SK154890A3 - Method for processing concentrated solution of sodium sulfite, sodium sulfate and sodium thiosulfate - Google Patents
Method for processing concentrated solution of sodium sulfite, sodium sulfate and sodium thiosulfate Download PDFInfo
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- SK154890A3 SK154890A3 SK1548-90A SK154890A SK154890A3 SK 154890 A3 SK154890 A3 SK 154890A3 SK 154890 A SK154890 A SK 154890A SK 154890 A3 SK154890 A3 SK 154890A3
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- Slovakia
- Prior art keywords
- sodium
- gypsum
- product liquor
- hydrochloric acid
- lime
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- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 title claims description 22
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 13
- 235000010265 sodium sulphite Nutrition 0.000 title claims description 11
- 235000011152 sodium sulphate Nutrition 0.000 title claims description 10
- 235000019345 sodium thiosulphate Nutrition 0.000 title claims description 9
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 title claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000003546 flue gas Substances 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000010440 gypsum Substances 0.000 claims description 11
- 229910052602 gypsum Inorganic materials 0.000 claims description 11
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 239000004133 Sodium thiosulphate Substances 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 5
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 5
- -1 CaCO ^ Substances 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- 235000012255 calcium oxide Nutrition 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000498 cooling water Substances 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- 235000019738 Limestone Nutrition 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000006028 limestone Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 235000011167 hydrochloric acid Nutrition 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 239000011734 sodium Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 4
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WKIXHBICUJIWNP-UHFFFAOYSA-K calcium;sodium;chloride;sulfate Chemical compound [Na+].[Cl-].[Ca+2].[O-]S([O-])(=O)=O WKIXHBICUJIWNP-UHFFFAOYSA-K 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/464—Sulfates of Ca from gases containing sulfur oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Treating Waste Gases (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Spôsob spracovania koncentrovaného roztoku siričitanu, síranu a tiosíranu sodnéhoA method of treating a concentrated solution of sodium sulfite, sulfate, and sodium thiosulfate
Oblasť technikyTechnical field
Vynález sa týka spôsobu spracovania koncentrovaného roztoku siričitanu, síranu a tiosíranu sodného, teda produktového lúhu, pochádzajúceho z odsírovania dymových plynov.The invention relates to a process for treating a concentrated solution of sodium sulfite, sulphate and sodium thiosulphate, i.e. the product liquor resulting from flue gas desulphurisation.
Doterajší stav technikyBACKGROUND OF THE INVENTION
Na základe nariadenia o veľkých kúreniskách platného v Nemeckej spolkovej republike sa musia dymové plyny z kúrenísk elektrární odsírovať. Pritom sa používa v 87 % spôsob prania vápnom a v 13 % špeciálne spôsoby. K špeciálnym spôsobom patrí okrem iných Wellmann-Lordov spôsob, pri ktorom sa dymové plyny perú roztokom siričitanu sodného. Vzniknutý lúh sa zahrieva a pritom sa z nej vypudí oxid siričitý, ale vedľajšou reakciou sa tiež oxiduje siričitan sodný. Spracovanie lúhu obsahujúceho siričitan sodný a síran sodný vznikajúceho v neočakávane veľkom množstve pri odsírovaní dymových plynov Wellmann-Lordovým spôsobom alebo iným spôsobom prania dymových plynov pri použití sodných solí je spojené s veľkými problémami. Jeho vypúšťanie je rovnako tak málo tolerovateľné, ako jeho ukladanie na skládku, z ekonomických dôvodov tiež nebol až dosiaľ v dohľade žiadny schodný spôsob spracovania produktového lúhu.On the basis of the Large Chimney Ordinance in force in the Federal Republic of Germany, flue gases from the heating plants of power plants must be desulphurised. Lime washing is used in 87% and special methods in 13%. Special processes include, among other things, the Wellmann-Lord process in which the flue gases are scrubbed with a sodium sulfite solution. The resulting liquor is heated to expel sulfur dioxide, but sodium sulfite is also oxidized by side reaction. Treatment of the liquor containing sodium sulphite and sodium sulphate formed in an unexpectedly large amount by flue gas desulfurization by the Wellmann-Lord method or by another method of flue gas scrubbing using sodium salts is associated with major problems. Its discharge is not as tolerable as its landfilling, and for economic reasons there has been no viable way of processing the product liquor up to now.
Úlohou tohto vynálezu je vyvinúť technicky schodný spôsob spracovania produktového lúhu, ktorý by bol tiež prijateľný z ekonomického hľadiska.SUMMARY OF THE INVENTION It is an object of the present invention to provide a technically viable method of treating product liquor which is also economically acceptable.
Podstata vynálezuSUMMARY OF THE INVENTION
Predmetom vynálezu je spôsob spracovania koncentrovaného roztoku siričitanu, síranu a tiosíranu sodného, teda produktového lúhu, pochádzajúceho z odsírovania dymových plynov, ktorého podstata spočíva v tom, že sa produktový lúh pridáva k chladiacej vode s pH nižším ako 1 obsahujúcej kyselinu chlorovodíkovú v predpieracej práčke zariadenia na odsírovanie dymových plynov z elektrárne na uhlí pracujúceho s vápencom, CaCO3, alebo páleným vápnom, CaO, pričom produktový lúh sa odmeriava tak, že zostáva prebytok kyseliny, oxid siričitý, SO2, vzniknutý reakciou siričitanu sodného a tiosíranu sodného s kyselinou chlorovodíkovou sa v absorbéri premieňa pôsobením vápenca alebo páleného vápna na sadru prebytok kyseliny chlorovodíkovej a síran sodný v chladiacej vode sa premieňa v číriacom zariadení pôsobením haseného vápna, Ca(OH)2, na chlorid sodný a sadru, CaSO4.2H2O, kal obsahujúci sadru z číriaceho zariadenia sa spaíuje v kúrenisku elektrárne a síra zo spáleného kalu sa premieňa v prídavnom zariadení pre odsírovanie plynov na sadru.SUMMARY OF THE INVENTION The present invention provides a process for treating a concentrated solution of sodium sulfite, sulphate and thiosulphate, a product liquor from flue gas desulfurization, comprising adding the product liquor to a cooling water having a pH of less than 1 containing hydrochloric acid in a scrubber. for the desulphurization of flue gases from a coal-fired power plant working with limestone, CaCO 3 , or quicklime, CaO, the product liquor being measured by leaving an excess of acid, sulfur dioxide, SO 2 resulting from the reaction of sodium sulfite and sodium thiosulphate with hydrochloric acid in the absorber, excess hydrochloric acid and sodium sulphate in the cooling water are converted into slaked lime, Ca (OH) 2 , into sodium chloride and gypsum, by CaSO 4 .2H 2 O, sludge containing gypsum from the clarifier it burns in the furnace furnace and the sulfur from the burnt sludge is converted into gypsum in an additional desulfurization plant.
f Spôsob pódia vynálezu rieši danú úlohu, pretože ponúka možnosť priviesť produktový lúh do systému, ktorý je k dispozícii a tu spracovať. Preto odpadajú špeciálne zariadenia na úpravy produktového lúhu a nie sú tiež potrebné žiadne prísady, takže je možné spôsob vykonávať neobyčajne hospodárne. Ďalšou výhodou je zníženie množstva haseného vápna potrebného inak na neutralizáciu kyseliny chlorovodíkovej v číriacom zariadení. Voda odvádzaná zo zariadenia na odsírovanie dymových plynov sa nezaťažuje ďalším síranom, pretože síran obsiahnutý prídavné v surovej odpadnej vode sa vyzráža ako sadra. Tiež hodnota chemickej spotreby kyslíka (CHSK), ovplyvnená obsahom organických zložiek vo vode, je iba nepatrná a mení sa v prípustnom rozmedzí. Siričitan a tiosíran nie sú v odpadnej vode dokázateíné.The method according to the invention solves the task by offering the possibility of introducing the product liquor into a system which is available and processed here. Therefore, there are no special plants for treating the product liquor and no additives are required, so that the process can be carried out extremely economically. Another advantage is to reduce the amount of slaked lime needed otherwise to neutralize the hydrochloric acid in the clarifier. The water discharged from the flue gas desulfurization plant is not burdened with additional sulphate, since the sulphate contained in the additional waste water is precipitated as gypsum. Also the value of chemical oxygen consumption (COD), influenced by the content of organic components in water, is only negligible and varies within the permissible range. Sulphite and thiosulphate are not detectable in waste water.
Uvedením produkového lúhu do chladiča síce stúpne koncentrácia síranu a koncentrácia sodíka, avšak nemohol byť zistený vplyv týchto parametrov na absorbér. Naopak sodné soli pozitívne ovplyvňujú znečistenie odlučovača kvapiek v chladiči vďaka zvýšeniu rozpustnosti sadry pôsobením chloridu sodného.While the production liquor was introduced into the cooler, the sulfate and sodium concentrations increased, but the effect of these parameters on the absorber could not be determined. Conversely, sodium salts have a positive effect on the contamination of the droplet separator in the cooler due to the increased solubility of gypsum by sodium chloride.
Prehlad obr;. na výkrese , kAn overview of FIG. in the drawing, k
Obr^CL ukazuje schematicky tok látok vnútri zariadenia na odsírovanie dymových plynov, v ktorom sa produktový lúh spracováva.Fig. CL shows schematically the flow of substances within the flue gas desulfurization plant in which the product liquor is treated.
Vynález je bližšie objasnený v nasledujúcom príklade. Tento príklad má výlučne ilustratívny charakter a rozsah vynálezu v žiadnom ohlade neobmedzuje.The invention is illustrated by the following example. This example is purely illustrative and does not limit the scope of the invention in any way.
Príklad rozpracovania vynálezu m3/h produktového lúhu skladajúceho sa z vodného roztoku síranu sodného (Na2SO4), siričitanu sodného (Na2SO3), j tiosíranu sodného (Na2S2O3) a do komplexu viazanej kyseliny etyléndiamíntetraoctovej (EDTA) sa privádza so 160 kg/h chlorovodíka z dymového plynu elektrárne a 36 t/h vody do predpieracej práčky (chladiča) zariadenia na odsírovanie dymových plynov. Prídavkom produktového lúhu ku kyslej vode v chladiči (pH menšie ako 1) prebiehajú so siričitanom sodným a tiosíranom sodným nasledujúce reakcie:Example of the invention m 3 / h of product liquor consisting of aqueous solution of sodium sulphate (Na 2 SO 4 ), sodium sulphite (Na 2 SO 3 ), sodium thiosulphate (Na 2 S 2 O 3 ) and ethylenediaminetetraacetic acid bound complex ( EDTA) is fed with 160 kg / h of flue gas of the power plant and 36 t / h of water to the scrubber (cooler) of the flue gas desulfurization plant. By adding the product liquor to the acidic water in the condenser (pH less than 1), the following reactions proceed with sodium sulfite and sodium thiosulfate:
HCI + Na2SO3 -> 2 NaCl + H20 + SO2 (l)HCl + Na 2 SO 3 -> 2 NaCl + H 2 0 + SO 2 (l)
HCI + N2S2O3 -> 2 NaCl + S + H2O + S02 (2)HCl + N 2 S 2 O 3 -> 2 NaCl + S + H 2 O + SO 2 (2)
Kyselina chlorovodíková prítomná v chladiči sa tak siričitanom a tiosíranom čiastočne neutralizuje a uvolní sa ekvivalent kyseliny ako oxid siričitý (SO2). Pridávanie pro4 duktového lúhu sa odmeriava tak, aby zostal prebytok kyseliny Týmto spôsobom sa zaistí, aby siričitan a tiosíran v chladiči kvantitatívne zreagoval. Vzniknutý oxid siričitý, v množstve 60 kg/h, sa vyperie v pripojenom absorbéri a spracuje pomocou 29 t/h vody a 100 kg/h vápenca (CaCO3) na sadru.Thus, the hydrochloric acid present in the condenser is partially neutralized with sulfite and thiosulfate, releasing the equivalent of sulfur dioxide (SO 2 ). The addition of the product liquor is measured to leave an excess of acid. In this way it is ensured that the sulphite and the thiosulphate are reacted quantitatively in the condenser. The resulting sulfur dioxide, at a rate of 60 kg / h, is washed in a connected absorber and treated with 29 t / h water and 100 kg / h limestone (CaCO 3 ) to gypsum.
Ťažké kovy sú obsiahnuté v produktovom lúhu len v nepodstatnej koncentrácii, takže sa bilancia ťažkých kovov podstatne nezmení.Heavy metals are contained in the product liquor only at an insignificant concentration, so that the balance of heavy metals does not change significantly.
Síran sodný privádzaný do predpieracej práčky spolu s produktovým lúhom opúšťa systém nezmenený s kalom odpadnej vody odvádzanej do číriaceho zariadenia.The sodium sulphate fed to the scrubber along with the product liquor leaves the system unchanged with the waste water sludge discharged to the clarifier.
Neutralizáciou haseným vápnom [Ca(OH)2] sa vytvorí z prebytočnej kyseliny chlorovodíkovej chlorid vápenatý podlá rovniceBy neutralizing slaked lime [Ca (OH) 2 ], calcium chloride is formed from excess hydrochloric acid according to the equation
Ca(OH)2 + 2HC1 -> CaCl2 + 2H2O (3)Ca (OH) 2 + 2HCl -> CaCl 2 + 2H 2 O (3)
Podvojným rozkladom sa vyzráža z chloridu vápenatého síranom sodným sadra h20Double decomposition precipitated calcium chloride sodium sulfate, gypsum h 2 0
CaCl2 + Na2SO4 -> CaSO4 + 2H2O + 2NaClCaCl 2 + Na 2 SO 4 -> CaSO 4 + 2H 2 O + 2NaCl
Reakcia je úplná, keď sa dodržiava prebytok chloridu vápenatého v množstve 200 kg/h oproti síranu sodnému (90 kg/h).The reaction is complete when an excess of 200 kg / h of calcium chloride is maintained over sodium sulfate (90 kg / h).
Miesto inak obyčajne odvádzaného chloridu vápenatého sa teraz odvádza do kanalizácie ekvivalentné množstvo chloridu sodného.Instead of otherwise removed calcium chloride, an equivalent amount of sodium chloride is now drained into the sewer.
Množstvo odpadnej vody odpadajúce zo zariadenia na odsírovanie dymových plynov sa nemení, pretože sa produktovým lúhom kryje časť potreby prídavnej vody v chladiči. Naproti tomu dôjde k úsporám pri spotrebe vápna v čistiacom zariadení.The amount of waste water from the flue gas desulfurization plant remains unchanged because the product liquor covers part of the make-up water demand in the cooler. On the other hand, there will be savings in lime consumption in the treatment plant.
ľZ 15W-90 TLAČlZ 15W-90 PRINT
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3910130A DE3910130C3 (en) | 1989-03-29 | 1989-03-29 | Process for the preparation of concentrated solutions of sodium sulfite and sodium sulfate originating from flue gas desulfurization |
Publications (2)
Publication Number | Publication Date |
---|---|
SK154890A3 true SK154890A3 (en) | 1999-05-07 |
SK279928B6 SK279928B6 (en) | 1999-05-07 |
Family
ID=6377373
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
SK1548-90A SK279928B6 (en) | 1989-03-29 | 1990-03-29 | Method for processing a concentrated solution of sodium sulphite, sodium sulphate and sodium thiosulphate |
Country Status (6)
Country | Link |
---|---|
CZ (1) | CZ283577B6 (en) |
DE (1) | DE3910130C3 (en) |
ES (1) | ES2019824A6 (en) |
IT (1) | IT1239442B (en) |
RU (1) | RU2049063C1 (en) |
SK (1) | SK279928B6 (en) |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3607357C1 (en) * | 1986-03-06 | 1987-05-07 | Babcock Anlagen Ag | Process for cleaning flue gases containing SO2 |
-
1989
- 1989-03-29 DE DE3910130A patent/DE3910130C3/en not_active Expired - Fee Related
-
1990
- 1990-03-28 IT IT47796A patent/IT1239442B/en active IP Right Grant
- 1990-03-28 ES ES9001119A patent/ES2019824A6/en not_active Expired - Lifetime
- 1990-03-29 CZ CS901548A patent/CZ283577B6/en unknown
- 1990-03-29 SK SK1548-90A patent/SK279928B6/en unknown
- 1990-03-29 RU SU904743537A patent/RU2049063C1/en active
Also Published As
Publication number | Publication date |
---|---|
DE3910130C2 (en) | 1991-01-03 |
ES2019824A6 (en) | 1991-07-01 |
IT9047796A0 (en) | 1990-03-28 |
SK279928B6 (en) | 1999-05-07 |
CZ154890A3 (en) | 1998-02-18 |
DE3910130C3 (en) | 1995-02-09 |
RU2049063C1 (en) | 1995-11-27 |
CZ283577B6 (en) | 1998-05-13 |
IT1239442B (en) | 1993-11-02 |
IT9047796A1 (en) | 1991-09-28 |
DE3910130A1 (en) | 1990-10-04 |
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