阅读说明：本技术 一种耐低温的复酸盐类稀土矿浮选捕收剂及其制备方法和应用 (A kind of low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector and its preparation method and application ) 是由 熊文良 张丽军 陈达 邓杰 邓善芝 胡泽松 陈炳炎 于 2019-09-16 设计创作，主要内容包括：本发明涉及矿石浮选捕收技术领域,公开了一种耐低温的复酸盐类稀土矿浮选捕收剂,包括烷基磷酸酯钠、硫酸化油酸钠、表面活性剂和乳化剂；其中,所述表面活性剂包括十二烷基苯磺酸钠,所述乳化剂包括OP-10。本发明的捕收剂具有耐低温性能好、捕收能力较强、生产成本较低、用量少等优点。本发明还公开了该捕收剂的制备方法和应用,所述制备方法包括以下步骤：将所述烷基磷酸酯钠、硫酸化油酸钠、表面活性剂和乳化剂混合搅拌均匀,得到所述捕收剂。所述捕收剂尤其在硅酸磷酸盐类稀土矿中应用时具备良好的分选效果,同时在浮选过程中无需添加起泡剂,能大幅度降低选矿成本,提高资源利用的经济效益和社会效益。(The present invention relates to ore floatation collecting technical fields, disclose a kind of low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector, including alkyl phosphate sodium, sulphation enuatrol, surfactant and emulsifier；Wherein, the surfactant includes neopelex, and the emulsifier includes OP-10.Collecting agent of the invention has many advantages, such as that resistance to low temperature is good, collecting ability is compared with strong, lower production costs, dosage are few.The invention also discloses the preparation method and application of the collecting agent, and the preparation method comprises the following steps: the alkyl phosphate sodium, sulphation enuatrol, surfactant and emulsifier being mixed evenly, the collecting agent is obtained.The collecting agent has good separating effect when applying especially in silicic acid phosphoric acid salt Rare Earth Mine, while beneficiation cost can be greatly lowered, improve the economic benefit and social benefit of the utilization of resources without adding foaming agent in floatation process.)

1. a kind of low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector, it is characterised in that: including alkyl phosphate sodium, sulphation Enuatrol, surfactant and emulsifier.

2. the low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector of one kind according to claim 1, it is characterised in that: by weight Measure part meter, comprising: 10~25 parts of alkyl phosphate sodium, 60~80 parts of phosphorylation enuatrol, 8~15 parts of surfactant and emulsification 0.8~2 part of agent.

3. the low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector of one kind according to claim 1, it is characterised in that: described Surfactant includes neopelex.

4. the low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector of one kind according to claim 1, it is characterised in that: described Emulsifier includes OP-10.

5. the low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector of one kind according to claim 1, it is characterised in that: described Alkyl phosphate sodium the preparation method comprises the following steps: by mixed alcohol, pyrophosphoric acid and solvent mix, in a heated condition reaction obtain alkyl phosphorus Acid esters；The alkyl phosphate and sodium hydroxide solution are mixed to get the alkyl phosphate sodium；Wherein, the mixed alcohol packet Include isooctanol and n-heptanol, the mass ratio of the isooctanol and n-heptanol is 2:1~1.5.

6. the low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector of one kind according to claim 1, it is characterised in that: described Sulphation enuatrol the preparation method comprises the following steps: under normal temperature conditions by the concentrated sulfuric acid be slowly added into stirring in oleic acid, heat and protect Temperature adds sodium hydroxide solution through saponification and obtains the sulphation enuatrol；The sodium hydroxide solution and oleic acid Mass ratio is 1:10.

7. the method for the low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector of the one kind of preparation as described in claim 1~6, special Sign is: it is the alkyl phosphate sodium, sulphation enuatrol, surfactant and emulsifier are mixed evenly, both.

8. the application of the low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector of one kind according to claims 1 to 7, feature It is: the collecting agent is used to answer the flotation of Barbiturates Rare Earth Mine.

9. the application of the low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector of one kind according to claim 8, feature exist In: the collecting agent is used for the flotation of silicic acid phosphoric acid salt Rare Earth Mine.

10. the application of the low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector of one kind according to claim 9, feature exist In: it is that flotation is carried out in the ore pulp that collecting agent and auxiliary agent are added to the Rare Earth Mine, the auxiliary agent includes inhibitor, the suppression Preparation is acidified sodium silicate.

Technical field

The present invention relates to ore floatation collecting technical field, specifically a kind of low temperature resistant multiple Barbiturates Rare Earth Mine flotation is caught Receive agent and its preparation method and application.

Background technique

It is 18,590,000 tons that rare earth oxide commercial reserves has been verified in China, accounts for about the world and has verified rare earth reserves 23.6%, rare earth resources deposit type is complete, is distributed wide and Relatively centralized, at present in the province in 2/3rds or more the whole nations (area) is it has been found that thousands of place mineral deposits, mine point and the mineralising place of production, and integrated distribution is in the Bayan Obo in the Inner Mongol, Southern Jiangxi, wide The ground such as eastern North Guangdong, Sichuan Liangshan District and Shandong Weishan, form the Distribution Pattern in north, south, west, east, and have the distribution of northern light south heavy Feature.There are many type of rare-earth industry mineral, and the most important three kinds of mineral of industrial abstract rare earth metal are bastnaesite at this stage [RECO₃F], monazite [(RE, Th, Y) PO₄] and xenotime [(Y, RE) PO₄].Rare earth metal be widely used in clean energy resource, The fields such as science and techniques of defence, industrial technology, electronic product.

Alkylhydroxamic acid is mostly used greatly, with the different of phenyl ring with the Rare-earth Mine that bastnaesite is main rare-earth mineral at present The mixing of one or more of hydroximic acid, naphthenic base hydroxamic acid, naphthalene hydroxamic acid is used as collecting agent, although such collecting agent Achieve better index in bastnaesite type rare earth flotation, but its that there are prices is high, dosage is big, resultant effect is used alone not Ideal, difficult with the agent degradation of phenyl ring and naphthalene nucleus, tailing water is difficult to the disadvantages of meeting the requirement of environmental protection；Meanwhile Silicic acid phosphoric acid salt Rare Earth Mine can not effectively be sorted.

Currently, the research and development and application for silicic acid phosphoric acid salt Rare Earth Mine collecting agent are detected in Chinese patent literature CN201711202681.X, the applying date 20171127, title are as follows: a kind of phosphosilicate type Rare Earth Mine flotation collector and its preparation Methods and applications disclose a kind of phosphosilicate type Rare Earth Mine flotation collector, are made of the material of following quality proportioning: 5~ 15 parts of Octyl Ether propyl-a- amino -1,1- diphosphonic acid, 60~80 parts of cocinic acids, 5~10 parts of cetyl sulfonate, 1~3 Part Tween-60.Above patent document discloses the laboratory room temperature separation index to silicic acid phosphoric acid salt Rare Earth Mine: to certain REO The extremely low-grade phosphosilicate Rare Earth Mine that content is 1.48% uses Octyl Ether propyl-a- in test through ore grinding-floatation process Amino -1,1- di 2 ethylhexyl phosphonic acid, cocinic acid, cetyl sulfonate and Tween-60 mixture are collecting agent, dosage about 0.5kg/ T raw ore, inhibitor are waterglass, can get the rare earth ore concentrate that REO grade is 18.43%, the rate of recovery is 82.99%.

Due to only having found the mineral deposit of silicic acid phosphoric acid salt Rare Earth Mine near the Arctic Circle at present, mine location it is normal Year temperature needs one all at 10 DEG C hereinafter, cause the hydrophily of such Rare Earth Mine much stronger than the conventional rares mine such as bastnaesite The strong and low temperature resistant collecting agent of kind collecting ability carries out FLOTATION SEPARATION to it.

Above patent document provides a kind of collecting agent of FLOTATION SEPARATION for silicic acid phosphoric acid salt Rare Earth Mine, the collecting Agent can apply under domestic normal temperature condition, that is, 20 DEG C or so, but about a kind of low temperature resistant and can be applied to silicic acid The technical solution of the collecting agent in the industrial utilization field of phosphate Rare Earth Mine then not yet proposes.If above-mentioned collecting agent is used for the mine Area then will lead to the dissolubility of collecting agent, collecting ability sharply declines.

In conclusion we need, a kind of resistance to low temperature is good, collecting ability is strong and lower production costs and dosage Less, the collecting agent of good separation effect when being applied especially in silicic acid phosphoric acid salt Rare Earth Mine.

Summary of the invention

It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of low temperature resistant multiple Barbiturates Rare Earth Mine flotation Collecting agent, with reach make that its resistance to low temperature is good, collecting ability is strong and lower production costs and dosage it is few, especially in silicon The effect of good separation effect when being applied in acid phosphoric acid salt Rare Earth Mine.

The purpose of the present invention is achieved through the following technical solutions: a kind of low temperature resistant multiple Barbiturates Rare Earth Mine flotation Collecting agent, including alkyl phosphate sodium, sulphation enuatrol, surfactant and emulsifier.

Through the above technical solutions, the alkyl phosphate sodium is that alkyl phosphate is fully saponified or partly-hydrolysed gained, Reach and has improved its selectivity with alkyl phosphate and water-soluble effect at low temperature；And the sulphation enuatrol is Using oleic acid as carrier, as obtained by sulphation and saponification, collecting ability is stronger, simultaneously synthesizing simple process, easy to operate, relatively Raising lower temperature resistance and water-soluble effect are reached by introducing sulfate radical in enuatrol.

Preferably, the collecting agent is by weight, comprising: 10~25 parts of alkyl phosphate sodium, phosphorylation enuatrol 60 ~80 parts, 8~15 parts of surfactant and 0.8~2 part of emulsifier.

Preferably, the surfactant includes neopelex.

Through the above technical solutions, the neopelex has stronger frothing capacity, also there is certain collecting Performance has achieved the effect that be not required in floatation process in addition to add foaming agent.

Preferably, the emulsifier includes OP-10.

Through the above technical solutions, joined the emulsifier op-10, so that each component preferably phase in the collecting agent Mutually dissolution, while having achieved the effect that the collecting agent is made to be not easy to be layered.

Preferably, the alkyl phosphate sodium the preparation method comprises the following steps: by mixed alcohol, pyrophosphoric acid and solvent mix, heating Under the conditions of reaction obtain alkyl phosphate；The alkyl phosphate and concentration are mixed to get institute for 20% sodium hydroxide solution State alkyl phosphate sodium；

Wherein, the mixed alcohol includes isooctanol and n-heptanol, the mass ratio of the isooctanol and n-heptanol be 2:1~ 1.5；If the carbochain of each component is lower than 8 in the mixed alcohol, the collecting performance of the alkyl phosphate sodium is too poor；Each component Carbochain is higher than 10, and the collecting performance of the alkyl phosphate sodium is too strong.Using isooctanol and n-heptanol as the mixed alcohol Component be conducive to obtain the preferable collecting agent of collecting performance because its carbon atom number is 8-10.

The solvent is ethyl alcohol, and the mass ratio of the mixed alcohol, pyrophosphoric acid and ethyl alcohol is 1:(0.65~0.75): (1.1~ 1.3), the mass ratio of the mixed alcohol and sodium hydroxide solution is 10:3.5~7, and the temperature of the heating is 40~50 DEG C, is protected The time of temperature is 3~5h.

Through the above technical solutions, being defined to heating temperature, the progress that reacts fully is reached, to generate purpose The effect of product；Soaking time is defined, has reached the conversion ratio for guaranteeing purpose product, has improved the effect of yield.

Chemical equation involved in synthesizing has:

ROPO(OH)₂+ NaOH --- ROP=O (OH) (ONa)+H₂O

ROP=O (OH) (ONa)+NaOH --- ROP=O (ONa)₂+H₂O

Preferably, the sulphation enuatrol stirs the preparation method comprises the following steps: being under normal temperature conditions slowly added into the concentrated sulfuric acid Oleic acid in mixing is heated and is kept the temperature, and is added sodium hydroxide solution through saponification and is obtained the sulphation enuatrol；It is described to add The temperature of heat is 40~50 DEG C, and the time of the heat preservation is 60~90min；The concentration of the sodium hydroxide solution is 20%, institute The mass ratio for stating sodium hydroxide solution and oleic acid is 1:10.

Through the above technical solutions, being defined to heating temperature, the progress that reacts fully is reached, to generate purpose The effect of product；Soaking time is defined, has reached the conversion ratio for guaranteeing purpose product, has improved the effect of yield.

Chemical equation involved in synthesizing has:

CH₃(CH₂)₇CH₂CH(SO₄H)(CH₂)₇COOH+NaOH—CH₃(CH₂)₇CH₂CH(SO₄H)(CH₂)₇COONa+H₂O

A kind of method for preparing low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector, be by the alkyl phosphate sodium, Sulphation enuatrol, surfactant and emulsifier are mixed evenly, both.Wherein, the alkyl phosphate sodium, sulphation The mass ratio of enuatrol, surfactant and emulsifier is (10~25): (60~80): (8~15): (0.8~2).

A kind of application of low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector, is used for the collecting agent to answer Barbiturates dilute The flotation of Tu Kuang.

Preferably, the collecting agent is used for the flotation of silicic acid phosphoric acid salt Rare Earth Mine.

It preferably, is that collecting agent and auxiliary agent are added in the ore pulp of the Rare Earth Mine to carry out flotation, the auxiliary agent includes Inhibitor, the inhibitor are acidified sodium silicate.

Wherein, the acidified sodium silicate is configured to obtain by waterglass and diluted acid, and the modulus of the waterglass is 2.3~2.8.

The modulus of waterglass be lower than 2.3 when, the rejection ability of the inhibitor is too weak, can generate dosage greatly and increase cost The problem of；When the modulus of waterglass is higher than 2.8, the rejection ability of the inhibitor is too strong, can reduce product yield.Therefore, will The modulus of waterglass is limited to 2.3~2.8, has reached while guaranteeing product yield and rejection ability, has reduced the effect of cost Fruit.

The beneficial effects of the present invention are:

1. the low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector of one kind of the invention, is added to the alkyl phosphate Sodium is that alkyl phosphate is fully saponified or partly-hydrolysed gained, has reached the selectivity and water for improving itself and alkyl phosphate Dissolubility effect.

2. the low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector of one kind of the invention, is added to the sulphation oleic acid Sodium is using oleic acid as carrier, and as obtained by sulphation and saponification, collecting ability is stronger, simultaneously synthesizing simple process, easily behaviour Make, opposite and enuatrol has reached raising lower temperature resistance and water-soluble effect by introducing sulfate radical.

3. the low temperature resistant multiple Barbiturates Rare Earth Mine flotation collector of one kind of the invention, is added to the detergent alkylate sulphur Sour sodium and OP-10, the neopelex have stronger frothing capacity, also have certain collecting performance, reached It is not required in addition add the effect of foaming agent in floatation process；The OP-10 makes each component in the collecting agent preferably mutual Dissolution, while having achieved the effect that the collecting agent is made to be not easy to be layered.

Detailed description of the invention

Fig. 1 is the flotation process figure in the embodiment of the present invention.

Specific embodiment

Technical solution of the present invention is described in further detail with reference to the accompanying drawing, but protection scope of the present invention is not limited to It is as described below.