CN101526514A - Determination method of COD value in glass raw material - Google Patents
Determination method of COD value in glass raw material Download PDFInfo
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- CN101526514A CN101526514A CN200910061652A CN200910061652A CN101526514A CN 101526514 A CN101526514 A CN 101526514A CN 200910061652 A CN200910061652 A CN 200910061652A CN 200910061652 A CN200910061652 A CN 200910061652A CN 101526514 A CN101526514 A CN 101526514A
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- frit
- ammonium sulfate
- iron ammonium
- nitration mixture
- cod
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Abstract
The invention provides a determination method of COD value in glass raw material. The method comprises the following steps of: heating the glass raw material in potassium dichromate and mixed acid (mixed acid for mineral raw materials is prepared by sulphuric acid and phosphoric acid according to volume ratio of 4:1 and mixed acid for chemical raw materials is prepared by sulphuric acid and phosphoric acid according to volume ratio of 6:1; boiling and back flowing for 28 to 32min and calculating the COD values of all the raw materials according to conversion formula through titration of standard solution of ferrous ammonium sulphate. Aiming at the problem of long back flow time, complex operation and large reagent consumption and the like of the potassium dichromate, the invention provides a method for fast measuring the COD values of all the raw materials in glass by using mixed acid process. According to measured result, the invention can adjust the proportion of materials in time and realize the application of clarification technology of reducing sulfur in the glass preparation.
Description
Technical field
The present invention relates to the field that frit is measured, be specifically related to the rapid assay methods of COD value in the frit.
Background technology
Glass ingredient control, granularity control and the control of COD value, be efficiently, the three elements of high-quality and low consumption fusion cast glass.In the glass smelting process, except that the clarificant saltcake, frit also can be brought reducing substances into, and often contain appreciable organism of quantity and oxidable inorganics in the frit, if this part reducing substances is not controlled, will be had influence on founding and clear quality of glass.In order to control the amount of this part reducing substances, can realize by the COD value of measuring frit.At present, for the mensuration of COD value in the frit, potassium dichromate method (seeing also the bioassay standard GB11914-1989 of hydrochemistry oxygen demand) commonly used, there are long, the problems such as reagent dosage is many, cost height of return time in this method.Therefore the method that needs the COD value of the easy quick and lower-cost mensuration frit of a kind of energy.
Summary of the invention
Technical matters to be solved by this invention is: provide the method for COD value in a kind of fast measuring frit, to overcome the problem that existing potassium dichromate method exists.
The present invention solves its technical matters by following technical scheme:
The present invention is to provide the nitration mixture method of COD value in a kind of fast measuring frit, this method may further comprise the steps:
(1) frit that takes by weighing is heated in potassium dichromate and nitration mixture, boiling reflux 28～32min, by the iron ammonium sulfate standard solution titration to terminal, institute's consumption is V
2, Unit; To raw mineral materials, nitration mixture is to be formed by sulfuric acid and by volume 4: 1 proportionings of phosphoric acid; To industrial chemicals, nitration mixture is formed by sulfuric acid and by volume 6: 1 proportionings of phosphoric acid.
Described frit is a kind of in silica sand, lime stone, feldspar, rauhkalk, soda ash and the saltcake, or multiple.Take by weighing the front glass raw material needs to get rid of the influence of moisture like this 100～108 ℃ of oven dry at every turn; Then the frit that is taken by weighing is heated in potassium dichromate and nitration mixture, and the fineness of this kind raw material must be consistent.The adding of each material must be pressed frit, HgSO
4, potassium dichromate standard solution, water, nitration mixture (adding the acid of phosphoric acid after vulcanization earlier) order add.
When boiling, return time must just pick up counting when frit comes to life, and prevents the sample bumping as far as possible.
(2) set by step (1) does blank test, to consume iron ammonium sulfate standard solution volume be V
1, Unit;
(3) accurately demarcate the concentration of l ferrous ammonium sulfate solution with the potassium dichromate standard solution, the consumption of iron ammonium sulfate is V
0, Unit;
(4) calculate the COD value of each batch then according to following reduction formula,
The calculating of iron ammonium sulfate standard titration solution concentration:
In the formula: V
0Be the concentration of iron ammonium sulfate standard solution, mL,
The COD value is represented with ppmC, is calculated as follows:
In the formula: C is the concentration of iron ammonium sulfate standard solution, mol/L; V
1Be the volume of the iron ammonium sulfate standard titration solution that blank assay consumed, mL; V
2The volume of the iron ammonium sulfate standard titration solution that measure to consume for frit, mL; M is the quality of frit, g;
3000 by
Molal weight be the scaled value of unit with g/mol.
The present invention can realize COD value in the frit is carried out fast measuring by above-mentioned steps.
The present invention compares with potassium dichromate method has following innovative point:
One. utilize mixed acid process to measure COD value in the frit, have very high precision.
They are two years old. and fast: shortened return time greatly, being refluxed by 2 hours of potassium dichromate method is reduced to backflow in 30 minutes.
They are three years old. and cost reduces: reagent dosage is few, has avoided simultaneously using valuable reagent such as silver sulfate, and it is about 20% that testing cost is reduced, and reduces environmental pollution.
In a word, the present invention has overcome the problem that existing potassium dichromate method exists, and for realizing that the application of reducible sulfur clarification technique in glass preparation provides scientific basis.
Embodiment
The invention will be further described below by embodiment, but do not limit the present invention.
Embodiment 1: industrial chemicals nitration mixture determination of ratio
Take by weighing the soda ash 2.0000g that is ground to certain particle size, the HgSO of 0.1g
4, add successively in the conical flask of 250mL, accurately add 10mL potassium dichromate standard solution again, add 20mL distilled water, shake up, load onto reflux condensing tube, add the 30mL nitration mixture from the condenser pipe upper end, heating (the electrothermal furnace temperature is set to 270 ℃), and keep boiling 30min, use 80mL distilled water flushing condenser pipe again after, take off the cooling back and add 3 1.10-phenanthroline indicators, to bronzing, be terminal point with the iron ammonium sulfate standard solution titration.Do blank test and parallel experiment by same operation steps.
By many tests, for example V
H2SO4: V
H3PO4=2: 1,3: 1,4: 1,5: 1,6: 1,7: 1, determined that just the optimal proportion of sulfuric acid and phosphoric acid is 6: 1 (seeing Table 3) in the nitration mixture.
Accurately demarcate the concentration of l ferrous ammonium sulfate solution with the potassium dichromate standard solution: get the 10.00mL potassium bichromate solution and place conical flask, with distilled water diluting to 100mL, add 30mL sulfuric acid, mix, after the cooling, add 3 1.10-phenanthroline indicators, become bronzing by yellow through blue-green, be terminal point with the color of iron ammonium sulfate volumetric soiutions.Note the consumption V of iron ammonium sulfate
0(mL).
Embodiment 2: raw mineral materials nitration mixture determination of ratio
Change the soda ash in the example 1 into the raw mineral materials lime stone, adopt identical method to measure the COD value of lime stone raw material.
The experimental data that records utilizes above-mentioned formula to calculate COD value such as table 3.By measured result as can be seen: to lime stone class raw mineral materials, the best proportioning of nitration mixture is 4: 1.
Embodiment 3: the raw mineral materials digestion time determines in the mixed acid process
According to the best nitration mixture ratio of example 2 determined raw mineral materials (V
H2SO4: V
H3PO4=4: 1), change return time, be followed successively by 15min, 30min, 60min, 120min, utilize mixed acid process that the COD value of lime stone is analyzed, the results are shown in Table 1.Can find out that by measurement result when digestion time was 30min, its result tended towards stability, so return time is chosen as 30min.
Embodiment 4: the determining of mixed acid process digestion time
The best nitration mixture of determining according to example 1 of industrial chemicals is than (V
H2SO4: V
H3PO4=6: 1), change return time, be followed successively by 5min, 10min, 15min, 30min, adopt mixed acid process that the COD value of soda ash is analyzed (seeing Table 1).Can find out that by measurement result when digestion time was 10～15min, its measured value tended towards stability substantially, but, reduce the complicacy of experimental implementation, therefore the return time unification is 30min in order to unify with the raw mineral materials digestion time.
Embodiment 5: the COD pH-value determination pH of frit
By embodiment 1～example 4 determined nitration mixture ratio and backflow digestion times, utilize mixed acid process that the COD value of each raw material of glass (silica sand, lime stone, feldspar, rauhkalk, soda ash, saltcake) is measured, it the results are shown in Table 2.
Subordinate list
The COD value of the lime stone of the different digestion times of table 1 or soda ash
The COD value of each batching of table 2 glass
The soda ash of the different nitration mixture ratios of table 3, the COD value of lime stone
Claims (5)
1. the assay method of COD in the frit is characterized in that the nitration mixture method of COD value in a kind of fast measuring frit, and this method may further comprise the steps:
(1) frit that takes by weighing is heated in potassium dichromate and nitration mixture, boiling reflux 28～32min, by the iron ammonium sulfate standard solution titration to terminal, institute's consumption is V
2, Unit; To raw mineral materials, nitration mixture is to be formed by sulfuric acid and by volume 4: 1 proportionings of phosphoric acid; To industrial chemicals, nitration mixture is formed by sulfuric acid and by volume 6: 1 proportionings of phosphoric acid;
(2) set by step (1) does blank test, to consume iron ammonium sulfate standard solution volume be V
1, Unit;
(3) accurately demarcate the concentration of l ferrous ammonium sulfate solution with the potassium dichromate standard solution, the consumption of iron ammonium sulfate is V
0, Unit;
(4) calculate the COD value of each material in the frit then according to following reduction formula,
The calculating of iron ammonium sulfate standard titration solution concentration:
In the formula: V
0Be the concentration of iron ammonium sulfate standard solution, mL,
The COD value is represented with ppmC, is calculated as follows:
In the formula: C is the concentration of iron ammonium sulfate standard solution, mol/L; V
1Be the volume of the iron ammonium sulfate standard titration solution that blank assay consumed, mL; V
2The volume of the iron ammonium sulfate standard titration solution that measure to consume for frit, mL; M is the quality of frit, g,
3000 by
Molal weight be the scaled value of unit with g/mol.
2. method according to claim 1 is characterized in that: take by weighing the front glass raw material needs 100～108 ℃ of oven dry at every turn, and the fineness of this kind raw material must be consistent.
3. method according to claim 1 and 2 is characterized in that: described frit is a kind of in silica sand, lime stone, feldspar, rauhkalk, soda ash and the saltcake, or multiple.
4. method according to claim 1 is characterized in that the adding of each material must add in the following order: frit, HgSO
4, potassium dichromate standard solution, water, nitration mixture; Should add phosphoric acid when adding nitration mixture earlier and add sulfuric acid again.
5. method according to claim 1 is characterized in that: the boiling reflux time must just pick up counting when frit comes to life, and prevents the sample bumping as far as possible.
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| CN200910061652A CN101526514A (en) | 2009-04-17 | 2009-04-17 | Determination method of COD value in glass raw material |
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|---|---|---|---|
| CN200910061652A CN101526514A (en) | 2009-04-17 | 2009-04-17 | Determination method of COD value in glass raw material |
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ID=41094490
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102628850A (en) * | 2012-03-31 | 2012-08-08 | 武汉钢铁(集团)公司 | Method for quickly calibrating concentration of potassium dichromate standard titration solution |
| CN105259172A (en) * | 2014-06-11 | 2016-01-20 | 天津市茂联科技有限公司 | Detection method for ferrous chloride in strong acid high cobalt solution |
| CN110221020A (en) * | 2019-07-04 | 2019-09-10 | 施国栋 | A kind of COD detection device and method |
| CN112485250A (en) * | 2020-10-22 | 2021-03-12 | 飞鸣科学仪器（武汉）有限公司 | Detection reagent for detecting COD content of wastewater based on potassium dichromate method and preparation process thereof |
-
2009
- 2009-04-17 CN CN200910061652A patent/CN101526514A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102628850A (en) * | 2012-03-31 | 2012-08-08 | 武汉钢铁(集团)公司 | Method for quickly calibrating concentration of potassium dichromate standard titration solution |
| CN102628850B (en) * | 2012-03-31 | 2015-07-01 | 武汉钢铁(集团)公司 | Method for quickly calibrating concentration of potassium dichromate standard titration solution |
| CN105259172A (en) * | 2014-06-11 | 2016-01-20 | 天津市茂联科技有限公司 | Detection method for ferrous chloride in strong acid high cobalt solution |
| CN110221020A (en) * | 2019-07-04 | 2019-09-10 | 施国栋 | A kind of COD detection device and method |
| CN112485250A (en) * | 2020-10-22 | 2021-03-12 | 飞鸣科学仪器（武汉）有限公司 | Detection reagent for detecting COD content of wastewater based on potassium dichromate method and preparation process thereof |
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Open date: 20090909 |