NO156685B - PROCEDURE FOR SEPARATING CADMIUM AND MERCURY OIL COMPOUNDS FROM RAA PHOSPHORIC ACID. - Google Patents
PROCEDURE FOR SEPARATING CADMIUM AND MERCURY OIL COMPOUNDS FROM RAA PHOSPHORIC ACID. Download PDFInfo
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- NO156685B NO156685B NO823584A NO823584A NO156685B NO 156685 B NO156685 B NO 156685B NO 823584 A NO823584 A NO 823584A NO 823584 A NO823584 A NO 823584A NO 156685 B NO156685 B NO 156685B
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- phosphoric acid
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims description 39
- 238000000034 method Methods 0.000 title claims description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims description 20
- 150000001875 compounds Chemical class 0.000 title claims description 14
- 229910052793 cadmium Inorganic materials 0.000 title claims description 13
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims description 10
- 238000000605 extraction Methods 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- -1 hydroxy, carboxy, carboxy Chemical group 0.000 claims description 13
- 229910001385 heavy metal Inorganic materials 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 230000029087 digestion Effects 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims 1
- 125000006526 (C1-C2) alkyl group Chemical group 0.000 claims 1
- 125000006704 (C5-C6) cycloalkyl group Chemical group 0.000 claims 1
- 229940065285 cadmium compound Drugs 0.000 claims 1
- 239000000295 fuel oil Substances 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 150000002731 mercury compounds Chemical class 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- 150000002903 organophosphorus compounds Chemical class 0.000 claims 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 description 22
- 235000011007 phosphoric acid Nutrition 0.000 description 16
- 239000012071 phase Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 235000021317 phosphate Nutrition 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 6
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FLQUDUCNBDGCRI-UHFFFAOYSA-N hydroxy-sulfanyl-sulfidophosphanium Chemical compound SP(S)=O FLQUDUCNBDGCRI-UHFFFAOYSA-N 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000184 acid digestion Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- JDVWGULGWXRMSD-UHFFFAOYSA-N butoxy-cyclohexyl-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCOP(S)(=S)C1CCCCC1 JDVWGULGWXRMSD-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- TYWAKIKWTGMYJY-UHFFFAOYSA-N dicyclohexyl-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound C1CCCCC1P(=S)(S)C1CCCCC1 TYWAKIKWTGMYJY-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- CLUOCCWZZAGLPM-UHFFFAOYSA-N diphenyl-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(=S)(S)C1=CC=CC=C1 CLUOCCWZZAGLPM-UHFFFAOYSA-N 0.000 description 1
- 239000010771 distillate fuel oil Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005192 partition Methods 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
- 238000005191 phase separation Methods 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000004685 tetrahydrates 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
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
- C01B25/237—Selective elimination of impurities
- C01B25/238—Cationic impurities, e.g. arsenic compounds
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/385—Thiophosphoric acids, or esters thereof
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Extraction Or Liquid Replacement (AREA)
- Fertilizers (AREA)
- Processing Of Solid Wastes (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Description
Oppfinnelsen vedrører en fremgangsmåte til adskillelse av tungmetallbestanddeler, spesielt kadmium og kvikksølv,fra råfosforsyrer som fremstilles ved oppslutning av råfosfater med salpetersyre og hvorfra hovedmengden av det dannede kalsiumnitrat er fjernet. The invention relates to a method for separating heavy metal constituents, especially cadmium and mercury, from raw phosphoric acids which are produced by digesting raw phosphates with nitric acid and from which the main amount of the formed calcium nitrate has been removed.
Fosforholdige gjødningsmidler fremstilles ofte ved sur oppslutning av fosforitt eller apatitt. Under innvirkning av mineralsyre spaltes råfosfatets tungtoppløselige trikalsium-fosfat. De anvendte mineralsyrers kalsiumsalter må deretter adskilles for å få den dannede rå fosforsyre som produkt. Phosphorus-containing fertilizers are often produced by acid digestion of phosphorite or apatite. Under the influence of mineral acid, the crude phosphate's sparingly soluble tricalcium phosphate is split. The calcium salts of the mineral acids used must then be separated to obtain the raw phosphoric acid formed as a product.
I råfosfatet inneholdte metalliske forurensninger som Cd, Pb, Hg og As, forblir for en stor del i fosforsyren. Da denne syre ikke er egnet for alle anvendelsesformål, er det alle-rede foretatt tallrike forsøk for å befri den fra uønskede metalliske forurensninger. For forarbeidelsen av rå fosforsyre til gjødningsmiddel byr disse forslag imidlertid på ingen teknisk gunstig vei. Metallic impurities such as Cd, Pb, Hg and As contained in the raw phosphate remain to a large extent in the phosphoric acid. As this acid is not suitable for all applications, numerous attempts have already been made to free it from unwanted metallic impurities. For the processing of raw phosphoric acid into fertiliser, however, these proposals do not offer a technically favorable route.
Således omtaler AMDEL Bull. 1976 (19) 1-10, for fjerning Thus mentions AMDEL Bull. 1976 (19) 1-10, for removal
av kadmium fra råfosfat ved kalsinering, en økonomisk meget omstendelig fremgangsmåte. Ifølge DE-OS 24 22 902 kan kadmium fjernes ved trykkfelling med hydrogensulfid. For-uten den vanskelighet å måtte arbeide med hydrogensulfid under trykk, er det for gjennomføring av fremgangsmåten nød-vendig med overholdelse av bestemte konsentrasjoner av P2°5' Ifølge japansk offentliggjort patentsøknad 1979/37 096 fore-slås en fremgangsmåte hvor i to trinn, ved behandling med et vannoppløselig organisk oppløsningsmiddel og destillasjon samt eventuelt ved etterfølgende ekstrahering, fosforsyre skal renses. Også kadmiumadskillelse ved hjelp av ioneut-vekslere er omtalt (japansk offentliggjort patentsøknad 1978/56 190). Heller ikke fastlagringselektrolyse (Metall-overflache 34 (1980) 494-501) byr noen måte til løsning av problemene. of cadmium from raw phosphate by calcination, an economically very cumbersome process. According to DE-OS 24 22 902, cadmium can be removed by pressure precipitation with hydrogen sulphide. In addition to the difficulty of having to work with hydrogen sulphide under pressure, for the implementation of the method it is necessary to comply with certain concentrations of P2°5' According to Japanese published patent application 1979/37 096, a method is proposed where in two steps, by treatment with a water-soluble organic solvent and distillation and possibly by subsequent extraction, phosphoric acid must be purified. Cadmium separation using ion exchangers is also discussed (Japanese published patent application 1978/56 190). Neither does fixed storage electrolysis (Metall-overflache 34 (1980) 494-501) offer any way to solve the problems.
De foreslåtte fremgangsmåter er spesielt uegnet til å befri den ved oppslutning av råfosfat ved hjelp av 60%-ig salpetersyre etter den kjente Odda-fremgangsmåte dannede rå fosforsyre for tungmetallioner. The proposed methods are particularly unsuitable for freeing the crude phosphoric acid formed by digestion of raw phosphate using 60% nitric acid according to the known Odda method from heavy metal ions.
Ved Odda-prosessen avkjøles den sterkt salpetersyreholdige våtfosforsyre av oppslutningen for utskillelse av kalsiumnitrat hvis oppløselighet er sterkt temperaturavhengig og kalsiumnitrat adskilles som tetrahydrat. I råfosfatet til-stedeværende tungmetallioner som Cd, Pb, Hg og As forblir for en stor del i oppslutningens oppløsning, den såkalte modersyre. Modersyren inneholder vanligvis 15-20 vekt-% P205, 30-35 vekt-% HN03 og 7-10 vekt-% CaO. In the Odda process, the highly nitric acid-containing wet phosphoric acid is cooled from the digestion to separate calcium nitrate, the solubility of which is strongly temperature-dependent, and calcium nitrate is separated as tetrahydrate. Heavy metal ions such as Cd, Pb, Hg and As present in the raw phosphate remain to a large extent in the digestion solution, the so-called mother acid. The mother acid usually contains 15-20 wt% P2O5, 30-35 wt% HN03 and 7-10 wt% CaO.
Deretter nøytraliseres vanligvis modersyren trinnvis med ammoniakk under fordampning av vann og den dannede krystall-grøt blandes med kalsiumsalter og granuleres til gjødnings-midler. The mother acid is then usually neutralized step by step with ammonia while evaporating water and the formed crystal slurry is mixed with calcium salts and granulated into fertilisers.
Til grunn for oppfinnelsen lå således den oppgave å frem-bringe en fremgangsmåte med hvis hjelp det kunne fremstilles kadmium- og kvikksølvfattige gjødningsmidler etter Odda-prosessen . The basis for the invention was thus the task of producing a method with the help of which cadmium- and mercury-poor fertilizers could be produced according to the Odda process.
Det er nå overraskende funnet at man fortrinnsvis kan løse denne oppgave ved at man innstiller den ved Odda-fremgangsmåten fremkomne modersyre med ammoniakk til en pH-verdi i området på 0,5-1,5, spesielt 0,6-1,2, og ekstraherer den således dannede fosforsyre-oppløsning, fortrinnsvis i mot-strøm med et med vann ikke eller bare litt blandbart opp-løsningsmiddel, idet som oppløsningsmiddel velges en fosforforbindelse fra gruppen ditiofosforsyre-di-ester, ditiofosfonsyre-O-ester og ditiofosfinsyre og anvendes fortrinnsvis i blanding med inert organisk fortynningsmiddel. It has now surprisingly been found that this task can preferably be solved by adjusting the mother acid produced by the Odda method with ammonia to a pH value in the range of 0.5-1.5, especially 0.6-1.2, and extracts the phosphoric acid solution thus formed, preferably in countercurrent with a solvent that is not or only slightly miscible with water, the solvent being a phosphorus compound selected from the group dithiophosphoric acid diester, dithiophosphonic acid O-ester and dithiophosphinic acid and used preferably in mixture with inert organic diluent.
Overholdelse av ovennevnte pH-verdiområde er fremfor alt spesielt viktig for ekstraksjon og adskillelse av kadmium. Compliance with the above pH value range is above all particularly important for the extraction and separation of cadmium.
I området av sure pH-verdier hindres på den annen side en ekstrahering av modersyren ved at det samtidig opptrer kom-plekse utfellinger av fosfater, kiselgel, kalsium-, magnesium-og aluminiumforbindelser. In the range of acidic pH values, on the other hand, extraction of the mother acid is prevented by the simultaneous occurrence of complex precipitations of phosphates, silica gel, calcium, magnesium and aluminum compounds.
For måling av pH-verdien i konsentrerte mineralsure oppløs-ninger anvendes glasselektroder,hensiktsmessig enstav-målekjeder med referansesystem Ag/AgCl, referanseelektrolytt 3m KCl+AgCl eller 3,5m KC1. Det kan anvendes spesielt hydrogensulfidsikre enstav-målekjeder som f.eks. er utrustet med to etter hverandre koplede ved hjelp av diafragmer adskilte elektrolyttkamre. pH-verdiene kan måles i den konsentrerte oppløsning uten fortynning og ved værelsestemperatur. For measuring the pH value in concentrated mineral acid solutions, glass electrodes are used, preferably single-stick measuring chains with reference system Ag/AgCl, reference electrolyte 3m KCl+AgCl or 3.5m KC1. Particularly hydrogen sulphide-proof single-bar measuring chains can be used, such as e.g. is equipped with two electrolyte chambers connected one after the other, separated by diaphragms. The pH values can be measured in the concentrated solution without dilution and at room temperature.
Det er kjent at ditiofosforsyredialkylester (sammenlign US-patent 2 523 147, 2 705 694 og 2 798 880) og ditiofosfin-syrer samt ditiofosfonsyre-O-estere (fransk patent 1 396 093 og US-patent 3 300 409) er lett oksyderbare og derfor kan anvendes som antioksydanter. Det måtte derfor ventes at nærvær av oksydasjonsmidler som høye konsentrasjoner av nitrationer i sur oppløsning er en hindring for en ekstraktiv behandling av ovennevnte modersyre ved hjelp av ekstraheringsmidlet ifølge oppfinnelsen. Modersyren inneholder fra oppslutningen dessuten nitroksyder (NOx). It is known that dithiophosphoric acid dialkyl esters (compare US Patent 2,523,147, 2,705,694 and 2,798,880) and dithiophosphinic acids as well as dithiophosphonic acid O-esters (French Patent 1,396,093 and US Patent 3,300,409) are easily oxidizable and can therefore be used as antioxidants. It should therefore be expected that the presence of oxidizing agents such as high concentrations of nitrate ions in acidic solution is an obstacle to an extractive treatment of the above-mentioned mother acid with the aid of the extractant according to the invention. The mother acid also contains nitroxides (NOx) from digestion.
De ifølge oppfinnelsen som ekstraheringsmiddel egnede fosforforbindelser, har den generelle formel I According to the invention, the phosphorus compounds suitable as extractants have the general formula I
hvori og 1*2 er like eller forskjellige og betyr mettede eller umettede alifatiske, aralifatiske eller aromatiske hydrokarbonrester med 1 til 18 C-atomer som eventuelt er substituert,og R^ og R2 har tilsammen 6 til 36 C-atomer, wherein and 1*2 are the same or different and mean saturated or unsaturated aliphatic, araliphatic or aromatic hydrocarbon residues with 1 to 18 C atoms which are optionally substituted, and R 1 and R 2 together have 6 to 36 C atoms,
fortrinnsvis 8 til 24 C-atomer, samt eventuelt også sammen danner en eventuelt substituert tobundet rest og n betyr hver gang uavhengig av hverandre tallene 0 eller 1. preferably 8 to 24 C atoms, and optionally also together form an optionally substituted double-bonded residue and n each time independently means the numbers 0 or 1.
Som eksempler for ekstraheringsmidler ifølge oppfinnelsen med formel I skal det bl.a. nevnes: ditiofosforsyre-di-(2-etyl-heksyl)-ester As examples of extractants according to the invention with formula I, there shall be i.a. are mentioned: dithiophosphoric acid di-(2-ethylhexyl)-ester
ditiofosforsyre-di-isotridecyl-ester dithiophosphoric acid diisotridecyl ester
ditiofosforsyre-di-sek-butyl-ester dithiophosphoric acid di-sec-butyl ester
ditiofosforsyre-di-kresyl-ester dithiophosphoric acid di-cresyl ester
cykloheksyl-ditiofosfonsyre-O-n-butylester cyclohexyl dithiophosphonic acid O-n-butyl ester
di-cykloheksyl-ditiofosfinsyre di-cyclohexyl-dithiophosphinic acid
di-fenyl-ditiofosfinsyre di-(tricyklo-(5,2,1,0 2 ' 6)decenyl)-ditiofosfinsyre naftalin-2-ditio-fosfonsyre-O-etylester. di-phenyl-dithiophosphinic acid di-(tricyclo-(5,2,1,0 2 ' 6)decenyl)-dithiophosphinic acid naphthalene-2-dithio-phosphonic acid O-ethyl ester.
Mengden av ekstraheringsmiddel san.skal anvendes ifølge oppfinnelsen er ikke kritisk og kan svinge innen vide om-råder. Fortrinnsvis anvendes de imidlertid i mengder på 0,05-50 vekt-%, spesielt i mengder på 0,1-10 vekt-%, referert til mengden av modersyre. The amount of extractant to be used according to the invention is not critical and can vary within wide ranges. Preferably, however, they are used in amounts of 0.05-50% by weight, especially in amounts of 0.1-10% by weight, referred to the amount of parent acid.
Ekstraheringsmidlene ifølge oppfinnelsen kan anvendes enkeltvis eller som blanding. Ved forbindelsene med formel I med substituerte rester R, og R2 kommer det fortrinnsvis på tale substitusjoner med halogen, hydroksy-, alkoksy-, karboksy- eller NC^-grupper, hvis de resulterende rester til sammen er tilstrekkelig hydrofobe for at forbindelsene med formel I i ønsket grad er tungt opp-løselige i vann. The extractants according to the invention can be used individually or as a mixture. In the case of the compounds of formula I with substituted residues R, and R2, substitutions with halogen, hydroxy, hydroxy, carboxy or NC^ groups are preferably used, if the resulting residues together are sufficiently hydrophobic for the compounds of formula I to the desired extent are poorly soluble in water.
Foretrukne forbindelser med formel I er videre slike hvori Preferred compounds of formula I are further those in which
R-j^ og R2 er lik (C1-C1Q )-alkyl, ( C^- C^ )-cykloalkyl, fenyl-(C1~C2 )-alkyl, fenyl, med (C-^-C^)-alkyl substituert f enyl, naftyl, som hver gang eventuelt er substituert med halogen, hydroksy, alkoksy, karboksy eller N02, eller tricyklodecenyl, idet R-^ og R2 sammen har 8 til 24 C-atomer. R-j^ and R2 are equal to (C1-C1Q )-alkyl, (C^-C^ )-cycloalkyl, phenyl-(C1-C2 )-alkyl, phenyl, with (C-^-C^)-alkyl substituted with phenyl .
Det i forhold til fosforforbindelsen ifølge oppfinnelsen anvendte begrep med tungt oppløselig i vann betyr imidlertid ikke at de angjeldende forbindelser må være fullstendig uoppløselige, men bare at forbindelsene i forhold til fasen av salpeter-syreholdig fosforsyre må ha en tilstrekkelig ikke-blandbarhet for å muliggjøre en adskillelse av væskene i to forskjellige faser. However, the term poorly soluble in water used in relation to the phosphorus compound according to the invention does not mean that the compounds in question must be completely insoluble, but only that the compounds in relation to the phase of nitric acid-containing phosphoric acid must have a sufficient immiscibility to enable a separation of the liquids into two different phases.
Enskjønt fosforforbindelsen ifølge oppfinnelsen med formel I Although the phosphorus compound according to the invention with formula I
i ufortynnet, flytende form er fremragende egnet til ekstrahering, er 'i.å foretrekke å anvende den i blanding med inerte organiske fortynningsmidler for å oppnå en enda bedre hånd-tering og regulering av ekstraheringen og bl.a. også av økonomiske grunner. in undiluted, liquid form is excellently suitable for extraction, it is preferable to use it in a mixture with inert organic diluents to achieve even better handling and regulation of the extraction and i.a. also for financial reasons.
Ved de organiske fortynningsmidler egnet til anvendelsen By the organic diluents suitable for the application
ifølge oppfinnelsen dreier det seg om slike organiske oppløs-ningsmidler, hvori forbindelsene med formel I er oppløselige og som dessuten praktisk talt er uoppløselig i de til pH according to the invention, it concerns such organic solvents in which the compounds of formula I are soluble and which are also practically insoluble in those at pH
0,5 til 1,5 innstilte rå nitrationeholdige fosforsyreoppløs-ninger og forholder seg kjemisk indifferente overfor sistnevnte. Det kommer her på tale et stort antall forskjellige organiske oppløsningsmidler som eksempelvis petroleumbensin, kerosin, fyringsolje ekstra lett, dekahydronaftalin, tetrabrometan eller xylen. Mengdeforholdet mellom forbindelsene med formel I og inerte organiske oppløsningsmidler kan varieres innen vide grenser. Foretrukket er vektforholdet fra 1:2 til 1:50, spesielt 1:5 til 1:20. 0.5 to 1.5 adjusted crude phosphoric acid solutions containing nitrate ions and are chemically indifferent to the latter. A large number of different organic solvents come into question here, such as petroleum petrol, kerosene, extra-light fuel oil, decahydronaphthalene, tetrabromoethane or xylene. The quantity ratio between the compounds of formula I and inert organic solvents can be varied within wide limits. The weight ratio is from 1:2 to 1:50, especially 1:5 to 1:20.
Ekstraheringsfremgangsmåten ifølge oppfinnelsen samt også tilbakeekstraherings- eller fjerningsfremgansmåten til eliminering av tungmetallbestanddelene fra ekstraheringsmiddel og gjenanvendelse av sistnevnte kan gjennomføres kontinuerlig eller diskontinuerlig, respektivt porsjonsvis. The extraction method according to the invention as well as the back-extraction or removal method for eliminating the heavy metal constituents from the extractant and reusing the latter can be carried out continuously or discontinuously, respectively in portions.
Ved diskontinuerlig fremgangsmåte kan det være nødvendig å gjenta ekstraheringen så ofte inntil det oppnås den ønskede grad av ekstraheringseffekt. In the case of a discontinuous method, it may be necessary to repeat the extraction as often until the desired degree of extraction effect is achieved.
Ved kontinuerlig fremgangsmåte kan det f.eks. fortrinnsvis arbeides i motstrøm med de fosforsure oppløsninger til ekstra-her ingsmiddel fasen . In a continuous process, it can e.g. preferably work in countercurrent with the phosphoric acid solutions for the extractant phase.
Ekstraheringen kan gjennomføres i et bredt temperaturområde ved lav eller forhøyet temperatur, fortrinnsvis mellom 5 og 120°C, spesielt ved 10 til 90°C. Spesielt foretrukket er normaltemperatur og omgivelsestemperatur. Det kan også arbeides ved normalt trykk eller forhøyet trykk. For bedring av faseadskillelsen kan den to-fasede ekstraheringsblanding has på en sentrifuge, f.eks. en separator. The extraction can be carried out in a wide temperature range at low or elevated temperature, preferably between 5 and 120°C, especially at 10 to 90°C. Particularly preferred are normal temperature and ambient temperature. It can also be worked at normal pressure or elevated pressure. To improve the phase separation, the two-phase extraction mixture can be centrifuged, e.g. a separator.
For fagmannen kunne det på ingen måte forutsees at ved fremgangsmåten ifølge oppfinnelsen ville lykkes fra konsentrerte fosforsyre-oppløsninger, hvis egenskap med tungmetallioner å danne stabile komplekser er kjent, med en høy fordelings-koeffisient praktisk talt fullstendig å ekstrahere tungmetall-ionene som f.eks. kadmium. Derved er fordelingskoeffisientene så store at selv et faseforhold mellom vandig og organisk fase (f.eks. 10%-ig oppløsning av ditiofosforsyre-di-esteren i tungbensin) på 50:1 i en-trinns ekstrahering medfører god adskillelse av elementene Cd og Hg. Dette resultat er desto mer overraskende når ekstrahering med sammenlignbare fosfor-syrediestere i stedet for ditiofosforsyre-di-estere svikter fullstendig (sammenlign sammenligningseksempler 1-2). For the person skilled in the art, it could in no way be foreseen that the method according to the invention would succeed in extracting the heavy metal ions practically completely from concentrated phosphoric acid solutions, whose property with heavy metal ions to form stable complexes is known, with a high partition coefficient . cadmium. Thereby, the distribution coefficients are so large that even a phase ratio between aqueous and organic phase (e.g. 10% solution of the dithiophosphoric acid diester in heavy petrol) of 50:1 in a one-stage extraction results in good separation of the elements Cd and Hg . This result is all the more surprising when extraction with comparable phosphoric acid diesters instead of dithiophosphoric acid diesters fails completely (compare Comparative Examples 1-2).
De metalliske forurensninger som er blitt ekstrahert i den organiske ekstraheringsmiddelfase kan generelt igjen fjernes fra denne fase ved tilbakeestrahering med vann eller sure vandige oppløsninger, f.eks. fortynnede mineralsyrer. På denne måte kan det organiske ekstraheringsmiddel regenereres på fordelaktig måte, mens tungmetall-bestanddelene går over i den vandige fase. Derved kan fortrinnsvis den organiske ekstrasjonsmiddelholdige fase i første rekke ekstraheres med en vandig oppløsning av en alkalisk forbindelse før man behandler den med fortynnet mineralsyre, som f.eks. fortynnet saltsyre. Alkalisk ekstrakt og surt ekstrakt kan deretter forenes. Ved det første av de to deltrinn ekstraheres arsen og delvis kadmium, mens ved annet trinn fjernes kvantitativt kadmium og kvikksølv. Ved endring av rekkefølgen eller økning av tallet av enkelttrinn ved reekstraheringen av tungmetallene fra den organiske fase kan bestemte tungmetaller anrikes i re-ekstraheringsoppløsningen. Fra de vandige reekstraherings-oppløsninger kan tungmetallene utskilles og isoleres ved felling, f.eks. som hydroksyder eller sulfider. The metallic impurities which have been extracted in the organic extractant phase can generally be removed again from this phase by back-extraction with water or acidic aqueous solutions, e.g. diluted mineral acids. In this way, the organic extractant can be advantageously regenerated, while the heavy metal components pass into the aqueous phase. Thereby, the organic extractant-containing phase can be primarily extracted with an aqueous solution of an alkaline compound before treating it with dilute mineral acid, such as e.g. dilute hydrochloric acid. Alkaline extract and acidic extract can then be combined. In the first of the two sub-steps, arsenic and some cadmium are extracted, while in the second step cadmium and mercury are quantitatively removed. By changing the sequence or increasing the number of individual steps in the re-extraction of the heavy metals from the organic phase, certain heavy metals can be enriched in the re-extraction solution. From the aqueous re-extraction solutions, the heavy metals can be separated and isolated by precipitation, e.g. such as hydroxides or sulfides.
Oppfinnelsen skal forklares nærmere ved hjelp av noen eksempler. The invention will be explained in more detail with the help of some examples.
Eksemp_el_l-16 Example_el_l-16
Ved hjelp av oppslutning av råfosfater med salpetersyre etter Odda-fremgangsmåten dannede og klarede modersyrer innstilles med gassformet ammoniakk på de i følgende tabell angitte pH-verdier (den fosforsure fase). Dertil settes de i tabell I oppførte ekstraheringsmidler ifølge oppfinnelsen i mengde-forhold mellom uorganisk fase og organisk fase mellom 5:1 By digesting raw phosphates with nitric acid according to the Odda method, mother acids formed and clarified are adjusted with gaseous ammonia to the pH values indicated in the following table (the phosphoric acid phase). In addition, the extractants according to the invention listed in table I are added in a quantity ratio between inorganic phase and organic phase of between 5:1
og 50:1 og behandles i 3-5 minutter under intens sammenblanding med røreapparat. Vekt-%-en av forbindelsene A refererer seg til fortynningsmiddel B. Ekstraheringstemperaturen ut-gjør 25°C, med unntak av eksemplene 8 og 9. Her ble det valgt en temperatur på 70°C. and 50:1 and processed for 3-5 minutes under intense mixing with a stirrer. The weight % of compounds A refers to diluent B. The extraction temperature is 25°C, with the exception of examples 8 and 9. Here, a temperature of 70°C was chosen.
Deretter sentrifugeres prøvene 2-5 minutter og den to- The samples are then centrifuged for 2-5 minutes and the two-
fasede blanding skilles i skilletrakt. De dannede fosforsyre-oppløsninger blandes med noe konsentrert saltsyre og analyseres ved hjelp av atomabsorbsjon. De funnede tung-metallinnhold omregnes til den ammoniakkbehandlede modersyre respektivt refereres til den organiske ekstraheringsmiddelfase. The phased mixture is separated in a separatory funnel. The phosphoric acid solutions formed are mixed with some concentrated hydrochloric acid and analyzed using atomic absorption. The heavy metal contents found are converted to the ammonia-treated mother acid or referred to the organic extractant phase.
Følgende tabell 1 gir detaljer og resultat av de gjennomførte eksempler 1-16 i sammenfattet form. The following table 1 gives details and results of the carried out examples 1-16 in a summarized form.
Eksemgel_17-18 Eczema_17-18
Analogt eksemplene 1-14 fremstilte og klaredé modersyrer innstilles med ammoniakk til pH 1,1 og ekstraheres med ditio-fosfosyre-di-(2-etylheksyl)-ester (10 vekt-% i petroleumbensin, kokepunkt 100-140°C) som omtalt i eksempel 11. Den resulterende organiske fase adskilles og reekstraheres deretter med konsentrert saltsyre i vektforhold 20:1 ved værelsestemperatur. Derved blandes godt blandingen av organisk fase og konsentrert saltsyre 5 minutter ved intens omrøring, deretter sentrifugeres. Den adskilte organiske fase har før og etter reekstraheringen de i tabell 2 sammenfattede gjen-gitte Cd-innhold: Analogous to examples 1-14, prepared and clarified mother acids are adjusted with ammonia to pH 1.1 and extracted with dithio-phosphoric acid di-(2-ethylhexyl)-ester (10% by weight in petroleum petrol, boiling point 100-140°C) as described in example 11. The resulting organic phase is separated and then re-extracted with concentrated hydrochloric acid in a weight ratio of 20:1 at room temperature. The mixture of organic phase and concentrated hydrochloric acid is thereby mixed well for 5 minutes with intense stirring, then centrifuged. The separated organic phase before and after re-extraction has the Cd contents summarized in table 2:
Analogt til eksemplene 1-16 fremstilte og klarede modersyrer innstilles med ammoniakk til pH 1,1 og ekstraheres med fosforsyre-di-(2-etylheksyl)-ester (forbindelse C) respektivt 2-merkapto-benz-tiazol (forbindelse D) i 10 vekt-%-ig organisk oppløsning i de i tabell 3 angitte organiske fortynningsmidler ved værelsestemperatur i bland-ingsforhold uorganisk:organisk fase = 10:1 (vektdeler) under intens sammenblanding ved omrøring. Etter utrøring og etterfølgende sentrifugering skilles fasene. Fosfor-syrefasen blandes med noe konsentrert saltsyre og analyseres ved hjelp av atojmabsorbsjon. Det fastslåtte Cd-innhold omregnes til den ammoniakkbehandlede modersyre. Resultatet er gjengitt i tabell 3. Analogous to examples 1-16, prepared and clarified mother acids are adjusted with ammonia to pH 1.1 and extracted with phosphoric acid di-(2-ethylhexyl) ester (compound C) or 2-mercapto-benz-thiazole (compound D) in 10 % by weight organic solution in the organic diluents specified in Table 3 at room temperature in a mixing ratio inorganic:organic phase = 10:1 (parts by weight) under intense mixing by stirring. After stirring and subsequent centrifugation, the phases are separated. The phosphoric acid phase is mixed with some concentrated hydrochloric acid and analyzed by atomic absorption. The determined Cd content is converted to the ammonia-treated mother acid. The result is reproduced in table 3.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813142666 DE3142666A1 (en) | 1981-10-28 | 1981-10-28 | Process for separating heavy-metal components from intermediates in the production of phosphorus fertilisers |
| DE19823209183 DE3209183A1 (en) | 1982-03-13 | 1982-03-13 | Process for separating heavy metal compounds from intermediates in the production of phosphate fertilisers |
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| Publication Number | Publication Date |
|---|---|
| NO823584L NO823584L (en) | 1983-04-29 |
| NO156685B true NO156685B (en) | 1987-07-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO823584A NO156685B (en) | 1981-10-28 | 1982-10-27 | PROCEDURE FOR SEPARATING CADMIUM AND MERCURY OIL COMPOUNDS FROM RAA PHOSPHORIC ACID. |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0078051B1 (en) |
| DE (1) | DE3273369D1 (en) |
| ES (1) | ES516846A0 (en) |
| NO (1) | NO156685B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| IL69100A (en) * | 1982-07-21 | 1986-11-30 | Hoechst Ag | Process for removing heavy metal ions and arsenic from wet-processed phosphoric acid |
| DE3341073A1 (en) * | 1983-11-12 | 1985-05-23 | Chemische Fabrik Budenheim Rudolf A. Oetker, 6501 Budenheim | Process for the simultaneous separation of cadmium(II) ions and uranium(IV) ions from phosphoric acid by combined extraction |
| DE3342211A1 (en) * | 1983-11-23 | 1985-05-30 | Chemische Fabrik Budenheim Rudolf A. Oetker, 6501 Budenheim | Process for extracting cadmium from acidic solutions |
| US4721605A (en) * | 1985-07-24 | 1988-01-26 | American Cyanamid Company | Selective removal of metals from aqueous solutions with dithiophosphinic acids |
| FR2629812B1 (en) * | 1988-04-12 | 1991-01-25 | Cerphos | PROCESS FOR REMOVAL OF HEAVY METALS, ESPECIALLY CADMIUM, CONTAINED IN PHOSPHORIC ACID |
| ES2020138A6 (en) * | 1990-04-27 | 1991-07-16 | Ercros Sa | Method for removing cadmium for phosphoric acid. |
| PH31603A (en) * | 1994-03-22 | 1998-11-03 | Goro Nickels S A | Process for the extraction and separation of nickel and/or cobalt. |
| DE10303177A1 (en) * | 2003-01-27 | 2004-07-29 | Max Bögl Bauunternehmung GmbH & Co. KG | Alignment of prefabricated parts in rigid roadway or track, especially for railway slab track permanent way, whereby a moving device with a tacheometer is used to measure target points and compare actual and set positions |
| ES2283207A1 (en) * | 2003-03-13 | 2007-10-16 | Cytec Tecnology Corp. | Process for removing metal impurities from wet process phosphoric acid and compositions thereof |
| US20040179984A1 (en) * | 2003-03-13 | 2004-09-16 | Nagaraj D. R. | Process for removing metal impurities from wet process phosphoric acid and compositions thereof |
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| US2523147A (en) * | 1948-06-14 | 1950-09-19 | Standard Oil Dev Co | Manufacture of organo-substituted acids of phosphorous |
| US4405722A (en) * | 1979-01-23 | 1983-09-20 | Asahi Glass Company Ltd. | Sealing glass compositions |
| FR2462481A1 (en) * | 1979-07-30 | 1981-02-13 | British Petroleum Co | METHOD FOR THE LIQUID-LIQUID EXTRACTION OF AQUEOUS SOLUTION-BASED METALS USING ORGANOPHOSPHORUS DERIVATIVES |
-
1982
- 1982-10-26 DE DE8282109876T patent/DE3273369D1/en not_active Expired
- 1982-10-26 ES ES516846A patent/ES516846A0/en active Granted
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| ES8501356A1 (en) | 1984-12-01 |
| DE3273369D1 (en) | 1986-10-23 |
| EP0078051A2 (en) | 1983-05-04 |
| EP0078051A3 (en) | 1984-03-28 |
| EP0078051B1 (en) | 1986-09-17 |
| ES516846A0 (en) | 1984-12-01 |
| NO823584L (en) | 1983-04-29 |
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