CN109633079A - A method of vanadium and ammonium content in detection metavanadate solution - Google Patents
A method of vanadium and ammonium content in detection metavanadate solution Download PDFInfo
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- CN109633079A CN109633079A CN201811609656.8A CN201811609656A CN109633079A CN 109633079 A CN109633079 A CN 109633079A CN 201811609656 A CN201811609656 A CN 201811609656A CN 109633079 A CN109633079 A CN 109633079A
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- 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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Abstract
The present invention provides a kind of method for detecting vanadium and ammonium content in metavanadate solution, comprising the following steps: is dashed forward more with standard solution of sodium hydroxide titration solution to be measured to first, records consumed standard solution of sodium hydroxide volume V1；Hydrogen peroxide is added into solution to be measured, is dashed forward more with standard solution of sodium hydroxide titration solution to be measured to second, records consumed standard solution of sodium hydroxide volume V2；PH value of solution to be measured is adjusted, and solution to be measured is titrated with standard solution of sodium hydroxide and is got over to third is prominent, records consumed standard solution of sodium hydroxide volume V3；The calculation formula of the concentration of metavanadic acid root, ammonium root concentration and total V density is as follows in solution to be measured: concentration=V of metavanadic acid root2×CNaOH；Ammonium root concentration=(V1‑V2)×CNaOH；Total V density=(V3+V2‑V1)×CNaOH.The present invention can fast and accurately realize the detection of vanadium and ammonium content.
Description
Technical field
The present invention relates to the hydrometallurgy of vanadium, the detection technique of chemical field more particularly to a kind of detection metavanadate are molten
The method of vanadium and ammonium content in liquid.
Background technique
Currently, in solution there are many measuring methods of ammonium content, including titration (arbitration law) after distillation, formaldehyde method, receive
Family name's reagent spectrophotometry, the chromatography of ions, fluorescence spectrophotometric method, capillary electrophoresis etc..Titration after wherein distilling,
It is complex for operation step, time-consuming, and distillation speed and distillation amount can impact testing result, it is necessary to it is controlled.Distillation
Excessive velocities will lead to the ammonia distilled out and absorb and overflow not in time；Distillation amount increases in receiving bottle, leads to pH value of solution liter
Height necessarily causes titration error.Formaldehyde method titration end-point is unstable, and accuracy is poor.Simultaneously its agents useful for same formaldehyde to skin,
Eyes, respiratory tract have certain toxicity, damage, should not use to operator；Berthelot spectrophotometry, ion color
Spectrometry, fluorescence spectrophotometric method, Capillary Electrophoresis rule are mainly used for surface water, underground water, sanitary sewage and industrial wastewater
In micro ammonium content detection, wherein most commonly seen with Berthelot spectrophotometry, but nessler reagent preparation method is more multiple
It is miscellaneous, and contain noxious material, it pollutes the environment, meanwhile, color, turbidity, sulfide, organic matter of solution etc. can interfere survey
It is fixed, it is necessary to be pre-processed, cumbersome complexity.
The measuring method of content of vanadium mainly has BPHA extraction spectrophotometric method, hydrogen peroxide colorimetric method, atom to inhale in solution
Receive spectroscopic methodology, inductive coupling plasma emission spectrum method (ICP-AES) etc..BPHA extraction spectrophotometric method is content of vanadium in water body
The standard method of measurement, but it is complex for operation step, it takes a long time, and use organic media chloroform, harm to the human body is larger.
Hydrogen peroxide colorimetric method is easy to operate, quick, but must be strictly controlled the additional amount of sulfuric acid and hydrogen peroxide.Excessive peroxidating
Hydrogen can make the sulfuric acid generated cross vanadyl and be changed into the positive pervanadic acid of yellow and influence colorimetric.Atomic absorption spectrography (AAS) and ICP-AES
Method detection sensitivity is higher, strong antijamming capability, but expensive equipment needed for detecting, regular job are costly with maintenance.
And in national standard and metallurgical standard, content of vanadium measuring method is mainly that potassium permanganate (or ammonium persulfate) oxidation-sulfuric acid is sub-
Iron ammonium titration, this method are classical chemical analysis methods, can be used for the links of production process control.But the inspection
Journey is complicated, and more demanding to reviewer, each reagent dosage can impact testing result, cause deviation.
In the solution, pentavalent vanadium mainly exists in the form of metavanadic acid root, pyrovanadium acid group, positive vanadic acid root, with sodium hydroxide
Sodium metavanadate solution is titrated, when vanadium is converted to pyrovanadium acid group, a current potential occurs and dashes forward more, inclined vanadium in the calculating solution that can be quantified
The concentration of acid group.The drop reaction of ammonium root and sodium hydroxide is similar, and titration end-point the prominent of a current potential occurs and gets over, Ke Yili
It is dashed forward with this and more carries out ammonium root test.But when not only containing ammonium in solution, but also containing vanadium, titrate with alkali directly cannot distinguish the two.
Summary of the invention
It is an object of the present invention to can not effectively detect vanadium and ammonium for the metavanadic acid solution at present simultaneously containing vanadium and ammonium
The problem of content, proposes a kind of method for detecting vanadium and ammonium content in metavanadate solution, can fast and accurately realize vanadium and ammonium
The detection of content.
To achieve the above object, the technical solution adopted by the present invention is that: vanadium and ammonium contain in a kind of detection metavanadate solution
The method of amount, comprising the following steps:
Step 1 is dashed forward more with standard solution of sodium hydroxide titration solution to be measured to first, and it is molten to record consumed sodium hydroxide standard
Liquid accumulates V1；
Step 2, into the solution to be measured that step 1 obtains, addition hydrogen peroxide is uniformly mixed, and is dripped with standard solution of sodium hydroxide
Fixed solution to be measured is dashed forward to second to be got over, and consumed standard solution of sodium hydroxide volume V2 is recorded；
The pH value of solution to be measured that step 3, set-up procedure 2 obtain, and solution to be measured is titrated to the with standard solution of sodium hydroxide
Three dash forward more, record consumed standard solution of sodium hydroxide volume V3；
The concentration, ammonium root concentration of metavanadic acid root and the calculation formula of total V density are as follows in step 4, solution to be measured:
Concentration=V of metavanadic acid root2×CNaOH
Ammonium root concentration=(V1-V2)×CNaOH；
Total V density=(V3+V2-V1)×CNaOH
Wherein CNaOHFor the concentration (molar concentration) of standard solution of sodium hydroxide.
Further, the addition volume of hydrogen peroxide described in step 2 and the volume ratio of solution to be measured are 0.05-50, preferably
5-20。
Further, the standard solution of sodium hydroxide degree is 0.1-1.0mol/L, preferably 0.2-0.8mol/L.
Further, adjustment pH value of solution to be measured described in step 3, the range of pH is 6.5-7.5.
Further, pH value of solution to be measured is adjusted using sulfuric acid or hydrochloric acid in step 3.
Further, content of vanadium is 1-50g/L in the solution to be measured；Ammonium content is 1-40g/L.
Further, when content of vanadium is greater than 6g/L, ammonium content is greater than 3g/L in solution to be measured, with sodium hydroxide standard
Before solution titration solution to be measured is dashed forward more to first, it is diluted with water solution to be measured, the volume ratio of solution and water to be measured is 1-10:40-
200.When being detected using potentiometric titration, titration unit has fixed volume, and the consumption of titrating solution is preferably titrated at one
It is completed in unit volume, to reduce detection error.
The present invention detects the principle of the method for vanadium and ammonium content in metavanadate solution:
The existence of pentavalent vanadium in the solution and pH value of solution and vanadium concentration are closely related, lower molten in acid and concentration
In liquid, vanadium assembles synthetic macromolecule ion, such as (V10O28) 6-, vanadium carries unionized hydrogen and forms (HV in acidity10O28)5-, dissociate
Hydrogen ion and unionized hydrogen ion and sodium hydroxide react that there are sequencings.In alkali in these polymeric form vanadium ion short time
Be in property solution it is stable, when titrating ammonium, vanadium ion is stable not react with hydroxyl.In addition, unionized hydrogen ion with
The combination ratio of vanadium, is influenced by acid group type, is influenced by ammonium, when in solution there are when ammonium, the combination ratio of hydrogen and vanadic acid root
Example is not influenced by acid group form.
The detection of sodium hydroxide titration measurement ammonium root is that accurately and rapidly method (such as measures the ammonium in ammonium sulfate
Root), but when in solution there are when vanadium, due to, there is also reacting, consuming volume, and vanadic acid root between vanadic acid root and sodium hydroxide
Existence form it is changeable, can not Accurate Determining ammonium content (such as the sodium metavanadate solution containing ammonium, knot if direct titration
Fruit is influenced by initial pH, can not Accurate Determining ammonium content).By being acidified first, the existence form of fixed vanadium, then titrate ammonium
Root can accurately obtain result.
Using the present invention detection metavanadate solution in vanadium and ammonium content method, can successively titrate measure free hydrogen from
The concentration of sub, unionized hydrogen ion, ammonium ion.As shown in figure 3, there are the prominent more point of three titration on titration curve, it is right respectively
Answer the reaction end (first prominent more) of free acid and sodium hydroxide, the hydrogen ion closed with vanadic acid root knot and sodium hydroxide react whole
Point (second dashes forward more), the reaction end of ammonium root and sodium hydroxide (third is prominent more).
When detecting content of vanadium, the volume dashed forward between more using first, second is consumed, and vanadium concentration is calculated, in order to eliminate possibility
Acid influence, the fixed hydrogen of ammonium root and vanadic acid root is added in unified calculation, and eliminate the influence of ammonium that may be present in solution
In conjunction with ratio；For the known solution without ammonium and anion species, it can be added without ammonium salt, directly titrated, according to
The combination ratio of the hydrogen ion and vanadic acid root known calculates and obtains vanadium concentration；
When detecting ammonium content, the existence form for being acidified fixed vanadium, second, third volume consumption between more of dashing forward, meter are utilized
Calculate ammonium root concentration.
The method of vanadium and ammonium content, has following compared with prior art in a kind of detection metavanadate solution of the present invention
Advantage:
1) present invention utilizes the complex reaction of hydrogen peroxide and metavanadic acid root, and quantitative releases hydrogen ion, then uses hydroxide
Sodium titration, the concentration for calculating vanadium that can be quantified.
2) be added hydrogen peroxide after, metavanadic acid root is converted to peroxide vanadic acid root, no longer with hydroxyl ining conjunction with, be changed to free hydrogen and
The reaction of sodium hydroxide, reaction end are neutrality, are separated with the alkaline reaction of ammonium root, so as to realize both vanadium and ammonium
Stepwise titration test.
3) method that the present invention detects vanadium and ammonium content in metavanadate solution, quickly, accurately, with traditional redox
Titration is compared, at low cost without using reagents such as potassium permanganate, urea, sodium nitrites, and titrating solution can directly return to the life of vanadium
Producing line, it is pollution-free.
Detailed description of the invention
Fig. 1 is the titration curve of embodiment 1；
Fig. 2 is the titration curve of embodiment 3；
Fig. 3 is the titration curve of embodiment 4.
Specific embodiment
The present invention is further described with reference to embodiments:
Embodiment 1
Present embodiment discloses a kind of methods of vanadium and ammonium content in detection metavanadate solution, the specific steps are as follows:
It takes without NH4 +Solution example A 2.00mL, add water to 150mL, be diluted with water convenient for stirring andpHDetection, solution
The main component of sample A is sodium sulphate and sodium metavanadate, using plum Teller-support benefit T50 potentiometric titrimeter, pH electrode, with
The sodium hydroxide solution of 0.5165mol/L carries out single dash forward as standard titration solution and more titrates, quota of expenditure titration solution volume
The metavanadic acid root concentration of solution can be calculated in 4.423mL, (titration curve is as shown in Figure 1) are as follows:
Wherein V is the volume of sample to be tested A.
Titration curve is as shown in Figure 1, have one to dash forward more, representative is turned with sodium hydroxide titration sodium metavanadate solution, vanadium in figure
Be melted into pyrovanadium acid group when it is prominent more.
Embodiment 2
Present embodiment discloses a kind of methods of vanadium and ammonium content in detection metavanadate solution, the specific steps are as follows:
It takes without NH4 +Solution example B 2.00mL, solution example B main component be sodium sulphate and sodium metavanadate, add
Water is to 150mL, and using plum Teller-support benefit T50 potentiometric titrimeter, pH electrode is made with the sodium hydroxide solution of 0.5165mol/L
It carries out single dash forward for standard titration solution more to titrate, the inclined vanadium of solution can be calculated in quota of expenditure titration solution volume 7.531mL
Acid group concentration are as follows:
Wherein V is the volume of sample to be tested B.
Embodiment 3
Present embodiment discloses a kind of methods of vanadium and ammonium content in detection metavanadate solution, the specific steps are as follows:
It takes containing NH4 +Solution example C (main ingredient is sulfuric acid and ammonium sulfate) 2.00mL, adds water to 150mL, uses Mei Te
Le-support benefit T50 potentiometric titrimeter 0.5165mol/L sodium hydroxide solution carries out double dash forward as standard titration solution and more drips
Fixed, quota of expenditure titration solution volume is respectively VEQ1=4.883mL, VEQ2=4.732mL, (titration curve is as shown in Figure 2)
The free H of solution can be calculated+And NH4 +Concentration are as follows:
Wherein V is the volume of sample to be tested C.
Titration curve is dashed forward more as shown in Fig. 2, sharing 2 in figure, and first prominent NaOH is reacted with free hydrogen, and second
A prominent NH4 +With reacting for NaOH.
Embodiment 4
Present embodiment discloses a kind of methods of vanadium and ammonium content in detection metavanadate solution, the specific steps are as follows:
It takes containing NH4 +(main ingredient is containing NH to solution example D4 +Metavanadate) 5.00mL, 150mL is added water to, with hydroxide
Sodium standard solution titration solution to be measured is dashed forward to first to be got over, and consumed standard solution of sodium hydroxide volume V1 is recorded；It is bis- that 5.00mL is added
Oxygen water is uniformly mixed, and is dashed forward more with standard solution of sodium hydroxide titration solution to be measured to second, it is molten to record consumed sodium hydroxide standard
Liquid accumulates V2；Sulfuric acid is added and adjusts pH value of solution to be measured to 6.5-7.5, and solution to be measured is titrated to the with standard solution of sodium hydroxide
Three dash forward more, record consumed standard solution of sodium hydroxide volume V3；Quota of expenditure titration solution volume is respectively VEQ1=
7.340mL, VEQ2=3.252mL, VEQ3=8.103mL, (titration curve is as shown in Figure 3) can be calculated in solution to be measured partially
Concentration, ammonium root concentration and the total V density of vanadic acid root are as follows:
Wherein V is the volume of sample to be tested D.
Titration curve is dashed forward more as shown in figure 3, sharing 3 in figure, and first prominent free hydrogen ion is reacted with NaOH's,
The reacting of second prominent unionized hydrogen ion and NaOH, the prominent ammonium ion of third is reacted with NaOH's.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (7)
1. a kind of method of vanadium and ammonium content in detection metavanadate solution, which comprises the following steps:
Step 1 is dashed forward more with standard solution of sodium hydroxide titration solution to be measured to first, records consumed standard solution of sodium hydroxide body
Product V1；
Hydrogen peroxide is added into the solution to be measured that step 1 obtains in step 2, titrates solution to be measured extremely with standard solution of sodium hydroxide
Second dashes forward more, records consumed standard solution of sodium hydroxide volume V2；
The pH value of solution to be measured that step 3, set-up procedure 2 obtain, and solution to be measured to third is titrated with standard solution of sodium hydroxide and is dashed forward
More, consumed standard solution of sodium hydroxide volume V3 is recorded；
The concentration, ammonium root concentration of metavanadic acid root and the calculation formula of total V density are as follows in step 4, solution to be measured:
Concentration=V of metavanadic acid root2×CNaOH
Ammonium root concentration=(V1-V2)×CNaOH；
Total V density=(V3+V2-V1)×CNaOH
Wherein CNaOHFor the concentration of standard solution of sodium hydroxide.
2. detecting the method for vanadium and ammonium content in metavanadate solution according to claim 1, which is characterized in that step 2 institute
The volume ratio of the addition volume and solution to be measured of stating hydrogen peroxide is 0.05-50.
3. detecting the method for vanadium and ammonium content in metavanadate solution according to claim 1, which is characterized in that the hydrogen-oxygen
Change sodium standard solution degree is 0.1-1.0mol/L.
4. detecting the method for vanadium and ammonium content in metavanadate solution according to claim 1, which is characterized in that step 3 institute
Adjustment pH value of solution to be measured is stated, the range of pH is 6.5-7.5.
5. detecting the method for vanadium and ammonium content in metavanadate solution according to claim 1, which is characterized in that in step 3
PH value of solution to be measured is adjusted using sulfuric acid or hydrochloric acid.
6. detecting the method for vanadium and ammonium content in metavanadate solution according to claim 1, which is characterized in that described to be measured
Content of vanadium is 1-50g/L in solution；Ammonium content is 1-40g/L.
7. detecting the method for vanadium and ammonium content in metavanadate solution according to claim 1, which is characterized in that when to be measured molten
When content of vanadium is greater than 6g/L in liquid, ammonium content is greater than 3g/L, dash forward with standard solution of sodium hydroxide titration solution to be measured to first
Before more, it is diluted with water solution to be measured, the volume ratio of solution and water to be measured is 1-10:40-200.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112180029A (en) * | 2020-09-17 | 2021-01-05 | 大连博融新材料有限公司 | Method for detecting ammonium content in metal ammonium salt |
| CN114354838A (en) * | 2021-12-15 | 2022-04-15 | 中国科学院大连化学物理研究所 | Method for measuring concentration of iron and vanadium ions in mixed solution |
| CN117269415A (en) * | 2023-11-17 | 2023-12-22 | 江苏艾科维科技股份有限公司 | Method for simultaneously measuring content of free acid, hydroxylamine and ammonium salt by potentiometric method |
| CN118032690A (en) * | 2024-03-20 | 2024-05-14 | 液流储能科技有限公司 | Method for measuring concentration of ammonium ions in electrolyte |
-
2018
- 2018-12-27 CN CN201811609656.8A patent/CN109633079A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112180029A (en) * | 2020-09-17 | 2021-01-05 | 大连博融新材料有限公司 | Method for detecting ammonium content in metal ammonium salt |
| CN114354838A (en) * | 2021-12-15 | 2022-04-15 | 中国科学院大连化学物理研究所 | Method for measuring concentration of iron and vanadium ions in mixed solution |
| CN114354838B (en) * | 2021-12-15 | 2023-08-08 | 中国科学院大连化学物理研究所 | Method for measuring concentration of iron and vanadium ions in mixed solution |
| CN117269415A (en) * | 2023-11-17 | 2023-12-22 | 江苏艾科维科技股份有限公司 | Method for simultaneously measuring content of free acid, hydroxylamine and ammonium salt by potentiometric method |
| CN118032690A (en) * | 2024-03-20 | 2024-05-14 | 液流储能科技有限公司 | Method for measuring concentration of ammonium ions in electrolyte |
| CN118032690B (en) * | 2024-03-20 | 2024-08-09 | 液流储能科技有限公司 | Method for measuring concentration of ammonium ions in electrolyte |
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Application publication date: 20190416 |