CN112945880A - Method for rapidly detecting total chromium content of raw material for cement production - Google Patents
Method for rapidly detecting total chromium content of raw material for cement production Download PDFInfo
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Abstract
The invention discloses a method for rapidly detecting the total chromium content of a raw material for cement production, which is realized by the steps of sample dissolution, solution oxidation treatment, color reaction, absorbance measurement, total chromium content calculation and the like. Compared with the hydrofluoric acid-perchloric acid low-temperature heating treatment in the prior art, the method has the advantages of shorter time consumption and more thorough treatment.
Description
Technical Field
The invention relates to the technical field of cement quality detection, in particular to a method for quickly detecting the total chromium content of a raw material for cement production.
Background
According to GB 31893-2015 Limit and determination method of water-soluble chromium (VI) in cement, the content of the water-soluble chromium (VI) in the cement is required to be not more than 10.00 mg/kg. According to the cement production process, the water-soluble chromium (VI) in the cement is basically introduced into clinker and mixed materials. Therefore, the water-soluble chromium (vi) of the clinker and the admixture must be accurately detected and controlled. For the mixed material for cement production, the detection method of the water-soluble chromium can directly refer to the determination method of the water-soluble chromium (VI) in the cement for detection, and is simple and convenient; for the water-soluble chromium in the clinker, the main sources of the water-soluble chromium in the clinker are raw materials and refractory materials, and at present, all enterprises of the refractory materials basically adopt chromium-free refractory materials, so that the control of the content of the chromium in the raw materials is the key for controlling the content of the chromium in the cement clinker. In the production process of clinker, raw materials can undergo a series of complex chemical reactions such as high-temperature calcination and the like, and most of total chromium finally generates water-soluble chromium after the clinker or cement is hydrated. Therefore, the total chromium content of the raw materials must be detected, and the raw materials with low total chromium content can be selected during production to ensure that the water-soluble chromium (VI) content in the cement and the clinker meets the national standard requirement.
At present, the detection methods of the total chromium content in the raw materials for cement are roughly two types: the first is ICP method: decomposing a sample by hydrofluoric acid-perchloric acid, leaching by hydrochloric acid, detecting the solution by ICP-OES, emitting characteristic spectra when atoms of different elements are excited or ionized, and respectively measuring the emission spectrum intensity of the elements to be measured; the intensity of the characteristic spectrum is related to the atomic concentration in the sample, and the content of the chromium element in the sample is quantitatively determined by comparing the intensity of the element spectrum corresponding to the standard solution; secondly, X-ray fluorescence analysis and detection method: firstly, grinding a sample to a proper fineness, pressing a powder sample into a sample sheet with certain strength, smooth analysis surface and no obvious crack and other defects under a certain pressure condition, then measuring the strength of the characteristic X-ray of the element to be detected of the sample sheet by using an X-ray fluorescence analyzer, analyzing according to a calibration curve or a correction equation, and calculating the content of the component to be detected.
Both methods need to purchase expensive instruments and equipment, have high requirements on competence and literacy of detection personnel, and are not suitable for quality control of common cement plants. The ICP method is high in detection precision, but the time consumption is long (the raw material decomposition needs 8-12 h, the instrument is started for preheating needs 8h, and the total detection process needs 2 days), the heavy metal standard solution is high in price, and the consumable cost of each detection is high; although the fluorescence analysis detection method is high in speed, the precision is insufficient, the repeatability is poor for ppm-level trace elements, and the accuracy of the detection result is greatly influenced by the result of the standard sample curve. Therefore, the method for detecting the total chromium content of the raw material for cement, which is disclosed by the invention, has the advantages of low price of detection equipment, easiness in mastering of a detection method, short time consumption and high detection accuracy, and has great significance for controlling the water-soluble chromium cement (VI) in the cement.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a rapid detection method for the total chromium content of the raw material for cement production, which has relatively low cost, short time consumption and high detection accuracy.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for rapidly detecting the total chromium content of a raw material for cement production is characterized by comprising the following steps:
(1) sample dissolving: weighing a sample, accurately measuring the sample to 0.1mg, placing the sample in a silver crucible, adding a proper amount of sodium hydroxide, covering a crucible cover, placing the crucible and the sample in a high-temperature furnace, heating the crucible to 650-700 ℃ from the normal temperature, melting the sample for 15-25 min in a heat preservation state, taking out the crucible, cooling the crucible, placing the crucible and the sample in a beaker filled with boiling water, covering a surface dish on the beaker, properly heating the beaker on an electric furnace, and taking out the crucible after the frit is completely leached; washing residues on the crucible and the crucible cover with water to a beaker, adding 25-30 mL of nitric acid solution into the beaker at one time under the stirring action, then washing the crucible and the crucible cover with hot nitric acid solution, and transferring all liquid in the washing process to the beaker; heating the solution in the beaker to slightly boil for about 1min, cooling to room temperature, transferring into a 250mL volumetric flask, diluting with water to a scale, and shaking up;
(2) solution oxidation treatment: absorbing a proper amount of the solution obtained in the step (1), adding the solution into a beaker, adding a proper amount of sulfuric acid and phosphoric acid, adding water for dilution, adding a proper amount of a potassium permanganate solution, changing a beaker, boiling, adding the potassium permanganate solution again if the solution red disappears in the boiling process so as to keep the solution red not to fade, taking down the solution for cooling when the solution is heated and boiled until the solution is remained to a target amount, adding a sodium chloride solution, boiling until the solution is colorless, taking down the solution for cooling;
(3) and (3) color development reaction: adding a diphenyl carbodihydrazide solution into the solution finally obtained in the step (2), adding a proper amount of water, adjusting the pH of the solution to 2.1-2.5 by using ammonia water, filtering the solution in a volumetric flask by using medium-speed quantitative filter paper, fully washing the precipitate by using hot water until the filter paper is colorless, diluting the precipitate to a scale by using water, and shaking up;
(4) and (3) absorbance measurement: after the solution obtained in the step (3) is placed for 12-15 min, measuring the absorbance of the solution at 540nm by using a spectrophotometer, deducting the absorbance of a blank test, and checking the concentration of chromium on a working curve;
(5) calculating the total chromium content: and (4) calculating according to the chromium concentration obtained in the step (4) and the dilution ratio of each step to obtain the total chromium content.
Further, in the step (1), after the crucible cover is covered, a gap is kept between the crucible cover and the crucible.
Further, in step (1), the crucible needs to be removed and sufficiently shaken at least once during melting at a high temperature.
Further, in the step (2), glass beads are added to the beaker to prevent the solution from bumping.
Compared with the prior art, the invention has the beneficial effects that:
1. the sample is processed by a high-temperature melting method, so that compared with hydrofluoric acid-perchloric acid low-temperature heating processing in the prior art, the time consumption is shorter, and the processing is more thorough;
2. cr in the solution can be oxidized by potassium permanganate3+All completely converted into Cr6+And adding sodium salt to make Cr6+The existence of the detection is more stable, and the stability of the detection result is ensured;
3. the spectrophotometer is adopted to measure the absorbance, so that the detection method is mastered, the requirement on the actual operation capability of technicians is not high, the equipment cost of an enterprise is reduced, and other expensive equipment does not need to be purchased additionally;
4. the chemical reagents used in the invention are basic chemical reagents, and the cost of consumables for single detection is lower than that of the prior art;
5. the invention quantifies the detection sample to 0.1g grade, has enough representativeness and convincing detection results.
Detailed Description
The technical scheme of the invention is clearly and completely described by combining the embodiment of the invention. The experimental methods in the following examples, which do not indicate specific conditions, are all conventional in the art or are prior art.
Example one
The method for rapidly detecting the total chromium content of the raw material for cement production in the embodiment is specifically realized by the following steps:
(1) sample dissolving: weighing 0.3g of sample, accurately measuring the sample to 0.1mg, placing the sample in a silver crucible, adding 6-7 g of sodium hydroxide, and covering a crucible cover (keeping a gap between the crucible cover and the crucible); putting the crucible and the sample into a high-temperature furnace, heating to 650-700 ℃ from normal temperature, melting for 20min in a heat preservation state, taking out, and fully shaking for 1 time; then taking out and cooling, putting the crucible together with the sample into a beaker (300 mL) filled with about 100mL of boiling water, covering a watch glass on the beaker, then putting the beaker on an electric furnace for proper heating, and taking out the crucible after the frit is completely leached; washing the crucible and the crucible cover with a small amount of quantitative water, and washing substances remained on the inner walls of the crucible and the crucible cover into the beaker; adding 25-30 mL of nitric acid solution of 15.2mol/L into a beaker at one time under the stirring action; because a small amount of frits are adhered to the inner wall of the crucible and can not be completely separated in boiling water, the crucible and the crucible cover are cleaned by proper amount and quantitative hot nitric acid (1 + 100) to be placed in a beaker, and the cleaned solution is required to be completely transferred back to the beaker, and the corresponding cleaning water and the amount of nitric acid are recorded; finally, heating the solution in the beaker to slightly boil for about 1min, cooling to room temperature, transferring into a 250mL volumetric flask, diluting with water to the maximum scale, and shaking up; (Note: the degree of dilution of the reagents is expressed in terms of volume ratio, e.g., nitric acid (1 + 100) means that 1 part by volume of concentrated nitric acid is mixed with 100 parts by volume of water, the same applies hereinafter);
(2) solution oxidation treatment: sucking 25mL of the solution obtained in the step (1), adding the solution into a 150 mL beaker, adding 0.5 mL of sulfuric acid solution (1 +1, specifically formed by mixing 1 volume of concentrated sulfuric acid with 1 volume of water) and phosphoric acid (1 +1, specifically formed by mixing 1 volume of concentrated sulfuric acid with 1 volume of water), adding water to dilute the solution to 50mL, then adding 2-3 drops of potassium permanganate solution, and adding a plurality of glass beads into the beaker to prevent the solution from boiling explosively; then, changing a surface dish, boiling, adding a potassium permanganate solution to keep the solution red not to fade if the solution red disappears in the boiling process, heating and boiling until the solution is left to 20 mL, taking down the solution for cooling slightly, adding 5mL of a sodium chloride solution (10 g/L), boiling until the solution is colorless, taking down the solution for cooling slightly;
(3) and (3) color development reaction: adding 5.0mL of a dibenzoyl dihydrazide solution into the solution finally obtained in the step (2), wherein the dibenzoyl dihydrazide solution is obtained by weighing 0.125g of dibenzoyl dihydrazide, dissolving the dibenzoyl dihydrazide with 25mL of acetone, transferring the solution into a 50mL volumetric flask, and then diluting the solution with acetone to a scale mark, wherein the concentration of the solution is 2.5 g/L; adding 30mL of water, adjusting the pH value of the solution to 2.1-2.5 by using ammonia water (1 + 1), filtering the solution in a 100mL volumetric flask by using medium-speed quantitative filter paper, fully washing the precipitate by using hot water until the filter paper is colorless, diluting the precipitate to the maximum scale of the volumetric flask by using water, and shaking up;
(4) and (3) absorbance measurement: after the solution obtained in the step (3) is placed for 15min, measuring the absorbance of the solution at 540nm by using a spectrophotometer, deducting the absorbance of a blank test, and checking the concentration of chromium on a working curve;
(5) calculating the total chromium content: and (4) calculating according to the chromium concentration obtained in the step (4) and the dilution ratio of each step to obtain the total chromium content.
The following are appended to the corresponding test data of the invention:
the above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (4)
1. A method for rapidly detecting the total chromium content of a raw material for cement production is characterized by comprising the following steps:
(1) sample dissolving: weighing a sample, accurately measuring the sample to 0.1mg, placing the sample in a silver crucible, adding a proper amount of sodium hydroxide, covering a crucible cover, placing the crucible and the sample in a high-temperature furnace, heating the crucible to 650-700 ℃ from the normal temperature, melting the sample for 15-25 min in a heat preservation state, taking out the crucible, cooling the crucible, placing the crucible and the sample in a beaker filled with boiling water, covering a surface dish on the beaker, properly heating the beaker on an electric furnace, and taking out the crucible after the frit is completely leached; washing residues on the crucible and the crucible cover with water to a beaker, adding 25-30 mL of nitric acid solution into the beaker at one time under the stirring action, then washing the crucible and the crucible cover with hot nitric acid solution, and transferring all liquid in the washing process to the beaker; heating the solution in the beaker to slightly boil for about 1min, cooling to room temperature, transferring into a 250mL volumetric flask, diluting with water to a scale, and shaking up;
(2) solution oxidation treatment: absorbing a proper amount of the solution obtained in the step (1), adding the solution into a beaker, adding a proper amount of sulfuric acid and phosphoric acid, adding water for dilution, adding a proper amount of a potassium permanganate solution, changing a beaker, boiling, adding the potassium permanganate solution again if the solution red disappears in the boiling process so as to keep the solution red not to fade, taking down the solution for cooling when the solution is heated and boiled until the solution is remained to a target amount, adding a sodium chloride solution, boiling until the solution is colorless, taking down the solution for cooling;
(3) and (3) color development reaction: adding a diphenyl carbodihydrazide solution into the solution finally obtained in the step (2), adding a proper amount of water, adjusting the pH of the solution to 2.1-2.5 by using ammonia water, filtering the solution in a volumetric flask by using medium-speed quantitative filter paper, fully washing the precipitate by using hot water until the filter paper is colorless, diluting the precipitate to a scale by using water, and shaking up;
(4) and (3) absorbance measurement: after the solution obtained in the step (3) is placed for 12-15 min, measuring the absorbance of the solution at 540nm by using a spectrophotometer, deducting the absorbance of a blank test, and checking the concentration of chromium on a working curve;
(5) calculating the total chromium content: and (4) calculating according to the chromium concentration obtained in the step (4) and the dilution ratio of each step to obtain the total chromium content.
2. The method for rapidly detecting the total chromium content in the raw material for cement production as recited in claim 1, wherein in the step (1), a gap is maintained between the crucible cover and the crucible after the crucible cover is covered.
3. The method for rapidly detecting the total chromium content in a raw material for cement manufacture according to claim 1 or 2, wherein in the step (1), the crucible is removed and sufficiently shaken at least once during the melting at the high temperature.
4. The method for rapidly detecting the total chromium content in the raw material for cement production as claimed in claim 3, wherein in the step (2), glass beads are added to the beaker to prevent the solution from bumping.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084969A (en) * | 1992-09-30 | 1994-04-06 | 华东师范大学 | Quick automatic analysis instrument for cement five elements |
| CN102718440A (en) * | 2011-03-29 | 2012-10-10 | 鞍钢股份有限公司 | Modified cement solidification body with blast furnace slag and method for treating chromium slag thereof |
| CN111693523A (en) * | 2020-06-22 | 2020-09-22 | 阳新娲石水泥有限公司 | Method for detecting total chromium content in raw materials of cement clinker |
-
2021
- 2021-03-08 CN CN202110252176.6A patent/CN112945880A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084969A (en) * | 1992-09-30 | 1994-04-06 | 华东师范大学 | Quick automatic analysis instrument for cement five elements |
| CN102718440A (en) * | 2011-03-29 | 2012-10-10 | 鞍钢股份有限公司 | Modified cement solidification body with blast furnace slag and method for treating chromium slag thereof |
| CN111693523A (en) * | 2020-06-22 | 2020-09-22 | 阳新娲石水泥有限公司 | Method for detecting total chromium content in raw materials of cement clinker |
Non-Patent Citations (2)
| Title |
|---|
| 张露瑶等: "一种新型的水泥原料和熟料的总铬检测方法", 《水泥》 * |
| 陆英等: "铬矿渣及掺有铬矿渣水泥中三氧化二铬的测定", 《无》 * |
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