NO843385L - PROCEDURE FOR THE PREPARATION OF METHANOLIC GAS - Google Patents

PROCEDURE FOR THE PREPARATION OF METHANOLIC GAS

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Publication number
NO843385L
NO843385L NO843385A NO843385A NO843385L NO 843385 L NO843385 L NO 843385L NO 843385 A NO843385 A NO 843385A NO 843385 A NO843385 A NO 843385A NO 843385 L NO843385 L NO 843385L
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NO
Norway
Prior art keywords
stated
aqueous liquid
steam
gasification
liquid
Prior art date
Application number
NO843385A
Other languages
Norwegian (no)
Inventor
James Ellis Scott
Brian Hoyle Thompson
John Aldwyn Lacey
Original Assignee
British Gas Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by British Gas Corp filed Critical British Gas Corp
Publication of NO843385L publication Critical patent/NO843385L/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02Fixed-bed gasification of lump fuel
    • C10J3/06Continuous processes
    • C10J3/16Continuous processes simultaneously reacting oxygen and water with the carbonaceous material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02Fixed-bed gasification of lump fuel
    • C10J3/06Continuous processes
    • C10J3/08Continuous processes with ash-removal in liquid state
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/093Coal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0959Oxygen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0973Water
    • C10J2300/0976Water as steam
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/16Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656Conversion of synthesis gas to chemicals
    • C10J2300/1662Conversion of synthesis gas to chemicals to methane
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/18Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807Recycle loops, e.g. gas, solids, heating medium, water

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Industrial Gases (AREA)

Description

Foreliggende oppfinnelse angår forgassing av kull.The present invention relates to the gasification of coal.

Under forgassing av kull ved hjelp av damp og oksygen fremkommer en vandig utløpsvæske som hovedsakelig består av løsbare fenolforbindelser, ammoniakk, hydrogensulfid, hydrogensyanid, alkalimetaller og alkalisalter. During the gasification of coal with the help of steam and oxygen, an aqueous effluent is produced which mainly consists of soluble phenolic compounds, ammonia, hydrogen sulphide, hydrogen cyanide, alkali metals and alkali salts.

Denne avløpsvæske kan ikke slippes ut uten forbehandling, da dens behov for biologisk oksygen er altfor stort til at omgivelsene kan ta hånd om dette uten alvorlige ekologiske virkninger. Dette problem er meget mer alvorlig ved aske-slaggende prosesser enn ved tørraske-prosesser, da prosessens dampbehov vanligvis er mindre og de avløpsvæsker som fremkommer som biprodukt har en ten-dens til å være mer konsentrert. This waste liquid cannot be discharged without pre-treatment, as its need for biological oxygen is far too great for the environment to take care of this without serious ecological effects. This problem is much more serious in ash-slagging processes than in dry-ash processes, as the steam requirement of the process is usually less and the waste liquids that appear as a by-product tend to be more concentrated.

Disse avløpsvæsker kan behandles på konvensjonell måte for å fjerne fenoler og ammoniakk før biologisk behandling. Alternativt kan ubehandlet eller delvis behandlet avløpsvæske forbrennes, og etterlater da fast stoff for søppelfylling. Alle disse behandlingsprosesser av av-løpsvann har imidlertid visse ulemper og innebærer tek-nologiske vanskeligheter. These wastewaters can be treated conventionally to remove phenols and ammonia before biological treatment. Alternatively, untreated or partially treated wastewater can be incinerated, leaving solids for landfill. However, all these wastewater treatment processes have certain disadvantages and entail technological difficulties.

Tilbakeføring av vandige avløpsvæsker som oppnås ved damp/oksygen-forgassing av kull er allerede kjent. I PCT-publikasjon nr. WO 80/00974 er det angitt en prosess hvor vandige avløpsvæsker som oppnås under tørraske-forgassing av kull i fast leie tilføres et tilsluttet leie for aske-slaggende forgassing. På lignende måte angir US patentskrift nr. 3971636 tilbakeføring av et vandig kondensat som er separert fra syntesegass oppnådd ved aske-slaggende forgassing av kull i fluidisert leie. I disse eksempler anvendes den vandige avløpsvæske som et redskap for tilførsel av finfordelt kull i form av opp-slemninger til forgassere. Skjønt i alle disse anførte tilfeller primærforgasseren er en aske-slaggende forgass er, arbeider disse i helt forskjellig arbeidsmodi. I ingen av tilfellene er den aske-slaggende forgasser utført som fast leie, og på grunn av dette foreligger åpenbare fordeler i det forhold at et arrangement med ikke fast leie tillater rask oppvarming av avløpsvæsken og således fjerner enhver fare for at reaksjonene skal opphøre. The return of aqueous waste liquids obtained by steam/oxygen gasification of coal is already known. In PCT publication No. WO 80/00974, a process is specified where aqueous waste liquids obtained during dry ash gasification of coal in a fixed bed are supplied to a connected bed for ash-slagging gasification. In a similar manner, US patent document No. 3971636 indicates the return of an aqueous condensate which is separated from synthesis gas obtained by ash-slag gasification of coal in a fluidized bed. In these examples, the aqueous waste liquid is used as a tool for supplying finely divided coal in the form of slurries to gasifiers. Although in all of these cases the primary gasifier is an ash-slagging gasifier, these work in completely different working modes. In none of the cases is the ash-slagging gasifier designed as a fixed bed, and because of this there are obvious advantages in that an arrangement with a non-fixed bed allows rapid heating of the waste liquid and thus removes any danger of the reactions ceasing.

Som det vil fremgå av det som er angitt i WO 80/00974, tilbakeføres den væske som oppnås fra trinnet med fast leie bare til det tilkoblede trinn. As will be apparent from what is stated in WO 80/00974, the liquid obtained from the fixed bed stage is returned only to the connected stage.

Ut i fra en betraktning av tidligere kjent teknikk kan det således ikke forventes at tilbakeført væskeinnsprøyt-ning med hell kan oppnås ved aske-slaggende forgassere i fast leie. I henhold til oppfinnelsen er det imidlertid overraskende funnet at ved effektiv drift av kullfor-gassing i fast leie kan aske-slagging oppnås ved direkte innsprøyting av vandig væske sammen med andre forgassingsmidler, samt at i tilfelle en sådan væske er en av-løpsvæske, kan utslippsproblemet i vesentlig grad over-vinnes . Based on a consideration of previously known technology, it can thus not be expected that reverse liquid injection can be successfully achieved with ash-slagging gasifiers in a fixed bed. According to the invention, however, it has surprisingly been found that with efficient operation of coal gasification in a fixed bed, ash slagging can be achieved by direct injection of an aqueous liquid together with other gasification agents, and that in the event such a liquid is a waste liquid, the emissions problem is largely overcome.

Foreliggende oppfinnelse gjelder således en fremgangsmåte for fremstilling av metan-holdige gasser, hvorunder et råstoff som omfatter fast karbonholdig material, forgasses i nærvær av damp og oksygen som forgassingsmiddel under aske-slaggende forhold i fast leie, og produktgassen etterbehandles for å befries for ureagert damp. Denne fremgangsmåte har da som særtrekk i henhold til oppfinnelsen at i det minste en del av reaksjonens gass-behov dekkes ved tilsats av en vandig væske i blanding med de øvrige forgassingsmidler. The present invention thus relates to a method for the production of methane-containing gases, during which a raw material comprising solid carbonaceous material is gasified in the presence of steam and oxygen as a gasification agent under ash-slagging conditions in a fixed bed, and the product gas is post-treated to free it of unreacted steam . This method then has as a distinctive feature according to the invention that at least part of the gas requirement of the reaction is covered by the addition of an aqueous liquid in mixture with the other gasification agents.

Den vandige væske er fortrinnsvis avløpsvæske som er fremkommet ved behandlingen av produktgassen. Den vandige væske kan imidlertid også utgjøres av renere former av vann, slik som det som anvendes for kjøleformål eller kjelemating. The aqueous liquid is preferably waste liquid which has resulted from the treatment of the product gas. However, the aqueous liquid can also be made up of purer forms of water, such as that used for cooling purposes or boiler feed.

Den tilbakeførte væske føres inn i det punkt hvor de øvrige forgassingsmidler tilsettes, nemlig gjennom slanger inn i matebanen. I praksis vil imidlertid damp-uttaket og tilførselsslangene være modifisert til å frem-bringe væske eller vann på det sted hvor dampen innføres. The returned liquid is fed into the point where the other gasification agents are added, namely through hoses into the feed path. In practice, however, the steam outlet and supply hoses will be modified to produce liquid or water at the place where the steam is introduced.

Tilsats av vandige bestanddeler medfører et antall overraskende fordeler, skjønt det var å forvente at sådant tilsats kunne ha en ugunstig virkning på arbeidsfunksjon-en av enten forgasseren eller de slaggtappende prosesser. I ingen av disse tilfeller ble det imidlertid merket vanskeligheter. Oksygenforbruket (på grunnlag av den forbrukte mengde av karbonmaterial) ble funnet å ha øket svakt, men dette ble mer enn utlignet ved innsparte om-kostninger ved ikke å utvikle damp. I tillegg ligger en betraktelig fordel i det forhold at hvis vedkommende væske utgjøres av vandig avløpsvæske er det ikke bare en vesentlig besparelse ved å være i stand til å anvende vannet på nytt, men også i at de oppløste og oppslemmede materialer blir borte i reaktoren. De organiske bestanddeler er naturligvis anvendbare som reaktant. The addition of aqueous components provides a number of surprising advantages, although it was to be expected that such addition could have an adverse effect on the working performance of either the gasifier or the slag draining processes. However, in none of these cases were difficulties noted. Oxygen consumption (on the basis of the amount of carbonaceous material consumed) was found to have increased slightly, but this was more than offset by the overheads saved by not generating steam. In addition, a considerable advantage lies in the fact that if the liquid in question consists of aqueous wastewater, there is not only a significant saving by being able to use the water again, but also in that the dissolved and suspended materials are lost in the reactor. The organic components are of course usable as a reactant.

Ved tilbakeføring av væske på denne måte nedsettes således i betraktelig grad dampbehovet ved forgassing, f.eks. til omkring 50% hvis hovedsakelig all væske som normalt frembringes fra bitumært kull tilbakeføres. Opptil 50% av den totale andel av H^ O som kreves for forgassingsreaksjonen kan foreligge som vandig væske, enten som vann i og for seg eller som tilbakeført avfallsvæske. En ytterligere fordel er at innorganisk material som inneholdes i avløpsvæsken tas opp av slagget og således fjernes fra systemet sammen med dette. Tungmetallinn-holdet i slagget, f.eks. sirkonium,økes sammenlignet med det tilfelle ingen væskeinnsprøytning anvendes. En av- tapping av noe av vassken kan væreønskelig for behandling med det formål å fjerne klorider og andre salter når opp-bygning av disse bestanddeler i den tilbakeførte væske begynner å finne sted. Den vandige væske kan inneholde visse organiske bestanddeler som er oppløst eller emul-gert i væsken. I tillegg kan vedkommende væske også anvendes som redskap for å overføre oppslemmet fast material, f.eks. finfordelt kull, til reaktoren. By returning liquid in this way, the steam requirement for gasification is thus considerably reduced, e.g. to around 50% if mainly all liquid normally produced from bituminous coal is returned. Up to 50% of the total proportion of H^O required for the gasification reaction can be present as an aqueous liquid, either as water in and of itself or as returned waste liquid. A further advantage is that inorganic material contained in the waste liquid is taken up by the slag and thus removed from the system together with it. The heavy metal content in the slag, e.g. zirconium, is increased compared to the case where no liquid injection is used. A draining of some of the liquid may be desirable for treatment with the purpose of removing chlorides and other salts when build-up of these components in the returned liquid begins to take place. The aqueous liquid may contain certain organic components which are dissolved or emulsified in the liquid. In addition, the liquid in question can also be used as a tool to transfer suspended solid material, e.g. finely divided coal, for the reactor.

Oppfinnelsen vil nå bli nærmere anskueliggjort ved hjelp av følgende utførelseeksempel: Et aske-slaggende kullforgassingsanlegg med fast leie, f.eks. av den art som er angitt i "The Chemistry of Coal Utilization", annet tilleggsbind, 1981, utgitt av John Wiley & Son, Inc, ble modifisert for å tillate innsprøyt-ning av flytende vanntilsatser nedover innblåsningsrørene for damp og oksygen. Anlegget ble satt i gang i samsvar med konvensjonell teknikk for damp/oksygen-forgassing på grunnlag av kull av typen Markam Mains ved et arbeids-trykk på 24,78 bar(g). Tilførselstaktene for reaktant og gassproduksjonstakten er summert opp i følgende tabell. The invention will now be illustrated more closely with the help of the following design example: An ash-slagging coal gasification plant with a fixed rent, e.g. of the type set forth in "The Chemistry of Coal Utilization", Second Supplemental Volume, 1981, published by John Wiley & Son, Inc, was modified to permit the injection of liquid water additives down the steam and oxygen inlet tubes. The plant was commissioned in accordance with conventional technique for steam/oxygen gasification on the basis of coal of the Markam Mains type at a working pressure of 24.78 bar(g). The supply rates for reactant and the gas production rate are summarized in the following table.

I spalte A er reaksjonstaktene før væskeinnsprøytning angitt. Væskeinnsprøytningen ble øket trinnvis som vist i spaltene B, C og D over en periode på 21 timer. In column A, the reaction rates before liquid injection are indicated. The liquid injection was increased stepwise as shown in columns B, C and D over a period of 21 hours.

Claims (6)

1. Fremgangsmåte for fremstilling av metan-holdige gasser, hvorunder et råstoff som omfatter fast karbonholdig material, forgasses i nærvær av damp og oksygen som forgassingsmidler under aske-slaggende forhold i fast leie, og produktgassen etterbehandles for å befries for ureagert damp, karakterisert ved at i det minste en del av reaksjonens dampbehov dekkes ved tilsats av en vandig væske i blanding med de øvrige forgassingsmidler.1. Process for the production of methane-containing gases, during which a raw material comprising solid carbonaceous material is gasified in the presence of steam and oxygen as gasification agents under ash-slagging conditions in a fixed bed, and the product gas is post-treated to free it from unreacted steam, characterized in that at least part of the reaction's steam requirement is covered by the addition of an aqueous liquid in mixture with the other gasification agents. 2. Fremgangsmåte som angitt i krav 1, karakterisert ved at nevnte vandige væske utgjøres av vanlig vann.2. Method as stated in claim 1, characterized in that said aqueous liquid consists of ordinary water. 3. Fremgangsmåte som angitt i krav 1, karakterisert ved at nevnte vandige væske omfatter en avlø psvæske med innhold av kondensert ureagert damp, vannlø selige forbindelser og kondenserte organiske forbindelser som er oppnådd ved behandling av nevnte produktgass.3. Method as stated in claim 1, characterized in that said aqueous liquid comprises a waste liquid containing condensed unreacted steam, water-soluble compounds and condensed organic compounds obtained by treating said product gas. 4. Fremgangsmåte som angitt i krav 2 eller 3, karakterisert ved at opptil 50% av det F^O som er påkrevet for forgassingsreaksjonen tilføres som vandig væske.4. Method as stated in claim 2 or 3, characterized in that up to 50% of the F^O required for the gasification reaction is supplied as an aqueous liquid. 5. Fremgangsmåte som angitt i krav 1, karakterisert ved at nevnte vandige væske utgjør et bæreredskap for oppslemmede materialer.5. Method as stated in claim 1, characterized in that said aqueous liquid constitutes a carrier for slurried materials. 6. Fremgangsmåte som angitt i krav 6, karakterisert ved at nevnte oppslemmede materialer er finfordelt kull.6. Method as stated in claim 6, characterized in that said slurried materials are finely divided coal.
NO843385A 1983-08-25 1984-08-24 PROCEDURE FOR THE PREPARATION OF METHANOLIC GAS NO843385L (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB838322899A GB8322899D0 (en) 1983-08-25 1983-08-25 Coal gasification process

Publications (1)

Publication Number Publication Date
NO843385L true NO843385L (en) 1985-02-26

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ID=10547868

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Application Number Title Priority Date Filing Date
NO843385A NO843385L (en) 1983-08-25 1984-08-24 PROCEDURE FOR THE PREPARATION OF METHANOLIC GAS

Country Status (10)

Country Link
EP (1) EP0148554B1 (en)
JP (1) JPS6076593A (en)
KR (1) KR860001121B1 (en)
CS (1) CS265208B2 (en)
DE (1) DE3474685D1 (en)
GB (3) GB8322899D0 (en)
IN (1) IN162228B (en)
NO (1) NO843385L (en)
PL (1) PL145182B1 (en)
ZA (1) ZA846540B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0220342A1 (en) * 1985-11-01 1987-05-06 Metallgesellschaft Ag Process for treating an aqueous condensate
DE102006041838B4 (en) * 2006-09-04 2010-08-05 Siemens Aktiengesellschaft Process for gasifying solid gasification substances in slag bath gasification reactors
CN101812323B (en) * 2009-08-14 2013-02-13 赛鼎工程有限公司 Method for using multi-element mixed gasification agent to prepare synthesis gas by dry slagging of fixed bed
DE102013113769B4 (en) * 2013-12-10 2020-07-16 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Process for the fixed bed pressure gasification of carbonaceous fuels

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB237883A (en) * 1924-07-29 1926-12-20 Louis Chavanne Improved process and apparatus for the gasification of solid fuel, applicable also to volatilizing or reducing ores
GB717484A (en) * 1952-01-17 1954-10-27 Kloeckner Humboldt Deutz Ag A method and a device for the disposal of phenol-containing waste water
DE1496384A1 (en) * 1965-12-31 1969-05-14 Projektierungs Konstruktions U Procedure for the containment and removal of the dust from the raw gas and the condensates during pressure gasification
NL189517C (en) * 1974-12-05 1993-05-03 Shell Int Research PROCESS FOR THE PREPARATION OF SYNTHESIS GAS.
US3971636A (en) * 1974-12-23 1976-07-27 Gulf Oil Corporation Condensate scrubbing of coal gasifier product
DE2607745C2 (en) * 1976-02-26 1984-03-15 Metallgesellschaft Ag, 6000 Frankfurt Process for treating condensate from the cooling of raw gas from the pressurized gasification of solid fuels
US4175929A (en) * 1978-08-29 1979-11-27 The United States Of America As Represented By The United States Department Of Energy Process for control of pollutants generated during coal gasification
US4199327A (en) * 1978-10-30 1980-04-22 Kaiser Engineers, Inc. Process for gasification of coal to maximize coal utilization and minimize quantity and ecological impact of waste products
JPS5699295A (en) * 1979-12-29 1981-08-10 Chiyouei Ko Gas generator
SE434163B (en) * 1981-03-10 1984-07-09 Skf Steel Eng Ab SET AND DEVICE FOR PREPARING A MAIN COOLOXIDE AND VETGAN CONTAINING GAS FROM COAL AND / OR CARBON-CONTAINING INGREDIENTS
EP0083670A1 (en) * 1982-01-07 1983-07-20 Ruhrkohle Aktiengesellschaft Process for the elimination of process water effluents containing tar acids
GB2116580B (en) * 1982-03-12 1985-04-11 British Gas Corp Gasifying coal in fixed bed ash-slagging gasifier

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CS642384A2 (en) 1988-07-15
DE3474685D1 (en) 1988-11-24
GB2146039B (en) 1987-10-14
KR860001121B1 (en) 1986-08-13
GB8420360D0 (en) 1984-09-12
PL249331A1 (en) 1985-05-07
EP0148554A2 (en) 1985-07-17
GB2146039A (en) 1985-04-11
JPS6076593A (en) 1985-05-01
EP0148554B1 (en) 1988-10-19
GB8322899D0 (en) 1983-09-28
PL145182B1 (en) 1988-08-31
ZA846540B (en) 1985-03-27
KR850001919A (en) 1985-04-10
IN162228B (en) 1988-04-16
GB8421038D0 (en) 1984-09-19
EP0148554A3 (en) 1986-01-22
CS265208B2 (en) 1989-10-13

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