CS227135B1 - Method of preparing tanning liquors from chromium-containing waste sludge - Google Patents
Method of preparing tanning liquors from chromium-containing waste sludge Download PDFInfo
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- CS227135B1 CS227135B1 CS326582A CS326582A CS227135B1 CS 227135 B1 CS227135 B1 CS 227135B1 CS 326582 A CS326582 A CS 326582A CS 326582 A CS326582 A CS 326582A CS 227135 B1 CS227135 B1 CS 227135B1
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- Czechoslovakia
- Prior art keywords
- chromium
- sludge
- solution
- extraction stage
- extraction
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- 239000011651 chromium Substances 0.000 title claims description 25
- 239000010802 sludge Substances 0.000 title claims description 25
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 17
- 229910052804 chromium Inorganic materials 0.000 title claims description 16
- 239000002699 waste material Substances 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 6
- 239000000243 solution Substances 0.000 claims description 26
- 238000000605 extraction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003929 acidic solution Substances 0.000 claims description 4
- 150000001844 chromium Chemical class 0.000 claims description 4
- 229940117975 chromium trioxide Drugs 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 description 12
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical class [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 229940037003 alum Drugs 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RSYUFYQTACJFML-DZGCQCFKSA-N afzelechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C=C1 RSYUFYQTACJFML-DZGCQCFKSA-N 0.000 description 1
- 239000002610 basifying agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SYUXAJSOZXEFPP-UHFFFAOYSA-N glutin Natural products COc1c(O)cc2OC(=CC(=O)c2c1O)c3ccccc3OC4OC(CO)C(O)C(O)C4O SYUXAJSOZXEFPP-UHFFFAOYSA-N 0.000 description 1
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Description
Vynález sa týká spósobu přípravy činiacich roztokov z odpadných kalov obsahujúcich chrom.The invention relates to a process for the preparation of tanning solutions from chromium-containing waste sludge.
V kožiarskej a kožušníckej výrobě sa využívaje roztoky trojmocného chrómu pri chromočinení. Tieto roztoky sú označované ako chromité brečky. Koncentrácia kysličníka chromičitého v brečke sa pohybuje v rozmedzí 30 až 150 g/l, bázicita brečky je obvykle 20 až 50 °Sch. Podl’a spósobu přípravy sa brečky rozdeTujú na kamencové, redukované a kombinované. Kamencové brečky sa pripravujú rozpúšťaním síranu chromitodraselného vo vodě, pričom požadovaná bázicita sa dosiahne přidáním bázifikačných činidiel. Při přípravě redukovanej brečky sa vychádza z dvojchromanu, ktorý sa rozpustí vo vodě, přidá sa potřebné množstvo· kyseliny sírovej a prevedie sa redukcia šestimocného chrómu na trojmocný přidáním redukovadla. Kombinovaná brečka sa připravuje zo síranu chromtodraselného a dvojchromanu sodného alebo draselného súčasne.In the leather and fur production, chromium (III) solutions are used in chromium tanning. These solutions are referred to as chromium slurries. The concentration of chromium trioxide in the sludge is in the range of 30 to 150 g / l, the sludge basicity is usually 20 to 50 ° Sch. According to the method of preparation, slices are divided into alum, reduced and combined. Alum slurries are prepared by dissolving chromium potassium sulfate in water, the desired basicity being achieved by the addition of basifying agents. The preparation of the reduced slurry starts from dichromate, which is dissolved in water, the required amount of sulfuric acid is added and the reduction of hexavalent chromium to trivalent is carried out by the addition of a reducing agent. The combined slurry is prepared from both potassium-potassium sulfate and sodium or potassium dichromate simultaneously.
V kožiarskej výrobě vznikajú často kaly s obsahom chrómu, a to například v odpadných vodách alebo pri spracovaní pri chromočinení, například pri výrobě doplňkového krmivá hydrolyzátů glutinu. Obsahujú obyčajne 5 - 15 % hmotnostných Cr20j na sušinu kalu. Tieto kaly sa priamo nevyužívájú ani nespracovávajú; výnimku tvoří iba alkalické zražanie hydroxik du chromitého z izolovaných odpadných roztokov pri chromoči- 2 .227 135 není, kedy sa získá hydroxid chromítý v dostatočnej čistotě, takže ho možno priamo přidávat do reakčnej zmesi při přípravě redukovanéj brečky. Tieto postupy sú známe pri takzvanéjrekuperácii odpadných činiacich kúpeTov pri chromočinení. Vo váěšine prípadov odpadajú kaly hydroxidu chromitého silno znečistěné, takže ich priame použitie při vaření brečiek nie je možné· Také kaly sa vozia na skládky alebo sa kanalizujú, čím prisjdevajú k zvyšovaniu obsahu chrómu v primárných kaloch v čistiarňach odpadových vod. Přítomnost chrómu sťažuje využitelnost čistiareriských kalov v polnohospodárstve, vzhladom k přísným hygienickým predpisom platným v ČSSR.In the leather industry, sludges containing chromium are often produced, for example in waste water or in the treatment of chromium tanning, for example in the production of supplementary feed of glutin hydrolyzates. They usually contain 5 - 15% by weight of Cr 2 O 3 per dry sludge. These sludges are not directly used or processed; the only exception is the alkaline precipitation of chromium (III) hydroxides from the isolated waste solutions in chromium-2 (227) 135, where chromium hydroxide is obtained in sufficient purity so that it can be directly added to the reaction mixture in the preparation of a reduced slurry. These processes are known in the so-called recovery of waste tanning baths in chrome tanning. In most cases, the slurries of chromium hydroxide are heavily contaminated, so that their direct use in boiling sludge is not possible. The presence of chromium makes it difficult to use sewage sludge in agriculture due to the strict hygiene regulations in force in Czechoslovakia.
Uvedené nevýhody v podstatnej miere odstraňuje spdsob přípravy činiacich roztokov z odpadných kalov obsahujúcich chrom, ktorého podstata spočívá v tom, že kaly sa extrahujú vodným roztokom obsahujúcim 1,5 až JO % hmotnostných kyseliny sírovej pri teplote 20 až 90 °C po dobu 5 až JO minút, potom sa extrahovaný roztok oddělí od nerozpustného zbytku kalu a získá sa kyslý roztok chromítých solí, ktorý sa ďalej upravuje až do koncentrácie chromitej soli JO až 150 g kysličníka chromitého na liter s bázicitou 20 až 50 °Sch.The above disadvantages are substantially eliminated by the process of preparing tanning solutions from chromium-containing waste sludge, which consists in extracting the sludge with an aqueous solution containing 1.5 to 10% by weight sulfuric acid at 20 to 90 ° C for 5 to 10%. minutes, then the extracted solution is separated from the insoluble residue of the sludge to give an acidic solution of chromium salts which is further treated to a chromium salt concentration of up to 150 g of chromium trioxide per liter with a basicity of 20 to 50 ° Sch.
Extrakcia je usporiadaná do trojstupňového protiprúdového systému, kde v prvom extrákčnom stupniprichádza do styku čerstvý chromí tý kal s kyslým roztokom získaným zmiešaním kyseliny sírovej a pracej vody oddelenej z druhého extrakčného stupňa, pričom táto pracia voda vznikne vypráním kalu odpadajúceho v 1. extrákčnom stupni pracou vodou získanou v treťom extrákčnom stupni, v ktorom kal odpadajúci v druhom extrakčnom stupni sa premyje vodou a odpadá ako odchrómovaný kal.The extraction is arranged in a three-stage countercurrent system, in which, in the first extraction stage, fresh chromium sludge comes into contact with the acidic solution obtained by mixing sulfuric acid and washing water separated from the second extraction stage. obtained in the third extraction stage, in which the sludge falling off in the second extraction stage is washed with water and discharged as a chromium sludge.
Na pripojenom obrázku je znázorněná schéma trojstupňovej protiprúdovej extrakcie chrómu z odpadných kalov podlá příkladu 2 oThe attached figure shows a diagram of a three-stage countercurrent extraction of chromium from waste sludge according to Example 2 o
-3 Příklad 1-3 Example 1
227 13S227 13S
Odpadný chromítý kal /sušina 37 %, popol 61 % na sušinu, obsah Cr^O^ 13 % na sušinu/ sa zriedi vodou v pomere 1:1a přidá sa 96 %-ná H^SO^ v. množstve 0,2θ kg na kg kalu. Zmes sa zahřeje do varu a nechá sa ochladit. Po ochladení sa oddělí extrahovaný roztok, ktorý má koncentráciu 2q g CrgO^/l a obsahuje 32 g voTnej HgSO^ /100 %-nej/ ná liter roztoku. Na 900 1 tohoto roztoku sa dávkuje 56 kg NagCr^O?^ HgO, súčasne sa zmec zahřeje na 90 °C a po rozpuštění dvojchrómanu sa prevedie jeho redukcia prídavkom sacharázy v množstve 11,2 kg. Po ochladení sa brečka doriedi do 1 000 1. Koncentrácia břečky je 55 g Cr20j/l, bázicita 4-5 °Sch.The waste chromium sludge (dry matter 37%, ash 61% dry matter, Cr? O? 13% dry matter) is diluted with water 1: 1 and 96% H 2 SO 4 is added. 0.2 kg / kg sludge. The mixture is heated to boiling and allowed to cool. After cooling, the extracted solution having a concentration of 2 g of CrgO4 / l was separated and contained 32 g of free HgSO4 / 100% liter solution. 900 kg of this solution is charged with 56 kg of NagCr2O2H2O, simultaneously heated to 90 [deg.] C. and after dissolution of the dichromate is reduced by addition of sucrose in an amount of 11.2 kg. After cooling, the slurry was diluted to 1000 L. The slurry concentration was 55 g Cr 20 0 / l, basicity 4-5 ° Sch.
Příklad 2Example 2
Získá sa extrahovaný roztok chromenu podl’a postupu na pripojenom obrázku. K odpadnému chromitého kalu /sušina 29 %, popol 53 % na sušinu, obsah Cr20^ 9,4 % na sušinu/ sa přidá 96 %-ná HgSO^ v množstve 0,15 kg na kg kalu a rovnaký objem roztoku po druhej separácii /1^/. Zmes sa zahřeje do varu.Po separácii roztoku R^ sa zostávajúci kal /Z2/ zriedi roztokom po tretej separácii /R^/. Z tejto zmesi sa pri druhej separácii oddělí roztok í^, zostávajúci kal /Z^/ sa zriedi vodou. Konečne po tretej separácii sa oddělí roztok Rj, pričom zostane vyextrahovaný kal Z^. Roztoky R> a R^ sa vracajú do predchádzajúcich stupňov extrakcie. Roztok R^ je výsledný extrahovaný roztok chrámu. Má koncentráciu 32 g Cr20-j/l. a obsahuje 37 g voTnej I^SO^ Αθθ %-nej/ na liter roztoku. Na 900 1 tohoto roztoku sa dávkuje’ 74,5 kg Na2Cr20^ · 2 H^O, súčasne sa zmes zahřeje na 90 °C a po rozpuštění dvojchromanu sa prevedie jeho postupná redukcia prídavkom sacharozy v množstve 15 kg. Po ochladení sa brečka doriedi na 1 000 litev. Koncentrácia chrámu je 67 g Cr20^/l, bázicita 45 °Sch.The extracted chromene solution is obtained as described in the attached figure. To the chromium waste sludge (dry matter 29%, ash 53% dry matter, Cr 2 O content ≥ 9.4% dry matter), 96% HgSO 4 is added in an amount of 0.15 kg per kg of sludge and an equal volume of solution for the second time separation (1). The mixture was heated to the separation varu.Po solution R, the remaining sludge / Z 2 / diluted solution of the third separation / R /. From this mixture the second solution is separated in a second separation, the remaining sludge (Z) is diluted with water. Finally, after the third separation, the solution R1 is separated, leaving the sludge Z ^ extracted. Solutions R1 and R2 are returned to the previous extraction steps. Solution R1 is the resulting extracted temple solution. It has a concentration of 32 g Cr 2 O / l. and it contains 37 g of free water per liter of solution. At 900 l of this solution, 74.5 kg of Na 2 Cr 2 O 2 · 2 H 2 O are metered in, simultaneously the mixture is heated to 90 ° C and after dissolution of dichromate is gradually reduced by adding sucrose in an amount of 15 kg. After cooling, the slurry was diluted to 1,000 liters. The concentration of the temple is 67 g Cr 2 O 4 / l, basicity 45 ° Sch.
- 4 Příklad 3- 4 Example 3
227 135227 135
Na 700 1 extrahovaného roztoku z příkladu 2 sa dávkuje 192 kg Na2Cr207 o 2 H20„ Po rozpuštění dvojchromanu sa přidá 164,5 kg 96 %-nej H2SO^. Zmes sa zahřeje na 90 °C a prevedie sa redukciou dvojchrómanu sacharozy v množstve 38>4 kg. Po ochladení sa brečka doriedi do 1 000 litorv. Koncentrácia chrómu v brečke je 150 g Cx^O^/l, bázicita 45 °Sch.To 700 l of the extracted solution of Example 2, 192 kg of Na 2 Cr 2 O 7 o 2 H 2 O are metered in. After dissolution of dichromate, 164.5 kg of 96% H 2 SO 4 are added. The mixture is heated to 90 ° C and carried out by reducing the sucrose dichromate in an amount of 38> 4 kg. After cooling, the slurry was diluted to 1000 liters. The concentration of chromium in the slurry was 150 g of Cx ^O ^ / l, basicity 45 ° Sch.
Příklad 4Example 4
K extrahovanému roztoku z příkladu 2 sa přidá síran chromitodraselný v množstve 0,6 kg na liter roztoku a rozvaří sa priamou parou. Takto vzniknutý roztok sa bazifikuje prídavkom pevného Na^CO^ až do dosiahnutia bázicity 35 °Sch. Koncentrácia brečky sa upraví na 100 g Cr20^/lo To the extracted solution of Example 2, 0.6 Kg of potassium sulfate was added per liter of solution and boiled by direct steam. The solution thus obtained is basified by the addition of solid Na 2 CO 3 until the basicity is 35 ° Sch. The concentration of the slurry is adjusted to 100 g of Cr 2 0 ^ / l o
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS326582A CS227135B1 (en) | 1982-05-06 | 1982-05-06 | Method of preparing tanning liquors from chromium-containing waste sludge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS326582A CS227135B1 (en) | 1982-05-06 | 1982-05-06 | Method of preparing tanning liquors from chromium-containing waste sludge |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS227135B1 true CS227135B1 (en) | 1984-04-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS326582A CS227135B1 (en) | 1982-05-06 | 1982-05-06 | Method of preparing tanning liquors from chromium-containing waste sludge |
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| Country | Link |
|---|---|
| CS (1) | CS227135B1 (en) |
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1982
- 1982-05-06 CS CS326582A patent/CS227135B1/en unknown
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