SE505270C2 - Black liquor combustion with mesate additive - Google Patents
Black liquor combustion with mesate additiveInfo
- Publication number
- SE505270C2 SE505270C2 SE9301920A SE9301920A SE505270C2 SE 505270 C2 SE505270 C2 SE 505270C2 SE 9301920 A SE9301920 A SE 9301920A SE 9301920 A SE9301920 A SE 9301920A SE 505270 C2 SE505270 C2 SE 505270C2
- Authority
- SE
- Sweden
- Prior art keywords
- mesa
- combustion
- temperature
- combustion chamber
- black liquor
- Prior art date
Links
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 40
- 239000000654 additive Substances 0.000 title 1
- 230000000996 additive effect Effects 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000011084 recovery Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- AGVJBLHVMNHENQ-UHFFFAOYSA-N Calcium sulfide Chemical compound [S-2].[Ca+2] AGVJBLHVMNHENQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 5
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 5
- 239000004571 lime Substances 0.000 abstract description 5
- 239000010802 sludge Substances 0.000 abstract 4
- 241001062472 Stokellia anisodon Species 0.000 abstract 1
- 238000001354 calcination Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 101100348017 Drosophila melanogaster Nazo gene Proteins 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/04—Regeneration of pulp liquors or effluent waste waters of alkali lye
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/0085—Introduction of auxiliary substances into the regenerating system in order to improve the performance of certain steps of the latter, the presence of these substances being confined to the regeneration cycle
- D21C11/0092—Substances modifying the evaporation, combustion, or thermal decomposition processes of black liquor
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/12—Combustion of pulp liquors
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/04—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Paper (AREA)
- Gasification And Melting Of Waste (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
Description
505 270 I 2 10 15 20 25 30 liema återvinns. Normalt överförs svavelinnehållet till för kokprocessen aktiv form, dvs till sulfid. Den del av natriumet som inte är bundet till svavel föreligger i huvudsak som karbonat. 505 270 I 2 10 15 20 25 30 liema recycled. Normally the sulfur content is transferred to an active form for the cooking process, ie to sul fi d. The part of the sodium which is not bound to sulfur is mainly present as carbonate.
De oorganiska kemikaliema lämnar förbränningsprocessen i huvudsak i smält form (exempelvis vid 750-850°C) och vidarebehandlas för återvinning av kemikaliema.The inorganic chemicals leave the combustion process mainly in molten form (for example at 750-850 ° C) and further processed for recycling of the chemicals.
Vid sådan vidarebehandling bildas bland annat svårlöslig CaC03, som kallas mesa. Denna tvättas med vatten före ombränning i roterugn, varvid en svagt alkalisk lösning (svaglut) erhålles. Ombränningen av mesan, dvs omvandlingen av CaCOa till CaO, är energikrävande och ställer höga krav på bränslets kvalitet, så att en hög flamtemperatur kan upprätthållas i roterugnens kalcineringszon.During such further treatment, among other things, sparingly soluble CaCO 3 is formed, which is called mesa. This is washed with water before burning in a rotary kiln, whereby a slightly alkaline solution (weak liquor) is obtained. The combustion of mesa, ie the conversion of CaCO 2 to CaO, is energy-intensive and places high demands on the quality of the fuel, so that a high fl am temperature can be maintained in the calcination zone of the rotary kiln.
Normalt åtgår ca 40-45 % av bränslets effektiva värme för kalcineringsreaktionen, varvid 15-20 % av förbrukat bränsle förloras genom vännestrålning från ugnens mantelyta och kalkkylare.Normally, about 40-45% of the fuel's efficient heat is consumed for the calcination reaction, whereby 15-20% of spent fuel is lost through friend radiation from the furnace's surface and lime cooler.
Vid försök i syfte att förbättra utnyttjandet av en lutförbränningsanläggning har man nu överraskande funnit att anläggningen kan användas för samtidig förbränning av svartlut och bearbetning av mesa, och att förbränningsförloppet modifieras i förbränningsrummet när svartlut förbränns i närvaro av en lämplig mängd mesa.In attempts to improve the utilization of an alkali incineration plant, it has now surprisingly been found that the plant can be used for simultaneous combustion of black liquor and processing of mesa, and that the combustion process is modified in the combustion chamber when black liquor is burned in the presence of a suitable amount of mesa.
El.. E.El .. E.
Uppfinningen är inriktad på samtidig förbränning av svartlut och bearbetning av meSa.The recovery is focused on simultaneous combustion of black liquor and processing of meSa.
Uppfinningen avser ett sätt att modifiera förbränningsförloppet i en sodapannas förbränningsrum vid förbränning av indunstad svartlut, genom att till förbrännings- rummet tillförs mesa, varigenom förbränningsförloppet modifieras så att temperaturen i förbränningsrummet höjs. och samtidigt bearbetas den tillförda 10 15 20 25 30 3 505 270 mesan, varvid typen av bearbetning av mesa styrs genom reglering av temperaturen iförbränningsrummet.The invention relates to a method of modifying the combustion process in the combustion chamber of a recovery boiler when burning evaporated black liquor, by adding mesa to the combustion chamber, whereby the combustion process is modified so that the temperature in the combustion chamber is raised. and at the same time the supplied mesa is processed, the type of processing of mesa being controlled by controlling the temperature in the combustion chamber.
Temperaturen i förbränningsrummet kan regleras så att mesan åtminstone partiellt kalcineras. Därtill kan temperaturen regleras så att mesan ger ökad bildning av kalciumsulfid iden iförbränningsanläggningen bildade smältan av oorganiska kemikalier.The temperature in the combustion chamber can be regulated so that the mesa is at least partially calcined. In addition, the temperature can be regulated so that the mesa increases the formation of calcium sulphide during the incineration plant formed the melt of inorganic chemicals.
Utnyttjande av sådan kalciumsulfidrik smälta av oorganiska kemikalier för framställning av vitlut med förhöjd och/eller minskad sulfiditet har beskrivits i den samtidigt inlämnade patentansökningen med titeln 'Vitlutsframställningï I en föredragen utföringsfonn av uppfinningen blandas svartluten och mesan innan de tillförs förbränningsrummet.Utilization of such calcium sulphide beverage melt of inorganic chemicals for the production of white liquor with increased and / or reduced sulphide has been described in the co-pending patent application entitled 'White liquor production'.
Den mängd mesa som skall tiilföras för att förbränningsförloppet skall modifieras, beror på flera processparametrar som kan variera mellan olika lutförbrännings- anläggningar. Dock kan en fackman med ledning av föreliggande beskrivning av uppfinningen, lätt avpassa den mängd mesa som krävs för att modifiera förbränningsförloppet i förbränningsrummet hos lutförbränningsanläggningar där föreliggande uppfinning kan utnyttjas.The amount of mesa that must be supplied in order for the combustion process to be modified depends on your process parameters, which can vary between different lye incineration plants. However, a person skilled in the art can, based on the present description of the invention, easily adjust the amount of mesa required to modify the combustion process in the combustion chamber of lye incineration plants where the present invention can be used.
Temperaturen i förbränningsrummet kan styras så att mesa åtminstone partiellt kalcineras och/eller att mesan ger ökad bildning av kalciumsulfid i den i förbränningsanläggningen bildade smältan av oorganiska kemikalier. Avgörande är, om temperaturen i förbränningsrummet når kalcineringstemperatur för mesa, eller om temperaturen hålles därunder. I nedanstående fonnler, som beskriver reaktionen med mesa (CaCO3) vid förbränning med svartlut har kalcinerings- temperaturen satts till 800°C, men den kan variera avsevärt, t ex med 1 70°C. 505 270 i 4 10 15 20 25 30 1. CaCO3 + Na2S -> CaS + Na2C03 över 600°C 2. CaS + Na2CO3 --> CaO + NazS + C02 över 800°C 3. CaO + NazS --> CaS + NazO under 800°C Vid fabriksförsök konstaterades följande samband: A caco3 _» oas .,_-----= cao 0% (1øo-A+B)% B (A-Bm l nedan beskrivna fabriksförsök var A =64,7 och B=44,9, dvs CaS=80,2 % och CaO=19,8 %. l ett laboratoneförsök med 10 g smälta + 1,9 g mesa erhölls, vid 750°C, 15 minuter, A=0 och B=0, med 75 % av Ca som CaS.The temperature in the combustion chamber can be controlled so that the mesa is at least partially calcined and / or that the mesa increases the formation of calcium sulphide in the melt formed by the incineration plant of inorganic chemicals. Decisive is whether the temperature in the combustion chamber reaches the calcination temperature of the mesa, or whether the temperature is kept below it. In the following formulas, which describe the reaction with mesa (CaCO3) during combustion with black liquor, the calcination temperature has been set to 800 ° C, but it can vary considerably, for example by 1,70 ° C. 505 270 i 4 10 15 20 25 30 1. CaCO3 + Na2S -> CaS + Na2CO3 over 600 ° C 2. CaS + Na2CO3 -> CaO + NazS + CO2 over 800 ° C 3. CaO + NazS -> CaS + NazO below 800 ° C In factory experiments the following correlations were found: A caco3 _ »oas., _----- = cao 0% (1øo-A + B)% B (A-Bm l the factory experiments described below were A = 64, 7 and B = 44.9, i.e. CaS = 80.2% and CaO = 19.8% In a laboratory experiment with 10 g melt + 1.9 g mesa was obtained, at 750 ° C, 15 minutes, A = 0 and B = 0, with 75% of Ca as CaS.
Vid fabriksförsök förblandades svartlut med mesa i ungefärligt torrsubstans- förhållande av 1521, (vilket motsvarade 20-30 % av den i processen uppkomna mesamängden) och tillfördes sodapannans förbränningsrum vid nonnal kapacitet.In factory experiments, black liquor was premixed with mesa in an approximately dry matter ratio of 1521, (which corresponded to 20-30% of the amount of mesa formed in the process) and was added to the incineration chamber's combustion chamber at normal capacity.
Den omfattande uppföljningen av analyseringen av försöken gav i samfattning följande resultat: - Smältans temperatur steg med ca 100°C, vilket indikerar en betydande höjning av förbränningsrumstemperaturen.In summary, the extensive follow-up of the analysis of the experiments gave the following results: - The temperature of the melt rose by about 100 ° C, which indicates a significant increase in the combustion chamber temperature.
- Stofthalten i rökgasema före elfiltren minskade med ca 40%.- The dust content in the flue gases before the electricity decreased by about 40%.
- Stoft-pH steg från 9,8 till 10,4 trots en minskad halt NazCOa i stoftet.- Dust pH rose from 9.8 to 10.4 despite a reduced content of NazCOa in the dust.
- Temperaturen på utgående överhettad ånga steg med ca 15°C under försöket, för att därefter återgå till en lägre nivå.- The temperature of outgoing superheated steam rose by about 15 ° C during the experiment, to then return to a lower level.
- Ca 65 % av tillsatt CaCOS hade reagerat till CaO enligt formel 1 ovan.About 65% of added CaCOS had reacted to CaO according to formula 1 above.
Anledningen till modifieringen av förbränningsförloppet, som ovanstående är uttryck för, är inte klarlagd, men den vid samtidig förbränning av svartlut och bearbetning av mesa bildade koldioxiden (enligt formel 2 ovan) torde ha betydelse för modifieringen. 10 15 20 s 505 270 Förhöjda temperaturer i en sodapannas förbränningsrum ger följande fördelar vid lutförbränning: Värrneupptagningen i förbränningsrummets nedre del förbättras markant.The reason for the modification of the combustion process, as expressed above, is not clear, but the carbon dioxide formed during the simultaneous combustion of black liquor and processing of mesa (according to formula 2 above) should be important for the modification. 10 15 20 s 505 270 Elevated temperatures in the combustion chamber of a recovery boiler provide the following advantages in the case of lye combustion: The heat absorption in the lower part of the combustion chamber is markedly improved.
Svavelreduktionen förbättras.Sulfur reduction is improved.
Stottavgången med rökgasema från förbränningsrumsnivån minskar avsevärt (i ovanstående exempel ca 40 %).The exhaust emission with the flue gases from the combustion chamber level decreases considerably (in the above example about 40%).
Stoftets karaktär ändras till det bättre, vilket minskar igensättningen av rökgasstråken i pannan samt underlättar rengöringen av vänneytoma och minskar sotångförbrukningen. i Minskade beläggningar på överhettarytor ger högre utgående ång- temperatur och därmed ökad elproduktion. Ökad kalcinering i sodapannan. Ökning av lutförbränningskapaciteten.The character of the dust changes for the better, which reduces the clogging of the flue gas streams in the boiler and facilitates the cleaning of the friend surfaces and reduces soot steam consumption. i Reduced coatings on superheated surfaces result in higher outgoing steam temperature and thus increased electricity production. Increased calcination in the recovery boiler. Increase in lye combustion capacity.
Andra fördelar som kan vinnas med att utföra bearbetning av mesa i sodapannan, är att kalcineringen kan ske med ett billigare bränsle och med lägre energibehov, på grund av att de stora strålningsförluster som uppstår i en roterugnsprocess undviks. Dessutom kan temperaturen i förbränningsrummet regleras så att bearbetningen styrs till bildning av ökade mängder kalciumsulfid i smältan av oorganiska kemikalier, om detta anses vara önskvärt.Other advantages that can be gained from performing processing of mesa in the recovery boiler are that the calcination can take place with a cheaper fuel and with lower energy requirements, due to the large radiation losses that occur in a rotary kiln process. In addition, the temperature in the combustion chamber can be regulated so that the processing is controlled to form increased amounts of calcium sulfate in the melt of inorganic chemicals, if this is considered desirable.
Claims (4)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE9301920A SE505270C2 (en) | 1993-06-04 | 1993-06-04 | Black liquor combustion with mesate additive |
| PCT/SE1994/000536 WO1994029518A1 (en) | 1993-06-04 | 1994-06-03 | Combustion of black liquor and processing of lime sludge in a recovery boiler |
| CA002164328A CA2164328C (en) | 1993-06-04 | 1994-06-03 | Combustion of black liquor and processing of lime sludge in a recovery boiler |
| FI955806A FI117564B (en) | 1993-06-04 | 1995-12-01 | Combustion of black liquor and treatment of mesa in a recovery boiler |
| US08/966,558 US5922172A (en) | 1993-06-04 | 1997-11-10 | Combustion of black liquid and processing of lime sludge in a recovery boiler |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE9301920A SE505270C2 (en) | 1993-06-04 | 1993-06-04 | Black liquor combustion with mesate additive |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| SE9301920D0 SE9301920D0 (en) | 1993-06-04 |
| SE9301920L SE9301920L (en) | 1994-12-05 |
| SE505270C2 true SE505270C2 (en) | 1997-07-28 |
Family
ID=20390168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE9301920A SE505270C2 (en) | 1993-06-04 | 1993-06-04 | Black liquor combustion with mesate additive |
Country Status (4)
| Country | Link |
|---|---|
| CA (1) | CA2164328C (en) |
| FI (1) | FI117564B (en) |
| SE (1) | SE505270C2 (en) |
| WO (1) | WO1994029518A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE500660C2 (en) * | 1992-12-03 | 1994-08-01 | Mo Och Domsjoe Ab | Process for the production of green liquor in chemical recycling in sulphate and sulphite pulp mills |
| GB0325578D0 (en) * | 2003-11-03 | 2003-12-03 | Bioregional Minimills Uk Ltd | Method for treating black liquor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3366535A (en) * | 1966-07-11 | 1968-01-30 | William T Neiman | Process for regenerating waste liquor for reuse in kraft pulping operation |
| FR2550245B3 (en) * | 1983-08-04 | 1986-02-28 | Nivelleau Bruniere Patrick M F | PROCESS FOR THE COMBUSTION OF WASTE BLACK LIQUORS FROM THE MANUFACTURE OF CELLULOSIC PASTE |
-
1993
- 1993-06-04 SE SE9301920A patent/SE505270C2/en unknown
-
1994
- 1994-06-03 WO PCT/SE1994/000536 patent/WO1994029518A1/en not_active Ceased
- 1994-06-03 CA CA002164328A patent/CA2164328C/en not_active Expired - Fee Related
-
1995
- 1995-12-01 FI FI955806A patent/FI117564B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FI955806A0 (en) | 1995-12-01 |
| CA2164328C (en) | 2005-04-12 |
| SE9301920D0 (en) | 1993-06-04 |
| SE9301920L (en) | 1994-12-05 |
| FI955806L (en) | 1995-12-01 |
| WO1994029518A1 (en) | 1994-12-22 |
| FI117564B (en) | 2006-11-30 |
| CA2164328A1 (en) | 1994-12-22 |
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