·大卫·琼斯 | 通过碳酸盐和/或碳酸氢盐无机物的共同产生从废弃流中除去二氧化碳 |
US7866638B2 (en) * | 2005-02-14 | 2011-01-11 | Neumann Systems Group, Inc. | Gas liquid contactor and effluent cleaning system and method |
CN100515545C (zh) * | 2005-07-18 | 2009-07-22 | 刘忠祥 | 氢氧化钠溶液循环喷淋过滤式废气处理器 |
US20070154374A1 (en) * | 2006-01-05 | 2007-07-05 | Envirosolv Energy Llc | Method for removing sulfur dioxide and other acid gases, mercury, and nitrogen oxides from a gas stream with the optional production of ammonia based fertilizers |
JP4845568B2 (ja) * | 2006-04-04 | 2011-12-28 | バブコック日立株式会社 | 湿式排煙脱硫装置 |
JP2008168262A (ja) * | 2007-01-15 | 2008-07-24 | Anemosu:Kk | 気液接触装置 |
US8425665B2 (en) * | 2007-01-19 | 2013-04-23 | Heartland Technology Partners, Llc | Fluid scrubber |
MX346694B (es) * | 2007-04-12 | 2017-03-29 | Cefco Llc * | Aparato para captura de carbono y eliminación de contaminantes múltiples en gas de chimeneas procedente de fuentes de combustible de hidrocarburo y recuperación de múltiples sub-productos. |
AP2010005213A0 (en) * | 2007-09-06 | 2010-04-30 | Richard Alan Haase | Means for sequestration and conversion of COX and NOX, CONOX |
RU2531827C2 (ru) * | 2007-09-20 | 2014-10-27 | Скайоник Корпорейшн | Способ отделения тяжелых металлов от воды в конденсате дымовых газов |
-
2010
- 2010-12-09 CN CN2010800671129A patent/CN102946976A/zh active Pending
- 2010-12-09 US US13/637,937 patent/US20130115151A1/en not_active Abandoned
- 2010-12-09 EP EP10849082.2A patent/EP2554244A4/en not_active Withdrawn
- 2010-12-09 WO PCT/MX2010/000149 patent/WO2011122925A1/es active Application Filing
- 2010-12-09 AU AU2010349824A patent/AU2010349824A1/en not_active Abandoned
-
2012
- 2012-09-28 CL CL2012002736A patent/CL2012002736A1/es unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3532595A (en) * | 1965-06-02 | 1970-10-06 | Mo Och Domsjoe Ab | Method for producing high-grade hot water by means of combustion gases from sulphite or sulphate cellulose processes and apparatus for carrying out the method |
US4369167A (en) * | 1972-03-24 | 1983-01-18 | Weir Jr Alexander | Process for treating stack gases |
US4690697A (en) * | 1986-02-20 | 1987-09-01 | Schwartz Arthur G | Long residence pollution control system |
EP1201290A1 (en) * | 1999-07-19 | 2002-05-02 | Ebara Corporation | Apparatus and method for cleaning acidic gas |
US20090104098A1 (en) * | 2007-10-19 | 2009-04-23 | Uday Singh | Method and apparatus for the removal of carbon dioxide from a gas stream |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013157912A1 (es) * | 2012-04-19 | 2013-10-24 | Miklos Ilkovics Roberto Tomas | Eliminación de sulfuro de hidrógeno y dióxido de carbono del gas natural mediante una absorción con solución de hidróxido de sodio y posterior tratamiento con hidróxido de amonio y oxidación para producir sulfato y carbonato de amonio |
CN104437049A (zh) * | 2014-11-12 | 2015-03-25 | 贵州开磷(集团)有限责任公司 | 一种耦合共生双碱烟气脱硫方法 |
CN104437049B (zh) * | 2014-11-12 | 2016-12-07 | 贵州开磷集团股份有限公司 | 一种耦合共生双碱烟气脱硫方法 |
WO2020124184A1 (pt) * | 2018-12-20 | 2020-06-25 | Universidade Federal De Minas Gerais | Processo de captura de co2 e processo de regeneração contínua de solvente |
US11484831B1 (en) * | 2021-08-18 | 2022-11-01 | Eric Phillips | Direct air capture system removing carbon dioxide |
CN115557476A (zh) * | 2022-09-20 | 2023-01-03 | 成都德美工程技术有限公司 | 二氧化氮制备装置及制备方法 |
CN115557476B (zh) * | 2022-09-20 | 2024-03-26 | 成都德美工程技术有限公司 | 二氧化氮制备装置及制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2554244A4 (en) | 2014-12-17 |
CN102946976A (zh) | 2013-02-27 |
CL2012002736A1 (es) | 2013-12-27 |
AU2010349824A1 (en) | 2012-10-25 |
EP2554244A1 (en) | 2013-02-06 |
US20130115151A1 (en) | 2013-05-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2011122925A1 (es) | Proceso de eliminación de gases ácidos del aire y gases de combustión de quemadores y motores de combustión interna mediante una absorción con solución de hidróxido de sodio y proceso de obtención de carbonato de sodio para acreditar bonos de carbono | |
ES2939178T3 (es) | Agente de desulfuración y desnitrificación | |
Ji et al. | Integrated absorption–mineralisation for energy-efficient CO2 sequestration: Reaction mechanism and feasibility of using fly ash as a feedstock | |
CN105344235B (zh) | 一种燃煤工业锅炉同时吸收NOx和SO2的设备及方法 | |
Guo et al. | Applications of high-gravity technologies in gas purifications: A review | |
ES2774083T3 (es) | Método para eliminar óxidos de nitrógeno de una corriente de gas | |
CN104043325B (zh) | 一种臭氧活化过硫酸盐的烟气净化方法和装置 | |
CN104383798B (zh) | 一种烟气脱硫脱硝的净化回收系统 | |
CN102438730B (zh) | 使用水洗的冷却式的基于氨的co2捕集系统和方法 | |
US20170029343A1 (en) | Sulfur enhanced nitrogen production from emission scrubbing | |
WO2009043108A1 (en) | Removal of pollutants from a gas flow | |
CN204891568U (zh) | 锅炉烟气一体化分布式脱硫脱硝装置 | |
US20110318231A1 (en) | Carbon Dioxide Capture System for Diminution of Global CO2 Levels | |
AU2010295749B2 (en) | Method and system for regenerating a solution used in a wash vessel | |
ES2833049T3 (es) | Depurador de gas de múltiples niveles con múltiples cabezales de depurador inundados | |
CN103505999A (zh) | 一种湿法脱硫脱硝的系统和方法 | |
CN105498500B (zh) | 一种双回路烟气净化的装置及方法 | |
CN103801177B (zh) | 一种钙镁法同时脱硫脱硝脱汞的烟气处理方法 | |
CN105032145A (zh) | 锅炉烟气一体化分布式脱硫脱硝装置 | |
CN202823140U (zh) | 用于船用燃机尾气处理的电解法海水脱硫装置 | |
CN102698583A (zh) | 用于船用燃机尾气处理的电解法海水脱硫方法和装置 | |
Long et al. | Advanced and intensified seawater flue gas desulfurization processes: Recent developments and improvements | |
CN101332410A (zh) | 排气处理装置以及排气处理方法 | |
RU2595289C1 (ru) | Комплексный воздухоподогреватель | |
WO2013157912A1 (es) | Eliminación de sulfuro de hidrógeno y dióxido de carbono del gas natural mediante una absorción con solución de hidróxido de sodio y posterior tratamiento con hidróxido de amonio y oxidación para producir sulfato y carbonato de amonio |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080067112.9 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10849082 Country of ref document: EP Kind code of ref document: A1 |
|
REEP | Request for entry into the european phase |
Ref document number: 2010849082 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010849082 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012002736 Country of ref document: CL |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2010349824 Country of ref document: AU Date of ref document: 20101209 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 3235/KOLNP/2012 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13637937 Country of ref document: US |