A flotation desulfurization collector for calcium-process vanadium extraction tailings and its preparation method

Abstract

The present invention discloses a collector for flotation desulfurization of calcium-process vanadium extraction tailings and a preparation method thereof, which includes 1-10 parts of octyldecanol polyoxyethylene ether phosphate; 1-10 parts of fatty alcohol polyoxyethylene ether phosphate; 1-10 parts of isomeric tridecanol polyoxyethylene ether; 1-10 parts of alkylphenol polyoxyethylene ether; 1-10 parts of octyldecanol polyoxyethylene ether phosphate; 1-10 parts of isooctanol polyoxyethylene ether phosphate; 1-30 parts of N-cocoyl propanediamine acetate; 1-10 parts of lauroyl glutamate; 1-10 parts of lauroyl sarcosinate; 1-10 parts of cocoyl glycinate; 1-10 parts of coconut oil fatty acid alaninate. Compared with the prior art, the collector of the present invention has a high recovery rate of gypsum products obtained by flotation, low impurity content, high iron and vanadium content and low sulfur content in the iron concentrate remaining after flotation. It has high solubility, good foam fluidity, controllable foam life, environmental friendliness, strong collecting performance, fast flotation rate and shorter flotation time.

Description

Technical Field

[0001] The present invention relates to a flotation desulfurization collector for calcium-process vanadium extraction tailings and a preparation method thereof, belonging to the field of comprehensive recycling and utilization of calcium-process vanadium extraction tailings resources. Background Art

[0002] More than 80% of the world's vanadium is obtained from vanadium-titanium magnetite every year. Usually, a rotary kiln - electric furnace or blast furnace is used to smelt vanadium-containing hot metal, and then vanadium slag is blown out from the vanadium-containing hot metal to enrich vanadium in the vanadium slag, so as to extract vanadium. In the process of extracting vanadium from vanadium slag, there are mainly two processes: water leaching vanadium extraction and acid leaching vanadium extraction. Among them, acid leaching vanadium extraction mainly involves roasting vanadium slag with lime or limestone to generate calcium vanadate, and using the acid solubility of calcium vanadate to transfer vanadium into the solution while generating calcium sulfate precipitation. After solid-liquid separation, calcium sulfate enters the vanadium slag; after acid leaching vanadium extraction, the tailings still contain 1 - 5% vanadium pentoxide, with an iron content of 15 - 30%, and also contain valuable elements such as chromium. Usually, when the sulfur trioxide content in the acid leached slag is less than 0.3%, it can be used as a blast furnace coolant or directly returned to the furnace to recover other useful elements. On the contrary, when the acid leached slag contains a large amount of calcium sulfate, the sulfur content in the vanadium extraction tailings increases; at this time, the vanadium extraction tailings cannot be returned to smelting and can only be piled up or landfilled as waste. Hu Peng et al. (Hu Peng, Rao Jiating, Xie Hongen, etc. Experimental study on adding calcium-process vanadium extraction tailings to sintering burden [J]. Sintering and Pelletizing, 2015, 40(4): 44 - 50.) achieved the comprehensive utilization of calcium-process vanadium extraction tailings by adding calcium-process vanadium extraction tailings to the sintering burden; however, the strength of the sinter decreased, and the sulfur content in the sintering flue gas increased sharply, resulting in a significant increase in the cost of flue gas desulfurization. The use of stacking or landfilling treatment for vanadium extraction tailings not only causes waste of resources but also environmental pollution. Therefore, it is necessary to reduce the sulfur content in the acid leached slag in order to recover the valuable elements therein and achieve the principles of solid waste resourceization, reduction, and harmless treatment.

[0003] Patent CN101812602A discloses a method for removing calcium sulfate from acid leaching vanadium extraction residues. This method mainly uses gravity separation to remove calcium sulfate, and its equipment involves a shaking table, a spiral classifier, a hydrocyclone, a centrifugal separator, or a chute, etc. Gravity separation has defects such as low efficiency, low recovery rate, and high mutual inclusion. Due to the large floor area of the equipment, the treatment efficiency of gravity separation is low, so it is impossible to treat calcium-process vanadium extraction tailings on a large scale.

[0004] Patent CN101811095B discloses a method for flotation desulfurization of acid leaching vanadium residue. The calcium sulfate collector used in this patent is one of sodium hexametaphosphate, ammonium sulfate, dodecyl ammonium chloride or a mixture of at least two of them. According to the composition of the collector, sodium hexametaphosphate is a dispersant, ammonium sulfate may be an activator, and dodecyl ammonium chloride should be a collector. As a collector, dodecyl ammonium chloride has problems such as poor selectivity, long flotation time, large amount of foam, and difficult control of flotation foam, so it is often difficult to be put into production.

[0005] Patent CN106179771A discloses a method for recycling calcium vanadium extraction tailings. The collectors used include sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium oleate, sodium salicylate, salicylhydroxamic acid, sodium dodecyl phosphate; the foaming agents mainly include pine oil, camphor oil, eucalyptus oil, pine needle oil, methyl amyl alcohol, butyl ether oil, etc.; the dispersants mainly include ethanol, water glass, cellulose, sodium hexametaphosphate, sodium pyrophosphate, sodium dodecyl sulfate, paraffin, glycerol, polypropylene; the activators are sulfuric acid, sulfurous acid, sodium sulfide, copper sulfate, oxalic acid, lime, sulfur dioxide, lead nitrate, sodium carbonate, sodium hydroxide, lead salt or barium salt; the inhibitors are sodium sulfide, zinc sulfate, sodium cyanide, potassium dichromate, water glass, lime, yellow prussiate of potash, tannin, starch, dextrin, carboxymethyl cellulose; the pH adjusters are sulfuric acid, hydrochloric acid, sodium hydroxide, lime, soda. A large amount of foaming agents, dispersants, activators, inhibitors and pH adjusters are used in the flotation process of this patent, resulting in a complex ore dressing process and more interference factors; the vanadium extraction tailings usually use an oxide ore collector (which has foaming properties itself), and no foaming agent needs to be added during the separation process. Adding both a collector and a foaming agent in this patent will result in a large amount of foam during the separation process, which is difficult to control, and ultimately leads to the inability to carry out normal production. Secondly, this patent uses more expensive hydroxamic acid, which will greatly increase the cost of ore dressing reagents.

[0006] Patent CN110218861A discloses a method for desulfurizing vanadium-extracted tailings by calcification. In this method, a carbonate solution is added to the calcified vanadium-extracted tailings, with a liquid-solid ratio of 2.5:1 to 5:1. Leaching is carried out at 30 - 80 °C under the condition of 200 - 400 r / min for 60 - 180 min. After filtration, desulfurized tailings and filtrate are obtained. The filter residue is used for subsequent treatment processes in blast furnace sintering, and the filtrate is processed by evaporation crystallization to obtain sodium sulfate, ammonium sulfate, and recycled water. This method uses relatively high-cost carbonate to react with calcium sulfate, ultimately converting calcium sulfate into calcium carbonate and sodium sulfate. Due to the high cost of sodium carbonate, the converted products calcium carbonate and sodium sulfate are both low-value products. Although it can achieve the purpose of desulfurization, it does not significantly increase economic benefits. Secondly, the main purpose of desulfurizing vanadium-extracted tailings is to recover the remaining iron, and the price of iron ore is also relatively low. Therefore, using a high-value commodity to produce low-value products is difficult to apply industrially.

[0007] In summary, the existing technologies are difficult to balance elements such as efficiency, selectivity, operability, and cost control. Therefore, it is impossible to make full and reasonable use of vanadium-extracted tailings by the calcium method. Eventually, the vanadium-extracted tailings are still disposed of by stacking or landfilling, wasting resources and polluting the environment at the same time. Therefore, there is an urgent need to develop a method with high efficiency, strong operability, and low cost to achieve harmless, reduction, and resource utilization of vanadium-extracted tailings by the calcium method. Flotation is one of the beneficiation methods with relatively low cost, especially when it comes to large-scale beneficiation, the flotation cost is relatively low. However, in the flotation process, flotation reagents are very important factors, and the quality of flotation reagents is directly related to production. Therefore, developing flotation reagents with good selectivity, strong operability, and low cost plays a very crucial role in solving the resource utilization of vanadium-extracted tailings. Summary of the Invention

[0008] The purpose of the present invention is to provide a flotation desulfurization collector for vanadium-extracted tailings by the calcium method and its preparation method to solve the above problems.

[0009] To achieve the above purpose, the technical solution adopted by the present invention is: A flotation desulfurization collector for vanadium-extracted tailings by the calcium method, the flotation desulfurization collector for vanadium-extracted tailings by the calcium method includes the following components by weight: 1 - 10 parts of octyldecanol polyoxyethylene ether phosphate; 1 - 10 parts of fatty alcohol polyoxyethylene ether phosphate; 1 - 10 parts of isomeric tridecanol polyoxyethylene ether; 1 - 10 parts of alkylphenol polyoxyethylene ether; 1 - 10 parts of octyldecanol polyoxyethylene ether phosphate; 1 - 10 parts of isooctanol polyoxyethylene ether phosphate; 1 - 30 parts of N-cocoyl propanediamine acetate; 1 - 10 parts of lauroyl glutamate; 1 - 10 parts of lauroyl sarcosinate; 1 - 10 parts of cocoyl glycinate; 1 - 10 parts of coconut oil fatty acid alaninate.

[0010] Among them, the main functions of decyl octyl polyoxyethylene ether phosphate, isomeric tridecyl polyoxyethylene ether and alkylphenol polyoxyethylene ether are to regulate the stability of foam during flotation, improve the fluidity of foam and control the foam life, thus facilitating the smooth flow of foam in production. Among them, fatty alcohol polyoxyethylene ether phosphate is used as a surfactant, which has characteristics such as low irritation, good biodegradability, strong stability, good water solubility and good emulsifying performance. Alkylphenol polyoxyethylene ether is a polyoxyethylene type non-ionic surfactant, which has characteristics such as stable properties, acid and alkali resistance and low cost.

[0011] Among them, decyl octyl polyoxyethylene ether phosphate, isooctyl polyoxyethylene ether phosphate, N-coconut oil propylenediamine acetate, lauroyl glutamate, lauroyl sarcosinate, cocoyl glycinate and coconut oil fatty acid alaninate are all collectors for calcium sulfate.

[0012] Through experiments, it is found that when using fatty alcohol polyoxyethylene ether phosphate, decyl octyl polyoxyethylene ether phosphate, isooctyl polyoxyethylene ether phosphate and N-coconut oil propylenediamine acetate alone as collectors, and using lauroyl glutamate, lauroyl sarcosinate, cocoyl glycinate and coconut oil fatty acid alaninate alone as collectors, most of the calcium sulfate can be floated. However, when using the agents alone, there are disadvantages such as large collector dosage, long flotation process, insufficient desulfurization, high iron-sulfur mutual inclusion and incomplete separation. Through a large number of experimental research results, it is surprisingly found that when these agents are mixed in a certain proportion, unexpected harvesting effects can be achieved. Through countless times of reagent compounding, the collector dosage is reduced, the flotation process is shortened, the desulfurization is relatively thorough, and the mutual inclusion is not high, and finally relatively ideal separation indexes can be obtained.

[0013] Usually, when using a single collector, the desulfurization rate in the first stage is only between 60% and 70%, the desulfurization rate in the second stage is between 70% and 80%, and the desulfurization in the third stage is only between 80% and 85%. Eventually, the sulfur trioxide content in the iron ore after desulfurization is as high as 1%, seriously exceeding the standard (the SO3 content requirement is less than 0.3%); under the same conditions, when using the compound collector of the present invention, the desulfurization rate in the first stage is between 80% and 85%, the desulfurization rate in the second stage is between 90% and 95%, and the desulfurization in the third stage is between 95% and 98%. After three-stage flotation desulfurization, the sulfur trioxide content in the final iron ore is less than 0.1%.

[0014] Preferably, 1-5 parts of octyldecanol polyoxyethylene ether phosphate; 1-5 parts of isooctanol polyoxyethylene ether phosphate; 1-10 parts of N-coconut oil propylenediamine acetate; 1-5 parts of lauroyl glutamate; 1-5 parts of lauroyl sarcosinate; 1-5 parts of cocoyl glycinate; 1-5 parts of coconut oil fatty acid alaninate. If the SO3 index in iron ore concentrate needs to be relaxed to 0.3%-0.6% in production, this formula can effectively reduce the entrainment of foam due to the reagent ratio, and can increase the iron recovery rate by 1-2%.

[0015] Preferably, 3-5 parts of octyldecanol polyoxyethylene ether phosphate; 2-3 parts of isooctanol polyoxyethylene ether phosphate; 3-9 parts of N-coconut oil propylenediamine acetate; 2-3 parts of lauroyl glutamate; 3-5 parts of lauroyl sarcosinate; 3-5 parts of cocoyl glycinate; 2-5 parts of coconut oil fatty acid alaninate. If the SO3 index in iron ore concentrate needs to be controlled to less than 0.1% in production, this formula can well meet the requirements, reduce entrainment, and ensure the obtaining of high-purity gypsum and high-grade iron ore concentrate.

[0016] Preferably, the octyldecanol polyoxyethylene ether phosphate, isooctyldecanol polyoxyethylene ether phosphate, N-coconut oil propylenediamine acetate, lauroyl glutamate, lauroyl sarcosinate, cocoyl glycinate and coconut oil fatty acid alaninate are mainly lithium salts, sodium salts, potassium salts and ammonium salts.

[0017] Preferably, the octyldecanol polyoxyethylene ether phosphate refers to C 8～10 alcohol polyoxyethylene ether phosphate, and its structural formula is RO-(CH2CH2O)n-PO3H2, R = C 8～10 , n = 1-5.

[0018] Preferably, the fatty alcohol polyoxyethylene ether phosphate mainly refers to fatty alcohol ether phosphates MOA-3P, MOA-6P and MOA-9P.

[0019] Preferably, the isomeric tridecanol polyoxyethylene ether, its structural formula is C 13 H 27 O(CH2CH2O)nH, R = iso-C 13 H 27 ; n = 3, 5, 6, 6.5, 7, 8, 10, 12, 15 or 20.

[0020] Preferably, the alkylphenol polyoxyethylene ether is composed of 75-80% of nonylphenol polyoxyethylene ether, 15-20% of octylphenol polyoxyethylene ether, 1-3% of dodecyl polyoxyethylene ether and 1-3% of dinonylphenol polyoxyethylene ether by mass percentage.

[0021] A collector for flotation desulfurization of vanadium extraction tailings by calcium method and its preparation method

[0022] Step a. Mix octyldecyl alcohol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, isomeric tridecyl alcohol polyoxyethylene ether, and alkylphenol polyoxyethylene ether according to a mass ratio, and stir at 45 - 100 °C for 0.5 - 24 h to obtain mixture A;

[0023] Step b. Mix octyldecyl alcohol polyoxyethylene ether phosphate salt, isooctyl alcohol polyoxyethylene ether phosphate, N-coconut oil propylenediamine acetate, sodium lauroyl glutamate, sodium lauroyl sarcosinate, sodium cocoyl glycinate, and coconut oil fatty acid alanine salt according to a mass ratio, and stir at 5 - 25 °C for 1 - 4 h to obtain mixture B;

[0024] Step c. Add mixture A and mixture B to a certain amount of water to prepare a 1 - 20% solution, and stir at 5 - 25 °C for 0.5 - 2 h to mix evenly to obtain collector C for flotation desulfurization of vanadium extraction tailings by calcium method.

[0025] Preferably, the collector for flotation desulfurization of vanadium extraction tailings by calcium method is applied in the field of comprehensive utilization of vanadium extraction tailings by calcium method, and high-efficiency separation of sulfur, iron, and vanadium in the tailings is achieved through flotation.

[0026] Compared with the prior art, the advantages of the present invention are as follows:

[0027] 1. The gypsum obtained by flotation with the collector of the present invention has high purity, and the gypsum recovery rate is 95 - 99%; the impurity Fe content in the gypsum product is <0.2%, the V content is <0.1%, and the gypsum purity is high. The iron concentrate remaining after flotation of the present invention has high iron and vanadium content and low sulfur content of less than 0.1%. The recovered gypsum can be used to prepare putty powder, whisker gypsum materials, coatings, mold materials, soil conditioners, etc., realizing high value-added. Under the same conditions, when using a general cationic collector on the market, the Fe content in its gypsum product reaches 0.7%, and the V content exceeds 0.4%, which undoubtedly causes the loss of iron and vanadium, and at the same time, the gypsum cannot be used for high-value utilization due to high impurity content.

[0028] 2. The collector of the present invention has good flotation desulfurization effect, can quickly separate sulfur from vanadium and iron, and has broad market prospects in the field of comprehensive utilization of vanadium extraction tailings by calcium method.

[0029] 3. Compared with conventional fatty acid soaps, the collector obtained by the present invention has high solubility, good low-temperature dispersibility, and can be dissolved without heating. Since the present invention uses a large amount of natural plant extracts and derivatives such as N-coconut oil-based propylenediamine acetate, lauroyl glutamate, lauroyl sarcosine, cocoyl glycine, and coconut oil fatty acid alanine, it has good biodegradability and is green and environmentally friendly. Since the present invention uses a phosphate ester collector, a more stable precipitate is formed after binding with calcium ions. At the same time, the phosphate ester series collector has better selectivity, stronger collecting performance, faster flotation rate, and shorter flotation time.

[0030] 4. Compared with conventional cationic collectors (amines and their derivatives), the collector obtained by the present invention has a moderate amount of foam, and the foam life can be controlled by adjusting the reagent components. In view of the relatively high solubility of the collector obtained by the present invention, the pipeline will not be blocked during the reagent addition process; (amines have low solubility, which easily causes blockage of the dosing system and increases the workload). The foam of the collector of the present invention has good fluidity and does not require a large amount of water flushing, effectively alleviating the pressure on the filtration system in production. Description of the Drawings

[0031] Figure 1 It is a process flow chart for flotation desulfurization of vanadium extraction tailings;

[0032] Figure 2 It is an analysis and detection report of the embodiment of the present invention. Detailed Embodiments

[0033] The following will further illustrate the present invention. The collector for flotation desulfurization of calcium method vanadium extraction tailings is applied in the field of comprehensive utilization of calcium method vanadium extraction tailings resources. High-efficiency separation of sulfur, iron, and vanadium in the tailings is achieved through flotation. For the process flow chart of flotation desulfurization of vanadium extraction tailings, see Figure 1 .

[0034] A collector for flotation desulfurization of calcium method vanadium extraction tailings, by weight, includes: 1-10 parts of octyldecanol polyoxyethylene ether phosphate; 1-10 parts of fatty alcohol polyoxyethylene ether phosphate; 1-10 parts of isomeric tridecanol polyoxyethylene ether; 1-10 parts of alkylphenol polyoxyethylene ether; 1-10 parts of octyldecanol polyoxyethylene ether phosphate; 1-10 parts of isooctanol polyoxyethylene ether phosphate; 1-30 parts of N-coconut oil-based propylenediamine acetate; 1-10 parts of lauroyl glutamate; 1-10 parts of lauroyl sarcosine; 1-10 parts of cocoyl glycine; 1-10 parts of coconut oil fatty acid alanine.

[0035] The octyldecanol polyoxyethylene ether phosphate refers to C 8～10 alcohol polyoxyethylene ether phosphate, and its structural formula is: RO-(CH2CH2O)n-PO3H2, R = C 8～10 , n = 1-5; specifically, during implementation, the C 8～101 to 10 parts of alcohol polyoxyethylene ether phosphate, preferably 5 to 8 parts; more preferably 5 to 6 parts; wherein n is preferably 1 to 3; more preferably 1 to 2; the selection of n is mainly based on adjusting the stability, uniformity, fluidity and foam life of the flotation foam;

[0036] The fatty alcohol polyoxyethylene ether phosphate mainly refers to fatty alcohol ether phosphate MOA-3P, MOA-6P and MOA-9P; in specific implementation, MOA-3P and MOA-6P are preferred, and more preferably MOA-3P; its selection is mainly based on improving the fluidity, uniformity, size and foam life of the foam;

[0037] The isomeric tridecyl alcohol polyoxyethylene ether has the structural formula: C 13 H 27 O(CH2CH2O)nH, R = iso-C 13 H 27 ; n = 3, 5, 6, 6.5, 7, 8, 10, 12, 15 or 20; in specific implementation, 1 to 10 parts of the isomeric tridecyl alcohol polyoxyethylene ether, preferably 1 to 5 parts, more preferably 3 to 5 parts; preferably n = 3, 5, 6, 6.5, 7, more preferably n = 3, 5, 6; the selection of n is mainly based on improving the fluidity, uniformity, size and foam life of the foam;

[0038] The alkylphenol polyoxyethylene ether is composed of 75 to 80% of nonylphenol polyoxyethylene ether, 15 to 20% of octylphenol polyoxyethylene ether, 1 to 3% of dodecyl polyoxyethylene ether and 1 to 3% of dinonylphenol polyoxyethylene ether by mass percentage; in the present invention, the scientific ratio and combination of the alkylphenol polyoxyethylene ether are defined, and by adjusting the different ratios of the alkylphenol polyoxyethylene ether, advantages such as rich flotation foam, good foam fluidity and suitable foam life can be obtained;

[0039] Through various preparations of octyldecanol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, isomeric tridecyl alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether in the present invention, scientific ratios can be made according to the on-site actual situation to achieve the purpose of precisely controlling the fluidity, uniformity, size and foam life of the foam.

[0040] The octyldecanol polyoxyethylene ether phosphate, isooctanol polyoxyethylene ether phosphate, N-coconut oil propylenediamine acetate, lauroyl glutamate, lauroyl sarcosine, cocoyl glycine, coconut oil fatty acid alanine are mainly lithium salts, sodium salts, potassium salts, ammonium salts, etc.; sodium salts and ammonium salts are preferred;

[0041] In a specific implementation manner, the flotation desulfurization collector for vanadium tailings by the lithium-calcium method is prepared by the following method:

[0042] a. Mix polyoxyethylene octyl decyl ether phosphate, polyoxyethylene fatty alcohol phosphate, isomeric tridecyl alcohol polyoxyethylene ether, and alkylphenol polyoxyethylene ether according to a mass ratio, and stir at 45 - 100 °C for 0.5 - 24 h. Preferably, the temperature is 25 - 80 °C, and the reaction time is preferably 2 - 8 h. After the reaction, mixture A is obtained;

[0043] Mix sodium polyoxyethylene octyl decyl ether phosphate, phosphate of polyoxyethylene isooctyl ether, N-coconut oil propanediamine acetate, sodium lauroyl glutamate, sodium lauroyl sarcosinate, sodium cocoyl glycinate, and alanine salt of coconut oil fatty acid according to a mass ratio, and stir at 5 - 25 °C for 1 - 4 h. Preferably, the temperature is 15 - 25 °C, and the reaction time is preferably 1 - 2 h. After the reaction, mixture B is obtained;

[0044] b. Obtain paste C from mixture A and mixture B, add C to a certain amount of water to prepare a 1 - 20% solution, preferably 5 - 10%; stir at 5 - 25 °C for 0.5 - 2 h to mix evenly. The stirring temperature is preferably 15 - 25 °C, and the stirring time is preferably 0.5 - 1 h; a flotation desulfurization collector for vanadium tailings by the calcium method is obtained.

[0045] During the on-site preparation process of the collector, it is found that due to the large number of components in the collector, it is difficult to distinguish and operate on-site. Most on-site operations mix all components together for stirring and use, resulting in unstable collector collection effects.

[0046] Therefore, we analyze the components of the collector. Considering that organic substances such as polyoxyethylene octyl decyl ether phosphate, polyoxyethylene fatty alcohol phosphate, isomeric tridecyl alcohol polyoxyethylene ether, and alkylphenol polyoxyethylene ether have high viscosities and good stabilities, heating can change their fluidity and it is easy to mix them first; while sodium polyoxyethylene octyl decyl ether phosphate, phosphate of polyoxyethylene isooctyl ether, N-coconut oil propanediamine acetate, sodium lauroyl glutamate, sodium lauroyl sarcosinate, sodium cocoyl glycinate, and alanine salt of coconut oil fatty acid are mainly in powder form and are not suitable for mixing under high-temperature conditions. Uniform mixing can be achieved by stirring at room temperature. By first preparing agents A and B and then mixing A and B, problems such as poor agent stability and difficult on-site operation are mainly solved.

[0047] After long-term large-scale experimental research, the present invention discovers that the use of the desulfurization collector mentioned in the present invention has the characteristics of high desulfurization efficiency, good selectivity, good foam controllability, easy operation, low cost, etc. Through the flotation operation, high-quality gypsum and high-quality iron concentrate can be obtained. It should be emphasized that the core of the present invention lies in the preparation of the desulfurization collector. According to the actual situation on site, by effectively adjusting the ratio between components, the rapid and efficient removal of sulfur from the calcium vanadium extraction tailings can be achieved; through the process of the present invention, high-quality gypsum and high-quality iron concentrate can be easily obtained. By adjusting the content and ratio of various reagents, finally, rich flotation foam, good foam fluidity, moderate foam life, and rapid floating of gypsum can be achieved, and finally, the rapid and efficient separation of gypsum and iron minerals can be realized, so as to obtain low-sulfur iron concentrate.

[0048] More notably, the gypsum obtained by flotation in the present invention can be directly used as a raw material for producing gypsum putty powder, whisker gypsum, molds, and soil improvers after filtration. The filtered water generated in the flotation section can be collected and returned to the flotation operation for reuse. The present invention does not produce wastewater discharge; considering that the moisture content of gypsum and iron concentrate in the product is between 20% and 30% (which will eventually carry away part of the moisture), finally, new water needs to be supplemented in the production process of the present invention to ensure the normal progress of production.

[0049] The following will further elaborate in combination with the specific implementation manners of the embodiments, and elaborate on the desulfurization collectors for flotation of calcium vanadium extraction tailings in Embodiments 1-15, which are applied to the flotation desulfurization of calcium vanadium extraction tailings, so as to obtain high-quality iron concentrate and gypsum, and finally realize the comprehensive recovery and utilization of resources.

[0050] The calcium vanadium extraction tailings in this experiment come from a vanadium extraction plant in Xichang. Its main components are shown in Table 1. After using the collectors of Embodiments 1 to 15 of the present invention and applying them to the separation of the tailings of a vanadium extraction plant in Xichang, their indexes are shown in Table 2. The analysis and detection results are shown in Figure 2 :

[0051] Table 1 Chemical composition of calcium vanadium extraction tailings

[0052] Component S CaO FeO MgO MnO Fe <![CDATA[SiO2]]> <![CDATA[TiO2]]> <![CDATA[V2O5]]> <![CDATA[Al2O3]]> <![CDATA[Cr2O3]]> Content 5.51 10.29 ＜0.5 1.96 4.25 25.71 10.98 9.98 2.01 1.87 1.78

[0053] Example 1:

[0054] First, mix 5 parts of octyldecyl alcohol polyoxyethylene ether phosphate, 5 parts of fatty alcohol polyoxyethylene ether phosphate, 2 parts of isomeric tridecyl alcohol polyoxyethylene ether, and 2 parts of alkylphenol polyoxyethylene ether evenly, and stir at 80 °C for 8 h to prepare mixture A.

[0055] Secondly, 1 part of sodium octyldecyl polyoxyethylene ether phosphate, 5 parts of sodium isooctyl polyoxyethylene ether phosphate, 20 parts of N-cocoyl propanediamine acetate, 5 parts of sodium lauroyl glutamate, 5 parts of sodium lauroyl sarcosinate, 5 parts of sodium cocoyl glycinate and 5 parts of alanine salt of coconut oil fatty acid were stirred at 25 °C for 1 h to obtain mixture B. Finally, mixture A and mixture B were mixed and stirred evenly to obtain paste C, and the paste was formulated into a solution with a solid content of 5%, thus obtaining a desulfurization collector for calcium process vanadium extraction tailings.

[0056] Example 2:

[0057] Firstly, 3 parts of octyldecyl polyoxyethylene ether phosphate, 3 parts of fatty alcohol polyoxyethylene ether phosphate, 3 parts of isomeric tridecyl polyoxyethylene ether and 3 parts of alkylphenol polyoxyethylene ether were mixed evenly and stirred at 80 °C for 8 h to prepare mixture A.

[0058] Secondly, 2 parts of sodium octyldecyl polyoxyethylene ether phosphate, 2 parts of sodium isooctyl polyoxyethylene ether phosphate, 15 parts of N-cocoyl propanediamine acetate, 3 parts of sodium lauroyl glutamate, 3 parts of sodium lauroyl sarcosinate, 3 parts of sodium cocoyl glycinate and 5 parts of sodium alanine salt of coconut oil fatty acid were stirred at 25 °C for 1 h to obtain mixture B.

[0059] Finally, mixture A and mixture B were mixed and stirred evenly to obtain paste C, and the paste was formulated into a solution with a solid content of 10%, thus obtaining a desulfurization collector for calcium process vanadium extraction tailings.

[0060] Examples 3 - 5:

[0061] Examples 3 - 5 are similar to Example 1. The only difference from Example 1 is that in Example 3, there are 10 parts of octyldecyl polyoxyethylene ether phosphate; in Example 4, there are 8 parts of fatty alcohol polyoxyethylene ether phosphate; in Example 5, there are 6 parts of isomeric tridecyl polyoxyethylene ether; in Example 6, there are 5 parts of alkylphenol polyoxyethylene ether.

[0062] Examples 6 - 12:

[0063] Examples 6 - 12 are similar to Example 1. The only difference from Example 1 is that in Example 6, there are 10 parts of sodium octyldecyl polyoxyethylene ether phosphate; in Example 7, there are 10 parts of sodium isooctyl polyoxyethylene ether phosphate; in Example 8, there are 30 parts of N-cocoyl propanediamine acetate; in Example 9, there are 2 parts of sodium lauroyl glutamate; in Example 10, there are 6 parts of sodium lauroyl sarcosinate; in Example 11, there are 8 parts of sodium cocoyl glycinate; in Example 12, there is 1 part of alanine salt of coconut oil fatty acid.

[0064] Example 13:

[0065] Example 13 is similar to Example 2. The only difference from Example 2 is that all salts in Example 13 are ammonium salts.

[0066] Example 14:

[0067] Example 14 is similar to Example 2. The only difference from Example 1 is that all salts in Example 14 are ammonium salts.

[0068] Example 15:

[0069] Example 15 is similar to Example 2. The only difference from Example 1 is that Example 15 contains 25 parts of sodium N-coco propylenediamine acetate.

[0070] Table 2 Test results of Examples 1 - 15

[0071]

[0072] Conclusion: The components of the collector can be proportioned in any ratio within the corresponding range. According to the corresponding ratio, the purpose of efficient flotation desulfurization of calcium-process vanadium extraction tailings can be achieved, and it is ensured that the gypsum content is greater than 95%, the impurity Fe content in the gypsum is <0.2%, and the V content is <0.1%. It provides high-quality raw materials for the subsequent preparation of gypsum putty powder, mold raw materials, whisker gypsum, and soil improvers; the impurity S content in the obtained iron concentrate is less than 0.1%.

[0073] The above has introduced in detail a flotation desulfurization collector for calcium-process vanadium extraction tailings and its preparation and use method provided by the present invention. Specific examples are used in this article to elaborate on the principle and implementation manner of the present invention. The description of the above examples is only used to help understand the method and its core idea of the present invention; at the same time, for those of ordinary skill in the art, according to the idea of the present invention, there will be changes in the specific implementation manner and application scope. It is possible to make changes and improvements to the present invention without exceeding the concept and scope defined by the appended claims. In summary, the content of this specification should not be construed as a limitation to the present invention.

Claims

1. A flotation desulfurization collector for calcium-process vanadium extraction tailings, characterized in that, The flotation desulfurization collector for calcium process vanadium extraction tailings slag comprises the following components by weight: 1-10 parts of octyldecyl alcohol polyoxyethylene ether phosphate; 1-10 parts of fatty alcohol polyoxyethylene ether phosphate; 1-10 parts of isomeric tridecyl alcohol polyoxyethylene ether; 1-10 parts of alkylphenol polyoxyethylene ether; 1-10 parts of octyldecyl alcohol polyoxyethylene ether phosphate salt; 1-10 parts of isooctyl alcohol polyoxyethylene ether phosphate salt; 1-30 parts of N-coconut oil propylenediamine acetate; 1-10 parts of lauroyl glutamate; 1-10 parts of lauroyl sarcosinate; 1-10 parts of cocoyl glycinate; 1-10 parts of coconut oil fatty acid alaninate.

2. The flotation desulfurization collector for calcium-process vanadium extraction tailings according to claim 1, wherein: 1-5 parts of octyldecyl alcohol polyoxyethylene ether phosphate salt; 1-5 parts of isooctyl alcohol polyoxyethylene ether phosphate salt; 1-10 parts of N-coconut oil propylenediamine acetate; 1-5 parts of lauroyl glutamate; 1-5 parts of lauroyl sarcosinate; 1-5 parts of cocoyl glycinate; 1-5 parts of coconut oil fatty acid alaninate.

3. The flotation desulfurization collector for calcium process vanadium extraction tailings and its preparation method according to claim 1, characterized in that: 3-5 parts of octyldecyl alcohol polyoxyethylene ether phosphate salt; 2-3 parts of isooctyl alcohol polyoxyethylene ether phosphate salt; 3-9 parts of N-coconut oil propylenediamine acetate; 2-3 parts of lauroyl glutamate; 3-5 parts of lauroyl sarcosinate; 3-5 parts of cocoyl glycinate; 2-5 parts of coconut oil fatty acid alaninate.

4. The flotation desulfurization collector for calcium-process vanadium extraction tailings according to claim 1, wherein: The octyldecyl alcohol polyoxyethylene ether phosphate salt, isooctyldecyl alcohol polyoxyethylene ether phosphate salt, N-coconut oil propylenediamine acetate, lauroyl glutamate, lauroyl sarcosinate, cocoyl glycinate and coconut oil fatty acid alaninate are mainly lithium salt, sodium salt, potassium salt and ammonium salt.

5. The flotation desulfurization collector for calcium-process vanadium extraction tailings slag according to claim 1, wherein: The octyldodecyl polyoxyethylene ether phosphate refers to C 8～10 alcohol polyoxyethylene ether phosphate, and its structural formula is RO~(CH2CH2O)n~PO3H2, where R = C 8～10 , n = 1 - 5.

6. The flotation desulfurization collector for calcium process vanadium extraction tailings according to claim 1, wherein: The fatty alcohol polyoxyethylene ether phosphate mainly refers to fatty alcohol ether phosphate MOA-3P, MOA-6P and MOA-9P.

7. The flotation desulfurization collector for calcium process vanadium extraction tailings and its preparation method according to claim 1, characterized in that: The isomeric tridecyl alcohol polyoxyethylene ether has a structural formula of C 13 H 27 O(CH2CH2O)nH, where R = iso-C 13 H 27 ; n = 3, 5, 6, 6.5, 7, 8, 10, 12, 15 or 20.

8. The flotation desulfurization collector for calcium-process vanadium extraction tailings according to claim 1, wherein: The alkylphenol polyoxyethylene ether is composed of 75-80% of nonylphenol polyoxyethylene ether, 15-20% of octylphenol polyoxyethylene ether, 1-3% of dodecyl polyoxyethylene ether and 1-3% of dinonylphenol polyoxyethylene ether by mass percentage.

9. The preparation method of a flotation desulfurization collector for calcium process vanadium extraction tailings slag according to claim 1, characterized in that: Step a. Mix octyldecyl alcohol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, isomeric tridecyl alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether according to a mass ratio, and stir at 45-100 °C for 0.5-24 h to obtain mixture A; Step b. Mix octyldecyl alcohol polyoxyethylene ether phosphate salt, isooctyl alcohol polyoxyethylene ether phosphate salt, N-coconut oil propylenediamine acetate, sodium lauroyl glutamate, sodium lauroyl sarcosinate, sodium cocoyl glycinate and coconut oil fatty acid alaninate together according to a mass ratio, and stir at 5-25 °C for 1-4 h to obtain mixture B; Step c. Add mixture A and mixture B into a certain amount of water to prepare a 1-20% solution, and stir at 5-25 °C for 0.5-2 h to mix evenly to obtain the flotation desulfurization collector C for calcium process vanadium extraction tailings slag.

10. The flotation desulfurization collector for calcium-process vanadium extraction tailings according to claim 1, characterized in that: The flotation desulfurization collector for calcium process vanadium extraction tailings slag is applied in the field of comprehensive utilization of calcium process vanadium extraction tailings slag resources, and realizes the efficient separation of sulfur, iron and vanadium in the tailings through flotation.

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