DE10009956A1 - Removal of nitrate from acidic, aqueous, particularly rare earth metal, solutions comprises adding formic acid and urea - Google Patents

Removal of nitrate from acidic, aqueous, particularly rare earth metal, solutions comprises adding formic acid and urea

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Publication number
DE10009956A1
DE10009956A1 DE10009956A DE10009956A DE10009956A1 DE 10009956 A1 DE10009956 A1 DE 10009956A1 DE 10009956 A DE10009956 A DE 10009956A DE 10009956 A DE10009956 A DE 10009956A DE 10009956 A1 DE10009956 A1 DE 10009956A1
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Prior art keywords
formic acid
urea
nitrate
acidic
solution
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Application number
DE10009956A
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German (de)
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DE10009956B4 (en
Inventor
Matthias Grehl
Sonja Kirchner
Horst Meyer
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Heraeus Deutschland GmbH and Co KG
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WC Heraus GmbH and Co KG
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    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • 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
    • C22B59/00—Obtaining rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • 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)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Treating Waste Gases (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Removal of nitrate from acidic, aqueous solutions comprises adding formic acid and urea, the solution having a H+> concentration of at least 3 mol./l and a temperature of at least 80[deg]C. Removal of nitrate from acidic, aqueous solutions comprises adding formic acid and urea, the solution having a H+> concentration of at least 3 mol./l and a temperature of at least 80[deg]C INDEPENDENT CLAIMS are included for the use of formic acid and urea in this process.

Description

Die Erfindung betrifft ein Verfahren zur Zerstörung von Nitrat in sauren, wässrigen Lösungen, insbesondere Edelmetall-Lösungen.The invention relates to a method for the destruction of nitrate in acidic, aqueous solutions, especially precious metal solutions.

Es ist allgemein bekannt, dass Nitrat aus nitrathaltigen wässrigen Lösungen, insbesondere Edelmetall-Lösungen, durch sogenanntes salzsaures Eindampfen entfernt werden kann. Hier­ bei werden die Lösungen zunächst auf ein kleines Volumen eingeengt und anschliessend ge­ gebenenfalls mehrmals mit konzentrierter HCl versetzt und wieder eingedampft, bis die Lösung ausreichend nitratfrei ist.It is well known that nitrate from nitrate-containing aqueous solutions, in particular Precious metal solutions can be removed by so-called hydrochloric evaporation. Here in the solutions are first concentrated to a small volume and then ge if necessary, mixed several times with concentrated HCl and evaporated again until the solution is sufficiently free of nitrates.

Bei diesem Verfahren muss in nachteiliger Weise Zeit- und engergieintensiv eingedampft wer­ den, wobei darüber hinaus NOx entsteht, das die Abluft bzw. die entsprechend nachgeschalte­ ten Abluftwäscher belastet.In this method, time and energy-intensive must be evaporated in a disadvantageous manner, which also creates NO x , which pollutes the exhaust air or the corresponding downstream exhaust air scrubber.

Problem der vorliegenden Erfindung ist es, die oben aufgeführten Nachteile zumindest teilweise zu vermeiden. Das der Erfindung zugrundeliegende Problem liegt insbesondere darin, ein Ver­ fahren zur Zerstörung von Nitrat in sauren, wässrigen Lösungen bereitzustellen, das die Abluft nicht mit NOx belastet und darüber hinaus ein aufwendiges und energieintensives Eindampfen der Lösungen vermeidet.The problem of the present invention is to at least partially avoid the disadvantages listed above. The problem on which the invention is based is in particular to provide a method for the destruction of nitrate in acidic, aqueous solutions which does not pollute the exhaust air with NO x and, moreover, avoids complex and energy-intensive evaporation of the solutions.

Dieses Problem wird erfindungsgemäss durch ein Verfahren nach Anspruch 1 gelöst.According to the invention, this problem is solved by a method according to claim 1.

Beim erfindungsgemässen Verfahren wird Ameisensäure und Harnstoff zu einer nitrathaltigen und wässrigen, sauren Lösung dazugegeben, wobei die Lösung eine H+-Konzentration von c(H+) ≧ 3 mol/l und eine Temperatur von T ≧ +80°C aufweist. Erfindungswesentlich beim Verfahren ist die Tatsache, dass Ameisensäure und Harnstoff in Kombination in einer nitrathaltigen Lösung zusammen eingesetzt werden, da zunächst das Nitrat durch die Ameisensäure in situ zum Nitrit reduziert wird, welches weiter mit Harnstoff zu Stickstoff reagiert.In the process according to the invention, formic acid and urea are added to a nitrate-containing and aqueous, acidic solution, the solution having an H + concentration of c (H + ) ≧ 3 mol / l and a temperature of T ≧ + 80 ° C. Essential to the invention in the method is the fact that formic acid and urea are used in combination in a nitrate-containing solution, since first the nitrate is reduced by the formic acid in situ to nitrite, which further reacts with urea to nitrogen.

  • 1. Nitrat-Reduktion
    2 HNO3 + HCOOH → 2 NO2 - + CO2 + CO2 + 2 H2O
    1. Nitrate reduction
    2 HNO 3 + HCOOH → 2 NO 2 - + CO 2 + CO 2 + 2 H 2 O
  • 2. Nitritzerstörung
    2 HNO2 + CO(NH2)2 → N2 + CO2 + 3 H2O
    2. Nitrite disorder
    2 HNO 2 + CO (NH 2 ) 2 → N 2 + CO 2 + 3 H 2 O

Zunächst ist es vorteilhaft, wenn vor Zugabe von Ameisensäure und Harnstoff der Harnstoff in der Ameisensäure gelöst wird, da hierdurch zu jeder Zeit sichergestellt ist, dass genügend Harnstoff zur Weiterreaktion gemäss Gleichung 2 zur Verfügung steht, sich jedoch nicht ein eventueller Harnstoff-Überschuss selbst zersetzen kann.First, it is advantageous if the urea in before adding formic acid and urea the formic acid is dissolved, as this ensures at all times that sufficient Urea is available for the further reaction according to equation 2, but not one any excess urea can decompose itself.

Weiterhin ist es vorteilhaft, wenn es sich bei der verwendeten Ameisenäure um konzentrierte Ameisensäure handelt, da hierdurch das Volumen der zu behandelnden Lösung nur geringfügig erhöht wird.It is also advantageous if the formic acid used is concentrated Formic acid acts because the volume of the solution to be treated is only minimal is increased.

In vorteilhafter Weise wird die ablaufende Reaktion potentialgesteuert durchgeführt, um den Endpunkt der Reaktion sicher zu erkennen und einen Überschuss an Harnstoff zu vermeiden.In an advantageous manner, the reaction taking place is carried out in a potential-controlled manner by the To reliably recognize the end point of the reaction and to avoid excess urea.

Darüber hinaus ist es von Vorteil, wenn die ablaufende Reaktion bei einer Temperatur von T = +85°C bis T = +95°C durchgeführt wird, um auf diese Art und Weise ein sicheres Abrea­ gieren der Ameisensäure zu gewährleisten, gleichzeitig jedoch die Selbstzersetzung des Harn­ stoffs in Grenzen zu halten.In addition, it is advantageous if the reaction taking place at a temperature of T = + 85 ° C to T = + 95 ° C is carried out to ensure a safe abrea to ensure yeast of formic acid, but at the same time self-decomposition of the urine to keep material within limits.

Schliesslich ist es vorteilhaft, wenn die Lösung eine H+-Konzentration von 4-5 mol/l aufweist, da dadurch in besonderem Maße sichergestellt ist, dass die gekoppelten Einzelreaktionen in gewünschter Weise ablaufen.Finally, it is advantageous if the solution has an H + concentration of 4-5 mol / l, since this ensures to a particular degree that the coupled individual reactions proceed in the desired manner.

Das nachfolgende Beispiel dient zur Erläuterung der Erfindung:The following example serves to explain the invention:

AnwendungsbeispielApplication example

Die NO3 --haltige EM-Lösung wird mit HCl auf eine Säurenormalität von 4-5 mol/l eingestellt und bei 85°C langsam eine stark saure Mischung aus CO(NH2)2/HCOOH-Lösung 6 : 1 zudo­ siert. Die CO2- und N2-Bildung ist anhand der Gasbildung deutlich sichtbar. Das Ende der NO3 -- bzw. NO2 --Zerstörung ist durch einen Potentialsprung von 900 mV auf 700 mV vs. Pt//Ag/AgCl erkennbar. Das Nitrat lässt sich bis auf Restgehalte zerstören, die die weitere Be­ arbeitung nach bestehenden Verfahren nicht beeinträchtigen.The NO 3 - -containing EM solution is adjusted to an acid normality of 4-5 mol / l with HCl and a strongly acidic mixture of CO (NH 2 ) 2 / HCOOH solution 6: 1 is slowly added at 85 ° C. The CO 2 and N 2 formation is clearly visible from the gas formation. The end of the NO 3 - or NO 2 - destruction is a potential jump from 900 mV to 700 mV vs. Pt // Ag / AgCl recognizable. The nitrate can be destroyed down to residual levels that do not affect further processing according to existing processes.

Ansatzapproach

100 ml Pt/Pd-Lösung, enthält Salpetersäure (NO3 - 100 ml Pt / Pd solution, contains nitric acid (NO 3 -

-Gehalt: 86 g/l)
HCOOH 85%-ig techn.
CO(NH2 -Content: 86 g / l)
HCOOH 85% techn.
CO (NH 2

)2 ) 2

/HCl-Lösung 20 g/l, c(H3 / HCl solution 20 g / l, c (H 3

O+ O +

): 9,6 mol/l): 9.6 mol / l

Durchführungexecution

Es wird eine CO(NH2)2/HCOOH-Lösung im Volumenverhältnis 6 : 1 der oben angegebenen Ausgangslösungen angesetzt.A CO (NH 2 ) 2 / HCOOH solution in a volume ratio of 6: 1 of the starting solutions given above is prepared.

100 ml Pt/Pd-Lösung wird mit HCl 10 n auf c(H3O+): 4,87 mol/l angesäuert und auf 85°C er­ wärmt, das Redoxpotential wird vs. Pt//Ag/AgCl-Redoxelektrode gemessen: 890 mV.100 ml of Pt / Pd solution is acidified with HCl 10 n to c (H 3 O + ): 4.87 mol / l and heated to 85 ° C, the redox potential is Pt // Ag / AgCl redox electrode measured: 890 mV.

Anschliessend wird über eine Dosierpumpe die CO(NH2)2/HCOOH-Lösung langsam zudosiert (Dosiergeschwindigkeit: 0,2 ml/min). Es ist deutliche Gasentwicklung sichtbar; keine NOx- Bildung. Nach 3 Stunden Dosierdauer und 50 ml CO(NH2)2/HCOOH-Lösungszugabe sinkt das Potential auf 670 mV.The CO (NH 2 ) 2 / HCOOH solution is then slowly metered in via a metering pump (metering speed: 0.2 ml / min). Clear gas evolution is visible; no NO x formation. After 3 hours of dosing and 50 ml CO (NH 2 ) 2 / HCOOH solution addition, the potential drops to 670 mV.

Die CO(NH2)2/HCOOH-Zugabe wird beendet, 15 ml HCl 10 n techn. zu der Lösung zugesetzt und nochmals für 0,5 Stunden bei einer Temperatur von ca. T = +85°C nachgerührt. In der Ausgangslösung und in der behandelten Pt/Pd-Lösung wird der NO2 --, NO3 -- und NH4 +-Gehalt gemessen.The CO (NH 2 ) 2 / HCOOH addition is ended, 15 ml of HCl 10 n tech. added to the solution and stirred again for 0.5 hours at a temperature of approx. T = + 85 ° C. -, NO 3 - - - in the starting solution and the treated Pt / Pd-solution of the NO 2 and NH 4 + content measured.

Claims (8)

1. Verfahren zur Zerstörung von Nitrat in sauren, wässrigen Lösungen, insbesondere Edel­ metall-Lösungen, gekennzeichnet durch:
  • - Zugabe von Ameisensäure und Harnstoff zu einer nitrathaltigen und wässrigen, sauren Lösung, wobei die Lösung eine H+-Konzentration von c(H+) ≧ 3 mol/l und eine Tempe­ ratur von T ≧ +80°C aufweist.
1. Process for the destruction of nitrate in acidic, aqueous solutions, in particular noble metal solutions, characterized by :
  • - Adding formic acid and urea to a nitrate-containing and aqueous, acidic solution, the solution having an H + concentration of c (H + ) ≧ 3 mol / l and a temperature of T ≧ + 80 ° C.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass vor Zugabe von Ameisensäure und Harnstoff zur Lösung der Harnstoff in der Ameisensäure gelöst wird.2. The method according to claim 1, characterized in that before the addition of formic acid and urea to dissolve the urea in the formic acid is dissolved. 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass es sich bei der verwendeten Ameisensäure um konzentrierte Ameisensäure handelt.3. The method according to claim 2, characterized in that it is used Formic acid is concentrated formic acid. 4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die ablaufende Reaktion potentialgesteuert durchgeführt wird.4. The method according to any one of claims 1 to 3, characterized in that the expiring Reaction is carried out under potential control. 5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die ablaufende Reaktion bei einer Temperatur von T = +85°C bis T = +95°C durchgeführt wird.5. The method according to any one of claims 1 to 4, characterized in that the expiring Reaction is carried out at a temperature of T = + 85 ° C to T = + 95 ° C. 6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Lösung eine H+-Konzentration von 4-5 mol/l aufweist. 6. The method according to any one of claims 1 to 5, characterized in that the solution has an H + concentration of 4-5 mol / l. 7. Verwendung von Ameisensäure und Harnstoff zur Zerstörung von Nitrat in sauren, wässri­ gen Lösungen, insbesondere Edelmetail-Lösungen.7. Use of formic acid and urea to destroy nitrate in acidic, aqueous solutions, especially precious metal solutions. 8. Verwendung von Ameisensäure und Harnstoff zur Durchführung eines Verfahrens nach einem der Ansprüche 1 bis 6.8. Use of formic acid and urea to carry out a process according to one of claims 1 to 6.
DE10009956A 2000-03-02 2000-03-02 Process for the destruction of nitrate in acidic, aqueous solutions, especially precious metal solutions Expired - Fee Related DE10009956B4 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3962114A (en) * 1975-04-11 1976-06-08 The United States Of America As Represented By The United States Energy Research And Development Administration Method for solidifying liquid radioactive wastes
US4344872A (en) * 1978-07-17 1982-08-17 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Method and apparatus for removing waste products from solutions of fission products

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3962114A (en) * 1975-04-11 1976-06-08 The United States Of America As Represented By The United States Energy Research And Development Administration Method for solidifying liquid radioactive wastes
US4344872A (en) * 1978-07-17 1982-08-17 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Method and apparatus for removing waste products from solutions of fission products

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JP 02191528 A2 (abstr.). HCAPLUS [online] [recher.am 07.12.00]. In: STN *
JP 03146116 A2 (abstr.). HCAPLUS [online] [recher.am 07.12.00]. In: STN *
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