Flotation process and chemical agent for barite powder purification

Abstract

The invention relates to the field of nonmetallic mineral processing, in particular to a froth flotation method for barium sulfate minerals. The invention discloses a formula for an agent for barite flotation. Sodium oleate (lauryl sodium sulfate) is used as a collecting agent, water glass is used as an inhibitor, terpilenol is used as a foaming agent, the content of barium sulfate in barite mineral powder in foam flotation can be increased by adjusting the content of the collecting agent and the content of the inhibitor, and impurities are enriched in tailings. The collecting agent for barite flotation is prepared from the following raw materials in percentage by weight: 0.05 to 0.1 percent of sodium oleate (lauryl sodium sulfate) and 0.1 to 0.2 percent of water glass; the flotation agent is high in selectivity and strong in ore loading capacity, and can achieve an excellent flotation effect on barite ore in Longnan Wenxian County, Gansu Province, and concentrate with higher purity and higher recovery rate are obtained. The density of the purified barite powder is remarkably improved, and the obtained barite product can meet the density requirements of grade II products and even grade I products as a weighting agent of drilling mud. The method is simple in process, excellent in collecting agent effect, low in cost, environmentally friendly and capable of being deployed in factories on a large scale.

Description

Technical Field

[0001] This application relates to the field of mineral processing technology, specifically to the preparation of a collector for barite flotation. The barite flotation process is mainly achieved through the selection and optimization of collectors and depressants, as well as the adjustment of operating conditions such as the pH value of the pulp. Background Technology

[0002] Barite is the most common barium-containing mineral in nature, and its main component is barium sulfate. It is chemically stable and insoluble in water and hydrochloric acid. Barium sulfate is an important non-metallic mineral with a high density (4.4–4.5 g / cm³). 3 Barite has a low Mohs hardness (2.5-3.5) and is widely used in petroleum, chemical, and building materials industries. As a major mineral resource in my country, barite is widely distributed in Guizhou, Gansu, Hunan, Guangxi, and Shaanxi provinces. The ore grade ranges widely (50%-90%), and it is often found intercalated with fluorite, celestite, and carbonate (barite) minerals, requiring beneficiation before application. Its mineralization patterns vary depending on the geological conditions of different regions. The barite mine in Wenxian County, Longnan, Gansu Province, does not contain fluorite; its impurities are mainly quartz, alumina, iron oxide, and calcium carbonate.

[0003] Barite ore, after being crushed to different finenesses (typically 200 mesh, ~74µm particle size), can be used as a weighting agent in oil and gas well drilling mud. High-grade minerals with impurities having a significantly different specific gravity from barite can be physically separated using methods such as jigging and spiral sluices to obtain barite concentrate. For low-grade barite minerals with finely embedded particles, traditional physical methods are unlikely to achieve good beneficiation results. With its widespread use, high-grade barite mines are gradually becoming depleted, and froth flotation is gradually becoming a necessary step in the application of low-grade barite.

[0004] The chemical interactions between collector molecules and barite minerals significantly affect the grade and recovery rate of barite concentrate. Furthermore, the pH of the pulp affects the surface charge of barite minerals, altering the form and distribution of collectors (such as oleic acid) in aqueous solution, and changing the chemical interactions between collector molecules and barite minerals, thus affecting the floatability of barite. The flotation process for barite exists within a specific pH range of 8–11. Simultaneously, when separating associated minerals with similar floatability to barite, the selectivity of the flotation process can be improved by suppressing associated minerals.

[0005] In the flotation process, different flotation collectors for barite ore need to be optimized and formulated according to different sources of barite ore. Fatty acids can interact with metal atoms on the surface of various minerals, and alkyl sulfates can interact with barium ions on the surface of barium sulfate. Both of these molecules also have certain foaming properties and are characterized by low toxicity, easy solubility in water, and good selectivity. Summary of the Invention

[0006] To address the aforementioned problems, this invention provides a novel barium sulfate flotation method that can effectively improve the grade of barite concentrate and enhance flotation efficiency.

[0007] This invention uses barite powder (BaSO4 content <70%) produced by Longnan Wenxian Tianyuan Co., Ltd. as raw material. The composition of the powder sample, as shown in Table 1 below, was determined by XRF testing.

[0008] Table 1: X-ray fluorescence analysis (XRF) of raw barite powder. Impurity content in the samples is expressed in oxide form.

[0009]

[0010] It can be seen that the BaSO4 content in the barite ore sample after jaw crushing and grinding is about 70%. The ore sample contains various non-metallic and metallic impurities. The main impurities are silicon, aluminum, calcium, and iron. Phase analysis of the barite ore powder was performed, and the XRD pattern of the sample is shown in the attached figure. Figure 1 As shown. Analysis indicates that the impurity phases in the ore sample are CaCO3 (calcite) and SiO2 (quartz). Further analysis suggests that iron impurities likely exist as Fe2O3, while Mg, Ca, and Sr impurities are most likely present as sulfates, and Al impurities as clay. The solid density of the barite powder was determined to be 3.84 g / cm³. 3 (Archimedes process, kerosene as liquid medium).

[0011] The process disclosed in this patent requires only one flotation step, which is simple, energy-efficient, and has a short process cycle, making it easy to adopt on an industrial scale.

[0012] This invention is achieved through the following technical solution:

[0013] 1. The raw barite ore, after being jaw crushed, is ground to a fineness of 200 mesh in a Raymond mill to ensure sufficient dissociation between mineral particles. It is then dispersed in water (conductivity <100μS / cm) to form a slurry.

[0014] 2. Add appropriate amounts of anionic collector and inhibitor to the slurry, and adjust the pH value of the slurry simultaneously. The anionic collector also has a certain foaming effect.

[0015] 3. Air is bubbled into the slurry to perform flotation. The upper froth layer is scraped off at different time points to obtain barium sulfate concentrate.

[0016] 4. Filter the foam layer containing barium sulfate concentrate, wash, heat and dry to obtain high-purity barium sulfate powder.

[0017] 5. Filter the mother liquor containing tailings, wash, heat and dry to obtain tailings enriched with impurities.

[0018] The collected concentrate is washed and dried to obtain high-purity barium sulfate powder. Attached Figure Description

[0019] Figure 1 X-ray diffraction (XRD) images of raw barite powder and barite powder treated with hydrochloric acid. Detailed Implementation

[0020] The present invention will be further described in detail below through specific examples. It should be noted that the following embodiments are preferred embodiments of the present invention and are only used to illustrate the technical concept and features of the present invention. Improvements and modifications made without departing from the structure and principle of the present invention should also be considered within the protection scope of the present invention.

[0021] Unless otherwise defined, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein is for descriptive purposes only and is not intended to limit the invention.

[0022] Example 1

[0023] Sodium oleate was used as an anion collector (4.0*10). -4 The flotation of barium sulfate ore powder was carried out using a flotation method with a concentration of mol / L. Approximately 100.0 g of BaSO4 barite powder was dispersed in a 3 L flotation cell to form a pulp. After adding collectors and depressants, the pH of the pulp was maintained between 8 and 11. Water glass was used primarily to inhibit the entrainment of quartz in the barite powder during the flotation process. A self-aspirating flotation machine (model XFD-1L) was used, and flotation products were scraped off at different time stages (5 min, 10 min, 20 min). The room temperature was 25℃. A small amount of terpineol (1.0*10 mol / L) was added during the process. -4 Using mol / L as a frother does not significantly affect the flotation effect.

[0024] The composition of barite powder samples collected at different stages of flotation was determined by XRF (PANalytical Axios). Typical post-flotation barite compositions are shown in the table below.

[0025] Table 2: X-ray fluorescence analysis (XRF) of barite powder after flotation.

[0026]

[0027] Comparing the elemental content of barite powder before and after flotation, it can be seen that the SiO2 content in the powder decreased significantly (from ~15% to below ~5%). In contrast, the BaSO4 content in the powder increased from about 70% to about 90%. This indicates that the flotation step effectively enriches BaSO4 in the concentrate.

[0028] The density of the barite powder after flotation was determined by Leigh flask method and was 4.25 g / cm³. 3 The density of the tailings obtained after flotation is 3.54 g / cm³. 3 After this flotation step, the yield of BaSO4 in the concentrate is over 40% (density 4.2-4.3 g / cm³). 3 Grade I), with a BaSO4 yield of over 70% in the concentrate (density 4.06-4.2 g / cm³). 3 Grade II product).

[0029] Example 2

[0030] Sodium dodecyl sulfate was used as the anion collector (1.0*10). -3 The flotation of barium sulfate ore powder was carried out using a flotation method with a concentration of mol / L. Approximately 100.0 g of BaSO4 barite powder was dispersed in a 3 L flotation cell to form a pulp. After adding collectors and depressants, the pH of the pulp was maintained between 8 and 11. Water glass was used primarily to inhibit the entrainment of quartz in the barite powder during the flotation process. A self-aspirating flotation machine (model XFD-1L) was used, and flotation products were collected at three time stages (5 min, 10 min, 20 min). The room temperature was 25℃. A small amount of terpineol (1.0*10 mol / L) was added during the process. -4 Using mol / L as a frother does not significantly affect the flotation effect.

[0031] Table 3: Composition analysis of barite powder after flotation (X-ray fluorescence, XRF).

[0032]

[0033] Comparing the elemental content of barite powder before and after flotation, it can be seen that the SiO2 content in the powder decreased significantly (from ~15% to below ~2%). In contrast, the BaSO4 content in the powder increased from about 70% to over 90%, indicating that BaSO4 was enriched in the concentrate.

[0034] The density of the barite powder after flotation, determined by Leigh flask method, was 4.28 g / cm³. 3 The density of the tailings obtained after flotation is 3.51 g / cm³. 3 After this flotation step, the yield of BaSO4 in the concentrate is >30% (density 4.2-4.3 g / cm³). 3Grade I), BaSO4 yield in concentrate >60% (density 4.06-4.2 g / cm³). 3 Grade II product).

[0035] Compared with the prior art, the barium sulfate flotation method of the present invention has the following advantages:

[0036] • For the barite mine in Wenxian County, Longnan, the types and amounts of collectors and inhibitors were optimized, which significantly increased the density of barium sulfate ore powder and the content of BaSO4 in the concentrate.

[0037] • For the barite mine in Wenxian County, Longnan, the types and dosages of collectors and inhibitors were optimized to minimize potential environmental pollution during the flotation process.

[0038] This invention provides an effective flotation method for barite ore, resulting in barium sulfate concentrate with higher added value in oil and gas extraction. High-purity barite powder, as a high-end white coating, may be used in space refrigeration and high-temperature insulation fields, possessing significant industrial application value and market prospects.

Claims

1. A barite flotation process, characterized in that, The barite powder used contains less than 70% BaSO4, and the main impurities are calcium carbonate, aluminum oxide, iron oxide, and quartz, but does not contain fluorite.

2. The barite flotation collector according to claim 1, characterized in that, It is prepared from raw materials comprising the following components, in weight proportion to barite ore powder: sodium oleate 0.05% to 0.2% wt, water glass 0.1% to 0.2%.

3. The other barite flotation collector according to claim 1, characterized in that, It is prepared from raw materials comprising the following components, in weight proportion to barite ore powder: sodium dodecyl sulfate 0.05%–0.2% wt, water glass 0.1%–0.2%.

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