CN107686898B - A method of hafnium oxide is prepared from recycling in waste material containing hafnium - Google Patents
A method of hafnium oxide is prepared from recycling in waste material containing hafnium Download PDFInfo
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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Abstract
The invention discloses a kind of method for preparing hafnium oxide from recycling in waste material containing hafnium, this method are as follows: one, the addition waste material containing hafnium into the mixed liquor of hydrofluoric acid and nitric acid obtain lysate after dissolution；Two, ammonium hydroxide is added into lysate, and heating stirring obtains precipitation slag；Three, precipitation slag is dissolved using nitric acid, obtains leachate；Four, leachate is adsorbed using cation exchange resin, obtains loaded resin；Five, loaded resin is eluted using nitric acid, washes off impurity element；Six, the desorption that hafnium is carried out using sulfuric acid, obtains the stripping liquid of hafnium；Seven, it is precipitated using stripping liquid of the ammonium hydroxide to hafnium, obtains the hydroxide precipitating of hafnium；Eight, the hydroxide of hafnium is heated, obtains hafnium oxide.The method that the present invention prepares hafnium oxide from recycling in waste material containing hafnium, so that the rate of recovery of hafnium is up to 90% or more in waste material containing hafnium, and the quality purity of product hafnium oxide, up to 99% or more, hafnium sponge can be made by existing sodium reduction in hafnium oxide.
Description
Technical field
The invention belongs to technical field of wet metallurgy, and in particular to a kind of side that hafnium oxide is prepared from recycling in waste material containing hafnium
Method.
Background technique
Hafnium is widely used in the national defense industry such as nuclear power and aerospace field, mainly using in nuclear power field as a kind of strategy metal
Rocket propulsion is used in atomic reactor reactor core material, aeronautical field.Hafnium can also make the control of the nuclear reactor
Stick.Pure hafnium has plasticity, easy processing, high-temperature-resistant and anti-corrosion, is atomic energy industry important materials, the thermal neutron capture cross section of hafnium
Greatly, it is comparatively ideal neutron absorber, the control rod and protective device of atomic pile can be made.Hafnium powder can make the propulsion of rocket
Device.The cathode of X-ray tube can be manufactured in electrical equipment industry.The alloy of hafnium can make rocket nozzle and what gliding type was reentried flies
The forward position protective layer of row device.Based on this, China has passed through " Chinese Nuclear Power safety program " and " the year two thousand twenty core on October 24th, 2012
Electric medium-term and long-term plans ", Construction of Nuclear Electricity to be restored is explicitly pointed out, hafnium is as nuclear power reactor core material important meals materials, atomic energy level
Hafnium demand is it is contemplated that will increase.China belongs to the poorer country of hafnium reserves, and in the smelting of hafnium, China about needs every year
The import volume of 3 tons of metal hafniums, and contain a considerable number of hafnium in waste metal containing hafnium, but these waste metals are mostly through degrading
Processing, causes the wasting of resources, environmental pollution.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, the technical problem to be solved by the present invention is that providing a kind of from containing hafnium
The method that recycling prepares hafnium oxide in waste material.The method that this method prepares hafnium oxide from recycling in waste material containing hafnium, so that useless containing hafnium
The rate of recovery of hafnium is up to 90% or more in material, and in product hafnium oxide quality purity up to 99% or more, hafnium oxide can be by existing
Hafnium sponge is made in some sodium reductions, while method of the invention can be reduced the downgrade processing of the waste and old metal containing hafnium, energy saving, right
It is more environment-friendly, there is good industrial prospect.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: one kind preparing oxygen from recycling in waste material containing hafnium
Change the method for hafnium, which is characterized in that method includes the following steps:
Step 1: waste material containing hafnium is added in the mixed solution being mixed by hydrofluoric acid solution and nitric acid solution, in temperature
Degree is stirring and dissolving under conditions of 40 DEG C~60 DEG C, and the time of stirring is 0.5h~1h, then obtains lysate after filtering and removing slag；
The ratio of the volume of the quality and mixed solution of the waste material containing hafnium is 1:(5~7), the mass unit of the waste material containing hafnium is g, is mixed
The volume unit for closing solution is mL；
Ammonium hydroxide is added in lysate obtained in step 1 Step 2: dividing 2~4 times, then in 70 DEG C~90 DEG C of item
Slag liquid mixture is stirred to get under part, is successively filtered, washed and dried the slag liquid mixture and is obtained precipitation slag；It is ammoniated every time
The volume of water is 0.5 times~1.5 times of the volume of the lysate；
Step 3: being added to precipitation slag is obtained in step 2 in nitric acid solution, under conditions of temperature is 60 DEG C~90 DEG C
Stirring and dissolving 0.5h~1h, obtains leachate；The volume of the nitric acid solution is 5 times~7 times of the quality of precipitation slag, precipitation slag
Mass unit be g, the volume unit of nitric acid solution is mL；
Step 4: using the pH of hafnium ion concentration and leachate in leachate obtained in deionized water regulating step three
Value, or using the hafnium ion concentration in leachate obtained in deionized water regulating step three, the leaching is adjusted using ammonium hydroxide
The pH value of liquid out；Then leachate is adsorbed at room temperature using cation exchange resin, obtains loaded resin；The leaching
The volume of liquid is 10 times~14 times of the cation exchange resin volume out；
Step 5: using concentration is the nitric acid solution of 0.4mol/L~1.0mol/L at room temperature to obtained in step 4
Loaded resin is eluted, and impurity element is washed off；The volume of the nitric acid solution is cation exchange resin described in step 4
10 times of volume~20 times；
Step 6: use concentration for the sulfuric acid solution of 1.0mol/L~2.0mol/L at room temperature in step 5 elute after
Loaded resin carry out hafnium desorption, obtain the stripping liquid of hafnium；The volume of the sulfuric acid solution is cation described in step 4
3~6 times of exchanger resin volume；
Step 7: being precipitated using stripping liquid of the ammonium hydroxide to hafnium obtained in step 6, the hydroxide for obtaining hafnium is heavy
It forms sediment；The volume of the ammonium hydroxide is 3 times~6 times of cation exchange resin volume described in step 4；
Step 8: the hydroxide to hafnium obtained in step 7 carries out 3h under conditions of temperature is 400 DEG C~600 DEG C
The heat treatment of~6h, obtains hafnium oxide.
A kind of above-mentioned method for preparing hafnium oxide from recycling in waste material containing hafnium, which is characterized in that contain described in step 1
Main metal element in hafnium waste material includes one or more of Hf and Cr, Fe, Mo, W, Ta, Nb and Ti.
A kind of above-mentioned method for preparing hafnium oxide from recycling in waste material containing hafnium, which is characterized in that contain described in step 1
The mass content of hafnium is 10%~40% in hafnium waste material.
A kind of above-mentioned method for preparing hafnium oxide from recycling in waste material containing hafnium, which is characterized in that mixed described in step 1
The nitric acid solution that the hydrofluoric acid solution and concentration that conjunction solution is 18mol/L~22mol/L by concentration are 10mol/L~14mol/L
It is mixed, the volume content of hydrofluoric acid solution is 28%~50% in the mixed solution.
A kind of above-mentioned method for preparing hafnium oxide from recycling in waste material containing hafnium, which is characterized in that step 2 and step 7
Described in the mass concentration of ammonium hydroxide be 23%~28%.
A kind of above-mentioned method for preparing hafnium oxide from recycling in waste material containing hafnium, which is characterized in that nitre described in step 3
The concentration of acid solution is 8mol/L~12mol/L.
A kind of above-mentioned method for preparing hafnium oxide from recycling in waste material containing hafnium, which is characterized in that after being adjusted in step 4
Leachate in hafnium ion concentration be 1g/L~5g/L, pH value be 0~1；The flow velocity of leachate and sun in the adsorption process
The ratio of ion exchange resin volume is 0.5~3, and the flow rate of leachate is mL/h, the volume list of cation exchange resin
Position is mL.
A kind of above-mentioned method for preparing hafnium oxide from recycling in waste material containing hafnium, which is characterized in that sun described in step 4
Ion exchange resin is hydrogen type cation exchange resin.
A kind of above-mentioned method for preparing hafnium oxide from recycling in waste material containing hafnium, which is characterized in that drenched described in step 5
The flow velocity of nitric acid solution and the ratio of cation exchange resin volume are 0.5~1.5 during washing, the flow rate of nitric acid solution
For mL/h, the volume unit of cation exchange resin is mL.
A kind of above-mentioned method for preparing hafnium oxide from recycling in waste material containing hafnium, which is characterized in that solved described in step 6
The ratio of the volume of the flow velocity and cation exchange resin of sulfuric acid solution is 0.5~1.5 during suction, the flow velocity list of sulfuric acid solution
Position is mL/h, and the volume unit of cation exchange resin is mL.
Method of the invention according to the waste material containing hafnium at the dissolution characteristics being grouped as and its in acid, using hydrofluoric acid solution
Waste material containing hafnium is dissolved with the mixed liquor of nitric acid solution, wherein the effective, fast of waste material may be implemented using hydrofluoric acid solution
Instant solution can reduce the dosage of hydrofluoric acid solution using nitric acid solution, and ammonium hydroxide is added in lysate after heating stirring thereafter
Filtering, obtains precipitation slag while fluorine removal, if containing W and Mo in waste material containing hafnium, while realizing the separation to Hf and W, Mo；
Using nitric acid solution to precipitation slag dissolve, obtain each metal ion leachate under nitric acid system, by adjust leachate in hafnium from
Effective absorption of the hafnium ion on cation exchange resin may be implemented to 1g/L~5g/L and pH value to 0~1 in sub- concentration, this
When, Sorption ratio of the hafnium ion on cation exchange resin is maximum, and the Sorption ratio of other metals is smaller, accordingly
The removal of major part foreign metal ion can be achieved, then pass through Non-leaching liquid HNO3The concentration of solution can will be adsorbed onto sun
Foreign ion on ion exchange resin elutes, and realizes the separation of hafnium and other metallic elements accordingly, then molten using sulfuric acid
Liquid desorbs cation exchange resin, can desorb completely hafnium, and ammonium hydroxide is added in stripping liquid and is precipitated, to heavy
Form sediment high-temperature heating, and hafnium oxide can be obtained.Relevant reaction equation is as follows in each step:
Step 1: Hf+6HF=H2HfF6+2H2
Step 2: H2HfF6+6NH3·H2O=Hf (OH)4↓+6NH4F+2H2O
Step 3: 2Hf (OH)4+6HNO3=Hf (NO3)4+HfO(NO3)2+7H2O
Step 4, wherein R represents cation exchange resin matrix, and M is impurity metallic elements, similarly hereinafter:
4R-H+Hf4+=R4-Hf+4H+
nR-H+Mn+=Rn-M+nH+
Step 5: Rn-M+nH+=nR-H+Mn+
Step 6: R4-Hf+4H+=4R-H+Hf4+
Step 7: Hf4++4NH3·H2O=Hf (OH)4↓+4NH4 +
Step 8: Hf (OH)4=HfO2+2H2O。
Compared with the prior art, the present invention has the following advantages:
1, downgrade processing and this low status of recovery utilization rate are carried out for most of existing hafnium waste material, proposed a kind of wet
The method that method separation prepares hafnium oxide, the present invention, at the dissolution characteristics being grouped as and its in acid, are used according to the waste material containing hafnium
Hydrofluoric acid solution and the mixed solution of nitric acid solution dissolve waste material containing hafnium, are added in lysate to heat by ammonium hydroxide thereafter and stir
It is filtered after mixing, fluorine removal is carried out to obtained precipitation slag, if containing W, Mo in waste material, and realize the separation to Hf and W, Mo；It adopts
Precipitation slag is dissolved with nitric acid, each metal ion leachate under nitric acid system is obtained, by adjusting hafnium ion concentration in leachate
Effective absorption of the hafnium ion on cation exchange resin may be implemented with pH value, realize the removal of most of impurity accordingly, and
Pass through Non-leaching liquid HNO afterwards3Concentration the impurity element being adsorbed on cation exchange resin is eluted, realize hafnium and
The separation of other elements, then cation exchange resin is desorbed using sulfuric acid, hafnium can be desorbed completely, in stripping liquid
Middle addition ammonium hydroxide is precipitated, and is heated at high temperature to precipitating, hafnium oxide can be obtained.Experimental implementation of the invention is easily achieved, hafnium
The rate of recovery be more than 90%, products obtained therefrom purity reaches 99%, be suitable for large-scale industrial production, be strategic metal hafnium height
Effect utilizes and provides a kind of feasible way.
2, the present invention carries out XRF to the hafnium oxide of preparation and analyzes, and there are mass content is 99% or more in product
Hafnium and minimal amount of other impurities element can thoroughly remove W and Mo if there are W and Mo in waste material containing hafnium, and significant drop
The low content of other metal impurities, the purity of hafnium oxide reaches 99% or more in the product of preparation, can be used for sodium reduction preparation
Hafnium sponge.
3, the hafnium oxide of present invention recycling preparation, can go out hafnium sponge by existing sodium reduction, final to realize to pure hafnium
Recycling, solves the wasting of resources and problem of environmental pollution that the waste metal of waste material containing hafnium is caused through downgrade processing.This hair simultaneously
Bright method can not only alleviate the dependence on external supply of China's hafnium resource, make up China's nuclear power and restart demand to hafnium, and can be with
Resource utilization is improved, basis is provided for preparation atomic energy level hafnium, protects China's hafnium Strategic Demand.
Below by embodiment, technical scheme of the present invention will be described in further detail.
Specific embodiment
Embodiment 1
The method of the present embodiment are as follows:
Step 1: into the polytetrafluoroethylene beaker for the 250mL for filling mixed solution be added 10g waste material containing hafnium, and with mould
Expect diaphragm seal beaker mouth, places the beaker and be stirred dissolution in 40 DEG C of water-bath, mixing time 0.5h is filtered to remove
Lysate is obtained after undissolved solid impurity；The ratio of the volume (mL) of the quality (g) and mixed solution of the waste material containing hafnium
For 1:7；The nitric acid that the hydrofluoric acid solution and 50mL concentration that the mixed solution is 18mol/L by 20mL concentration are 10mol/L is molten
Liquid is mixed；The ingredient of main metal element is (by mass percentage): Hf 39.75%, Ti in the waste material containing hafnium
50.27%, W 1.73%, Mo 0.74%, Fe 4.15%, Cr 3.36%；
Step 2: in lysate obtained in point 2 ammonium hydroxide addition step 1 by mass concentration for 23%, then in temperature
Stirring 1h obtains slag liquid mixture under conditions of 70 DEG C of degree, filters and is washed with deionized 3 times after the slag liquid mixture, then
Dry 1h, finally obtains precipitation slag under conditions of 90 DEG C；The volume of added ammonium hydroxide is 35mL every time；Step 2 is to remove and contain
In hafnium waste material be dissolved come out W, Mo, W, Mo exist in filtrate；
Step 3: being placed in precipitation slag is obtained in step 2 in 250mL beaker, the nitre that 110mL concentration is 8mol/L is measured
Acid solution is added in beaker, and the stirring and dissolving 0.5h at 60 DEG C obtains leachate, and hafnium ion concentration is 36.14g/ in leachate
L, pH are -0.58；The ratio of the volume (mL) of the quality (g) and nitric acid solution of precipitation slag is 1:7；
Leachate is diluted to 800mL Step 4: deionized water 690mL is added into the leachate that step 3 obtains, it is dilute
Hafnium ion concentration in leachate after releasing is 4.97g/L, pH value 0.28, the leachate work after measuring wherein 700mL dilution
To adsorb preceding liquid, the washed 001*4 cation exchange resin for being transformed into H-type of 50mL is placed in chromatographic column, using peristaltic pump
Feed liquor at room temperature adsorbs leachate, obtains loaded resin；The volume of liquid is cation exchange resin before the absorption
14 times of volume；The flow velocity of liquid is 25mL/h before adsorbing in the adsorption process；
Step 5: using 500mL concentration is the nitric acid solution of 0.4mol/L at room temperature to load obtained in step 4
Resin is eluted, and impurity element Ti, Fe and Cr are washed off；The flow velocity (mL/h) of nitric acid solution is 75mL/ in the lessivation
h；
Step 6: use 300mL concentration for the sulfuric acid solution of 2.0mol/L at room temperature in step 5 after eluting
Loaded resin carries out the desorption of hafnium, obtains the stripping liquid of hafnium；The flow velocity of sulfuric acid solution is 25mL/h in the desorption process；
Step 7: being precipitated using 28% ammonium hydroxide of 300mL mass content to the stripping liquid of hafnium obtained in step 6, obtain
Hydroxide to hafnium precipitates；
Step 8: carrying out the heat treatment of 6h under conditions of 600 DEG C to the hydroxide for the hafnium that step 7 obtains, oxygen is obtained
Change hafnium (HfO2)。
Product hafnium oxide manufactured in the present embodiment is analyzed using X-ray fluorescence spectra analysis (XRF), analyzes result
Are as follows: a large amount of Hf and minimal amount of Ti, Fe, Cr impurity element are rich in product hafnium oxide, and product hafnium oxide is carried out through XRF
Semi-quantitative analysis, the quality purity of hafnium oxide is 99.1% as the result is shown, again using chemical analysis to Ti, Fe, Cr in product
The test analysis of metal element content is carried out with Hf, metal quality content is respectively Ti 0.191%, Fe 0.039%, Cr
0.007%, surplus Hf.The result illustrate the present embodiment method can by waste material containing hafnium W and Mo completely remove, and show
Write the content for reducing Ti, Fe, Cr.Thus illustrate, the purity is high for the hafnium oxide that the present embodiment is prepared can be used existing
Sodium reduction method prepares hafnium sponge, this improves the utilization rate of the resource of the waste material containing hafnium, has good industrial prospect.
Embodiment 2
The method of the present embodiment are as follows:
Step 1: into the polytetrafluoroethylene beaker for the 250mL for filling mixed solution be added 10g waste material containing hafnium, and with mould
Expect diaphragm seal beaker mouth, places the beaker and be stirred dissolution in 60 DEG C of water-bath, mixing time 1h is filtered to remove not
Lysate is obtained after the solid impurity of dissolution；The quality (g) of the waste material containing hafnium and the ratio of the volume (mL) of mixed solution are
1:6；The nitric acid that the hydrofluoric acid solution and 40mL concentration that the mixed solution is 21.8mol/L by 20mL concentration are 13.9mol/L
Solution mixing system at；The ingredient of main metal element is (by mass percentage): Hf 10.21%, Ta in the waste material containing hafnium
48.12%, Nb 28.01%, Ti 8.33%, W 1.13%, Mo 0.32%, Fe 0.68%, Cr 3.20%；
Step 2: in lysate obtained in point 3 ammonium hydroxide addition step 1 by mass concentration for 28%, then 90
1h is stirred under conditions of DEG C and obtains slag liquid mixture, is washed with deionized 3 times after filtering the slag liquid mixture, then 90
Dry 1h, finally obtains precipitation slag under conditions of DEG C；The volume of added ammonium hydroxide is 90mL every time；W, Mo is present in filtrate and realizes
With the separation of precipitation slag；
Step 3: being placed in precipitation slag is obtained in step 2 in 250mL beaker, the nitre that 84mL concentration is 12mol/L is measured
Acid solution is added in beaker, and the stirring and dissolving 1h at 90 DEG C obtains leachate, and hafnium ion concentration is 12.14g/L in leachate,
PH is -0.83；The ratio of the volume (mL) of the quality (g) and nitric acid solution of precipitation slag is 1:5.5；
Step 4: the ammonium hydroxide of deionized water 409.5mL and mass concentration 28% are added into the leachate that step 3 obtains
Filtrate is diluted to 500mL by 6.5mL, and the hafnium ion concentration being diluted in the leachate of 500mL is 2.04g/L, and pH value 0 is dilute
The leachate of 500mL after releasing sets the washed 003*7 cation exchange resin for being transformed into H-type of 50mL as liquid before adsorbing
In chromatographic column, using peristaltic pump feed liquor, leachate is adsorbed at room temperature, obtains loaded resin；Liquid before the absorption
Volume be 10 times of cation exchange resin volume；The flow velocity of liquid is 150mL/h before adsorbing in the adsorption process；
Step 5: using 1000mL concentration is the nitric acid solution of 1.0mol/L at room temperature to load obtained in step 4
Resin is eluted, and impurity element Ta, Nb, Ti, Fe and Cr are washed off；The flow velocity of nitric acid solution is 25mL/ in the lessivation
h；
Step 6: use 150mL concentration for the sulfuric acid solution of 1.0mol/L at room temperature in step 5 after eluting
Loaded resin carries out the desorption of hafnium, obtains the stripping liquid of hafnium；The flow velocity of sulfuric acid solution is 75mL/h in the desorption process；
Step 7: being precipitated using 23% ammonium hydroxide of 150mL mass content to the stripping liquid of hafnium obtained in step 6, obtain
Hydroxide to hafnium precipitates；
Step 8: the heat treatment of 3h is carried out under conditions of temperature is 400 DEG C to the hydroxide for the hafnium that step 7 obtains,
Obtain hafnium oxide.
Product hafnium oxide manufactured in the present embodiment is analyzed using X-ray fluorescence spectra analysis (XRF), analyzes result
Are as follows: a large amount of Hf and minimal amount of Ta, Nb, Ti, Fe, Cr impurity element are rich in product hafnium oxide, and product hafnium oxide passes through
XRF carries out semi-quantitative analysis, and the quality purity of hafnium oxide is 99.2% as the result is shown, again using chemical analysis in product
Ta, Nb, Ti, Fe, Cr and Hf carry out the test analysis of metal element content, and metal quality content is respectively Ta 0.013%,
Nb 0.01%, Ti 0.202%, Fe 0.011%, Cr 0.007%, surplus Hf.The result illustrates the method for the present embodiment
Can by waste material containing hafnium W and Mo completely remove, and significantly reduce the content of Ta, Nb, Ti, Fe, Cr.Thus illustrate, this
The purity is high for the hafnium oxide that embodiment is prepared can be used existing sodium reduction method and prepare hafnium sponge, this improves useless containing hafnium
The utilization rate of the resource of material has good industrial prospect.
Embodiment 3
The method of the present embodiment are as follows:
Step 1: into the polytetrafluoroethylene beaker for the 250mL for filling mixed solution be added 10g waste material containing hafnium, and with mould
Expect diaphragm seal beaker mouth, places the beaker and be stirred dissolution in 55 DEG C of water-bath, mixing time 0.8h is filtered to remove
Lysate is obtained after undissolved solid impurity；The ratio of the volume (mL) of the quality (g) and mixed solution of the waste material containing hafnium
For 1:5；The nitre that the hydrofluoric acid solution and 30mL concentration that the mixed solution is 21.2mol/L by 20mL concentration are 12.3mol/L
Acid solution is mixed；The ingredient of main metal element is (by mass percentage): Hf 26.11% in the waste material containing hafnium,
Ta 29.65%, Nb 8.65%, Ti 18.71%, W 7.83%, Mo 3.29%, Fe 1.73%, Cr 4.03%；
Step 2: in lysate obtained in point 4 ammonium hydroxide addition step 1 by mass concentration for 26%, then 85
1h is stirred under conditions of DEG C and obtains slag liquid mixture, is washed with deionized 3 times after filtering the slag liquid mixture, then 90
Dry 1h, finally obtains precipitation slag under conditions of DEG C；The volume of added ammonium hydroxide is 55mL every time；W, Mo is present in filtrate and realizes
With the separation of precipitation slag；
Step 3: being placed in precipitation slag is obtained in step 2 in 250mL beaker, measuring 80mL concentration is 10.5mol/L's
Nitric acid solution is added in beaker, and the stirring and dissolving 0.8h at 85 DEG C obtains leachate, and hafnium ion concentration is in leachate
32.64g/L, pH are -0.69；The ratio of the volume (mL) of the quality (g) and nitric acid solution of precipitation slag is 1:5；
Step 4: the ammonium hydroxide of deionized water 693mL and mass concentration 28% are added into the leachate that step 3 obtains
Filtrate is diluted to 800mL by 20.3mL, and the hafnium ion concentration in the leachate after being diluted to 800mL is 3.26g/L, and pH value is
1, the leachate after measuring wherein 600mL dilution is as liquid before adsorbing, by the washed 001*7 cation for being transformed into H-type of 50mL
Exchanger resin is placed in chromatographic column, using peristaltic pump feed liquor, is adsorbed at room temperature to leachate, is obtained loaded resin；Institute
The volume for stating liquid before adsorbing is 12 times of cation exchange resin volume；The flow velocity of liquid is before adsorbing in the adsorption process
75mL/h；
Step 5: using 800mL concentration is the nitric acid solution of 0.65mol/L at room temperature to obtained in step 4 negative
It carries resin to be eluted, washes off impurity element Ta, Nb, Ti, Fe and Cr；The flow velocity of nitric acid solution is in the lessivation
50mL/h；
Step 6: use 220mL concentration for the sulfuric acid solution of 1.55mol/L at room temperature in step 5 after eluting
Loaded resin carries out the desorption of hafnium, obtains the stripping liquid of hafnium；The flow velocity of sulfuric acid solution is 50mL/h in the desorption process；
Step 7: being precipitated using 26% ammonium hydroxide of 220mL mass content to the stripping liquid of hafnium obtained in step 6, obtain
Hydroxide to hafnium precipitates；
Step 8: the heat treatment of 4h is carried out under conditions of temperature is 500 DEG C to the hydroxide for the hafnium that step 7 obtains,
Obtain hafnium oxide.
Product hafnium oxide manufactured in the present embodiment is analyzed using X-ray fluorescence spectra analysis (XRF), analyzes result
Are as follows: a large amount of Hf and minimal amount of Ta, Nb, Ti, Fe, Cr impurity element are rich in product hafnium oxide, and product hafnium oxide passes through
XRF carries out semi-quantitative analysis, and the quality purity of hafnium oxide is 99.0% as the result is shown, again using chemical analysis in product
Ta, Nb, Ti, Fe, Cr and Hf carry out the test analysis of metal element content, and metal quality content is respectively Ta 0.009%,
Nb 0.008%, Ti 0.091%, Fe 0.018%, Cr 0.009%, surplus Hf.The result illustrates the method for the present embodiment
Can by waste material containing hafnium W and Mo completely remove, and significantly reduce the content of Ta, Nb, Ti, Fe and Cr.Thus illustrate, this
The purity is high for the hafnium oxide that embodiment is prepared can be used existing sodium reduction method and prepare hafnium sponge, this improves useless containing hafnium
The utilization rate of the resource of material has good industrial prospect.
Embodiment 4
The method of the present embodiment are as follows:
Step 1: into the polytetrafluoroethylene beaker for the 250mL for filling mixed solution be added 10g waste material containing hafnium, and with mould
Expect diaphragm seal beaker mouth, places the beaker and be stirred dissolution in 60 DEG C of water-bath, mixing time 1h is filtered to remove not
Lysate is obtained after the solid impurity of dissolution；The quality (g) of the waste material containing hafnium and the ratio of the volume (mL) of mixed solution are
1:6；The nitric acid that the hydrofluoric acid solution and 30mL concentration that the mixed solution is 20.2mol/L by 30mL concentration are 11.5mol/L
Solution mixing system at；The ingredient of main metal element is (by mass percentage): Hf 19.78%, Ta in the waste material containing hafnium
80.22%；
Step 2: in lysate obtained in point 4 ammonium hydroxide addition step 1 by mass concentration for 28%, then 85
1h is stirred under conditions of DEG C and obtains slag liquid mixture, is washed with deionized 3 times after filtering the slag liquid mixture, then 90
Dry 1h, finally obtains precipitation slag under conditions of DEG C；The volume of added ammonium hydroxide is 80mL every time；
Step 3: being placed in precipitation slag is obtained in step 2 in 250mL beaker, the nitre that 80mL concentration is 11mol/L is measured
Acid solution is added in beaker, and the stirring and dissolving 0.8h at 85 DEG C obtains leachate, and hafnium ion concentration is 24.73g/ in leachate
L, pH are -0.86；The ratio of the volume (mL) of the quality (g) and nitric acid solution of precipitation slag is 1:5；
Step 4: the ammonium hydroxide of deionized water 707.8mL and mass concentration 28% are added into the leachate that step 3 obtains
Filtrate is diluted to 800mL by 12.2mL, is diluted to the hafnium ion concentration in the leachate of 800mL to 2.747g/L, pH value is extremely
0.3, measure wherein 650mL dilution after leachate as adsorb before liquid, by the washed 001*7 sun for being transformed into H-type of 50mL from
Sub-exchange resin is placed in chromatographic column, using peristaltic pump feed liquor, is adsorbed at room temperature to leachate, is obtained loaded resin；
The volume of liquid is 13 times of cation exchange resin volume before the absorption；The flow velocity of liquid is before adsorbing in the adsorption process
75mL/h；
Step 5: using 800mL concentration is the nitric acid solution of 0.65mol/L at room temperature to obtained in step 4 negative
It carries resin to be eluted, washes off impurity element Ta；The flow velocity of nitric acid solution is 50mL/h in the lessivation；
Step 6: use 220mL concentration for the sulfuric acid solution of 1.55mol/L at room temperature in step 5 after eluting
Loaded resin carries out the desorption of hafnium, obtains the stripping liquid of hafnium；The flow velocity of sulfuric acid solution is 50mL/h in the desorption process；
Step 7: being precipitated using 26% ammonium hydroxide of 220mL mass content to the stripping liquid of hafnium obtained in step 6, obtain
Hydroxide to hafnium precipitates；
Step 8: the heat of 4.5h is carried out under conditions of temperature is 550 DEG C to the hydroxide of the hafnium obtained to step 7
Processing, obtains hafnium oxide.
Product hafnium oxide manufactured in the present embodiment is analyzed using X-ray fluorescence spectra analysis (XRF), analyzes result
Are as follows: a large amount of Hf and minimal amount of Ta impurity element are rich in product hafnium oxide, and product hafnium oxide carries out sxemiquantitative through XRF
Analysis, the quality purity of hafnium oxide is 99.1% as the result is shown, carries out metal to Ta in product and Hf using chemical analysis again
The test analysis of constituent content, metal quality content are respectively Ta 0.012%, surplus Hf.The result illustrates the present embodiment
Method can significantly reduce the content of Ta.Thus illustrate, the purity is high for the hafnium oxide that the present embodiment is prepared can be used
Existing sodium reduction method prepares hafnium sponge, this improves the utilization rate of the resource of the waste material containing hafnium, has good industrial prospect.
Embodiment 5
The method of the present embodiment are as follows:
Step 1: into the polytetrafluoroethylene beaker for the 250mL for filling mixed solution be added 10g waste material containing hafnium, and with mould
Expect diaphragm seal beaker mouth, places the beaker and be stirred dissolution in 50 DEG C of water-bath, mixing time 0.8h is filtered to remove
Lysate is obtained after undissolved solid impurity；The ratio of the volume (mL) of the quality (g) and mixed solution of the waste material containing hafnium
For 1:7；The nitre that the hydrofluoric acid solution and 50mL concentration that the mixed solution is 19.8mol/L by 20mL concentration are 10.2mol/L
Acid solution is mixed；The ingredient of main metal element is (by mass percentage): Hf 10.87% in the waste material containing hafnium,
Ta 22.05%, W 67.08%；
Step 2: in lysate obtained in point 2 ammonium hydroxide addition step 1 by mass concentration for 25%, then 90
1h is stirred under conditions of DEG C and obtains slag liquid mixture, is washed with deionized 3 times after filtering the slag liquid mixture, then 90
Dry 1h, finally obtains precipitation slag under conditions of DEG C；W is present in filtrate the separation realized with precipitation slag；Added ammonium hydroxide every time
Volume be 105mL；
Step 3: being placed in precipitation slag is obtained in step 2 in 250mL beaker, the nitre that 78mL concentration is 12mol/L is measured
Acid solution is added in beaker, and the stirring and dissolving 1h at 90 DEG C obtains leachate, and hafnium ion concentration is 13.94g/L in leachate,
PH is -0.88；The ratio of the volume (mL) of the quality (g) and nitric acid solution of precipitation slag is 1:5；
Step 4: deionized water 922mL is added into the leachate that step 3 obtains, filtrate is diluted to 1000mL, it is dilute
The hafnium ion concentration released into the leachate of 1000mL is 1.09g/L, pH value 0.23, the leaching after measuring wherein 500mL dilution
The washed 003*7 cation exchange resin for being transformed into H-type of 50mL is placed in chromatographic column by liquid as liquid before adsorbing out, is used
Peristaltic pump feed liquor, at room temperature adsorbs leachate, obtains loaded resin；The volume of liquid is that cation is handed over before the absorption
10 times for changing resin volume；The flow velocity of liquid is 150mL/h before adsorbing in the adsorption process；
Step 5: using 1000mL concentration is the nitric acid solution of 1.0mol/L at room temperature to load obtained in step 4
Resin is eluted, and impurity element Ta is washed off；The flow velocity of nitric acid solution is 25mL/h in the lessivation；
Step 6: use 150mL concentration for the sulfuric acid solution of 1.0mol/L at room temperature in step 5 after eluting
Loaded resin carries out the desorption of hafnium, obtains the stripping liquid of hafnium；The flow velocity of sulfuric acid solution is 75mL/h in the desorption process；
Step 7: being precipitated using 24% ammonium hydroxide of 150mL mass content to the stripping liquid of hafnium obtained in step 6, obtain
Hydroxide to hafnium precipitates；
Step 8: the hydroxide of the lower hafnium obtained to step 7 carries out the heat treatment of 3h in the condition that temperature is 500 DEG C,
Obtain hafnium oxide.
Product hafnium oxide manufactured in the present embodiment is analyzed using X-ray fluorescence spectra analysis (XRF), analyzes result
Are as follows: a large amount of Hf and minimal amount of Ta impurity element are rich in product hafnium oxide, and product hafnium oxide carries out sxemiquantitative through XRF
Analysis, the quality purity of hafnium oxide is 99.0% as the result is shown, carries out metal to Ta in product and Hf using chemical analysis again
The test analysis of constituent content, metal quality content are respectively Ta 0.007%, surplus Hf.The result illustrates the present embodiment
Method the W in waste material containing hafnium can be completely removed, and significantly reduce the content of Ta.Thus illustrate, the present embodiment preparation
The purity is high of obtained hafnium oxide can be used existing sodium reduction method and prepare hafnium sponge, this improves the resource of the waste material containing hafnium
Utilization rate has good industrial prospect.
The above is only the embodiment of the present invention, is not intended to limit the invention in any way, all technologies according to the present invention
Essence any simple modification to the above embodiments, change and equivalent structural changes, still fall within the technology of the present invention side
In the protection scope of case.
Claims (10)
1. a kind of method for preparing hafnium oxide from recycling in waste material containing hafnium, which is characterized in that method includes the following steps:
Step 1: being added to waste material containing hafnium in the mixed solution being mixed by hydrofluoric acid solution and nitric acid solution, it is in temperature
The time of stirring and dissolving under conditions of 40 DEG C~60 DEG C, stirring is 0.5h~1h, then obtains lysate after filtering and removing slag；It is described
The ratio between quality and the volume of the mixed solution of the waste material containing hafnium are 1:(5~7), the mass unit of the waste material containing hafnium is g, is mixed molten
The volume unit of liquid is mL；
Ammonium hydroxide is added in lysate obtained in step 1 Step 2: dividing 2~4 times, then under conditions of 70 DEG C~90 DEG C
Slag liquid mixture is stirred to get, the slag liquid mixture is successively filtered, washed and dried and obtains precipitation slag；Ammonium hydroxide added by every time
Volume is 0.5 times~1.5 times of the lysate volume；
Step 3: being added to precipitation slag is obtained in step 2 in nitric acid solution, stirred under conditions of temperature is 60 DEG C~90 DEG C
0.5h~1h dissolves precipitation slag, obtains leachate；The volume of the nitric acid solution is 5 times~7 times of the precipitation slag quality, is sunk
The mass unit of mud is g, and the volume unit of nitric acid solution is mL；
Step 4: adjusting institute using ammonium hydroxide using the hafnium ion concentration in leachate obtained in deionized water regulating step three
State the pH value of leachate；Then leachate is adsorbed at room temperature using cation exchange resin, obtains loaded resin；Institute
The volume for stating leachate is 10 times~14 times of the cation exchange resin volume；
Step 5: using concentration is the nitric acid solution of 0.4mol/L~1.0mol/L at room temperature to load obtained in step 4
Resin is eluted, and impurity element is washed off；The volume of the nitric acid solution is cation exchange resin volume described in step 4
10 times~20 times；
Step 6: using concentration is the sulfuric acid solution of 1.0mol/L~2.0mol/L at room temperature to negative after eluting in step 5
The desorption that resin carries out hafnium is carried, the stripping liquid of hafnium is obtained；The volume of the sulfuric acid solution is the exchange of cation described in step 4
3~6 times of resin volume；
Step 7: precipitating using stripping liquid of the ammonium hydroxide to hafnium obtained in step 6, the hydroxide precipitating of hafnium is obtained；Institute
The volume for stating ammonium hydroxide is 3 times~6 times of cation exchange resin volume described in step 4；
Step 8: the hydroxide to hafnium obtained in step 7 carries out 3h~6h under conditions of temperature is 400 DEG C~600 DEG C
Heat treatment, obtain hafnium oxide.
2. a kind of method for preparing hafnium oxide from recycling in waste material containing hafnium according to claim 1, which is characterized in that step
Main metal element in waste material containing hafnium described in one includes one or both of Hf and Cr, Fe, Mo, W, Ta, Nb and Ti
More than.
3. a kind of method for preparing hafnium oxide from recycling in waste material containing hafnium according to claim 1, which is characterized in that step
The mass content of hafnium is 10%~40% in waste material containing hafnium described in one.
4. a kind of method for preparing hafnium oxide from recycling in waste material containing hafnium according to claim 1, which is characterized in that step
The hydrofluoric acid solution and concentration that mixed solution described in one is 18mol/L~22mol/L by concentration are 10mol/L~14mol/L
Nitric acid solution be mixed, in the mixed solution volume content of hydrofluoric acid solution be 28%~50%.
5. a kind of method for preparing hafnium oxide from recycling in waste material containing hafnium according to claim 1, which is characterized in that step
Two and step 7 described in the mass concentration of ammonium hydroxide be 23%~28%.
6. a kind of method for preparing hafnium oxide from recycling in waste material containing hafnium according to claim 1, which is characterized in that step
The concentration of nitric acid solution described in three is 8mol/L~12mol/L.
7. a kind of method for preparing hafnium oxide from recycling in waste material containing hafnium according to claim 1 or 5, which is characterized in that
The concentration of hafnium ion is 1g/L~5g/L in leachate after adjusting in step 4, and pH value is 0~1；It is soaked in the adsorption process
The flow velocity of liquid and the ratio of cation exchange resin volume are 0.5~3 out, and the flow rate of leachate is mL/h, and cation is handed over
The volume unit for changing resin is mL.
8. a kind of method for preparing hafnium oxide from recycling in waste material containing hafnium according to claim 1, which is characterized in that step
Cation exchange resin described in four is hydrogen type cation exchange resin.
9. a kind of method for preparing hafnium oxide from recycling in waste material containing hafnium according to claim 1, which is characterized in that step
The flow velocity of nitric acid solution and the ratio of cation exchange resin volume are 0.5~1.5 in lessivation described in five, nitric acid solution
Flow rate be mL/h, the volume unit of cation exchange resin is mL.
10. a kind of method for preparing hafnium oxide from recycling in waste material containing hafnium according to claim 1, which is characterized in that step
The ratio of the volume of the flow velocity and cation exchange resin of sulfuric acid solution is 0.5~1.5 in desorption process described in rapid six, sulfuric acid
The flow rate of solution is mL/h, and the volume unit of cation exchange resin is mL.
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| US5112493A (en) * | 1990-12-10 | 1992-05-12 | Westinghouse Electric Corp. | Zirconium-hafnium production in a zero liquid discharge process |
| CN102417986A (en) * | 2010-09-28 | 2012-04-18 | 北京有色金属研究总院 | Preparation method of high-purity low-zirconium hafnium oxide |
| CN102978406B (en) * | 2012-12-14 | 2014-02-12 | 西北有色金属研究院 | Regeneration method for rhenium-containing high-temperature alloy scrap |
| CN103045862B (en) * | 2013-01-04 | 2014-08-13 | 中国原子能科学研究院 | Separation and purification method of trace hafnium in rock |
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