2017年10月23日星期一

Tungsten Flotation Inhibitor—Modified Sodium Silicate

Inhibitor as well as known retarder, it can retardant or reduce the chemical reaction speed of the material, the function is the same as the negative catalyst. Tungsten flotation inhibitor can be divided into two types: Organic inhibitor and inorganic inhibitor. 

modified sodium silicate image

The most commonly used for modified sodium silicate inorganic inhibitors, metal ion+sodium silicate, ammonium salt, sodium silicate, sodium silicofluoride, pyrophosphate, etc. They each have their own strong points. Here introduces a kind of inorganic inhibitors tungsten flotation-modified sodium silicate.

Modified sodium silicate is  through the water glass for modification, acidification or the use of other agents in combination with the way to achieve the water glass can improve the inhibitory effect of calcium-containing gangue minerals purposes. Modified sodium silicate is the activator after decomposition of sodium silicate, it can produce a large number of single molecule silicate, the single molecule has a high activity, and it can adsorption on the purpose mineral by selective, forming strong hydrophilic layer, so as to achieve inhibitory effect.

Modified sodium silicate is divided into two categories, physical modification and chemical modification. Physical modified sodium silicate by magnetic field, ultrasonic, high-frequency or heat energy into the system, make the polysilicic acid molecules to homogenization, thus eliminating its aging phenomenon; Chemical modified sodium silicate is fused sodium silicate with other chemicals, some potions itself does not inhibit gangue mineral, but after adding water glass, inhibition effect was like the icing on the cake, has reached the unexpected enhancement.

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Tungsten Flotation Collector—Combination Collector

Commonly used tungsten flotation collector can be divided into anionic collector, cationic collector, amphoteric collector and nonpolar collector and complexing or chelating collector dosage form five categories, these collector is known as the fatty acid, phosphoric acid, chelation, amine, petroleum and so on.

Tungsten Flotation Collector—Combination Type of Collector image

Full of beautiful collectors are always dazzling, objectively speaking, every collector has different strengths and weakness, for example, the fatty acid collector has strong ability of flotation but the ability of selectivity is poor. The selectivity of chelating collector is good but it is expensive. The selectivity of phosphoric acid, sulfonic acid, amine are good but the flotation ability is a bit poor and there exists environmental pollution. In great abundance of choices, it says suitable is the best, but it is hard to choose the right thing in one in a million, after continuously experiment again and again, people found that is also can go with “mix and match” style based on lessons drawn from others’ mistakes, and the result is quite good.

Theoretically, in the flotation system of two or more than two collector can exist mutual effect, can produce synergies in the flotation process, play a better role, the “synergistic effect” mechanism of drug combination is more complex, it can be roughly summed up as a total adsorption mechanism, the aojiang mechanism, charge compensation mechanism, function complement mechanism, etc. Practice has proved that most selectivity of the sequestration collectors and amphoteric collectors are better than fatty acids, but collecting ability is weak, therefore use a variety of types of mixed collector to add, the synergistic effect can happen in tungsten flotation, not only can improve the flotation effect of drugs, but also can reduce the dosage of the drug. Of course “mix and match” is not “faulty”, after all, they are all chemicals.

Successful “mix and match” is never happen overnight, the group of “mix and match’ is selected by rigorous selection theory and experiment practices. Which are frequently used in current industrial mix combinations are: combination of oleic acid and kerosene, sodium oleic acid and oleic acid ammonium, petroleum sulfonic acid and sodium oleate combination, fatty acids combined with six fluorine butadiene, hydroxylamine acid and alkyl sulfonate, CKY combined with sodium oleate, benzene armour hydroxyl oxime acid and oleic acid combination and so on. There is no doubt that the application of combination types of collector for various mineral processing enterprise promoted economic and environmental benefits are indisputable facts.

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Combination Collector Mechanism--Adsorption Effect

In flotation system of two or more than two collector mixture, through collection makes collector produces generate synergies, this kind of tungsten ore flotation collector called combination collector in the industry. 

combination type of collector image

Practice has proved that many function of combination has better and more effective flotation effect than single collector, there are many opinions as for the effect.

Combinations collector mechanism has the adsorption effect is comparing the identity and the mechanism of the most studied, some scholars think that mineral surface formed in the process of mineralization, the processing is uneven physical and chemical reagents of adsorption of mineralogy basis. Adsorption effect including physical adsorption, double electrode layer, synonym ion exchange adsorption, molecular adsorption and chemical adsorption.

Total absorption effect is a variety of collector to produce interaction between each other, eventually lead to promote and strengthen the flotation process. There are two kinds of common phenomena of total adsorption model: cascade and penetration. Cascade type is collecting on the strong adsorption in the mineral surface, weak collector force to rely on all sorts of function of adsorption on the surface of the mineral that has adsorption agent, to strengthen the hydrophobicity of the mineral surface; Penetration type is a kind of collector adsorption after the mineral surface, another collector with active point can stuck and adsorption on the gap of mineral surface, to increase the medicament density of the mineral.
Some scholars use benzyl arsenic acid and butyl xanthate flotation of wolframite adsorption studies have shown that there are two different types of wolframite surface active points, the first point of high energy, activity, obvious under drug interactions. Putting benzyl arsenic acid and then adding xanthate, mineral surface adsorption dose of medicine largely. When the butyl xanthate and benzyl arsenic acid combination by 1:2, synergy effect is obvious, research think that between the collectors are generated with molecular beam or "composite half micelles".

In addition to the mine will share with light fat acid octyl benzyl swollen acid to improve the recovery of wolframite, expand the best flotation pH range, reduce the dosage of collector, improve the separation efficiency. The common mechanism of two kinds of medicament is, benzyl arsenic acid iron point of wolframite surface with high selectivity, and octyl hydroxyl oxime acid manganese particles with surface effect, at the same time collector on the base of hydrogen atoms to have adsorption on the surface of the wolframite, octyl hydroxyl oxime acid and benzyl arsenic acid molecules CLP negative high nitrogen, oxygen, hydrogen bonding key cooperation with, to form a high stability and strong hydrophobic surface hydrophobic membrane.

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Classification of Tungsten Ore Flotation Reagents

From dressing industrial progress of history suggests that mineral processing reagents application significance is self-evident. Since its discovery in 1924 xanthate has the function of collecting sulfide ore, the development of the flotation industry started by leaps and bounds, the inundated mineral processing reagents has been invented and created with a steady stream.

tungsten ore flotation reagents image

However, how many dressing agent are they? How to classification, which is often confused about.

In western countries, most of dressing agent were issued in the form of “patent certificate”.

Therefore some names are quite chaotic, sometimes it only some numbers. At the same time, the dressing agent is more cheaper in general, other impure industrial by-product, its composition is not very sure; And several kinds of medicine emulsion mixture or the product of interactions, often name after the new potion. According to a German experts statistics, there are 7702 species the name of the material can be used as a flotation reagents. Of course, many of which are of the same compound has several names, or the same agents has several patents registered brand, according to rough estimates, about two or three thousand kinds of flotation reagents.

In the face of two or three thousand kinds of flotation reagents, how to classify them with well-regulated, there are different opinions. Currently internationally recognized common flotation classification method is classified by pharmaceutical function, can be divided into: collecting agent, foaming agent, activator, inhibitors, pH adjusting agent, flocculant six types, classification of tungsten ore flotation reagents are also the same. Usually we use tungsten collector with fatty acid, sulfonic acid, phosphoric acid, chelation, amine, oil; Activator mainly lead nitrate; Inhibitors have organic and inorganic inhibitors inhibitors; PH adjustment mainly sodium hydroxide and sodium carbonate, in addition, most of tungsten ore flotation collector has a sparkling performance, so the tungsten flotation use fewer special foaming agent.


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Scheelite Flotation Collector—Y-17 Fatty Acid Sodium Salt

In recent years, the fatty acid with microbial fermentation system of sulphide ore collector, has attracted a lot of interest, because it is a fatty acid collector substitute another very promising source, and confirmed by experiment.

Scheelite Flotation Collector—Y-17 fatty acid sodium salt image

The effect is better than the average oleic acid substitute. Y-17 fatty acid sodium salt is the system of a microbe scheelite flotation collector developed by our country.

Y-17 fatty acid sodium salt is in1974, Shanghai institute of organic chemistry research units such as microbial collector of success, is a kind of mixed fatty acid sodium salt. Its appearance is soft solid tan, containing unsaturated acid about 79%, hydroscopicity,soluble in water, its aqueous solution, 5% still not set at 5°C, used as a collector can use cold water can also be used as configured to any concentration of less than 10% of the hot water. 

Hunan some tungsten mines to use Y-17 grade of WO3 3.91% fatty acid sodium salt heating flotation of scheelite, and with the traditional 731 oxidized paraffin soap and oleic acid comparing test, the results are as follows:

The experiment results showed that the Y-17 separation effect is better than oleic acid, the income of the concentrate quality is better than oxidized paraffin soap, the recovery rate is closed to oxidized paraffin soap.

Y-17 fatty acid sodium salt is a new kind of collector scheelite, good selectivity, in normal conditions it can effective segregation from white scheelite to calcite, fluorite, quartz, the result is better than general oleic acid substitute, in ambient temperature condition can be obtained under the condition of the low sulfur, low silicon and high quality white tungsten concentrate, the indicators are better than that of oleic acid, in terms of quality is better than that of the oxidized paraffin soap. But Y-17 fatty acid sodium salt still belongs to the long chain hydrocarbon compounds, poorly soluble in water, poor plants. The flotation effect, pharmaceutical blister performance is weaker, not suitable for low concentration of roughing, if used with oxidized paraffin soap is beneficial to overcome the weakness of their own, improving the index of sorting.

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The Scheelite Flotation Process—Lime Method

In our country the white tungsten deposit is mostly a skarn shape deposit, this kind of characteristic of scheelite ore bed is “lean, multiple, thin, miscellaneous”, especially the “miscellaneous”, caused a variety of obstacles to white tungsten ore dressing.

The scheelite flotation process—lime method image

Most white tungsten deposit are associated with calcite, fluorite, barite, such as calcium containing gangue, because of the flotability is close to scheelite so is hard to separate.

For many years Petrov method is commonly used for the white tungsten flotation method, namely high temperature flotation process, this process must be heating flotation, high energy consumption, the operation is complicated. Following the development of the technology, finally developed a flotation process at room temperature in the 70s.The most representative of flotation process at room temperature is 731 flotation method at room temperature and method of lime, here’s to emphatically introduce lime method.

Scheelite flotation process- lime method first invented by the American company, is to stir with the right amount of lime slurry, then adding sodium carbonate, sodium silicate, selective inhibition of containing ore vein, and white tungsten can still maintain good flotability. This method not only can be carry on at room temperature, also the dosage of sodium silicate can be greatly reduced, especially in the presence of fluorite scheelite has excellent selectivity.

Mechanism of lime method is: the addition of lime white tungsten and fluorite surface adsorption Ca2+,and lead to different change of their surface potential, surface potential of fluorite from negative to positive, surface potential of scheelite remains in negative territory. Join the Ca2+ in aqueous solution of sodium carbonate, can adsorption in the positively charged surface of fluorite and formed by the Ca2+ and formed into CaCO3 covering layer, after the coating with sodium silicate strong inhibition to fluorite. Since tungsten surface without any precipitation, so it can continue to the role of fatty acid and plankton.

The most typical used of lime method w polymetallic tungsten ore in Hunan province, the mine flotation ore grade of WO3 in the method of lime is 0.39% of scheelite, through roughing closed-circuit test obtained WO3 grade is 3.53%,recovery 77.01% of white tungsten rough concentrate. The acidification of the select open circuit test, by adding sodium silicate, obtained the final WO3 of flotation concentrate grade of 42.12%,a good indicator of recovery is 46.26%. Concentrate product XRD spectra analysis shows that the fluorite and calcite in lime method roughing and select a strong inhibitory effect have been obtained respectively, sheelite and gangue mineral calcium can achieve effective separation, the research result shows that lime method is an effective way to achieve white tungsten plants the flotation.

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