CN104085921B - Method for extracting niobium from mixed acid waste liquid obtained after chemical cleaning of superconductive niobium cavity - Google Patents
Method for extracting niobium from mixed acid waste liquid obtained after chemical cleaning of superconductive niobium cavity Download PDFInfo
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Abstract
The invention relates to a method for extracting niobium from a mixed acid waste liquid obtained after chemical cleaning of a superconductive niobium cavity. The method comprises the following steps: 1, respectively sending a niobium-containing mixed acid waste liquid and an extractant into a mixed clarification tank, and extracting at room temperature to respectively obtain a loaded organic phase and a raffinate phase; 2, adding pure water to the loaded organic phase, and back-extracting to obtain an organic phase and a back-extraction liquid; 3, adding ammonia water to the back-extraction liquid to adjust the pH value in order to obtain a white solid precipitate niobium hydroxide, and filtering and calcining the precipitate niobium hydroxide to obtain niobium pentaoxide; and 4, dividing the raffinate phase into two parts, diluting one of the two parts with water, carrying out phosphoric acid and nitric acid concentration measurement on the one part, diluting the other one of the two parts by an acetic acid-sodium acetate buffer solution, carrying out hydrofluoric acid concentration measurement, comparing with the concentration of the mixed acid used by the chemical cleaning of the superconductive niobium cavity, calibrating, supplementing, and using the obtained liquid as a chemical cleaning liquid of the superconductive niobium cavity. The method has the advantages of simplicity, simple operation and suitableness for industrial application.
Description
Technical field
The present invention relates in etching process the process field mixing spent acid, particularly relate to a kind of method of chemically cleaning extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity.
Background technology
Superconduction is one of metal niobium field with development prospect, and over nearly 10 years, the application of metal niobium in this field has obtained extensive progress, and nearly all industrial superconductor device all adopts niobium titanium (NbTi) and niobium three tin (Nb
3sn) superconductor is done.The construction and development of current China accelerator, need to consume a large amount of high pure metal niobiums and come processing and manufacturing superconductor cavity and relevant niobium parts, and the matting on superconductor cavity surface create a large amount of high density mixing acid waste liquids.Under current environmental protection policy, these waste acid liquors can not directly be discharged in environment, and technique also not relevant at present processes and reclaims these spent acid.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of technique method of chemically cleaning extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity simple, easy and simple to handle.
For solving the problem, a kind of method of chemically cleaning extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity of the present invention, comprises the following steps:
(1) will send into respectively in mixer-settler by comparing O/A=1/1 ~ 1/3 with extraction agent containing niobium mixing acid waste liquid, extract 1 ~ 4 time at ambient temperature, each extraction time is 5 ~ 30 min, merges, obtains load organic phases and raffinate aqueous phase respectively;
(2) add pure water by comparing O/A=1/1 ~ 1/3 in described load organic phases, at ambient temperature back extraction 1 ~ 3 time, each Stripping times is 10 ~ 30 min, merges and obtains organic phase and strip liquor respectively; Described organic phase return described step (1) in;
(3) add ammoniacal liquor adjust ph to 8 ~ 9 in described strip liquor, obtain white solid precipitates niobium hydroxide, this throw out niobium hydroxide after filtration, calcining after namely obtain Niobium Pentxoxide;
(4) described raffinate aqueous phase is divided into two parts, after a copy of it dilute with water 5 ~ 10 times, continuous chemical volumetry is adopted to carry out measurement of concetration according to a conventional method to phosphoric acid wherein and nitric acid, another part is with after NaAc_HAc buffer solution dilution 5 ~ 10 times, adopt Fluoride ion selective electrode method to carry out measurement of concetration according to a conventional method to hydrofluoric acid concentration wherein, then through with carry out the increasing mixed acid concentration that matting Superconducting Niobium Cavity utilizes compare, demarcate, supplementary after again as the chemical cleaning solution of Superconducting Niobium Cavity.
Described step (1) in refer to containing niobium mixing acid waste liquid and utilize dense hydrofluoric acid, concentrated nitric acid and strong phosphoric acid to mix in the ratio of 1 L:1 L:2 L and mixed acid solution by obtaining after chemical milling Superconducting Niobium Cavity.
Described step (1) in extraction agent refer to one in tributyl phosphate TBP, methyl iso-butyl ketone (MIBK) MIBK or n-Octanol.
Described step (3) middle calcining temperature is 400 ~ 800 DEG C, and calcination time is 1 ~ 4 h.
Described step (4) in continuous chemical volumetry accepted standard volumetric soiutions be the aqueous sodium hydroxide solution of 1 mol/L, indicator is tropeolin-D and phenolphthalein.
Described step (4) in the pH value of NaAc_HAc buffer solution be 5 ~ 7.
The present invention compared with prior art has the following advantages:
1, raw material of the present invention is the high density mixed acid solution after chemical milling Superconducting Niobium Cavity, and require no process and directly add extraction agent and extract, back extraction reagent is water, decreases the operations such as neutralization, wastewater treatment, reduces production cost; Strip liquor obtains niobium hydroxide without purification Direct precipitation, and calcining can obtain the higher Niobium Pentxoxide of purity; 98% is greater than from the waste acid liquor after process Superconducting Niobium Cavity to the rate of recovery of strip liquor process niobium.
2, extracting-back extraction process of the present invention is simply controlled, and extraction mixer-settler industrial application technology maturation, is convenient to scale operation.Organic phase after back extraction can return extraction process recycling, spent acid after extraction is through demarcating process, effective utilization can be repeated, not only reduce production cost, and greatly reduce the discharge of the mixed acid solution containing strong acid components, effectively reduce the pollution to environment, simultaneously economic benefit, social benefit are remarkable.
3, present invention process is simple, easy and simple to handle, obtains niobium oxides, have good practicality with lower production cost, is applicable to industrial applications.
Embodiment
embodiment 1chemically clean a method for extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity, comprise the following steps:
(1) will send into respectively in mixer-settler by comparing O/A=1/1 with extraction agent containing niobium mixing acid waste liquid, extract 1 time at ambient temperature, extraction time is 10 min, static phase-splitting 1 min, obtains load organic phases and raffinate aqueous phase respectively.The extraction efficiency of extracting and separating gained niobium is 90.65%.
Wherein:
Referring to containing niobium mixing acid waste liquid utilizes dense hydrofluoric acid, concentrated nitric acid and strong phosphoric acid to mix in the ratio of 1 L:1 L:2 L and mixed acid solution by obtaining after chemical milling Superconducting Niobium Cavity; Wherein containing niobium mass concentration in waste liquid is 12.38 g/L.
Extraction agent refers to that volumetric concentration is the tributyl phosphate TBP of 100%.
(2) add pure water by comparing O/A=1/1 in load organic phases, at ambient temperature back extraction 2 times, each Stripping times is 10 min, merges and obtains organic phase and strip liquor respectively; Organic phase return step (1) in.Back extraction ratio is 94.21%.
(3) add ammoniacal liquor adjust ph to 8 in strip liquor, obtain white solid precipitates niobium hydroxide, this throw out niobium hydroxide after filtering, is calcine 2 h under the condition of 600 DEG C in calcining temperature, obtains Niobium Pentxoxide.
(4) raffinate aqueous phase is divided into two parts, after a copy of it dilute with water 5 times, adopts continuous chemical volumetry to carry out the measurement of concetration of phosphoric acid and nitric acid according to a conventional method to phosphoric acid wherein and nitric acid.With the mixed acid solution after the dilution of 1mol/L sodium hydroxide solution chemistry titration, with tropeolin-D and phenolphthalein for indicator, first calculated the concentration of phosphoric acid by the volume of the sodium hydroxide consumed.
After another part dilutes 5 times with the NaAc_HAc buffer solution that pH value is 6, adopt Fluoride ion selective electrode method to carry out hydrofluoric acid concentration measurement according to a conventional method to hydrofluoric acid concentration wherein, calculate the concentration of nitric acid above in conjunction with the sodium hydroxide volume consumed again.Measuring result, phosphoric acid in mixed acid system after extraction of Nb, nitric acid and hydrofluoric acid concentration are respectively 7.2 mol/L, 2.7 mol/L and 2.4 mol/L, phosphoric acid, nitric acid and hydrofluoric acid concentration in chemical etching process forward slip value solution are respectively 7.3 mol/L, 4 mol/L and 5.75 mol/L.Then through with carry out the increasing mixed acid concentration that matting Superconducting Niobium Cavity utilizes and compare, demarcate, supplement after nitric acid and hydrofluoric acid again as the chemical cleaning solution of Superconducting Niobium Cavity.
embodiment 2chemically clean a method for extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity, comprise the following steps:
(1) will send into respectively in mixer-settler by comparing O/A=1/2 with extraction agent containing niobium mixing acid waste liquid, extract 2 times at ambient temperature, each extraction time is 20 min, and static phase-splitting 1 min, obtains load organic phases and raffinate aqueous phase respectively.The extraction efficiency of extracting and separating gained niobium is 91.89%.
Wherein:
Referring to containing niobium mixing acid waste liquid utilizes dense hydrofluoric acid, concentrated nitric acid and strong phosphoric acid to mix in the ratio of 1 L:1 L:2 L and mixed acid solution by obtaining after chemical milling Superconducting Niobium Cavity; Wherein containing niobium mass concentration in waste liquid is 13.24g/L.
Extraction agent refers to that volumetric concentration is the tributyl phosphate TBP of 100%.
(2) add pure water by comparing O/A=1/2 in load organic phases, at ambient temperature back extraction 3 times, each Stripping times is 20 min, merges and obtains organic phase and strip liquor respectively; Organic phase return step (1) in.Back extraction ratio is 95.25%.
(3) add ammoniacal liquor adjust ph to 8 in strip liquor, obtain white solid precipitates niobium hydroxide, this throw out niobium hydroxide after filtering, is calcine 1 h under the condition of 800 DEG C in calcining temperature, obtains Niobium Pentxoxide.
(4) raffinate aqueous phase is divided into two parts, after a copy of it dilute with water 10 times, continuous chemical volumetry is adopted to carry out the measurement of concetration of phosphoric acid and nitric acid according to a conventional method to phosphoric acid wherein and nitric acid, with the mixed acid solution after 1 mol/L sodium hydroxide solution chemistry titration dilution, with tropeolin-D and phenolphthalein for indicator, first calculated the concentration of phosphoric acid by the volume of the sodium hydroxide consumed.
After another part dilutes 5 times with the NaAc_HAc buffer solution that pH value is 6, adopt Fluoride ion selective electrode method to carry out hydrofluoric acid concentration measurement according to a conventional method to hydrofluoric acid concentration wherein, calculate the concentration of nitric acid above in conjunction with the sodium hydroxide volume consumed again.Measuring result, the phosphoric acid in the mixed acid system after extraction of Nb, nitric acid and hydrofluoric acid concentration are respectively 7.2 mol/L, 1.6mol/L and 1.4 mol/L.Phosphoric acid, nitric acid and hydrofluoric acid concentration in etch process forward slip value solution are respectively 7.3 mol/L, 4 mol/L and 5.75 mol/L.Then through with carry out the increasing mixed acid concentration that matting Superconducting Niobium Cavity utilizes and compare, demarcate, supplement after nitric acid and hydrofluoric acid again as the chemical cleaning solution of Superconducting Niobium Cavity.
embodiment 3chemically clean a method for extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity, comprise the following steps:
(1) will send into respectively in mixer-settler by comparing O/A=1/1 with extraction agent containing niobium mixing acid waste liquid, extract 1 time at ambient temperature, extraction time is 10 min, and static phase-splitting 1 min, obtains load organic phases and raffinate aqueous phase respectively.The extraction efficiency of extracting and separating gained niobium is 89.89%.
Wherein:
Referring to containing niobium mixing acid waste liquid utilizes dense hydrofluoric acid, concentrated nitric acid and strong phosphoric acid to mix in the ratio of 1 L:1 L:2 L and mixed acid solution by obtaining after chemical milling Superconducting Niobium Cavity; Wherein containing niobium mass concentration in waste liquid is 8.76 g/L.
Extraction agent refers to that volumetric concentration is the tributyl phosphate TBP of 100%.
(2) add pure water by comparing O/A=1/1 in load organic phases, at ambient temperature back extraction 2 times, each Stripping times is 10 min, merges and obtains organic phase and strip liquor respectively; Organic phase return step (1) in.
(3) add ammoniacal liquor adjust ph to 9 in strip liquor, obtain white solid precipitates niobium hydroxide, this throw out niobium hydroxide after filtering, is calcine 4 h under the condition of 400 DEG C in calcining temperature, obtains Niobium Pentxoxide.
(4) raffinate aqueous phase is divided into two parts, after a copy of it dilute with water 10 times, continuous chemical volumetry is adopted to carry out the measurement of concetration of phosphoric acid and nitric acid according to a conventional method to phosphoric acid wherein and nitric acid, with the mixed acid solution after 1 mol/L sodium hydroxide solution chemistry titration dilution, with tropeolin-D and phenolphthalein for developer, first calculated the concentration of phosphoric acid by the volume of the sodium hydroxide consumed.
After another part dilutes 10 times with the NaAc_HAc buffer solution that pH value is 7, adopt Fluoride ion selective electrode method to carry out hydrofluoric acid concentration measurement according to a conventional method to hydrofluoric acid concentration wherein, calculate the concentration of nitric acid above in conjunction with the sodium hydroxide volume consumed again.Measuring result, the phosphoric acid in the mixed acid system after extraction of Nb, nitric acid and hydrofluoric acid concentration are respectively 7.0 mol/L, 2.3 mol/L and 2.1mol/L.Phosphoric acid, nitric acid and hydrofluoric acid concentration in etch process forward slip value solution are respectively 7.3 mol/L, 4mol/L and 5.75mol/L.Then through with carry out the increasing mixed acid concentration that matting Superconducting Niobium Cavity utilizes and compare, demarcate, supplement after nitric acid and hydrofluoric acid again as the chemical cleaning solution of Superconducting Niobium Cavity.
embodiment 4chemically clean a method for extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity, comprise the following steps:
(1) will send into respectively in mixer-settler by comparing O/A=1/1 with extraction agent containing niobium mixing acid waste liquid, extract 2 times at ambient temperature, each extraction time is 10 min, and static phase-splitting 1 min, obtains load organic phases and raffinate aqueous phase respectively.The extraction efficiency of extracting and separating gained niobium is 91.98%.
Wherein:
Referring to containing niobium mixing acid waste liquid utilizes dense hydrofluoric acid, concentrated nitric acid and strong phosphoric acid to mix in the ratio of 1 L:1 L:2 L and mixed acid solution by obtaining after chemical milling Superconducting Niobium Cavity; Wherein containing niobium mass concentration in waste liquid is 5.35 g/L.
Extraction agent refers to that volumetric concentration is the tributyl phosphate TBP of 100%.
(2) add pure water by comparing O/A=1/1 in load organic phases, at ambient temperature back extraction 1 time, Stripping times is 20 min, merges and obtains organic phase and strip liquor respectively; Organic phase return step (1) in.
(3) add ammoniacal liquor adjust ph to 8.5 in strip liquor, obtain white solid precipitates niobium hydroxide, this throw out niobium hydroxide after filtering, is calcine 2 h under the condition of 600 DEG C in calcining temperature, obtains Niobium Pentxoxide.
(4) raffinate aqueous phase is divided into two parts, after a copy of it dilute with water 8 times, continuous chemical volumetry is adopted to carry out the measurement of concetration of phosphoric acid and nitric acid according to a conventional method to phosphoric acid wherein and nitric acid, with the mixed acid solution after the dilution of 1mol/L sodium hydroxide solution chemistry titration, with tropeolin-D and phenolphthalein for developer, first calculated the concentration of phosphoric acid by the volume of the sodium hydroxide consumed.
After another part dilutes 8 times with the NaAc_HAc buffer solution that pH value is 6, adopt Fluoride ion selective electrode method to carry out hydrofluoric acid concentration measurement according to a conventional method to hydrofluoric acid concentration wherein, calculate the concentration of nitric acid above in conjunction with the sodium hydroxide volume consumed again.Measuring result, the phosphoric acid in the mixed acid system after extraction of Nb, nitric acid and hydrofluoric acid concentration are respectively 7.1 mol/L, 1.85 mol/L and 1.9 mol/L.Phosphoric acid, nitric acid and hydrofluoric acid concentration in etch process forward slip value solution are respectively 7.3 mol/L, 4 mol/L and 5.75 mol/L.Then through with carry out the increasing mixed acid concentration that matting Superconducting Niobium Cavity utilizes and compare, demarcate, supplement after nitric acid and hydrofluoric acid again as the chemical cleaning solution of Superconducting Niobium Cavity.
embodiment 5chemically clean a method for extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity, comprise the following steps:
(1) will send into respectively in mixer-settler by comparing O/A=1/1 with extraction agent containing niobium mixing acid waste liquid, extract 3 times at ambient temperature, each extraction time is 30 min, static phase-splitting 1 min, merges, obtains load organic phases and raffinate aqueous phase respectively.Extraction efficiency is 95.65%.
Wherein:
Referring to containing niobium mixing acid waste liquid utilizes dense hydrofluoric acid, concentrated nitric acid and strong phosphoric acid to mix in the ratio of 1 L:1 L:2 L and mixed acid solution by obtaining after chemical milling Superconducting Niobium Cavity; Wherein containing niobium mass concentration in waste liquid is 12.38 g/L.
Extraction agent refers to that volumetric concentration is the tributyl phosphate TBP of 100%.
(2) add pure water by comparing O/A=1/3 in load organic phases, at ambient temperature back extraction 3 times, each Stripping times is 30 min, merges and obtains organic phase and strip liquor respectively; Organic phase return step (1) in.Back extraction ratio is 95.89%.
(3) add ammoniacal liquor adjust ph to 9 in strip liquor, obtain white solid precipitates niobium hydroxide, this throw out niobium hydroxide after filtering, is calcine 3 h under the condition of 600 DEG C in calcining temperature, obtains Niobium Pentxoxide.
(4) raffinate aqueous phase is divided into two parts, after a copy of it dilute with water 5 times, continuous chemical volumetry is adopted to carry out the measurement of concetration of phosphoric acid and nitric acid according to a conventional method to phosphoric acid wherein and nitric acid, with the mixed acid solution after the dilution of 1mol/L sodium hydroxide solution chemistry titration, with tropeolin-D and phenolphthalein for developer, first calculated the concentration of phosphoric acid by the volume of the sodium hydroxide consumed.
After another part dilutes 5 times with the NaAc_HAc buffer solution that pH value is 5, adopt Fluoride ion selective electrode method to carry out hydrofluoric acid concentration measurement according to a conventional method to hydrofluoric acid concentration wherein, calculate the concentration of nitric acid above in conjunction with the sodium hydroxide volume consumed again.Measuring result, the phosphoric acid in the mixed acid system after extraction of Nb, nitric acid and hydrofluoric acid concentration are respectively 6.9 mol/L, 1.45 mol/L and 1.5 mol/L.Phosphoric acid, nitric acid and hydrofluoric acid concentration in etch process forward slip value solution are respectively 7.3 mol/L, 4 mol/L and 5.75 mol/L.Then through with carry out the increasing mixed acid concentration that matting Superconducting Niobium Cavity utilizes and compare, demarcate, supplement after nitric acid and hydrofluoric acid again as the chemical cleaning solution of Superconducting Niobium Cavity.
embodiment 6chemically clean a method for extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity, comprise the following steps:
(1) will send into respectively in mixer-settler by comparing O/A=1/1 with extraction agent containing niobium mixing acid waste liquid, extract 2 times at ambient temperature, each extraction time is 30 min, static phase-splitting 1 min, merges, obtains load organic phases and raffinate aqueous phase respectively.Extraction efficiency is 96.89%.
Wherein:
Referring to containing niobium mixing acid waste liquid utilizes dense hydrofluoric acid, concentrated nitric acid and strong phosphoric acid to mix in the ratio of 1 L:1 L:2 L and mixed acid solution by obtaining after chemical milling Superconducting Niobium Cavity; Wherein containing niobium mass concentration in waste liquid is 12.38 g/L.
Extraction agent refers to that volumetric concentration is the tributyl phosphate TBP of 100%.
(2) add pure water by comparing O/A=1/2 in load organic phases, at ambient temperature back extraction 2 times, each Stripping times is 10 min, merges and obtains organic phase and strip liquor respectively; Organic phase return step (1) in.Back extraction ratio is 94.58%.
(3) add ammoniacal liquor adjust ph to 9 in strip liquor, obtain white solid precipitates niobium hydroxide, this throw out niobium hydroxide after filtering, is calcine 2 h under the condition of 600 DEG C in calcining temperature, obtains Niobium Pentxoxide.
(4) raffinate aqueous phase is divided into two parts, after a copy of it dilute with water 5 times, continuous chemical volumetry is adopted to carry out the measurement of concetration of phosphoric acid and nitric acid according to a conventional method to phosphoric acid wherein and nitric acid, with the mixed acid solution after the dilution of 1mol/L sodium hydroxide solution chemistry titration, with tropeolin-D and phenolphthalein for developer, first calculated the concentration of phosphoric acid by the volume of the sodium hydroxide consumed.
After another part dilutes 5 times with the NaAc_HAc buffer solution that pH value is 6, adopt Fluoride ion selective electrode method to carry out hydrofluoric acid concentration measurement according to a conventional method to hydrofluoric acid concentration wherein, calculate the concentration of nitric acid above in conjunction with the sodium hydroxide volume consumed again.Measuring result, phosphoric acid in mixed acid system after extraction of Nb, nitric acid and hydrofluoric acid concentration are respectively 7.1 mol/L, 1.98 mol/L and 2.18 mol/L, phosphoric acid, nitric acid and hydrofluoric acid concentration in etch process forward slip value solution are respectively 7.3 mol/L, 4 mol/L and 5.75 mol/L.Then through with carry out the increasing mixed acid concentration that matting Superconducting Niobium Cavity utilizes and compare, demarcate, supplement after nitric acid and hydrofluoric acid again as the chemical cleaning solution of Superconducting Niobium Cavity.
embodiment 7chemically clean a method for extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity, comprise the following steps:
(1) will send into respectively in mixer-settler by comparing O/A=1/1 with extraction agent containing niobium mixing acid waste liquid, extract 4 times at ambient temperature, each extraction time is 5 min, static phase-splitting 1 min, merges, obtains load organic phases and raffinate aqueous phase respectively.Extraction efficiency is 99.56%.
Wherein:
Referring to containing niobium mixing acid waste liquid utilizes dense hydrofluoric acid, concentrated nitric acid and strong phosphoric acid to mix in the ratio of 1 L:1 L:2 L and mixed acid solution by obtaining after chemical milling Superconducting Niobium Cavity; Wherein containing niobium mass concentration in waste liquid is 12.38 g/L.
Extraction agent refers to that volumetric concentration is the tributyl phosphate TBP of 100%.
(2) add pure water by comparing O/A=1/3 in load organic phases, at ambient temperature back extraction 3 times, each Stripping times is 10 min, merges and obtains organic phase and strip liquor respectively; Organic phase return step (1) in.Back extraction ratio is 95.58%.
(3) add ammoniacal liquor adjust ph to 9 in strip liquor, obtain white solid precipitates niobium hydroxide, this throw out niobium hydroxide after filtering, is calcine 2 h under the condition of 700 DEG C in calcining temperature, obtains Niobium Pentxoxide.
(4) raffinate aqueous phase is divided into two parts, after a copy of it dilute with water 10 times, continuous chemical volumetry is adopted to carry out the measurement of concetration of phosphoric acid and nitric acid according to a conventional method to phosphoric acid wherein and nitric acid, with the mixed acid solution after the dilution of 1mol/L sodium hydroxide solution chemistry titration, with tropeolin-D and phenolphthalein for developer, first calculated the concentration of phosphoric acid by the volume of the sodium hydroxide consumed.
After another part dilutes 5 times with the NaAc_HAc buffer solution that pH value is 6, adopt Fluoride ion selective electrode method to carry out hydrofluoric acid concentration measurement according to a conventional method to hydrofluoric acid concentration wherein, calculate the concentration of nitric acid above in conjunction with the sodium hydroxide volume consumed again.Measuring result, the phosphoric acid in the mixed acid system after extraction of Nb, nitric acid and hydrofluoric acid concentration are respectively 7.1 mol/L, 1.55 mol/L and 1.6 mol/L.Phosphoric acid, nitric acid and hydrofluoric acid concentration in etch process forward slip value solution are respectively 7.3 mol/L, 4 mol/L and 5.75 mol/L.Then through with carry out the increasing mixed acid concentration that matting Superconducting Niobium Cavity utilizes and compare, demarcate, supplement after nitric acid and hydrofluoric acid again as the chemical cleaning solution of Superconducting Niobium Cavity.
embodiment 8chemically clean a method for extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity, comprise the following steps:
(1) will send into respectively in mixer-settler by comparing O/A=1/3 with extraction agent containing niobium mixing acid waste liquid, extract 1 time at ambient temperature, each extraction time is 5 min, merges, obtains load organic phases and raffinate aqueous phase respectively.Extraction efficiency is 91.56%.
Wherein:
Referring to containing niobium mixing acid waste liquid utilizes dense hydrofluoric acid, concentrated nitric acid and strong phosphoric acid to mix in the ratio of 1 L:1 L:2 L and mixed acid solution by obtaining after chemical milling Superconducting Niobium Cavity; Wherein containing niobium mass concentration in waste liquid is 3g/L.
Extraction agent is means methyl isobutyl keton MIBK.
(2) add pure water by comparing O/A=1/2 in load organic phases, at ambient temperature back extraction 1 time, each Stripping times is 10min, merges and obtains organic phase and strip liquor respectively; Organic phase return step (1) in.Back extraction ratio is 90.58%.
(3) add ammoniacal liquor adjust ph to 8 in strip liquor, obtain white solid precipitates niobium hydroxide, this throw out niobium hydroxide after filtering, is calcine 2 h under the condition of 600 DEG C in calcining temperature, obtains Niobium Pentxoxide.
(4) raffinate aqueous phase is divided into two parts, after a copy of it dilute with water 10 times, continuous chemical volumetry is adopted to carry out the measurement of concetration of phosphoric acid and nitric acid according to a conventional method to phosphoric acid wherein and nitric acid, with the mixed acid solution after the dilution of 1mol/L sodium hydroxide solution chemistry titration, with tropeolin-D and phenolphthalein for developer, first calculated the concentration of phosphoric acid by the volume of the sodium hydroxide consumed.
After another part dilutes 10 times with the NaAc_HAc buffer solution that pH value is 6, adopt Fluoride ion selective electrode method to carry out hydrofluoric acid concentration measurement according to a conventional method to hydrofluoric acid concentration wherein, calculate the concentration of nitric acid above in conjunction with the sodium hydroxide volume consumed again.Measuring result, the phosphoric acid in the mixed acid system after extraction of Nb, nitric acid and hydrofluoric acid concentration are respectively 7.3 mol/L, 3.1 mol/L and 4.2 mol/L.Phosphoric acid, nitric acid and hydrofluoric acid concentration in etch process forward slip value solution are respectively 7.3 mol/L, 4 mol/L and 5.75 mol/L.Then through with carry out the increasing mixed acid concentration that matting Superconducting Niobium Cavity utilizes and compare, demarcate, supplement after nitric acid and hydrofluoric acid again as the chemical cleaning solution of Superconducting Niobium Cavity.
embodiment 9chemically clean a method for extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity, comprise the following steps:
(1) will send into respectively in mixer-settler by comparing O/A=1/2 with extraction agent containing niobium mixing acid waste liquid, extract 4 times at ambient temperature, each extraction time is 30 min, merges, obtains load organic phases and raffinate aqueous phase respectively.Extraction efficiency is 90.56%.
Wherein:
Referring to containing niobium mixing acid waste liquid utilizes dense hydrofluoric acid, concentrated nitric acid and strong phosphoric acid to mix in the ratio of 1 L:1 L:2 L and mixed acid solution by obtaining after chemical milling Superconducting Niobium Cavity; Wherein containing niobium mass concentration in waste liquid is 14 g/L.
Extraction agent refers to n-Octanol.
(2) add pure water by comparing O/A=1/3 in load organic phases, at ambient temperature back extraction 3 times, each Stripping times is 10 min, merges and obtains organic phase and strip liquor respectively; Organic phase return step (1) in.Back extraction ratio is 90.88%.
(3) add ammoniacal liquor adjust ph to 9 in strip liquor, obtain white solid precipitates niobium hydroxide, this throw out niobium hydroxide after filtering, is calcine 2 h under the condition of 600 DEG C in calcining temperature, obtains Niobium Pentxoxide.
(4) raffinate aqueous phase is divided into two parts, after a copy of it dilute with water 5 times, continuous chemical volumetry is adopted to carry out the measurement of concetration of phosphoric acid and nitric acid according to a conventional method to phosphoric acid wherein and nitric acid, with the mixed acid solution after the dilution of 1mol/L sodium hydroxide solution chemistry titration, with tropeolin-D and phenolphthalein for developer, first calculated the concentration of phosphoric acid by the volume of the sodium hydroxide consumed.
After another part dilutes 5 times with the NaAc_HAc buffer solution that pH value is 7, adopt Fluoride ion selective electrode method to carry out hydrofluoric acid concentration measurement according to a conventional method to hydrofluoric acid concentration wherein, calculate the concentration of nitric acid above in conjunction with the sodium hydroxide volume consumed again.Measuring result, the phosphoric acid in the mixed acid system after extraction of Nb, nitric acid and hydrofluoric acid concentration are respectively 6.9 mol/L, 1.45 mol/L and 1.5 mol/L.Phosphoric acid, nitric acid and hydrofluoric acid concentration in etch process forward slip value solution are respectively 7.3 mol/L, 4 mol/L and 5.75 mol/L.Then through with carry out the increasing mixed acid concentration that matting Superconducting Niobium Cavity utilizes and compare, demarcate, supplement after nitric acid and hydrofluoric acid again as the chemical cleaning solution of Superconducting Niobium Cavity.
Claims (5)
1. chemically clean a method for extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity, comprise the following steps:
(1) will send into respectively in mixer-settler by comparing O/A=1/1 ~ 1/3 with extraction agent containing niobium mixing acid waste liquid, extract 1 ~ 4 time at ambient temperature, each extraction time is 5 ~ 30 min, merges, obtains load organic phases and raffinate aqueous phase respectively; Described referring to containing niobium mixing acid waste liquid utilizes dense hydrofluoric acid, concentrated nitric acid and strong phosphoric acid to mix in the ratio of 1 L:1 L:2 L and mixed acid solution by obtaining after chemical milling Superconducting Niobium Cavity;
(2) add pure water by comparing O/A=1/1 ~ 1/3 in described load organic phases, at ambient temperature back extraction 1 ~ 3 time, each Stripping times is 10 ~ 30 min, merges and obtains organic phase and strip liquor respectively; Described organic phase return described step (1) in;
(3) add ammoniacal liquor adjust ph to 8 ~ 9 in described strip liquor, obtain white solid precipitates niobium hydroxide, this throw out niobium hydroxide after filtration, calcining after namely obtain Niobium Pentxoxide;
(4) described raffinate aqueous phase is divided into two parts, after a copy of it dilute with water 5 ~ 10 times, continuous chemical volumetry is adopted to carry out measurement of concetration according to a conventional method to phosphoric acid wherein and nitric acid, another part is with after NaAc_HAc buffer solution dilution 5 ~ 10 times, adopt Fluoride ion selective electrode method to carry out measurement of concetration according to a conventional method to hydrofluoric acid concentration wherein, then through with carry out the increasing mixed acid concentration that matting Superconducting Niobium Cavity utilizes compare, demarcate, supplementary after again as the chemical cleaning solution of Superconducting Niobium Cavity.
2. a kind of method of chemically cleaning extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity as claimed in claim 1, is characterized in that: described step (1) in extraction agent refer to one in tributyl phosphate TBP, methyl iso-butyl ketone (MIBK) MIBK or n-Octanol.
3. a kind of method of chemically cleaning extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity as claimed in claim 1, is characterized in that: described step (3) in calcining temperature be 400 ~ 800 DEG C, calcination time is 1 ~ 4 h.
4. a kind of method of chemically cleaning extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity as claimed in claim 1, it is characterized in that: described step (4) in continuous chemical volumetry accepted standard volumetric soiutions be the aqueous sodium hydroxide solution of 1 mol/L, indicator is tropeolin-D and phenolphthalein.
5. a kind of method of chemically cleaning extraction of Nb in the mixed acid waste liquor of Superconducting Niobium Cavity as claimed in claim 1, is characterized in that: described step (4) in the pH value of NaAc_HAc buffer solution be 5 ~ 7.
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