Method and device for continuously measuring carbon and sulfur in ore

Abstract

The invention provides a method and a device for continuously measuring carbon and sulfur in ore, and belongs to the field of metal smelting. The device for continuously measuring carbon and sulfur in ore is composed of a reaction device and a titration device; wherein the titration device comprises a plurality of sulfur absorption titration devices connected with the reaction device and a carbon absorption titration device connected with the sulfur absorption titration devices; the sulfur absorption titration devices are sequentially connected end to end; the method comprises the following steps: burning a sample in high-temperature oxygen flow to convert sulfur into sulfur dioxide and carbon into carbon dioxide, absorbing by using a hydrogen peroxide solution and oxidizing into sulfuric acid and carbonic acid, decomposing carbonic acid to generate carbon dioxide and water, separating the carbon dioxide and the water from the sulfur dioxide, enabling the carbon dioxide to enter absorption liquid containing ethanol-ethanolamine along with the oxygen flow, and titrating. According to the invention, the determination of carbon and sulfur can be realized at the same time, and on the premise that the experiment cost can be reduced, the relatively high test precision of the sample is ensured.

Description

Technical Field

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

[0002] During the determination of carbon content in ores, the sulfur contained in the sample will greatly interfere with its determination. If appropriate measures are not taken to absorb the sulfides produced during the combustion process in time, white precipitates will appear in the absorption liquid for carbon determination, making the absorption liquid turbid, making it impossible to determine the end point and achieving accurate carbon determination.

[0003] There are many methods for the separate determination of carbon and sulfur in ores. In the national standard, there are corresponding separate determination methods for gold ore and gold concentrate. If they are determined separately in actual production, it will waste both time and cost. In most ore samples, the sulfur content is generally high, and it is more suitable to be detected by volumetric method. At present, there are very few continuous determination methods. Most of the methods for continuous determination of carbon and sulfur are high-frequency infrared absorption methods, and volumetric methods are rarely seen. The instrumental method is costly and has a narrow measurement range. It is also difficult to achieve continuous determination of carbon and sulfur in many companies. And the continuous determination of carbon and sulfur in ores is even rarer. In addition, for some types of ores, such as the determination of sulfur in lead concentrate and zinc concentrate, the high-frequency infrared absorption method is not suitable. At this time, in order to achieve the continuous determination of the carbon and sulfur content in lead concentrate and zinc concentrate, the volumetric method needs to be used.

[0004] If the national standard methods for determining carbon and sulfur in gold concentrate and gold ore are combined separately, if the generated sulfuric acid is not titrated in time, 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 device for continuous determination of carbon and sulfur in ore to solve the above problems. Summary of the invention

[0006] In view of the technical problems existing in the background technology, the present application provides a method and device for continuous determination of carbon and sulfur in ore. According to the device for continuous determination of carbon and sulfur in ore, when determining the carbon and sulfur content in ore, there is no need to digest the sample separately, and continuous determination of the sample can be achieved.

[0007] In a first aspect, an embodiment of the present application provides a device for continuous determination of carbon and sulfur in an ore, comprising: 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 comprises 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 device; the plurality of sulfur absorption titration devices are connected end to end in sequence; A 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 n-stage sulfur absorption titration device connected to the n-1-stage sulfur absorption titration device; The plurality of carbon absorption titration devices include a channel A1 carbon absorption titration device connected to the n-stage sulfur absorption titration device.

[0008] In the technical solution of the embodiment of the present application, by improving the absorption bottles for measuring sulfur and carbon, multi-stage absorption of sulfur with different contents can be achieved, making the determination of sulfur in the sample more accurate and reliable.

[0009] In some embodiments, the plurality of carbon absorption titration devices further include a passage A2 carbon absorption titration device connected to a branch of a pipeline connecting the primary sulfur absorption titration device and the secondary sulfur absorption titration device, a passage A3 carbon absorption titration device connected to a branch of a pipeline connecting the secondary sulfur absorption titration device and the tertiary sulfur absorption titration device, ..., a passage A4 carbon absorption titration device connected to a branch of a pipeline connecting the n-1 stage sulfur absorption titration device and the n stage sulfur absorption titration device. m Carbon absorption titration apparatus.

[0010] 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; The pathway A m The carbon absorption titration device includes a passage A m Carbon absorption titration bottle, and passage A m A burette and a light source for use with the carbon absorption titration bottle; and / or, The pipelines for connecting the plurality of sulfur absorption titration devices are all provided with control valves, and the pipelines for connecting the sulfur absorption titration device and the carbon absorption titration device are provided with control valves.

[0011] By setting up a multi-channel carbon absorption titration device, it is possible to optimize the determination for ore samples with different sulfur contents, making the device more adaptable.

[0012] In a second aspect, an embodiment of the present application provides a method for continuous determination of carbon and sulfur in an ore, using the above-mentioned device for continuous determination of carbon and sulfur in an ore, comprising the following steps: S1. preparing sulfur absorption solution, sulfur standard titration solution, carbon absorption solution, and carbon standard titration solution; The sulfur absorption liquid is placed in the first-level sulfur absorption titration bottle, the second-level sulfur absorption titration bottle, ..., the n-level sulfur absorption titration bottle, and the sulfur standard titration solution is placed in a burette used in conjunction with several sulfur absorption titration bottles. The carbon absorption liquid is placed in the carbon absorption titration bottle of channel A1, the carbon absorption titration bottle of channel A2, ..., channel A m In a carbon absorption titration bottle, the carbon standard titration solution is placed in a burette used in conjunction with a number of carbon absorption titration bottles; S2. In an oxygen atmosphere, the target sample is calcined at a high temperature; at the same time, the light sources at the sulfur absorption titration bottle and the carbon absorption titration bottle are turned on; the control valve on the pipeline connecting the plurality of sulfur absorption titration devices is opened, the control valve on the pipeline connecting the n-1-level sulfur absorption titration device and the carbon absorption titration device of the passage A1 is opened, and the branch of the pipeline connecting the n-1-level sulfur absorption titration device and the n-level sulfur absorption titration device and the passage A1 is closed. m A control valve on the pipeline connected to the carbon absorption titration device; S3. When path A is found m When the carbon absorption liquid in the carbon absorption titration bottle fades, immediately open the m The burette used with the carbon absorption titration bottle is titrated with the carbon standard titration solution. When the carbon absorption solution turns into a stable bright blue, it is the titration end point, and the volume of the carbon standard titration solution consumed at this time is recorded. V C1 , calculate the carbon content; S4. After the above steps are completed, close the control valve on the pipeline connecting the n-stage sulfur absorption titration device and the carbon absorption titration device in the passage A1; Open the burette used with the n-grade sulfur absorption titration bottle, and titrate the sulfur absorption solution in the n-grade sulfur absorption titration bottle 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） , calculate the sulfur content in the n-stage sulfur absorption titration bottle W ( S )(n); 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; Open the burette used with the n-1 grade sulfur absorption titration bottle, and titrate the sulfur absorption solution in the n-1 grade sulfur absorption titration bottle with the sulfur standard titration solution until the color of the solution changes from purple to a stable bright green, which is the titration endpoint, and record the volume of the sulfur standard titration solution consumed at this time. V S（n-1） , calculate the sulfur content in the n-1 level sulfur absorption titration bottle W ( S )(n-1); ……; Until the sulfur content in the primary sulfur absorption titration bottle is calculated W ( S )1; The total sulfur content is W ( S )= W ( S )(n)+ W ( S )(n-1)+……+ W ( S )1.

[0013] In some embodiments, in step S3, the carbon content is calculated as: ; W ( C )——mass fraction of carbon, %; T C / KOH ——Carbon titer; V C1 ——The volume of carbon standard titration solution consumed by the sample, ml; m ——mass of the sample, g; Carbon titer T C / KOH The determination process includes: calcining dried calcium carbonate and copper oxide at high temperature under oxygen atmosphere; at the same time, turning on the light source at the carbon absorption titration device of channel A2; opening the control valve on the pipeline connecting the primary sulfur absorption titration device and the carbon absorption titration device of channel A2, and closing the control valve on the pipeline connecting the primary sulfur absorption titration device and the secondary sulfur absorption titration device; When the carbon absorption liquid in the carbon absorption titration bottle of channel A2 is found to fade, immediately open the burette used with the carbon absorption titration bottle of channel A2 and titrate with the carbon standard titration solution. When the carbon absorption liquid turns into a stable bright blue, it is the titration end point, and record the volume of the carbon standard titration solution consumed at this time. V KOH , calculate carbon titer T C / KOH ; Among them, carbon titer T C / KOH The calculation formula is: ; V KOH —— Volume of carbon standard titration solution consumed by calcium carbonate, ml; m 1——Mass of dried calcium carbonate, g.

[0014] In some embodiments, the sulfur content in the n-stage sulfur absorption titration bottle is W ( S )(n)is calculated as: ; W ( S ) (n)——mass fraction of sulfur in the n-level sulfur absorption titration bottle, %; T S / NaOH - Sulfur titer; V S（n） ——The volume of sulfur standard titration solution in the n-stage sulfur absorption titration device consumed by the sample, ml; m ——mass of the sample, g; Sulfur titer T S / NaOH The determination process includes: calcining dried lead sulfate and copper oxide at high temperature under oxygen atmosphere; at the same time, turning on the light source at the first-stage sulfur absorption titration device, ..., and the n-stage sulfur absorption titration device; opening the control valve on the pipeline connecting the first-stage sulfur absorption titration device and the second-stage sulfur absorption titration device, ..., opening the control valve on the pipeline connecting the n-1-stage sulfur absorption titration device and the n-stage sulfur absorption titration device; closing the control valve on the pipeline connecting the first-stage sulfur absorption titration device and the carbon absorption titration device of the passage A2, ..., closing the control valve on the pipeline connecting the n-1-stage sulfur absorption titration device and the passage A m A control valve on the pipeline connected to the carbon absorption titration device; When the sulfur absorption solution in the sulfur absorption titration bottle is found to be discolored, immediately open the burette used in conjunction with the sulfur absorption titration bottle 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 endpoint, and record the volume of the sulfur standard titration solution consumed at this time. V NaOH , calculate sulfur titer T S / NaOH ; Among them, sulfur titer T S / NaOH The calculation formula is: ; V NaOH ——The volume of sulfur standard titration solution consumed by lead sulfate, ml; m 2——Mass of dried lead sulfate, g.

[0015] In some embodiments, the preparation process of the sulfur absorption liquid 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: taking 0.12 g of methyl red and 0.83 g of methylene blue and dissolving them in 100 mL of anhydrous ethanol.

[0016] In this embodiment, hydrogen peroxide is used as a desulfurizing agent to mask the influence of sulfur on carbon determination, make the carbon absorption liquid solution clear, and make the endpoint easy to observe. At the same time, sulfur determination can be achieved, thereby reducing experimental costs and increasing sample testing speed. At the same time, the disadvantages of high cost and narrow determination range of carbon and sulfur by instrumental methods are solved. It does not affect the carbon determination, eliminates the interference of sulfur oxides on carbon determination, and can continue titration after the sulfur is completely absorbed.

[0017] In some embodiments, the sulfur standard titration solution is prepared by dissolving 40 g of sodium hydroxide in H2O and diluting to 10 L.

[0018] In some embodiments, the preparation process of the carbon absorption liquid includes: dissolving ethanolamine in anhydrous ethanol, adding potassium hydroxide, and after the potassium hydroxide is completely dissolved, adding thymolphthalein, then mixing, filtering and storing for later use; wherein, the carbon absorption liquid contains ethanolamine: anhydrous ethanol: potassium hydroxide: thymolphthalein = 30ml: 970ml: 3g: 150mg.

[0019] In some embodiments, the preparation process of the carbon standard titration solution includes: dissolving ethanolamine in anhydrous ethanol, adding potassium hydroxide, and after the potassium hydroxide is completely dissolved, adding thymolphthalein, then mixing, filtering and storing for later use, wherein the carbon standard titration solution has ethanolamine: anhydrous ethanol: potassium hydroxide: thymolphthalein = 30ml: 970ml: 3g: 150mg.

[0020] In this embodiment, the sample is placed in a high-temperature oxygen flow and burned. Under the action of a combustion aid, a hydrogen peroxide solution is used to absorb sulfur dioxide and carbon dioxide generated by the combustion, and carbonic acid and sulfuric acid are formed. The generated carbonic acid is decomposed into carbon dioxide and water, thereby achieving separation of carbon and sulfur. The carbon dioxide is absorbed by ethanolamine and calibrated with a standard potassium hydroxide solution in a configured carbon standard titration solution. In the calibration method for carbon dioxide here, the carbon standard titration solution used has the same composition as the carbon absorption liquid used. This has the advantage that when the ethanolamine content in the carbon absorption liquid is excessive, the carbon can be completely absorbed and reversely calibrated. If the ethanolamine content in the carbon absorption liquid is insufficient, the carbon standard titration solution can be continuously supplemented and calibration is performed at the same time. This method provides another idea for the carbon calibration method. The generated sulfuric acid is calibrated with a sodium hydroxide solution. Compared with the separate determination methods of carbon and sulfur, this method only requires one combustion of the sample to determine the carbon and sulfur contents in the target sample; and by determining carbon in this way, the carbon content in the sample within the range of 0.10%-25.00% can be accurately determined, thus greatly expanding the determination range of carbon.

[0021] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solution of the present application, the following is a brief introduction to the drawings used in the present application. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0023] Figure 1 This is a schematic diagram of the structure of the device for continuous determination of carbon and sulfur in ore in the embodiment of the present application.

[0024] Reference numerals 11. Oxygen cylinder; 12. Electronic flow meter; 13. Gas washing device; 21. Power supply; 22. Voltage meter; 23. High temperature combustion carbon setting furnace; 311. Primary sulfur absorption titration bottle; 312. Burette one; 313. Light source; 314. Pipeline one; 321. Secondary sulfur absorption titration bottle; 322. Burette two; 323. Pipeline two; 331. Drying device; 332. Channel A1 carbon absorption titration bottle; 333. Burette three; 334. Pipeline three; 341. Channel A2 carbon absorption titration bottle; 342. Burette four; 343. Pipeline four; 35. Control valve. DETAILED DESCRIPTION

[0025] The following embodiments of the technical solution of the present application are described in detail in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present application.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians 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" in the specification and claims of this application and the above-mentioned figure descriptions and any variations thereof are intended to cover non-exclusive inclusions.

[0027] In the description of the embodiments of the present application, the technical terms "first", "second", etc. are only used to distinguish different objects, and cannot be understood as indicating or implying relative importance or implicitly indicating the number, specific order or primary and secondary relationship of the indicated technical features. In the description of the embodiments of the present application, the meaning of "multiple" is more than two, unless otherwise clearly and specifically defined.

[0028] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0029] In the description of the embodiments of the present application, the term "and / or" is only a description of the association relationship of the associated objects, indicating that there may be three relationships. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0030] In the description of the embodiments of the present application, the term "multiple" refers to more than two (including two). Similarly, "multiple groups" refers to more than two groups (including two groups), and "multiple pieces" refers to more than two pieces (including two pieces).

[0031] In the description of the embodiments of the present application, the technical terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, which are only for the convenience of describing the embodiments of the present application and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the embodiments of the present application.

[0032] In the description of the embodiments of the present application, unless otherwise clearly specified and limited, technical terms such as "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, and it can be the internal connection of 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 the specific circumstances.

[0033] In the prior art, separate determination methods are often used for carbon and sulfur in ores. If they are determined separately in actual production, it will waste both time and cost. In most ore samples, the sulfur content is generally high, and it is more suitable to be detected by volumetric method. Currently, there are few continuous determination methods. Most of the continuous determination methods for carbon and sulfur are high-frequency infrared absorption methods, and volumetric methods are rarely seen. The instrument method is costly and has a narrow determination range. It is also difficult to achieve continuous determination of carbon and sulfur in many enterprises.

[0034] In order to solve the above technical problems, the present application provides a method and device for continuous determination of carbon and sulfur in ore, by using a multi-stage sulfur absorption titration device in combination with a carbon absorption titration device, and converting sulfur into sulfur dioxide and then into sulfuric acid, and converting carbon into carbon dioxide and then into carbonic acid; then calibrating with a standard potassium hydroxide solution in a configured carbon standard titration solution; and calibrating the generated sulfuric acid with a sodium hydroxide solution; in this way, the carbon and sulfur contents in the target sample can be measured by burning the sample only once.

[0035] For the convenience of description, the following embodiments are described by taking a method and device for continuous determination of carbon and sulfur in ore according to an embodiment of the present application as an example.

[0036] Please refer to Figure 1 , Figure 1 A schematic diagram of the structure of a device for continuous determination of carbon and sulfur in ore provided in some embodiments of the present application.

[0037] In a first aspect, in some embodiments of the present application, a device for continuous determination of carbon and sulfur in 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 comprises 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 device; the plurality of sulfur absorption titration devices are connected end to end in sequence; A 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 n-stage sulfur absorption titration device connected to the n-1-stage sulfur absorption titration device; The plurality of carbon absorption titration devices include a channel A1 carbon absorption titration device connected to the n-stage sulfur absorption titration device.

[0038] By improving the absorption bottles for measuring sulfur and carbon, multi-stage absorption of sulfur with different contents can be achieved, which improves work efficiency and makes the determination of sulfur in samples more accurate and reliable.

[0039] Further, in the embodiment of the present application, the plurality of carbon absorption titration devices also include a passage A2 carbon absorption titration device connected to a branch of a pipeline connecting the primary sulfur absorption titration device and the secondary sulfur absorption titration device, a passage A3 carbon absorption titration device connected to a branch of a pipeline connecting the secondary sulfur absorption titration device and the tertiary sulfur absorption titration device, ..., a passage A4 carbon absorption titration device connected to a branch of a pipeline connecting the n-1 stage sulfur absorption titration device and the n stage sulfur absorption titration device. m Carbon absorption titration device; Further, in the embodiment of the present application, the n-stage sulfur absorption titration device comprises an n-stage sulfur absorption titration bottle, a burette n used in conjunction with the n-stage sulfur absorption titration bottle, and a light source 313; the n-stage sulfur absorption titration bottle comprises a flask, an L-shaped air guide tube used in conjunction with the flask, the L-shaped air guide tube extending to the bottom end of the flask is sealed, and the bottom end of the L-shaped air guide tube extending to the flask is provided with a plurality of orifices; The pathway A m The carbon absorption titration device includes a passage A m Carbon absorption titration bottle, and passage A m The burette and light source 313 used in conjunction with the carbon absorption titration bottle; the passage A m The carbon absorption titration bottle comprises a reflux bottle and an L-shaped air guide tube used with the reflux bottle sleeve, wherein the L-shaped air guide tube extends to the bottom end of the reflux bottle and is sealed, and a plurality of orifices are arranged at the bottom end of the L-shaped air guide tube extending to the reflux bottle; The pipelines for connecting the plurality of sulfur absorption titration devices are all provided with control valves 35 , and the pipelines for connecting the sulfur absorption titration device and the carbon absorption titration device are provided with control valves 35 .

[0040] In a second aspect, the present application also provides a method for continuous determination of carbon and sulfur in an ore, using the above-mentioned device for continuous determination of carbon and sulfur in an ore, comprising the following steps: S1. preparing sulfur absorption solution, sulfur standard titration solution, carbon absorption solution, and carbon standard titration solution; The sulfur absorption liquid is placed in the first-level sulfur absorption titration bottle 311, the second-level sulfur absorption titration bottle 321, ..., and the n-level sulfur absorption titration bottle, and the sulfur standard titration solution is placed in a burette used in conjunction with several sulfur absorption titration bottles. The carbon absorption liquid is placed in the carbon absorption titration bottle 332 of channel A1, the carbon absorption titration bottle 341 of channel A2, ..., channel A m In the carbon absorption titration bottle, the carbon standard titration solution is placed in a burette used with several carbon absorption titration bottles; S2. In an oxygen atmosphere, the target sample is calcined at a high temperature of 1250°C to 1300°C; at the same time, the light source 313 at the sulfur absorption titration bottle and the carbon absorption titration bottle is turned on; the control valve 35 on the pipeline connecting the plurality of sulfur absorption titration devices is opened, the control valve 35 on the pipeline connecting the n-1-level sulfur absorption titration device and the carbon absorption titration device of the passage A1 is opened, and the branch of the pipeline connecting the n-1-level sulfur absorption titration device and the n-level sulfur absorption titration device and the passage A1 is closed. m A control valve 35 on the pipeline connected to the carbon absorption titration device; Oxygen flow rate is 0.15 L / min to 0.2 L / min; S3. When path A is found m When the carbon absorption liquid in the carbon absorption titration bottle fades, immediately open the m The burette used with the carbon absorption titration bottle is titrated with the carbon standard titration solution. When the carbon absorption solution turns into a stable bright blue, it is the titration end point, and the volume of the carbon standard titration solution consumed at this time is recorded. V C1 , calculate the carbon content; The calculation formula for carbon content is: ; W ( C )——mass fraction of carbon, %; T C / KOH ——Carbon titer; V C1——The volume of carbon standard titration solution consumed by the sample, ml; m ——mass of the sample, g; Carbon titer T C / KOH The determination process includes: calcining dried calcium carbonate and copper oxide at high temperature under oxygen atmosphere; at the same time, turning on the light source 313 at the carbon absorption titration device of channel A2; opening the control valve on the pipeline connecting the primary sulfur absorption titration device and the carbon absorption titration device of channel A2, and closing the control valve 35 on the pipeline connecting the primary sulfur absorption titration device and the secondary sulfur absorption titration device; When the carbon absorption liquid in the carbon absorption titration bottle 341 of channel A2 is found to fade, immediately open the burette used in conjunction with the carbon absorption titration bottle 341 of channel A2, and titrate with the carbon standard titration solution. When the carbon absorption liquid turns into a stable bright blue, it is the titration end point, and record the volume of the carbon standard titration solution consumed at this time. V KOH , calculate carbon titer T C / KOH ; Among them, carbon titer T C / KOH The calculation formula is: ; V KOH —— Volume of carbon standard titration solution consumed by calcium carbonate, ml; m 1——The mass of dried calcium carbonate, g; 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 the passage A1; Open the burette used with the n-grade sulfur absorption titration bottle, and titrate the sulfur absorption solution in the n-grade sulfur absorption titration bottle 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） , calculate the sulfur content in the n-stage sulfur absorption titration bottle W ( S )(n); 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; Open the burette used with the n-1 sulfur absorption titration bottle, and titrate the sulfur absorption solution in the n-1 sulfur absorption titration bottle with the sulfur standard titration solution until the solution color 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） , calculate the sulfur content in the n-1 level sulfur absorption titration bottle W ( S )(n-1); ……; Until the sulfur content in the primary sulfur absorption titration bottle 311 is calculated W ( S )1; The total sulfur content is W ( S )= W ( S )(n)+ W ( S )(n-1)+……+ W ( S )1; Sulfur content in n-grade sulfur absorption titration bottle W ( S )(n)is calculated as: ; W ( S ) (n)——mass fraction of sulfur in the n-level sulfur absorption titration bottle, %; T S / NaOH - Sulfur titer; V S（n） ——The volume of sulfur standard titration solution in the n-stage sulfur absorption titration device consumed by the sample, ml; m ——mass of the sample, g; Sulfur titer T S / NaOH The determination process includes: calcining dried lead sulfate and copper oxide at high temperature under oxygen atmosphere; at the same time, turning on the light source 313 at the primary sulfur absorption titration device, ..., and the n-th sulfur absorption titration device; opening the control valve 35 on the pipeline connecting the primary sulfur absorption titration device and the secondary sulfur absorption titration device, ..., opening the control valve 35 on the pipeline connecting the n-1-th sulfur absorption titration device and the n-th sulfur absorption titration device; closing the control valve 35 on the pipeline connecting the primary sulfur absorption titration device and the carbon absorption titration device of the passage A2, ..., closing the control valve 35 on the pipeline connecting the n-1-th sulfur absorption titration device and the passage A m A control valve 35 on the pipeline connected to the carbon absorption titration device; When the sulfur absorption solution in the sulfur absorption titration bottle is found to be discolored, immediately open the burette used in conjunction with the sulfur absorption titration bottle 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 endpoint, and record the volume of the sulfur standard titration solution consumed at this time. V NaOH , calculate sulfur titer T S / NaOH ; Among them, sulfur titer T S / NaOH The calculation formula is: ; V NaOH ——The volume of sulfur standard titration solution consumed by lead sulfate, ml; m 2——Mass of dried lead sulfate, g.

[0041] In this method, the sample is placed in a high-temperature oxygen flow for combustion, and a hydrogen peroxide solution is used to absorb the sulfur dioxide and carbon dioxide generated by the combustion, 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; the carbon dioxide is absorbed by ethanolamine, and calibrated with the standard potassium hydroxide solution in the configured 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 liquid used, but the content of each component in the carbon absorption liquid is not limited: when the content of ethanolamine in the carbon absorption liquid is excessive, the carbon can be completely absorbed and reversely calibrated. 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 carbon calibration method; and the generated sulfuric acid is calibrated with sodium hydroxide solution. Compared with the separate determination methods of carbon and sulfur, this method only requires one combustion of the sample to determine the carbon and sulfur contents in the target sample; and by determining carbon in this way, the carbon content in the sample can be accurately determined within the range of 0.10%-25.00%, thus greatly expanding the determination range of carbon.

[0042] Further, in the embodiment of the present application, if the value of the sulfur content calculated in the n-level sulfur absorption titration bottle is less than 4%, the method for continuous determination of carbon and sulfur in ore includes: Open the branch of the pipeline connecting the n-stage sulfur absorption titration device and the n-1-stage sulfur absorption titration device to the passage A. m The control valve 35 on the pipeline connected to the carbon absorption titration device is closed at the same time, and the control valve 35 on the pipeline connected to the n-stage sulfur absorption titration device and the n-1-stage sulfur absorption titration device is closed. When it is found that passage A mWhen the carbon absorption liquid in the carbon absorption titration bottle fades, immediately open the m The burette used with the carbon absorption titration bottle is titrated with the carbon standard titration solution. When the carbon absorption solution turns bright blue and remains stable, it is the titration end point, and the volume of the carbon standard titration solution is recorded. V C1 , calculate the carbon content; after the above steps are completed, close the branch of the pipeline connecting the n-level sulfur absorption titration device and the n-1-level sulfur absorption titration device and the 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), the burette used in conjunction with the first-stage sulfur absorption titration titration bottle, ..., the burette used in conjunction with the n-1-stage sulfur absorption titration titration bottle, the sulfur absorption solution is titrated with the sulfur standard titration solution until the color of the solution changes from purple to bright green, which is the titration end point, and the volume of the sulfur standard titration solution is recorded, the sulfur content in each sulfur absorption titration bottle is calculated, and finally the sulfur content in all the sulfur absorption titration bottles obtained is added up to obtain the total sulfur content.

[0043] Furthermore, in an embodiment of the present application, the preparation process of the sulfur absorption liquid 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.

[0044] The preparation method of the mixed indicator includes: taking 0.12g of methyl red and 0.83g of methylene blue and dissolving them in 100mL of anhydrous ethanol.

[0045] Using hydrogen peroxide as a desulfurizer can mask the effect of sulfur on carbon determination, make the carbon absorption liquid solution clear, and make the end point easy to observe. At the same time, the sulfur determination can be achieved, which reduces the experimental cost and improves the test speed of the sample. At the same time, it solves the shortcomings of high cost and narrow determination range of carbon and sulfur in instrumental methods. It does not affect the carbon determination, eliminates the interference of sulfur oxides on carbon determination, and can continue titration after the sulfur is completely absorbed.

[0046] Furthermore, in the examples of the present application, the preparation process of the sulfur standard titration solution is: dissolve 40g of sodium hydroxide in H2O and dilute to 10L.

[0047] Furthermore, in an embodiment of the present application, the preparation process of the carbon absorption liquid includes: dissolving ethanolamine in anhydrous ethanol, adding potassium hydroxide, and after the potassium hydroxide is completely dissolved, adding thymolphthalein, then mixing, filtering and storing for standby use; wherein, the carbon absorption liquid has ethanolamine: anhydrous ethanol: potassium hydroxide: thymolphthalein = 30ml: 970ml: 3g: 150mg.

[0048] Furthermore, in an embodiment of the present application, the preparation process of the carbon standard titration solution includes: dissolving ethanolamine in anhydrous ethanol, adding potassium hydroxide, and after the potassium hydroxide is completely dissolved, adding thymolphthalein, then mixing, filtering and storing for standby use, wherein the carbon standard titration solution includes ethanolamine: anhydrous ethanol: potassium hydroxide: thymolphthalein = 30ml: 970ml: 3g: 150mg.

[0049] The principle of carbon titration is as follows: ethanolamine absorbs carbon dioxide: HOC2H4NH2+CO2→HOCH2CH2NH-COOH (ethyl bicarbonate); Ethanol reacts with potassium hydroxide: CH3CH2OH+KOH→CH3CH2OK+H2O; Reaction during titration: HOCH2CH2NH-COOH+CH3CH2OK→HOCH2CH2NH2+CH3CH2O-C=OOK.

[0050] Example 1 A device for continuous determination of carbon and sulfur in ore, comprising a gas supply device, a reaction device connected to the gas supply device, and a titration device connected to the reaction device; The gas supply device includes an oxygen cylinder 11, an electronic flow meter 12, and a gas washing device 13; The reaction device includes a power supply 21, a voltmeter 22, and a high-temperature combustion carbon setting furnace 23; The titration device includes a primary sulfur absorption titration device (a primary sulfur absorption titration bottle 311, a burette 312 used in conjunction with the primary sulfur absorption titration bottle 311, and a light source 313) connected to the high temperature combustion carbon determination furnace 23 through a pipeline 1 314, a secondary sulfur absorption titration device (a secondary sulfur absorption titration bottle 321, a burette 322 used in conjunction with the secondary sulfur absorption titration bottle 321, and a light source 313) connected to the primary sulfur absorption titration device through a pipeline 2 323, and a secondary sulfur absorption titration device (a secondary sulfur absorption titration bottle 321, a burette 322 used in conjunction with the secondary sulfur absorption titration bottle 321, and a light source 313) connected to the secondary sulfur absorption titration device through a pipeline 334. The carbon absorption titration device of passage A1 connected to the absorption titration device (the drying device 331 (the drying bottle containing color-changing silica gel) connected to the secondary sulfur absorption titration device, the carbon absorption titration bottle 332 of passage A1 connected to the drying device 331, the burette 3 333, and the light source 313), and the carbon absorption titration device of passage A2 connected to the branch port of the passage 2 323 through the pipe 4 343 (the carbon absorption titration bottle 341 of passage A2 connected to the branch port on the pipe 1 314, the burette 4 342, and the light source 313). The pipe 1 314, the pipe 3 34, and the pipe 4 343 are all provided with a control valve 35; the pipe 2 323 located between the branch port of the pipe 2 323 and the secondary sulfur absorption titration device is provided with a control valve 35.

[0051] A method for continuously measuring carbon and sulfur in an ore, using the above-mentioned device for continuously measuring carbon and sulfur in an ore, comprises the following steps: S1. Prepare sulfur absorption solution and sulfur standard titration solution; carbon absorption solution and carbon standard titration solution; The sulfur absorption liquid is prepared as follows: 30 mL of mixed indicator is added to 100 mL of hydrogen peroxide with a mass concentration of 30%, and then diluted to 2 L with H2O; The mixed indicator was prepared as follows: 0.12 g of methyl red and 0.83 g of methylene blue were weighed and dissolved in 100 mL of anhydrous ethanol; The sulfur standard titration solution is prepared as follows: 40 g of sodium hydroxide (molecular weight 40) is dissolved in H2O and diluted to 10 L; The preparation process of the carbon absorption liquid is as follows: 30 ml of ethanolamine is dissolved in 970 ml of anhydrous ethanol, and then 3.0 g of potassium hydroxide is added. After the potassium hydroxide is completely dissolved, 150 mg of thymolphthalein is added, and then mixed, filtered and stored for future use; the potassium hydroxide concentration of this solution is 0.05 mol / L; The preparation process of the carbon standard titration solution is as follows: 30 ml of ethanolamine is dissolved in 970 ml of anhydrous ethanol, and then 3.0 g of potassium hydroxide is added. After the potassium hydroxide is completely dissolved, 150 mg of thymolphthalein is added, and then mixed, filtered and stored for future use; the potassium hydroxide concentration of this solution is 0.05 mol / L; The sulfur absorption liquid is placed in the first sulfur absorption titration bottle 311 and the second sulfur absorption titration bottle 321, and the sulfur standard titration solution is placed in the burette 1 312 and the burette 2 322. Place the carbon absorption liquid in the carbon absorption titration bottle 332 of channel A1 and the carbon absorption titration bottle 341 of channel A2, and place the carbon standard titration solution in burette three 333 and burette four 342; S2, turn on the light source 313 at the sulfur absorption titration bottle and the carbon absorption titration bottle; open the control valve 35 on the pipeline 1 314, the pipeline 2 323, and the pipeline 3 334, and close the control valve 35 on the pipeline 4 343; adjust the flow rate of oxygen to 0.2L / min; raise the temperature in the combustion carbon setting furnace to 1300°C; In an oxygen atmosphere, a porcelain boat containing a sample (0.1015 g of gold concentrate No. 1 sample and 0.2000 g of copper oxide) is quickly pushed into the highest temperature of the conical porcelain tube in the combustion carbon setting furnace using a nickel-chromium wire, and the combustion carbon setting furnace is immediately sealed to calcine the sample at 1300°C; at the same time, the generated gas flows into the primary sulfur absorption titration bottle 311, the secondary sulfur absorption titration bottle 321, and the passage A1 carbon absorption titration bottle 332 in sequence; S3. When the carbon absorption liquid in the carbon absorption titration bottle 332 of passage A1 is found to be discolored, immediately open the burette 333 and titrate with the carbon standard titration solution. When the carbon absorption liquid turns bright blue and remains stable for more than 60 seconds, it is the titration endpoint, and record the volume of the carbon standard titration solution consumed at this time. V C1 (5.2800ml), calculate the carbon content; The calculation formula for carbon content is: ; W ( C )——mass fraction of carbon, %; T C / KOH ——Carbon titer; V C1 ——The volume of carbon standard titration solution consumed by the sample, ml; m ——mass of the sample, g; V 空白 ——The volume of carbon standard titration solution consumed when doing blank test on the sample, ml; Carbon titer T C / KOH The determination process is as follows: calcium carbonate (0.1000 g) and copper oxide (0.2000 g) dried at 110°C are calcined at 1300°C in an oxygen atmosphere; at the same time, the light source 313 at the carbon absorption titration device of channel 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 channel 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; When the carbon absorption liquid in the carbon absorption titration bottle 341 of channel A2 is found to fade, immediately open the burette used in conjunction with the carbon absorption titration bottle 341 of channel A2, and titrate with the carbon standard titration solution. When the carbon absorption liquid turns into a stable bright blue, it is the titration end point, and record the volume of the carbon standard titration solution consumed at this time. V KOH (20ml), calculate carbon titer T C / KOH ; Among them, carbon titer T C / KOH The calculation formula is: ; V KOH —— Volume of carbon standard titration solution consumed by calcium carbonate, ml; m 1——The mass of dried calcium carbonate, g; S4, after the above steps are completed, close the control valve 35 on the pipeline 3 334; Open the second burette 322 and titrate the sulfur absorption solution in the secondary sulfur absorption titration bottle 321 with the sulfur standard titration solution until the color of the solution changes from purple to a stable bright green, which is the end point. Record the volume of the sulfur standard titration solution consumed at this time. V S2 (2.05mL), calculate the sulfur content in the secondary sulfur absorption titration bottle 321 W ( S )2 (4.04%); S5. After the above steps are completed, close the control valve 35 on the second pipeline 323; Open the burette 312 and titrate the sulfur absorption solution in the primary sulfur absorption titration bottle 311 with the sulfur standard titration solution until the color of the solution changes from purple to a stable bright green, which is the titration endpoint. 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 bottle 311 W ( S )1 (28.34%); The total sulfur content is W ( S )= W ( S )2+ W ( S )1; Sulfur content in n-grade sulfur absorption titration bottle W ( S )(n)is calculated as: ; W ( S ) (n)——mass fraction of sulfur in the n-level sulfur absorption titration bottle, %; T S / NaOH - Sulfur titer; V S（n） ——The volume of sulfur standard titration solution in the n-stage sulfur absorption titration device consumed by the sample, ml; m ——mass of the sample, g; V 空白 ——The volume of sulfur standard titration solution consumed when doing blank test on the sample, ml; Sulfur titer TS / NaOH The determination process is as follows: lead sulfate (0.3700 g) and copper oxide (0.2000 g) dried at 110°C are placed at a high temperature of 1300°C for calcination under an oxygen atmosphere; at the same time, the light source 313 at the primary sulfur absorption titration device and the secondary sulfur absorption titration device is turned on; the control valve 35 on the pipeline connecting the primary sulfur absorption titration device and the secondary sulfur absorption titration device is opened; the control valve 35 on the pipeline connecting the primary sulfur absorption titration device and the carbon absorption titration device of the passage A2 is closed; the control valve 35 on the pipeline connecting the secondary sulfur absorption titration device and the carbon absorption titration device of the passage A1 is closed; When the sulfur absorption solution in the sulfur absorption titration bottle is found to be discolored, immediately open the burette used in conjunction with the sulfur absorption titration bottle 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 endpoint, and record the volume of the sulfur standard titration solution consumed at this time. V NaOH (19.55ml), calculate sulfur titer T S / NaOH ; Among them, sulfur titer T S / NaOH The calculation formula is: ; V NaOH ——The volume of sulfur standard titration solution consumed by lead sulfate, ml; m 2——Mass of dried lead sulfate, g; Finally, the sulfur content was measured to be 32.38% and the carbon content was 3.12%.

[0052] Among them, because the value of the sulfur content calculated by the secondary stage is less than 4%, the control valve 35 on the pipeline 4 343 can also be opened, and the control valve on the pipeline 2 323 can be closed at the same time. When it is found that the carbon absorption liquid in the carbon absorption titration bottle 341 of the passage A2 fades, the burette 4 342 is immediately opened and titrated with the carbon standard titration solution. When the carbon absorption liquid turns blue and remains stable for more than 60 seconds, it is the titration end point, and the volume of the carbon standard titration solution is recorded. V C2 , calculate the carbon content; after the end, close the control valve 35 on the pipeline 4 343 (and close the control valve 35 on the pipeline 2 323), open the burette 1 312, and titrate the sulfur absorption liquid in the primary sulfur absorption titration bottle 311 with the sulfur standard titration solution until the color of the solution 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.

[0053] National Standard Law: The national standard method GB / T 7739.8-2022 gravimetric method is used to measure sulfur: weigh 0.1045g of gold concentrate No. 1 sample, semi-melt it at 780℃ with a mixed flux of sodium carbonate, zinc oxide and potassium permanganate, dissolve the soluble matter with water, and convert the sulfur into sulfate ions into the solution. Then, barium chloride is used to precipitate the sulfate ions in the solution. The precipitate is filtered, burned and weighed. The sulfur content in the sample is calculated based on the mass of barium sulfate, which is 32.40%.

[0054] The national standard method GB / T 6730.61-2022 high-frequency combustion infrared absorption method is adopted: 0.1012g of sample is weighed and heated and burned in the oxygen flow of a high-frequency induction furnace. The generated carbon dioxide (or carbon monoxide) is carried by oxygen to the measuring chamber of the infrared analyzer. Carbon dioxide (or carbon monoxide) absorbs infrared energy of a specific wavelength, and its absorption energy is proportional to its concentration. The carbon content is measured to be 3.20% based on the change in the energy received by the detector.

[0055] The sulfur content measured by the national standard method is 32.40% and the carbon content is 3.2%.

[0056] The above experimental results are the average values ​​taken after repeating the experiment 5 times.

[0057] Embodiment 2~6 Examples 2 to 6 provide a method for continuous determination of carbon and sulfur in an ore, which differs from Example 1 in that different target samples are selected. The target samples selected in Examples 2 to 6 are respectively gold concentrate sample No. 2, cast iron powder carbon sulfur, arsenic ore, gold concentrate standard sample GBW07231 (standard value of sulfur content is 31.00%, standard value of carbon content is 0.28%), and sample 6. The remaining steps are consistent with Example 1 and will not be repeated here.

[0058] The final measured sulfur content of gold concentrate No. 2 sample was 15.66% and the carbon content was 6.15% (the values ​​tested using the national standard method were 15.65% sulfur content and 6.13% carbon content); The sulfur content of cast iron powder spray carbon-sulfur is 5.52% and the carbon content is 4.15% (the values ​​tested using the national standard method are 5.50% sulfur content and 4.16% carbon content).

[0059] The sulfur content of arsenic ore is 4.50% and the carbon content is 3.08% (the values ​​tested using the national standard method are 4.51% sulfur content and 3.05% carbon content).

[0060] The sulfur content of the gold concentrate standard sample GBW07231 is 30.96% and the carbon content is 0.26%.

[0061] The sulfur content in sample 6 is 8.25% and the carbon content is 20.80% (the values ​​tested using the national standard method are 8.30% sulfur content and 20.93% carbon content).

[0062] Compared with the national standard method, it can be seen that the measurement method provided by this application has higher accuracy.

[0063] Please also read Figure 1 According to one or more embodiments of the present application, the present application provides a continuous determination device for carbon and sulfur in ore composed of a gas supply device, 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 plurality of carbon absorption titration devices connected to the sulfur absorption titration device; 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, a secondary sulfur absorption titration device, ..., an n-stage sulfur absorption titration device connected to the reaction device; the plurality of carbon absorption titration devices include a passage A1 carbon absorption titration device connected to the n-stage sulfur absorption titration device; the sample is placed in a high-temperature oxygen flow for combustion, and the sulfur dioxide and carbon dioxide generated by the combustion are absorbed by a hydrogen peroxide solution to form carbonic acid and sulfuric acid. The generated carbonic acid is decomposed into carbon dioxide and water to separate carbon and sulfur and remove the interference of sulfur dioxide on carbon determination; 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 liquid used, but the content of each component in the carbon absorption liquid is not limited: when the content of ethanolamine in the carbon absorption liquid is excessive, carbon can be completely absorbed and reverse calibration can be performed. If the content of ethanolamine in the carbon absorption liquid is insufficient, the carbon standard titration solution can be continuously supplemented and calibration can be performed at the same time. This method provides another idea for carbon calibration; and the generated sulfuric acid is calibrated with sodium hydroxide solution. Compared with the separate determination methods of carbon and sulfur, this method only requires one combustion of the sample to determine the carbon and sulfur contents in the target sample; and determining carbon in this way can mask the influence of sulfur on carbon determination, making the carbon absorption liquid solution clear and the end point easy to observe. The carbon content in the sample within the range of 0.10%-25.00% can be accurately determined, thus greatly expanding the determination range of carbon.

[0064] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and the embodiments having the same structure as the technical idea and exerting the same effect within the scope of the technical solution of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the main purpose of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of combining some of the constituent elements in the embodiments are also included in the scope of the present application.

Claims

1. A device for continuous determination of carbon and sulfur in ore, characterized in that: include: 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 comprises 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 device; the plurality of sulfur absorption titration devices are connected end to end in sequence; A 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 n-stage sulfur absorption titration device connected to the n-1-stage sulfur absorption titration device; The plurality of carbon absorption titration devices include a channel A1 carbon absorption titration device connected to the n-stage sulfur absorption titration device.

2. The device for continuous determination of carbon and sulfur in ore according to claim 1, characterized in that: The plurality of carbon absorption titration devices further include a passage A2 carbon absorption titration device connected to a branch of a pipeline connecting the primary sulfur absorption titration device and the secondary sulfur absorption titration device, a passage A3 carbon absorption titration device connected to a branch of a pipeline connecting the secondary sulfur absorption titration device and the tertiary sulfur absorption titration device, ..., a passage A4 carbon absorption titration device connected to a branch of a pipeline connecting the n-1 stage sulfur absorption titration device and the n stage sulfur absorption titration device. m Carbon absorption titration apparatus.

3. The device for continuous determination of carbon and sulfur in ore according to claim 2, characterized in that: The n-level sulfur absorption titration device comprises an n-level sulfur absorption titration bottle, a burette used in conjunction with the n-level sulfur absorption titration bottle, and a light source; The pathway A m The carbon absorption titration device includes a passage A m Carbon absorption titration bottle, and passage A m A burette and a light source for use with the carbon absorption titration bottle; and / or, The pipelines for connecting the plurality of sulfur absorption titration devices are all provided with control valves, and the pipelines for connecting the sulfur absorption titration device and the carbon absorption titration device are provided with control valves.

4. A method for continuous determination of carbon and sulfur in ore, characterized in that: The device for continuous determination of carbon and sulfur in ore according to any one of claims 1 to 3 comprises the following steps: S1. preparing sulfur absorption solution, sulfur standard titration solution, carbon absorption solution, and carbon standard titration solution; The sulfur absorption liquid is placed in the first-level sulfur absorption titration bottle, the second-level sulfur absorption titration bottle, ..., the n-level sulfur absorption titration bottle, and the sulfur standard titration solution is placed in a burette used in conjunction with several sulfur absorption titration bottles. The carbon absorption liquid is placed in the carbon absorption titration bottle of channel A1, the carbon absorption titration bottle of channel A2, ..., channel A m In a carbon absorption titration bottle, the carbon standard titration solution is placed in a burette used in conjunction with a number of carbon absorption titration bottles; S2. In an oxygen atmosphere, the target sample is calcined at a high temperature; at the same time, the light sources at the sulfur absorption titration bottle and the carbon absorption titration bottle are turned on; the control valve on the pipeline connecting the plurality of sulfur absorption titration devices is opened, the control valve on the pipeline connecting the n-1-level sulfur absorption titration device and the carbon absorption titration device of the passage A1 is opened, and the branch of the pipeline connecting the n-1-level sulfur absorption titration device and the n-level sulfur absorption titration device and the passage A1 is closed. m A control valve on the pipeline connected to the carbon absorption titration device; S3. When path A is found m When the carbon absorption liquid in the carbon absorption titration bottle fades, immediately open the m The burette used with the carbon absorption titration bottle is titrated with the carbon standard titration solution. When the carbon absorption solution turns into a stable bright blue, it is the titration end point, and the volume of the carbon standard titration solution consumed at this time is recorded. V C1 , calculate the carbon content; S4. After the above steps are completed, close the control valve on the pipeline connecting the n-stage sulfur absorption titration device and the carbon absorption titration device in the passage A1; Open the burette used with the n-grade sulfur absorption titration bottle, and titrate the sulfur absorption solution in the n-grade sulfur absorption titration bottle 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） , calculate the sulfur content in the n-stage sulfur absorption titration bottle W ( S )(n); 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; Open the burette used with the n-1 grade sulfur absorption titration bottle, and titrate the sulfur absorption solution in the n-1 grade sulfur absorption titration bottle with the sulfur standard titration solution until the color of the solution changes from purple to a stable bright green, which is the titration endpoint, and record the volume of the sulfur standard titration solution consumed at this time. V S（n-1） , calculate the sulfur content in the n-1 level sulfur absorption titration bottle W ( S )(n-1); ……； Until the sulfur content in the primary sulfur absorption titration bottle is calculated W ( S )1; The total sulfur content is W ( S )= W ( S )(n)+ W ( S )(n-1)+……+ W ( S )1.

5. The method for continuous determination of carbon and sulfur in ore according to claim 4, characterized in that: In step S3, the calculation formula of carbon content is: ； W ( C )——mass fraction of carbon, %; T C / KOH ——Carbon titer; V C1 ——The volume of carbon standard titration solution consumed by the sample, ml; m ——mass of the sample, g; Carbon titer T C / KOH The determination process includes: calcining dried calcium carbonate and copper oxide at high temperature under oxygen atmosphere; at the same time, turning on the light source at the carbon absorption titration device of channel A2; opening the control valve on the pipeline connecting the primary sulfur absorption titration device and the carbon absorption titration device of channel A2, and closing the control valve on the pipeline connecting the primary sulfur absorption titration device and the secondary sulfur absorption titration device; When the carbon absorption liquid in the carbon absorption titration bottle of channel A2 is found to fade, immediately open the burette used with the carbon absorption titration bottle of channel A2 and titrate with the carbon standard titration solution. When the carbon absorption liquid turns into a stable bright blue, it is the titration end point, and record the volume of the carbon standard titration solution consumed at this time. V KOH , calculate carbon titer T C / KOH ; Among them, carbon titer T C / KOH The calculation formula is: ； V KOH —— Volume of carbon standard titration solution consumed by calcium carbonate, ml; m 1——Mass of dried calcium carbonate, g.

6. The method for continuous determination of carbon and sulfur in ore according to claim 4, characterized in that: Sulfur content in n-grade sulfur absorption titration bottle W ( S )(n)is calculated as: ； W ( S ) (n)——mass fraction of sulfur in the n-level sulfur absorption titration bottle, %; T S / NaOH - Sulfur titer; V S（n） ——The volume of sulfur standard titration solution in the n-stage sulfur absorption titration device consumed by the sample, ml; m ——mass of the sample, g; Sulfur titer T S / NaOH The determination process includes: calcining dried lead sulfate and copper oxide at high temperature under oxygen atmosphere; at the same time, turning on the light source at the first-stage sulfur absorption titration device, ..., and the n-stage sulfur absorption titration device; opening the control valve on the pipeline connecting the first-stage sulfur absorption titration device and the second-stage sulfur absorption titration device, ..., opening the control valve on the pipeline connecting the n-1-stage sulfur absorption titration device and the n-stage sulfur absorption titration device; closing the control valve on the pipeline connecting the first-stage sulfur absorption titration device and the carbon absorption titration device of the passage A2, ..., closing the control valve on the pipeline connecting the n-1-stage sulfur absorption titration device and the passage A m A control valve on the pipeline connected to the carbon absorption titration device; When the sulfur absorption solution in the sulfur absorption titration bottle is found to be discolored, immediately open the burette used in conjunction with the sulfur absorption titration bottle 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 endpoint, and record the volume of the sulfur standard titration solution consumed at this time. V NaOH , calculate sulfur titer T S / NaOH ; Among them, sulfur titer T S / NaOH The calculation formula is: ； V NaOH ——The volume of sulfur standard titration solution consumed by lead sulfate, ml; m 2——Mass of dried lead sulfate, g.

7. The method for continuous determination of carbon and sulfur in ore according to claim 4, characterized in that: The preparation process of the sulfur absorption liquid includes: adding 30 mL of a mixed indicator to 100 mL of hydrogen peroxide with a mass concentration of 30%, and then diluting to 2 L with H2O; the configuration method of the mixed indicator includes: taking 0.12 g of methyl red and 0.83 g of methylene blue and dissolving them in 100 mL of anhydrous ethanol.

8. The method for continuous determination of carbon and sulfur in ore according to claim 4, characterized in that: The preparation process of the sulfur standard titration solution is as follows: 40 g of sodium hydroxide is dissolved in H2O and diluted to 10 L.

9. The method for continuous determination of carbon and sulfur in ore according to claim 4, characterized in that: The preparation process of the carbon absorption liquid comprises: dissolving ethanolamine in anhydrous ethanol, adding potassium hydroxide, and adding thymolphthalein after the potassium hydroxide is completely dissolved, and then mixing, filtering and storing for future use; wherein, in the carbon absorption liquid, ethanolamine: anhydrous ethanol: potassium hydroxide: thymolphthalein = 30ml: 970ml: 3g: 150mg.

10. The method for continuous determination of carbon and sulfur in ore according to claim 4, characterized in that: The preparation process of the carbon standard titration solution includes: dissolving ethanolamine in anhydrous ethanol, adding potassium hydroxide, and adding thymolphthalein after the potassium hydroxide is completely dissolved, and then mixing, filtering and storing for future use. In the carbon standard titration solution, ethanolamine: anhydrous ethanol: potassium hydroxide: thymolphthalein = 30ml: 970ml: 3g: 150mg.

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