NO832550L - PROCEDURE FOR SEPARATING HEAVY METAL METIONS FROM RAA PHOSPHATE - Google Patents
PROCEDURE FOR SEPARATING HEAVY METAL METIONS FROM RAA PHOSPHATEInfo
- Publication number
- NO832550L NO832550L NO832550A NO832550A NO832550L NO 832550 L NO832550 L NO 832550L NO 832550 A NO832550 A NO 832550A NO 832550 A NO832550 A NO 832550A NO 832550 L NO832550 L NO 832550L
- Authority
- NO
- Norway
- Prior art keywords
- phosphate
- halogen
- raw
- raw phosphate
- halogens
- Prior art date
Links
- 229910019142 PO4 Inorganic materials 0.000 title claims description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 35
- 239000010452 phosphate Substances 0.000 title claims description 35
- 238000000034 method Methods 0.000 title claims description 31
- 229910001385 heavy metal Inorganic materials 0.000 title description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 25
- 150000002367 halogens Chemical class 0.000 claims description 18
- 229910052793 cadmium Inorganic materials 0.000 claims description 14
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000002366 halogen compounds Chemical class 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002506 iron compounds Chemical class 0.000 claims description 2
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- -1 CC 14 Chemical class 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 241000838698 Togo Species 0.000 description 4
- 230000002140 halogenating effect Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000184 acid digestion Methods 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- CBWUNQZJGJFJLZ-UHFFFAOYSA-N [Cl].Cl Chemical compound [Cl].Cl CBWUNQZJGJFJLZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 229910052585 phosphate mineral Inorganic materials 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/01—Treating phosphate ores or other raw phosphate materials to obtain phosphorus or phosphorus compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Fertilizers (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
Oppfinnelsen vedrører en fremgangsmåte hvor det ved opp-varming av råfosfat i nærvær av halogener eller halogenforbindelser oppnås en adskillelse av tungmetallioner fra råfosfat. The invention relates to a method in which, by heating raw phosphate in the presence of halogens or halogen compounds, a separation of heavy metal ions from raw phosphate is achieved.
Fosforholdige gjødningsmidler fremstilles ofte ved sur oppslutning av fosforit.: eller apatit. Under innvirkning av mineralsyre spaltes det tungtoppløselige trikalsium-forsfat fra råfosfatet. Kalsiumsaltene av den anvendte mineralsyren må deretter adskilles for å få den dannede rå fosforsyre som produkt. I råfosfatet inneholdte metalliske forurensninger som kadmium, kvikksølv, bly, tallium og arsen forblir for en stor del fosforsyren. Phosphorus-containing fertilizers are often produced by acid digestion of phosphorite or apatite. Under the influence of mineral acid, the sparingly soluble tricalcium phosphate is split from the crude phosphate. The calcium salts of the mineral acid used must then be separated to obtain the raw phosphoric acid formed as a product. Metallic impurities such as cadmium, mercury, lead, thallium and arsenic contained in the raw phosphate remain to a large extent the phosphoric acid.
Da denne syre ikke er egnet for alle anvendelsesformål er det allerede blitt foretatt tallrike forsøk for å befri den for uønskede metalliske forurensninger. For forarbeid-elsen av rå fosforsyre til gjødningsmidler bød de tidligere forsøksresultater imidlertid hittil ingen teknisk gunstig måte. As this acid is not suitable for all applications, numerous attempts have already been made to rid it of unwanted metallic impurities. For the processing of raw phosphoric acid into fertilisers, however, the previous experimental results have so far offered no technically favorable method.
I US patent 3.133.791 er det omtalt en fremgangsmåte til adskillelse av jern fra råfosfat, idet råproduktet ved temperaturer i området fra 400°C til 1000°C behandles med en definert blanding av klorhydrogen og klor. US patent 3,133,791 describes a method for separating iron from raw phosphate, the raw product being treated at temperatures in the range from 400°C to 1000°C with a defined mixture of hydrogen chloride and chlorine.
Ifølge US patent 2.629.650 kan jernet fjernes fra råfosfatet med klorhydrogen ved 350 - 4 00°C. According to US patent 2,629,650, the iron can be removed from the raw phosphate with hydrogen chloride at 350 - 400°C.
Til adskillelse av tungmetall-elementer fra det periodiske systems annen bigruppe som kadmium og kvikksølv, spesielt kadmium fra råfosfat var det hittil ikke kjent noen økono-misk fremgangsmåte. Til termisk fjerning må man anvende temperaturer rundt 1200°C. Hittil eksisterte bare frem-gangsmåter til ekstrahering respektiv adskillelse av kadmium fra råfosforsyre (se Kongressberetning, side 6, kadmium-seminar den 20.11.1980 i Rosslyn, Virginia). Fjerningen av kadmium fra råfosfat er av spesiell vanskelighet da kadmium-ionene setter kalsiums gittersteder i krystallen og derfor er spesielt fininnbygget i råfosfatmineralene (se overnevnte Kongressberetning). For the separation of heavy metal elements from the periodic system's other sub-group such as cadmium and mercury, in particular cadmium from raw phosphate, no economical method was known until now. For thermal removal, temperatures around 1200°C must be used. Until now, only methods existed for the extraction or separation of cadmium from raw phosphoric acid (see Congress report, page 6, cadmium seminar on 20/11/1980 in Rosslyn, Virginia). The removal of cadmium from raw phosphate is particularly difficult as the cadmium ions set calcium lattice sites in the crystal and are therefore particularly finely embedded in the raw phosphate minerals (see the above-mentioned Congress report).
Det ble nu overraskende funnet at tungmetallioner, spesielt elementer fra det periodiske systems annen bigruppe som kadmium eller kvikksølv på enkel måte kan fjernes fra råfosfat. Fremgangsmåten erkarakterisert vedat råfosfat behandles med halogener, halogenhydrogener, organiske eller uorganiske halogenforbindelser eller en blanding av disse ved trykk mellom 0,001 og 50 bar, fortrinnsvis mellom 0,01 og 2 0 bar, spesielt ved normaltrykk samt ved temperaturer i området på 400 - 1100°C, fortrinnsvis ved temperaturer mellom 500 og 800°C. Råfosfatet kan eventuelt deretter ekstraheres med vann. Fremgangsmåten finner fortrinnsvis anvendelse til adskillelse av kadmium. It was now surprisingly found that heavy metal ions, especially elements from the periodic table's second subgroup such as cadmium or mercury, can be easily removed from crude phosphate. The method is characterized in that raw phosphate is treated with halogens, halogen hydrogens, organic or inorganic halogen compounds or a mixture of these at pressures between 0.001 and 50 bar, preferably between 0.01 and 20 bar, especially at normal pressure and at temperatures in the range of 400 - 1100° C, preferably at temperatures between 500 and 800°C. The raw phosphate can optionally then be extracted with water. The method is preferably used for the separation of cadmium.
Som halogener og halogenhydrogener kommer det fortrinnsvis på tale klor, brom, klorhydrogen og bromhydrogen, spesielt fortrinnsvis fluor og klorhydrogen. Det kan også fordelaktig anvendes brom og/eller bromhydrogen i blanding med klorhydrogen eller også brom i blanding med klor og klorhydrogen . Halogens and halogen hydrogens are preferably chlorine, bromine, hydrogen chloride and hydrogen bromine, particularly preferably fluorine and hydrogen chloride. It is also advantageous to use bromine and/or hydrogen bromine in a mixture with hydrogen chloride or bromine in a mixture with chlorine and hydrogen chloride.
Som organiske halogenforbindelser kan det anvendes halogen-erte hydrokarboner f.eks. CC14, C^Cl^, CH2Clg, C2H2Br4, CHC13, C2HCL3eller syrehalogenider, f.eks. C0C12, Halogenated hydrocarbons can be used as organic halogen compounds, e.g. CC 14 , C 2 Cl 3 , CH 2 Cl 2 , C 2 H 2 Br 4 , CHC 13 , C 2 HCL 3 or acid halides, e.g. C0C12,
(C0C1)2, spesielt CCL4eller som uorganiske halogenforbindelser, f.eks. NH4C1, NH4Br metallklorider som SiCl4, A1C13, FeCl3eller klorerte svovelforbindelser som SO2CI,, eller S2C12, spesielt NH4C1. (C0C1)2, especially CCL4 or as inorganic halogen compounds, e.g. NH4C1, NH4Br metal chlorides such as SiCl4, AlC13, FeCl3 or chlorinated sulfur compounds such as SO2CI,, or S2C12, especially NH4C1.
Halogenene eller halogenhydrogene kan anvendes som sådanne for fremgangsmåten ifølge oppfinnelsen eller frigjøres ._ under prosessen fra andre forbindelser f.eks. ved tilsetning av klorider i kombinasjon med tungt flyktige mineralsyrer som fosforsyre eller dens anhydrider eventuelt i nærvær av oksydasjonsmidler som oksygen eller natriumperklorat. The halogens or halogen hydrogens can be used as such for the method according to the invention or released during the process from other compounds, e.g. by adding chlorides in combination with highly volatile mineral acids such as phosphoric acid or its anhydrides, possibly in the presence of oxidizing agents such as oxygen or sodium perchlorate.
Det er mulig å tilblande halogenene respektiv halogenholdige forbindelser til råfosfatet før prosessen eller å tilsette under røstingen. Halogenene respektiv de halogenholdige forbindelser kan anvendes så vel i ren tilstand som også i blanding med inerte gasser eller fordampbare inerte gpp-løsningsmidler. It is possible to mix the halogens or halogen-containing compounds into the raw phosphate before the process or to add during roasting. The halogens or the halogen-containing compounds can be used in their pure state as well as in a mixture with inert gases or vaporizable inert gpp solvents.
Røsteprosessen gjennomføres i en reaktor, idet det kommer til anvendelse forskjellige reaktortyper som eksempelvis virvelsjiktovner, dreierørsovner, etasje-røsteovner, herde-røsteovner, støvrøsteovner eller sinterrøsteapparater. The roasting process is carried out in a reactor, as different reactor types are used, such as fluidized bed furnaces, rotary tube furnaces, floor roasting furnaces, hardening roasting furnaces, dust roasting furnaces or sintering apparatus.
Den for fremgangsmåten ifølge oppfinnelsen nødvendige tilsetning av de.halogenholdige forbindelser utgjør minst den til tungmetallinnholdet av råfosfatet støkiometrisk svarende mengde, vanligvis imidlertid flere ganger dette. Fordelaktig anvendes til fremgangsmåten ifølge oppfinnelsen halogenene respektiv halogenforbindelsene direkte idet hensiktsmessig det føres en mengdestrøm på 0,3 til 10 The addition of halogen-containing compounds necessary for the method according to the invention amounts to at least the amount stoichiometrically corresponding to the heavy metal content of the raw phosphate, but usually several times this. Advantageously, for the method according to the invention, the halogens or the halogen compounds are used directly, with a flow rate of 0.3 to 10
2 2
Normliter/h cm av halogen, jjalogenhydrogen eller den for-dampede halogenholdige forbindelse eventuelt sammen med en inert gass gjennom reaktoren. Oppholdstidene kan herved utgjøre mellom 1 og 6 0 minutter, fortrinnsvis mellom 10 og 30 minutter. Avhengig av reaktortypen er det også mulig med større eller mindre gjennomgangsmengder. Standard liter/h cm of halogen, halogen hydrogen or the vaporized halogen-containing compound, possibly together with an inert gas through the reactor. The residence times can thereby amount to between 1 and 60 minutes, preferably between 10 and 30 minutes. Depending on the reactor type, it is also possible to have larger or smaller flow rates.
Råfosfatet kan hensiktsmessig tilføres til reaktoren i malt tilstand, eksempelvis i en finhet på 100-200 ym korndiameter. The raw phosphate can suitably be supplied to the reactor in a ground state, for example in a fineness of 100-200 µm grain diameter.
Ifølge oppfinnelsen er en tilsetning av jern eller jernforbindelser, spesielt av jern(III)klorid til råfosfatet i området fra 1 til 10 vekt-% referert til råfosfat for gjennomføringen av den halogenerende røsteprosess fordelaktig da innholdet av uønsket tungmetall dessuten kan senkes videre. Dette berør tydeligvis ikke på en direkte fortrengningprosess av eksempelvis kadmium- mot jernioner, da tilsatte natrium-ioner (i form av natriumklorid) ikke viser effekten av jern(III)klorid. According to the invention, an addition of iron or iron compounds, in particular of iron (III) chloride to the raw phosphate in the range from 1 to 10% by weight referred to raw phosphate for carrying out the halogenating roasting process is advantageous as the content of unwanted heavy metal can also be further lowered. This clearly does not concern a direct displacement process of, for example, cadmium against iron ions, as added sodium ions (in the form of sodium chloride) do not show the effect of iron (III) chloride.
Fremgangsmåten ifølge oppfinnelsen kan også anvendes til bortføring av bly, tallium eller arsen fra råfosfat. The method according to the invention can also be used to remove lead, thallium or arsenic from raw phosphate.
Etter den halogenerende røsting har råfosfatet et halogen-innehold på ca. 1-3%. Da et slikt halogeninnhold ville forstyrre den videre forarbeidelse av råfosfatet til fremstilling av gjødningsmiddél ved sur oppslutning i henhold til Odda-fremgangsmåten kan det til den halogenerende røst-ing slutte seg en etterbehandling av råfosfatet, idet man ekstraherer dette etter avkjøling med vann som er mest mulig fritt for halogenioner. After the halogenating roasting, the raw phosphate has a halogen content of approx. 1-3%. As such a halogen content would interfere with the further processing of the raw phosphate for the production of fertilizer by acid digestion according to the Odda method, a post-treatment of the raw phosphate can be added to the halogenating roasting, extracting this after cooling with water that is the most possibly free of halogen ions.
Generelt er det tilstrekkelig når det fortsettes med vaskeprosessen så lenge inntil det er oppnådd et halogenidinnhold av råfosfatet på 0,005%. Vaskeprosessen kan foretas på kjent måte ved digerering, oppslemming, filtrering og lignende. In general, it is sufficient when the washing process is continued until a halide content of the raw phosphate of 0.005% has been achieved. The washing process can be carried out in a known manner by digestion, slurrying, filtration and the like.
Det benyttede vann kan etter adskillelse av halogenidionene, f.eks. ved hjelp av en ioneutveksler tilbakeføres i vaskeprosessen. The water used can, after separation of the halide ions, e.g. with the help of an ion exchanger is returned in the washing process.
Fremgangsmåten skal forklares nærmere ved hjelp av følgende eksempler. The procedure shall be explained in more detail using the following examples.
Eksempel 1Example 1
Togo-fosfat med et innhold på 35,5% P2°5'50,2% Ca0'1,1% Fe203, 1.1% Al2°3'2'2% H2°°958 Cd/g ble behandlet Togo phosphate with a content of 35.5% P2°5'50.2% Ca0'1.1% Fe2O3, 1.1% Al2°3'2'2% H2°°958 Cd/g was treated
i en elektrisk oppvarmet røreovn som var utrustet med et rør av kvartsglass (diameter 35 mm) under de i.følgende tabell I nevnte betingelser med klor. Prøvenes kadmiumkonsentrasjon in an electrically heated stirring oven which was equipped with a tube of quartz glass (diameter 35 mm) under the conditions mentioned in the following table I with chlorine. The samples' cadmium concentration
ble bestemt ved atomabsorbsjon. was determined by atomic absorption.
Eksempel 2 Example 2
Det ble gått frem som omtalt i eksempel 1, men istedenfor klor ble det anvendt klorhydrogen. Følgende tabell II gjengir forsøksresultatene. The procedure was as described in example 1, but instead of chlorine hydrogen chloride was used. The following Table II reproduces the experimental results.
Eksempel 3 Example 3
Det ble gått frem ifølge eksempel 1, men til råfosfatet på forhånd blandet 10% natriumklorid respektiv 5% jern(III)klorid. Som det fremgår av tabell III fører behandlingen bare i til-felle av jern(III)klorid til en forbedring av resultatene. The procedure was carried out according to example 1, but 10% sodium chloride and 5% iron(III) chloride, respectively, were mixed beforehand with the raw phosphate. As can be seen from Table III, the treatment only leads to an improvement in the results in the case of iron (III) chloride.
Eksempel 4 Example 4
Råfosfatet ble etter den klorerende røstning slik den er omtalt i eksempel 1, vasket med destillert vann (forhold råfosfat til vann 1:5), filtrert og ettervasket med noe vann (forhold råfosfat til vann 2:1). Kloriddelen kunne således for en stor del fjernes. After the chlorinating roasting as described in example 1, the raw phosphate was washed with distilled water (ratio of raw phosphate to water 1:5), filtered and rewashed with some water (ratio of raw phosphate to water 2:1). The chloride part could thus be largely removed.
Eksempel 5 Example 5
Togo-fosfat med et innhold på 5 3 yg Cd/g ble behandlet i en elektrisk oppvarmet røreovn som var utrustet med rør av kvartsglass (diameter 35 mm) under de i følgende tabell nevnte betingelser med en blanding av nitrogen og CC14. Til fremstilling av blandingen ble nitrogen ved 50°C ført gjennom flytende tetraklorkarbon. Prøvenes kadmiumkosentra-sjon ble bestemt ved atmonabsorbsjon. Togo phosphate with a content of 53 µg Cd/g was treated in an electrically heated stirring furnace equipped with quartz glass tubes (diameter 35 mm) under the conditions mentioned in the following table with a mixture of nitrogen and CC14. To prepare the mixture, nitrogen at 50°C was passed through liquid carbon tetrachloride. The samples' cadmium concentration was determined by atmospheric absorption.
Eksempel 6 Example 6
Togo-fosfat blandet med 10% ammoniumklorid og i blandingen analysert et innhold på 4 8 ygCd/g. Av blandingen ble prøver (30 g) oppvarmet i røreovn ifølge eksempel 1 i luftstrøm. Prøvenes kadmiuminnhold gjengir i avhengighet av tempera-turen tabellen: Togo phosphate mixed with 10% ammonium chloride and in the mixture analyzed a content of 4 8 ygCd/g. Samples (30 g) of the mixture were heated in a stirrer according to example 1 in a stream of air. The cadmium content of the samples, depending on the temperature, is reproduced in the table:
Eksempel 7 Example 7
Over Togo-fosfatprøver (35-40 g) med et innhold på 53 ygCd/g ble det i røreovn ført en blanding av ammoniumkloriddamp og luft. Råfosfatprøvene ble oppvarmet til de i tabellen nevnte temperaturer. Etter behandlingen ble det bestemt følgende kadmiumkonsentrasj oner: A mixture of ammonium chloride vapor and air was passed over Togo phosphate samples (35-40 g) with a content of 53 ygCd/g in a stirring oven. The raw phosphate samples were heated to the temperatures mentioned in the table. After the treatment, the following cadmium concentrations were determined:
Claims (9)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823226306 DE3226306A1 (en) | 1982-07-14 | 1982-07-14 | Process for the separation of heavy metal ions from crude phosphate |
| DE19823242354 DE3242354A1 (en) | 1982-11-16 | 1982-11-16 | Method of separating heavy-metal ions from crude phosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO832550L true NO832550L (en) | 1984-01-16 |
Family
ID=25803044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO832550A NO832550L (en) | 1982-07-14 | 1983-07-13 | PROCEDURE FOR SEPARATING HEAVY METAL METIONS FROM RAA PHOSPHATE |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0099096A1 (en) |
| ES (1) | ES8403834A1 (en) |
| NO (1) | NO832550L (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3922073A1 (en) * | 1989-07-05 | 1991-01-17 | Metallgesellschaft Ag | METHOD FOR REMOVING THALLIUM FROM WORK LEAD |
| DE19615297A1 (en) * | 1996-04-18 | 1997-10-23 | Sachsenwerk Ag | Control panel with shutter covers |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2773736A (en) * | 1952-08-08 | 1956-12-11 | Smith Douglass Company Inc | Treatment of phosphate rock to recover phosphorus, fluorine, calcium, and uranium |
| FR1083310A (en) * | 1953-09-12 | 1955-01-07 | Osakeyhtio Vucksenniska Aktieb | Treatment of ores by chlorination |
| US3133791A (en) * | 1961-06-14 | 1964-05-19 | Nat Distillers Chem Corp | Method of sludge inhibition in phosphoric acid |
| US3383181A (en) * | 1965-04-08 | 1968-05-14 | American Potash & Chem Corp | Process of halogenating a phosphate ore |
-
1983
- 1983-07-11 EP EP83106783A patent/EP0099096A1/en not_active Withdrawn
- 1983-07-12 ES ES524057A patent/ES8403834A1/en not_active Expired
- 1983-07-13 NO NO832550A patent/NO832550L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES524057A0 (en) | 1984-04-16 |
| EP0099096A1 (en) | 1984-01-25 |
| ES8403834A1 (en) | 1984-04-16 |
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