DK172993B1 - Process for wet flue gas desulphurisation and apparatus for implementing it - Google Patents

Process for wet flue gas desulphurisation and apparatus for implementing it Download PDF

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Publication number
DK172993B1
DK172993B1 DK199700036A DK3697A DK172993B1 DK 172993 B1 DK172993 B1 DK 172993B1 DK 199700036 A DK199700036 A DK 199700036A DK 3697 A DK3697 A DK 3697A DK 172993 B1 DK172993 B1 DK 172993B1
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washer
flue gas
absorbent
container
sump
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DK199700036A
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Danish (da)
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DK3697A (en
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Helmut Welp
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Krc Umwelttechnik Gmbh
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    • 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
    • B01D53/504—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 device

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)

Description

i DK 172993 B1in DK 172993 B1

Opfindelsen angår en fremgangsmåde til våd røggasafsvovling i en vasker med sprøjteindretninger til absorptionsmidlet og en beholder til absorptionsmidlet på basis af suspensioner, der indeholder calciumforbindelser, og hvor det calciumsulfit, 5 der opstår til at begynde med, i det mindste delvis også kan oxideres til calciumsulfat ved hjælp af luftens oxygen eller røggassens restoxygen.BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a wet flue gas desulphurisation process in an absorbent washer washer and an absorbent container based on suspensions containing calcium compounds and at least partially capable of oxidizing calcium sulfite to calcium sulfate. using the oxygen of the air or the residual oxygen of the flue gas.

Ved fremgangsmåden og indretningen til gennemførelse af denne fremgangsmåde har det hidtil været almindeligt, at anbringe 10 beholderen til absorptionsmidlet neden under vaskeren og forsyne sprøjteindretningerne fra denne beholder.In the method and device for carrying out this method, it has hitherto been customary to place the container of the absorbent below the washer and to supply the spraying devices from this container.

Denne beholder er ved enkreds-røggasafsvovlingsanlæg en ren forrådsbeholder, i hvilken absorptionsmidlet eventuelt også udrøres eller tilmæskes. Ved tokreds-røggasafsvovlingsanlæg 15 bliver en del af det øvre kredsløbs forbrugte absorptionsmiddel ført tilbage til denne beholder, så at reaktionen mellem svovloxidforbindelserne og calciumforbindelserne fortsætter der.This container is a single storage tank in a single-circuit flue gas desulphurisation system, in which the absorbent is also possibly stirred or soaked. At two-circuit flue gas desulphurisation plant 15, a portion of the upper circuit's consumed absorbent is returned to this container so that the reaction between the sulfur oxide compounds and the calcium compounds continues there.

Disse fremgangsmåder og indretninger har i princippet vist 20 deres værdi, men der er dog et behov for at sænke energiforbruget og investeringsomkostningerne yderligere. Endvidere er der et behov for at forøge driftsikkerheden, især under skiftende røggasmængder og svovlbelastning. Endvidere er der et behov for at holde pladsbehovet for sådanne indretninger så 25 lavt som muligt.These methods and devices have in principle shown their value, but there is a need, however, to further reduce energy consumption and investment costs. Furthermore, there is a need to increase reliability, especially under changing flue gas volumes and sulfur loading. Furthermore, there is a need to keep the space requirement for such devices as low as possible.

Disse formål kan overraskende let opnås ved at absorptionsmidlet tilvejebringes i vaskerens indre i en opadtil åben beholder, og efter vaskeoperationen i det mindste delvis atter opfanges i denne, og at væskeoverfladen i beholderen lig-30 ger højere end væskeoverfladen i vaskerens sump.Surprisingly, these objects can easily be achieved by the absorbent being provided in the interior of the washer in an upwardly open container and, after the washing operation, at least partially recaptured therein and the liquid surface of the container being higher than the liquid surface in the sump of the washer.

Fortrinsvis udtages absorptionsmidlet tæt oven over forråds-beholderens bund og først uden for vaskeren fordeles til 2 DK 172993 B1 sprøjteindretningerne. Det har den fordel, at aflejringer kan undgås på bunden af beholderen, og sprøjteindretningerne kan , efterses og renses separat, især sierne foran sprøjtedyserne.Preferably, the absorbent is withdrawn tightly above the bottom of the storage container and first distributed outside the washer to the spraying devices. It has the advantage that deposits can be avoided on the bottom of the container, and the spraying devices can be inspected and cleaned separately, especially the grouts in front of the spray nozzles.

! Endvidere har det vist sig hensigtsmæssigt, at den røggas, 5 der skal renses, ledes ind i vaskeren oven over sumpens væ-s skeoverflade. Dette medfører en forlængelse af røggasbanen i vaskerens nedre del og forøger dermed vaskeoperationens effektivitet. Ved denne variant af fremgangsmåden er det fordelagtigt at røggassen, allerede inden den kommer ind i va-10 skeren, afkøles eller eventuelt sågar forvaskes. Derfor bliver røggasstrømmen allerede besprøjtet, før den kommer ind i den egentlige vasker og dette enten med vand eller med absorptionsmiddel. Ved denne forkøling kort før indstrømningen i vaskeren bliver der atter sparet plads, og investeringsom-15 kostningerne bliver derved også sænket. Herved har det vist sig fordelagtigt, at der sprøjtes i medstrøm, idet trykfaldet derved formindskes, og sprøjtedysernes impuls adderes til røggassens hastighed.! Furthermore, it has been found convenient that the flue gas to be purified is fed into the washer above the liquid surface of the sump. This results in an extension of the flue gas path in the lower part of the washer, thus increasing the efficiency of the washing operation. In this variant of the process, it is advantageous for the flue gas to be cooled or possibly pre-washed, even before it enters the dryer. Therefore, the flue gas stream is already sprayed before it enters the actual washer and this either with water or with absorbent. With this cold shortly before the inflow into the washer space is saved again, and the investment costs are thereby also lowered. Hereby, it has been found advantageous to co-spray, thereby reducing the pressure drop and adding the spray nozzle impulse to the flue gas velocity.

Samtidig medfører dette en bedre fordeling af absorptionsmid-20 let i røggasstrømmen.At the same time, this results in a better distribution of the absorbent in the flue gas stream.

Ved de yderligere sprøjteindretninger i vaskerens nedre del, er det ligeledes fordelagtigt, at sprøjteretningen indrettes således, at røggassens rotationsstrømning afbøjes i en opadgående strømning. I vaskerens øvre del, har røggasstrømmen 25 overvejende kun en opadgående strømning.With the additional spraying devices in the lower part of the washer, it is also advantageous to arrange the spraying direction so that the rotational flow of the flue gas is deflected in an upward flow. In the upper part of the washer, the flue gas stream 25 has predominantly only upward flow.

Når det ønskes så fuldstændigt som muligt, at overføre calci-umsulfiten til calciumsulfat, bliver suspensionen beluftet i vaskerens sump. Dette sker fortrinsvis ved hjælp af beluft-ningslanser. Især ved tokreds-vaskere udpumpes suspensionen i 30 sumpen, eventuelt efter fraskillelse af grovere calciumsul-fatdele og udsprøjtes i røggasstrømmen via sprøjteindretninger i vaskerens nedre del, medens vaskerens øvre del besprøj-tes med absorptionsmidlet fra forrådsbeholderen.When it is desired to transfer the calcium sulfite to calcium sulfate as completely as possible, the suspension is aerated in the sump of the washer. This is preferably done by means of aeration lances. Particularly with two-cycle washers, the suspension is pumped into the sump, optionally after separation of coarser calcium sulfate moieties, and is injected into the flue gas stream via syringes in the lower part of the washer, while the upper part of the washer is sprayed with the absorbent from the storage container.

3 DK 172993 B13 DK 172993 B1

Indretning til gennemførelse af fremgangsmåden består af en vasker, sprøjteindretninger til absorptionsmidlet, en beholder til absorptionsmidlet samt til- og fraledninger og pumper til absorptionsmidlet og er kendetegnet ved, at beholderen er 5 anbragt i vaskerens indre, og består af et opadtil åbent kar.Apparatus for carrying out the method consists of a washer, absorber spraying means, an absorbent container and absorbers and inlet pipes and pumps and is characterized in that the container is arranged in the interior of the washer and consists of an upwardly open vessel.

Fortrinsvis har karret en konisk bund med en central anbragt udsugningsstuds. Dette medfører, at eventuelle aflejringer kan opfanges og eventuelt undgås. Eventuelt kan der også pumpes i et kredsløb for at undgå at suspensionen aflejres.Preferably, the tub has a tapered bottom with a centrally located suction outlet. This means that any deposits can be intercepted and possibly avoided. Optionally, a circuit may also be pumped to prevent the suspension from depositing.

10 Indløbsstudsen for røggassen er fortrinsvis anbragt tangenti-alt på den egentlige vasker. Vaskerens sump omfatter fortrinsvis beluftningslanser. For bedre at udnytte vaskerens kapacitet og forhindre påbrændinger på forrådsbeholderens væg på grund af overopvarmning, omfatter indløbsstudsene sprøjte-15 indretninger, som er anbragt uden for den egentlige vasker.The inlet spout for the flue gas is preferably arranged tangentially on the actual washer. The washer sump preferably comprises aeration lances. In order to better utilize the capacity of the washer and prevent burns on the wall of the storage tank due to overheating, the inlet nozzles comprise syringe devices located outside the actual washer.

Disse sprøjteindretninger indkobles fortrinsvis i medstrøm, og sørger for en bedre fordeling af absorptionsmidlet i røggasstrømmen.These syringes are preferably engaged in co-flow and provide a better distribution of the absorbent in the flue gas stream.

En typisk indretning til en tokreds-vasker fremgår af fig. 1.A typical device for a two-circuit washer is shown in FIG. First

20 Tværsnit gennem en sådan vaskers hoved samt gennem den nedre del af vaskeren fremgår af fig. 2 og 3.20 Cross-section through the head of such a washer as well as through the lower part of the washer is shown in FIG. 2 and 3.

I disse figurer betyder: 1 vaskerens ydervæg 2 væggen af beholderen til absorptionsmidlet 25 3 indløb for den røggas, der skal vaskes 4 udløb for den rensede røggas 5 sprøjteindretninger 6 udsugningsstuds for absorptionsmiddel 7 tilledninger for absorptionsmiddel til sprøjteindretnin- 30 gerne.In these figures: 1 the outer wall of the washer 2 means the wall of the container for the absorbent 25 3 inlet for the flue gas to be washed 4 outlets for the purified flue gas 5 spraying devices 6 suction outlet for absorbent 7 for injector absorbent pipes 30.

4 DK 172993 B14 DK 172993 B1

Fig. 2 viser hovedet af en typisk vasker i området 2 i fig.FIG. 2 shows the head of a typical washer in the region 2 of FIG.

1.First

Fig. 3 viser et snit gennem den nedre del af vaskeren efter planet III.FIG. 3 shows a section through the lower part of the washer after plane III.

! 5 Ved ifølge opfindelsen af anbringe beholderen til absorpti-‘ onsmidlet i vaskerens indre, opnås en række fordele, der kan være af væsentlig betydning. For det første bortfalder fundamentet og pladsen til den ellers neden under vaskeren opstillede forrådsbeholder. Endvidere kan der gives afkald på et 10 røreværk i beholderen. Beholderen har heller ikke noget tag. Sedimentation undgås fuldstændig ved ompumpning og konisk udformning af beholderen. Beholderens materiale kan vælges som et billig materiale. På grund af den lave mekaniske påvirkning og kravene til sikkerhed, kan der endog anvendes 15 fiberforstærket plast eller beton. Herved bortfalder også i nogle tilfælde en tilsvarende platform på fundamentet.! According to the invention of applying the container to the absorbent in the interior of the washer, a number of advantages can be obtained which can be of significant importance. Firstly, the foundation and the space for the otherwise stored storage tank underneath the washer will lapse. Furthermore, a stirrer can be dispensed with in the container. The container also has no roof. Sedimentation is completely avoided by re-pumping and tapering of the container. The material of the container can be selected as a cheap material. Due to the low mechanical impact and safety requirements, even 15 fiber reinforced plastics or concrete can be used. In this case, a similar platform on the foundation also lapses in some cases.

Af afgørende betydning er en formindskelse af energiforbruget til absorptionsmiddelforsyningspumperne (sprøjteindretning), idet væskeoverfladen i beholderen kan vælges højere end ved 20 sædvanlige anlæg. Der skal derfor overvindes en mindre højdeforskel til de øvre sprøjtedyser. Dette medfører en energibesparelse på 10 til 15%.Crucially important is a reduction in the energy consumption of the absorbent supply pumps (spray device), since the liquid surface in the container can be selected higher than at 20 conventional plants. Therefore, a smaller height difference must be overcome for the upper spray nozzles. This results in an energy saving of 10 to 15%.

En yderligere fordel er, at absorptionsmiddelforsyningspumpernes sugekurve kan renses under drift uden at tømme behol-25 deren. Det er endvidere muligt at tømme absorptionsmiddelforsyningsbeholderen uden at fjerne restsediment. Eventuelle tømningstider nedsættes væsentligt. Endvidere bortfalder i vaskerens indre afstivningskonstruktionen til opsamlingsbeholderen og udløbsrøret; dette gælder især for tokreds-vaske-3 0 re.A further advantage is that the suction curve of the absorbent supply pumps can be cleaned during operation without emptying the container. Furthermore, it is possible to empty the absorbent supply container without removing residual sediment. Any emptying times are significantly reduced. Further, in the washer's internal stiffener structure for the collection vessel and the outlet tube, lapses; this is especially true for two-circuit washes.

En inddosering af absorptionsmidlet, f.eks. kalksten, i beholderen kan ske via en studs oven over beholderens rand.An dosage of the absorbent, e.g. Limestone in the container can be via a stud above the container rim.

as DK 172993 B1 5as DK 172993 B1 5

Kalkstenssuspensionen når således med den udløbende absorp-. tionsmiddelsuspension ind i absorptionsmiddelforsyningsbehol deren. Det er også muligt, at indosere kalksten tørt eller mæske uden for vaskeren og dernæst pumpe denne ind i denne 5 beholder, eksempelvis gennem en neddykket gummislange.The limestone suspension thus reaches with the expiring absorber. suspension agent into the absorbent supply container. It is also possible to induce limestone dry or mesh outside the washer and then pump it into this container, for example through a submerged rubber hose.

Specielt ved tokreds-vaskere bortfalder ifølge opfindelsen opsamlingstragtene og udløbsledningerne i absorptionsmidlets forrådsbeholder. Endvidere er en dampudsugningsblæser ikke længere nødvendig.Especially by two-circuit washers according to the invention, the collection funnels and the outlet lines in the reservoir of the absorbent lapse. Furthermore, a steam extraction fan is no longer necessary.

10 Ved fremgangsmåden ifølge opfindelsen forløber også den yderligere fremtvungne oxidation til calciumsulfat lettere, idet den udstrømmende oxidationsluft endnu engang blandes intensivt med den i beholderen indstrømmende forsurede absorptionsmiddelsuspension. Ved anlæg uden fremtvungen calciumsul-15 fitoxidation kan der ligeledes iagttages en forøgelse af den naturlige oxidation og dette på grund af den bedre røggasindføring i absorptionsmidlets øvre lag, idet der iagttages lavere pH-værdier, som forøger oxidationen.In the process of the invention, the further induced oxidation to calcium sulfate also proceeds more readily, the flowing oxidation air again being intensively mixed with the acidified absorbent suspension flowing into the container. In plants without forced calcium sulphite oxidation, an increase in the natural oxidation can also be observed, due to the better flue gas introduction into the upper layer of the absorbent, observing lower pH values which increase the oxidation.

En yderligere energibesparelse opstår på grund af den delvise 20 køling af røggassen inden røggassens indstrømning i den e-gentlige vasker, idet også gasstrømmens volumen mindskes ved køling. Rørenergi i køleren spares ved at udnytte røggasstrømmens og sprøjtemidlets impulser. Den bedre blanding af væske og gas i køleren medfører en bedre stofovergang fra gas 25 til væske.An additional energy saving is due to the partial cooling of the flue gas prior to the flow of the flue gas into the e-gentle washer, as the volume of the gas stream is also reduced by cooling. Stirring energy in the cooler is saved by utilizing the impulses of the flue gas stream and the spraying agent. The better mixing of liquid and gas in the cooler results in a better dust transition from gas 25 to liquid.

aa

Claims (15)

1. Fremgangsmåde til våd røggasafsvovling i en vasker med sprøjteindretninger til absorptionsmidlet og en beholder til i 5 absorptionsmidlet på basis af suspensioner, der indeholder calciumforbindelser, og hvor det calciumsulfit, der opstår til at begynde med, i det mindste delvis også oxideres til calciumsulfat ved hjælp af luftens oxygen eller røggassens restoxygen, kendetegnet ved, at absorptionsmidlet 10 forefindes i vaskerens indre i en opadtil åben beholder og efter vaskeoperationen i det mindste delvis atter opfanges i denne, og at væskeoverfladen i beholderen ligger højere end væskeoverfladen i vaskerens sump.A process for wet flue gas desulphurisation in a washer with spraying means for the absorbent and a container for the absorbent on the basis of suspensions containing calcium compounds and wherein the calcium sulphite that initially arises is also at least partially oxidized to calcium sulphate by by means of the oxygen of the air or the residual oxygen of the flue gas, characterized in that the absorbent 10 is present in the interior of the washer in an upwardly open container and after the washing operation is at least partially recaptured therein and that the liquid surface of the container is higher than the liquid surface in the sump of the washer. 2. Fremgangsmåde ifølge krav 1, kendetegnet ved, 15 at absorptionsmidlet udtages tæt oven over forrådsbeholderens bund og først uden for vaskeren fordeles til sprøjteindret-ningeme.Method according to claim 1, characterized in that the absorbent is withdrawn tightly above the bottom of the storage container and first distributed outside the washer to the spraying devices. 3. Fremgangsmåde ifølge krav i eller 2, kendetegnet ved, at den røggas, der skal renses, ledes tangentielt 20 ind i vaskeren oven over sumpens væskeoverflade.Method according to claim 1 or 2, characterized in that the flue gas to be cleaned is guided tangentially 20 into the washer above the liquid surface of the sump. 4. Fremgangsmåde ifølge krav l, kendetegnet ved, at røggasstrømmen besprøjtes inden den kommer ind i den e-gentlige vasker.Method according to claim 1, characterized in that the flue gas stream is sprayed before it enters the e-gentle washer. 5. Fremgangsmåde ifølge krav 4, kendetegnet ved, 25 at den besprøjtes i medstrøm.Method according to claim 4, characterized in that it is sprayed in co-current. 6. Fremgangsmåde ifølge et af kravene 3 til 5, kendetegnet ved, at i det mindste nogle af sprøjteindretningerne er anbragt, så at røggassens rotationsstrømning afbøjes i en opadgående strømning. 7 DK 172993 B1Method according to one of claims 3 to 5, characterized in that at least some of the spraying devices are arranged so that the rotational flow of the flue gas is deflected in an upward flow. 7 DK 172993 B1 6 DK 172993 B1 i ———————————————————6 DK 172993 B1 i ——————————————————— 7. Fremgangsmåde ifølge et af kravene l til 6, kendetegnet ved, at suspensionen i vaskerens sump beluftes med henblik på oxidation af calciumsulfit til calciumsulfat.Process according to one of claims 1 to 6, characterized in that the suspension is aerated in the sump of the washer for oxidation of calcium sulphite to calcium sulphate. 8. Fremgangsmåde ifølge et af kravene l til 7, kende-5 tegnet ved, at en del af suspensionen indsprøjtes allerede før røggassen kommer ind i den egentlige vasker.Process according to one of claims 1 to 7, characterized in that part of the suspension is injected even before the flue gas enters the actual washer. 9. Fremgangsmåde ifølge et af kravene l til 8, kendetegnet ved, at suspensionen i sumpen udpumpes, eventuelt efter fraskillelse af grovere calciumsulfatdele, og via 10 sprøjteindretninger sprøjtes ind i røggasstrømmen i vaskerens nedre del.Process according to one of claims 1 to 8, characterized in that the suspension in the sump is pumped out, optionally after separation of coarser calcium sulphate parts, and via 10 spraying devices is injected into the flue gas stream in the lower part of the washer. 10. Indretning til gennemførelse af fremgangsmåden ifølge et af kravene 1 til 9, og som består af en vasker, sprøjteindretninger til absorptionsmidlet, en beholder til absorptions- 15 midlet samt til- og fraledninger og pumper til absorptionsmidlet, kendetegnet ved, at beholderen er anbragt i vaskerens indre, og består af et opadtil åbent kar.Apparatus for carrying out the method according to any one of claims 1 to 9, comprising a washer, absorbent spraying device, an absorbent container as well as absorbers and inlet pipes and pumps, characterized in that the container is arranged in the interior of the washer, and consists of an upwardly open vessel. 11. Indretning ifølge krav 10, kendetegnet ved, at forrådsbeholderen har en konisk bund, og en centralt anbragt 20 udsugningsstuds.Device according to claim 10, characterized in that the storage container has a tapered bottom and a centrally located 20 suction nozzle. 12. Indretning ifølge krav 10 eller 11, kendetegnet ved, at indløbsstudsen for røggassen er anbragt tangentielt på vaskeren.Device according to claim 10 or 11, characterized in that the inlet spigot for the flue gas is arranged tangentially on the washer. 13. Indretning ifølge krav 12, kendetegnet ved, at 25 indløbsstudsen indeholder sprøjteindretninger, som er anbragt uden for den egentlige vasker.Device according to claim 12, characterized in that the inlet nozzle contains spraying devices which are arranged outside the actual washer. 14. Indretning ifølge krav 13, kendetegnet ved, at sprøjteindretningerne arbejder i medstrøm med røggasstrømmen. 8 DK 172993 B1Device according to claim 13, characterized in that the spraying devices work in co-flow with the flue gas flow. 8 DK 172993 B1 15. Indretning ifølge et af kravene 10 til 14, kende -tegnet ved, at vaskerens sump omfatter beluftningslan-ser. 5 iDevice according to one of claims 10 to 14, characterized in that the sump of the washer comprises aeration lances. 5 i
DK199700036A 1996-01-15 1997-01-10 Process for wet flue gas desulphurisation and apparatus for implementing it DK172993B1 (en)

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DE19601193 1996-01-15
DE19601193A DE19601193C2 (en) 1996-01-15 1996-01-15 Process for wet flue gas desulfurization and device for carrying it out

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DK3697A DK3697A (en) 1997-07-16
DK172993B1 true DK172993B1 (en) 1999-11-01

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FI (1) FI970146A (en)
IL (1) IL119845A (en)
PL (1) PL317818A1 (en)
TR (1) TR199700014A2 (en)

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DE10058548C1 (en) * 2000-11-24 2001-10-25 Lurgi Lentjes Bischoff Gmbh Scrubbing tower, used in plant for desulfurizing flue gas arranged behind boiler firing system, has flue gas inlets arranged at same height on opposite-lying sections of tower which open out into adsorption zone
EP3135364B1 (en) 2015-08-31 2021-04-21 Steinmüller Engineering GmbH Method for exhaust gas desulfurization

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JPS60179120A (en) * 1984-02-28 1985-09-13 Mitsubishi Heavy Ind Ltd Process for treating waste gas with separation and recovery of gypsum and dust
US4696805A (en) * 1985-02-05 1987-09-29 Mitsubishi Jukogyo Kabushiki Kaisha Method for desulfurizing exhaust gas
DE3525665C1 (en) * 1985-07-18 1986-05-28 L. & C. Steinmüller GmbH, 5270 Gummersbach Process for desulphurising exhaust gases and producing gypsum and apparatus for carrying out the process

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FI970146A (en) 1997-07-16
IL119845A0 (en) 1997-03-18
PL317818A1 (en) 1997-07-21
TR199700014A2 (en) 1997-08-21
IL119845A (en) 1999-11-30
FI970146A0 (en) 1997-01-14
DE19601193A1 (en) 1997-07-17
DE19601193C2 (en) 1999-01-14
DK3697A (en) 1997-07-16

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B1 Patent granted (law 1993)
PBP Patent lapsed