CN106053718A - Method for continuously measuring rare earth oxide, calcium oxide, magnesium oxide and barium oxide in rare earth ore concentrate - Google Patents
Method for continuously measuring rare earth oxide, calcium oxide, magnesium oxide and barium oxide in rare earth ore concentrate Download PDFInfo
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Abstract
The invention discloses a method for continuously measuring rare earth oxide, calcium oxide, magnesium oxide and barium oxide in a rare earth ore concentrate, and belongs to the technical field of metallurgical analysis methods. The invention aims at providing a method for continuously measuring rare earth oxide, calcium oxide, magnesium oxide and barium oxide in the rare earth ore concentrate with short analysis time, accurate measurement result, and low detection cost. The method disclosed by the invention comprises the following steps: 1, preparing a sample; 2, implementing primary sedimentation; 3, implementing secondary sedimentation; 4, preparing measurement; 5, measuring the content of calcium oxide; 6, measuring the total content of calcium oxide and magnesium oxide; 7, measuring the content of rare earth oxide; 8, measuring the content of barium oxide; 9, calculating the contents of rare earth oxide, calcium oxide, magnesium oxide and barium oxide. The method is easy to master, is high in result accuracy, and can be popularized in and applied to production. The method is suitable for rapid continuous measurement of rare earth oxide, calcium oxide, magnesium oxide and barium oxide in the rare earth ore concentrate.
Description
Technical field
Present invention relates particularly to a kind of rare earth ore concentrate middle rare earth, calcium oxide, magnesium oxide, barytic METHOD FOR CONTINUOUS DETERMINATION
Method, belongs to metallurgical analysis method and technology field.
Background technology
Rare earth has the title of industry " gold " to have the physical characteristics such as excellent photoelectromagnetic due to it to form with other materials
Different properties, new material various in style, its most significant function is exactly quality and the performance increasing substantially other products.
Such as increase substantially for manufacturing tank, aircraft, the steel of guided missile, aluminium alloy, magnesium alloy, the tactical qualities of titanium alloy.And
And rare earth is many high-tech lubricants such as electronics, laser, nuclear industry, superconduction equally.Rare earth science and technology, must once for military affairs
So bringing rising to of military science and technology, rare earth is in metallurgical industry, and petrochemical industry, the aspect such as glass ceramics also has and is widely used.
Mensuration rare earth ore concentrate middle rare earth, calcium oxide, magnesium oxide, barytic method generally use inductive etc.
Ion method, needs to use platinum crucible to melt, needs to control salt amount, simultaneously need to Matrix Match, said method needs behaviour simultaneously
Author has higher operating experience, simultaneously need to be equipped with main equipment, cost of determination is high.
Summary of the invention
Therefore, it is an object of the invention to provide a kind of analysis time short, measure accurately, in the rare earth ore concentrate that testing cost is low
Rare earth oxide, calcium oxide, magnesium oxide, barytic method for continuously measuring, it is characterised in that described method includes following step
Rapid:
Step one: sample prepares
Rare earth ore concentrate sample is put in crucible with sodium hydroxide and sodium peroxide and mixs homogeneously, molten in high temperature furnace
Melt, from high temperature furnace, take out crucible, cooling；
Step 2: precipitation for the first time
Put in the beaker filling triethanolamine and sodium carbonate after step one cooling and boil leaching, wash crucible, cold
Filter with quantitative filter paper the most afterwards, wash beaker with sodium carbonate liquor, wash precipitation with sodium carbonate liquor；
Step 3: second time precipitation
Precipitation step 2 obtained moves in the beaker that step 2 is used together with quantitative filter paper, adds nitric acid and high chlorine
Acid, cap upper surface ware is put in heating evaporation on electric furnace, takes off cooling after solution reaction calmness, continues heating and is heated to being dried,
With nitric acid (1+1) purging walls of beaker and surface plate, instill hydrogen peroxide after adding water, take off cooling after boiling, use quantitative middling speed
Filter paper filtering, washes beaker and precipitation with nitric acid, is removed by residue；
Step 4: preparation of determine
In the filtrate that step 3 obtains, add ammonium chloride, be neutralized to PH=8 with ammonia after boiling, instill hydrogen peroxide,
Adding ammonia, boil, precipitation is filled in beaker with quantitative Medium speed filter paper after declining, it is thus achieved that rare earth oxide precipitates, rare earth oxygen
Compound precipitation and quantitatively Medium speed filter paper are for measuring the content of rare earth oxide, after the filtrate in beaker being concentrated, instill methyl
Orange indicator, is adjusted to redness occur with hydrochloric acid, is being stirred continuously lower addition sulphuric acid, stand after insulation a period of time, with the slowest
Speed filter paper filtering is in volumetric flask, it is thus achieved that barium sulfate precipitate, and barium sulfate precipitate and the most at a slow speed filter paper are used for measuring Barium monoxide and contain
Amount, is diluted to volumetric flask scale constant volume by filtrate, point takes two parts of test solutions and puts in beaker, a for measuring containing of calcium oxide
Amount, another part is for measuring the total content of calcium oxide and magnesium oxide；
Step 5: the mensuration of the content of calcium oxide
Be firstly added triethanolamine for measuring in the test solution of calcium oxide content, be then sequentially added into water, oxammonium hydrochloride.,
Potassium hydroxide solution, instills calcein, is titrated to fluorescence green with EDTA standard solution and disappears, and record EDTA standard solution consumes
Amount VCa；
Step 6: calcium oxide and the mensuration adding up to content of magnesium oxide
In the test solution adding up to content for measuring calcium oxide and magnesium oxide, it is firstly added triethanolamine, adds the most successively
Entering water, oxammonium hydrochloride., ammonia ammonium chloride solution, instill C.I. 14645., being titrated to test solution with EDTA standard solution is pure blue, record
EDTA standard solution consumption V(Mg+Ca)；
Step 7: rare earth oxide content measures
The rare earth oxide precipitation and the quantitative Medium speed filter paper that step 4 are obtained are put in beaker, add water, are beaten by filter paper
Broken, it is subsequently adding oxalic acid, takes off after boiling, be incubated half an hour at 60 70 degree, filter with quantitative filter paper after standing a period of time,
By oxalic acid solution washing beaker and precipitation, precipitation is put in crucible jointly together with quantitative filter paper, process through low temperature dry ashing, burn
Quality m is weighed after burning, cooling1；
Step 8: the mensuration of Barium monoxide content
The barium sulfate precipitate first obtained by sulfuric acid scrubbing step 4, the barium sulfate that reusable heat water wash step four obtains sinks
Form sediment, with sulfuric acid scrubbing step 4 filtering the beaker after barium sulfate precipitate, by barium sulfate precipitate together with filter paper the most at a slow speed together
Put in crucible, after low temperature dry ashing process, calcination, cooling, weigh quality m (BaSO4)1；
Step 9: rare earth oxide, calcium oxide, magnesium oxide, the calculating of Barium monoxide content.
Further, described step one particularly as follows:
Weigh sample 0.5000g to be placed in the corundum crucible filling the 1-2 gram of sodium hydroxide removing moisture content, then add 2-3
Gram sodium peroxide, mixing, surface covers one layer of sodium peroxide again, and in Muffle furnace, 700 degree melt 10 minutes, take from Muffle furnace
Go out crucible, cooling.
Further, described step 2 particularly as follows:
Put in the 400mL beaker filling 150mL triethanolamine (1+10) and 2 grams of sodium carbonate after step one cooling and boil leaching
Take, wash crucible, by solution heated and boiled 1-2 minute in beaker, filter, with sodium carbonate (1 with quantitative filter paper after cooling
+ 100) solution washes beaker 3-4 time, washes precipitation 4-5 time.
Further, described step 3 particularly as follows:
Precipitation step 2 obtained moves in the beaker that step 2 is used together with quantitative filter paper, adds 20mL nitric acid
(67%), adding 5mL perchloric acid (69%), cap upper surface ware is put on electric furnace heating, is evaporated to nitrogen dioxide and disperses completely, high
Chloric acid is smoldered in a large number, takes off beaker after solution reaction calmness, cooling, continues to be heated to being dried, and purges with 10mL nitric acid (1+1)
Walls of beaker and surface plate, add 80mL hot water, then adds 0.1mL hydrogen peroxide (35%), boils 1-2 minute, cools down after taking off, and uses
Quantitatively Medium speed filter paper filters, and washes beaker 3-4 time with nitric acid (1+100), washes precipitation 7-8 time, is removed by residue.
Further, described step 4 particularly as follows:
In the filtrate that step 3 obtains, add ammonium chloride 3 grams, be neutralized to PH=8 with ammonia (1+1) after boiling, instilled
Hydrogen oxide 0.1mL, adds 20mL ammonia (1+1), boils 2 minutes, and precipitation is filled into 500mL with quantitative Medium speed filter paper after declining and burns
In Bei, it is thus achieved that rare earth oxide precipitates, rare earth oxide precipitation and quantitatively Medium speed filter paper are used for measuring the content of rare earth oxide,
Filtrate in 500mL beaker is concentrated into 150 200mL, instills methyl orange indicator (1+1000), be adjusted to hydrochloric acid (1+1)
Redness occurs, is being stirred continuously lower addition 5mL sulphuric acid (1+1), stand more than 12 hours after being incubated 1 hour, with quantitatively filtering at a slow speed
Paper adds feet and is filled in 250mL volumetric flask, it is thus achieved that barium sulfate precipitate, and barium sulfate precipitate and the most at a slow speed filter paper are used for measuring oxygen
Changing barium content, filtrate is diluted to 250mL volumetric flask scale constant volume, point taking two parts of 50mL test solutions puts in beaker, and portion is used for
Measuring the content of calcium oxide, another part is for measuring the total content of calcium oxide and magnesium oxide.
Further, described step 5 particularly as follows:
In the test solution for measuring calcium oxide content, it is firstly added 50mL triethanolamine (12%), is then sequentially added into
50mL water, adds oxammonium hydrochloride., adds 40mL potassium hydroxide solution (20%), instills calcein, drips with EDTA standard solution
Fixed to fluorescence green disappearance, record EDTA standard solution consumption VCa。
Further, described step 6 particularly as follows:
In the test solution adding up to content for measuring calcium oxide and magnesium oxide, it is firstly added 50mL triethanolamine
(12%), then it is sequentially added into 50mL water, adds oxammonium hydrochloride., add 10mL ammonia-ammonium chloride solution, instill chromium black T indicator, use
It is pure blue that EDTA standard solution is titrated to test solution, records EDTA standard solution consumption V(Mg+Ca)。
Further, described step 7 particularly as follows:
The rare earth oxide precipitation and the quantitative Medium speed filter paper that step 4 are obtained are put in beaker, add boiling water 50mL, will
Filter paper is smashed, and is subsequently adding oxalic acid (1+25) 100mL, takes off after boiling, and is incubated half an hour at 60 70 degree, after standing two hours
Filter with quantitative filter paper, wash beaker with oxalic acid (1+100) solution, precipitate 10 times with the washing of oxalic acid (1+100) solution, will precipitation
Jointly put in porcelain crucible together with quantitative filter paper, put in Muffle furnace and weigh quality after 850 DEG C of ashing, calcination 40 minutes, coolings
m1。
Further, described step 8 particularly as follows:
The barium sulfate precipitate that first use sulfuric acid scrubbing step 4 obtains 78 times, the sulphuric acid that reusable heat water wash step four obtains
Precipitated barium 45 times, with the beaker filtered in sulfuric acid scrubbing step 4 after barium sulfate precipitate 34 times, by barium sulfate precipitate together with
Filter paper is together put in porcelain crucible the most at a slow speed, puts in Muffle furnace and weighs quality m after 850 DEG C of ashing, calcination 40 minutes, coolings
(BaSO4)1。
Further, in described method, step 9 is pressed formula one, formula two and is calculated calcium oxide content W (CaO) and oxygen respectively
Change content of magnesium W (MgO), calculate rare earth oxide content W (RExOy) with formula three, calculate Barium monoxide quality W with formula four
(BaO):
W (CaO) %=C (V-V01) M (CaO) 100/m K × 100 (formula one)
In formula: the molal weight (g/mol) of M (CaO): calcium oxide
M: sample mass (g)
K: sample separatory ratio (50/250=1/5)
C:EDTA concentration of standard solution (mol/L)
V: sample consumes the volume (mL) of EDTA standard solution
V01: the volume (mL) of blank solution consumption EDTA standard solution during titration calcium oxide content
W (MgO) %=C (V(Mg+Ca)-VCa-(V02-V01) M (MgO) 100/m K × 1000 (formula two)
In formula: the molal weight (g/mol) of M (CaO): calcium oxide
M: sample mass (g)
K: sample separatory ratio
C:EDTA concentration of standard solution (mol/L)
V(Mg+Ca): the volume (mL) of calcium and magnesium resultant consumed EDTA standard solution
V02: titration calcium oxide and the volume (mL) of blank solution consumption EDTA standard solution when adding up to content of magnesium oxide；
W (RExOy) (%)=m1х 100/m (formula three)
In formula: W (RExOy) (%): rare earth oxide content
m1: the final quality weighed in rare earth oxide quality (g), i.e. step 7；
Rare earth ore concentrate quality used in m: sample mass (g), i.e. step one.
W (BaO) (%)=m (BaSO4)1× 100 × 0.6570/m (formula four)
In formula: m (BaSO4)1: the final quality weighed in barium sulfate precipitate quality (g), i.e. step 8；
Rare earth ore concentrate quality used in m: sample mass (g), i.e. step one；
0.6570 is BaO and BaSO4Conversion coefficient.
The beneficial effects of the present invention is: a kind of rare earth ore concentrate middle rare earth of the present invention, calcium oxide, magnesium oxide,
Barytic method for continuously measuring, after sample dissolution, directly carries out rare-earth precipitation mensuration, and the solution after filtration first carries out sulphuric acid
The mensuration of precipitated barium, and then obtain Barium monoxide content, then carry out the mensuration of calcium oxide, magnesium oxide, single test realizes dilute simultaneously
Soil oxide, calcium oxide, magnesium oxide, barytic METHOD FOR CONTINUOUS DETERMINATION.Method is prone to grasp and result precision height, it is possible to producing
Middle popularization and application.Use equipment is simple, has feature accurately, it is adaptable to rare earth ore concentrate middle rare earth, calcium oxide, oxidation
Magnesium, barytic Fast Continuous Determination.
Accompanying drawing explanation
Fig. 1 is one rare earth ore concentrate middle rare earth of the present invention, calcium oxide, magnesium oxide, barytic METHOD FOR CONTINUOUS DETERMINATION side
The flow chart of method.
Detailed description of the invention
Below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is illustrated:
The method step of this detailed description of the invention, as it is shown in figure 1, select three kinds of samples, respectively rare-earth tailings, is numbered
1, rare-earth original ore, label 2, rare earth ore concentrate is numbered 3, carries out sample according to sampling iron ore standard and produces, and per sample (p.s.) divides
Not being 4 groups of contrast experiments by following method, the basic process of assay method is: by sample alkali fusion, molten at triethanolamine
Liquid separates the interference elements such as ferrum, aluminum, manganese.After removing silicon dioxide, with elements such as ammonia precipitation process separating calcium, magnesium, rare earth is in PH
The slightly acidic solution of=2 uses oxalic acid precipitation.Calcination becomes rare earth oxide to weigh.The filtrate of the element such as separating calcium, magnesium is concentrated,
Being acidified with hydrochloric acid, sulfuric acid precipitation barium, with gravimetric detemination Barium monoxide amount.By filtering the filtrate of barium sulfate, at PH > 12 time add appropriate
Calcein, titrates with EDTA standard solution, measures calcium oxide, adds appropriate black T when PH=10, drip with EDTA standard solution
Fixed, measure the resultant of calcium oxide+magnesium oxide.Concrete operation method is:
Weigh sample 0.5000g to be placed in the corundum crucible filling the 1-2 gram of sodium hydroxide removing moisture content, then add 2-3
Gram sodium peroxide, mixing, surface covers one layer of sodium peroxide again, and in Muffle furnace, 700 degree melt 10 minutes, take from Muffle furnace
Go out crucible, cooling.Put into after cooling to fill in the 400mL beaker of 150mL triethanolamine (1+10) and 2 grams of sodium carbonate and boil leaching
Take, wash crucible, by solution heated and boiled 1-2 minute in beaker, filter, with sodium carbonate (1 with quantitative filter paper after cooling
+ 100) solution washes beaker 3-4 time, washes precipitation 4-5 time.The precipitation obtained is moved into the original beaker used together with quantitative filter paper
In, adding 20mL nitric acid (67%), add 5mL perchloric acid (69%), cap upper surface ware is put on electric furnace heating, is evaporated to titanium dioxide
Nitrogen disperses completely, and perchloric acid is smoldered in a large number, and when smoldering, solution occurs that brown or black should add 2mL nitric acid (67%) in time, treats
Beaker is taken off after solution reaction calmness, cooling, continue to be heated to being dried, purge walls of beaker and surface plate with 10mL nitric acid (1+1),
Add 80mL hot water, then add 0.1mL hydrogen peroxide (35%), boil 1-2 minute, it is therefore an objective to drive the hydrogen peroxide of surplus, take
Cool down after Xia, filter with quantitative Medium speed filter paper, wash beaker 3-4 time with nitric acid (1+100), wash precipitation 7-8 time, residue is removed.
In filtrate, add ammonium chloride 3 grams, be neutralized to PH=8 with ammonia (1+1) after boiling, instill hydrogen peroxidase 10 .1mL, add 20mL
Ammonia (1+1), boils 2 minutes, and precipitation is filled in 500mL beaker with quantitative Medium speed filter paper after declining, it is thus achieved that rare earth oxide
Precipitation, rare earth oxide precipitation and quantitatively Medium speed filter paper are used for measuring the content of rare earth oxide, by the filtrate in 500mL beaker
It is concentrated into 150 200mL, instills methyl orange indicator (1+1000), be adjusted to that redness occurs with hydrochloric acid (1+1), be stirred continuously
Lower addition 5mL sulphuric acid (1+1), stands more than 12 hours after being incubated 1 hour, adds feet with filter paper the most at a slow speed and is filled into 250mL
In volumetric flask, it is thus achieved that barium sulfate precipitate, barium sulfate precipitate and the most at a slow speed filter paper are used for measuring Barium monoxide content, filtrate are diluted
To 250mL volumetric flask scale constant volume, point taking two parts of 50mL test solutions puts in beaker, a content for measuring calcium oxide, separately
The a total content for measuring calcium oxide and magnesium oxide.
In the test solution for measuring calcium oxide content, being firstly added 50mL triethanolamine (12%), first adds three
Ethanolamine, is to first be sheltered by the interference element such as ferrum and aluminum, is then sequentially added into 50mL water, adds to play and shelters further
The oxammonium hydrochloride. of effect, adds 40mL potassium hydroxide solution (20%), and potassium hydroxide solution plays the effect of buffer solution, pH value
Being 12, instill calcein indicator, calcein indicator manufacture method is: the chlorination after 1g calcein and 100g drying
The finely ground mixing of sodium, is placed in port grinding bottle standby.It is titrated to fluorescence green with EDTA standard solution disappear, EDTA standard solution C
(EDTA)=0.01783mol/L, records EDTA standard solution consumption VCa。
In the test solution adding up to content for measuring calcium oxide and magnesium oxide, it is firstly added 50mL triethanolamine
(12%), being then sequentially added into 50mL water, add oxammonium hydrochloride., add 10mL ammonia-ammonium chloride solution, ammonia-ammonium chloride solution plays
The effect of buffer solution, pH value is 10, and ammonia-ammonium chloride buffer solution (PH=10) preparation method is: be dissolved in by 67g ammonium chloride
In 200mL water, add 570mL strong aqua ammonia, be diluted to 1000mL with water.Instill chromium black T indicator, chromium black T indicator preparation side
Method is: the finely ground mixing of sodium chloride after being dried with 100g by 1g C.I. 14645., is placed in port grinding bottle standby.Drip with EDTA standard solution
Fixed is pure blue to test solution, records EDTA standard solution consumption V(Mg+Ca)。
The rare earth oxide of acquisition is precipitated and quantitatively Medium speed filter paper is put in beaker, add boiling water 50mL, filter paper is beaten
Broken, it is subsequently adding oxalic acid (1+25) 100mL, takes off after boiling, be incubated half an hour at 60 70 degree, with quantitatively after standing two hours
Filter paper filtering, washs beaker with oxalic acid (1+100) solution, precipitates 10 times with the washing of oxalic acid (1+100) solution, will precipitate together with fixed
Amount filter paper is put in porcelain crucible jointly, puts in Muffle furnace and weighs quality m after 850 DEG C of ashing, calcination 40 minutes, coolings1。
First use sulfuric acid scrubbing barium sulfate precipitate 78 times, reusable heat water washing barium sulfate precipitate 45 times, use sulfuric acid scrubbing
Beaker after filtration barium sulfate precipitate 34 times, together puts into barium sulfate precipitate in porcelain crucible together with filter paper the most at a slow speed, puts
Enter in Muffle furnace and weigh quality m (BaSO after 850 DEG C of ashing, calcination 40 minutes, coolings4)1。
Calculate calcium oxide content W (CaO) and content of magnesia W (MgO) by formula one, formula two respectively, count with formula three
Calculate rare earth oxide content W (RExOy), calculate Barium monoxide quality W (BaO) with formula four:
W (CaO) %=C (V-V01) M (CaO) 100/m K × 100 (formula one)
In formula: the molal weight (g/mol) of M (CaO): calcium oxide
M: sample mass (g)
K: sample separatory ratio (50/250=1/5)
C:EDTA concentration of standard solution (mol/L)
V: sample consumes the volume (mL) of EDTA standard solution
V01: the volume (mL) of blank solution consumption EDTA standard solution, i.e. blank value during titration calcium oxide content；
W (MgO) %=C (V(Mg+Ca)-VCa-(V02-V01) M (MgO) 100/m K × 1000 (formula two)
In formula: the molal weight (g/mol) of M (CaO): calcium oxide
M: sample mass (g)
K: sample separatory ratio (50/250=1/5)
C:EDTA concentration of standard solution (mol/L)
V(Mg+Ca): the volume (mL) of calcium and magnesium resultant consumed EDTA standard solution
V02: titration calcium oxide and the volume (mL) of blank solution consumption EDTA standard solution when adding up to content of magnesium oxide.
W (RExOy) (%)=m1х 100/m formula three
In formula: W (RExOy) (%): rare earth oxide content (g)
m1: the most final quality m weighed of rare earth oxide quality (g)1；
The rare earth ore concentrate sample mass that m: sample mass is i.e. used.
W (BaO) (%)=m (BaSO4)1× 100 × 0.6570/m (formula four)
In formula: m (BaSO4)1: the final quality weighed in barium sulfate precipitate quality (g), i.e. step 8；
Rare earth ore concentrate quality used in m: sample mass (g), i.e. step one；
0.6570 is BaO and BaSO4Conversion coefficient.
Three kinds of samples measure calcium oxide, magnesium oxide, Barium monoxide content result as shown in table 1,
Table 1
The result measuring rare earth oxide content of three kinds of samples is as shown in table 2,
Table 2
By table 1, table 2 it can be seen that for three kinds of different samples, respectively organize the rare earth oxide of contrast experiment, oxidation
Calcium, magnesium oxide, Barium monoxide content measurement result relatively, illustrate that the method precision of the present invention is fine, the present invention simultaneously
Method can also be generalized to rare-earth tailing and rare-earth original ore and use.
Utilize the baotite R-715 of known standard value, baotite R-716, tri-kinds of rare earth ore concentrate checkings of baotite R-717 originally
Method measures the accuracy of calcium oxide content, and measurement result is as shown in table 3, and checking this method measures the standard of rare earth oxide content
Really property, measurement result is as shown in table 4,
Table 3
Table 4
Baotite R-717 i.e. certain rare earth ore concentrate utilizing known standard value verifies that this method measures the standard of content of magnesia
Really property, measurement result is as shown in table 5,
Table 5
By table 3, table 4, table 5 it can be seen that rare earth oxide, calcium oxide, magnesium oxide, Barium monoxide content measured value with
Known standard value is closely, it was demonstrated that the accuracy of the present invention is the highest.
Utilized the rare earth ore concentrate sample being numbered ore deposit-34 to carry out precision and the accuracy of Barium monoxide content by this method
Experiment, result as shown in table 6, table 7,
Table 6
Table 7
| The name of an article | Extreme difference | 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 it can be seen that the method for the present invention has the highest precision equally for measuring Barium monoxide content
Degree and accuracy.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, on the premise of without departing from principle of the present invention, it is also possible to make some improvements and modifications, these improvements and modifications are also
Should be regarded as protection scope of the present invention.
Claims (10)
1. a rare earth ore concentrate middle rare earth, calcium oxide, magnesium oxide, barytic method for continuously measuring, it is characterised in that
Said method comprising the steps of:
Step one: sample prepares
Rare earth ore concentrate sample is put in crucible with sodium hydroxide and sodium peroxide and mixs homogeneously, melted in high temperature furnace, from
High temperature furnace takes out crucible, cooling；
Step 2: precipitation for the first time
Put in the beaker filling triethanolamine and sodium carbonate after step one cooling and boil leaching, wash crucible, after cooling
Filter with quantitative filter paper, wash beaker with sodium carbonate liquor, wash precipitation with sodium carbonate liquor；
Step 3: second time precipitation
Precipitation step 2 obtained moves in the beaker that step 2 is used together with quantitative filter paper, adds nitric acid and perchloric acid,
Cap upper surface ware is put in heating evaporation on electric furnace, takes off cooling after solution reaction calmness, continues heating and is heated to being dried, uses nitre
Acid (1+1) purging walls of beaker and surface plate, instill hydrogen peroxide after adding water, take off cooling, use quantitative Medium speed filter paper after boiling
Filter, wash beaker and precipitation with nitric acid, residue is removed；
Step 4: preparation of determine
In the filtrate that step 3 obtains, add ammonium chloride, be neutralized to PH=8 with ammonia after boiling, instill hydrogen peroxide, add
Ammonia, boils, and precipitation is filled in beaker with quantitative Medium speed filter paper after declining, it is thus achieved that rare earth oxide precipitates, rare earth oxide
Precipitation and quantitatively Medium speed filter paper are for measuring the content of rare earth oxide, after the filtrate in beaker being concentrated, instill methyl orange and refer to
Show agent, be adjusted to that redness occurs with hydrochloric acid, be stirred continuously lower addition sulphuric acid, stand after insulation a period of time, with quantitatively filtering at a slow speed
Paper is filled in volumetric flask, it is thus achieved that barium sulfate precipitate, and barium sulfate precipitate and the most at a slow speed filter paper are used for measuring Barium monoxide content, will
Filtrate is diluted to volumetric flask scale constant volume, point takes two parts of test solutions and puts in beaker, a content for measuring calcium oxide, another
Part is for measuring the total content of calcium oxide and magnesium oxide；
Step 5: the mensuration of the content of calcium oxide
In the test solution for measuring calcium oxide content, it is firstly added triethanolamine, is then sequentially added into water, oxammonium hydrochloride., hydrogen-oxygen
Change potassium solution, instill calcein, be titrated to fluorescence green with EDTA standard solution and disappear, record EDTA standard solution consumption
VCa；
Step 6: calcium oxide and the mensuration adding up to content of magnesium oxide
In the test solution adding up to content for measuring calcium oxide and magnesium oxide, it is firstly added triethanolamine, is then sequentially added into
Water, oxammonium hydrochloride., ammonia ammonium chloride solution, instill C.I. 14645., and being titrated to test solution with EDTA standard solution is pure blue, record
EDTA standard solution consumption V(Mg+Ca)；
Step 7: rare earth oxide content measures
The rare earth oxide precipitation and the quantitative Medium speed filter paper that step 4 are obtained are put in beaker, add water, are smashed by filter paper, so
Rear addition oxalic acid, takes off after boiling, and is incubated half an hour at 60 70 degree, filters, with grass with quantitative filter paper after standing a period of time
Acid solution wash beaker and precipitation, put in crucible together with quantitative filter paper jointly by precipitation, through low temperature dry ashing process, calcination, cold
Weigh quality m the most afterwards1；
Step 8: the mensuration of Barium monoxide content
The barium sulfate precipitate first obtained by sulfuric acid scrubbing step 4, the barium sulfate precipitate that reusable heat water wash step four obtains, use
Sulfuric acid scrubbing step 4 filters the beaker after barium sulfate precipitate, barium sulfate precipitate is together put into earthenware together with filter paper the most at a slow speed
In crucible, after low temperature dry ashing process, calcination, cooling, weigh quality m (BaSO4)1；
Step 9: rare earth oxide, calcium oxide, magnesium oxide, the calculating of Barium monoxide content.
2. rare earth ore concentrate middle rare earth, calcium oxide, magnesium oxide, barytic METHOD FOR CONTINUOUS DETERMINATION side as claimed in claim 1
Method, it is characterised in that described step one particularly as follows:
Weigh sample 0.5000g to be placed in the corundum crucible filling the 1-2 gram of sodium hydroxide removing moisture content, then add 2-3 gram of mistake
Sodium oxide, mixing, surface covers one layer of sodium peroxide again, 700 degree melted 10 minutes in Muffle furnace, takes out earthenware from Muffle furnace
Crucible, cooling.
3. rare earth ore concentrate middle rare earth, calcium oxide, magnesium oxide, barytic METHOD FOR CONTINUOUS DETERMINATION side as claimed in claim 2
Method, it is characterised in that described step 2 particularly as follows:
Put in the 400mL beaker filling 150mL triethanolamine (1+10) and 2 grams of sodium carbonate after step one cooling and boil leaching,
Wash crucible, by solution heated and boiled 1-2 minute in beaker, filter, with sodium carbonate (1+ with quantitative filter paper after cooling
100) solution washes beaker 3-4 time, washes precipitation 4-5 time.
4. rare earth ore concentrate middle rare earth, calcium oxide, magnesium oxide, barytic METHOD FOR CONTINUOUS DETERMINATION side as claimed in claim 3
Method, it is characterised in that described step 3 particularly as follows:
Precipitation step 2 obtained moves in the beaker that step 2 is used together with quantitative filter paper, adds 20mL nitric acid (67%),
Adding 5mL perchloric acid (69%), cap upper surface ware is put on electric furnace heating, is evaporated to nitrogen dioxide and disperses completely, and perchloric acid is big
Amount is smoldered, and takes off beaker after solution reaction calmness, cooling, continues to be heated to being dried, and purges walls of beaker with 10mL nitric acid (1+1)
And surface plate, add 80mL hot water, then add 0.1mL hydrogen peroxide (35%), boil 1-2 minute, cool down after taking off, in quantitatively
Speed filter paper filtering, washes beaker 3-4 time with nitric acid (1+100), washes precipitation 7-8 time, is removed by residue.
5. rare earth ore concentrate middle rare earth, calcium oxide, magnesium oxide, barytic METHOD FOR CONTINUOUS DETERMINATION side as claimed in claim 4
Method, it is characterised in that described step 4 particularly as follows:
In the filtrate that step 3 obtains, add ammonium chloride 3 grams, be neutralized to PH=8 with ammonia (1+1) after boiling, instill peroxidating
Hydrogen 0.1mL, adds 20mL ammonia (1+1), boils 2 minutes, and precipitation is filled into 500mL beaker with quantitative Medium speed filter paper after declining
In, it is thus achieved that rare earth oxide precipitates, and rare earth oxide precipitation and quantitatively Medium speed filter paper, will for measuring the content of rare earth oxide
Filtrate in 500mL beaker is concentrated into 150 200mL, instills methyl orange indicator (1+1000), is adjusted to out with hydrochloric acid (1+1)
Existing redness, is being stirred continuously lower addition 5mL sulphuric acid (1+1), stands more than 12 hours after being incubated 1 hour, with filter paper the most at a slow speed
Adding feet to be filled in 250mL volumetric flask, it is thus achieved that barium sulfate precipitate, barium sulfate precipitate and the most at a slow speed filter paper are used for measuring oxidation
Barium content, is diluted to 250mL volumetric flask scale constant volume by filtrate, point takes two parts of 50mL test solutions and puts in beaker, and portion is used for surveying
Determining the content of calcium oxide, another part is for measuring the total content of calcium oxide and magnesium oxide.
6. rare earth ore concentrate middle rare earth, calcium oxide, magnesium oxide, barytic METHOD FOR CONTINUOUS DETERMINATION side as claimed in claim 5
Method, it is characterised in that described step 5 particularly as follows:
In the test solution for measuring calcium oxide content, it is firstly added 50mL triethanolamine (12%), is then sequentially added into 50mL
Water, adds oxammonium hydrochloride., adds 40mL potassium hydroxide solution (20%), instills calcein, is titrated to EDTA standard solution
Fluorescence green disappears, and records EDTA standard solution consumption VCa。
7. rare earth ore concentrate middle rare earth, calcium oxide, magnesium oxide, barytic METHOD FOR CONTINUOUS DETERMINATION side as claimed in claim 5
Method, it is characterised in that described step 6 particularly as follows:
In the test solution adding up to content for measuring calcium oxide and magnesium oxide, it is firstly added 50mL triethanolamine (12%), so
After be sequentially added into 50mL water, add oxammonium hydrochloride., add 10mL ammonia-ammonium chloride solution, instill chromium black T indicator, use EDTA standard
It is pure blue that solution is titrated to test solution, records EDTA standard solution consumption V(Mg+Ca)。
8. rare earth ore concentrate middle rare earth, calcium oxide, magnesium oxide, barytic METHOD FOR CONTINUOUS DETERMINATION side as claimed in claim 5
Method, it is characterised in that described step 7 particularly as follows:
The rare earth oxide precipitation and the quantitative Medium speed filter paper that step 4 are obtained are put in beaker, add boiling water 50mL, by filter paper
Smash, be subsequently adding oxalic acid (1+25) 100mL, take off after boiling, be incubated half an hour at 60 70 degree, with fixed after standing two hours
Amount filter paper filtering, with oxalic acid (1+100) solution wash beaker, with oxalic acid (1+100) solution washing precipitation 10 times, will precipitation together with
Quantitative filter paper is put in porcelain crucible jointly, puts in Muffle furnace and weighs quality m after 850 DEG C of ashing, calcination 40 minutes, coolings1。
9. rare earth ore concentrate middle rare earth, calcium oxide, magnesium oxide, barytic METHOD FOR CONTINUOUS DETERMINATION side as claimed in claim 5
Method, it is characterised in that described step 8 particularly as follows:
The barium sulfate precipitate that first use sulfuric acid scrubbing step 4 obtains 78 times, the barium sulfate that reusable heat water wash step four obtains sinks
Form sediment 45 times, with the beaker filtered in sulfuric acid scrubbing step 4 after barium sulfate precipitate 34 times, by barium sulfate precipitate together with quantitatively
Filter paper is together put in porcelain crucible at a slow speed, puts in Muffle furnace and weighs quality m after 850 DEG C of ashing, calcination 40 minutes, coolings
(BaSO4)1。
10. rare earth ore concentrate middle rare earth, calcium oxide, magnesium oxide, barytic METHOD FOR CONTINUOUS DETERMINATION side as claimed in claim 1
Method, it is characterised in that in described method, step 9 is pressed formula one, formula two and calculated calcium oxide content W (CaO) and magnesium oxide respectively
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 separatory ratio
C:EDTA concentration of standard solution
V: sample consumes the volume of EDTA standard solution
V01: the volume of blank solution consumption EDTA standard solution during 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 magnesium oxide
M: sample mass
K: sample separatory ratio
C:EDTA concentration of standard solution
V(Mg+Ca): the volume of calcium and magnesium resultant consumed EDTA standard solution
V02: titration calcium oxide and the volume of blank solution consumption EDTA standard solution when adding up to content of magnesium oxide；
W (RExOy) (%)=m1× 100/m formula three
In formula: W: rare earth oxide content
m1: the final quality weighed in rare earth oxide quality i.e. step 7；
Rare earth ore concentrate quality used in m: sample mass i.e. step one；
W (BaO) (%)=m (BaSO4)1× 100 × 0.6570/m formula four
In formula: m (BaSO4)1: barium sulfate precipitate quality
M: sample mass
0.6570 is BaO and BaSO4Conversion coefficient.
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| SU495595A1 (en) * | 1974-07-23 | 1975-12-15 | Государственный ордена Октябрьской Революции научно-исследовательский и проектный институт редкометаллической промышленности | Method for determination of oxygen in rare earth metals |
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| SU495595A1 (en) * | 1974-07-23 | 1975-12-15 | Государственный ордена Октябрьской Революции научно-исследовательский и проектный институт редкометаллической промышленности | Method for determination of oxygen in rare earth metals |
| JP2002082107A (en) * | 2000-09-08 | 2002-03-22 | Shin Etsu Chem Co Ltd | Quantitative analysis method for rare earth element/ aluminum-based composite oxide |
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| CN104569126A (en) * | 2014-12-29 | 2015-04-29 | 内蒙古包钢钢联股份有限公司 | Method for determining content of single rear earth-included sulfur oxide in steel |
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