A method for calculating the metallization rate of reduced ilmenite and its application.

Abstract

This invention relates to the field of metallurgical technology, specifically to a method for calculating the metallization rate of reduced ilmenite and its application. The method for calculating the metallization rate of reduced ilmenite includes: where a is the mass fraction of titanium dioxide in the ilmenite; b is the mass fraction of total iron in the ilmenite; c is the mass fraction of FeO in the ilmenite; and d is the mass fraction of titanium dioxide in the reduction product obtained after reducing the ilmenite. The determination of the mass fraction d of titanium dioxide in the reduction product includes XRF detection. This calculation method is simple, time-efficient, highly efficient, and highly accurate.

Description

Technical Field

[0001] This invention relates to the field of metallurgical technology, and more specifically, to a method for calculating the metallization rate of titanium-containing iron minerals after reduction and its application. Background Technology

[0002] In the comprehensive utilization of ilmenite-bearing minerals, reduction is a common and widely applicable treatment method. The main method involves reacting a reducing agent (such as carbon monoxide gas or coal) with the ilmenite to reduce the iron oxides in the minerals to elemental iron. The reduction products are then further processed using methods such as magnetic separation or hydrometallurgical methods such as acid leaching to separate the ilmenite from the titanium, thereby achieving the goal of enriching either titanium or iron.

[0003] Metallization rate is the most important indicator in the reduction process. Theoretically, it is the ratio of metallic iron to total iron in the reduction product. The closer the metallization rate is to 1, the better the reduction effect. The closer the metallization rate is to 0, the worse the reduction effect.

[0004] The commonly used method for titrating metallization rate is to titrate metallic iron and total iron separately using chemical analysis titration. The methods for metallic iron and total iron can be found in national standards. In practice, this method requires at least 2 hours.

[0005] In actual production and laboratory research, the same type and batch of ilmenite often require several, dozens, or even hundreds of reduction and testing cycles. Each test takes more than 2 hours, which is relatively long and affects subsequent research and production. The commonly used metallization titration method is time-consuming and does not meet the principle of high efficiency in research and production.

[0006] Therefore, providing a rapid method for metallization rate detection and calculation is of great significance for the production and research of titanium-containing mineral reduction.

[0007] In view of this, the present invention is hereby proposed. Summary of the Invention

[0008] The first objective of this invention is to provide a method for calculating the metallization rate of titanium-containing minerals after reduction, which is a time-efficient method.

[0009] The second objective of this invention is to provide the application of the method for calculating the metallization rate of titanium-containing iron minerals after reduction, as described above, in metallurgy.

[0010] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted:

[0011] This invention provides a method for calculating the metallization rate of ilmenite after reduction and a rapid detection method thereon. The method for calculating the metallization rate η includes:

[0012]

[0013] Where a is the mass fraction of titanium dioxide in the ilmenite;

[0014] b is the mass fraction of total iron in the ilmenite;

[0015] c is the mass fraction of FeO in the ilmenite;

[0016] d represents the mass fraction of titanium dioxide in the reduction product obtained after reducing the titanium-containing iron mineral;

[0017] The method for determining the mass fraction d of titanium dioxide in the reduction product includes XRF detection.

[0018] Preferably, the method for determining the mass fraction 'a' of titanium dioxide in the ilmenite includes XRF detection.

[0019] Preferably, the method for determining the mass fraction b of total iron in the ilmenite includes the potassium dichromate titration method for total iron.

[0020] Preferably, the total iron potassium dichromate titration method includes the following steps: 1 g of the titanium-containing iron mineral is mixed with ammonium sulfate and concentrated sulfuric acid and heated to a gentle boil for 40-60 min. After cooling, water and concentrated hydrochloric acid are added. After heating to a gentle boil, tin dichloride is added dropwise until the solution changes from yellow to colorless. 2 drops are added in excess and the solution is rapidly cooled. A saturated mercuric chloride solution is then added dropwise. After standing for a period of time, water, concentrated phosphoric acid, and sodium diphenylamine sulfonate are added. The solution is titrated with a potassium dichromate solution with a molar concentration of c1 mol / L until the endpoint is purple. The volume of potassium dichromate used in the titration is V1 mL. The total iron mass fraction b is calculated as (55.85 × 6c1V1 / 1000mL) × 100%.

[0021] Preferably, m1 = 0.05 to 0.1 and c1 = 0.005 to 0.02.

[0022] Preferably, the method for determining the mass fraction c of FeO in the ilmenite includes the potassium dichromate titration method for ferrous iron.

[0023] Preferably, the potassium dichromate titration method for ferrous iron includes the following steps: adding sodium bicarbonate, sodium fluoride, and concentrated hydrochloric acid to m2 g of the ilmenite, heating to a gentle boil for a period of time, and then stopping the heating; immediately adding saturated boric acid solution, sodium bicarbonate, water, sulfuric acid-phosphoric acid mixture, and sodium diphenylamine sulfonate indicator, and then titrating with potassium dichromate solution with a molar concentration of c2 mol / L until the endpoint is purple, the volume of potassium dichromate used for titration is V2 mL, and calculating the mass fraction of FeO c = (71.85c2V2 / 1000m2) × 100%;

[0024] Where m2 = 0.3 to 0.5, c2 = 0.005 to 0.02.

[0025] Preferably, the reduction method of the ilmenite includes:

[0026] The titanium-containing iron mineral and the reducing agent are mixed evenly and then subjected to a reduction reaction to obtain the reduction product.

[0027] Preferably, the ilmenite-bearing minerals include at least one of titanomagnetite, seashore placer deposits, and brookite;

[0028] Preferably, the reducing agent includes at least one of coal, carbon monoxide, semi-coke, and metallurgical coke;

[0029] Preferably, the mass of the reducing agent is 40% to 80% of the mass of the titanium-iron mineral.

[0030] Preferably, an activator is also added during the mixing process;

[0031] Preferably, the activator is 2% to 5% of the amount of the titanium-iron mineral.

[0032] Preferably, the activator includes at least one of borax, sodium carbonate, sulfur, and iron sulfide.

[0033] Preferably, the temperature of the reduction reaction is 900–1200°C, and the time of the reduction reaction is 1–5 hours.

[0034] The present invention also provides the application of the method for calculating the metallization rate of titanium-containing iron minerals after reduction as described above in metallurgy.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0036] (1) The method for calculating the metallization rate of titanium-containing iron minerals after reduction provided by the present invention is simple, time-saving and efficient.

[0037] (2) The method for calculating the metallization rate of titanium-containing iron minerals after reduction provided by the present invention uses XRF to detect the mass fraction of titanium dioxide in the reduction product. It has a high degree of automation, high accuracy, fast detection speed, and can also save labor costs. Detailed Implementation

[0038] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0039] In a first aspect, the present invention provides a method for calculating the metallization rate η after reduction of ilmenite, wherein the method for calculating the metallization rate η includes:

[0040]

[0041] Where a is the mass fraction of titanium dioxide in the ilmenite;

[0042] b is the mass fraction of total iron in the ilmenite;

[0043] c represents the mass fraction of FeO in the ilmenite.

[0044] d represents the mass fraction of titanium dioxide in the reduction product obtained after reducing the titanium-containing iron mineral.

[0045] The method for determining the mass fraction d of titanium dioxide in the reduction product obtained after reducing the titanium-containing iron mineral includes XRF detection.

[0046] The titanium-containing iron minerals refer to minerals containing titanium and iron elements.

[0047] Total iron refers to the total iron content in the ilmenite, expressed as a mass fraction.

[0048] After reduction, the titanium-containing iron mineral yields a reduction product, the main components of which are elemental iron and titanium dioxide. d represents the mass fraction of titanium dioxide in the reduction product.

[0049] To address the problems of time-consuming and inefficient metallization titration detection methods in existing technologies, this invention provides a method for calculating and rapidly detecting the reduced metallization rate of titanium-containing minerals.

[0050] The present invention obtains the metallization rate by measuring the titanium dioxide content, total iron content, and FeO content of titanium-containing iron minerals, and by measuring the titanium dioxide content of reduction products. After substituting the above values ​​into the calculation formula of η, the metallization rate can be obtained.

[0051] The method for calculating the metallization rate of ilmenite after reduction provided by this invention is simple and time-saving, and is suitable for experimental research and industrial production of ilmenite reduction.

[0052] Furthermore, the XRF method is used to detect the mass fraction of titanium dioxide in the reduction product, which is highly automated, accurate, and fast, and can complete the detection in about 10 minutes.

[0053] Furthermore, the method for calculating the metallization rate of ilmenite after reduction provided by this invention, once the relevant indicators of ilmenite (i.e., the titanium dioxide content, total iron content, and FeO content in the ilmenite) are known, only requires testing the titanium dioxide content in the reduction product to obtain the metallization rate result, which greatly shortens the metallization rate detection process.

[0054] In some specific embodiments of the present invention, the specific values ​​of a, b, and c can be obtained by any conventional measurement method, such as XRF detection and chemical titration, but are not limited thereto.

[0055] The XRF mentioned in this invention refers to X-ray fluorescence spectroscopy. XRF uses physical principles to detect the elements in a substance, enabling qualitative and quantitative analysis. Specifically, X-rays penetrate the electrons inside atoms, and the outer electrons replenish the characteristic X-rays generated. Based on the intensity of the characteristic X-rays of each element, the content information of each element can be obtained.

[0056] In some specific embodiments of the present invention, the mass fraction of titanium dioxide (a), the mass fraction of total iron (b), and the mass fraction of FeO (c) in the titanium-containing iron mineral are first determined and / or calculated. Then, the titanium-containing iron mineral is reduced to obtain a reduction product, and the mass fraction of titanium dioxide (d) in the reduction product is measured. Finally, the results are calculated using the method (formula) for calculating the metallization rate (η).

[0057] The derivation principle and derivation process of the method for calculating the metallization rate of ilmenite after reduction provided by this invention are as follows:

[0058] In natural ilmenite, +3 valence Fe ions and +2 valence Fe iron ions generally exist, which can be considered as Fe₂O₃ and FeO, respectively. Elemental Fe does not exist. The reduction process involves reducing the +3 and +2 valence Fe ions to remove oxygen and obtain elemental Fe. Furthermore, according to the reduction principle, the +3 valence ions are more easily reduced, so the order of reduction reactivity is Fe. 3+ >Fe 2+ Fe 3+ The process of reducing to Fe can be broken down into Fe... 3+ Reduced to Fe 2+ Fe 2+ If reduced to Fe, the overall reduction process can be viewed as two steps: Fe... 3+ Reduced to Fe 2+ Fe 2+ The reduction is to Fe. In the two steps of reduction, iron ions decrease in valence state while the reduced iron oxides lose oxygen. Due to the loss of oxygen during reduction, the proportion of unreduced titanium dioxide increases. Let the total oxygen lost in both reduction steps be A. Then, the relationship between A and the proportions of titanium dioxide before and after reduction, a and d, is:

[0059] Right now:

[0060] Since the proportion of total iron increases due to oxygen loss during reduction, the relationship between total oxygen A and the proportions of total iron before and after reduction, b and e, is as follows:

[0061] Substituting into formula (1), we get:

[0062] The total iron (e) in the raw ore can be represented by the sum of the iron content in the FeO (c) and Fe2O3 (f) proportions in the raw ore, where the iron content in FeO is... (The relative atomic mass of Fe is 55.85, and the relative molecular mass of FeO is 71.85). Similarly, the iron content in Fe₂O₃ is... but:

[0063]

[0064] The total oxygen lost during the reduction process is A, let Fe be the oxygen lost. 3+ Reduced to Fe 2+ The oxygen lost during the process is B, Fe. 2+ The oxygen lost during the reduction to Fe is C, then: A=B+C (4).

[0065] Fe 3+ Reduced to Fe 2+ The oxygen lost during the process is B, which can be represented by the proportion f of Fe2O3 before reduction:

[0066]

[0067] Fe 2+ Let C be the oxygen lost during the reduction to Fe, and let g represent the percentage of elemental iron after reduction:

[0068]

[0069] Metallization rate is the ratio of reduced elemental iron to total iron, i.e.:

[0070] Combining equations (1) to (7) above, we can obtain the formula for calculating the metallization rate η:

[0071]

[0072] Preferably, the method for determining the mass fraction 'a' of titanium dioxide in the ilmenite includes XRF detection.

[0073] Using the above-mentioned measurement method can help to further shorten the detection and calculation time.

[0074] In some specific embodiments of the present invention, the method for determining the mass fraction b of total iron in the ilmenite can be any conventional detection method, such as potassium dichromate titration, but is not limited thereto.

[0075] Preferably, the method for determining the mass fraction b of total iron in the ilmenite includes the potassium dichromate titration method for total iron.

[0076] The principle of the total iron potassium dichromate titration method is as follows: iron is reduced by tin dichloride, excess tin dichloride is oxidized by mercuric chloride, sodium diphenylamine sulfonate is used as an indicator, and potassium dichromate standard solution is used for titration.

[0077] Preferably, the total iron potassium dichromate titration method includes the following steps: Mix m1 g of the titanium-containing iron mineral with ammonium sulfate and concentrated sulfuric acid, then heat to a gentle boil for 40–60 min (including but not limited to the point value of any one of 45 min, 50 min, and 55 min, or the range between any two). After cooling, add water and concentrated hydrochloric acid, heat to a gentle boil, and then add tin dichloride dropwise until the solution changes from yellow to colorless. Add 2 drops in excess and cool rapidly. Then add saturated mercuric chloride solution dropwise. After standing for a period of time, add water, concentrated phosphoric acid, and sodium diphenylamine sulfonate. Titrate with potassium dichromate solution with a molar concentration of c1 mol / L until the endpoint is purple. The volume of potassium dichromate used in the titration is V1 mL. Calculate the total iron mass fraction b = [(55.85 × 6 × c1 × V1) / (1000 × m1)] × 100%.

[0078] Preferably, m1 = 0.05 to 0.1, including but not limited to point values ​​of any one of 0.06, 0.07, 0.08, and 0.09, or a range between any two. The unit of m1 is g.

[0079] The c1 value is between 0.005 and 0.02, including but not limited to point values ​​of any one of 0.007, 0.009, 0.01, 0.013, 0.015, and 0.018, or a range between any two. The unit of c1 is mol / L.

[0080] The term "heating to a state of slight boiling" refers to the state just before boiling, that is, heating the mixture to a state of slight boiling. In some specific embodiments of the present invention, the temperature of the heating to a state of slight boiling is 100-120°C, including but not limited to any one of 105°C, 110°C, 115°C, and 118°C, or a range between any two.

[0081] In some specific embodiments of the present invention, the mass of the ammonium sulfate is 150 to 200 times the mass of the ilmenite, including but not limited to a value of any one of 160, 170, 180, or 190 times, or a range between any two. The mass of the concentrated sulfuric acid is 550 to 600 times the mass of the ilmenite, including but not limited to a value of any one of 560, 570, 580, or 590 times, or a range between any two.

[0082] In some specific embodiments of the present invention, during the process of adding water and concentrated hydrochloric acid after cooling, the mass of the water is 550 to 650 times the mass of the titanium-iron mineral; including but not limited to any one of 560 times, 570 times, 580 times, 590 times, 600 times, 610 times, 620 times, 630 times, 640 times or any range between two of them.

[0083] In some specific embodiments of the present invention, during the process of adding water and concentrated hydrochloric acid after cooling, the mass of the concentrated hydrochloric acid is 100 to 150 times the mass of the titanium-iron mineral, including but not limited to any one of 110 times, 120 times, 130 times, and 140 times, or any range between two of them.

[0084] In some specific embodiments of the present invention, the mass fraction of tin dichloride is 8% to 15%, including but not limited to any one of 9%, 10%, 11%, 12%, 13%, and 14%, or any range between two of them.

[0085] In some specific embodiments of the present invention, the mass of the saturated mercuric dichloride solution is 100 to 150 times the mass of the titanium-iron mineral, including but not limited to a point value of any one of 110 times, 120 times, 130 times, and 140 times, or a range between any two.

[0086] In some specific embodiments of the present invention, the settling time is 1 to 5 minutes, including but not limited to any one of 2 minutes, 3 minutes, and 4 minutes or any range between two; preferably 1 to 2 minutes.

[0087] In some specific embodiments of the present invention, during the addition of water, concentrated phosphoric acid, and sodium diphenylamine sulfonate, the mass of the water is 500 to 600 times the mass of the titanium-iron mineral; including but not limited to values ​​of 520, 540, 550, 570, and 590 times, or any range between any two. The mass of the concentrated phosphoric acid is 50 to 80 times the mass of the titanium-iron mineral; including but not limited to values ​​of 55, 60, 65, 70, and 75 times, or any range between any two. The amount of sodium diphenylamine sulfonate added is 4 to 8 drops (e.g., 4, 5, 6, or 7 drops) of sodium diphenylamine sulfonate with a mass fraction of 1%.

[0088] In some specific embodiments of the present invention, the method for determining the mass fraction c of FeO in the ilmenite can be any conventional detection method, such as potassium dichromate titration, but is not limited thereto.

[0089] Preferably, the method for determining the mass fraction c of FeO in the ilmenite includes the potassium dichromate titration method.

[0090] Preferably, the potassium dichromate titration method for ferrous iron includes the following steps: adding sodium bicarbonate, sodium fluoride, and concentrated hydrochloric acid to m2 g of the ilmenite, heating to a gentle boil for a period of time, and then stopping the heating; immediately adding saturated boric acid solution, sodium bicarbonate, water, sulfuric acid-phosphoric acid mixture, and sodium diphenylamine sulfonate indicator, and then titrating with potassium dichromate solution with a molar concentration of c2 mol / L until the endpoint is purple, the volume of potassium dichromate used for titration is V2 mL, and calculating the mass fraction of FeO c = [(71.85×c2×V2) / (1000×m2)]×100%.

[0091] Where m2 = 0.3 to 0.5, including but not limited to point values ​​of any one of 0.35, 0.4, and 0.45, or range values ​​between any two. Wherein, the unit of m2 is g.

[0092] c2 = 0.005 to 0.02, including but not limited to point values ​​of any one of 0.007, 0.009, 0.01, 0.013, 0.015, and 0.018, or a range between any two. The unit of c2 is mol / L.

[0093] In some specific embodiments of the present invention, during the process of adding sodium bicarbonate, sodium fluoride and concentrated hydrochloric acid to m2 g of the titanium-iron mineral, the mass of sodium bicarbonate is 1 to 2 times (or 1.5 times) the mass of the titanium-iron mineral; the mass of sodium fluoride is 1 to 2 times (or 1.5 times) the mass of the titanium-iron mineral.

[0094] In some specific embodiments of the present invention, the mass of the concentrated hydrochloric acid is 70 to 115 times the mass of the titanium-iron mineral, including but not limited to any one of 80 times, 90 times, 100 times, or 110 times, or any range between two of them.

[0095] In some specific embodiments of the present invention, the heating and simmering time is 15 to 30 minutes, including but not limited to any one of 17 minutes, 20 minutes, 23 minutes, 25 minutes, and 28 minutes, or any range between two of them.

[0096] In some specific embodiments of the present invention, during the process of immediately adding saturated boric acid solution, sodium bicarbonate, water, sulfuric acid mixture, and sodium diphenylamine sulfonate indicator, the mass of the saturated boric acid solution is 20 to 30 times the mass of the titanium-iron mineral; including but not limited to a value of 22 times, 25 times, or 28 times, or a range between any two. The mass of the sodium bicarbonate is 1 to 4 times the mass of the titanium-iron mineral; including but not limited to a value of 2 times, 3 times, or 4 times, or a range between any two. The mass of the water is 200 to 250 times the mass of the titanium-iron mineral; including but not limited to a value of 210 times, 220 times, 230 times, or 240 times, or a range between any two. The mass of the sulfuric acid mixture is 40 to 60 times the mass of the titanium-iron mineral, including but not limited to a value of 45 times, 50 times, 55 times, or 58 times, or a range between any two. The amount of sodium diphenylamine sulfonate indicator used is 4 to 8 drops (e.g., 4, 5, 6 or 7 drops) of sodium diphenylamine sulfonate indicator with a mass fraction of 1%.

[0097] The sulfur-phosphoric acid mixture is prepared by mixing concentrated sulfuric acid (98% by mass), concentrated phosphoric acid (85% by mass), and water in a volume ratio of 15:15:70.

[0098] In some specific embodiments of the present invention, the concentrated sulfuric acid has a mass fraction of 98%, the concentrated hydrochloric acid has a mass fraction of 37%, and the concentrated phosphoric acid has a mass fraction of 85%.

[0099] Preferably, the reduction method of the ilmenite includes:

[0100] After the titanium-containing iron mineral and the reducing agent are mixed evenly, a reduction reaction is carried out at a certain temperature to obtain the reduction product.

[0101] The main components of the reduction product include elemental iron and titanium dioxide.

[0102] In some specific embodiments of the present invention, the titanium-containing iron mineral can be any conventional mineral containing titanium and iron, and the reducing agent can be any conventional reducing agent that can be purchased.

[0103] Preferably, the titanium-bearing minerals include at least one of titanomagnetite, seashore placer deposits, and brookite.

[0104] Preferably, the reducing agent includes at least one of coal, carbon monoxide, semi-coke, and metallurgical coke.

[0105] Preferably, the mass of the reducing agent is 40% to 80% of the mass of the titanium-iron mineral; including but not limited to a point value of any one of 50%, 60%, and 70% or a range between any two.

[0106] Preferably, an activator is also added during the mixing process. The activator can improve the reduction efficiency.

[0107] Preferably, the mass of the activator is 2% to 5% of the amount of the titanium-iron mineral, including but not limited to a point value of any one of 2.5%, 3%, 3.5%, 4%, or 4.5%, or a range between any two.

[0108] In some specific embodiments of the present invention, the activator can be any conventional activator with a reduction-promoting effect.

[0109] Preferably, the activator includes at least one of borax, sodium carbonate, sulfur, and iron sulfide.

[0110] In some specific embodiments of the present invention, the temperature and time of the reduction reaction of the ilmenite can be any conventional reduction temperature and holding time.

[0111] Preferably, the temperature of the reduction reaction is 900 to 1200°C, including but not limited to any one of 950°C, 1000°C, 1050°C, 1100°C, and 1150°C, or any range between two of them.

[0112] The (heating) time for the reduction reaction is 1 to 5 hours, including but not limited to any one of 1.5 hours, 2 hours, 3 hours, and 4 hours, or any range between two of them.

[0113] Secondly, the present invention provides the application of the method for calculating the metallization rate of titanium-containing iron minerals after reduction as described above in metallurgy.

[0114] Applying the above method for calculating the metallization rate of reduced titanium-containing iron minerals to the metallurgical field can shorten production time, improve production efficiency, and is more suitable for in-depth research and mass production of titanium-containing iron minerals.

[0115] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0116] In the following embodiments and comparative examples of the present invention, the method for determining the mass fraction b of total iron in ilmenite is the potassium dichromate titration method for total iron, which specifically includes the following steps:

[0117] Place 0.1g of ilmenite in an Erlenmeyer flask, add 15g of ammonium sulfate and 55g of 98% concentrated sulfuric acid, mix well, heat to a gentle boil for 50 minutes, cool to room temperature, add 60g of water and 11g of 37% concentrated hydrochloric acid, heat to a gentle boil, then add 10% tin dichloride dropwise until the solution changes from yellow to colorless. Add 2 drops in excess and cool rapidly. Add 11g of saturated mercuric dichloride solution, let stand for 2 minutes, then add 50g of water, 5.6g of 85% concentrated phosphoric acid and 4 drops of 1% sodium diphenylamine sulfonate. Titrate with 0.01mol / L potassium dichromate solution until the endpoint is purple. The volume of potassium dichromate used in the titration is V1 mL. Finally, calculate the total iron mass fraction b = (55.85 × 6 × 0.01 × V1) / (1000 × 0.1) × 100%.

[0118] In the following embodiments and comparative examples of the present invention, the method for determining the mass fraction c of FeO in ilmenite is the potassium dichromate titration method for ferrous iron, which specifically includes the following steps:

[0119] Weigh 0.5g of ilmenite into an Erlenmeyer flask, add 0.5g of sodium bicarbonate, 0.5g of sodium fluoride, and 46g of 37% hydrochloric acid. Seal with a rubber stopper and heat to a gentle boil for 20 minutes, then stop heating. Immediately add 11g of saturated boric acid solution, 2g of sodium bicarbonate, 100g of water, 21g of a sulfuric-phosphoric acid mixture (prepared by mixing 98% sulfuric acid, 85% phosphoric acid, and water in a volume ratio of 15:15:70), and 4 drops of 1% sodium diphenylamine sulfonate indicator. Titrate with 0.01mol / L potassium dichromate solution until a purple endpoint is reached. The volume of potassium dichromate used in the titration is V² L. Finally, calculate the mass fraction of FeO: c = (71.85 × 0.01 × V²) / (1000 × 0.5) × 100%.

[0120] In the following embodiments and comparative examples of the present invention, the test parameters for determining the mass fraction 'a' of titanium dioxide in ilmenite and the mass fraction 'd' of titanium dioxide in the reduction product using XRF detection are as follows:

[0121]

[0122] Example 1

[0123] (1) The titanium-containing iron mineral is a vanadium-titanium magnetite in Panzhihua (containing titanium, iron and impurities such as silicon, aluminum, calcium, iron, vanadium and manganese). XRF analysis showed that the mass fraction of titanium dioxide in the titanium-containing iron mineral was a = 11.93%.

[0124] The mass fraction b of total iron in ilmenite was determined and calculated using the potassium dichromate titration method. The mass fraction b of total iron in ilmenite was 56.27%.

[0125] The mass fraction c of FeO in ilmenite was determined and calculated using the potassium dichromate titration method. The mass fraction c of FeO in ilmenite was 40.59%.

[0126] (2) The above-mentioned vanadium-titanium magnetite from the Panzhihua-Xichang region was mixed evenly with coal and borax, and then subjected to a reduction reaction at 1000℃. After holding at this temperature for 5 hours, the reduction product was obtained. The mass of coal was 80% of the mass of the vanadium-titanium magnetite from the Panzhihua-Xichang region, and the mass of borax was 2% of the mass of the vanadium-titanium magnetite from the Panzhihua-Xichang region.

[0127] (3) The reduction product obtained in step (2) was subjected to XRF detection. The mass fraction of titanium dioxide in the reduction product was d = 14.69%.

[0128] (4) Calculate the metallization rate η: Substitute the values ​​of a, b, c, and d into the following formula for calculation. The result is that the metallization rate η = 94.58%.

[0129] The formula is:

[0130] Example 2

[0131] (1) The titanium-containing iron mineral is a seaside sandy deposit (containing titanium, iron, and impurities such as silicon, aluminum, calcium, iron, vanadium, and manganese). XRF analysis showed that the mass fraction of titanium dioxide in the titanium-containing iron mineral was a = 60.38%.

[0132] The mass fraction b of total iron in ilmenite was determined and calculated using the potassium dichromate titration method. The mass fraction b of total iron in ilmenite was 21.03%.

[0133] The mass fraction c of FeO in ilmenite was determined and calculated using the potassium dichromate titration method. The mass fraction c of FeO in ilmenite was 16.08%.

[0134] (2) The above-mentioned coastal sand mineral was mixed evenly with coal and borax, and then subjected to a reduction reaction at 1100℃ for 3 hours to obtain the reduction product. The mass of coal was 40% of the mass of the coastal sand mineral.

[0135] (3) The reduction product obtained in step (2) was subjected to XRF detection. The mass fraction of titanium dioxide in the reduction product was d = 64.42%.

[0136] (4) Calculate the metallization rate η: Substitute the values ​​of a, b, c, and d into the following formula for calculation. The result is that the metallization rate η = 83.87%.

[0137] The formula is:

[0138] Example 3

[0139] (1) The titanium-containing iron mineral is a seaside sandy deposit (containing titanium, iron, and impurities such as silicon, aluminum, calcium, iron, vanadium, and manganese). XRF analysis showed that the mass fraction of titanium dioxide in the titanium-containing iron mineral was a = 55.23%.

[0140] The mass fraction b of total iron in ilmenite was determined and calculated using the potassium dichromate titration method. The mass fraction b of total iron in ilmenite was 25.77%.

[0141] The mass fraction c of FeO in ilmenite was determined and calculated using the potassium dichromate titration method. The mass fraction c of FeO in ilmenite was 12.18%.

[0142] (2) The above-mentioned coastal sand mineral was mixed evenly with coal and borax, and then subjected to a reduction reaction at 1150℃. After holding at this temperature for 1.5 hours, the reduction product was obtained. The mass of coal was 40% of the mass of the coastal sand mineral.

[0143] (3) The reduction product obtained in step (2) was subjected to XRF detection. The mass fraction of titanium dioxide in the reduction product was d = 62.45%.

[0144] (4) Calculate the metallization rate η: Substitute the values ​​of a, b, c, and d into the following formula for calculation. The result is that the metallization rate η = 88.26%.

[0145] The formula is:

[0146] Comparative Example 1

[0147] This is essentially the same as Example 1, except that steps (3) and (4) are different. Steps (3) and (4) of this comparative example are as follows:

[0148] (3) The mass fraction x of total iron in the reduction product was determined and calculated using the total iron potassium dichromate titration method, and x = 69.06%. The mass fraction y of FeO in the reduction product was determined and calculated using the ferrous potassium dichromate titration method, and y = 65.48%.

[0149] (4) Calculate the metallization rate η: η = y / x × 100% = 94.81%.

[0150] Comparative Example 2

[0151] This is essentially the same as Example 2, except that steps (3) and (4) are different. Steps (3) and (4) of this comparative example are as follows:

[0152] (3) The mass fraction x of total iron in the reduction product was determined and calculated using the total iron potassium dichromate titration method, and x = 26.79%. The mass fraction y of FeO in the reduction product was determined and calculated using the ferrous potassium dichromate titration method, and y = 22.39%.

[0153] (4) Calculate the metallization rate η: η = y / x × 100% = 83.57%.

[0154] Comparative Example 3

[0155] This is essentially the same as Example 2, except that steps (3) and (4) are different. Steps (3) and (4) of this comparative example are as follows:

[0156] (3) The mass fraction x of total iron in the reduction product was determined and calculated using the total iron potassium dichromate titration method, and x = 34.75%. The mass fraction y of FeO in the reduction product was determined and calculated using the ferrous potassium dichromate titration method, and y = 30.72%.

[0157] (4) Calculate the metallization rate η: η = y / x × 100% = 88.40%

[0158] By comparing the results of the metallization rate η of Example 1 with Comparative Example 1, Example 2 with Comparative Example 2, and Example 3 with Comparative Example 3, it can be found that the values ​​are not significantly different.

[0159] It is evident that the method for calculating the metallization rate of titanium-containing iron minerals after reduction provided by this invention is feasible and highly accurate.

[0160] Although the present invention has been illustrated and described with specific embodiments, it should be understood that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; those skilled in the art should understand that modifications can be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein, without departing from the spirit and scope of the present invention; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention; therefore, this means that all such substitutions and modifications that fall within the scope of the present invention are included in the appended claims.

Claims

1. A method for calculating the metallization rate of ilmenite after reduction, characterized in that, The method for calculating the metallization rate ƞ includes: ； Where a is the mass fraction of titanium dioxide in the ilmenite; b is the mass fraction of total iron in the ilmenite; c is the mass fraction of FeO in the ilmenite; d represents the mass fraction of titanium dioxide in the reduction product obtained after reducing the titanium-containing iron mineral; The method for determining the mass fraction d of titanium dioxide in the reduction product includes XRF detection.

2. The method for calculating the metallization rate of titanium-containing iron minerals after reduction according to claim 1, characterized in that, The method for determining the mass fraction 'a' of titanium dioxide in the titanium-containing iron mineral includes XRF detection.

3. The method for calculating the metallization rate of titanium-containing iron minerals after reduction according to claim 1, characterized in that, The method for determining the mass fraction b of total iron in the ilmenite includes the potassium dichromate titration method for total iron.

4. The method for calculating the metallization rate of titanium-containing iron minerals after reduction according to claim 3, characterized in that, The total iron potassium dichromate titration method includes the following steps: Mix m1 g of the titanium-containing iron mineral with ammonium sulfate and concentrated sulfuric acid, heat to a gentle boil for 40-60 minutes, cool, add water and concentrated hydrochloric acid, heat to a gentle boil, add tin dichloride dropwise until the solution changes from yellow to colorless, add 2 drops in excess, cool rapidly, add saturated mercuric chloride solution, let stand for a period of time, add water, concentrated phosphoric acid, and sodium diphenylamine sulfonate, titrate with potassium dichromate solution with a molar concentration of c1 mol / L until the endpoint is purple, the volume of potassium dichromate used in the titration is V1 mL, calculate the total iron mass fraction b = (55.85 × 6c1V1 / 1000m1) × 100%.

5. The method for calculating the metallization rate of ilmenite after reduction according to claim 4, characterized in that, The m1 is 0.05~0.1, and the c1 is 0.005~0.

02.

6. The method for calculating the metallization rate of titanium-containing iron minerals after reduction according to claim 1, characterized in that, The method for determining the mass fraction c of FeO in the ilmenite includes the potassium dichromate titration method.

7. The method for calculating the metallization rate of ilmenite after reduction according to claim 6, characterized in that, The potassium dichromate titration method for ferrous iron includes the following steps: Sodium bicarbonate, sodium fluoride, and concentrated hydrochloric acid are added to m2 g of the titanium-containing iron mineral. The mixture is heated to a gentle boil for a period of time, after which heating is stopped. Immediately, saturated boric acid solution, sodium bicarbonate, water, a sulfuric-phosphoric acid mixture, and sodium diphenylamine sulfonate indicator are added. The solution is then titrated with a potassium dichromate solution with a molar concentration of c2 mol / L until a purple endpoint is reached. The volume of potassium dichromate used in the titration is V2 mL. The mass fraction of FeO is calculated as c = (71.85c2V2 / 1000m2) × 100%. Where m2 = 0.3~0.5, c2 = 0.005~0.

02.

8. The method for calculating the metallization rate of ilmenite after reduction according to claim 1, characterized in that, The reduction method of the titanium-iron mineral includes: The titanium-containing iron mineral and the reducing agent are mixed evenly and then subjected to a reduction reaction to obtain the reduction product.

9. The method for calculating the metallization rate of titanium-containing iron minerals after reduction according to claim 8, characterized in that, The titanium-bearing minerals include at least one of titanomagnetite, seashore placer deposits, and brookite.

10. The method for calculating the metallization rate of ilmenite after reduction according to claim 8, characterized in that, The reducing agent includes at least one of coal, carbon monoxide, semi-coke, and metallurgical coke.

11. The method for calculating the metallization rate of ilmenite after reduction according to claim 8, characterized in that, The mass of the reducing agent is 40% to 80% of the mass of the titanium-iron mineral.

12. The method for calculating the metallization rate of ilmenite after reduction according to claim 8, characterized in that, An activator was also added during the mixing process.

13. The method for calculating the metallization rate of titanium-containing iron minerals after reduction according to claim 12, characterized in that, The activator is 2% to 5% of the amount of the titanium-iron mineral.

14. The method for calculating the metallization rate of ilmenite after reduction according to claim 12, characterized in that, The activator includes at least one of borax, sodium carbonate, sulfur, and iron sulfide.

15. The method for calculating the metallization rate of titanium-containing iron minerals after reduction according to claim 8, characterized in that, The reduction reaction is carried out at a temperature of 900~1200℃ for 1~5 hours.

16. The application of the method for calculating the metallization rate of titanium-containing iron minerals after reduction as described in any one of claims 1 to 15 in metallurgy.

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