CN112378900A - Method for determining tungsten in tungsten catalyst with activated carbon as carrier - Google Patents
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 79
- 239000010937 tungsten Substances 0.000 title claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 37
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 19
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 239000010431 corundum Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000004380 ashing Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000005352 clarification Methods 0.000 claims description 7
- 238000005485 electric heating Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 7
- 238000010309 melting process Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LWZXEPVULXGSQV-UHFFFAOYSA-N [Sn].[Bi].[W] Chemical compound [Sn].[Bi].[W] LWZXEPVULXGSQV-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000005259 measurement Methods 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 56
- 239000002253 acid Substances 0.000 description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000003513 alkali Substances 0.000 description 8
- 238000003916 acid precipitation Methods 0.000 description 5
- 150000001722 carbon compounds Chemical class 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000002798 spectrophotometry method Methods 0.000 description 5
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 4
- 238000011978 dissolution method Methods 0.000 description 4
- 238000004993 emission spectroscopy Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 239000011975 tartaric acid Substances 0.000 description 4
- 235000002906 tartaric acid Nutrition 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012490 blank solution Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- WUTHJWCAESRVMV-UHFFFAOYSA-N [W].[Bi] Chemical compound [W].[Bi] WUTHJWCAESRVMV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Plasma & Fusion (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Engineering & Computer Science (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention belongs to the technical field of catalysts, and discloses a method for determining tungsten in a tungsten catalyst with activated carbon as a carrier, which has the advantages of accurate measurement, effective interference reduction and simple operation.
Description
Technical Field
The invention belongs to the technical field of catalysts, relates to a method for measuring tungsten, and particularly relates to a method for measuring tungsten in a tungsten catalyst taking activated carbon as a carrier.
Background
At present, the industries related to the chemical field of tungsten metal in China mainly include the industries of pigment, catalysis, electroplating and the like, and research shows that the tungsten-containing catalyst has high-efficiency catalytic action on chemical reactions such as dehydrogenation, alkylation, esterification, dehydration and the like, and is further known as a 'star catalyst' in the industries of smelting, petrochemical industry and the like.
According to the use condition of tungsten catalysis at home and abroad in recent years, the tungsten catalyst which is commonly used at present mainly comprises tungsten sulfide, tungsten oxide, simple substance tungsten, heteropolytungstic acid and the like, and the carrier of the tungsten catalyst mainly comprises active carbon, magnesium silicate, aluminum silicate, ion exchange resin silica gel and the like; the activated carbon has the characteristics of good specific surface area, small environmental pollution, no corrosion to equipment and the like, and the activated carbon has catalytic activity, so that the tungsten catalyst taking the activated carbon as a carrier has great interest of researchers, and the researches of the researchers at present show that the activated carbon is the most effective carrier of heteropolytungstic acid.
Aiming at the determination of tungsten in ores, steel and iron alloy, catalysts, surface water, underground water, industrial wastewater and the like, the conventional methods comprise a volumetric method, a gravimetric method, a spectrophotometry method, an oscillography, an inductively coupled plasma emission spectrometry and the like; wherein, the volumetric method and the gravimetric method are only suitable for the determination of high content tungsten (W is more than 5 percent), and the analysis process is long, the impurity inclusion is more during precipitation, the interference factor is more during titration, and the method is rarely used at present; the common method for measuring tungsten by the spectrophotometry is the thiocyanate spectrophotometry, the measuring range of the method is 0.05-5%, but the method has the defects of low analysis speed, complex operation and the like; although the oscillography is relatively rapid in determination, short in flow and simple, the risk of mercury contact and body injury exists in the determination process, and the method is not common; the inductively coupled plasma emission spectrometry is well accepted by people due to the characteristics of high sensitivity, simple operation, wide linear range, low interference and the like.
When the inductively coupled plasma emission spectrometry (ICP-AES), spectrophotometry, or oscillography is used to measure tungsten in the catalyst, the sample needs to be dissolved, and the current methods for dissolving the catalyst include acid dissolution and alkali melting.
1. Acid dissolution method
The acid dissolution method of the tungsten catalyst comprises the conventional steps of adding hydrochloric acid, nitric acid, hydrofluoric acid or phosphoric acid and the like into a sample for dissolution, adding nitric acid or perchloric acid for decarbonization after smoking, adding citric acid or tartaric acid, adding hydrochloric acid to keep a certain acidity of a sample solution, and measuring by ICP-AES after constant volume.
The catalyst using the active carbon as the carrier contains high-content carbon compounds and part of organic substances added for increasing the catalytic activity, if a sample adopts an acid dissolution method, three problems exist, firstly, a large amount of nitric acid or perchloric acid is needed to be added for carbon removal when the sample is dissolved; secondly, if the sample is not completely decarbonized, the sample inlet pipe of the ICP-AES analyzer is blocked and the rectangular pipe is damaged during measurement; thirdly, when a large amount of acid is added during sample dissolution, tungstic acid precipitation is easily generated, so that the determination result is low; therefore, the conventional acid dissolution method is not suitable for the determination of the tungsten catalyst using the activated carbon as the carrier.
2. Alkali fusion process
The alkali sample dissolving conventional process of the tungsten catalyst comprises the following steps: weighing a sample, putting the sample into a crucible, adding sodium peroxide, putting the mixture into a muffle furnace for high-temperature melting, cooling, then soaking the mixture with water, adding citric acid or tartaric acid, adding hydrochloric acid to keep the acidity of a sample solution to be 5-10%, and measuring the volume by using ICP-AES after constant volume.
Firstly, because a sample contains a large amount of carbon compounds and partial organic matters, the reaction is violent when the sample is melted at high temperature in a muffle furnace, a bursting or flying phenomenon can be generated to cause sample loss, and the sample can generate small explosion and potential safety hazard under the most unfavorable condition; secondly, the sample contains a large amount of carbon compounds, so that incomplete melting or wrapping of the sample is easy to occur, and the result is low; and thirdly, when the citric acid or the tartaric acid is used as a complexing agent at the acidity of 5-10 percent (the PH is negative and belongs to a strong acid environment), the citric acid or the tartaric acid has larger acid effect coefficient, so that the complex compound formed by the tungsten and the complexing agent is unstable, and particularly, the result is lower for a sample with high tungsten content (W is more than 15 percent).
In summary, the tungsten catalyst using activated carbon as a carrier in the prior art has disadvantages no matter the conventional acid dissolution or alkali dissolution is adopted.
Disclosure of Invention
The invention aims to provide a method for measuring tungsten in a tungsten catalyst taking activated carbon as a carrier, which has the advantages of accurate measurement, effective interference reduction and simple operation.
In order to achieve the purpose, the invention adopts the following technical scheme: a method for measuring tungsten in a tungsten catalyst taking activated carbon as a carrier comprises the following steps:
(1) weighing 0.1000-0.3000g of a tungsten catalyst sample taking active carbon as a carrier in a corundum crucible, firstly carbonizing at low temperature on a constant-temperature electric heating plate, then putting the sample in a muffle furnace for ashing at 600 ℃ to white or grey-white, taking out and cooling, then adding 0.5-1.5g of sodium peroxide, stirring the mixture by using a glass rod and uniformly mixing the mixture with the sample, spreading 0.5-1.0g of sodium peroxide on the mixture, then putting the mixture in the muffle furnace for slowly heating to 650 ℃ and 720 ℃ for melting for 10-15min, shaking the crucible once in the melting process, taking out and cooling;
(2) placing the crucible in a 250-plus 400mL beaker, covering a watch glass, adding hot water at 30-50 ℃ for leaching, adding 1.0-2.0g of oxalic acid, placing the beaker on an electric furnace for boiling at low temperature for 5-10min, taking down and cooling, washing the crucible with water, moving the crucible into a 100-plus 250mL volumetric flask, and performing constant volume and shaking uniformly;
(3) and (3) placing the sample prepared in the step (2) for 1-2h for clarification or carrying out dry filtration, taking a proper amount of supernatant or dry filtrate into a 100-sample 250mL volumetric flask, adding 2-4mL of hydrogen peroxide solution with the volume fraction of 20%, placing for a moment, shaking up uniformly, adding 25.0-60.0mL of HCI (1+4), keeping the acidity at about 5%, fixing the volume and shaking up uniformly, and measuring by using ICP-AES.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, the tungsten catalyst taking the activated carbon as the carrier is sequentially carbonized and ashed before being added with alkali for melting, so that the purposes of removing carbon compounds, thoroughly decomposing and destroying organic matters and removing part of matrix interference are achieved, the phenomena of collapse, flying or small explosion generated during alkali melting are avoided, and the purpose of completely melting a sample subsequently is achieved; according to the invention, oxalic acid with a smaller acid effect coefficient under a strong acid condition is selected as a complexing agent, and forms a tungsten synergistic complexing agent with subsequently added hydrogen peroxide, so that the stability of a tungsten complex is increased to the maximum extent, tungstic acid precipitation during acidification is effectively avoided, and the accuracy of a measurement result is improved; the method not only provides a reliable basis for measuring the content of tungsten in catalysts of other carriers, but also provides a reference basis for a sample dissolving method of ore samples or catalysts with higher carbon content.
Detailed Description
Example 1
A method for measuring tungsten in a tungsten catalyst taking activated carbon as a carrier comprises the following steps:
weighing 0.1000-0.3000g of a tungsten catalyst sample taking active carbon as a carrier in a corundum crucible, firstly carbonizing at low temperature on an electric heating plate, then putting the sample in a muffle furnace for ashing at 600 ℃ plus, taking out and cooling, then adding 0.5-1.5g of sodium peroxide, stirring the mixture by using a glass rod and uniformly mixing the mixture with the sample, paving 0.5-1.0g of sodium peroxide on the mixture, then putting the mixture in the muffle furnace for melting at 650 ℃ plus for 720 ℃ for 10-15min, shaking the crucible once in the melting process, taking out and cooling. Wherein, the sample is put on an electric hot plate for low-temperature carbonization, and the purpose of preliminary decomposition is achieved by preliminary incomplete combustion of organic matters in the sample; and then the mixture is put into a muffle furnace to be incinerated to white or grey white at the temperature of 500-600 ℃, so as to eliminate carbon compounds and completely burn and decompose organic matters, thereby achieving the purposes of completely removing the interference of a sample matrix, increasing the safety during subsequent alkali melting and ensuring complete melting of the sample. Shaking the sample crucible once in the melting process to ensure that the sample is heated uniformly and prevent local overheating;
and (2) placing the crucible into a 400mL beaker with the temperature of 250-. Wherein the crucible is cooled and then leached by hot water of 30-50 ℃ so as to avoid the phenomena of violent reaction and sample overflow in the leaching by boiling water; 1.0-2.0g of oxalic acid is added because the oxalic acid has smaller acid effect coefficient under strong acid condition, the stability of the complex formed by the oxalic acid and the tungsten is high, and tungstic acid precipitation is avoided when acid is added later;
and (3) standing the sample prepared in the step (2) for 1-2h for clarification or dry filtration, dividing a proper amount of supernatant or dry filtrate into 100-250mL volumetric flasks, adding 2-4mL of hydrogen peroxide solution with the volume fraction of 20%, standing for a moment, shaking up, adding 25.0-60.0mL of HCI (1+4), keeping the acidity at about 5%, fixing the volume, shaking up, and measuring by ICP-AES. Wherein, the purpose of adding the hydrogen peroxide solution into the tapping liquid is to ensure that the hydrogen peroxide solution and the oxalic acid added in the front form a synergistic complexing agent to complex tungsten together, thereby effectively avoiding tungstic acid precipitation when hydrochloric acid is added subsequently; the added HCI is 1+4 diluted hydrochloric acid, so as to prevent the transient tungstic acid precipitation phenomenon caused by adding concentrated hydrochloric acid;
step (4) making a whole procedure blank along with the sample;
preparing 5-8 tungsten standard series with concentration, performing constant volume by using a whole-process blank solution with the same sampling multiple as the sample, and determining by using ICP-AES (inductively coupled plasma-atomic emission Spectrometry); wherein, the volume fixing is carried out by using a whole-process blank solution with the same sample dividing times during the standard series volume fixing so as to eliminate part of matrix interference.
Example 2
A method for measuring tungsten in a tungsten catalyst taking activated carbon as a carrier comprises the following steps:
step (1), respectively weighing 0.1500g of a tungsten catalyst sample taking activated carbon as a carrier and a tungsten-tin-bismuth ore standard substance (GBW 07369) in a corundum crucible, firstly carbonizing at low temperature on an electric heating plate, then putting the carbonized tungsten catalyst sample and the standard substance into a muffle furnace to ash at 500 ℃, taking out and cooling the tungsten catalyst sample and the standard substance, adding 1.0 of sodium peroxide, stirring the mixture by using a glass rod to be uniformly mixed with the sample, paving 0.5g of sodium peroxide on the carbonized tungsten catalyst sample, putting the carbonized tungsten catalyst sample and the cooled tungsten-tin-bismuth ore standard substance into the muffle furnace to melt at 680 ℃ for 10 min;
step (2), placing the crucible into a 250mL beaker, covering a watch glass, adding hot water at about 30-50 ℃ for leaching for a moment, adding 1.0g of oxalic acid, placing the beaker on a constant temperature electric furnace, boiling for 6-7min at low temperature, taking the beaker down for slight cooling, washing the crucible with water, transferring the crucible into a 100mL volumetric flask, and carrying out constant volume and shaking uniformly;
step (3) placing the sample prepared in the step (2) for clarification or dry filtration, taking a proper amount of supernatant or dry filtrate into a 100mL volumetric flask, adding 2mL of hydrogen peroxide solution with the volume fraction of 20%, placing for a moment, shaking up, adding 25.0mL of HCI (1+4), keeping the acidity at about 5%, fixing the volume, shaking up, and measuring by using ICP-AES;
step (4) making a whole procedure blank along with the sample;
step (5) preparation of standard solution: 10.00mL of tungsten standard solution with the number of GSBG62063-90(7401) and the concentration of 1000ug/mL is measured and put into a 100mL volumetric flask to prepare 100ug/mL of tungsten standard mother solution, a certain amount of the mother solution is measured and prepared into a standard series with the concentrations of 0.0, 0.5, 1.0, 5.0, 10.0 and 20.0ug/mL, and 10 times of whole process blank is used for constant volume and keeping the acidity at about 5 percent.
The operating conditions of the measuring apparatus are as follows. Plasma observation: horizontal; pump speed: 100 rmp; RF power: 1150 Hz; analyzing the pump speed: 50 rmp; auxiliary air flow rate: 0.5L/min; atomizer gas flow: 0.45L/min; cooling air flow: 12L/min; and (3) measuring a spectral line: w239.709 nm.
The results of measuring the tungsten content of the tungsten catalyst using activated carbon as a carrier and the standard sample in this example are shown in table 1.
Example 3
A method for measuring tungsten in a tungsten catalyst taking activated carbon as a carrier comprises the following steps:
step (1), respectively weighing 5 parts of 0.2000g of tungsten catalyst sample taking activated carbon as a carrier into a corundum crucible, respectively adding 0.0500, 0.1000g, 0.1500g, 0.2000g and 0.2500g of GBW07284 tungsten bismuth ore (the tungsten content is 3.66%), firstly carbonizing at low temperature on an electric heating plate, then putting into a muffle furnace for ashing at 550 ℃, taking out and cooling, then adding 1.0-1.5g of sodium peroxide, stirring with a glass rod and uniformly mixing with the sample, paving 0.5-1.0g of sodium peroxide on the sample, then putting into the muffle furnace for melting at 700 ℃ for 12min, shaking the crucible once in the melting process, taking out and cooling;
step (2), placing the crucible into a 400mL beaker, covering a watch glass, adding hot water at about 30-50 ℃ for leaching for a moment, adding 1.0-2.0g of oxalic acid, placing the beaker on a constant temperature electric furnace, boiling the beaker for 10-12min at low temperature, taking the beaker down for slight cooling, washing the crucible with water, transferring the beaker into a 250mL volumetric flask, and carrying out constant volume and shaking uniformly;
step (3) placing the sample prepared in the step (2) for clarification or dry filtration, taking a proper amount of supernatant or dry filtrate into a 200mL volumetric flask, adding 3-4mL of hydrogen peroxide solution with the volume fraction of 20%, placing for a moment, shaking up, adding 50.0mL of HCI (1+4), keeping the acidity at about 5%, fixing the volume, shaking up, and measuring by using ICP-AES;
step (4) making a whole procedure blank along with the sample; the preparation and the apparatus conditions of the standard solution were the same as in example 2.
The results of measuring the tungsten content of the tungsten catalyst using activated carbon as a carrier and the standard sample in this example are shown in table 2.
Example 4
A method for measuring tungsten in a tungsten catalyst taking activated carbon as a carrier comprises the following steps:
respectively weighing 0.3000g of 5 tungsten catalyst samples with different tungsten contents (the tungsten contents are about 0.5%, 1.0%, 5.0%, 10% and 35%) and taking activated carbon as a carrier in a corundum crucible, firstly carbonizing the samples at a low temperature on an electric heating plate, then putting the carbonized samples into a muffle furnace for ashing at 600 ℃, taking out the carbonized samples and cooling the carbonized samples, adding 1.0 to 1.5g of sodium peroxide, stirring the carbonized samples by using a glass rod and uniformly mixing the samples, paving 0.5 to 1.0g of sodium peroxide on the carbonized samples, then putting the samples into the muffle furnace for melting at 720 ℃ for 10min, shaking the crucible once in the melting process, taking out and cooling the crucible;
step (2), placing the crucible into a 400mL beaker, covering a watch glass, adding hot water of about 40-50 ℃ for leaching for a moment, adding 1.0-2.0g of oxalic acid, placing the beaker on a constant temperature electric furnace for boiling at low temperature for 12-15min, taking down the beaker for slight cooling, washing the crucible with water, transferring the beaker into a 100mL or 250mL volumetric flask, and carrying out constant volume and shaking uniformly;
step (3) placing the sample prepared in the step (2) for clarification or dry filtration, taking a proper amount of supernatant or dry filtrate into a 100-sample 250mL volumetric flask, adding 3-4mL of hydrogen peroxide solution with the volume fraction of 20%, placing for a moment, shaking up uniformly, adding 25.0-60.0mL of HCI (1+4), keeping the acidity at about 5%, fixing the volume and shaking up uniformly, and measuring by using inductively coupled plasma emission spectrometry (ICP-AES), wherein the measurement result is shown in Table 3;
(4) making a blank of the whole procedure along with the sample;
(5) the preparation of the standard solution and the ICP-AES apparatus conditions were the same as in example 1;
(6) weighing 4 parts of tungsten catalyst samples with the same amount in the step (5), treating by adopting the steps (1) to (3), and measuring the tungsten content by using a flame atomic absorption method, wherein the measurement results are shown in a table 3;
(7) respectively weighing 3 parts of tungsten catalyst samples with the same quantity (the tungsten content is lower than 5%) in the step (1), sequentially carrying out carbonization, ashing and alkali fusion in the step (1), and then analyzing according to the tungsten measuring flow of a thiocyanate spectrophotometry, wherein the measuring results are shown in table 3.
Claims (3)
1. A method for measuring tungsten in a tungsten catalyst taking activated carbon as a carrier is characterized by comprising the following steps:
weighing 0.1000-0.3000g of a tungsten catalyst sample taking active carbon as a carrier in a corundum crucible, firstly carbonizing at low temperature on a constant-temperature electric heating plate, then putting the sample in a muffle furnace to ash at 600 ℃ to white or grey white, taking out and cooling, then adding 0.5-1.5g of sodium peroxide, stirring the mixture by using a glass rod to be uniformly mixed with the sample, paving 0.5-1.0g of sodium peroxide on the mixture, then putting the mixture in the muffle furnace to slowly heat to 650 ℃ and 720 ℃ to melt for 10-15min, shaking the crucible once in the melting process, taking out and cooling;
step (2), placing the crucible into a 250-plus 400mL beaker, covering a watch glass, adding hot water at 30-50 ℃ for leaching, adding 1.0-2.0g of oxalic acid, placing the beaker on an electric furnace for boiling at low temperature for 5-10min, taking down and cooling, washing the crucible with water, moving the crucible into a 100-plus 250mL volumetric flask, and performing constant volume and shaking uniformly;
and (3) standing the sample prepared in the step (2) for 1-2h for clarification or dry filtration, dividing a proper amount of supernatant or dry filtrate into 100-250mL volumetric flasks, adding 2-4mL of hydrogen peroxide solution with the volume fraction of 20%, standing for a moment, shaking up, adding 25.0-60.0mL of HCI (1+4), keeping the acidity at about 5%, fixing the volume, shaking up, and measuring by ICP-AES.
2. The method for determining tungsten in the tungsten catalyst taking the activated carbon as the carrier according to the claim 1, characterized in that 0.1500g of a tungsten catalyst sample taking the activated carbon as the carrier and a tungsten-tin-bismuth ore standard substance (GBW 07369) are weighed and respectively put in a corundum crucible in the step (1), firstly carbonized on an electric heating plate at a low temperature, then put in a muffle furnace for ashing at 500 ℃, taken out and cooled, added with 1.0g of sodium peroxide, stirred by a glass rod and uniformly mixed with the sample, laid with 0.5g of sodium peroxide on the surface and then put in the muffle furnace for melting at 680 ℃ for 10min, the crucible is shaken once in the melting process, taken out and cooled; step (2) placing the crucible cooled in the step (1) into a 250mL beaker, covering a watch glass, adding hot water at about 30-50 ℃ for leaching for a moment, adding 1.0g of oxalic acid, placing the crucible on a constant temperature electric furnace for low-temperature boiling for 6-7min, taking the crucible down for slight cooling, washing the crucible with water, moving the crucible into a 100mL volumetric flask, and carrying out constant volume and shaking uniformly; and (3) standing the sample prepared in the step (2) for clarification or dry filtration, taking a proper amount of supernatant or dry filtrate into a 100mL volumetric flask, adding 2mL of 20% hydrogen peroxide solution by volume fraction, standing for a moment, shaking up, adding 25.0mL of HCI (1+4), keeping the acidity at about 5%, fixing the volume, shaking up, and measuring by using ICP-AES.
3. The method for determining tungsten in the tungsten catalyst taking the activated carbon as the carrier according to claim 1, wherein 0.2000g of the tungsten catalytic sample taking the activated carbon as the carrier is weighed in the step (1) and put into a corundum crucible, 0.0500g, 0.1000g, 0.1500g, 0.2000g and 0.2500g of the tungsten-tin-bismuth ore standard substance (GBW 07284) are respectively added, the tungsten content in the tungsten-tin-bismuth ore standard substance is 3.66 percent, the ashing temperature in a muffle furnace is 550 ℃, and the tungsten catalytic sample is put into the muffle furnace again to be melted for 12min at 700 ℃ after the sodium peroxide is added; adding oxalic acid in the step (2), placing on a constant temperature electric furnace, boiling for 10-12min, washing out the crucible, and transferring into a 250ml volumetric flask; and (3) putting the supernatant or the dry filtrate into a 200ml volumetric flask, adding 3-4ml of 20 volume percent hydrogen peroxide solution, standing for a moment, shaking up, adding 50.0ml of HCI (1+4), and keeping the acidity at about 5%.
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