NO122155B - - Google Patents
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- NO122155B NO122155B NO3711/69A NO371169A NO122155B NO 122155 B NO122155 B NO 122155B NO 3711/69 A NO3711/69 A NO 3711/69A NO 371169 A NO371169 A NO 371169A NO 122155 B NO122155 B NO 122155B
- Authority
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- Norway
- Prior art keywords
- roasting
- sulphation
- gas
- sulphating
- rust
- Prior art date
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- 239000007789 gas Substances 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 11
- 239000005569 Iron sulphate Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 238000010586 diagram Methods 0.000 claims description 6
- -1 ferrous metals Chemical class 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 239000011343 solid material Substances 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 238000005243 fluidization Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims 3
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims 2
- 238000000926 separation method Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910017356 Fe2C Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/10—Roasting processes in fluidised form
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Description
Fremgangsmåte ved sulfaterende behandling av sul- Procedure for sulphating treatment of sul-
fidiske jernmaterialer. fidic iron materials.
Jernsulfidholdige malmer inneholder som regel ikke-jernmetaller, som Cu, Cp,_.Ni, Zn, Mn, Cd og Ag. Det er blitt foreslått flere forskjellige fremgangsmåter for å behandle slike malmer og tillempet med det formål delvis å utvinne metallene og delvis å rense det jern-holdige rostgods slik at det kan anvendes for fremstilling av jern og stål. Iron sulphide ores usually contain non-ferrous metals, such as Cu, Cp,_.Ni, Zn, Mn, Cd and Ag. Several different methods have been proposed for treating such ores and applied with the aim of partly extracting the metals and partly cleaning the iron-containing rust so that it can be used for the production of iron and steel.
En lenge kjent fremgangsmåte for å utvinne disse metaller går A long-known method for extracting these metals goes
ut på ved rosting å overfore disse st sulfater som derefter kan ut-lutes. by roasting to transfer these st sulphates which can then be leached out.
En slik sulfaterende rosting er allerede blitt utfort- i forskjellige ovnstyper. i og med innforingen av rosteovner med fluidisert skikt er det blitt okonomisk mulig å utfore en sulfaterende rosting av metallholdig jernsulfidmateriale, og store anlegg for denne fremgangsmåte er blitt bygget f.eks. i Japan. Such sulphating roasting has already been carried out in different types of ovens. with the introduction of fluidized bed roasting furnaces, it has become economically possible to carry out a sulphating roasting of metal-containing iron sulphide material, and large facilities for this method have been built, e.g. in Japan.
Sulfateringen utfores derved under samtidig avrosting av i materialet forekommende jernsulfider, og dannet SOp utnyttes som regel for fremstilling av svovelsyre. The sulphation is thereby carried out while simultaneously removing iron sulphides present in the material, and the SOp formed is usually used for the production of sulfuric acid.
De faktorer som forst og fremst påvirker reaksjonene ved sulfatering av ikke-jernmetallene, er temperaturen og rostgassens innhold av SO^ og O^. En noyaktig temperaturinnstilling er av spesiell betydning, og dette fremgår av fig. 1 hvor likevektsdamp-trykket (P) over de forskjellige sulfater ved forskjellige temperaturer er vist. Det fremgår av tegningen at området mellom termisk spaltning av på den ene side Cu-, Co-, Zn- og Ni-sulfat og på den annen side det ved rosting ikke onskelige jernsulfat er snevert. Dette er spesielt tilfellet hva gjelder Cu-sulfat. I den neden-stående tabell er spaltningstemperaturene for visse metallsulfåter angitt avhengig av det samlede svoveloxydtrykk. Tabellen tilsvarer kurvene på fig. 1 for Fe2(S01+)l+, CuSO^ og CuO.CuSO^. The factors that primarily affect the reactions during sulphation of the non-ferrous metals are the temperature and the SO^ and O^ content of the rust gas. An accurate temperature setting is of particular importance, and this is evident from fig. 1 where the equilibrium vapor pressure (P) over the different sulphates at different temperatures is shown. It is clear from the drawing that the area between thermal decomposition of Cu, Co, Zn and Ni sulphate on the one hand and iron sulphate, which is not desirable during roasting, on the other hand is narrow. This is especially the case with Cu sulphate. In the table below, the decomposition temperatures for certain metal sulphates are indicated as a function of the overall sulfur oxide pressure. The table corresponds to the curves in fig. 1 for Fe2(SO1+)l+, CuSO^ and CuO.CuSO^.
For å kunne sulfatere metallene uten samtidig dannelse av store mengder jernsulfat er'det derfor nodvendig med en noyaktig tempera-turkohtroll. Dette er mulig i en ovn med fluidisert skikt. For å i oppnå et tjfcdt utbytte ved metallutlutingen og en akseptertar lav ■. jernsulfatdannelse bor temperaturen under rastingen holdes mellom 1 ' £00 og 750°C. Slike rastinger utfOres 'SWTegBl- ved en temperatur av 650-675°C In order to be able to sulphate the metals without the simultaneous formation of large amounts of iron sulphate, it is therefore necessary to have a precise temperature control. This is possible in a fluidized bed furnace. In order to achieve a high yield in the metal leaching and an acceptor low ■. iron sulphate formation, the temperature during roasting must be kept between 1 '£00 and 750°C. Such rests are carried out 'SWTegBl' at a temperature of 650-675°C
For å gjennomfore sulfateringsreaksjonene er det nodvendig med et tilstrekkelig hoyt partialtrykk av SO^ i rostgassen. Av denne grunn må rostingen utfores med et stort luftoverskudd, og luft tilfores som regel i en slik mengde at rostgassen får et innhold av 7-8 % S02. In order to carry out the sulphation reactions, a sufficiently high partial pressure of SO^ in the rust gas is necessary. For this reason, the roasting must be carried out with a large excess of air, and air is usually supplied in such a quantity that the roasting gas has a content of 7-8% S02.
Når sulfidrbstingen utfores samtidig med sulfater ingen, vil hele rostgassmengden inneholde det nodvendige, hoye innhold av SO^, og rostgodset får et hoyt innhold av jernsulfat. På grunn av dette blir svoveltapene store, og dette er en vesentlig ulempe ved de kjente sulfateringsprosesser. Det er en ytterligere ulempe at dersom slike grunnstoffer som As, Sb, Sn, Bi og Pb foreligger i materialet, kan disse ikke avdrives ved rostingen. When the sulphide reduction is carried out simultaneously with no sulphates, the entire amount of rust gas will contain the necessary, high content of SO^, and the rust material will have a high content of iron sulphate. Because of this, the sulfur losses become large, and this is a significant disadvantage of the known sulphation processes. It is a further disadvantage that if such elements as As, Sb, Sn, Bi and Pb are present in the material, these cannot be removed during roasting.
De store luft- og rostgassmengder som anvendes i forbindelse med denne rosteprosess, medforer en lav kapasitet pr. rostearealen-het og et gassrenseanlegg med store dimensjoner. Utbyttet ved en ivaretagelse av rostvarmen er dessuten lavt. The large amounts of air and rust gas used in connection with this roasting process result in a low capacity per the roasting area and a gas purification plant with large dimensions. The yield from taking care of the rust heat is also low.
Oppfinnelsen angår en fremgangsmåte hvorved alle de ovefnfor angitte ulemper elimineres, ved sulfaterende behandling av sulfidiske jernmaterialer som angitt i krav l's overbegrep, og fremgangsmåten er særpreget ved de i krav l's karakteriserende del angitte trekk. The invention relates to a method by which all the disadvantages stated above are eliminated, by sulphating treatment of sulphidic iron materials as stated in claim 1's preamble, and the method is characterized by the features stated in claim 1's characterizing part.
Rostingen kan enten utfores som en oxyderende rosting til Fe20^ med et lite luftoverskudd eller som en magnetittgivende rosting, f.eks. i overensstemmelse med svensk patentskrift nr. 201+002. En temperaturregulering i det fluidiserte skikt kan utfores ved inn-sprøyting av væske og/eller ved anvendelse av kjolespiraler. -Dersom rostingen utfores magnetittgivende, er det mulig fra roste-godset sanrtridig å fjerne slike grunnstoffer som arsen, antimon, tinn, vismuth og bly. Dessuten oppnåes den fordel at ikke-jernmetallene, spesielt Cu og Zn, ikke bindes i form av feritter som er vanskelige å sulfatere. Ved fremstilling av svovelsyre oppnåes en praktisk talt SO^-fri gass, og dette er fordelaktig ved en påfSigende rensing. Dersom rostingen utfores oxyderende, d.v.s.. til Fe20^, bor rostingen utfores ved lavere temperaturer for å unngå dannelse av Cu- og Zn-feritt. En oxyderende rosting forer til en viss SO^-dannelse, og dette gir vanskeligheter ved utvinningen og anvendelsen av rostgassens svovelinnhold. Når rostgassen er befridd fra meddrevet rostgods, for-brennes eventuelt tilstedeværende svovel i en efterforbrenningssone, f.eks. i overensstemmelse med svensk patentskrift nr. 20^002. Rostgassen kan derefter avkjoles enten i en avgassdampkjeie eller ved inn-sprøyting av vann. Eventuelt tilstedeværende svovel kan også for-brennes i en forbrenningssone anordnet efter avgasskjelen, f.eks. The roasting can either be carried out as an oxidizing roasting to Fe20^ with a small excess of air or as a magnetite-yielding roasting, e.g. in accordance with Swedish patent document no. 201+002. A temperature regulation in the fluidized layer can be carried out by injecting liquid and/or by using dress spirals. -If the roasting is carried out to produce magnetite, it is possible to immediately remove such elements as arsenic, antimony, tin, bismuth and lead from the roasted goods. In addition, the advantage is achieved that the non-ferrous metals, especially Cu and Zn, are not bound in the form of ferrites which are difficult to sulphate. In the production of sulfuric acid, a practically SO^-free gas is obtained, and this is advantageous in the case of subsequent purification. If the roasting is carried out oxidizingly, i.e. to Fe20^, the roasting should be carried out at lower temperatures to avoid the formation of Cu and Zn ferrite. An oxidizing roasting leads to a certain formation of SO^, and this causes difficulties in the extraction and use of the sulfur content of the roasting gas. When the rust gas is freed from entrained rust goods, any sulfur present is burned in an afterburning zone, e.g. in accordance with Swedish patent document no. 20^002. The rust gas can then be cooled either in an exhaust steam boiler or by injecting water. Any sulfur present can also be burned in a combustion zone arranged after the exhaust gas boiler, e.g.
i overensstemmelse med svensk patentskrift nr. 227188. Det er også mulig å utfore efterforbrenningen av svovelet på en slik måte at den delvis gjores for avgasskjelen og delvis efter avgasskjelen. Gassen kan derefter renses på vanlig måte, f.eks. i et vasketårn eller på et elektrafilter. in accordance with Swedish patent no. 227188. It is also possible to carry out the afterburning of the sulfur in such a way that it is partly done before the exhaust gas boiler and partly after the exhaust gas boiler. The gas can then be purified in the usual way, e.g. in a washing tower or on an electric filter.
Fra rostetrinnet fores materialet til sulfateringstrinnet. From the roasting stage, the material is fed to the sulphation stage.
Materialet kan tilfores direkte fra skiktet og/eller fra varme-sykloner hvor irostgassene meddrevet rostgods fraskilles. I sulfater ing strinnet behandles godset ved en temperatur av fortrinnsvis ca. 650-675°C. For gjennomfaring av sulfateringen kan rostetrinnet innstilles slik at det fåes et lavt innhold av sulfider i rostgodset og som rostes med et luftoverskudd for dannelse av S0^ og sulfater. Alternativt kan jernsulfider settes til sulfateringstrinnet. Dersom magnetitt forekommer i rostgodset fra rostetrinnet, oxyderes denne til Fe2C>2 som katalyserer dannelsen av SO^ som er gunstig for sulfateringsreaksjonen. Det kan nevnes at denne katalyserende virkning er optimal innen det aktuelle rosteområda> Fra rostetrinnet. tilbakeført rostgass blandet med oxygenholdig gass har vist seg å være et virk-somt sulfateringsmiddel. Også i dette tilfelle katalyseres SO-^-dannelsen av tilstedeværende Fe20^. S0^ kan også tilfores direkte til sulfateringstrinnet, og dette kan vere gunstig spesielt dersom idet er knyttet en svovelsyrefabrikk til rostovnene. Som sulfateringsmiddel kan dtt også méd fordel anvendes svovelsyre og metallsulfater, The material can be supplied directly from the layer and/or from heat cyclones where the rust gases entrained by rust are separated. In the sulphation step, the goods are treated at a temperature of preferably approx. 650-675°C. To carry out the sulphation, the roasting step can be set so that a low content of sulphides is obtained in the roasting material, which is roasted with an excess of air to form S0^ and sulphates. Alternatively, iron sulphides can be added to the sulphation step. If magnetite occurs in the rusting material from the rusting step, this is oxidized to Fe2C>2, which catalyzes the formation of SO^, which is beneficial for the sulphation reaction. It can be mentioned that this catalytic effect is optimal within the rusting area in question> From the rusting stage. returned rust gas mixed with oxygen-containing gas has proven to be an effective sulphating agent. Also in this case, the formation of SO-^ is catalyzed by the Fe2O^ present. SO^ can also be supplied directly to the sulphation step, and this can be particularly beneficial if a sulfuric acid factory is connected to the roasting furnaces. Sulfuric acid and metal sulphates can also be used with advantage as sulphating agents,
•som jernsulfat og alkalisulfat, f.eks. natriumsulfat og natrlum-kiydrosulfat. Hva gjelder svovelutbyttet er det spesielt gunstig å bnyende oppl&sninger inneholdende >ernsulfat fra den efterfblgende luting og eventuelle sementeringer. Små mengder klorid og nitrat i • such as iron sulphate and alkali sulphate, e.g. sodium sulfate and natrlum-kiydrosulfate. As far as the sulfur yield is concerned, it is particularly beneficial to use solutions containing ferrous sulphate from the subsequent leaching and possible cementations. Small amounts of chloride and nitrate in
råmaterialet som tilfores sulfateringstrinnet, forstyrrer ikke fremgangsmåten. Rostgods som taes ut ved 800-1000 C fra rostetrinnet, må avkjoles til sulfateringstemperatur. Dette kan gjbres ved indirekte avkjøling med kjoleror under dannelse av damp, ved tilfbrsel av kaldt, fast materiale eller ved innsprøyting av væske, som vann, svovelsyre eller oppløsninger av jernsulfat eller andre sulfater. Sulfidrostingen og hematittdannelsen gir en betraktelig varmeutvikling som er spesielt stor dersom rostetrinnet anvendes for rosting til magnetitt. Denne varmeutvikling i sulfateringstrinnet gjor det mulig å tilsette betraktelige mengder vannholdige sulfateringsmidler, hvorved det er mulig å oppnå et hoyt SO^- innhold. Temperaturen ved sulfateringsreaksjonen kan okes med bkende SO^-trykk, og dette fremgår av fig. 1. Ved f.eks. et likevektsdamptrykk av P = 0,3 atm må det således i sulfateringsreaktoren opprettholdes en temperatur av minst 675° C for spaltning av Fe2(S0i+K og hoyst 750 C for a unngå spaltning av CuSO^. Dersom CuSO^ spaltes, dannes CuO.CuSO^ som i sin tur spaltes ved ca. 800 C dersom P=0,3a"tm. Det er dessuten mulig å tilsette oxygenanriket luft eller oxygen til sulf ateringsreaktoren for å forskyve likevekten 2S0t,<*>2S02 + 02the raw material fed to the sulphation step does not interfere with the process. Rusted goods that are removed at 800-1000 C from the roasting stage must be cooled to sulphation temperature. This can be achieved by indirect cooling with cooling pipes during the formation of steam, by supplying cold, solid material or by injecting liquid, such as water, sulfuric acid or solutions of iron sulphate or other sulphates. The sulphide roasting and the formation of hematite give rise to considerable heat development, which is particularly large if the roasting step is used for roasting to magnetite. This generation of heat in the sulphation step makes it possible to add considerable amounts of aqueous sulphating agents, whereby it is possible to achieve a high SO^ content. The temperature during the sulphation reaction can be increased with rising SO^ pressure, and this is evident from fig. 1. By e.g. an equilibrium vapor pressure of P = 0.3 atm, a temperature of at least 675° C must be maintained in the sulphation reactor for decomposition of Fe2(S0i+K and a maximum of 750 C to avoid decomposition of CuSO^. If CuSO^ is decomposed, CuO is formed. CuSO^ which in turn decomposes at approx. 800 C if P=0.3a"tm. It is also possible to add oxygen-enriched air or oxygen to the sulphation reactor to shift the equilibrium 2S0t,<*>2S02 + 02
i retning mot et høyere innhold av S0^. in the direction of a higher content of S0^.
Avgassene fra sulfateringstrinnet tilbakeføres til rostetrinnet hvor innkommende SO-^ omdannes til S02. Det anvendes i sulfateringstrinnet ifolge foreliggende fremgangsmåte meget små gassmengder i forhold til den som oppnåes ved kjente 1-trinns fremgangsmåter. Dette innebærer at en betraktelig mindre mengde sulfateringsmiddel behover å tilsettes ved foreliggende fremgangsmåte. Det kan med fordel inn-fores oxydiske materialer som det er bnskelig å behandle ved sulfatering, både i rostetrinnet og i sulfateringstrinnet, hvorved det The exhaust gases from the sulphation stage are returned to the roasting stage where incoming SO-^ is converted to SO2. Very small amounts of gas are used in the sulphation step according to the present method compared to that obtained by known 1-step methods. This means that a considerably smaller amount of sulphating agent needs to be added in the present method. It is advantageous to introduce oxidic materials which it is desirable to treat by sulphation, both in the roasting step and in the sulphation step, whereby the
bare ér nodvendig å passe på at temperaturen i rostetrinnet kan opprettholdes.~ Kaldt oxydert materiale kan anvendes som kjolemiddel i sulfateringstrinnet. it is only necessary to ensure that the temperature in the roasting step can be maintained.~ Cold oxidized material can be used as a cooling agent in the sulphation step.
Ved foreliggende fremgangsmåte utfores rostingen enten oxydisk , eller magnetittgivende. Dersom rostingen utfores oxydisk, er det gunstig å begrense oxygentilforselen slik at eventuelt tilstedeværende arsen ikke kan danne jernarsenater. Betingelsene for dette fremgår av fig. 2 hvor det er satt opp et diagram for de termodynamiske betingelser ved rosting, idet oxygenpartialtrykket i de dannede rdst^-gasser i atmosfærer (logaritmisk skala med grunntallet 10) er avsatt som ordinat og temperaturen i °C som abscisse. Betingelsene for i dannelse av FeAsO^ er representert av en kurve (I) hvorunder FeAsO^ ikke er stabilt, og som går gjennom folgende punkter In the present method, the roasting is carried out either oxidically or magnetite-producing. If the roasting is carried out oxidatively, it is beneficial to limit the oxygen supply so that any arsenic present cannot form iron arsenates. The conditions for this appear from fig. 2 where a diagram has been set up for the thermodynamic conditions during roasting, with the oxygen partial pressure in the formed rdst^ gases in atmospheres (logarithmic scale with the base number 10) set as the ordinate and the temperature in °C as the abscissa. The conditions for the formation of FeAsO^ are represented by a curve (I) under which FeAsO^ is not stable, and which passes through the following points
For i praksis å kunne holde oxygentrykket under det nivå hvor jernarsenater kan dannes, bor det, avhengig av tilfeldige fluktua-sjoner, anvendes betingelser under en kurve (IV) som representeres av folgende verdier Dersom rostingen utfores magnetittgivende, må oxygentrykket begrenses slik at det faller under en kurve (II) i diagrammet og som representeres av folgende sammenhorende verdier , men ikke under en kurve (III) som representeres av folgende sammenhorende verdier In order to be able in practice to keep the oxygen pressure below the level where iron arsenates can form, depending on random fluctuations, conditions must be used under a curve (IV) which is represented by the following values. If the roasting is carried out to produce magnetite, the oxygen pressure must be limited so that it falls under a curve (II) in the diagram and which is represented by the following related values, but not under a curve (III) which is represented by the following related values
, hvorved den senere kurve representerer det laveste oxygenpartial-trykk ved den angjeldende temperatur hvor svovel ved rosting fjernes fra FeS. Dersom sulfateringen skal gjennomfores med gjenværende sulfider i rostgodset, kan rostingen utfores slik at det anvendes betingelser som ligger nær eller noe under kurven, hvorved det fra rostetrinnet oppnåes et materiale som inneholder en viss mengde ikke-avrostede jernsulfider som i sulfateringstrinnet kan gi den nodvendige mengde svovelholdig materiale. , whereby the later curve represents the lowest oxygen partial pressure at the relevant temperature where sulfur is removed from FeS during roasting. If the sulphation is to be carried out with remaining sulphides in the rusted goods, the roasting can be carried out so that conditions are used that are close to or slightly below the curve, whereby a material is obtained from the roasting step that contains a certain amount of non-rusted iron sulphides which in the sulphation step can provide the required amount sulphurous material.
På fig. 3 er det vist et prosesskjema for foreliggende fremgangsmåte og hvor 1 er en rostovn med et fluidisert skikt som tilfores en oxygenholdig gass 2, som regel luft, et jernsulfidholdig råmateriale 3 og eventuelle tilsetninger <*>f, som oxydiske materialer. Rostgassen fores via 5 til en varmsyklon 6 hvor rostgodset fraskilles. Rostgassen fores videre til en efterforbrenningssone 8 som tilfores' en oxygenholdig gass, fortrinnsvis luft 9. Efter forbrenningen av gjenværende elementært svovel avkjoles gassen, fortrinnsvis i en av-gassdampkjele 10, og fores videre til en skilleanordning 11, f.eks. et elektrofilter, hvorfra uttaes dels en renset svoveldioxydgass via'12 og dels kondenserte, avdrevne produkter via 13. In fig. 3 shows a process diagram for the present method and where 1 is a roasting furnace with a fluidized layer which is supplied with an oxygen-containing gas 2, usually air, an iron sulphide-containing raw material 3 and any additives <*>f, such as oxidic materials. The rust gas is fed via 5 to a hot cyclone 6 where the rust material is separated. The rust gas is further fed to an afterburning zone 8 which is supplied with an oxygen-containing gas, preferably air 9. After the combustion of remaining elemental sulphur, the gas is cooled, preferably in an off-gas steam boiler 10, and fed further to a separating device 11, e.g. an electrofilter, from which partly a purified sulfur dioxide gas is extracted via '12 and partly condensed, driven off products via 13.
Efterforbrenningen kan alternativt utfores efter avgassdamp-kjelen 10 i en efterforbrenningssone 8' som tilfores luft 9'. Dessuten kan efterforbrenningen utfores i begge efterforbrennings-sonene 8, 8'. I varmsyklonen 6 fjernes meddrevet rostgods og fores via 15 til sulfateringstrinnet som utgjores av en mindre fluidiserings-reaktor 16. Rostgodset kan også fores via 17 direkte fra skiktet i rosteovnen 1 til sufateringsreaktoren 16 som avkjoles av inn-sproytet væske eller kaldt, fast materiale 18 og/eller ved anvendelse av en kjolespiral 19 i skiktet. Et sulfateringsmiddel 20 tilfores o.gså til sulfateringsreaktoren 16, og dette kan til og med erstatte avkjolingen 18 dersom det utgjores av en vannopplosning av f.eks. metallsulfater som f.eks. er oppnådd ved utlutingen og sementeringen 21. Fra sulfateringsreaktoren 16 fores via 22 re-.aksjonsgassen til en syklon 23 hvor meddrevet gods fraskilles, og reaksjonsgassen tilbakefores via 2h til rostovnen 1. Det sulfa-terte rostgods fra sulfateringsreaktoren 16 fjernes fra skiktet og fores via 25 sammen med i syklonen fraskilt gods 26 til kjoletanker. The afterburning can alternatively be carried out after the exhaust gas steam boiler 10 in an afterburning zone 8' which is supplied with air 9'. Furthermore, the afterburning can be carried out in both afterburning zones 8, 8'. In the hot cyclone 6, entrained rust material is removed and fed via 15 to the sulphation step, which is made up of a smaller fluidization reactor 16. The rust material can also be fed via 17 directly from the layer in the roasting furnace 1 to the sulphation reactor 16, which is cooled by injected liquid or cold, solid material 18 and/or by using a dress spiral 19 in the layer. A sulphating agent 20 is also supplied to the sulphating reactor 16, and this can even replace the cooling 18 if it is made up of a water solution of e.g. metal sulphates such as is obtained by the leaching and cementation 21. From the sulphation reactor 16, the reaction gas is fed via 22 to a cyclone 23 where entrained material is separated, and the reaction gas is fed back via 2h to the roasting furnace 1. The sulphated rust material from the sulphation reactor 16 is removed from the layer and fed via 25 together with goods separated in the cyclone 26 for dress tanks.
27 og derfra via 28 til en utlutingsanordning 29 som via 30 tilfores utlutingsvæske, fortrinnsvis vann. Det utlutede gods fores bort via 32, og vannopplosningen fores via 31 til et vanlig ut-vinningsanlegg 33 hvor metallinnholdet f.eks. sementeres ut og fjernes via 3<*>f. Utlutingsvæsken inneholdende jernsulfat kan derefter tilbakeføres via 21 til sulfateringsreaktoren 16. 27 and from there via 28 to a leaching device 29 which via 30 is supplied with leaching liquid, preferably water. The leached material is fed away via 32, and the water solution is fed via 31 to a normal extraction facility 33 where the metal content, e.g. cemented out and removed via 3<*>f. The leach liquid containing iron sulphate can then be returned via 21 to the sulphation reactor 16.
Claims (7)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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SE12585/68A SE322632B (en) | 1968-09-18 | 1968-09-18 |
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NO122155B true NO122155B (en) | 1971-05-24 |
Family
ID=20295992
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Application Number | Title | Priority Date | Filing Date |
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NO3711/69A NO122155B (en) | 1968-09-18 | 1969-09-17 |
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JP (1) | JPS516605B1 (en) |
BE (1) | BE738963A (en) |
DE (1) | DE1946558B2 (en) |
DK (1) | DK131242B (en) |
ES (1) | ES371601A1 (en) |
FI (1) | FI50140C (en) |
FR (1) | FR2018330A1 (en) |
IE (1) | IE33849B1 (en) |
NL (1) | NL6914173A (en) |
NO (1) | NO122155B (en) |
PL (1) | PL80195B1 (en) |
RO (1) | RO61553A (en) |
SE (1) | SE322632B (en) |
YU (1) | YU33984B (en) |
ZM (1) | ZM14369A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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SE396968B (en) * | 1975-07-01 | 1977-10-10 | Boliden Ab | PROCEDURE FOR EXTRACTING NON-IRON METALS FROM SULPHIDY MATERIALS BY ROASTING AND LACHING |
FI65088C (en) * | 1979-05-25 | 1984-03-12 | Pekka Juhani Saikkonen | FOERFARANDE FOER AOTERVINNING AV ICKE-JAERNMETALLER UR DERAS MINERALIER MINERALSLIG OXIDISKA ROSTNINGSPRODUKTER OCH SLAGG |
US4387642A (en) * | 1980-07-17 | 1983-06-14 | Mannesmann Tally Corporation | Bi-directional, constant velocity, carriage shuttling mechanisms |
SE446276B (en) * | 1980-11-17 | 1986-08-25 | Boliden Ab | PROCEDURE FOR Separating and Extracting Nickel and Copper from Complex Sulfide Minerals |
ES2038535B1 (en) * | 1991-06-14 | 1994-04-01 | Riotinto Minera Sa | PROCEDURE FOR THE HYDROMETALLURGICAL RECOVERY OF NON-IRON METALS IN ASHES OF PIRITAS. |
ES2046126B1 (en) * | 1992-06-11 | 1994-09-01 | Riotinto Minera Sa | RETOSTATION PROCEDURE FOR THE HYDROMETALLURGICAL RECOVERY OF NON-IRON METALS IN PIRITA ASHES. |
DE19960132A1 (en) * | 1999-12-14 | 2001-06-21 | Alexander Beckmann | Process for the extraction of copper and other metals |
DE10024972A1 (en) * | 2000-05-19 | 2001-11-29 | Klaus Plath | Crank mechanism |
JP6539922B1 (en) * | 2018-08-30 | 2019-07-10 | 日揮株式会社 | Method for producing nickel sulfate compound |
JPWO2020075288A1 (en) * | 2018-10-12 | 2021-09-02 | 日揮グローバル株式会社 | Nickel oxide ore treatment method and treatment equipment |
-
1968
- 1968-09-18 SE SE12585/68A patent/SE322632B/xx unknown
-
1969
- 1969-09-09 IE IE1259/69A patent/IE33849B1/en unknown
- 1969-09-13 DE DE1946558A patent/DE1946558B2/en not_active Withdrawn
- 1969-09-16 PL PL1969135843A patent/PL80195B1/pl unknown
- 1969-09-17 ES ES371601A patent/ES371601A1/en not_active Expired
- 1969-09-17 YU YU2359/69A patent/YU33984B/en unknown
- 1969-09-17 FR FR6931565A patent/FR2018330A1/en not_active Withdrawn
- 1969-09-17 BE BE738963D patent/BE738963A/xx unknown
- 1969-09-17 NO NO3711/69A patent/NO122155B/no unknown
- 1969-09-17 FI FI692651A patent/FI50140C/en active
- 1969-09-18 DK DK497169AA patent/DK131242B/en unknown
- 1969-09-18 NL NL6914173A patent/NL6914173A/xx not_active Application Discontinuation
- 1969-09-18 RO RO61050A patent/RO61553A/ro unknown
- 1969-09-18 ZM ZM143/69A patent/ZM14369A1/en unknown
- 1969-09-18 JP JP44074330A patent/JPS516605B1/ja active Pending
Also Published As
Publication number | Publication date |
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FI50140B (en) | 1975-09-01 |
PL80195B1 (en) | 1975-08-30 |
IE33849L (en) | 1970-03-18 |
ES371601A1 (en) | 1971-11-01 |
YU33984B (en) | 1978-09-08 |
DK131242B (en) | 1975-06-16 |
FR2018330A1 (en) | 1970-05-29 |
DE1946558A1 (en) | 1970-06-11 |
BE738963A (en) | 1970-03-02 |
ZM14369A1 (en) | 1970-03-16 |
RO61553A (en) | 1977-02-15 |
IE33849B1 (en) | 1974-11-27 |
DK131242C (en) | 1975-11-17 |
JPS516605B1 (en) | 1976-03-01 |
SE322632B (en) | 1970-04-13 |
DE1946558B2 (en) | 1978-06-22 |
YU235969A (en) | 1978-02-28 |
NL6914173A (en) | 1970-03-20 |
FI50140C (en) | 1975-12-10 |
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