CN102661907B - Method for measuring rhenium content in ammonium rhenate - Google Patents

Method for measuring rhenium content in ammonium rhenate Download PDF

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CN102661907B
CN102661907B CN201210150425.1A CN201210150425A CN102661907B CN 102661907 B CN102661907 B CN 102661907B CN 201210150425 A CN201210150425 A CN 201210150425A CN 102661907 B CN102661907 B CN 102661907B
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acid ammonium
rhenium
rehenic acid
solution
chloride hydrochloride
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CN102661907A (en
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张永中
杨加桂
刘君侠
沈丽
李朝阳
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Yanggu Xiangguang Copper Co Ltd
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Yanggu Xiangguang Copper Co Ltd
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Abstract

The invention discloses a method for measuring rhenium content in ammonium rhenate, comprising the following steps of: a) dissolving ammonium rhenate into water, and adding ammonia water to the ammonium rhenate solution to adjust the pH value to a range from 11 to 12; b) adding tetraphenylarsonium chloride hydrochloride to the obtained solution for reaction; and c) performing precipitation and filtering after the completion of the reaction, and drying the precipitate; and finally, calculating the mass fraction of rhenium according to a formula W(Re)=(m2-m1)*0.2941/m0 *100. The method for measuring the rhenium content provided in the invention is capable of accurately measuring a sample with high rhenium content, such as ammonium rhenate by a weight method; the measurement range is from 60.0% to 60.0%; the accuracy and precision of measurement both are high; and the process flow is simple; therefore, the method can be used for production process control and finished product detection.

Description

A kind of method of measuring rhenium content in rehenic acid ammonium
Technical field
The present invention relates to tenor and measure field, be specifically related to a kind of method of measuring rhenium content in rehenic acid ammonium.
Background technology
Rhenium (Re) belongs to the rare element of high dispersion, at occurring in nature, is mainly distributed in molybdenite, Rare Earth Mine and niobium tantalum ore, and its content is extremely low.Because of the compound of rhenium, the catalytic activity of alloy, the excellent specific property such as high temperature resistant, corrosion-resistant are widely used in the fields such as petroleum refining catalyst, high temperature alloy, electronic tubular construction material, Aero-Space specific alloy, environmental protection.
Rehenic acid ammonium (NH 4reO 4) be one of main industrial compound of rhenium, be white plates crystal, be slightly soluble in cold water, be very easily dissolved in hot water, there is stronger oxidisability; Rehenic acid ammonium adds thermal decomposition distillation can obtain Re 2o 7with containing ReO 2black precipitate; Rehenic acid ammonium available hydrogen reduces and obtains rhenium metal, and this is the best method of preparing simple metal rhenium.
Yet, in the rehenic acid ammonium of industrial generation, usually containing certain impurity, the contamination of its impurity has a strong impact on the purity of sample, because rhenium content is just the important indicator of judgement sample purity in rehenic acid ammonium.The method of measuring for rhenium in the lower rhenium alloys of rhenium content, ore is at present more, as photometry, ICP-AES etc.
Photometry is by measuring the absorbance log of measured matter light in certain wave strong point or certain wavelength coverage, this material is carried out to the method for qualitative and quantitative analysis, needs drawing curve before sample determination.First by hydrogen peroxide (H for sample 2o 2) solution dissolves, remaining hydrogen peroxide for NaOH (NaOH) decompose, after the yellow disappearance of solution, low-temperature heat is micro-boils, and takes off cooling, dilution, constant volume; Draw a certain amount of solution, add the tungsten in citric acid masking solutions; In hydrochloric acid medium, add stannous chloride (SnCl 2) will high price rhenium (Re 7+) be reduced at a low price rhenium (Re 5+), make itself and the follow-up dimethylglyoxime adding generate stable orange red complex compound; Finally on spectrophotometer, survey its extinction value.
The Main Analysis step of ICP-AES method is: sample is placed in to teflon crucible, adds hydrofluorite (HF), nitric acid (HNO 3), perchloric acid (HClO 4), be heated to white cigarette and emit to the greatest extent, slightly cold, add (1+1) hydrochloric acid (HCl), residue thing is dissolved, move into volumetric flask, shake up after being diluted to scale, then with Liberty-110 type ICP-AES, rhenium in uranium ore is measured.
Adopt in the tungsten-rhenium alloy that spectrphotometric method for measuring rhenium content is lower rhenium and adopt ICP-AES method to measure the rhenium in the uranium ore that contains Determination of Trace Rhenium, the major defect all existing has:
(1), only for the mensuration of low content rhenium, be not suitable for the material that rhenium content is higher (as rehenic acid ammonium).The measurement range 0.5%～5.0% of photometry wherein, ICP-AES method is limited to 0.016 μ g/mL under measuring, and detects and is limited to 0.005 μ g/mL, in measuring sample during rhenium content higher (as rehenic acid ammonium), due to the impact of luminosity transmission, make between its measurement result and actual value deviation larger;
(2) measure operation comparatively loaded down with trivial details, two kinds of assay methods all need preparing standard solution just to analyze mensuration after Criterion curve, and need know in advance the approximate range of rhenium content, can Criterion curve;
(3) need the instrument cost of employing higher, condition determination is had relatively high expectations.
And for the assay method that is applicable to (as rehenic acid ammonium) rhenium in sample that rhenium content is higher, also there is no so far clear and definite bibliographical information.
Summary of the invention
The technical matters that the present invention solves is to provide a kind of method of measuring rhenium content in rehenic acid ammonium, and measurement result is accurate, and precision is high.
For addressing the above problem, the present invention by the following technical solutions:
A method of measuring rhenium content in rehenic acid ammonium, comprises the following steps:
A) rehenic acid ammonium is water-soluble, to adding in rehenic acid ammonium salt solution ammoniacal liquor to regulate pH value, be 11～12;
B) in the solution obtaining, add tetraphenylarsonium chloride hydrochloride to react;
C) reaction finishes postprecipitation, filtration, by drying precipitate;
According to formula (1), calculate the massfraction of rhenium:
W ( Re ) = ( m 2 - m 1 ) × 0.2941 m 0 × 100 · · · ( 1 )
In formula:
The massfraction of rhenium in W (Re)-rehenic acid ammonium, numerical value represents with %;
M 0the quality of-rehenic acid ammonium, unit is gram (g);
M 1the quality of-glass sand core funnel, unit is gram (g);
M 2the quality of-glass sand core funnel and precipitation, unit is gram (g);
The conversion factor of 0.2941-precipitation to rhenium.
As preferably, described a) in the concentration of rehenic acid ammonium salt solution be 5g/L～10g/L.
As preferably, describedly a) in rehenic acid ammonium salt solution, add before ammoniacal liquor, in solution, add sodium chloride, ethane diacid tetraacethyl sodium.
As preferably, the mass ratio of described sodium chloride and rehenic acid ammonium is 1.5: 1～3: 1.
As preferably, the mass ratio of described ethane diacid tetraacethyl sodium and rehenic acid ammonium is 2: 1～4: 1.
As preferably, described b) in, to before adding tetraphenylarsonium chloride hydrochloride to react in the solution obtaining, by solution heating, temperature is below 50 ℃.
As preferably, the mass ratio of described tetraphenylarsonium chloride hydrochloride and rehenic acid ammonium is 1.8: 1～2.3: 1.
As preferably, described b) in, add after tetraphenylarsonium chloride hydrochloride, solution is heated to boiling.
While filtering as preferably, described c), to deposit repeatedly washing on a small quantity, the cleansing solution of use contains ammoniacal liquor and tetraphenylarsonium chloride hydrochloride.
As preferably, in described cleansing solution, the mass percent concentration of ammoniacal liquor is 4%～7%, and the mass percent concentration of tetraphenylarsonium chloride hydrochloride is 2%～5%.
The method of mensuration rhenium content provided by the invention adopts gravimetric method, the higher rehenic acid ammonium sample of energy Accurate Determining rhenium content, measurement range is 60.0%～69.0%, the accuracy of its mensuration and precision are all higher, and technological process is succinct, can be used for production run and control and finished product detection.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The invention provides a kind of method of measuring rhenium content in rehenic acid ammonium, comprise the following steps:
A) rehenic acid ammonium is water-soluble, the concentration of rehenic acid ammonium salt solution is preferably 5g/L～10g/L, because rehenic acid ammonium is slightly soluble in cold water, is very easily dissolved in hot water, while therefore dissolving rehenic acid ammonium, suitably heats, and without adding other lytic agent, avoids introducing other impurity and interference.
Then to adding in rehenic acid ammonium salt solution ammoniacal liquor to regulate pH value, be 11～12.For more favourable reaction environment is provided, preferably in rehenic acid ammonium salt solution, add before ammoniacal liquor, in solution, add sodium chloride (NaCl), ethane diacid tetraacethyl sodium (EDTA), the mass ratio of sodium chloride and rehenic acid ammonium can be 1.5: 1～and 3: 1, the mass ratio of ethane diacid tetraacethyl sodium and rehenic acid ammonium can be 2: 1～and 4: 1.
B) in the solution obtaining, add precipitation agent tetraphenylarsonium chloride hydrochloride to react, generate deposit, the mass ratio of tetraphenylarsonium chloride hydrochloride and rehenic acid ammonium is 1.8: 1～2.3: 1, preferably before adding tetraphenylarsonium chloride hydrochloride, solution is suitably heated, excess Temperature can make a large amount of ammonias overflow, and therefore preferably temperature is below 50 ℃.
Add after tetraphenylarsonium chloride hydrochloride, solution can be heated to boiling, be conducive to form the associated matter that surface area is larger.
C) reaction finishes postprecipitation, filtration, by drying precipitate.During filtration, should adopt the funnel that is dried to constant weight, as 5 flint glass F sand core funnels, during filtration, to deposit, should repeatedly wash on a small quantity, the cleansing solution of use preferably contains ammoniacal liquor and tetraphenylarsonium chloride hydrochloride, can prevent precipitation redissolution.The mass percent concentration of ammoniacal liquor can be 4%～7%, and the mass percent concentration of tetraphenylarsonium chloride hydrochloride can be 2%～5%.
Can use oven drying sediment, bake out temperature can be 105 ℃～110 ℃, precipitation should be dried to constant weight, is convenient to follow-up weighing.
According to formula (1), calculate the massfraction of rhenium:
W ( Re ) = ( m 2 - m 1 ) × 0.2941 m 0 × 100 · · · ( 1 )
In formula:
The massfraction of rhenium in W (Re)-rehenic acid ammonium, numerical value represents with %;
M 0the quality of-rehenic acid ammonium, unit is gram (g);
M 1the quality of-glass sand core funnel, unit is gram (g);
M 2the quality of-glass sand core funnel and precipitation, unit is gram (g);
The conversion factor of 0.2941-precipitation to rhenium.
Embodiment 1:
A) 0.1502g rehenic acid ammonium is water-soluble, suitably heating adds 0.2348g NaCl, 0.5002gEDTA in solution, then adds ammoniacal liquor to regulate pH value.
B) solution is suitably heated to 35 ℃, then adds 0.2778g tetraphenylarsonium chloride hydrochloride to be heated to boiling and react, generate deposit.
C) reaction finishes postprecipitation, filtration, and drying precipitate is weighed to constant weight.
Embodiment 2:
A) 0.1499g rehenic acid ammonium is water-soluble, suitably heating adds 0.2855g NaCl, 0.5534gEDTA in solution, then adds ammoniacal liquor to regulate pH value.
B) solution is suitably heated to 40 ℃, then adds 0.2878g tetraphenylarsonium chloride hydrochloride to be heated to boiling and react, generate deposit.
C) reaction finishes postprecipitation, filtration, and drying precipitate is weighed to constant weight.
Embodiment 3:
A) 0.1500g rehenic acid ammonium is water-soluble, suitably heating adds 0.4431g NaCl, 0.3746gEDTA in solution, then adds ammoniacal liquor to regulate pH value.
B) solution is suitably heated to 30 ℃, then adds 0.3240g tetraphenylarsonium chloride hydrochloride to be heated to boiling and react, generate deposit.
C) reaction finishes postprecipitation, filtration, and drying precipitate is weighed to constant weight.
Embodiment 4:
A) 0.1503g rehenic acid ammonium is water-soluble, suitably heating adds 0.3165g NaCl, 0.4321gEDTA in solution, then adds ammoniacal liquor to regulate pH value.
B) solution is suitably heated to 35 ℃, then adds 0.3040g tetraphenylarsonium chloride hydrochloride to be heated to boiling and react, generate deposit.
C) reaction finishes postprecipitation, filtration, and drying precipitate is weighed to constant weight.
Embodiment 5:
A) 0.1501g rehenic acid ammonium is water-soluble, suitably heating adds 0.3875g NaCl, 0.3437gEDTA in solution, then adds ammoniacal liquor to regulate pH value.
B) solution is suitably heated to 45 ℃, then adds 0.3327g tetraphenylarsonium chloride hydrochloride to be heated to boiling and react, generate deposit.
C) reaction finishes postprecipitation, filtration, and drying precipitate is weighed to constant weight.
Embodiment 1-5 adopts gravimetric method of the present invention to carry out 5 replicate determinations to the content of rhenium in same rehenic acid ammonium sample, and it the results are shown in Table 1.As can be known from the results of Table 1, the present invention adopt gravimetric method substantially can Accurate Determining rehenic acid ammonium in the content of rhenium, its mean relative deviation (RSD) is 0.021%, illustrates that the precision of this determination method is high.The present invention to the measurement range of the content of rhenium in rehenic acid ammonium is: 60.0%～69.0%.
Table 1 degree of accuracy measurement result
Five samples are carried out respectively to mark-on and reclaim mensuration, be that identical sample is got two parts, a copy of it adds quantitative pure rhenium powder (ingredient standard substance to be measured), two parts simultaneously by gravimetric determination rhenium content provided by the invention (adopting identical analytical procedure), the result that adds a gained of target deducts the not result of a gained of mark-on, and its difference is with adding the ratio of the theoretical value of the pure rhenium powder of standard substance to be sample recovery of standard addition.The recovery of standard addition of measuring is as shown in table 2, in five duplicate samples, add respectively high-purity rhenium powder each 0.0500,0.1000,0.1300g, to it, adopt gravimetric method of the present invention to carry out mark-on and reclaim and measure, find that its recovery is higher.Illustrate that gravimetric method that the present invention adopts records the accuracy of rhenium content in rehenic acid ammonium higher.
Table 2 mark-on reclaims the data statistics of measuring
Above a kind of method of measuring rhenium content in rehenic acid ammonium provided by the present invention is described in detail.Applied specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.

Claims (6)

1. a method of measuring rhenium content in rehenic acid ammonium, is characterized in that, comprises the following steps:
A) rehenic acid ammonium is water-soluble, add sodium chloride and EDTA, to adding in rehenic acid ammonium salt solution ammoniacal liquor to regulate pH value, be 11～12;
B) in the solution obtaining, add tetraphenylarsonium chloride hydrochloride to react;
C) reaction finishes postprecipitation, filtration, by drying precipitate;
The mass ratio of described sodium chloride and rehenic acid ammonium is 1.5:1～3:1;
The mass ratio of described EDTA and rehenic acid ammonium is 2:1～4:1;
Described a) the concentration of middle rehenic acid ammonium salt solution is 5g/L～10g/L;
According to formula (1), calculate the massfraction of rhenium:
W ( Re ) = ( m 2 - m 1 ) × 0.2941 m 0 × 100 . . . ( 1 )
In formula:
The massfraction of rhenium in W (Re)-rehenic acid ammonium, numerical value represents with %;
M 0the quality of-rehenic acid ammonium, unit is gram (g);
M 1the quality of-glass sand core funnel, unit is gram (g);
M 2the quality of-glass sand core funnel and precipitation, unit is gram (g);
The conversion factor of 0.2941-precipitation to rhenium.
2. method according to claim 1, is characterized in that, described b) in to before adding tetraphenylarsonium chloride hydrochloride to react in the solution obtaining, by solution heating, temperature is below 50 ℃.
3. method according to claim 1, is characterized in that, described tetraphenylarsonium chloride hydrochloride and rehenic acid ammonium mass ratio are 1.8:1～2.3:1.
4. according to the method described in claim 1 or 3, it is characterized in that described b) in add after tetraphenylarsonium chloride hydrochloride, by solution be heated to boiling.
5. method according to claim 1, is characterized in that, described c) in while filtering to deposit repeatedly washing on a small quantity, the cleansing solution of use contains ammoniacal liquor and tetraphenylarsonium chloride hydrochloride.
6. method according to claim 5, is characterized in that, in described cleansing solution, the mass percent concentration of ammoniacal liquor is 4%～7%, and the mass percent concentration of tetraphenylarsonium chloride hydrochloride is 2%～5%.
CN201210150425.1A 2012-05-15 2012-05-15 Method for measuring rhenium content in ammonium rhenate Expired - Fee Related CN102661907B (en)

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CN103725885B (en) * 2012-10-10 2016-07-06 湖南中铼工业科技有限公司 The method of tungsten-rhenium alloy leftover pieces and waste recovery recycling
CN105372197A (en) * 2015-12-23 2016-03-02 福州大学 Spectrophotometric method for measuring concentration of perrhenate in aqueous solution simply and conveniently
CN105758853A (en) * 2016-03-30 2016-07-13 商洛学院 Method for detecting content of rhenium in rhenium containing test solution
CN106093014B (en) * 2016-08-22 2019-08-20 金堆城钼业股份有限公司 The method that inductively coupled plasma spectrometry method quickly measures rhenium content in rehenic acid ammonium
CN111351832B (en) * 2020-04-01 2022-03-11 中国原子能科学研究院 Nuclear material tracing method

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