A method for improving the utilization efficiency of barium element in barite mineral

Abstract

The application relates to the technical field of barium element utilization in barite minerals, and specifically discloses a method for improving the utilization efficiency of barium elements in barite minerals. The method comprises the following steps: mixing crushed barite and crushed coal in a weight ratio of 1:(0.2-0.25), and then extruding and balling to obtain pellets, wherein the particle size of the pellets is 20-80 mm; the pellets are subjected to microwave roasting and crushing, the crushing product is subjected to water leaching to obtain a barium sulfide solution, and the barium residue is subjected to acid liquid dissolution and leaching, and then subjected to solid-liquid separation to obtain a barium ion solution and a residue stone. The method can significantly improve the yield of water-soluble BaS and the comprehensive utilization rate of barium elements in barite, and the process is environmentally friendly, low in pollution and high in production efficiency.

Description

Technical Field

[0001] This application relates to the technical field of barium utilization in barite minerals, and more specifically, to a method for improving the utilization efficiency of barium in barite minerals. Background Technology

[0002] Barite, as a basic mineral material for the production of barium-containing inorganic salts, is widely used in the production of various barium salts. Currently, the most common production method involves reducing and roasting crushed barite ore and reducing coal in a long rotary kiln. The resulting barium sulfide ash is then extracted by water leaching to obtain a barium sulfide solution, which is then used to produce various barium-containing inorganic salts. This technology is mature, but it has significant drawbacks: the long rotary kiln has two heating methods: pulverized coal and air heating and natural gas heating. However, regardless of the method used, a high-velocity flue gas flow is generated within the kiln. Combined with the kiln's own rotation, this results in a large amount of dust being carried into the flue gas at the kiln's tail end. This dust includes both unreacted coal powder and reacted materials. Directly treating this dust would increase the load on the dust removal system and lead to significant material waste; however, leaving the dust untreated would severely pollute the environment and fail to meet environmental protection requirements. Therefore, this has been a persistent pain point and challenge in the industry.

[0003] Furthermore, if larger particles are used for roasting, there is a problem that the material cannot be fully roasted within a short roasting time, resulting in a low barium sulfide content in the roasted product. On the other hand, extending the roasting time will lead to high costs and excessive by-products, which in turn will affect the barium sulfide yield. These are also insurmountable drawbacks in the traditional rotary kiln roasting process.

[0004] Based on the above problems, most barium sulfate producers use relatively short roasting times. This results in a barium utilization rate of only 70-80% when obtaining barium ions through water leaching after barite processing. Even with an additional acid leaching step after water leaching, the utilization rate is only 80-90%. Therefore, using this process to process barite not only wastes valuable barite resources but also affects the comprehensive utilization of subsequent slag, leading to the accumulation of large amounts of slag. In today's increasingly stringent environmental protection requirements, the environmental problems caused by the accumulation of large amounts of slag have seriously affected the survival and development of enterprises.

[0005] To further address the issues of low barium utilization and excessive slag accumulation, related technologies employ microwave calcination to replace traditional calcination processes. This reduces the cost of rotary kiln exhaust gas treatment and is both more environmentally friendly and lower in cost.

[0006] However, when using microwave calcination of barite minerals, a large amount of caking occurs in the calcination product, which directly leads to the following problems: 1. The outer surface of the caking product undergoes over-calcination, resulting in an increase in by-products on the outer surface (such as non-water-soluble barium carbonate), affecting the barium sulfide yield; 2. The interior of the caking product is not thoroughly calcined, resulting in a large amount of barium sulfate not reacting into barium sulfide, thus affecting the barium sulfide yield; 3. Caking also directly increases the difficulty of subsequent crushing, making it difficult to obtain purified barium sulfide through crushing and washing even if barium sulfide is obtained through microwave calcination.

[0007] Therefore, it is essential to improve the utilization efficiency of barium in barite minerals and increase the yield of water-soluble barium ions while obtaining barium sulfide using a relatively environmentally friendly microwave calcination method. Summary of the Invention

[0008] In order to improve the yield of water-soluble barium in microwave calcination process, this application provides a method to improve the utilization efficiency of barium element in barite minerals.

[0009] This application provides a method for improving the utilization efficiency of barium in barite minerals, which adopts the following technical solution: A method for improving the utilization efficiency of barium in barite minerals, the method comprising the following steps:

[0010] Crushed barite and crushed coal are mixed at a weight ratio of 1:(0.2-0.25) and then extruded to form pellets, with the pellets having a particle size of 20-80 mm.

[0011] The pellets were microwave roasted and crushed. The crushed product was extracted with water to obtain a barium sulfide solution. The barium slag was leached with acid. After solid-liquid separation, a barium ion solution and slag were obtained.

[0012] Microwave heating offers penetration and uniformity, enabling barite to undergo a reduction reaction in a short time, thus increasing its conversion rate. Simultaneously, the static roasting method avoids dust pollution. However, this static roasting method also leads to the formation of caking products after roasting. When crushed barite and crushed coal (reduced coal) are directly heated at high temperatures, the silica in the barite gradually transforms into a molten state at around 1200℃, causing the raw materials to aggregate and gradually caking. Furthermore, the coal contains a certain amount of coal tar, which gradually becomes viscous at 600-800℃, further causing the materials to adhere and promoting caking.

[0013] By adopting the above technical solution, the applicant pre-treats barite and coal to form pellets. Its advantages are: 1. Appropriate gaps exist between the pellets, preventing direct contact and effectively avoiding material adhesion and caking. 2. When barium sulfate in barite is converted to barium sulfide, the reaction processes involved include: barium sulfate reacting with carbon to produce barium sulfide and carbon monoxide; barium sulfate reacting with carbon to produce barium sulfide and carbon dioxide; barium sulfate reacting with carbon monoxide to produce barium sulfide and carbon dioxide; therefore, this process is actually a solid-solid reaction and a solid-gas reaction. The gaps between the pellets provide more space for gas, facilitating gas flow and making the gas-solid reaction more complete. 3. Adjusting the particle size of the pellets to an appropriate range effectively avoids caking while ensuring sufficient reaction of the material within each individual pellet. If the pellet size is too small, the gaps between the pellets will be too small, leading to caking and adhesion, which will affect the subsequent crushing and water leaching results. If the pellet size is too large, on the one hand, there will be problems with incomplete calcination due to the size of a single pellet, and on the other hand, there will be problems with the availability of suitable microwave calcination equipment. Therefore, pre-forming the raw materials into pellets of appropriate size can effectively solve the problems of adhesion and caking that occur when the raw materials are directly mixed and microwave calcined. This facilitates subsequent crushing, water leaching, and acid leaching treatments, ultimately significantly improving the utilization efficiency of barium in barite minerals, increasing the barium utilization rate from 70-80% in traditional methods to over 90%. The subsequent barium slag can also be used harmlessly, making it more environmentally friendly.

[0014] Optionally, the conditions for extrusion pelletizing include: extrusion pelletizing under a pressure of ≥10MPa.

[0015] By employing the above technical solution, pellets of suitable particle size can be obtained. In some embodiments, the pressure is 10-15 MPa.

[0016] Optionally, the barite contains 60-90 wt% barium sulfate, and the coal contains 60-90 wt% fixed carbon.

[0017] Optionally, the barite is crushed and passed through a 50-200 mesh sieve, and the coal is crushed and passed through a 20-100 mesh sieve.

[0018] Optionally, the microwave roasting temperature is 1100-1300℃ and the roasting time is 20-60min.

[0019] Compared with the traditional rotary kiln roasting of barite, which takes 90-120 minutes, microwave roasting has a shorter roasting time of only 20-60 minutes. This process significantly improves efficiency and greatly reduces energy consumption. At the same time, the process in this application uses electricity to replace coal, achieving clean production.

[0020] Optionally, the pH value of the acid solution is 0-5.

[0021] Optionally, the acid in the acid solution is selected from any one or two of hydrochloric acid and nitric acid.

[0022] Optionally, microwave roasting can be carried out in an inert gas atmosphere.

[0023] Optionally, the product obtained after microwave calcination contains ≥75wt% water-soluble barium and 10-20wt% acid-soluble barium.

[0024] Optionally, the free barium content in the barium slag obtained after water leaching is ≤1.0 wt%; the slag obtained after acid leaching contains no free barium.

[0025] In summary, this application has the following beneficial effects:

[0026] 1. This application describes a static microwave roasting method for preparing water-soluble barium sulfate, which has the advantages of being environmentally friendly and low-pollution. Microwave heating has penetrating and uniform properties, enabling barite to undergo a reduction reaction in a short time, thus improving the conversion rate of barite. Compared to the 90-120 minutes required for traditional rotary kiln roasting of barite, the microwave roasting process only requires 20-60 minutes, significantly improving efficiency and greatly reducing energy consumption. Furthermore, compared to traditional rotary kilns, microwave roasting uses electricity instead of coal, achieving cleaner production. In addition, this application further combines microwave roasting with a water leaching process to obtain water-soluble barium sulfate, and then combines this with an acid leaching process to convert barium carbonate into soluble barium salts, ultimately achieving a highly efficient conversion of barite with a conversion rate exceeding 95%.

[0027] 2. Before microwave roasting in this application, the raw materials need to be pre-granulated to effectively prevent caking and sticking during the roasting process, thus avoiding difficulty in crushing and obtaining water-soluble barium sulfate through sufficient water immersion. Static reaction of the raw materials in pellet form can significantly improve the yield of water-soluble barium sulfide.

[0028] 3. In this application, when pelletizing the raw materials, the pellet size is adjusted to 20-80mm to ensure that the raw materials react fully while avoiding caking and sticking. Detailed Implementation

[0029] The following detailed description of this application is provided in conjunction with the embodiments. It should be noted that: unless otherwise specified, the conditions in the following embodiments are performed under conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, the raw materials used in the following embodiments are all from commercially available sources.

[0030] Performance testing methods

[0031] 1. Determination of water-soluble barium ion content

[0032] After crushing the sample to be tested, the sample was placed in a 250ml beaker, and hot water was added at a material-to-liquid ratio of 1g:120ml. The beaker was placed in a heat-collecting constant-temperature magnetic stirrer and stirred for 3 hours at 100℃ (generally controlled within the range of 95-100℃). Then, the sample was filtered, and the filtrate was placed in a 250ml volumetric flask, diluted to the mark, and shaken well to obtain a BaS solution. The residue after filtration was barium slag.

[0033] Referring to the JC / T1021.7-2007 standard, the water-soluble barium ion content was determined, and the BaS yield was calculated using Formula 1 and expressed as a mass fraction ω(BaS), with the value expressed as a percentage (%).

[0034] In the formula:

[0035] m1 -- Mass of precipitate added to the crucible, in grams (g);

[0036] m2 -- Mass of the crucible, in grams (g);

[0037] V S --Total volume of the test solution, in milliliters (ml);

[0038] M s --Raw material mass, in grams (g);

[0039] ω BaSO4 --Mass fraction of BaSO4 in raw materials, expressed as a percentage;

[0040] V1 -- The volume of the test solution dispensed, in milliliters (ml).

[0041] 2. Determination of acid-soluble barium ion content

[0042] However, after the sample was soaked in hot water and the residue was filtered, it was dissolved in 40ml of hydrochloric acid (1+9); it was heated on an electric furnace and boiled gently for 30 minutes, then about 50ml of water was added and boiled gently for another 3 minutes, and then cooled; it was filtered with quantitative slow filter paper, and the filtrate was collected in a 250ml volumetric flask and diluted to volume.

[0043] Referring to the JC / T1021.7-2007 standard, the content of acid-soluble barium ions was determined, and the yield of BaCO3 was calculated as a mass fraction ω(BaCO3) using Formula 2. 2+ The values ​​are expressed as % (%).

[0044] In the formula:

[0045] m1 -- Mass of precipitate added to the crucible, in grams (g);

[0046] m2 -- Mass of the crucible, in grams (g);

[0047] VS --Total volume of the test solution, in milliliters (ml);

[0048] M s --Raw material mass, in grams (g);

[0049] ωBaSO4 -- Mass fraction of BaSO4 in the raw material, expressed as a percentage;

[0050] V1 -- The volume of the test solution dispensed, in milliliters (ml).

[0051] Example

[0052] The barite sample was purchased from a mixed sample from Guizhou, Shaanxi, and Henan provinces. Its barium sulfate content was determined to be 81.50 wt%, and its silicon dioxide content was 12.51 wt%. The coal was reduced coal, purchased from Yangquan, Shanxi province, and its fixed carbon content was determined to be 84.38 wt%.

[0053] Example 1

[0054] A method for improving the utilization efficiency of barium in barite minerals comprises the following steps:

[0055] Take 1000g of the above sample barite and crush it until all the barite can pass through a 100-mesh sieve to obtain 1000g of raw material A; take 230g of the above sample reduced coal and crush it until all the reduced coal can pass through a 20-mesh sieve to obtain 230g of raw material B.

[0056] After thoroughly mixing raw materials A and B, pellets were formed using a CJL-290 briquetting machine at a pressure of 12MPa to obtain pellets with a diameter of 40mm. These pellets were in the form of lumpy materials.

[0057] The pellets were placed in an RWS-3 microwave pyrolysis apparatus, which was then filled with nitrogen. High-temperature static calcination was then performed at 2450 MHz microwaves, with the calcination temperature controlled at 1200℃ and the holding time at 45 min, while the nitrogen flow rate was 2 L / min. After calcination, barium sulfide black ash was obtained. The black ash was subjected to a three-stage leaching process with 90℃ hot water, resulting in a free barium ion content in the barium slag ≤1.0 wt%. The barium slag was then acidified with hydrochloric acid to a final pH of 4, filtered, and subjected to a three-stage washing process, yielding slag with a free barium content of 0.

[0058] The yield of water-soluble BaS, expressed as mass fraction ω(BaS), was determined using the above detection methods to be 82.49%; the yield of acid-soluble BaCO3, expressed as mass fraction ω(BaS), was also determined to be... 2+ The total content of barium in the sample is 16.90%; the comprehensive utilization rate of barium in barite (the sum of water-soluble barium and acid-soluble barium) is 99.39%.

[0059] Example 2

[0060] A method for improving the utilization efficiency of barium in barite minerals comprises the following steps:

[0061] Take 1000g of barite purchased from the market and crush it until all the barite can pass through a 100-mesh sieve to obtain 1000g of raw material A; take 230g of the sample of reducing coal and crush it until all the reducing coal can pass through a 20-mesh sieve to obtain 230g of raw material B.

[0062] After thoroughly mixing raw materials A and B, pellets were formed using a CJL-290 briquetting machine at a pressure of 10 MPa to obtain pellets with a diameter of 30 mm. These pellets were in the form of lumpy materials.

[0063] The pellets were placed in an RWS-3 microwave pyrolysis apparatus, which was then filled with nitrogen. High-temperature static calcination was then performed at 1200℃ for 40 minutes under 2450MHz microwaves, with a nitrogen flow rate of 3L / min. After calcination, barium sulfide black ash was obtained. The resulting black ash underwent three-stage hot water extraction at 90℃, resulting in a free barium ion content ≤1.0wt% in the barium slag. The barium slag was then acidified with hydrochloric acid to a final pH of 3, filtered, and subjected to three-stage washing, resulting in a free barium content of 0%.

[0064] The yield of water-soluble BaS, expressed as mass fraction ω(BaS), was determined using the above detection methods to be 81.58%; the yield of acid-soluble BaCO3, expressed as mass fraction ω(BaS), was also determined to be... 2+ The total content of barium in the sample is 18.42%; the comprehensive utilization rate of barium in barite (the sum of water-soluble barium and acid-soluble barium) is 100%.

[0065] Example 3

[0066] A method for improving the utilization efficiency of barium in barite minerals comprises the following steps:

[0067] Take 1000g of barite sample purchased from the market, crush it until all barite can pass through a 140-mesh sieve, and obtain 1000g of raw material A; take 230g of the above sample of reducing coal, crush it until all reducing coal can pass through a 40-mesh sieve, and obtain 230g of raw material B.

[0068] After thoroughly mixing raw materials A and B, pellets were formed using a CJL-290 briquetting machine at a pressure of 13MPa to obtain pellets with a diameter of 50mm. These pellets were in the form of lumpy materials.

[0069] The pellets were placed in an RWS-3 microwave pyrolysis apparatus, which was then filled with nitrogen. High-temperature static calcination was then performed at 2450 MHz microwaves, with the calcination temperature controlled at 1250℃ and the holding time at 30 min, while the nitrogen flow rate was 2 L / min. After calcination, barium sulfide black ash was obtained. The obtained black ash underwent three-stage leaching with 90℃ hot water, resulting in a free barium ion content in the barium slag ≤1.0 wt%. The barium slag was then acidified with hydrochloric acid to a final pH of 3, filtered, and subjected to three-stage washing, ultimately achieving a free barium content of 0% in the slag.

[0070] The yield of water-soluble BaS, expressed as mass fraction ω(BaS), was determined using the above detection methods to be 82.34%; the yield of acid-soluble BaCO3, expressed as mass fraction ω(BaS), was also determined to be... 2+ The total content of barium in the sample is 17.15%; the comprehensive utilization rate of barium in barite (the sum of water-soluble barium and acid-soluble barium) is 99.49%.

[0071] Example 4

[0072] A method for improving the utilization efficiency of barium in barite minerals comprises the following steps:

[0073] Take 1000g of barite sample purchased from the market, crush it until all barite can pass through a 140-mesh sieve, and obtain 1000g of raw material A; take 230g of the above sample of reducing coal, crush it until all reducing coal can pass through a 40-mesh sieve, and obtain 230g of raw material B.

[0074] After thoroughly mixing raw materials A and B, pellets are formed using a CJL-290 briquetting machine at a pressure of 10 MPa to obtain pellets with a diameter of 30 mm. These pellets are in the form of lumpy materials.

[0075] The pellets were placed in an RWS-3 microwave pyrolysis apparatus, which was then filled with nitrogen. High-temperature static calcination was then performed at 2450 MHz microwaves, with the calcination temperature controlled at 1150℃ and the holding time at 45 min, while the nitrogen flow rate was 3 L / min. After calcination, barium sulfide black ash was obtained. The obtained black ash underwent three-stage extraction with 90℃ hot water, resulting in a free barium ion content in the barium slag ≤1.0 wt%. The barium slag was then acidified with hydrochloric acid to a final pH of 2, filtered, and subjected to three-stage washing, ultimately yielding a free barium content of 0% in the residue.

[0076] The yield of water-soluble BaS, expressed as mass fraction ω(BaS), was determined using the above detection methods to be 82.22%; the yield of acid-soluble BaCO3, expressed as mass fraction ω(BaS), was also determined to be... 2+ The total content of barium in the sample is 17.60%; the comprehensive utilization rate of barium in barite (the sum of water-soluble barium and acid-soluble barium) is 99.82%.

[0077] Example 5

[0078] A method for improving the utilization efficiency of barium in barite minerals comprises the following steps:

[0079] Take 1000g of barite sample purchased from the market, crush it until all barite can pass through a 200-mesh sieve, and obtain 1000g of raw material A; take 250g of the above sample of reducing coal, crush it until all reducing coal can pass through a 100-mesh sieve, and obtain 250g of raw material B.

[0080] After thoroughly mixing raw materials A and B, pellets were formed using a CJL-290 briquetting machine at a pressure of 10 MPa to obtain pellets with a diameter of 30 mm. These pellets were in the form of lumpy materials.

[0081] The pellets were placed in an RWS-3 microwave pyrolysis apparatus, which was then filled with nitrogen. High-temperature static calcination was then performed at 2450 MHz microwaves, with the calcination temperature controlled at 1300℃ and the holding time at 20 min, while the nitrogen flow rate was 3 L / min. After calcination, barium sulfide black ash was obtained. The obtained black ash underwent three-stage extraction with 90℃ hot water, resulting in a free barium ion content in the barium slag ≤1.0 wt%. The barium slag was then acidified with hydrochloric acid to a final pH of 2, filtered, and subjected to three-stage washing, ultimately yielding a free barium content of 0% in the residue.

[0082] The yields of water-soluble BaS, expressed as mass fraction ω(BaS), were determined using the above detection methods and were 82.04%; the yields of acid-soluble BaCO3, expressed as mass fraction ω(BaS), were also determined. 2+ The total utilization rate of barium in barite (the sum of water-soluble barium and acid-soluble barium) is 17.14%; the comprehensive utilization rate of barium (the sum of water-soluble barium and acid-soluble barium) is 99.18%.

[0083] Example 6

[0084] A method for improving the utilization efficiency of barium in barite minerals comprises the following steps:

[0085] Take 1000g of barite sample purchased from the market, crush it until all barite can pass through a 50-mesh sieve, and obtain 1000g of raw material A; take 200g of the above sample of reducing coal, crush it until all reducing coal can pass through a 20-mesh sieve, and obtain 200g of raw material B.

[0086] After thoroughly mixing raw materials A and B, pellets were formed using a CJL-290 briquetting machine at a pressure of 10 MPa to obtain pellets with a diameter of 30 mm. These pellets were in the form of lumpy materials.

[0087] The pellets were placed in an RWS-3 microwave pyrolysis apparatus, which was then filled with nitrogen. High-temperature static calcination was then performed at 2450 MHz microwaves, with the calcination temperature controlled at 1100℃ and the holding time at 60 min, while the nitrogen flow rate was 3 L / min. After calcination, barium sulfide black ash was obtained. The obtained black ash underwent three-stage leaching with 90℃ hot water, resulting in a free barium ion content in the barium slag ≤1.0 wt%. The barium slag was then acidified with hydrochloric acid to a final pH of 2, filtered, and subjected to three-stage washing, ultimately yielding a free barium content of 0% in the residue.

[0088] The yield of water-soluble BaS, expressed as mass fraction ω(BaS), was determined using the above detection methods to be 81.99%; the yield of acid-soluble BaCO3, expressed as mass fraction ω(BaS), was also determined to be... 2+ The total content of barium in the sample is 17.61%; the comprehensive utilization rate of barium in barite (the sum of water-soluble barium and acid-soluble barium) is 99.60%.

[0089] Examples 7-9

[0090] The difference between the following examples and Example 2 is that the resulting pellets have different particle sizes, as detailed below:

[0091] In Example 7, the obtained pellets had a particle size of 20 mm.

[0092] In Example 8, the obtained pellets had a particle size of 60 mm.

[0093] In Example 9, the obtained pellets had a particle size of 80 mm.

[0094] Comparative Example

[0095] Comparative Examples 1-2

[0096] The difference between the following comparative examples and Example 2 is that the resulting pellets have different particle sizes, as detailed below:

[0097] In Comparative Example 1, the obtained pellets had a particle size of 10 mm.

[0098] In Comparative Example 2, the obtained pellets had a particle size of 90 mm.

[0099] The water-soluble BaS yields of Examples 7-9 and Comparative Examples 1-2 were determined using the above detection methods, expressed as mass fraction ω(BaS); the acid-soluble BaCO3 yields were also determined, expressed as mass fraction ω(BaS). 2+ The specific results are shown in Table 1.

[0100] Table 1. Yields of water-soluble BaS, yields of acid-soluble BaCO3, and comprehensive utilization rate of barium in different implementation schemes.

[0101] Implementation Plan Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Water-soluble BaS yield % 81.29 82.03 80.95 77.36 74.96 <![CDATA[Yield % of acid-soluble BaCO3]]> 17.70 17.92 17.96 21.60 18.92 Barium element comprehensive utilization rate % 98.99 99.95 98.91 98.96 93.88

[0102] Comparative Example 3

[0103] The difference between this comparative example and Example 2 is that the raw materials were not subjected to a pelletizing step, but were directly subjected to microwave roasting, as detailed below:

[0104] A method for collecting barium from barite minerals comprises the following steps:

[0105] Take 1000g of barite purchased from the market and crush it until all the barite can pass through a 100-mesh sieve to obtain 1000g of raw material A; take 230g of the sample of reducing coal and crush it until all the reducing coal can pass through a 20-mesh sieve to obtain 230g of raw material B.

[0106] Raw materials A and B were thoroughly mixed and placed into an RWS-3 microwave pyrolysis apparatus, which was then filled with nitrogen. High-temperature static calcination was then performed at 1200℃ under 2450MHz microwaves for 40 minutes, with a nitrogen flow rate of 3L / min. After calcination, barium sulfide black ash was obtained. The obtained black ash underwent three-stage leaching with 90℃ hot water, resulting in a free barium ion content ≤1.0wt% in the barium slag. The barium slag was then acidified with hydrochloric acid to a final pH of 3, filtered, and subjected to three-stage washing, resulting in a free barium content of 0%.

[0107] The yield of water-soluble BaS, expressed as mass fraction ω(BaS), was determined using the above detection methods and was 60.55%; the yield of acid-soluble BaCO3, expressed as mass fraction ω(BaS), was also determined. 2+ The total utilization rate of barium in barite (the sum of water-soluble barium and acid-soluble barium) is 37.45%; the comprehensive utilization rate of barium (the sum of water-soluble barium and acid-soluble barium) is 98.00%.

[0108] Comparative Example 4

[0109] A method for improving the utilization efficiency of barium in barite minerals comprises the following steps:

[0110] Take a sample of barite purchased from the market, crush it until all the barite can pass through a 140-mesh sieve, and obtain 1000g of raw material A; take 230g of the above sample of reducing coal, crush it until all the reducing coal can pass through a 40-mesh sieve, and obtain 230g of raw material B.

[0111] After thoroughly mixing raw materials A and B, pellets were formed using a CJL-290 briquetting machine at a pressure of 12MPa to obtain pellets with a diameter of 40mm. These pellets were in the form of lumpy materials.

[0112] The pellets were statically calcined in an electrically heated muffle furnace, which was filled with nitrogen gas at a temperature of 1200℃ for 60 minutes, with a nitrogen flow rate of 2 L / min. After calcination, barium sulfide black ash was obtained. The black ash was then subjected to a three-stage leaching process with 90℃ hot water, resulting in a free barium ion content in the barium slag of ≤1.0 wt%. The barium slag was then acidified with hydrochloric acid to a final pH of 3, filtered, and subjected to three stages of washing, ultimately yielding a residue with a free barium content of 0.

[0113] The yield of water-soluble BaS, expressed as mass fraction ω(BaS), was determined using the above detection methods to be 82.06%; the yield of acid-soluble BaCO3, expressed as mass fraction ω(BaS), was also determined to be... 2+ The total content of barium in the sample is 10.12%; the comprehensive utilization rate of barium in barite (the sum of water-soluble barium and acid-soluble barium) is 92.18%.

[0114] Comparative Example 5

[0115] A method for improving the utilization efficiency of barium in barite minerals comprises the following steps:

[0116] Take 1000g of barite purchased from the market and crush it until all the barite can pass through a 100-mesh sieve to obtain 1000g of raw material A; take 230g of the sample of reducing coal and crush it until all the reducing coal can pass through a 20-mesh sieve to obtain 230g of raw material B.

[0117] After thoroughly mixing raw materials A and B, pellets were formed using a CJL-290 briquetting machine at a pressure of 10 MPa to obtain pellets with a diameter of 30 mm. These pellets were in the form of lumpy materials.

[0118] The pellets were statically calcined in an electrically heated muffle furnace, which was filled with nitrogen gas at 1150℃ for 75 minutes, with a nitrogen flow rate of 3 L / min. After calcination, barium sulfide black ash was obtained. The black ash was then subjected to three-stage leaching with 90℃ hot water, resulting in a free barium ion content in the barium slag ≤1.0 wt%. The barium slag was then acidified with hydrochloric acid to a final pH of 2, filtered, and subjected to three-stage washing, ultimately yielding a residue with a free barium content of 0.

[0119] The yield of water-soluble BaS, expressed as mass fraction ω(BaS), was determined using the above detection methods to be 81.59%; the yield of acid-soluble BaCO3, expressed as mass fraction ω(BaS), was also determined to be... 2+ The total content of barium in the sample is 9.43%; the comprehensive utilization rate of barium in barite (the sum of water-soluble barium and acid-soluble barium) is 91.02%.

[0120] The above experimental results show that treating barite with the method of this application can significantly increase the yield of water-soluble barium sulfide and reduce the yield of acid-soluble barium carbonate, providing more high-quality raw materials for the production of barium-related products in the later stage.

[0121] A comparison of the results from Example 2 and Comparative Example 3 revealed that when collecting barium from barite using microwave roasting, extruding and pelletizing the raw material before microwave roasting significantly improved the yield of water-soluble barium sulfide. Further analysis of the data from Examples 7-9 and Comparative Examples 1-2 showed that the particle size of the pellets had a certain impact on the yield of water-soluble barium sulfide during extrusion pelletizing; it is recommended that the pellet particle size be within the range of 20-80 mm, otherwise the yield of water-soluble barium sulfide will be lower than 80 wt%.

[0122] Comparing Comparative Example 4 with Example 1 (or Comparative Example 5 with Example 2), it was found that even with pretreatment of the raw materials by extrusion into pellets, if conventional muffle furnace static roasting was used instead of the microwave static roasting method of this application, the yield of water-soluble barium sulfide could exceed 80 wt%, but the yield of acid-soluble barium carbonate was significantly reduced to below 11 wt%. This directly leads to a decrease in the utilization rate of barium in barite. Therefore, in order to improve the yield of barium sulfide and the utilization rate of barium, it is necessary to combine the pre-extrusion into pellets of the raw materials with microwave roasting to achieve this goal.

[0123] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A method for improving the utilization efficiency of barium element in barite minerals, characterized in that, The method includes the following steps: Crushed barite and crushed coal are mixed at a weight ratio of 1:(0.2-0.25) and then extruded to form pellets, with the pellets having a particle size of 20-80 mm. The pellets were microwave roasted and crushed. The crushed product was extracted with water to obtain a barium sulfide solution. The barium slag was leached with acid and separated into solid and liquid to obtain a barium ion solution and slag. The conditions for extrusion pelletizing include: extrusion pelletizing under a pressure of ≥10MPa; The microwave roasting temperature is 1100-1300℃, the roasting time is 20-60min, and the microwave roasting is carried out in an inert gas atmosphere.

2. The method for improving the utilization efficiency of barium element in barite minerals according to claim 1, characterized in that, The barite contains 60-90 wt% barium sulfate, and the coal contains 60-90 wt% fixed carbon.

3. The method for improving the utilization efficiency of barium element in barite minerals according to claim 1, characterized in that, The barite is crushed and passed through a 50-200 mesh sieve, and the coal is crushed and passed through a 20-100 mesh sieve.

4. The method for improving the utilization efficiency of barium element in barite minerals according to claim 1, characterized in that, The pH value of the acid solution is 0-5.

5. A method for improving the utilization efficiency of barium element in barite minerals according to claim 4, characterized in that, The acid in the acid solution is selected from any one or two of hydrochloric acid and nitric acid.

6. The method for improving the utilization efficiency of barium element in barite minerals according to claim 1, characterized in that, The product obtained after microwave calcination contains ≥75wt% water-soluble barium and 10-20wt% acid-soluble barium.

7. A method for improving the utilization efficiency of barium element in barite minerals according to claim 1, characterized in that, The free barium content in the barium slag obtained after water leaching is ≤1.0wt%; the slag obtained after acid leaching contains no free barium.