CN1514807A - Process for producing ammonium cerium (IV) nitrate - Google Patents

Process for producing ammonium cerium (IV) nitrate Download PDF

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Publication number
CN1514807A
CN1514807A CNA02811728XA CN02811728A CN1514807A CN 1514807 A CN1514807 A CN 1514807A CN A02811728X A CNA02811728X A CN A02811728XA CN 02811728 A CN02811728 A CN 02811728A CN 1514807 A CN1514807 A CN 1514807A
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cerium
nitric acid
aqueous solution
acidic aqueous
concentration
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石川诚
之
齐藤范之
三好胜
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Mitsubishi Chemical Corp
Mitsubishi Kasei Corp
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Mitsubishi Kasei Corp
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/10—Preparation or treatment, e.g. separation or purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other metallic material

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Inorganic Chemistry (AREA)
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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Analytical Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • ing And Chemical Polishing (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Catalysts (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

A method of recovering a high-purity cerium compound from a solution containing cerium in a short time in a high yield. Specifically, the method is for recovering cerium as ammonium cerium (IV) nitrate from an acidic aqueous solution of cerium, such as a waste liquid resulting from etching. The process is for producing ammonium cerium (IV) nitrate from an acidic aqueous solution containing at least trivalent cerium, tetravalent cerium, ammonium ions, and nitric acid. It is characterized in that the acidic aqueous solution contains a metal having an oxidation potential as measured at a pH of 2 or lower of 0.7 to 1.6 V, and that the nitric acid concentration of this acidic aqueous solution is increased to thereby precipitate ammonium cerium (IV) nitrate crystals.

Description

The manufacture method of cerium ammonium nitrate (IV)
Technical field
The present invention industrial be important, and relate to from containing the cerium aqueous solution with highly purified cerium ammonium nitrate (IV) (composition formula: (NH 4) 2Ce (NO 3) 6) method of form manufacturing high price cerium of (below be abbreviated as CAN).Be particularly related to the method that reclaims cerium from the waste liquid of the etching solution that the manufacturing processed of semiconductor device and liquid crystal display device etc., uses.
Background technology
If there is reducing substance in the aqueous solution, the oxidation valency of the cerium ion in this aqueous solution becomes trivalent from tetravalence.The oxidation valency of cerium is when tetravalence is reduced into trivalent, and the oxidizing potential of cerium is higher than very with other metallographic phase at acidic region.This explanation can be with many burnings and dissolving (ionization).Utilize this specific character, contain the ceric aqueous solution and be widely used industrial as the etching reagent of metal.Particularly, as the effect height of the etching reagent of the high metal of the such oxidizing potential of chromium, industrial be important.
In the etching solution of this oxidation capacity of utilizing cerium, the acid that exists in the etching solution is consumed.Therefore, usually, in this etching solution, can add acidic components such as sulfuric acid, nitric acid and perchloric acid.
Cerium belongs to rare earth class, and the ratio that exists on earth with element form is little, and price is higher.Therefore, proposed to reclaim the method for refining cerium from the used etching solution (etching waste liquor) that contains cerium.For example special opening proposed in flat 11-236217 communique and the flat 11-236632 communique of Te Kai etc. the method for the cerium in the solution with the form recovery of etching solution raw material CAN.Adopt the wherein method of record,, have a plurality of manufacturing processes, therefore, have time-consuming problem though can reclaim a large amount of ceriums with high purity.And in order to remove the impurity such as basic metal that exist in the CAN manufacturing process, useful pure water washs the operation of the throw out (cerous hydroxide) that produces in this process for making, therefore, exist the wastewater flow rate that produces in the whole C AN manufacturing process to increase, its draining handling height, and the problem big to the load of surrounding enviroment.
Usually, the CAN solubleness in the known aqueous nitric acid is that high more it is more little for concentration of nitric acid.Based on this understanding, if the acidic aqueous solution distillation by will containing cerium and nitric acid etc. concentrate, the concentration of nitric acid in the solution improves, the result, partial crystallization takes place in CAN, therefore, if it is reclaimed refining, recovery CAN easily just.But, in the method, though quadrivalent cerium can be reclaimed with the CAN form,, can't reclaim a large amount of trivalent cerium that exist in the acidic aqueous solution, therefore, there is the insufficient problem of the rate of recovery.
Summary of the invention
Present inventors in view of the above problems, to from containing cerium, contain the method that reclaims the high purity cerium in trivalent cerium and the ceric acidic aqueous solution in the short period of time with high yield particularly, particularly, the method that reclaims refining cerium with cerium ammonium nitrate (IV) crystalline form the acidic aqueous solution that contains cerium from etching waste liquor etc. has been carried out research with keen determination.
Found that if there is the metal with specific oxidizing potential in containing the acidic aqueous solution of cerium, by improving the concentration of nitric acid in this acidic aqueous solution, the CAN crystallization is just separated out with very high purity, and the raising of the rate of recovery of cerium, thereby the present invention finished.
Main points of the present invention are manufacture method of cerium ammonium nitrate (IV), this method is to make the method for cerium ammonium nitrate (IV) from the acidic aqueous solution that contains trivalent cerium, quadrivalent cerium, ammonium ion and nitric acid at least, it is characterized in that the oxidizing potential that this acidic aqueous solution contains below pH2 is the metal of 0.7～1.6V, improve the concentration of nitric acid in this acidic aqueous solution, separate out cerium ammonium nitrate (IV) crystallization.
The preferred plan that is used to carry out an invention
Describe the present invention below in detail.
The acidic aqueous solution that contains cerium used in the present invention contains trivalent cerium, quadrivalent cerium, nitric acid and ammonium ion at least.The preferred used etching solution that uses in the etching of chromium, nickel, copper etc. that uses, i.e. etching waste liquor especially preferably uses the etching waste liquor of etching chromium.If with the etching solution etching metal that contains cerium ammonium nitrate (IV), a ceric part becomes trivalent cerium, therefore, in etching waste liquor, there are trivalent cerium and quadrivalent cerium usually.
Contained cerium comprises two kinds of trivalent cerium and quadrivalent ceriums in the acidic aqueous solution.According to the present invention, trivalent cerium also can reclaim with the form of cerium ammonium nitrate (IV).Can enumerate cerium ammonium nitrate (III), cerium ammonium nitrate (IV), cerous hydroxide (III), cerous hydroxide (IV) etc. as the cerium source.
The cerium concentration of the acidic aqueous solution among the present invention is arbitrarily.Usually, cerium concentration is high more, and the crystallization content of the cerium ammonium nitrate (IV) of separating out when improving concentration of nitric acid is many more, and the concentration of slurry with acidic aqueous solution improves, the tendency that the operability that crystallization is reclaimed reduces.On the other hand, cerium concentration is high more, and the rate of recovery that reclaims cerium ammonium nitrate (IV) from acidic aqueous solution is high more.
Therefore, the concentration of cerium ammonium nitrate in the acidic aqueous solution (IV) is generally 0.1～15 weight % in the weight % of cerium, wherein preferred 0.5～10 weight %, preferred especially 1～8 weight %.
For example when carrying out the inventive method,, evaporate a large amount of water and improve concentration of nitric acid if the cerium concentration in the acidic aqueous solution is low excessively with intermittent mode, not preferred economically.Otherwise if cerium concentration is too high, concentration of slurry increases, and the CAN crystalline collection of coming out from thickener is for example arranged and contain a large amount of CAN crystalline slurries to transport situation of difficult.Therefore, the cerium concentration in the acidic aqueous solution of the present invention is 1～10 weight %, is preferably 1.5～4 weight %, preferred especially 1.8～3.8 weight %.
When carrying out, the roughly certain mode of liquid level of carrying out the acidic aqueous solution in the spissated container of nitric acid is carried out with intermittent mode.For example, when vaporize water from acidic aqueous solution improved concentration of nitric acid, along with the evaporation of moisture, the interim liquid level of acidic aqueous solution reduced, and separates out crystallization on the container wall.This crystallization might concentrate impurity such as chromium and carry out crystallization, therefore, preferably avoids this crystalline to separate out.
On the other hand, when carrying out the inventive method in a continuous manner, therefore the cerium ammonium nitrate (IV) that extraction is separated out outside reactive system etc., can make the crystallization concentration of cerium ammonium nitrate (IV) in the reaction system, and promptly concentration of slurry substantially necessarily carries out concentrating of nitric acid.
Therefore, carrying out with continous way when of the present invention, the cerium concentration in the acidic aqueous solution serve as that basis is carried out just passable with the solubleness of the cerium ammonium nitrate (IV) of aqueous nitric acid under thickening temperature of the high concentration of nitric acid after concentrating.And in the acidic aqueous solution of extracting out, contain cerium ammonium nitrate (IV) crystallization, and therefore, to filter Extract and the cyclical operation mode that the part of the filtrate that obtains turns back in the thickener adjusted concentration of slurry.
Concentration of nitric acid in the acidic aqueous solution of the present invention is for arbitrarily.Concentration of nitric acid is 5～50 weight % in the acidic aqueous solution before improving concentration usually, is preferably 5～40 weight %, because the load when improving concentration of nitric acid is little, therefore preferred.
But, separate out with CAN crystalline form in order to make all ceriums in the acidic aqueous solution, must contain with respect to cerium in acidic aqueous solution is 6 moles of nitric acid more than doubly.Therefore, the concentration of nitric acid in the acidic aqueous solution is more than 6 moles times with respect to cerium preferably.
Acidic aqueous solution can also contain the acidic component except nitric acid.Usually can enumerate perchloric acid and sulfuric acid etc. as acidic component contained in the acidic aqueous solution.When using perchloric acid etc. to have outburst decomposability sour as acidic component, for example, in order to improve the concentration of nitric acid in the acidic aqueous solution, when concentration operation is carried out in the acidic aqueous solution heating, if the crystallization attached to the perchlorate on the wall of container forms drying regime, can break out the danger of decomposition.Therefore, by preventing to separate out processing such as crystallizing and drying, can avoid outburst to decompose.
The concentration of acidic component is arbitrarily, in the acidic aqueous solution before improving concentration of nitric acid, can adjust to 5～40 weight % usually with the concentration that above-mentioned nitric acid adds up to.Concentration of nitric acid in the acidic aqueous solution is high more, the solubleness of CAN is low more, therefore, in order to reclaim CAN, concentration of nitric acid in the acidic aqueous solution is high more, reduces with the corresponding concentration of nitric acid rising part of cerium ammonium nitrate (IV) the crystallization amount of separating out, therefore, energy during the concentrated acidic aqueous solution reduces, and is effective.
The pH of acidic aqueous solution of the present invention is generally below the pH2, is preferably below the pH1.If surpass pH2, quadrivalent cerium, sexavalent chrome and trivalent chromium can be separated out sometimes.
Contained ammonium ion uses ceric ammonium nitrate to be fed in the acidic aqueous solution in the cerium source by as the modulation acidic aqueous solution time usually in the acidic aqueous solution.During as the cerium source outside the cerium source use ceric ammonium nitrate, can use ammoniacal liquor and ammonium nitrate etc. as the ammonium source.
Ammonium concentration in the acidic aqueous solution is arbitrarily.Ammonium concentration is 0.1～5 weight % with respect to acidic aqueous solution usually, preferred 0.2～1.6 weight %.But, separate out with the CAN form in order to make all ceriums in the acidic aqueous solution, in acidic aqueous solution, must contain with respect to cerium and be at least 2 moles of ammonium ions more than doubly.Therefore, the ammonium concentration in the acidic aqueous solution is more than 2 moles times with respect to cerium preferably, if but ammonium concentration is too high, the crystallization of ammonium nitrate is separated out sometimes when improving concentration of nitric acid, therefore, be 2～3 times of moles preferably with respect to cerium, more preferably 2～2.5 times of moles.
If improve the concentration of nitric acid of acidic aqueous solution, CAN separates out.This is high more because of the concentration of nitric acid of the acidic aqueous solution that contains CAN, and it is more little that the solubleness of CAN will become.The method that improves concentration of nitric acid is arbitrarily.Specifically, for example can enumerate methods such as distillation, underpressure distillation, stripping, wherein, owing to can reduce the CAN partial crystallization temperature of thickener, therefore can reduce CAN crystalline foreign matter content, and reclaim the high CAN crystallization of purity, therefore preferably improve concentration of nitric acid by distillation, underpressure distillation, particularly underpressure distillation.
As distillation condition at this moment, in order to obtain highly purified CAN crystallization, preferred distillation temperature is low more good more.Usually carrying out below 100 ℃, preferably carrying out below 70 ℃.Concrete is room temperature～100 ℃, preferred 40～70 ℃, preferred especially 45～70 ℃.Distillation pressure is generally 466.6[hPa] below (about 350mmHg), preferred 133.3[hPa] (about 100mmHg), preferred especially 40～133.3[hPa] (about 30～about 100mmHg).If the distillation hypotony, the condensed liquid temperature drop of evaporation section is low, exists in to be difficult to condensing situation under the common water temperature.At this moment, can carry out the condenser cooling by refrigerator (cold blast engine) etc.
In air distillation, usually since distillation temperature more than 100 ℃, the CAN crystalline is separated out under the high temperature more than 100 ℃ and is carried out, therefore, the impurity that enters into the CAN crystallization might increase.On the other hand, in underpressure distillation, because distillation temperature is low, therefore, the CAN crystalline is separated out at low temperatures and is carried out, and therefore, the impurity that enters crystallization inside is few, obtains highly purified CAN easily.Therefore, preferably use underpressure distillation.
It is more than the 50 weight % that concentration of nitric acid is enhanced with respect to acidic aqueous solution usually, more than the preferred 60 weight %, for example, under situation, especially preferably concentration of nitric acid is brought up to the azeotropic of nitric acid and water and formed upper limit of concentration (67 weight %) by concentrated solutions such as (decompression) distillations.If the concentration of nitric acid after improving is low excessively, owing to improve with respect to the CAN crystalline solubleness of mother liquor, therefore, the yield of cerium and the rate of recovery reduce.
When distillation etc. improved concentration of nitric acid by heating, acidic aqueous solution was cooled to normal temperature usually, was accompanied by temperature and reduced, and undissolvable partial C AN separates out.
The invention is characterized in that when improving the concentration of nitric acid of acidic aqueous solution, the oxidizing potential that contains below the pH2 is the metal of 0.7～1.6V in acidic aqueous solution.
As the oxidizing potential below the pH2 is the metal of 0.7～1.6V, specifically can enumerate for example chromium, nickel, cobalt etc., preferably uses chromium.Under the situation of using chromium, its valence mumber can significantly be brought into play effect of the present invention between sexavalence and trivalent.The following oxidizing potential of pH2 in the acidic aqueous solution is that the concentration of metal of 0.7～1.6V can be formed suitably selection according to cerium, ammonium ion and concentration of nitric acid in the acidic aqueous solution that reclaims CAN etc.
Usually can be for below the 0.3 weight %, in order from acidic aqueous solution, to reclaim cerium with the form of cerium ammonium nitrate (IV) effectively, be more than the 0.001 weight %, more than the preferred 0.005 weight %, further more than the preferred 0.01 weight %, more than the preferred especially 0.05 weight %.And this metal preferably exists with the ionic form in acidic aqueous solution.
For example, when the metal that as the oxidizing potential below the pH2 is 0.7～1.6V uses chromium, the concentration of chromium is 1/2～1/10 times of volumetric molar concentration with respect to cerous concentration, is preferably 1/4～1/7 times of volumetric molar concentration, near 1/6 times of volumetric molar concentration in preferred especially this scope.If the chromium content in the acidic aqueous solution is too much, chromium is attached in the CAN crystallization sometimes, and purity drop is therefore not preferred.
In the present invention, be the metal of 0.7～1.6V and improve concentration of nitric acid by the oxidizing potential that in acidic aqueous solution, contains below the pH2, can be with the form recovery cerium of high-recovery with cerium ammonium nitrate (IV).Its reason is presumed as follows.
If the concentration of nitric acid in the raising acidic aqueous solution, then the solubleness of CAN reduces, and quadrivalent cerium is separated out with CAN crystalline form earlier.In case the quadrivalent cerium in the solution is removed with CAN crystalline form, whole oxidizing potential reduces, otherwise the following oxidizing potential of pH2 is that the metal of 0.7～1.6V forms the ion with highest oxidation current potential.Therefore, this metal ion plays the effect of oxygenant, and trivalent cerium is oxidized to quadrivalent cerium.This metal ion is reduced itself like this, becomes the low ion of valence mumber.
The solubleness of quadrivalent cerium in the high acidic aqueous solution of concentration of nitric acid that generates is low, further separates out with CAN crystalline form.Like this, in this application, can will can't separate out recovery with the form of CAN with the trivalent cerium that the CAN form reclaims at present, so yield improves epoch-makingly.
The present invention is lower than quadrivalent cerium (being 1.6V during pH=1) by contain oxidizing potential in acidic aqueous solution, but than trivalent cerium (the being 0.7V during pH=1) metal that oxidizing potential is high, acidic aqueous solution below pH2 can be oxidized to quadrivalent cerium effectively with trivalent cerium, thereby finish the present invention.
The CAN crystallization of separating out is separated from mother liquor by filtering.In order to remove attached to the mother liquor in the crystallization, the CAN crystallization that obtains with the washing of high purity concentrated nitric acid usually.
If increase the washing times that adopts high purity nitric acid, can will be present in the impurity stripping of CAN crystal surface, therefore, can further improve the purity of CAN, reduce the yield of CAN.Application target according to the CAN that reclaims can suitably determine washing times.As high purity nitric acid, use more than the concentration of nitric acid 60 weight % concentrated nitric acid that preferred 65 weight % are above usually.At this moment total concentration of metallic impurities is low in the preferred high purity concentrated nitric acid, uses usually below following, the preferred 1ppm of 5ppm.
After employing high purity concentrated nitric acid washs, by with the rare nitric acid washing of a spot of high purity CAN crystallization, further improve purity, and suppress nitric acid gas etc., therefore preferred.At this moment the concentration of nitric acid of the rare nitric acid of high purity of Shi Yonging is arbitrarily, is generally 1～20 weight %, below the preferred 10 weight %, below the preferred especially 5 weight %.And what the total concentration of metallic impurities in the rare nitric acid of high purity was low is preferred, use usually below the 5ppm, below the preferred 1ppm.
Concentration of nitric acid in improving acidic aqueous solution and separating out filters the quadrivalent cerium that is dissolved with trivalent cerium and trace in the filtrate behind the CAN usually.
Below to using the example of etching waste liquor to be specifically described as acidic aqueous solution.This etching waste liquor contains cerium, ammonium ion and nitric acid, further contains the chromium as " the following oxidizing potential of pH2 is the metal of the oxidizing potential between 0.7～1.6V ".
If use the etching solution etching metal chromium that is made of the acidic aqueous solution that contains cerium, ammonium ion and nitric acid, chromium metal (0 valency) by the quadrivalent cerium oxidation, becomes hexavalent chromium, is dissolved in the acidic solution.Quadrivalent cerium is reduced, and generates trivalent cerium.Etching solution (etching waste liquor after etching finishes, be acidic aqueous solution) when having a large amount of quadrivalent cerium ion, because ceric oxidizing potential remains on the level of the oxidizing potential that is higher than the chromium in the acidic aqueous solution, therefore, hexavalent chromium can stably be present in the acidic aqueous solution.
But for example, if the concentration operation by under reduced pressure etc. improve concentration of nitric acid, its solubleness reduces, and therefore, quadrivalent cerium forms cerium ammonium nitrate (IV) crystallization and separates out.If like this, reduce from acidic aqueous solution owing to keep the quadrivalent cerium of high oxidation potential, therefore, keep the sexavalent chrome of high oxidation potential to be positioned at dominant position gradually.Therefore, hexavalent chromium plays the effect of oxygenant, the oxidized quadrivalent cerium that becomes of dissolved trivalent cerium.This quadrivalent cerium solubleness under high concentration of nitric acid is low, therefore, further separates out with the CAN form.Owing to there is sexavalent chrome, be not limited to valence mumber, the cerium in the acidic aqueous solution can be separated out with the form of cerium ammonium nitrate (IV) and make and reclaim.
In the aqueous nitric acid of separating out by ceric ammonium nitrate (IV) crystallization that improves concentration of nitric acid when finishing, can think the quadrivalent cerium that is dissolving a spot of sexavalent chrome, a large amount of trivalent chromium, trivalent cerium and trace.
Acidic aqueous solution after removing CAN contains trivalent cerium and micro-quadrivalent cerium as mentioned above.Therefore, for the form of these ceriums with cerium ammonium nitrate (IV) reclaimed, can separate out with the CAN form by adding hydrogen peroxide in the acidic aqueous solution after removing CAN.Hydrogen peroxide adds in the mode of aqueous hydrogen peroxide solution usually.At this moment, in acidic aqueous solution, preferably do not exist the following oxidizing potential of pH2 to be higher than the metal ion of hydrogen peroxide basically, do not have the following metal of oxidizing potential more than 1.5V of pH2 specifically basically.The reason of separating out CAN by adding hydrogen peroxide in the acidic aqueous solution that does not have above-mentioned metal basically is also indeterminate, but, if exist the following oxidizing potential of pH2 to be higher than the metal ion of hydrogen peroxide in a large number, hydrogen peroxide plays the effect of reductive agent with respect to this ion, and can infer do not exist oxidizing potential below the pH2 to be higher than under the situation of metal ion of hydrogen peroxide basically, hydrogen peroxide plays the effect of oxygenant with respect to trivalent cerium ion.
The following oxidizing potential of so-called pH2 the metal more than the 1.5V specifically the oxidizing potential below the pH2 be metal more than the 1.6V, can enumerate quadrivalent cerium, sexavalence manganese, tetravalence lead etc. usually.
The add-on of hydrogen peroxide normally make quadrivalent cerium can with the form crystallization of cerium ammonium nitrate (IV) separate out and solution in residual trivalent cerium bring up to the necessary amount of ceric valence mumber, with respect to remaining cerous volumetric molar concentration, be generally 1/5 times more than the mole, preferred 1/3 times more than the mole, be generally etc. below the mole preferred 2/3 times below the mole.In this scope, about preferred 1/2 times of mole.And, existing at acidic aqueous solution under the situation of sexavalent chrome etc., the add-on of hydrogen peroxide can be less than above-mentioned scope.
The metal that the following oxidizing potential of pH2 is higher than hydrogen peroxide does not exist basically at acidic aqueous solution, and this can not confirm by do not produce gas (oxygen) when joining hydrogen peroxide in the acidic aqueous solution.That is to say that if there are these metals, hydrogen peroxide plays the effect of reductive agent, hydrogen peroxide itself is oxidized, generates oxygen.Otherwise hydrogen peroxide plays the time spent of doing of oxygenant, and therefore the oxygen performance oxygenizement of hydrogen peroxide itself, does not produce oxygen.
The so-called metal ion that does not exist the following oxidizing potential of pH2 to be higher than hydrogen peroxide basically is meant that the content of these metal ions is usually below number 10ppm.
Because the CAN crystallization that obtains by the inventive method is highly purified, therefore, can former state raw material during as the etching solution of adjusting above-mentioned chromium use.
Embodiment
Represent embodiment below, the present invention is carried out specific description more.Among below the embodiment and comparative example, unless otherwise specified, " % " be expression " weight % " just.
The analytical procedure of cerium
Quadrivalent cerium and cerous total amount (total cerium), sexavalent chrome and chromic total amount (total chromium) are measured by ICP (luminescence analysis), and quadrivalent cerium is measured with redox titration, deducts quadrivalent cerium from total cerium, calculates trivalent cerium.For crystallization, make the aqueous solution by ordinary method, it is carried out sample analysis.
Embodiment 1
Employing is carried out simple distillation at the there-necked flask that pipeline is installed 1000 milliliters of (ml) glass of water condensing tube that distillates that comes out from top of tower.Drawdown pump is installed at rear portion at water condensing tube, can carry out underpressure distillation.The thermometer that is used to measure still liquid temperature is installed on flask then.
The chromium etching waste liquor 600g that in flask, adds the following composition of representing, under reduced pressure 53.3[hPa] heat under (40mmHg).
Quadrivalent cerium: 1.96% (being converted into cerium ammonium nitrate (IV) is 7.67%)
Trivalent cerium: 1.00% (being converted into cerium ammonium nitrate (III) is 3.48%)
Total chromium: 0.07%
Nitric acid: 35%
Remainder: water
At the about 40 ℃ of beginning distilled of still temperature simultaneously, in still liquid, separate out fine crystallization, still liquid band black.This black is inferred that dissolving causes in order to be generated by trivalent chromium.Distill, until distillate from top of tower, condensing liquid measure is 400g, promptly becomes 200g until still liquid, still liquid has been concentrated three times.Still temperature when distillation finishes is about 50 ℃.
The still raffinate filters separately filtrate and crystallization after placing and being cooled to normal temperature, and the total content that obtains nitric acid and moisture is 5.9% crystallization 60g.Analyze the composition of filtrate, wet crystallization (not washing product) by aforesaid method.This wet crystallization (not washing product) composed as follows:
Quadrivalent cerium concentration: 21.78% (being converted into cerium ammonium nitrate (IV) is 85.17%)
Trivalent cerium concentration: 2.56% (being converted into cerium ammonium nitrate (III) is 8.88%)
Total chromium: 0.05%
Remainder: aqueous nitric acid
Total cerium concentration of filtrate is 2.66%, and total chromium concn is 0.26%, and remainder is water, nitric acid, metallic impurity etc.The major part of the chromium in the filtrate is a trivalent chromium, is dissolved in the filtrate.
Then, in order to remove attached to the mother liquor in the crystallization, the high purity concentrated nitric acid of the concentration 69.5% of employing and this crystallization identical weight (total impurities amount of metal 1ppm is following) suspends and washs and filter, and obtains the crystallization (once washing product) of 52.5g.
The wet crystallization that obtains (once washing product) composed as follows assert that eutectic does not take place trivalent cerium.
Quadrivalent cerium: 24.06% (being converted into cerium ammonium nitrate (IV) is 94.11%)
Trivalent cerium: 0% (being converted into cerium ammonium nitrate (III) is 0%)
Total chromium: 0.007%
Remainder: aqueous nitric acid
It is 71.1% that the rate of recovery of total cerium is obtained by following formula.
[(52.5g×(0.2406+0))/(600g×(0.0196+0.0100))]×100＝71.1％
Being obtained by following formula with respect to the ceric rate of recovery in the liquid that feeds intake is 107.4%.
[(52.5g×0.2406)/(600g×0.0196)]×100＝107.4％
This expression, the quadrivalent cerium that exists in waste liquid, the part of the cerium that exists with the trivalent cerium form reclaims with the form of cerium ammonium nitrate (IV).
Adopt with this crystallization (once washing product) with nitric acid (below the total impurities amount of metal 1ppm) this crystallization of repetitive scrubbing of the concentration 69.5% of weight three times, washing the wet crystallization (four washing products) that obtains four times altogether is cerium ammonium nitrate (IV) crystallizations of metals content impurity below 1ppm such as chromium, iron, and its receipts amount is 30g.Should wet shown in the crystalline formula composed as follows, and can confirm that eutectic does not take place trivalent cerium, and contain chromium hardly.
Quadrivalent cerium: 24.10% (being converted into cerium ammonium nitrate (IV) is 94.29%)
Trivalent cerium: 0% (being converted into cerium ammonium nitrate (III) is 0%)
Total chromium: below 0.0001%
Remainder: aqueous nitric acid
At this moment it is 61.5% that the ceric rate of recovery is obtained by following formula.
[(30g×0.241)/(600g×0.0196)]×100＝61.5％
It is 40.7% that the rate of recovery of total cerium is obtained by following formula.
[(30g×(0.241+0))/(600g×(0.0196+0.0100))]×100＝40.7％
Beginning to finish required fate to four washings from distillation is 1 day.The chromium rate of removing by four washings is 99.9%.
Embodiment 2
In embodiment 1,, carry out similarly to Example 1 except underpressure distillation is become air distillation.
Come to life under 110 ℃ of the temperature of still liquid, the still liquid temp when distillation finishes is about 118 ℃.The wet crystallization that obtains (not washing product) is 60g.The composed as follows described of crystallization (not washing product) should wet:
Quadrivalent cerium: 18.66% (being converted into cerium ammonium nitrate (IV) is 73.00%)
Trivalent cerium: 5.48% (being converted into cerium ammonium nitrate (III) is 19.00%)
Total chromium: 0.09%
Remainder: aqueous nitric acid
It is 81.6% that the rate of recovery of at this moment total cerium is obtained by following formula.
[(60g×(0.1866+0.0548))/(600g×(0.0196+0.01))]×100＝81.6％
Being obtained by following formula with respect to the ceric rate of recovery in the liquid that feeds intake is 95.2%.
[(60g×0.1866)/(600g×0.0196)]×100＝95.2％
Similarly to Example 1, should wet crystallization (not washing product) once with the high purity concentrated nitric acid washing of concentration of nitric acid 69.5%.
The wet crystallization that obtains (once washing product) is 52g.Shown in it is composed as follows.
Quadrivalent cerium: 20.12% (being converted into cerium ammonium nitrate (IV) is 78.76%)
Trivalent cerium: 3.81% (being converted into cerium ammonium nitrate (III) is 13.21%)
Total chromium: 0.02%
Remainder: aqueous nitric acid
It is 70.0% that the rate of recovery of at this moment total cerium is obtained by following formula.
[(52g×(0.2012+0.0381))/(600g×(0.0196+0.01))]×100＝70.0％
Being obtained by following formula with respect to the ceric rate of recovery in the liquid that feeds intake is 89.0%.
[(52g×0.2012)/(600g×0.0196)]×100＝89.0％
If under normal pressure, distill, can infer owing at high temperature crystallization takes place and separate out, so cerium ammonium nitrate (III) crystallization generation eutectic separates out, to compare with embodiment 1, ceric output reduces.
(comparative example 1)
In embodiment 1, replace the chromium etching solution to use the aqueous solution 600g that contains cerium ammonium nitrate (IV) and following composition (III) that does not contain chromium, in addition, test similarly to Example 1.
Quadrivalent cerium: 3% (being converted into cerium ammonium nitrate (IV) is 11.74%)
Trivalent cerium: 1% (being converted into cerium ammonium nitrate (III) is 3.48%)
Nitric acid: 35%
Remainder: water
The crystallization of separating out similarly to Example 1.Owing to do not contain chromium etc., therefore, do not carry out the nitric acid washing.
The wet crystallization that obtains (not washing product) is 71.3g.And, shown in it is composed as follows.
Quadrivalent cerium: 24.25% (being converted into cerium ammonium nitrate (IV) is 94.88%)
Trivalent cerium: 0.0008% (being converted into cerium ammonium nitrate (III) is 0%)
Remainder: aqueous nitric acid
It is 72.0% that the rate of recovery of total cerium is obtained by following formula.
[(71.3g×0.2425)/(600g×(0.03+0.01))]×100＝72.0％
Being obtained by following formula with respect to the ceric rate of recovery in the liquid that feeds intake is 96.1%.
[(71.3g×0.2425)/(600g×0.03)]×100＝96.1％
Thus the result as seen, the ceric amount of recovery does not increase along with the quadrivalent cerium that contains in the cerium solution, can not trivalent cerium be become quadrivalent cerium as shown in the present, can't reach the purpose of the receipts amount that increases cerium ammonium nitrate (IV).
Above result is summarised in following table.
Table 1
Total Ce rate of recovery (weight %) The quadrivalent cerium rate of recovery (weight %)
Embodiment 1 Decompression system 4 washings of 1 washing of 0 washing ????82.0 ????71.1 ????40.7 ????111 ????107 ????61.4
Embodiment 2 The normal pressure system 1 washing of 0 washing ????81.6 ????70 ????95.2 ????89
Comparative example 1 Decompression system 0 washing ????72 ????96
(embodiment 3)
Employing is installed 500 liters of (L) glass lining grooves of lining system water condensing tube (band stirrer and water jacket) at the pipeline that distillates that comes out from top of tower, carries out simple distillation.The drawdown pump of hydrolock is installed at the rear portion of glass lining system water condensing tube, can be carried out underpressure distillation.
The pressure transmitter of pressing in the temperature sensor of the interior liquid temp be used to measure still and jacket water temperature and mensuration and the control still is installed in the glass lining groove.
The chromium etching waste liquor 400kg (about 388L) that in the glass lining groove, adds composition as follows, under reduced pressure 53.3[hPs] (40mmHg), temperature in the water jacket is heated to 70 ℃.
Quadrivalent cerium concentration: 2.16% (being converted into cerium ammonium nitrate (IV) is 8.45%)
Trivalent cerium concentration: 1.54% (being converted into cerium ammonium nitrate (III) is 5.36%)
Total chromium concn: 0.10%
Nitric acid: 14%
Remainder: water
Begin distillation under about 40 ℃ of temperature in the kettle, the speed that distillates that will branch away with the top of tower above-mentioned chromium etching waste liquor of capacity much at one joins in the glass lining groove (following simply be called " still ") continuously, continues distillation and makes the liquid level in the still certain substantially.Distillation is 800kg until the amount of the condensing liquid that obtains.That is, raffinate is 400kg in the still when distillation finishes, and the temperature the when distillation that the chromium etching waste liquor in the still is concentrated to three times (1200kg chromium etching waste liquor is concentrated to 400kg) finishes in the still is approximately 50 ℃.
After returning to normal atmosphere in the still, in water jacket, feed water, temperature in the kettle is cooled to normal temperature.Then, adopt the centrifuge separator of fluoro-resin lining, the concentrated solution in the still is separated into crystallization and filtrate.The wet crystallization that obtains (not washing product) is 106.6kg, composed as follows shown in.
Quadrivalent cerium concentration: 25.1% (being converted into cerium ammonium nitrate (IV) is 98.20%)
Trivalent cerium concentration: 0%
Total chromium concn: 0.012%
Remainder: aqueous nitric acid
Total cerium concentration in the separated filtrate is 5.7%, and total chromium concn is 0.39%, and remainder is water, nitric acid, metallic impurity etc.
Then, the concentration of employing and crystallization identical weight is 69.5% high purity concentrated nitric acid (total impurities metal concentration 1ppm is following) wash crystallization.This washing is undertaken by the crystallizing layer that supplies to continuously in the separating centrifuge with the state in the rotating centrifugal separating machine.
The weight of carrying out the wet crystallization (four washing products) that four these washings obtain is 79.3kg.And crystallization is composed as follows.By this result as can be seen, having removed trivalent cerium and chromium in this crystallization (four washing products), is cerium ammonium nitrate (IV) crystallization of based on very high purity.
Quadrivalent cerium concentration: 25.1% (being converted into cerium ammonium nitrate (IV) is 98.2%)
Trivalent cerium concentration: 0%
Total chromium concn: below 0.0001%
Remainder: aqueous nitric acid
Obtain the rate of recovery of the cerium in the wet crystallization (four washing products) among this embodiment similarly to Example 1.
The rate of recovery=44.8% ((79.3 * 0.251)/(1200 * 0.037) * 100) of total cerium
The ceric rate of recovery=76.8% ((79.3 * 0.251)/(1200 * 0.0216) * 100)
The concentrated nitric acid wash filtrate that obtains when washing unwashed wet crystallization with the high purity concentrated nitric acid turns back in the still as concentrating raw material, can more effectively reclaim cerium thus.
Describe the present invention in more detail or with reference to particular, but obviously can under the situation that does not depart from spirit and scope of the invention, make various changes and correction for a person skilled in the art.
The application is based on the Japanese patent application (special hope 2001-175181) of application on June 11 calendar year 2001, and its content is herein incorporated by reference.
Industrial utilizability
Have following effect according to the present invention:
(1) can reclaim cerium with high-recovery.
(2) cerium can be reclaimed with the form as the useful cerium ammonium nitrate (IV) such as the raw material of etching solution.
(3) etching waste liquor of etching chromium contains the toxic substance sexavalent chrome.Usually, in containing chromic waste liquid, add reductive agent, handle after hexavalent chrome reduction is become the low trivalent chromium of toxicity.If use the chromium etching waste liquor as acidic solution of the present invention, because the chromic major part in this acidic aqueous solution is reduced into trivalent chromium, therefore, the consumption of the reductive agent that uses during liquid waste disposal reduces, and can carry out liquid waste disposal with low cost.
(4) owing to do not generate the intermediate product cerous hydroxide, therefore, do not need the washing procedure of cerous hydroxide, wastewater treatment capacity reduces, and the manufacturing cost of whole technology reduces, and can reach the purpose that reduces carrying capacity of environment.
(5) compare with existing method, simplified operation, can finish recovery in the short period of time.

Claims (16)

1, the manufacture method of cerium ammonium nitrate ((IV)), this method is to make the method for cerium ammonium nitrate (IV) from the acidic aqueous solution that contains trivalent cerium, quadrivalent cerium, ammonium ion and nitric acid at least, it is characterized in that the oxidizing potential that this acidic aqueous solution contains below pH2 is the metal of 0.7～1.6V, improve the concentration of nitric acid in this acidic aqueous solution, separate out cerium ammonium nitrate (IV) crystallization.
2, the manufacture method of claim 1 record is characterized in that the content of ammonium ion is more than 2 moles times of cerium concentration in acidic aqueous solution.
3, the manufacture method of claim 1 or 2 records is characterized in that the concentration of nitric acid in the acidic aqueous solution is brought up to more than the 50 weight %.
4, the manufacture method of any record of claim 1 to 3 is characterized in that also containing nitric acid acidic component in addition.
5, the manufacture method of cerium ammonium nitrate (IV) is characterized in that cerium ammonium nitrate (IV) crystallization that the manufacture method with any record by claim 1 to 4 obtains is with the following concentrated nitric acid solution washing of above, the total metals content impurity 1ppm of concentration of nitric acid 60 weight %.
6, the manufacture method of claim 5 record is characterized in that washing with the diluted nitric acid aqueous solution below the concentration of nitric acid 10 weight % after with the concentrated nitric acid solution washing again.
7, the manufacture method of any record of claim 1 to 6 is characterized in that oxidizing potential when pII2 is following is that the metal of 0.7～1.6V is a sexavalent chrome.
8, the manufacture method of any record of claim 1 to 7 is characterized in that improving concentration of nitric acid in the temperature below 100 ℃.
9, the manufacture method of any record of claim 1 to 8 is characterized in that improving concentration of nitric acid by acidic aqueous solution is carried out underpressure distillation.
10, the manufacture method of claim 9 record is characterized in that by carry out underpressure distillation under the decompression below the 100mmHg.
11, the manufacture method of any record of claim 1 to 10 after the concentration of nitric acid that it is characterized in that improving acidic aqueous solution is separated out cerium ammonium nitrate (IV) crystallization, adds hydrogen peroxide in acidic aqueous solution, separate out cerium ammonium nitrate (IV) crystallization again.
12, the manufacture method of claim 11 record, the oxidizing potential the when acidic aqueous solution that it is characterized in that adding hydrogen peroxide is substantially free of pH2 is the above metal ion of 1.5V.
13, the manufacture method of any record of claim 1 to 12 is characterized in that acidic aqueous solution is the etching solution after using in etching work procedure.
14, the manufacture method of claim 13 record is characterized in that it being the etching solution after the use in the chromium etching work procedure.
15, the manufacture method of etching solution is characterized in that cerium ammonium nitrate (IV) crystallization that the manufacture method by claim 13 or claim 14 is obtained is used as the raw material of etching solution.
16, the etching solution of the manufacture method of claim 15 manufacturing.
CNA02811728XA 2001-06-11 2002-06-07 Process for producing ammonium cerium (IV) nitrate Pending CN1514807A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102443805A (en) * 2010-10-13 2012-05-09 江德馨 Method for circularly using alkaline waste etching liquid
CN110904456A (en) * 2019-12-28 2020-03-24 苏州天承化工有限公司 Copper etching solution and preparation method and application thereof

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KR100605365B1 (en) * 2004-12-23 2006-07-31 재단법인 포항산업과학연구원 Method for manufacturing cerium ammonium nitrate and withdrawing nitric acid from waste chrome etching solution

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JPH11236633A (en) 1998-02-24 1999-08-31 Mitsubishi Chemical Corp Cerium recovering method
JP2000007332A (en) * 1998-06-18 2000-01-11 Mitsubishi Chemicals Corp Recovery of cerium
JP3788185B2 (en) * 1999-04-27 2006-06-21 三菱化学株式会社 Method for recovering cerium from a solution containing chromium and cerium
JP2002068741A (en) * 2000-08-24 2002-03-08 Asahi Kagaku Kogyo Co Ltd Method for manufacturing cerium (iv) ammonium nitrate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102443805A (en) * 2010-10-13 2012-05-09 江德馨 Method for circularly using alkaline waste etching liquid
CN110904456A (en) * 2019-12-28 2020-03-24 苏州天承化工有限公司 Copper etching solution and preparation method and application thereof

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