CN106053718B - A kind of rare earth ore concentrate middle rare earth, calcium oxide, magnesia, barium monoxide method for continuously measuring - Google Patents
A kind of rare earth ore concentrate middle rare earth, calcium oxide, magnesia, barium monoxide method for continuously measuring Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/42—Low-temperature sample treatment, e.g. cryofixation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
- G01N2001/386—Other diluting or mixing processes
Abstract
The invention discloses a kind of rare earth ore concentrate middle rare earth, calcium oxide, magnesia, barium monoxide method for continuously measuring, belong to metallurgical analysis method and technology field.It is short that purpose is to provide a kind of analysis time, and measurement is accurate, the low rare earth ore concentrate middle rare earth of testing cost, calcium oxide, magnesia, barium monoxide method for continuously measuring, the described method comprises the following steps: step 1: sample prepares；Step 2: it precipitates for the first time；Step 3: second of precipitating；Step 4: measurement prepares；Step 5: the measurement of the content of calcium oxide；Step 6: the measurement of total content of calcium oxide and magnesia；Step 7: rare earth oxide content measurement；Step 8: the measurement of barium monoxide content；Step 9: the calculating of rare earth oxide, calcium oxide, magnesia, barium monoxide content.This method is easy to grasp and result precision is high, can promote and apply in production.Suitable for rare earth ore concentrate middle rare earth, calcium oxide, magnesia, barium monoxide Fast Continuous Determination.
Description
Technical field
Present invention relates particularly to the METHOD FOR CONTINUOUS DETERMINATIONs of a kind of rare earth ore concentrate middle rare earth, calcium oxide, magnesia, barium monoxide
Method belongs to metallurgical analysis method and technology field.
Background technique
Rare earth is by the title of industrial " gold " since it can form with physical characteristics such as excellent photoelectromagnetics with other materials
Different properties, new material various in style, most significant function are exactly to increase substantially the quality and performance of other products.
For example increase substantially the tactical qualities of steel for manufacturing tank, aircraft, guided missile, aluminium alloy, magnesium alloy, titanium alloy.And
And rare earth is equally many high-tech lubricants such as electronics, laser, nuclear industry, superconduction.Rare earth science and technology, must once for military affairs
Rising to for military science and technology is so brought, rare earth is in metallurgical industry, and petrochemical industry, glass ceramics etc., which also has, to be widely applied.
The method of rare earth ore concentrate middle rare earth, calcium oxide, magnesia, barium monoxide is measured usually using inductive coupling etc.
Ion method needs to melt using platinum crucible, needs to control salt amount, while needing Matrix Match, while the above method needs to grasp
Author has higher operating experience, while needing to be equipped with large scale equipment, and cost of determination is high.
Summary of the invention
Therefore, the purpose of the present invention is to provide a kind of analysis time is short, measurement is accurate, in the low rare earth ore concentrate of testing cost
Rare earth oxide, calcium oxide, magnesia, barium monoxide method for continuously measuring, which is characterized in that the method includes following steps
It is rapid:
Step 1: sample prepares
Rare earth ore concentrate sample is put into crucible and is uniformly mixed with sodium hydroxide and sodium peroxide, is melted in high temperature furnace
Melt, crucible is taken out from high temperature furnace, it is cooling；
Step 2: it precipitates for the first time
It is put into the beaker for filling triethanolamine and sodium carbonate after step 1 is cooling and boils leaching, crucible is eluted with water, it is cold
But it is filtered afterwards with quantitative filter paper, washes beaker with sodium carbonate liquor, wash precipitating with sodium carbonate liquor；
Step 3: second of precipitating
The precipitating that step 2 is obtained moves into beaker used in step 2 together with quantitative filter paper, and nitric acid and high chlorine is added
Acid, cap upper surface ware are put in heating evaporation on electric furnace, remove cooling after solution reaction is tranquil, continue to be heated to drying,
Walls of beaker and surface plate are purged with nitric acid (1+1), hydrogen peroxide is instilled after water is added, cooling is removed after boiling, with quantitative middling speed
Filter paper filtering, washes beaker and precipitating with nitric acid, residue is removed；
Step 4: measurement prepares
Ammonium chloride is added in the filtrate that step 3 obtains, is neutralized to PH=8 with ammonium hydroxide after boiling, instills hydrogen peroxide,
Ammonium hydroxide is added, boils, is filled into beaker after precipitating decline with quantitative Medium speed filter paper, obtains rare earth oxide precipitating, rare earth oxygen
Compound precipitating and quantitative Medium speed filter paper are used to measure the content of rare earth oxide, after the filtrate concentration in beaker, instill methyl
Orange indicator, is adjusted to occur red with hydrochloric acid, and sulfuric acid is added under constant stirring, stands after keeping the temperature a period of time, with quantitatively slow
Fast filter paper is filled into volumetric flask, obtains barium sulfate precipitate, and barium sulfate precipitate and quantitative slow filter paper contain for measuring barium monoxide
Amount, is diluted to volumetric flask scale constant volume for filtrate, is divided to and two parts of test solutions is taken to be put into beaker, and portion is for measuring containing for calcium oxide
Amount, another is used to measure total content of calcium oxide and magnesia；
Step 5: the measurement of the content of calcium oxide
Triethanolamine is firstly added in the test solution for measuring calcium oxide content, then sequentially add water, hydroxylamine hydrochloride,
Potassium hydroxide solution instills calcein, is titrated to fluorescence green with EDTA standard solution and disappears, record EDTA standard solution consumption
Measure VCa；
Step 6: the measurement of total content of calcium oxide and magnesia
It is firstly added triethanolamine in the test solution of total content for measuring calcium oxide and magnesia, is then successively added
Enter water, hydroxylamine hydrochloride, ammonia-ammonium chloride solution, instill eriochrome black T, is titrated to test solution in pure blue, record with EDTA standard solution
EDTA standard solution consumption V(Mg+Ca)；
Step 7: rare earth oxide content measurement
The rare earth oxide that step 4 obtains is precipitated and quantitative Medium speed filter paper is put into beaker, water is added, filter paper is beaten
It is broken, oxalic acid is then added, is removed after boiling, in 60-70 degree heat preservation half an hour, is filtered after standing a period of time with quantitative filter paper,
Beaker and precipitating are washed with oxalic acid solution, precipitating is put into crucible jointly together with quantitative filter paper, through low temperature dry ashing processing, is burnt
Weighing quality m after burning, being cooling1；
Step 8: the measurement of barium monoxide content
The barium sulfate precipitate first obtained with sulfuric acid scrubbing step 4, the barium sulfate that reusable heat water wash step four obtains are heavy
Form sediment, in sulfuric acid scrubbing step 4 filter barium sulfate precipitate after beaker, together together with quantitative slow filter paper by barium sulfate precipitate
It is put into crucible, weighs quality m (BaSO after low temperature dry ashing processing, calcination, cooling4)1；
Step 9: the calculating of rare earth oxide, calcium oxide, magnesia, barium monoxide content.
Further, the step 1 specifically:
It weighs sample 0.5000g to be placed in the corundum crucible for having filled the sodium hydroxide of 1-2 grams of removing moisture content, then plus 2-3
Gram sodium peroxide mixes, and surface covers one layer of sodium peroxide again, and 700 degree melting 10 minutes, take from Muffle furnace in Muffle furnace
Crucible out, it is cooling.
Further, the step 2 specifically:
It is put into the 400mL beaker for filling 150mL triethanolamine (1+10) and 2 grams of sodium carbonate after step 1 is cooling and boils leaching
It takes, crucible is eluted with water, the solution heating in beaker is boiled 1-2 minutes, is filtered after cooling with quantitative filter paper, with sodium carbonate (1
+ 100) solution washes beaker 3-4 times, washes precipitating 4-5 times.
Further, the step 3 specifically:
The precipitating that step 2 is obtained moves into beaker used in step 2 together with quantitative filter paper, adds 20mL nitric acid
(67%), 5mL perchloric acid (69%) is added, cap upper surface ware is put on electric furnace and heats, is evaporated to nitrogen dioxide and disperses completely, high
Chloric acid is largely smoldered, and removes beaker after solution reaction is tranquil, cooling, is continued to be heated to drying, be purged with 10mL nitric acid (1+1)
Then plus 0.1mL hydrogen peroxide (35%) walls of beaker and surface plate add 80mL hot water, boil 1-2 minutes, cooling after removing, and use
Quantitative Medium speed filter paper filtering, washes beaker 3-4 times with nitric acid (1+100), washes precipitating 7-8 times, residue is removed.
Further, the step 4 specifically:
3 grams of ammonium chloride are added in the filtrate that step 3 obtains, is neutralized to PH=8 with ammonium hydroxide (1+1) after boiling, instilled
Hydrogen oxide 0.1mL is added 20mL ammonium hydroxide (1+1), boils 2 minutes, is filled into 500mL with quantitative Medium speed filter paper after precipitating decline and burns
In cup, rare earth oxide precipitating is obtained, rare earth oxide precipitating and quantitative Medium speed filter paper are used to measure the content of rare earth oxide,
Filtrate in 500mL beaker is concentrated into 150-200mL, instills methyl orange indicator (1+1000), is adjusted to hydrochloric acid (1+1)
There is red, 5mL sulfuric acid (1+1) is added under constant stirring, heat preservation stood 12 hours or more after 1 hour, was filtered at a slow speed with quantitative
Paper cushioning foot is filled into 250mL volumetric flask, obtains barium sulfate precipitate, barium sulfate precipitate and quantitative slow filter paper are for measuring oxygen
Change barium content, filtrate is diluted to 250mL volumetric flask scale constant volume, is divided to and two parts of 50mL test solutions is taken to be put into beaker, portion is used for
The content of calcium oxide is measured, another is used to measure total content of calcium oxide and magnesia.
Further, the step 5 specifically:
In the test solution for measuring calcium oxide content, it is firstly added 50mL triethanolamine (12%), is then sequentially added
Hydroxylamine hydrochloride is added in 50mL water, is added 40mL potassium hydroxide solution (20%), instills calcein, is dripped with EDTA standard solution
It is fixed to disappear to fluorescence green, record EDTA standard solution consumption VCa。
Further, the step 6 specifically:
In the test solution of total content for measuring calcium oxide and magnesia, it is firstly added 50mL triethanolamine
(12%), 50mL water is then sequentially added, hydroxylamine hydrochloride is added, adds 10mL ammonia-ammonium chloride solution, instills chromium black T indicator, is used
EDTA standard solution is titrated to test solution in pure blue, records EDTA standard solution consumption V(Mg+Ca)。
Further, the step 7 specifically:
The rare earth oxide that step 4 obtains is precipitated and quantitative Medium speed filter paper is put into beaker, boiling water 50mL is added, it will
Filter paper is smashed, and oxalic acid (1+25) 100mL is then added, removes after boiling, in 60-70 degree heat preservation half an hour, after standing two hours
It is filtered with quantitative filter paper, washs beaker with oxalic acid (1+100) solution, washed precipitating 10 times with oxalic acid (1+100) solution, will precipitate
Be put into porcelain crucible jointly together with quantitative filter paper, be put into Muffle furnace 850 DEG C of ashing, calcination 40 minutes, it is cooling after weigh quality
m1。
Further, the step 8 specifically:
Barium sulfate precipitate 7-8 times first obtained with sulfuric acid scrubbing step 4, the sulfuric acid that reusable heat water wash step four obtains
Precipitated barium 4-5 times, in sulfuric acid scrubbing step 4 filter barium sulfate precipitate after beaker 3-4 times, by barium sulfate precipitate together with
Quantitative slow filter paper is put into porcelain crucible together, be put into 850 DEG C of ashing in Muffle furnace, calcination 40 minutes, it is cooling after weigh quality m
(BaSO4)1。
Further, step 9 by formula one, formula two calculates separately calcium oxide content W (CaO) and oxygen in the method
Change content of magnesium W (MgO), calculate rare earth oxide content W (RExOy) with formula three, calculates barium monoxide quality W with formula four
(BaO):
W (CaO) %=C (V-V01) K × 100 M (CaO) 100/m (formula one)
In formula: M (CaO): the molal weight (g/mol) of calcium oxide
M: sample mass (g)
K: sample liquid separation ratio (50/250=1/5)
C:EDTA concentration of standard solution (mol/L)
V: the volume (mL) of sample consumption EDTA standard solution
V01: the volume (mL) of blank solution consumption EDTA standard solution when titration calcium oxide content
W (MgO) %=C (V(Mg+Ca)-VCa-(V02-V01) K × 1000 M (MgO) 100/m (formula two)
In formula: M (CaO): the molal weight (g/mol) of calcium oxide
M: sample mass (g)
K: sample liquid separation ratio
C:EDTA concentration of standard solution (mol/L)
V(Mg+Ca): the volume (mL) of the consumed EDTA standard solution of calcium and magnesium resultant
V02: the volume (mL) of blank solution consumption EDTA standard solution when total content of titration calcium oxide and magnesia；
W (RExOy) (%)=m1х 100/m (formula three)
In formula: W (RExOy) (%): rare earth oxide content
m1: rare-earth oxidation amount of substance (g), i.e., the quality finally weighed in step 7；
M: sample mass (g), i.e. rare earth ore concentrate quality used in step 1.
W (BaO) (%)=m (BaSO4)1× 100 × 0.6570/m (formula four)
In formula: m (BaSO4)1: barium sulfate precipitate quality (g), i.e., the quality finally weighed in step 8；
M: sample mass (g), i.e. rare earth ore concentrate quality used in step 1；
0.6570 is BaO and BaSO4Conversion coefficient.
The beneficial effects of the present invention are a kind of: rare earth ore concentrate middle rare earth of the invention, calcium oxide, magnesia,
The method for continuously measuring of barium monoxide, after sample dissolution, directly progress rare-earth precipitation measurement, filtered solution first carries out sulfuric acid
The measurement of precipitated barium, and then barium monoxide content is obtained, then carry out the measurement of calcium oxide, magnesia, it is primary to test while realizing dilute
The METHOD FOR CONTINUOUS DETERMINATION of native oxide, calcium oxide, magnesia, barium monoxide.Method is easy to grasp and result precision is high, can produce
Middle popularization and application.Simple using equipment, it is accurate to have the characteristics that, is suitable for rare earth ore concentrate middle rare earth, calcium oxide, oxidation
The Fast Continuous Determination of magnesium, barium monoxide.
Detailed description of the invention
Fig. 1 is the METHOD FOR CONTINUOUS DETERMINATION side of a kind of rare earth ore concentrate middle rare earth of the present invention, calcium oxide, magnesia, barium monoxide
The flow chart of method.
Specific embodiment
Description of specific embodiments of the present invention with reference to the accompanying drawing:
The method and step of present embodiment as shown in Figure 1, three kinds of samples of selection, respectively rare-earth tailing, marked as
1, rare-earth original ore, label 2, rare earth ore concentrate carries out sample according to sampling iron ore standard and produces marked as 3, per sample (p.s.) point
4 groups of comparative experimentss, the basic process of measuring method are not done by following methods are as follows: molten in triethanolamine by sample alkali fusion
The interference elements such as iron, aluminium, manganese are separated in liquid.After removing silica, with elements such as ammonia precipitation process separating calcium, magnesium, rare earth is in PH
Oxalic acid precipitation is used in=2 slightly acidic solution.Calcination is weighed at rare earth oxide.The filtrate of the elements such as separating calcium, magnesium is concentrated,
It is acidified with hydrochloric acid, sulfuric acid precipitation barium, with gravimetric detemination barium monoxide amount.The filtrate of barium sulfate will be filtered, added in PH > 12 appropriate
Calcein is titrated with EDTA standard solution, measures calcium oxide, appropriate eriochrome black T is added in PH=10, is dripped with EDTA standard solution
It is fixed, measure calcium oxide+magnesia resultant.Concrete operation method are as follows:
It weighs sample 0.5000g to be placed in the corundum crucible for having filled the sodium hydroxide of 1-2 grams of removing moisture content, then plus 2-3
Gram sodium peroxide mixes, and surface covers one layer of sodium peroxide again, and 700 degree melting 10 minutes, take from Muffle furnace in Muffle furnace
Crucible out, it is cooling.It is put into after cooling in the 400mL beaker for filling 150mL triethanolamine (1+10) and 2 grams of sodium carbonate and boils leaching
It takes, crucible is eluted with water, the solution heating in beaker is boiled 1-2 minutes, is filtered after cooling with quantitative filter paper, with sodium carbonate (1
+ 100) solution washes beaker 3-4 times, washes precipitating 4-5 times.The precipitating of acquisition is moved into the beaker used originally together with quantitative filter paper
In, add 20mL nitric acid (67%), be added 5mL perchloric acid (69%), cap upper surface ware is put on electric furnace and heats, and is evaporated to titanium dioxide
Nitrogen disperses completely, and perchloric acid is largely smoldered, and brown or black occurs in solution when smoldering should add 2mL nitric acid (67%) in time, to
Beaker is removed after solution reaction is tranquil, it is cooling, continue to be heated to drying, purges walls of beaker and surface plate with 10mL nitric acid (1+1),
Then plus 0.1mL hydrogen peroxide (35%) add 80mL hot water, boil 1-2 minutes, it is therefore an objective to drive superfluous hydrogen peroxide, take
It is cooling after lower, it is filtered with quantitative Medium speed filter paper, washes beaker 3-4 times with nitric acid (1+100), wash precipitating 7-8 times, residue is removed.
3 grams of ammonium chloride are added in filtrate, is neutralized to PH=8 with ammonium hydroxide (1+1) after boiling, instills hydrogen peroxidase 10 .1mL, 20mL is added
Ammonium hydroxide (1+1) boils 2 minutes, is filled into 500mL beaker after precipitating decline with quantitative Medium speed filter paper, obtains rare earth oxide
Precipitating, rare earth oxide precipitating and quantitative Medium speed filter paper are used to measure the content of rare earth oxide, by the filtrate in 500mL beaker
150-200mL are concentrated into, are instilled methyl orange indicator (1+1000), is adjusted to red occur with hydrochloric acid (1+1), is being stirred continuously
Lower addition 5mL sulfuric acid (1+1), heat preservation stand 12 hours or more after 1 hour, are filled into 250mL with quantitative slow filter paper cushioning foot
In volumetric flask, barium sulfate precipitate is obtained, barium sulfate precipitate and quantitative slow filter paper dilute filtrate for measuring barium monoxide content
To 250mL volumetric flask scale constant volume, it is divided to and two parts of 50mL test solutions is taken to be put into beaker, portion is for measuring the content of calcium oxide, separately
Portion is for measuring total content of calcium oxide and magnesia.
It in the test solution for measuring calcium oxide content, is firstly added 50mL triethanolamine (12%), first is added three
Ethanol amine is then to sequentially add 50mL water to first shelter the interference elements such as iron and aluminium, and further masking is played in addition
The hydroxylamine hydrochloride of effect, is added 40mL potassium hydroxide solution (20%), and potassium hydroxide solution plays the role of buffer solution, pH value
It is 12, instills calcein indicator, calcein indicator production method are as follows: the chlorination after 1g calcein and 100g drying
The finely ground mixing of sodium is placed on spare in port grinding bottle.It is titrated to fluorescence green with EDTA standard solution to disappear, EDTA standard solution C
(EDTA)=0.01783mol/L records EDTA standard solution consumption VCa。
In the test solution of total content for measuring calcium oxide and magnesia, it is firstly added 50mL triethanolamine
(12%), 50mL water is then sequentially added, hydroxylamine hydrochloride is added, adds 10mL ammonia-ammonium chloride solution, ammonia-ammonium chloride solution plays
The effect of buffer solution, pH value 10, ammonia-ammonium chloride buffer solution (PH=10) is the preparation method comprises the following steps: 67g ammonium chloride is dissolved in
In 200mL water, 570mL concentrated ammonia liquor is added, 1000mL is diluted to water.Instill chromium black T indicator, chromium black T indicator preparation side
Method are as follows: by the finely ground mixing of sodium chloride after 1g eriochrome black T and 100g drying, be placed on spare in port grinding bottle.It is dripped with EDTA standard solution
Determine to test solution to be in pure blue, records EDTA standard solution consumption V(Mg+Ca)。
The rare earth oxide precipitating of acquisition and quantitative Medium speed filter paper are put into beaker, boiling water 50mL is added, filter paper is beaten
It is broken, oxalic acid (1+25) 100mL is then added, is removed after boiling, in 60-70 degree heat preservation half an hour, with quantitative after standing two hours
Filter paper filtering, washs beaker with oxalic acid (1+100) solution, precipitating is washed 10 times with oxalic acid (1+100) solution, by precipitating together with fixed
Amount filter paper is put into porcelain crucible jointly, be put into Muffle furnace 850 DEG C of ashing, calcination 40 minutes, it is cooling after weigh quality m1。
It first uses sulfuric acid scrubbing barium sulfate precipitate 7-8 times, reusable heat water washing barium sulfate precipitate 4-5 times, uses sulfuric acid scrubbing
Beaker 3-4 times after filtering barium sulfate precipitate, barium sulfate precipitate is put into porcelain crucible together together with quantitative slow filter paper, is put
Enter in Muffle furnace 850 DEG C of ashing, calcination 40 minutes, it is cooling after weigh quality m (BaSO4)1。
Calcium oxide content W (CaO) and content of magnesia W (MgO) are calculated separately by formula one, formula two, is counted with formula three
It calculates rare earth oxide content W (RExOy), calculates barium monoxide quality W (BaO) with formula four:
W (CaO) %=C (V-V01) K × 100 M (CaO) 100/m (formula one)
In formula: M (CaO): the molal weight (g/mol) of calcium oxide
M: sample mass (g)
K: sample liquid separation ratio (50/250=1/5)
C:EDTA concentration of standard solution (mol/L)
V: the volume (mL) of sample consumption EDTA standard solution
V01: the volume (mL) of blank solution consumption EDTA standard solution, i.e. blank value when titration calcium oxide content；
W (MgO) %=C (V(Mg+Ca)-VCa-(V02-V01) K × 1000 M (MgO) 100/m (formula two)
In formula: M (CaO): the molal weight (g/mol) of calcium oxide
M: sample mass (g)
K: sample liquid separation ratio (50/250=1/5)
C:EDTA concentration of standard solution (mol/L)
V(Mg+Ca): the volume (mL) of the consumed EDTA standard solution of calcium and magnesium resultant
V02: the volume (mL) of blank solution consumption EDTA standard solution when total content of titration calcium oxide and magnesia.
W (RExOy) (%)=m1х 100/m formula three
In formula: W (RExOy) (%): rare earth oxide content (g)
m1: rare-earth oxidation amount of substance (g) is the quality m finally weighed1；
M: the i.e. used rare earth ore concentrate sample mass of sample mass.
W (BaO) (%)=m (BaSO4)1× 100 × 0.6570/m (formula four)
In formula: m (BaSO4)1: barium sulfate precipitate quality (g), i.e., the quality finally weighed in step 8；
M: sample mass (g), i.e. rare earth ore concentrate quality used in step 1；
0.6570 is BaO and BaSO4Conversion coefficient.
The measurement calcium oxide of three kinds of samples, magnesia, the results are shown in Table 1 for barium monoxide content,
Table 1
The results are shown in Table 2 for the measurement rare earth oxide content of three kinds of samples,
Table 2
By table 1, table 2 as can be seen that the sample different for three kinds, the rare earth oxide of each group comparative experiments, oxidation
Calcium, magnesia, barium monoxide content measurement result relatively, illustrate that method precision of the invention is fine, at the same the present invention
Method can also be generalized to rare-earth tailing and rare-earth original ore and use.
Originally using tri- kinds of the baotite R-715 of known standard value, baotite R-716, baotite R-717 rare earth ore concentrate verifyings
Method measures the accuracy of calcium oxide content, and measurement result is as shown in table 3, the standard of verifying this method measurement rare earth oxide content
True property, measurement result is as shown in table 4,
Table 3
Table 4
The standard of this method measurement content of magnesia is verified using baotite R-717 i.e. certain rare earth ore concentrate of known standard value
True property, measurement result is as shown in table 5,
Table 5
By table 3, table 4, table 5 as can be seen that rare earth oxide, calcium oxide, magnesia, barium monoxide content measured value with
Known standard value is very close, it was demonstrated that accuracy of the invention is very high.
The precision and accuracy of barium monoxide content are carried out using the rare earth ore concentrate sample marked as mine -34 by this method
Experiment, as a result as shown in table 6, table 7,
Table 6
Table 7
| The name of an article | It is very poor | Tolerance | Measured value W (BaO) (%) | Standard value W (BaO) (%) |
| Rare earth ore concentrate | -0.07 | 0.15 | 3.60 | 3.67 |
By table 6, table 7 as can be seen that method of the invention has very high precision for measuring barium monoxide content equally
Degree and accuracy.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. the method for continuously measuring of a kind of rare earth ore concentrate middle rare earth, calcium oxide, magnesia, barium monoxide, which is characterized in that
It the described method comprises the following steps:
Step 1: sample prepares
Rare earth ore concentrate sample is put into crucible and is uniformly mixed with sodium hydroxide and sodium peroxide, is melted in high temperature furnace, from
Crucible is taken out in high temperature furnace, it is cooling；
Step 2: it precipitates for the first time
It is put into the beaker for filling triethanolamine and sodium carbonate after step 1 is cooling and boils leaching, crucible is eluted with water, after cooling
It is filtered with quantitative filter paper, washes beaker with sodium carbonate liquor, wash precipitating with sodium carbonate liquor；
Step 3: second of precipitating
The precipitating that step 2 is obtained moves into beaker used in step 2 together with quantitative filter paper, and nitric acid and perchloric acid is added,
Cap upper surface ware is put in heating evaporation on electric furnace, removes cooling after solution reaction is tranquil, continues to be heated to drying, use 1+
1 nitric acid purging walls of beaker and surface plate, instills hydrogen peroxide after water is added, cooling is removed after boiling, with quantitative Medium speed filter paper
Filtering, washes beaker and precipitating with nitric acid, residue is removed；
Step 4: measurement prepares
Ammonium chloride is added in the filtrate that step 3 obtains, is neutralized to PH=8 with ammonium hydroxide after boiling, instills hydrogen peroxide, is added
Ammonium hydroxide boils, and is filled into beaker after precipitating decline with quantitative Medium speed filter paper, obtains rare earth oxide precipitating, rare earth oxide
Precipitating and quantitative Medium speed filter paper are used to measure the content of rare earth oxide, after the filtrate concentration in beaker, instill methyl orange and refer to
Show agent, be adjusted to red occur with hydrochloric acid, sulfuric acid is added under constant stirring, stood after keeping the temperature a period of time, is filtered at a slow speed with quantitative
Paper is filled into volumetric flask, obtains barium sulfate precipitate, and barium sulfate precipitate and quantitative slow filter paper, will for measuring barium monoxide content
Filtrate is diluted to volumetric flask scale constant volume, is divided to and two parts of test solutions is taken to be put into beaker, and portion is another for measuring the content of calcium oxide
Part is for measuring total content of calcium oxide and magnesia；
Step 5: the measurement of the content of calcium oxide
It is firstly added triethanolamine in the test solution for measuring calcium oxide content, then sequentially adds water, hydroxylamine hydrochloride, hydrogen-oxygen
Change potassium solution, instill calcein, is titrated to fluorescence green with EDTA standard solution and disappears, record EDTA standard solution consumption
VCa；
Step 6: the measurement of total content of calcium oxide and magnesia
It is firstly added triethanolamine in the test solution of total content for measuring calcium oxide and magnesia, is then sequentially added
Water, hydroxylamine hydrochloride, ammonia-ammonium chloride solution instill eriochrome black T, are titrated to test solution in pure blue, record with EDTA standard solution
EDTA standard solution consumption V(Mg+Ca)；
Step 7: rare earth oxide content measurement
The rare earth oxide that step 4 obtains is precipitated and quantitative Medium speed filter paper is put into beaker, water is added, filter paper is smashed, so
After oxalic acid is added, removed after boiling, 60-70 degree heat preservation half an hour, stand a period of time after filtered with quantitative filter paper, with grass
Precipitating is put into crucible together with quantitative filter paper by acid solution wash beaker and precipitating jointly, through low temperature dry ashing processing, calcination, cold
But quality m is weighed afterwards1；
Step 8: the measurement of barium monoxide content
The barium sulfate precipitate first obtained with sulfuric acid scrubbing step 4, the barium sulfate precipitate that reusable heat water wash step four obtains are used
The beaker after barium sulfate precipitate is filtered in sulfuric acid scrubbing step 4, and barium sulfate precipitate is put into earthenware together with quantitative slow filter paper together
In crucible, quality m (BaSO is weighed after low temperature dry ashing processing, calcination, cooling4)1；
Step 9: the calculating of rare earth oxide, calcium oxide, magnesia, barium monoxide content.
2. the METHOD FOR CONTINUOUS DETERMINATION side of rare earth ore concentrate middle rare earth as described in claim 1, calcium oxide, magnesia, barium monoxide
Method, which is characterized in that the step 1 specifically:
It weighs sample 0.5000g to be placed in the corundum crucible for having filled the sodium hydroxide of 1-2 grams of removing moisture content, then plus 2-3 grams of mistake
Sodium oxide molybdena mixes, and surface covers one layer of sodium peroxide again, melts 10 minutes for 700 degree in Muffle furnace, earthenware is taken out from Muffle furnace
Crucible, it is cooling.
3. the METHOD FOR CONTINUOUS DETERMINATION side of rare earth ore concentrate middle rare earth as claimed in claim 2, calcium oxide, magnesia, barium monoxide
Method, which is characterized in that the step 2 specifically:
It is put into the 400mL beaker of the triethanolamine for filling 150mL 1+10 and 2 grams of sodium carbonate after step 1 is cooling and boils leaching,
Crucible is eluted with water, the solution heating in beaker is boiled 1-2 minutes, is filtered after cooling with quantitative filter paper, with the carbonic acid of 1+100
Sodium solution washes beaker 3-4 times, washes precipitating 4-5 times.
4. the METHOD FOR CONTINUOUS DETERMINATION side of rare earth ore concentrate middle rare earth as claimed in claim 3, calcium oxide, magnesia, barium monoxide
Method, which is characterized in that the step 3 specifically:
The precipitating that step 2 is obtained moves into beaker used in step 2 together with quantitative filter paper, adds the nitric acid of 20mL 67%,
The perchloric acid of 5mL 69% is added, cap upper surface ware is put on electric furnace and heats, is evaporated to nitrogen dioxide and disperses completely, perchloric acid is big
Amount is smoldered, and removes beaker after solution reaction is tranquil, cooling, continues to be heated to drying, purges beaker with the nitric acid of 10mL 1+1
Then plus the hydrogen peroxide of 0.1mL35% wall and surface plate add 80mL hot water, boil 1-2 minutes, cooling after removing, with quantitative
Medium speed filter paper filtering, washes beaker 3-4 times with the nitric acid of 1+100, washes precipitating 7-8 times, and residue is removed.
5. the METHOD FOR CONTINUOUS DETERMINATION side of rare earth ore concentrate middle rare earth as claimed in claim 4, calcium oxide, magnesia, barium monoxide
Method, which is characterized in that the step 4 specifically:
3 grams of ammonium chloride are added in the filtrate that step 3 obtains, is neutralized to PH=8 with the ammonium hydroxide of 1+1 after boiling, instills peroxidating
The ammonium hydroxide of 20mL1+1 is added in hydrogen 0.1mL, boils 2 minutes, is filled into 500mL beaker with quantitative Medium speed filter paper after precipitating decline
In, rare earth oxide precipitating is obtained, rare earth oxide precipitating and quantitative Medium speed filter paper are used to measure the content of rare earth oxide, will
Filtrate in 500mL beaker is concentrated into 150-200mL, instills the methyl orange indicator of 1+1000, is adjusted to out with the hydrochloric acid of 1+1
The sulfuric acid of 5mL1+1 is added in existing red under constant stirring, and heat preservation stood 12 hours or more after 1 hour, with quantitative slow filter paper
Cushioning foot is filled into 250mL volumetric flask, obtains barium sulfate precipitate, barium sulfate precipitate and quantitative slow filter paper are for measuring oxidation
Filtrate is diluted to 250mL volumetric flask scale constant volume, is divided to and two parts of 50mL test solutions is taken to be put into beaker by barium content, and portion is for surveying
Determine the content of calcium oxide, another is used to measure total content of calcium oxide and magnesia.
6. the METHOD FOR CONTINUOUS DETERMINATION side of rare earth ore concentrate middle rare earth as claimed in claim 5, calcium oxide, magnesia, barium monoxide
Method, which is characterized in that the step 5 specifically:
In the test solution for measuring calcium oxide content, it is firstly added the triethanolamine of 50mL 12%, then sequentially adds 50mL
Hydroxylamine hydrochloride is added in water, and the potassium hydroxide solution of 40mL 20% is added, and instills calcein, is titrated to EDTA standard solution
Fluorescence green disappears, and records EDTA standard solution consumption VCa。
7. the METHOD FOR CONTINUOUS DETERMINATION side of rare earth ore concentrate middle rare earth as claimed in claim 5, calcium oxide, magnesia, barium monoxide
Method, which is characterized in that the step 6 specifically:
In the test solution of total content for measuring calcium oxide and magnesia, it is firstly added the triethanolamine of 50mL 12%, so
After sequentially add 50mL water, hydroxylamine hydrochloride is added, adds 10mL ammonia-ammonium chloride solution, chromium black T indicator is instilled, with EDTA standard
Solution is titrated to test solution in pure blue, records EDTA standard solution consumption V(Mg+Ca)。
8. the METHOD FOR CONTINUOUS DETERMINATION side of rare earth ore concentrate middle rare earth as claimed in claim 5, calcium oxide, magnesia, barium monoxide
Method, which is characterized in that the step 7 specifically:
The rare earth oxide that step 4 obtains is precipitated and quantitative Medium speed filter paper is put into beaker, boiling water 50mL is added, by filter paper
It smashes, the oxalic acid 100mL of 1+25 is then added, is removed after boiling, in 60-70 degree heat preservation half an hour, with fixed after standing two hours
Measure filter paper filtering, wash beaker with the oxalic acid solution of 1+100, with the oxalic acid solution of 1+100 wash precipitate 10 times, will precipitate together with
Quantitative filter paper is put into porcelain crucible jointly, be put into Muffle furnace 850 DEG C of ashing, calcination 40 minutes, it is cooling after weigh quality m1。
9. the METHOD FOR CONTINUOUS DETERMINATION side of rare earth ore concentrate middle rare earth as claimed in claim 5, calcium oxide, magnesia, barium monoxide
Method, which is characterized in that the step 8 specifically:
Barium sulfate precipitate 7-8 times first obtained with sulfuric acid scrubbing step 4, the barium sulfate that reusable heat water wash step four obtains are heavy
It forms sediment 4-5 times, with being filtered in sulfuric acid scrubbing step 4 beaker 3-4 times after barium sulfate precipitate, by barium sulfate precipitate together with quantitative
Slow filter paper is put into porcelain crucible together, be put into Muffle furnace 850 DEG C of ashing, calcination 40 minutes, it is cooling after weigh quality m
(BaSO4)1。
10. the METHOD FOR CONTINUOUS DETERMINATION side of rare earth ore concentrate middle rare earth as described in claim 1, calcium oxide, magnesia, barium monoxide
Method, which is characterized in that step 9 calculates separately calcium oxide content W (CaO) and magnesia by formula one, formula two in the method
Content W (MgO), calculates rare earth oxide content W (RExOy) with formula three, calculates barium monoxide quality W (BaO) with formula four:
W (CaO) %=C (V-V01) M (CaO) 100/m K × 100 formula one
In formula: M (CaO): the molal weight of calcium oxide
M: sample mass
K: sample liquid separation ratio
C:EDTA concentration of standard solution
V: the volume of sample consumption EDTA standard solution
V01: the volume of blank solution consumption EDTA standard solution when titration calcium oxide content
W (MgO) %=C (V(Mg+Ca)-VCa-(V02-V01) M (MgO) 100/m K × 1000 formula two
In formula: M (MgO): the molal weight of magnesia
M: sample mass
K: sample liquid separation ratio
C:EDTA concentration of standard solution
V(Mg+Ca): the volume of the consumed EDTA standard solution of calcium and magnesium resultant
V02: the volume of blank solution consumption EDTA standard solution when total content of titration calcium oxide and magnesia；
W (RExOy) (%)=(m1-m0) × 100/m formula three
In formula: W: rare earth oxide content
m1: the quality finally weighed in rare-earth oxidation amount of substance, that is, step 7；
m0: the rare-earth oxidation amount of substance of blank sample；
M: rare earth ore concentrate quality used in sample mass, that is, step 1；
W (BaO) (%)=(m (BaSO4)1-m(BaSO4)0) × 100 × 0.6570/m formula four
In formula: m (BaSO4)1: barium sulfate precipitate quality；
m(BaSO4)0: the barium sulfate precipitate quality of blank sample；
M: sample mass；
0.6570 is BaO and BaSO4Conversion coefficient.
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