Method and device for continuously determining carbon and sulfur in ore

Abstract

The present application provides a method and a device for continuously determining carbon and sulfur in ores, belonging to the field of metal smelting. Among them, by setting up a device for continuously determining carbon and sulfur in ores composed of a reaction device and a titration device, wherein the titration device includes a plurality of sulfur absorption titration devices connected to the reaction device and a carbon absorption titration device connected to the sulfur absorption titration device; the plurality of sulfur absorption titration devices are connected end to end in sequence; the sample is placed in a high-temperature oxygen stream for combustion, so that sulfur is converted into sulfur dioxide and carbon is converted into carbon dioxide. The sulfur dioxide and carbon dioxide are absorbed by hydrogen peroxide solution and oxidized into sulfuric acid and carbonic acid, wherein the carbonic acid decomposes into carbon dioxide and water to separate it from sulfur dioxide. The carbon dioxide enters the absorption solution containing ethanol-ethanolamine along with the oxygen stream and is titrated. The present application can simultaneously determine carbon and sulfur, and on the premise of reducing the experimental cost, ensure a high test accuracy for the sample.

Description

Technical Field

[0001] The present application relates to the technical field of metal smelting, and particularly relates to a method and a device for continuously determining carbon and sulfur in ores. Background Art

[0002] During the determination of the carbon content in ores, sulfur contained in the sample will cause great interference to its determination. If corresponding measures are not taken to timely absorb the sulfides generated during the combustion process, white precipitates will appear in the absorption liquid for determining carbon, making the absorption liquid turbid, resulting in the inability to judge the end point and the inability to accurately determine carbon.

[0003] There are many methods for separately determining carbon and sulfur in ores, and there are corresponding separate determination methods in national standards for gold ores and gold concentrates. In actual production, if determined separately, it will waste both time and cost. In most ore samples, the sulfur content is generally high, and it is more suitable to use the volumetric method for detection. Currently, there are few continuous determination methods, and most of the methods for continuously determining carbon and sulfur are high-frequency infrared absorption methods, and the volumetric method is rarely seen. Moreover, the instrumental method has a high cost and a narrow determination range, and it is also difficult to achieve the continuous determination of carbon and sulfur in many enterprises. And the continuous determination of carbon and sulfur in ores is even more rare. In addition, for the determination of sulfur in some ore types, such as lead concentrates and zinc concentrates, it is not applicable to the high-frequency infrared absorption method. At this time, if one wants to achieve the continuous determination of the carbon and sulfur contents in lead concentrates and zinc concentrates, the volumetric method needs to be used.

[0004] If the determination methods of carbon and sulfur in national standard gold concentrates and gold ores are simply fused, without timely titrating the generated sulfuric acid, hydrogen peroxide cannot completely absorb the generated sulfur dioxide, which will still interfere with the determination of carbon, and the water generated during the reaction will also interfere with the determination of carbon.

[0005] In view of this, it is necessary to design a method and a device for continuously determining carbon and sulfur in ores to solve the above problems. Summary of the Invention

[0006] In view of the technical problems existing in the background art, the present application provides a method and a device for continuously determining carbon and sulfur in ores. According to the device for continuously determining carbon and sulfur in ores, when determining the contents of carbon and sulfur in ores, it is not necessary to separately digest the sample, and continuous determination of the sample can be achieved.

[0007] In a first aspect, an embodiment of the present application provides a device for continuously determining carbon and sulfur in ores, including: a gas supply device, a reaction device connected to the gas supply device, and a titration device connected to the reaction device;

[0008] The titration device includes a plurality of sulfur absorption titration devices connected to the reaction device, and a plurality of carbon absorption titration devices connected to the sulfur absorption titration devices; the plurality of sulfur absorption titration devices are connected end to end in sequence;

[0009] The plurality of sulfur absorption titration devices include a first-stage sulfur absorption titration device connected to the reaction device, a second-stage sulfur absorption titration device connected to the first-stage sulfur absorption titration device, ……, an n-stage sulfur absorption titration device connected to the (n - 1)-stage sulfur absorption titration device;

[0010] The plurality of carbon absorption titration devices include a path A1 carbon absorption titration device connected to the n-stage sulfur absorption titration device.

[0011] In the technical solution of the embodiment of the present application, by improving the absorption bottles for sulfur measurement and carbon measurement, multi-stage absorption of sulfur with different contents can be realized, making the determination of sulfur in the sample more accurate and reliable.

[0012] In some embodiments, the plurality of carbon absorption titration devices further include a path A2 carbon absorption titration device connected to a branch of the pipeline connecting the first-stage sulfur absorption titration device and the second-stage sulfur absorption titration device, a path A3 carbon absorption titration device connected to a branch of the pipeline connecting the second-stage sulfur absorption titration device and the third-stage sulfur absorption titration device, ……, a path A m carbon absorption titration device connected to a branch of the pipeline connecting the (n - 1)-stage sulfur absorption titration device and the n-stage sulfur absorption titration device.

[0013] In some embodiments, the n-stage sulfur absorption titration device includes an n-stage sulfur absorption titration bottle, a burette used in conjunction with the n-stage sulfur absorption titration bottle, and a light source;

[0014] The path A m carbon absorption titration device includes a path A m carbon absorption titration bottle, a burette used in conjunction with the path A m carbon absorption titration bottle, and a light source; and / or,

[0015] Control valves are provided on the pipelines for connecting the plurality of sulfur absorption titration devices, and control valves are provided on the pipelines for connecting the sulfur absorption titration devices and the carbon absorption titration devices.

[0016] By providing multiple path carbon absorption titration devices, optimized determination can be carried out for ore samples with different sulfur contents, making the device more adaptable.

[0017] In a second aspect, the embodiment of the present application provides a method for continuously determining carbon and sulfur in ore, using the above-mentioned device for continuously determining carbon and sulfur in ore, including the following steps:

[0018] S1. Prepare a sulfur absorption solution, a sulfur standard titration solution, a carbon absorption solution, and a carbon standard titration solution;

[0019] Place the sulfur absorption solution in the first-stage sulfur absorption titration flask, the second-stage sulfur absorption titration flask,..., the n-stage sulfur absorption titration flask respectively, and place the sulfur standard titration solution in the burette used in conjunction with several sulfur absorption titration flasks.

[0020] Place the carbon absorption solution in the path A1 carbon absorption titration flask, the path A2 carbon absorption titration flask,..., the path A m carbon absorption titration flask, and place the carbon standard titration solution in the burette used in conjunction with several carbon absorption titration flasks;

[0021] S2. Under an oxygen atmosphere, calcine the target sample at a high temperature; at the same time, turn on the light source at the sulfur absorption titration flask and the carbon absorption titration flask; open the control valve on the pipeline connecting several sulfur absorption titration devices, open the control valve on the pipeline connecting the n-stage sulfur absorption titration device and the path A1 carbon absorption titration device, and close the control valve on the branch of the pipeline connecting the n - 1-stage sulfur absorption titration device and the n-stage sulfur absorption titration device and the pipeline connecting to the path A m carbon absorption titration device;

[0022] S3. When it is found that the carbon absorption solution in the path A m carbon absorption titration flask fades, immediately open the burette used in conjunction with the path A m carbon absorption titration flask, titrate with the carbon standard titration solution, and when the carbon absorption solution becomes a stable bright blue color, it is the titration end point, and record the volume of the carbon standard titration solution consumed at this time V C1 , and calculate the carbon content;

[0023] S4. After the above steps are completed, close the control valve on the pipeline connecting the n-stage sulfur absorption titration device and the path A1 carbon absorption titration device;

[0024] Open the burette used in conjunction with the n-stage sulfur absorption titration flask, and titrate the sulfur absorption solution in the n-stage sulfur absorption titration flask with the sulfur standard titration solution until the color of the solution changes from purple to a stable bright green color, which is the titration end point, and record the volume of the sulfur standard titration solution consumed at this time V S（n） , and calculate the sulfur content in the n-stage sulfur absorption titration flask W ( S ) (n);

[0025] S5. After the above steps are completed, close the control valve on the pipeline connecting the n - 1-stage sulfur absorption titration device and the n-stage sulfur absorption titration device;

[0026] Open the burette used in conjunction with the sulfur absorption titration flask at the n-1 level, and titrate the sulfur absorption solution in the sulfur absorption titration flask at the n-1 level with the sulfur standard titration solution until the color of the solution changes from purple to a stable bright green, which is the titration end point, and record the volume of the sulfur standard titration solution consumed at this time. V S（n-1） , calculate the sulfur content in the sulfur absorption titration flask at the n-1 level W ( S ) (n-1);

[0027] ……;

[0028] Until the sulfur content in the sulfur absorption titration flask at the first level is calculated W ( S ) 1;

[0029] Then the total sulfur content is W ( S ) = W ( S ) (n) + W ( S ) (n-1) + …… + W ( S ) 1.

[0030] In some embodiments, in step S3, the calculation formula for the carbon content is:

[0031] ;

[0032] W ( C ) —— mass fraction of carbon, %;

[0033] T C / KOH —— carbon titration degree;

[0034] V C1 —— volume of the carbon standard titration solution consumed by the sample, ml;

[0035] m —— mass of the sample, g;

[0036] Carbon titration degree T C / KOH The determination process of includes: placing the dried calcium carbonate and copper oxide in a high-temperature calcination under an oxygen atmosphere; at the same time, turning on the light source at the A2 carbon absorption titration device of the passage; opening the control valve on the pipeline connecting the first-level sulfur absorption titration device and the A2 carbon absorption titration device of the passage, and closing the control valve on the pipeline connecting the first-level sulfur absorption titration device and the second-level sulfur absorption titration device;

[0037] When it is found that the carbon absorption solution in the carbon absorption titration flask of passage A2 fades, immediately open the burette used in conjunction with the carbon absorption titration flask of passage A2, and titrate with the carbon standard titration solution. When the carbon absorption solution turns into a stable bright blue color, it is the titration end point, and record the volume of the carbon standard titration solution consumed at this time. V KOH Calculate the carbon titration degree. T C / KOH Among them, the carbon titration degree T C / KOH is calculated by the formula:

[0038] ;

[0039] V KOH —— The volume of the carbon standard titration solution consumed by calcium carbonate, ml;

[0040] m 1 - The mass of dried calcium carbonate, g.

[0041] In some embodiments, the sulfur content in the sulfur absorption titration flask of the nth level W ( S ) (n) is calculated by the formula:

[0042] ;

[0043] W ( S ) (n) - The mass fraction of sulfur in the sulfur absorption titration flask of the nth level, %;

[0044] T S / NaOH - Sulfur titration degree;

[0045] V S（n） - The volume of the sulfur standard titration solution consumed by the sample in the sulfur absorption titration device of the nth level, ml;

[0046] m - The mass of the sample, g;

[0047] Sulfur titration degree T S / NaOHThe determination process includes: calcining dried lead sulfate and copper oxide at high temperature in an oxygen atmosphere; meanwhile, turning on the light sources at the first-stage sulfur absorption titration device, …, the n-stage sulfur absorption titration device; opening the control valves on the pipelines connecting the first-stage sulfur absorption titration device and the second-stage sulfur absorption titration device, …, opening the control valves on the pipelines connecting the (n - 1)-stage sulfur absorption titration device and the n-stage sulfur absorption titration device; closing the control valves on the pipelines connecting the first-stage sulfur absorption titration device and the passage A2 carbon absorption titration device, …, closing the control valves on the pipelines connecting the (n - 1)-stage sulfur absorption titration device and the passage A m carbon absorption titration device;

[0048] When it is found that the sulfur absorption solution in the sulfur absorption titration flask fades, immediately open the burette used in conjunction with the sulfur absorption titration flask, titrate with the sulfur standard titration solution, and when the sulfur absorption solution changes from purple to stable bright green, it is the titration end point, and record the volume of the sulfur standard titration solution consumed at this time V NaOH , and calculate the sulfur titration degree T S / NaOH ; among them, the sulfur titration degree T S / NaOH The calculation formula is:

[0049] ;

[0050] V NaOH ——The volume of the sulfur standard titration solution consumed by lead sulfate, ml;

[0051] m 2——The mass of dried lead sulfate, g.

[0052] In some embodiments, the preparation process of the sulfur absorption solution includes: adding 30 mL of mixed indicator to 100 mL of hydrogen peroxide with a mass concentration of 30%, and then diluting to 2 L with H2O; the preparation method of the mixed indicator includes: dissolving 0.12 g of methyl red and 0.83 g of methylene blue in 100 mL of absolute ethanol.

[0053] In this embodiment, by using hydrogen peroxide as a sulfur removal agent, it masks the influence of sulfur on carbon determination, makes the carbon absorption solution clear, the end point is easy to observe, and can simultaneously achieve the determination of sulfur, reducing the experimental cost, improving the testing speed of samples, and at the same time solving the disadvantages of high cost and narrow determination range in the determination of carbon and sulfur by instrumental methods. It does not affect the determination of carbon, eliminates the interference of sulfur oxides on carbon determination, and can continue titration after completely absorbing sulfur.

[0054] In some embodiments, the preparation process of the sulfur standard titration solution is: dissolving 40 g of sodium hydroxide in H2O and diluting to 10 L.

[0055] In some embodiments, the preparation process of the carbon absorption liquid includes: dissolving ethanolamine in absolute ethanol, then adding potassium hydroxide, and after the potassium hydroxide is completely dissolved, adding thymolphthalein, then mixing evenly, filtering, and storing for later use; wherein, in the carbon absorption liquid, ethanolamine:absolute ethanol:potassium hydroxide:thymolphthalein = 30 ml:970 ml:3 g:150 mg.

[0056] In some embodiments, the preparation process of the carbon standard titration solution includes: dissolving ethanolamine in absolute ethanol, then adding potassium hydroxide, and after the potassium hydroxide is completely dissolved, adding thymolphthalein, then mixing evenly, filtering, and storing for later use, wherein, in the carbon standard titration solution, ethanolamine:absolute ethanol:potassium hydroxide:thymolphthalein = 30 ml:970 ml:3 g:150 mg.

[0057] In this embodiment, the sample is placed in a high-temperature oxygen stream for combustion. Under the action of a combustion aid, sulfur dioxide and carbon dioxide generated by combustion are absorbed by hydrogen peroxide solution, and then carbonic acid and sulfuric acid are formed. The generated carbonic acid is decomposed into carbon dioxide and water to achieve the separation of carbon and sulfur; among them, carbon dioxide is absorbed by ethanolamine, and is titrated with the standard potassium hydroxide solution in the prepared carbon standard titration solution. In the calibration method of carbon dioxide here, the composition of the carbon standard titration solution used is the same as that of the carbon absorption liquid used. The advantage of this is that when the content of ethanolamine in the carbon absorption liquid is excessive, it can completely absorb carbon and perform reverse calibration. If the content of ethanolamine in the carbon absorption liquid is insufficient, the carbon standard titration solution can be continuously supplemented and calibrated at the same time. This method provides another idea for the calibration method of carbon; while the generated sulfuric acid is titrated with sodium hydroxide solution. Compared with the separate determination methods of carbon and sulfur, only one combustion of the sample is required to measure the contents of carbon and sulfur in the target sample; and by measuring carbon in this way, the carbon content in the sample within the range of 0.10% - 25.00% can be accurately measured, thus greatly expanding the measurement range of carbon.

[0058] The above description is only an overview of the technical solution of the present application. In order to be able to understand the technical means of the present application more clearly, it can be implemented according to the content of the specification. And in order to make the above and other purposes, features and advantages of the present application more obvious and understandable, the following specific embodiments of the present application are specifically given. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] In order to more clearly illustrate the technical solution of the present application, the drawings used in the present application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0060] Figure 1 This is a schematic structural diagram of the device for continuously determining carbon and sulfur in ore in the embodiments of the present application.

[0061] Reference numerals

[0062] 11. Oxygen cylinder; 12. Electronic flowmeter; 13. Gas washing device;

[0063] 21. Power supply; 22. Voltmeter; 23. High-temperature combustion carbon determination furnace;

[0064] 311. First-stage sulfur absorption titration flask; 312. First burette; 313. Light source; 314. First pipeline; 321. Second-stage sulfur absorption titration flask; 322. Second burette; 323. Second pipeline; 331. Drying device; 332. Carbon absorption titration flask for passage A1; 333. Third burette; 334. Third pipeline; 341. Carbon absorption titration flask for passage A2; 342. Fourth burette; 343. Fourth pipeline; 35. Control valve. Detailed implementation manners

[0065] Next, embodiments of the technical solution of the present application will be described in detail with reference to the drawings. The following embodiments are only used to illustrate the technical solution of the present application more clearly, so they are only examples and cannot be used to limit the protection scope of the present application.

[0066] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in the specification and claims of this application and the above drawings are intended to cover non-exclusive inclusion.

[0067] In the description of the embodiments of the present application, technical terms such as "first" and "second" are only used to distinguish different objects and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity, specific order or primary-secondary relationship of the indicated technical features. In the description of the embodiments of the present application, "a plurality of" means more than two unless otherwise specifically defined.

[0068] Referring to "embodiments" herein means that the specific features, structures or characteristics described in connection with the embodiments may be included in at least one embodiment of this application. The phrase appears in various places in the specification and does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment mutually exclusive with other embodiments. Those skilled in the art will explicitly and implicitly understand that the embodiments described herein may be combined with other embodiments.

[0069] In the description of the embodiments of the present application, the term "and / or" is merely a description of the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can represent three situations: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " in this article generally represents an "or" relationship between the preceding and following associated objects.

[0070] In the description of the embodiments of the present application, the term "plurality" refers to two or more (including two). Similarly, "multiple groups" refers to two or more groups (including two groups), and "multiple pieces" refers to two or more pieces (including two pieces).

[0071] In the description of the embodiments of the present application, for technical terms such as "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc., the orientation or positional relationship indicated is based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the embodiments of the present application and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, it should not be construed as a limitation to the embodiments of the present application.

[0072] In the description of the embodiments of the present application, unless otherwise clearly specified and limited, technical terms such as "installation", "connection", "connection", "fixation", etc. should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or integrated; it can also be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the communication inside two elements or the interaction relationship between two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the embodiments of the present application can be understood according to specific circumstances.

[0073] In the prior art, the carbon and sulfur in ores are mostly determined by separate determination methods. In actual production, if determined separately, it is both time-consuming and costly. In most ore samples, the sulfur content is generally relatively high, and it is more suitable to be detected by the volumetric method. At present, there are few continuous determination methods, and most of the methods for continuous determination of carbon and sulfur are high-frequency infrared absorption methods, and the volumetric method is rarely seen. Moreover, the instrument method has a high cost and a narrow determination range, and it is also difficult to achieve continuous determination of carbon and sulfur in many enterprises.

[0074] To solve the above technical problems, the present application provides a method and device for continuously determining carbon and sulfur in ores. By using a multi-stage sulfur absorption titration device in combination with a carbon absorption titration device, sulfur is converted into sulfur dioxide and then into sulfuric acid, and carbon is converted into carbon dioxide and then into carbonic acid. Then, it is calibrated with the standard potassium hydroxide solution in the prepared carbon standard titration solution, and the generated sulfuric acid is calibrated with sodium hydroxide solution. In this way, the contents of carbon and sulfur in the target sample can be measured by burning the sample only once.

[0075] For the convenience of description, the following examples will illustrate a method and device for continuously determining carbon and sulfur in ores according to an embodiment of the present application.

[0076] Please refer to Figure 1 , Figure 1 which is a schematic structural diagram of a device for continuously determining carbon and sulfur in ores provided by some embodiments of the present application.

[0077] In a first aspect, in some embodiments of the present application, a device for continuously determining carbon and sulfur in ores includes: a gas supply device, a reaction device connected to the gas supply device, and a titration device connected to the reaction device.

[0078] The titration device includes a plurality of sulfur absorption titration devices connected to the reaction device and a plurality of carbon absorption titration devices connected to the sulfur absorption titration devices; the plurality of sulfur absorption titration devices are connected end to end in sequence.

[0079] The plurality of sulfur absorption titration devices include a first-stage sulfur absorption titration device connected to the reaction device, a second-stage sulfur absorption titration device connected to the first-stage sulfur absorption titration device,..., and an n-stage sulfur absorption titration device connected to the (n - 1)-stage sulfur absorption titration device.

[0080] The plurality of carbon absorption titration devices include a path A1 carbon absorption titration device connected to the n-stage sulfur absorption titration device.

[0081] By improving the absorption bottles for measuring sulfur and carbon, multi-stage absorption of sulfur with different contents can be achieved, improving work efficiency and making the determination of sulfur in the sample more accurate and reliable.

[0082] Further, in the embodiments of the present application, the plurality of carbon absorption titration devices further include a path A2 carbon absorption titration device connected to a branch of the pipeline connecting the first-stage sulfur absorption titration device and the second-stage sulfur absorption titration device, a path A3 carbon absorption titration device connected to a branch of the pipeline connecting the second-stage sulfur absorption titration device and the third-stage sulfur absorption titration device,..., and a path A m carbon absorption titration device connected to a branch of the pipeline connecting the (n - 1)-stage sulfur absorption titration device and the n-stage sulfur absorption titration device;

[0083] Further, in the embodiments of the present application, the n-stage sulfur absorption titration device includes an n-stage sulfur absorption titration flask, a burette n used in conjunction with the n-stage sulfur absorption titration flask, and a light source 313; the n-stage sulfur absorption titration flask includes a flask and an L-shaped gas guide tube used in conjunction with the flask. The L-shaped gas guide tube extends to the bottom of the flask and is sealed, and a plurality of orifices are provided at the bottom of the flask where the L-shaped gas guide tube extends;

[0084] The passage A m The carbon absorption titration device includes the passage A m A carbon absorption titration flask, and a burette used in conjunction with the passage A m A carbon absorption titration flask, and a light source 313; the passage A m The carbon absorption titration flask includes a reflux flask and an L-shaped gas guide tube used in conjunction with the reflux flask. The L-shaped gas guide tube extends to the bottom of the reflux flask and is sealed, and a plurality of orifices are provided at the bottom of the reflux flask where the L-shaped gas guide tube extends;

[0085] Control valves 35 are provided on the pipelines for connecting a plurality of sulfur absorption titration devices, and control valves 35 are provided on the pipelines for connecting the sulfur absorption titration device and the carbon absorption titration device.

[0086] In a second aspect, the present application further provides a method for continuously determining carbon and sulfur in ores. Using the above-mentioned device for continuously determining carbon and sulfur in ores, the method includes the following steps:

[0087] S1. Prepare a sulfur absorption solution, a sulfur standard titration solution, a carbon absorption solution, and a carbon standard titration solution;

[0088] And place the sulfur absorption solution in the first-stage sulfur absorption titration flask 311, the second-stage sulfur absorption titration flask 321,..., the n-stage sulfur absorption titration flask respectively, and place the sulfur standard titration solution in the burette used in conjunction with a plurality of sulfur absorption titration flasks.

[0089] Place the carbon absorption solution in the passage A1 carbon absorption titration flask 332, the passage A2 carbon absorption titration flask 341,..., the passage A m Carbon absorption titration flask, and place the carbon standard titration solution in the burette used in conjunction with a plurality of carbon absorption titration flasks;

[0090] S2. Under an oxygen atmosphere, place the target sample in a high-temperature furnace at 1250 °C to 1300 °C for calcination; meanwhile, turn on the light source 313 at the sulfur absorption titration flask and the carbon absorption titration flask; open the control valve 35 on the pipeline connecting several sulfur absorption titration devices, open the control valve 35 on the pipeline connecting the n-stage sulfur absorption titration device and the carbon absorption titration device of the passage A1, and close the branch of the pipeline connecting the n-1 stage sulfur absorption titration device and the n-stage sulfur absorption titration device and the control valve 35 on the pipeline connecting to the carbon absorption titration device of the passage A m on the pipeline connecting to the carbon absorption titration device;

[0091] The oxygen flow rate is 0.15 L / min to 0.2 L / min;

[0092] S3. When it is found that the carbon absorption liquid in the carbon absorption titration flask of the passage A m fades, immediately open the burette used in conjunction with the carbon absorption titration flask of the passage A m and titrate with a carbon standard titration solution. Wait until the carbon absorption liquid turns into a stable bright blue color, which is the titration end point, and record the volume of the carbon standard titration solution consumed at this time V C1 , and calculate the carbon content;

[0093] The calculation formula for the carbon content is:

[0094] ;

[0095] W ( C )——The mass fraction of carbon, %;

[0096] T C / KOH ——Carbon titration degree;

[0097] V C1 ——The volume of the carbon standard titration solution consumed by the sample, ml;

[0098] m ——The mass of the sample, g;

[0099] Carbon titration degree T C / KOH The determination process of

[0100] When it is found that the carbon absorption liquid in the carbon absorption titration flask 341 of passage A2 fades, immediately open the burette used in conjunction with the carbon absorption titration flask 341 of passage A2, titrate with the carbon standard titration solution, and wait until the carbon absorption liquid turns into a stable bright blue color, which is the titration end point, and record the volume of the carbon standard titration solution consumed at this time V KOH , and calculate the carbon titration degree T C / KOH ; among them, the formula for calculating the carbon titration degree T C / KOH is as follows:

[0101] ;

[0102] V KOH —— Volume of the carbon standard titration solution consumed by calcium carbonate, ml;

[0103] m 1 - Mass of the dried calcium carbonate, g;

[0104] S4. After the above steps are completed, close the control valve 35 on the pipeline connecting the n - stage sulfur absorption titration device and the carbon absorption titration device of passage A1;

[0105] Open the burette used in conjunction with the n - stage sulfur absorption titration flask, and titrate the sulfur absorption liquid in the n - stage sulfur absorption titration flask with the sulfur standard titration solution until the solution color changes from purple to a stable bright green color, which is the titration end point, and record the volume of the sulfur standard titration solution consumed at this time V S（n） , and calculate the sulfur content in the n - stage sulfur absorption titration flask W ( S ) (n);

[0106] S5. After the above steps are completed, close the control valve 35 on the pipeline connecting the (n - 1) - stage sulfur absorption titration device and the n - stage sulfur absorption titration device;

[0107] Open the burette used in conjunction with the (n - 1) - stage sulfur absorption titration flask, and titrate the sulfur absorption liquid in the (n - 1) - stage sulfur absorption titration flask with the sulfur standard titration solution until the solution color changes from purple to a stable bright green color, which is the titration end point, and record the volume of the sulfur standard titration solution consumed at this time V S（n-1） , and calculate the sulfur content in the (n - 1) - stage sulfur absorption titration flask W ( S ) (n - 1);

[0108] ……;

[0109] Until the sulfur content in the primary sulfur absorption titration flask 311 is calculated W ( S )1;

[0110] Then the total sulfur content is W ( S ) = W ( S )(n) + W ( S )(n - 1) + …… + W ( S )1;

[0111] The sulfur content in the n - level sulfur absorption titration flask W ( S )(n) is calculated by the formula:

[0112] ;

[0113] W ( S )(n) —— the mass fraction of sulfur in the n - level sulfur absorption titration flask, %;

[0114] T S / NaOH —— sulfur titration degree;

[0115] V S（n） —— the volume of the sulfur standard titration solution consumed by the sample in the n - level sulfur absorption titration device, ml;

[0116] m —— the mass of the sample, g;

[0117] Sulfur titration degree T S / NaOH The determination process of m includes: Under an oxygen atmosphere, calcine the dried lead sulfate and copper oxide at high temperature; meanwhile, turn on the light sources 313 at the primary sulfur absorption titration device, ……, the n - level sulfur absorption titration device; open the control valves 35 on the pipelines connecting the primary sulfur absorption titration device and the secondary sulfur absorption titration device, ……, open the control valves 35 on the pipelines connecting the (n - 1) - level sulfur absorption titration device and the n - level sulfur absorption titration device; close the control valves 35 on the pipelines connecting the primary sulfur absorption titration device and the passage A2 carbon absorption titration device, ……, close the control valves 35 on the pipelines connecting the (n - 1) - level sulfur absorption titration device and the passage A m carbon absorption titration device;

[0118] When it is found that the sulfur absorption solution in the sulfur absorption titration flask fades, immediately open the burette used in conjunction with the sulfur absorption titration flask, and titrate with the sulfur standard titration solution. When the sulfur absorption solution changes from purple to a stable bright green, it is the titration end point, and record the volume of the sulfur standard titration solution consumed at this time. V NaOH , calculate the sulfur titration degree T S / NaOH ; Among them, the sulfur titration degree T S / NaOH The calculation formula is:

[0119] ;

[0120] V NaOH —— The volume of the sulfur standard titration solution consumed by lead sulfate, ml;

[0121] m 2—— The mass of dried lead sulfate, g.

[0122] In this method, the sample is placed in a high-temperature oxygen stream for combustion, and the sulfur dioxide and carbon dioxide generated by combustion are absorbed by hydrogen peroxide solution to form carbonic acid and sulfuric acid. The generated carbonic acid is decomposed into carbon dioxide and water to achieve the separation of carbon and sulfur; among them, carbon dioxide is absorbed by ethanolamine and calibrated with the standard potassium hydroxide solution in the prepared carbon standard titration solution. In the calibration method of carbon dioxide here, the carbon standard titration solution used has the same composition as the carbon absorption solution used, but the content of each component in the carbon absorption solution is not limited: when the content of ethanolamine in the carbon absorption solution is excessive, it can completely absorb carbon and perform reverse calibration. If the content of ethanolamine in the carbon absorption solution is insufficient, the carbon standard titration solution can be continuously supplemented and calibrated at the same time. This method provides another idea for the calibration method of carbon; and the generated sulfuric acid is calibrated with sodium hydroxide solution. Compared with the separate determination methods of carbon and sulfur, only one combustion of the sample is required to measure the carbon and sulfur contents in the target sample; and by measuring carbon in this way, the carbon content in the sample can be accurately measured in the range of 0.10% - 25.00%, thus greatly expanding the measurement range of carbon.

[0123] Furthermore, in the embodiment of the present application, when the calculated sulfur content value in the nth-level sulfur absorption titration flask is less than 4%, the method for continuously determining carbon and sulfur in ore includes:

[0124] Open the branch and path A of the pipeline connecting the nth-level sulfur absorption titration device and the (n - 1)th-level sulfur absorption titration device mThe control valve 35 on the pipeline connected to the carbon absorption titration device, while closing the control valves 35 of the pipelines connected to the n-stage sulfur absorption titration device and the n-1-stage sulfur absorption titration device. When it is found that the passage A m When the carbon absorption solution in the carbon absorption titration flask fades, immediately open the burette used in conjunction with the carbon absorption titration flask for passage A m Titrate with a carbon standard titration solution until the carbon absorption solution turns bright blue and remains stable, which is the titration end point, and record the volume of the carbon standard titration solution V C1 , calculate the carbon content; after the above steps are completed, then close the branch of the pipeline connecting the n-stage sulfur absorption titration device and the n-1-stage sulfur absorption titration device and passage A m The control valve 35 on the pipeline connected to the carbon absorption titration device (at this time, the control valve 35 on the pipeline connecting the n-stage sulfur absorption titration device and the n-1-stage sulfur absorption titration device is also closed), open the burettes used in conjunction with the first-stage sulfur absorption titration flask, ……, the burettes used in conjunction with the n-1-stage sulfur absorption titration flask, and titrate the sulfur absorption solution with a sulfur standard titration solution until the solution color changes from purple to bright green, which is the titration end point, and record the volume of the sulfur standard titration solution, calculate the sulfur content in each sulfur absorption titration flask, and finally add up the sulfur contents in all the obtained sulfur absorption titration flasks, which is the total sulfur content.

[0125] Furthermore, in the embodiment of the present application, the preparation process of the sulfur absorption solution includes: adding 30 mL of mixed indicator to 100 mL of hydrogen peroxide with a mass concentration of 30%, and then diluting to 2 L with H2O.

[0126] The preparation method of the mixed indicator includes: dissolving 0.12 g of methyl red and 0.83 g of methylene blue in 100 mL of absolute ethanol.

[0127] Using hydrogen peroxide as a desulfurizing agent can mask the influence of sulfur on carbon determination, make the carbon absorption solution clear, the end point is easy to observe, and can simultaneously achieve sulfur determination, reduce the experimental cost, improve the test speed of the sample, and at the same time solve the disadvantages of high cost and narrow determination range of carbon and sulfur by instrumental methods. It does not affect the carbon determination, eliminates the interference of sulfur oxides on carbon determination, and can continue titration after completely absorbing sulfur.

[0128] Furthermore, in the embodiment of the present application, the preparation process of the sulfur standard titration solution is: dissolving 40 g of sodium hydroxide in H2O and diluting to 10 L.

[0129] Further, in the embodiment of the present application, the preparation process of the carbon absorption liquid includes: dissolving ethanolamine in absolute ethanol, then adding potassium hydroxide, and after the potassium hydroxide is completely dissolved, adding thymolphthalein, then mixing evenly, filtering and storing for standby; wherein, in the carbon absorption liquid, ethanolamine:absolute ethanol:potassium hydroxide:thymolphthalein = 30 ml:970 ml:3 g:150 mg.

[0130] Further, in the embodiment of the present application, the preparation process of the carbon standard titration solution includes: dissolving ethanolamine in absolute ethanol, then adding potassium hydroxide, and after the potassium hydroxide is completely dissolved, adding thymolphthalein, then mixing evenly, filtering and storing for standby, wherein, in the carbon standard titration solution, ethanolamine:absolute ethanol:potassium hydroxide:thymolphthalein = 30 ml:970 ml:3 g:150 mg.

[0131] The principle of titrating carbon is as follows: Ethanolamine absorbs carbon dioxide: HOC2H4NH2 + CO2 → HOCH2CH2NH-COOH (ethyl bicarbonate);

[0132] Ethanol reacts with potassium hydroxide: CH3CH2OH + KOH → CH3CH2OK + H2O;

[0133] The reaction during titration:

[0134] HOCH2CH2NH-COOH + CH3CH2OK → HOCH2CH2NH2 + CH3CH2O-C=OOK.

[0135] Example 1

[0136] An apparatus for continuously determining carbon and sulfur in an ore includes a gas supply device, a reaction device connected to the gas supply device, and a titration device connected to the reaction device;

[0137] The gas supply device includes an oxygen cylinder 11, an electronic flowmeter 12, and a gas washing device 13;

[0138] The reaction device includes a power supply 21, a voltmeter 22, and a high-temperature combustion carbon determination furnace 23;

[0139] The titration device includes a primary sulfur absorption titration device (a primary sulfur absorption titration flask 311, a first burette 312 used in conjunction with the primary sulfur absorption titration flask 311, a light source 313) connected to the high-temperature combustion carbon determination furnace 23 through a first pipeline 314, a secondary sulfur absorption titration device (a secondary sulfur absorption titration flask 321, a second burette 322 used in conjunction with the secondary sulfur absorption titration flask 321, a light source 313) connected to the primary sulfur absorption titration device through a second pipeline 323, a path A1 carbon absorption titration device (a drying device 331 (a drying bottle containing discolored silica gel) connected to the secondary sulfur absorption titration device, a path A1 carbon absorption titration flask 332 connected to the drying device 331, a third burette 333, a light source 313) connected to the secondary sulfur absorption titration device through a third pipeline 334, and a path A2 carbon absorption titration device (a path A2 carbon absorption titration flask 341 connected to a branch nozzle on the first pipeline 314, a fourth burette 342, a light source 313) connected to a branch port of the second pipeline 323 through a fourth pipeline 343. Control valves 35 are provided on the first pipeline 314, the third pipeline 334, and the fourth pipeline 343; a control valve 35 is provided on the second pipeline 323 between the branch port of the second pipeline 323 and the secondary sulfur absorption titration device.

[0140] A method for continuously determining carbon and sulfur in an ore, using the above-mentioned device for continuously determining carbon and sulfur in an ore, includes the following steps:

[0141] S1. Prepare a sulfur absorption solution, a sulfur standard titration solution; a carbon absorption solution, a carbon standard titration solution;

[0142] The preparation process of the sulfur absorption solution is as follows: Add 30 mL of a mixed indicator to 100 mL of hydrogen peroxide with a mass concentration of 30%, and then dilute it to 2 L with H2O;

[0143] The preparation method of the mixed indicator is: Weigh 0.12 g of methyl red and 0.83 g of methylene blue and dissolve them in 100 mL of absolute ethanol;

[0144] The preparation process of the sulfur standard titration solution is as follows: Dissolve 40 g of sodium hydroxide (molecular weight 40) in H2O and dilute it to 10 L;

[0145] The preparation process of the carbon absorption solution is as follows: Dissolve 30 ml of ethanolamine in 970 ml of absolute ethanol, then add 3.0 g of potassium hydroxide. After the potassium hydroxide is completely dissolved, add 150 mg of thymolphthalein, then mix well, filter and store for later use; the concentration of potassium hydroxide in this solution is 0.05 mol / L;

[0146] The preparation process of the carbon standard titration solution is as follows: Dissolve 30 ml of ethanolamine in 970 ml of absolute ethanol, then add 3.0 g of potassium hydroxide. After the potassium hydroxide is completely dissolved, add 150 mg of thymolphthalein, then mix well, filter and store for later use; the concentration of potassium hydroxide in this solution is 0.05 mol / L;

[0147] And place the sulfur absorption solution in the first-stage sulfur absorption titration flask 311 and the second-stage sulfur absorption titration flask 321, and place the sulfur standard titration solution in burette 1 312 and burette 2 322.

[0148] Place the carbon absorption solution in the path A1 carbon absorption titration flask 332 and the path A2 carbon absorption titration flask 341, and place the carbon standard titration solution in burette 3 333 and burette 4 342;

[0149] S2. Turn on the light source 313 at the sulfur absorption titration flask and the carbon absorption titration flask; Open the control valves 35 on pipeline 1 314, pipeline 2 323, and pipeline 3 334, and close the control valve 35 on pipeline 4 343; Adjust the flow rate of oxygen to 0.2 L / min; Raise the temperature in the combustion carbon determination furnace to 1300 °C;

[0150] Under an oxygen atmosphere, quickly push the porcelain boat containing the test sample (0.1015 g of No. 1 gold concentrate and 0.2000 g of copper oxide) into the highest temperature part of the conical porcelain tube in the combustion carbon determination furnace with a nickel-chromium wire, immediately seal the combustion carbon determination furnace, and calcine the sample at 1300 °C; At the same time, the generated gas flows into the first-stage sulfur absorption titration flask 311, the second-stage sulfur absorption titration flask 321, and the path A1 carbon absorption titration flask 332 in sequence;

[0151] S3. When it is found that the carbon absorption solution in the path A1 carbon absorption titration flask 332 fades, immediately open burette 3 333 and titrate with the carbon standard titration solution. When the carbon absorption solution turns bright blue and remains stable for more than 60 s, it is the titration end point, and record the volume of the carbon standard titration solution consumed at this time V C1 (5.2800 ml), and calculate the carbon content;

[0152] The calculation formula for the carbon content is:

[0153] ;

[0154] W ( C ) —— mass fraction of carbon, %;

[0155] T C / KOH —— carbon titration degree;

[0156] VC1 —— Volume of the carbon standard titration solution consumed by the test sample, ml;

[0157] m —— Mass of the test sample, g;

[0158] V 空白 —— Volume of the carbon standard titration solution consumed during the blank test on the test sample, ml;

[0159] Carbon titration degree T C / KOH The determination process of is as follows: Under an oxygen atmosphere, calcium carbonate (0.1000 g) and copper oxide (0.2000 g) dried at 110 °C are placed in a calciner at 1300 °C; at the same time, the light source 313 at the carbon absorption titration device of passage A2 is turned on; the control valve 35 on the pipeline connecting the primary sulfur absorption titration device and the carbon absorption titration device of passage A2 is opened, and the control valve 35 on the pipeline connecting the primary sulfur absorption titration device and the secondary sulfur absorption titration device is closed;

[0160] When it is found that the carbon absorption liquid in the carbon absorption titration flask 341 of passage A2 fades, immediately open the burette used in conjunction with the carbon absorption titration flask 341 of passage A2, and titrate with the carbon standard titration solution. Wait until the carbon absorption liquid becomes a stable bright blue color, which is the titration end point, and record the volume of the carbon standard titration solution consumed at this time V KOH (20 ml), and calculate the carbon titration degree T C / KOH ; among them, the carbon titration degree T C / KOH The calculation formula is:

[0161] ;

[0162] V KOH —— Volume of the carbon standard titration solution consumed by calcium carbonate, ml;

[0163] m 1—— Mass of the dried calcium carbonate, g;

[0164] S4. After the above steps are completed, close the control valve 35 on pipeline three 334;

[0165] Open burette two 322, and titrate the sulfur absorption liquid in the secondary sulfur absorption titration flask 321 with the sulfur standard titration solution until the color of the solution changes from purple to a stable bright green color, which is the end point, and record the volume of the sulfur standard titration solution consumed at this time V S2(2.05 mL), calculate the sulfur content in the secondary sulfur absorption titration flask 321. W ( S )2 (4.04%);

[0166] S5. After the above steps are completed, close the control valve 35 on the pipeline two 323.

[0167] Open the burette one 312, and titrate the sulfur absorption solution in the primary sulfur absorption titration flask 311 with the sulfur standard titration solution until the color of the solution changes from purple to stable bright green, which is the titration end point, and record the volume of the sulfur standard titration solution consumed at this time. V S1 (14.38 ml), calculate the sulfur content in the primary sulfur absorption titration flask 311. W ( S )1 (28.34%);

[0168] Then the total sulfur content is W ( S ) = W ( S )2 + W ( S )1;

[0169] The sulfur content in the n - level sulfur absorption titration flask W ( S ) (n) is calculated by the formula:

[0170] ;

[0171] W ( S ) (n) —— the mass fraction of sulfur in the n - level sulfur absorption titration flask, %;

[0172] T S / NaOH — sulfur titration degree;

[0173] V S（n） —— the volume of the sulfur standard titration solution consumed by the sample in the n - level sulfur absorption titration device, ml;

[0174] m —— the mass of the sample, g;

[0175] V 空白 —— the volume of the sulfur standard titration solution consumed in the blank experiment of the sample, ml;

[0176] Sulfur titration degree T S / NaOHThe determination process is as follows: Under an oxygen atmosphere, lead sulfate (0.3700 g) dried at 110 °C and copper oxide (0.2000 g) are placed in a high-temperature furnace at 1300 °C for calcination; meanwhile, turn on the light source 313 at the first-stage sulfur absorption titration device and the second-stage sulfur absorption titration device; open the control valve 35 on the pipeline connecting the first-stage sulfur absorption titration device and the second-stage sulfur absorption titration device; close the control valve 35 on the pipeline connecting the first-stage sulfur absorption titration device and the passage A2 carbon absorption titration device; close the control valve 35 on the pipeline connecting the second-stage sulfur absorption titration device and the passage A1 carbon absorption titration device;

[0177] When it is found that the sulfur absorption solution in the sulfur absorption titration flask fades, immediately open the burette used in conjunction with the sulfur absorption titration flask, and titrate with the sulfur standard titration solution. When the sulfur absorption solution changes from purple to stable bright green, it is the titration end point, and record the volume of the sulfur standard titration solution consumed at this time V NaOH (19.55 ml), and calculate the sulfur titration degree T S / NaOH ; Among them, the sulfur titration degree T S / NaOH The calculation formula is:

[0178] ;

[0179] V NaOH ——The volume of the sulfur standard titration solution consumed by lead sulfate, ml;

[0180] m 2——The mass of dried lead sulfate, g;

[0181] Finally, the measured sulfur content is 32.38% and the carbon content is 3.12%.

[0182] Among them, since the value of the sulfur content calculated in the second stage is less than 4%, the control valve 35 on the pipeline four 343 can also be opened, and at the same time, the control valve on the pipeline two 323 is closed. When it is found that the carbon absorption solution in the passage A2 carbon absorption titration flask 341 fades, immediately open the burette four 342 and titrate with the carbon standard titration solution. When the carbon absorption solution turns blue and remains stable for more than 60 s, it is the titration end point, and record the volume of the carbon standard titration solution V C2 , calculate the carbon content; after completion, then close the control valve 35 on the pipeline four 343 (and close the control valve 35 on the pipeline two 323), open the burette one 312, and titrate the sulfur absorption solution in the first-stage sulfur absorption titration flask 311 with the sulfur standard titration solution until the solution color changes from purple to bright green, which is the end point, and record the volume of the sulfur standard titration solution V C3, calculate the sulfur content.

[0183] National standard method:

[0184] Using the national standard method GB / T 7739.8-2022 gravimetric method to measure sulfur: Weigh 0.1045 g of the first gold concentrate sample. After semi-fusing it at 780 °C with a mixed flux of sodium carbonate, zinc oxide, and potassium permanganate, dissolve the soluble substances with water. Sulfur is converted into sulfate and enters the solution. Then, precipitate the sulfate in the solution with barium chloride. After filtration and burning of the precipitate, weigh it. Calculate the sulfur content in the test sample as 32.40% based on the mass of barium sulfate.

[0185] Using the national standard method GB / T 6730.61-2022 high-frequency combustion infrared absorption method: Weigh 0.1012 g of the test sample and heat it in an oxygen stream in a high-frequency induction furnace for combustion. The generated carbon dioxide (or carbon monoxide) is carried by oxygen to the measurement chamber of the infrared analyzer. Carbon dioxide (or carbon monoxide) absorbs infrared energy of a specific wavelength, and the absorbed energy is proportional to its concentration. Measure the carbon content as 3.20% according to the change in energy received by the detector.

[0186] The sulfur content measured by the national standard method is 32.40%, and the carbon content is 3.2%.

[0187] The above experimental results are all the average values taken after repeating the experiment 5 times.

[0188] Examples 2 - 6

[0189] Examples 2 - 6 provide a method for continuous determination of carbon and sulfur in ores. The difference from Example 1 is the different target test samples selected. The target test samples selected in Examples 2 - 6 are the second gold concentrate sample, cast iron powder injection carbon and sulfur, arsenic ore, gold concentrate standard sample GBW07231 (the standard value of sulfur content is 31.00%, and the standard value of carbon content is 0.28%), and sample 6 respectively. The remaining steps are the same as those in Example 1 and will not be elaborated here.

[0190] The finally measured sulfur content of the second gold concentrate sample is 15.66%, and the carbon content is 6.15% (the values measured by the national standard method are sulfur content 15.65% and carbon content 6.13%);

[0191] The sulfur content of cast iron powder injection carbon and sulfur is 5.52%, and the carbon content is 4.15% (the values measured by the national standard method are sulfur content 5.50% and carbon content 4.16%).

[0192] The sulfur content of arsenic ore is 4.50%, and the carbon content is 3.08% (the values measured by the national standard method are sulfur content 4.51% and carbon content 3.05%).

[0193] The sulfur content in the gold concentrate standard sample GBW07231 is 30.96%, and the carbon content is 0.26%.

[0194] The sulfur content in Sample 6 is 8.25%, and the carbon content is 20.80% (the values measured by the national standard method are sulfur content of 8.30% and carbon content of 20.93%).

[0195] Compared with the national standard method, it can be seen that the measurement method of the method provided by this application has higher accuracy.

[0196] Please refer to Figure 1 , according to one or more embodiments of this application, this application sets up a continuous carbon and sulfur determination device for ores composed of a gas supply device, a reaction device, and a titration device. The titration device includes a number of sulfur absorption titration devices connected to the reaction device and a number of carbon absorption titration devices connected to the sulfur absorption titration devices; the number of sulfur absorption titration devices are connected end to end in sequence; the number of sulfur absorption titration devices includes a primary sulfur absorption titration device, a secondary sulfur absorption titration device,..., an n-level sulfur absorption titration device connected to the reaction device; the number of carbon absorption titration devices includes a passage A1 carbon absorption titration device connected to the n-level sulfur absorption titration device; the sample is placed in a high-temperature oxygen stream for combustion, and the sulfur dioxide and carbon dioxide generated by combustion are absorbed by hydrogen peroxide solution, and then carbonic acid and sulfuric acid are formed, and the generated carbonic acid is decomposed into carbon dioxide and water to achieve the separation of carbon and sulfur and remove the interference of sulfur dioxide on carbon determination; among them, carbon dioxide is absorbed by ethanolamine, thymolphthalein is used as an indicator, and the standard potassium hydroxide solution in the prepared carbon standard titration solution is used for calibration. In the calibration method of carbon dioxide here, the carbon standard titration solution used has the same composition as the carbon absorption solution used, but the content of each component in the carbon absorption solution is not limited: when the content of ethanolamine in the carbon absorption solution is excessive, it can completely absorb carbon and perform reverse calibration. If the content of ethanolamine in the carbon absorption solution is insufficient, the carbon standard titration solution can be continuously supplemented and calibrated at the same time. This method provides another idea for the calibration method of carbon; and the generated sulfuric acid is calibrated with sodium hydroxide solution. Compared with the separate determination methods of carbon and sulfur, only one combustion of the sample is required to measure the carbon and sulfur contents in the target sample; and by measuring carbon in this way, the influence of sulfur on carbon measurement can be masked, making the carbon absorption solution clear, the end point easy to observe, and the carbon content in the sample can be accurately measured within the range of 0.10% - 25.00%, thus greatly expanding the carbon measurement range.

[0197] It should be noted that this application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and embodiments with the same composition and the same effect as the technical idea within the scope of the technical solution of this application are all included in the technical scope of this application. In addition, within the scope of not departing from the gist of this application, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways constructed by combining some of the constituent elements in the embodiments are also included in the scope of this application.

Claims

1. A method for continuously determining carbon and sulfur in an ore, characterized in that, The continuous determination method of carbon and sulfur in the ore is carried out by using a continuous determination device for carbon and sulfur in the ore. The continuous determination device for carbon and sulfur in the ore includes: a gas supply device, a reaction device connected to the gas supply device, and a titration device connected to the reaction device; The titration device includes a plurality of sulfur absorption titration devices connected to the reaction device and a plurality of carbon absorption titration devices connected to the sulfur absorption titration devices; the plurality of sulfur absorption titration devices are connected end to end in sequence; The plurality of sulfur absorption titration devices include a primary sulfur absorption titration device connected to the reaction device, a secondary sulfur absorption titration device connected to the primary sulfur absorption titration device,..., an nth-stage sulfur absorption titration device connected to the (n - 1)th-stage sulfur absorption titration device; The plurality of carbon absorption titration devices include a path A1 carbon absorption titration device connected to the nth-stage sulfur absorption titration device; A number of carbon absorption titration devices further include a path A2 carbon absorption titration device connected to a branch of a pipeline connecting a primary sulfur absorption titration device and a secondary sulfur absorption titration device, a path A3 carbon absorption titration device connected to a branch of a pipeline connecting a secondary sulfur absorption titration device and a tertiary sulfur absorption titration device, ……, a path An carbon absorption titration device connected to a branch of a pipeline connecting an (n-1)-th stage sulfur absorption titration device and an n-th stage sulfur absorption titration device m carbon absorption titration device; The continuous determination method of carbon and sulfur in the ore includes the following steps: S1. Prepare a sulfur absorption solution, a sulfur standard titration solution, a carbon absorption solution, and a carbon standard titration solution; And place the sulfur absorption solution in a primary sulfur absorption titration flask, a secondary sulfur absorption titration flask,..., an nth-stage sulfur absorption titration flask respectively, and place the sulfur standard titration solution in a burette used in conjunction with the plurality of sulfur absorption titration flasks, Place the carbon absorption liquid in the carbon absorption titration flask of path A1, the carbon absorption titration flask of path A2, ……, the carbon absorption titration flask of path A m Place the carbon standard titration solution in a burette used in conjunction with a number of carbon absorption titration flasks; S2. Under an oxygen atmosphere, place the target sample in a high-temperature calcination; meanwhile, turn on the light sources at the sulfur absorption titration flask and the carbon absorption titration flask; open the control valve on the pipeline connecting several sulfur absorption titration devices, open the control valve on the pipeline connecting the nth-stage sulfur absorption titration device and the carbon absorption titration device of the passage A1, and close the control valve on the pipeline connecting the branch of the pipeline connecting the (n - 1)th-stage sulfur absorption titration device and the nth-stage sulfur absorption titration device and the passage A m carbon absorption titration device; S3. When it is found that the carbon absorption liquid in the carbon absorption titration flask of passage A1 fades, immediately open the burette used in conjunction with the carbon absorption titration flask of passage A1, titrate with the carbon standard titration solution, and wait until the carbon absorption liquid turns into a stable bright blue color, which is the titration end point, and record the volume of the carbon standard titration solution consumed at this time. V C1 , and calculate the carbon content. S4. After the above steps are completed, close the control valve on the pipeline connecting the nth-stage sulfur absorption titration device and the path A1 carbon absorption titration device; Open the burette used in conjunction with the n-level sulfur absorption titration flask, and titrate the sulfur absorption solution in the n-level sulfur absorption titration flask with the sulfur standard titration solution until the color of the solution changes from purple to a stable bright green, which is the titration end point, and record the volume of the sulfur standard titration solution consumed at this time V S（n） , and calculate the sulfur content in the n-level sulfur absorption titration flask W ( S ) (n); S5. After the above steps are completed, close the control valve on the pipeline connecting the (n - 1)th-stage sulfur absorption titration device and the nth-stage sulfur absorption titration device; Open the burette used in conjunction with the sulfur absorption titration flask at the n-1 level, and titrate the sulfur absorption solution in the sulfur absorption titration flask at the n-1 level with the sulfur standard titration solution until the color of the solution changes from purple to stable bright green, which is the titration end point, and record the volume of the sulfur standard titration solution consumed at this time V S（n-1） , and calculate the sulfur content in the sulfur absorption titration flask at the n-1 level W ( S )(n - 1); ……； Until the sulfur content in the primary sulfur absorption titration flask is calculated W ( S ) 1; Then the total sulfur content is W ( S ) = W ( S )(n) + W ( S )(n - 1) + …… + W ( S )1.

2. The method for continuously determining carbon and sulfur in ores according to claim 1, characterized in that, In step S3, the calculation formula for the carbon content is: ； W ( C ) —— mass fraction of carbon, %; T C / KOH —— Carbon titration degree; V C1 —— Volume of the standard titration solution of carbon consumed by the test sample, ml; m —— mass of the test sample, g; Carbon titration T C / KOH The determination process includes: under an oxygen atmosphere, calcining the dried calcium carbonate and copper oxide at high temperature; meanwhile, turning on the light source at the A2 carbon absorption titration device of the passage; opening the control valve on the pipeline connecting the primary sulfur absorption titration device and the A2 carbon absorption titration device of the passage, and closing the control valve on the pipeline connecting the primary sulfur absorption titration device and the secondary sulfur absorption titration device. When it is found that the carbon absorption solution in the carbon absorption titration flask of passage A2 fades, immediately open the burette used in conjunction with the carbon absorption titration flask of passage A2, and titrate with the carbon standard titration solution. When the carbon absorption solution turns into a stable bright blue color, it is the titration end point, and record the volume of the carbon standard titration solution consumed at this time V KOH , and calculate the carbon titration degree T C / KOH ; among them, the formula for calculating the carbon titration degree T C / KOH is as follows: ； V KOH —— Volume of the standard titration solution of carbon consumed by calcium carbonate, ml; m 1—the mass of dried calcium carbonate, g.

3. The method for continuously determining carbon and sulfur in ore according to claim 1, characterized in that, Sulfur content in the sulfur absorption titration flask of n levels W ( S ) The calculation formula of (n) is as follows: ； W ( S ) (n) —— mass fraction of sulfur in the sulfur absorption titration flask of level n, %; T S / NaOH —— Sulfur titration; V S（n） —— The volume of the sulfur standard titration solution consumed by the sample in the n-level sulfur absorption titration device, ml; m —— mass of the test sample, g; Sulfur titration T S / NaOH The determination process includes: under an oxygen atmosphere, calcining dried lead sulfate and copper oxide at high temperature; meanwhile, turning on the light sources at the first-stage sulfur absorption titration device, ……, the n-stage sulfur absorption titration device; opening the control valves on the pipelines connecting the first-stage sulfur absorption titration device and the second-stage sulfur absorption titration device, ……, opening the control valves on the pipelines connecting the (n - 1)-stage sulfur absorption titration device and the n-stage sulfur absorption titration device; closing the control valves on the pipelines connecting the first-stage sulfur absorption titration device and the A2 carbon absorption titration device of the passage A, ……, closing the control valves on the pipelines connecting the (n - 1)-stage sulfur absorption titration device and the m carbon absorption titration device of the passage A; When it is found that the sulfur absorption solution in the sulfur absorption titration flask fades, immediately open the burette used in conjunction with the sulfur absorption titration flask, and titrate with the sulfur standard titration solution. When the sulfur absorption solution changes from purple to a stable bright green color, that is the titration end point, and record the volume of the sulfur standard titration solution consumed at this time. V NaOH , calculate the sulfur titration factor T S / NaOH ; among them, the calculation formula for the sulfur titration factor T S / NaOH is as follows: ； V NaOH —— Volume of the standard titration solution of sulfuric acid consumed by lead sulfate, ml; m 2—the mass of dried lead sulfate, g.

4. The method for continuously determining carbon and sulfur in ore according to claim 1, characterized in that, The preparation process of the sulfur absorption solution includes: adding 30 mL of a mixed indicator to 100 mL of hydrogen peroxide with a mass concentration of 30%, and then diluting it to 2 L with H2O; the preparation method of the mixed indicator includes: dissolving 0.12 g of methyl red and 0.83 g of methylene blue in 100 mL of absolute ethanol.

5. The method for continuously determining carbon and sulfur in ore according to claim 1, characterized in that, The preparation process of the sulfur standard titration solution is: dissolving 40 g of sodium hydroxide in H2O and diluting it to 10 L.

6. The method for continuously determining carbon and sulfur in ore according to claim 1, wherein The preparation process of the carbon absorption solution includes: dissolving ethanolamine in absolute ethanol, then adding potassium hydroxide, and after the potassium hydroxide is completely dissolved, adding thymolphthalein, then mixing evenly, filtering, and storing for later use; among them, in the carbon absorption solution, ethanolamine: absolute ethanol: potassium hydroxide: thymolphthalein = 30 ml: 970 ml: 3 g: 150 mg.

7. The method for continuously determining carbon and sulfur in ore according to claim 1, characterized in that, The preparation process of the carbon standard titration solution includes: dissolving ethanolamine in absolute ethanol, then adding potassium hydroxide, and after the potassium hydroxide is completely dissolved, adding thymolphthalein, then mixing evenly, filtering, and storing for later use, where in the carbon standard titration solution, ethanolamine: absolute ethanol: potassium hydroxide: thymolphthalein = 30 ml: 970 ml: 3 g: 150 mg.

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