NO301321B1 - Process for thermal decomposition of metal sulfates - Google Patents
Process for thermal decomposition of metal sulfates Download PDFInfo
- Publication number
- NO301321B1 NO301321B1 NO900069A NO900069A NO301321B1 NO 301321 B1 NO301321 B1 NO 301321B1 NO 900069 A NO900069 A NO 900069A NO 900069 A NO900069 A NO 900069A NO 301321 B1 NO301321 B1 NO 301321B1
- Authority
- NO
- Norway
- Prior art keywords
- residual product
- mixture
- reactor
- finely divided
- metal
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 20
- 239000002184 metal Substances 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 18
- 150000003467 sulfuric acid derivatives Chemical class 0.000 title description 7
- 238000005979 thermal decomposition reaction Methods 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 8
- 230000004992 fission Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 5
- 239000003546 flue gas Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005200 wet scrubbing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/501—Preparation of sulfur dioxide by reduction of sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/501—Preparation of sulfur dioxide by reduction of sulfur compounds
- C01B17/507—Preparation of sulfur dioxide by reduction of sulfur compounds of iron sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Fluidized-Bed Combustion And Resonant Combustion (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte for termisk spaltning av en metallsulfatblanding i en reaktor med fluidisert sjikt ved temperaturer fra 800 til 1100°C under oksyderende betingelser, hvorved metallsulfatblandingen "blandes med resirkulert restprodukt og sammen med brennstoffer bringes til reaksjon i spaltningsreaktoren under dannelse av restprodukt og SOg-holdige røstegasser, og den finfordelte fraksjonen av det derved dannede restproduktet fraskilles i en elektrostatisk gassrensing. The present invention relates to a method for thermally splitting a metal sulfate mixture in a fluidized bed reactor at temperatures from 800 to 1100°C under oxidizing conditions, whereby the metal sulfate mixture is "mixed with recycled residual product and, together with fuels, is brought into reaction in the splitting reactor with the formation of residual product and SOg-containing flue gases, and the finely divided fraction of the resulting residual product are separated in an electrostatic gas purification.
Metallsulfater, spesielt svovelsyreholdige metallsulfatblandinger, oppstår ved forskjellige prosesser som rest-stoffer. Spesielt for de overveiende jernsulfatholdige metallsulfatblandingene som dannes ved gjenvinningen av svovelsyre fra tynnsyren som dannes ved TiC^-fremstilling ifølge sulfatprosessen, finnes det ingen nevneverdige anvendelsesmuligheter. Metal sulfates, especially sulfuric acid-containing metal sulfate mixtures, occur as residues in various processes. In particular, there are no significant application possibilities for the predominantly iron sulfate-containing metal sulfate mixtures that are formed by the recovery of sulfuric acid from the thin acid that is formed by TiC 2 production according to the sulfate process.
Som eneste miljøvennlige avhendingsmulighet for disse avfallsproduktene kommer hittil bare den termiske spaltningen til SOg, O2 og metalloksyder (i det følgende betegnet restprodukt eller resirkulert restprodukt) ved temperaturer på 800 til 1100°C i betraktning (Ullmanns Encyclopådie der technischen Chemie, 4. opplag, bind 18, side 579-580, Verlag Chemie, Weinheim, 1978). Herved innvirker imidlertid innholdet av magnesiumsulfat i negativ retning, fordi dette bare spaltes tilstrekkelig raskt ved reduserende betingelser i det teknisk relevante temperaturområdet. Reduserende betingelser, som f.eks. foreslått i DE-A 1 173 074, kan knapt nok realiseres i reaktorer med fluidisert sjikt som er fordelaktige for denne prosessen. As the only environmentally friendly disposal option for these waste products, so far only the thermal decomposition into SOg, O2 and metal oxides (hereinafter referred to as residual product or recycled residual product) at temperatures of 800 to 1100°C is considered (Ullmann's Encyclopådie der technischen Chemie, 4th edition, volume 18, pages 579-580, Verlag Chemie, Weinheim, 1978). This, however, affects the content of magnesium sulphate in a negative direction, because this only decomposes sufficiently quickly under reducing conditions in the technically relevant temperature range. Reducing conditions, such as e.g. proposed in DE-A 1 173 074, can hardly be realized in fluidized bed reactors which are advantageous for this process.
Vanligvis innføres metallsulfåtene med brennstoffene, som er påkrevde for den sterkt endoterme spaltningsreaksjonen, i reaktoren med fluidisert sjikt. Nedenfra blåses det inn så mye luft eller luft-oksygenblanding gjennom et stasjonært fluidisert sjikt av grovt restprodukt, at gassene som øverst trer ut fra reaktoren har et lavt oksygeninnhold i området fra 0,5 til 2 volum-#. Under reduserende betingelser inneholder disse gassene elementært svovel, ved høyere oksygeninnhold betydelige mengder SO3, hvilket begge deler er uønsket. Gassene inneholder under normalbetingelser ved siden av SO2, O2, HgO, N2 og eventuelt CO2» tilnærmet hele restproduktet som støv. Typically, the metal sulfates are introduced with the fuels, which are required for the highly endothermic fission reaction, into the fluidized bed reactor. From below, so much air or an air-oxygen mixture is blown in through a stationary fluidized layer of coarse residual product, that the gases emerging from the top of the reactor have a low oxygen content in the range from 0.5 to 2 volume-#. Under reducing conditions these gases contain elemental sulphur, at higher oxygen content significant amounts of SO3, both of which are undesirable. Under normal conditions, the gases contain, in addition to SO2, O2, HgO, N2 and possibly CO2, almost the entire residual product as dust.
Vanligvis avkjøles gassene i avkjølingsbeholder fra 800 til 1100°C til 300 til 350°C, hvorved en betydelig del av restproduktet fraskilles. De mer finfordelte delene av restproduktet fjernes i et elektrostatisk gassrenseanlegg (EGR) fra gasstrømmen før denne underkastes en våtvasking. Usually the gases are cooled in a cooling vessel from 800 to 1100°C to 300 to 350°C, whereby a significant part of the residual product is separated. The more finely divided parts of the residual product are removed in an electrostatic gas cleaning system (EGR) from the gas stream before it is subjected to a wet scrubbing.
Oppgaven ved foreliggende oppfinnelse er tilveiebringelsen av en fremgangsmåte som ikke oppviser de omtalte ulempene. The task of the present invention is to provide a method which does not exhibit the mentioned disadvantages.
Det er nå funnet at spaltningsreaksjonen i reaktor med fluidisert sjikt fordelaktig kan påvirkes når metallsulfatene blandes med finfordelt restprodukt fra gassrenseanlegget (EGR). Spesielt fremmes ved fremgangsmåten ifølge oppfinnelsen dannelsen av grovt restprodukt, som er viktig for oppnåelsen av det stasjonære fluidiserte sjiktet. It has now been found that the cleavage reaction in a fluidized bed reactor can be beneficially influenced when the metal sulphates are mixed with finely divided residual product from the gas treatment plant (EGR). In particular, the method according to the invention promotes the formation of coarse residual product, which is important for the achievement of the stationary fluidized bed.
Gjenstanden for foreliggende oppfinnelse er følgelig en fremgangsmåte for termisk spaltning av en metallsulfatblanding i en reaktor med fluidisert sjikt ved temperaturer fra 800 til 1100°C under oksyderende betingelser, hvorved metallsulfatblandingen blandes med resirkulert restprodukt og sammen med brennstoffer bringes til reaksjon i spaltningsreaktoren under dannelse av restprodukt og SC^-holdige røstegasser, og den finfordelte fraksjonen av det derved dannede restproduktet fraskilles i en elektrostatisk gassrensing. Fremgangsmåten er kjennetegnet ved at den finfordelte fraksjonen av det derved dannede restproduktet føres tilbake til spaltningsreaktoren og utgjør det resirkulerte restprodukt. The object of the present invention is therefore a method for thermally splitting a metal sulfate mixture in a fluidized bed reactor at temperatures from 800 to 1100°C under oxidizing conditions, whereby the metal sulfate mixture is mixed with recycled residual product and, together with fuels, is reacted in the splitting reactor with the formation of residual product and SC^-containing flue gases, and the finely divided fraction of the resulting residual product is separated in an electrostatic gas purification. The method is characterized by the fact that the finely divided fraction of the resulting residual product is fed back to the fission reactor and constitutes the recycled residual product.
Videre påvirkes ikke bare dannelsen av grovt restprodukt i positiv retning, men spesielt reduseres restproduktets inn-hold av uspaltede vannoppløselige sulfater i tydelig grad. Furthermore, not only is the formation of coarse residual product affected in a positive direction, but in particular the residual product's content of undecomposed water-soluble sulphates is clearly reduced.
Ved anvendelsen av fremgangsmåten ifølge oppfinnelsen kan innholdet av vannoppløselige metallsulfater i restproduktet reduseres betydelig. I en foretrukket utførelsesform av fremgangsmåten ifølge oppfinnelsen blandes brennstoffene og det finfordelte restproduktet før innføring i spaltningsreaktoren. Spesielt fordelaktig er anvendelsen av denne fremgangsmåten når metallsulfåtene før den termiske spaltningen kompakteres, f.eks. pelletiseres, sammen med brennstoffene og det finfordelte restproduktet. Som brennstoffer i forbindelse med foreliggende oppfinnelse kommer ikke bare kull, tjære, melass osv. i betraktning, men også pyritt eller svovel. When using the method according to the invention, the content of water-soluble metal sulphates in the residual product can be significantly reduced. In a preferred embodiment of the method according to the invention, the fuels and the finely divided residual product are mixed before introduction into the fission reactor. The use of this method is particularly advantageous when the metal sulphates are compacted before the thermal decomposition, e.g. is pelletized, together with the fuels and the finely divided residual product. As fuels in connection with the present invention, not only coal, tar, molasses etc. come into consideration, but also pyrite or sulphur.
I en spesielt foretrukket utførelsesform inneholder metall-sulf atb landingene som fuktighet svovelsyre med 5 til 96 vekt-# H2S04. In a particularly preferred embodiment, the metal sulfate landings contain as moisture sulfuric acid with 5 to 96 wt% H 2 SO 4 .
Fordelene ved fremgangsmåten ifølge oppfinnelsen skal tydeliggjøres ved hjelp av eksempler. The advantages of the method according to the invention shall be made clear by means of examples.
Sammenligningseksempel Comparative example
Ved opparbeidelsen av tynnsyre som ble dannet ved TiC^-fremstilling ifølge sulfatfremgangsmåten ble en svovel-syreholdig metallsulfatblanding av følgende sammensetning fraskilt (alle angivelser som vekt-#). During the processing of thin acid which was formed by TiC^ production according to the sulphate method, a sulphur-acid-containing metal sulphate mixture of the following composition was separated (all indications as weight-#).
Metallsulfatblanding, kull og restprodukt ble blandet i vektforhold 1:0,3:0,1 og formet til grønn pellets ifølge DE-A 1 173 074. Som restprodukt ble en del av det totalt dannede restproduktet ved den termiske spaltningen anvendt. Grønn-pellesene ble innført i reaktoren med fluidisert sjikt fra en doseringsbunker og bragt til reaksjon ved 980 ± 5°C. Metal sulfate mixture, coal and residual product were mixed in a weight ratio of 1:0.3:0.1 and formed into green pellets according to DE-A 1 173 074. As residual product, part of the total residual product formed during the thermal decomposition was used. The green pellets were introduced into the reactor with a fluidized bed from a dosing bunker and brought to reaction at 980 ± 5°C.
Restproduktet som ble tatt fra anlegget etter at stasjonære betingelser var oppnådd hadde følgende sammensetning: The residual product that was taken from the plant after stationary conditions had been achieved had the following composition:
Eksempel Example
En metallsulfatblanding (analog sammenligningseksemplet) ble blandet med kull og restprodukt i vektforhold 1:0,3:0,1, hvorved imidlertid ikke en del av den samlede restproduktet, men bare restprodukt fra EGR ble anvendt. Den videre bear-beidelsen og spaltningsreaksjonen foregikk under de samme betingelsene som angitt i sammenligningseksemplet. A metal sulphate mixture (analogous to the comparison example) was mixed with coal and residual product in a weight ratio of 1:0.3:0.1, whereby, however, not part of the overall residual product, but only residual product from EGR, was used. The further processing and cleavage reaction took place under the same conditions as stated in the comparative example.
Det fra anlegget fjernede og ikke tilbakeførte restproduktet hadde følgende sammensetning: The residual product removed from the facility and not returned had the following composition:
Claims (4)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3901459A DE3901459A1 (en) | 1989-01-19 | 1989-01-19 | METHOD FOR THE THERMAL DECOMPOSITION OF METAL SULFATES |
Publications (3)
Publication Number | Publication Date |
---|---|
NO900069D0 NO900069D0 (en) | 1990-01-08 |
NO900069L NO900069L (en) | 1990-07-20 |
NO301321B1 true NO301321B1 (en) | 1997-10-13 |
Family
ID=6372379
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO900069A NO301321B1 (en) | 1989-01-19 | 1990-01-08 | Process for thermal decomposition of metal sulfates |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0379016B1 (en) |
JP (1) | JPH02233507A (en) |
CA (1) | CA2007902A1 (en) |
DE (2) | DE3901459A1 (en) |
ES (1) | ES2055169T3 (en) |
FI (1) | FI92046C (en) |
NO (1) | NO301321B1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19506252A1 (en) * | 1995-02-23 | 1996-09-19 | Bayer Ag | Prodn. of magnesium sulphate-contg. metal oxide mixt. useful as fertiliser |
DE19512614C2 (en) * | 1995-04-05 | 1998-05-20 | Bayer Ag | Use of solutions containing magnesium sulfate as fertilizer |
DE19513511C2 (en) * | 1995-04-10 | 1998-04-30 | Bayer Ag | Process for the production of a lime-magnesium mixture for sustainable soil improvement |
DE19623408C1 (en) * | 1996-06-12 | 1998-02-12 | Bayer Ag | Production of coarse grained metal oxide(s) |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL273476A (en) * | 1961-01-26 | 1900-01-01 |
-
1989
- 1989-01-19 DE DE3901459A patent/DE3901459A1/en not_active Withdrawn
-
1990
- 1990-01-06 DE DE9090100248T patent/DE59001379D1/en not_active Expired - Fee Related
- 1990-01-06 EP EP90100248A patent/EP0379016B1/en not_active Expired - Lifetime
- 1990-01-06 ES ES90100248T patent/ES2055169T3/en not_active Expired - Lifetime
- 1990-01-08 NO NO900069A patent/NO301321B1/en unknown
- 1990-01-16 JP JP2004639A patent/JPH02233507A/en active Pending
- 1990-01-17 CA CA002007902A patent/CA2007902A1/en not_active Abandoned
- 1990-01-17 FI FI900264A patent/FI92046C/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
FI92046B (en) | 1994-06-15 |
NO900069D0 (en) | 1990-01-08 |
DE3901459A1 (en) | 1990-07-26 |
DE59001379D1 (en) | 1993-06-17 |
NO900069L (en) | 1990-07-20 |
JPH02233507A (en) | 1990-09-17 |
EP0379016B1 (en) | 1993-05-12 |
FI92046C (en) | 1994-09-26 |
EP0379016A1 (en) | 1990-07-25 |
ES2055169T3 (en) | 1994-08-16 |
FI900264A0 (en) | 1990-01-17 |
CA2007902A1 (en) | 1990-07-19 |
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