CN108480055A - A kind of Scheelite Flotation collecting agent and preparation method thereof - Google Patents

A kind of Scheelite Flotation collecting agent and preparation method thereof Download PDF

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Publication number
CN108480055A
CN108480055A CN201810332750.7A CN201810332750A CN108480055A CN 108480055 A CN108480055 A CN 108480055A CN 201810332750 A CN201810332750 A CN 201810332750A CN 108480055 A CN108480055 A CN 108480055A
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parts
acid
collecting agent
scheelite
fatty acid
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CN201810332750.7A
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CN108480055B (en
Inventor
凌石生
王中明
肖巧斌
呼振峰
刘方
谭欣
张云海
刘书杰
苏建芳
赵杰
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BGRIMM Technology Group Co Ltd
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BGRIMM Technology Group Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/001Flotation agents
    • B03D1/004Organic compounds
    • B03D1/012Organic compounds containing sulfur
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/001Flotation agents
    • B03D1/004Organic compounds
    • B03D1/008Organic compounds containing oxygen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00Specified effects produced by the flotation agents
    • B03D2201/02Collectors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00Specified effects produced by the flotation agents
    • B03D2201/04Frothers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00Specified materials treated by the flotation agents; specified applications
    • B03D2203/02Ores

Abstract

The present invention provides a kind of Scheelite Flotation collecting agents and preparation method thereof.The Scheelite Flotation collecting agent of the present invention, by weight, it includes following components to prepare raw material:40~60 parts of sulfonation unsaturated fatty acid, 10~20 parts of hydroxy fatty acid, 5~10 parts of hydroximic acid, 5~10 parts of diesel oil, 5~10 parts of foaming agent.The Scheelite Flotation collecting agent of the present invention is used for Scheelite Flotation, and low temperature resistant good, selectivity is good, and collecting ability is strong, can obtain the white tungsten rough concentrate compared with high-grade and higher recovery.The preparation method of the Scheelite Flotation collecting agent of the present invention, have the advantages that raw material sources are extensive, preparation process is simple, Scheelite Flotation collecting agent solubility property obtained is good, collecting power is strong, selectivity, lower temperature resistance are good, especially resistance to 12~20 DEG C of flotation at low temperature, beneficiating technology index can be effectively improved, remarkable in economical benefits has good market promotion prospect.

Description

A kind of Scheelite Flotation collecting agent and preparation method thereof
Technical field
The invention belongs to technical field of mineral processing, it is related to a kind of Scheelite Flotation collecting agent and preparation method thereof, especially It is related to a kind of low-temperature type Scheelite Flotation collecting agent and preparation method thereof.
Background technology
The tungsten ore resource rich reserves in China, wherein scheelite account for 70% or more of tungsten ore resource gross reserves, but scheelite Poor in reserves, thin, miscellaneous mineral deposit occupies the majority, and floatation process is the most important beneficiation method of scheelite.
CN1321547A discloses a kind of collecting agent compound for floatation of tungsten mineral, the chemical name of the collecting agent compound Referred to as benzene formhydroxamic acid ammonium, the collecting agent good water solubility, is easy to prepare, and can dissolve by convention stir, flotation is black, white tungsten When mine, rough concentrate index improves to some extent.But the benzene formhydroxamic acid ammonium of the invention has hypotoxicity, and it is produced Cost is higher, limits its wide popularization and application in mineral floating.
CN106733217A discloses a kind of preparation method of high calcareous Scheelite Flotation collecting agent, and its step are as follows:(1) Hydroxylamine hydrochloride aqueous solution is added in oil foot in cocounut oil subtractive process, the rear sodium hydroxide solution that is added dropwise is reacted, and reaction terminates After carry out acidification, then through be dehydrated, wash obtain Cocoalkyl hydroximic acid, (2) by the Cocoalkyl hydroximic acid of acquisition with Soybean oleic acid carries out compounding and forms mixture, most afterwards through saponification process up to high calcareous Scheelite Flotation collecting agent;The invention High calcareous Scheelite Flotation collecting agent made from preparation method can realize scheelite stone and calcic mine in high calcareous scheelite stone Object efficiently separates, and its preparation process is simple, properties of product are stable, floatation indicators are high, foam is stable, adaptable, cost It is cheap and nontoxic, it is suitable for commercial introduction application.But the calcareous Scheelite Flotation collecting agent of height of the invention is of low cost and nothing Poison, be used for minerals separation when, in order to obtain preferable separating effect, need multiple roughing, scan with it is selected, process conditions are multiple It is miscellaneous.
Currently, industrially mostly using oxidized paraffin wax soap or oleic acid, enuatrol progress flotation, there are dosings for the technique Greatly, medicament poor selectivity and to flotation temperature require it is high the shortcomings of.Using such medicament, once slurry temperature is even less than 15 DEG C At 20 DEG C, collecting agent easily forms micelle, activity declines, and flotation effect is deteriorated, and production target is caused significantly to decline.It is low in winter When warm weather, many ore dressing plants are all forced to stop production because of index error, cause the huge wasting of resources.Therefore, low-temperature type is researched and developed Scheelite Flotation collecting agent has very great meaning.
Invention content
In view of the deficiencies of the prior art, resistance to one of the objects of the present invention is to provide a kind of Scheelite Flotation collecting agent Low temperature is good, and selectivity is good, and collecting ability is strong.
For this purpose, the present invention uses following technical scheme:
A kind of Scheelite Flotation collecting agent, by weight, it includes following components to prepare raw material:
The Scheelite Flotation collecting agent of the present invention, by weight, it includes following components to prepare raw material:
40~60 parts of sulfonation unsaturated fatty acid, for example, sulfonation unsaturated fatty acid parts by weight be 40 parts, 41 parts, 42 Part, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 Part, 58 parts, 59 parts, 60 parts.
10~20 parts of hydroxy fatty acid, for example, hydroxy fatty acid parts by weight be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts.
5~10 parts of hydroximic acid, such as the parts by weight of hydroximic acid are 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts.
5~10 parts of diesel oil, such as the parts by weight of diesel oil are 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts.
5~10 parts of foaming agent, such as the parts by weight of foaming agent are 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts.
The sulfonation unsaturated fatty acid is sulfonated oleic acid and/or sulfonation tall oil.
The sulfonation unsaturated fatty acid by weight, including 40~60 parts of unsaturated fatty acid and 6~10 parts Sulfonated reagent.Such as the parts by weight of unsaturated fatty acid be 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 Part, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts;The weight of sulfonated reagent Part is 6 parts, 7 parts, 8 parts, 9 parts, 10 parts.
The unsaturated fatty acid is the mixture of one kind or at least two in oleic acid, linoleic acid and tall oil.It is described Mixture it is typical but unrestricted be combined as oleic acid, linoleic mixture, oleic acid, tall oil mixture, linoleic acid and appropriate You oil mixture, oleic acid, linoleic acid and tall oil mixture.
The sulfonated reagent is the concentrated sulfuric acid and/or sulfurous acid.
The hydroxy fatty acid is hydroxy oleate and/or ricinoleic acid.
The hydroximic acid is benzyl hydroximic acid, naphthalene hydroximic acid and one kind in Salicyl Hydroximic Acid or at least two mixing Object.The mixture typical case but the unrestricted mixture for being combined as benzyl hydroximic acid, naphthalene hydroximic acid, benzyl hydroximic acid, bigcatkin willow The mixture of hydroximic acid, the mixture of naphthalene hydroximic acid and Salicyl Hydroximic Acid, benzyl hydroximic acid, naphthalene hydroximic acid and Salicyl Hydroximic Acid Mixture.
The diesel oil is -10# diesel oil and/or -20# diesel oil.
Preferably, the foaming agent is terpenic oil, MIBC and one kind in octanol class foaming agent or at least two mixing Object, the mixture is typical but the unrestricted mixture for being combined as terpenic oil, MIBC, terpenic oil, octanol class foaming agent it is mixed Close object, the mixture of MIBC and octanol class foaming agent, terpenic oil, MIBC and octanol class foaming agent mixture.
The second object of the present invention is to provide a kind of preparation method of Scheelite Flotation collecting agent, the preparation method packet Include following steps:
1) by weight, the hydroxy fatty acid of 10~20 parts of addition, 5 into 40~60 parts of sulfonation unsaturated fatty acid ~10 parts of hydroximic acid, 5~10 parts of diesel oil and 5~10 parts of foaming agent, are uniformly mixing to obtain compounding mixture;
2) lye is added in the compounding mixture obtained to step 1), it is floating to obtain the scheelite through saponification for stirring Select collecting agent.
In step 1), the sulfonation unsaturated fatty acid is prepared in accordance with the following methods:By weight, 40 are weighed~ 6~10 parts of sulfonated reagent is added in 60 parts of unsaturated fatty acid, is heated to 30~90 DEG C of stirrings fully 2~4h of reaction, cooling After obtain sulfonation unsaturated fatty acid.
Preferably, in step 2), the weight part ratio of the lye and the compounding mixture is (1~5):1, for example, it is described The weight part ratio of lye and the compounding mixture is 1:1、2:1、3:1、4:1、5:1.
Preferably, in step 2), the lye is a kind of the water-soluble of alkali in sodium hydroxide, sodium bicarbonate and sodium carbonate Liquid.Wherein, by weight, the alkali in lye is 15~20 parts, remaining is water.
Preferably, in step 2), the temperature of the saponification is 30~45 DEG C, such as the temperature of saponification is 30 ℃、31℃、32℃、33℃、34℃、35℃、36℃、37℃、38℃、39℃、40℃、41℃、42℃、43℃、44℃、45 ℃;The time of the saponification be 45~90min, such as saponification time be 45min, 50min, 55min, 60min, 65min、70min、75min、80min、85min、90min。
As the preferred embodiment of the present invention, the preparation method of Scheelite Flotation collecting agent, the preparation method includes as follows Step:
1 ') 40~60 parts of unsaturated fatty acid by weight, is weighed, 6~10 parts of sulfonated reagent is added, is heating To 30~90 DEG C of stirrings fully 2~4h of reaction, sulfonation unsaturated fatty acid is obtained after cooling;
2 ') by weight, to 40~60 parts of step 1 ') 10~20 parts are added in obtained sulfonation unsaturated fatty acid Hydroxy fatty acid, 5~10 parts of hydroximic acid, 5~10 parts of diesel oil and 5~10 parts of foaming agent, be uniformly mixing to obtain compounding Mixture;
3 ') lye is added in the compounding mixture obtained to step 1), wherein the lye and the compounding mixture Weight part ratio is (1~5):1,45~90min of saponification at a temperature of 30~45 DEG C of stirring obtain the Scheelite Flotation collecting Agent.
Compared with prior art, beneficial effects of the present invention are:
(1) Scheelite Flotation collecting agent of the invention, belongs to the composite modified product of aliphatic acid and hydroximic acid, is suitable for white Floatation of tungsten mineral, low temperature resistant good, especially resistance to 12~20 DEG C of flotation at low temperature, selectivity is good, and collecting ability is strong, can obtain higher The white tungsten rough concentrate of grade and higher recovery, for WO3The middle-low grade sample ore that grade is 0.39~0.67%, through scheelite After flotation collector one roughing flotation, rough concentrate WO3Grade can be improved to 5.24~7.24%, operation recovery 86~ 87%.
(2) Scheelite Flotation collecting agent of the invention, it is multiple by mixing aliphatic acid with hydroximic acid, diesel oil and foaming agent Match, and the dissolubility, selectivity and its lower temperature resistance of collecting agent can be substantially improved through saponification, to realize the low of scheelite Warm flotation.
(3) preparation method of Scheelite Flotation collecting agent of the invention, has that raw material sources are extensive, preparation process is simple Advantage, Scheelite Flotation collecting agent solubility property obtained is good, collecting power is strong, selectivity, lower temperature resistance are good, especially resistance to 12~ 20 DEG C of flotation at low temperature, can effectively improve beneficiating technology index, and remarkable in economical benefits has good market promotion prospect.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.
Unless specific instructions, various raw materials of the invention are commercially available buys, or is prepared according to the conventional method of this field It obtains.
The Scheelite Flotation collecting agent of the present invention, by weight, it includes following components to prepare raw material:
The preparation method of the Scheelite Flotation collecting agent of the present invention, the preparation method include the following steps:
1) by weight, the hydroxy fatty acid of 10~20 parts of addition, 5 into 40~60 parts of sulfonation unsaturated fatty acid ~10 parts of hydroximic acid, 5~10 parts of diesel oil and 5~10 parts of foaming agent, are uniformly mixing to obtain compounding mixture;
2) lye is added in the compounding mixture obtained to step 1), it is floating to obtain the scheelite through saponification for stirring Select collecting agent.
Embodiment 1
By weight, 45 parts of sulfonated oleic acids, 15 parts of hydroxy oleates, 5 parts of benzyl hydroximic acids and 5 parts of -20# diesel oil are weighed, 20min is mixed at room temperature, 7 parts of foaming agent terpenic oils are then added, continues to obtain a homogeneous mixture after stirring 20min. 15 parts of sodium hydroxides are dissolved in 100 parts of water, are then slowly added into said mixture, it is equal in 30 DEG C of condition stirrings Even reaction 90min makes its abundant saponification, obtains a kind of Scheelite Flotation collecting agent.
Use Scheelite Flotation collecting agent that the embodiment of the present invention 1 provided in the prior art using oxidized paraffin wax soap as The technical solution of collecting agent carries out contrast test:Selected sample ore WO3Grade is 0.39%, with sodium carbonate adjust pH values of pulp 9.5~ 10.0, waterglass 3000g/t is then added and inhibits gangue, then embodiment 1 and the impact of performance comparison of the prior art are as follows:
The optimum implementation using oxidized paraffin wax soap as collecting agent in the prior art is chosen to be carried with the embodiment of the present invention 1 The scheelite collecting agent of confession carries out flotation effect comparison, and particular technique effect can be as shown in table 1:
Table 1
As can be seen from Table 1:Scheelite Flotation is carried out under 15 DEG C of cryogenic conditions, the embodiment of the present invention 1 is provided white The WO obtained after tungsten ore collecting agent one roughing3After grade is higher than the prior art using oxidized paraffin wax soap as collecting agent one roughing Obtained WO3Grade, WO3Operation recovery is far above the prior art.Therefore, under cryogenic, using institute of the embodiment of the present invention The scheelite collecting agent of offer, which carries out Scheelite Flotation, can obtain the white tungsten rough concentrate that grade is higher than the prior art, and white tungsten The mine rate of recovery is also above the prior art;As it can be seen that under cryogenic, the scheelite collecting agent that the embodiment of the present invention is provided can It obtains and is better than flotation effect of the prior art using oxidized paraffin wax soap as collecting agent.
Embodiment 2
By weight, 50 parts of sulfonated oleic acids, 10 parts of hydroxy stearic acids, 10 parts of naphthalene hydroximic acids and 10 parts of -10# bavins are weighed 20min is mixed in oil at room temperature, and 10 parts of foaming agent MIBC are then added, and continues stirring 20min and obtains a homogeneous mixture. 17 parts of sodium hydroxides are dissolved in 100 parts of water, are then slowly added into said mixture, it is equal in 32 DEG C of condition stirrings Even reaction 75min makes its abundant saponification, obtains a kind of Scheelite Flotation collecting agent.
Use Scheelite Flotation collecting agent that the embodiment of the present invention 2 provided in the prior art using oleic acid as collecting agent Technical solution carry out contrast test:Selected sample ore WO3Grade is 0.67%, adjusts pH values of pulp 9.5~10.0 with sodium carbonate, so Waterglass 3000g/t is added afterwards and inhibits gangue, then the impact of performance comparison of the two is as follows:
Choose in the prior art the optimum implementation using oleic acid as collecting agent provided with the embodiment of the present invention 2 it is white Tungsten ore collecting agent carries out flotation effect comparison, and particular technique effect can be as shown in table 2:
Table 2
As can be seen from Table 2:Scheelite Flotation is carried out under 15 DEG C of cryogenic conditions, the embodiment of the present invention 2 is provided white The WO obtained after tungsten ore collecting agent one roughing3What grade obtained after being higher than the prior art using oleic acid as collecting agent one roughing WO3Grade, WO3Operation recovery is far above the prior art.Therefore, under cryogenic, provided using the embodiment of the present invention Scheelite collecting agent, which carries out Scheelite Flotation, can obtain the white tungsten rough concentrate that grade is higher than the prior art, and scheelite recycles Rate is also above the prior art;As it can be seen that under cryogenic, the scheelite collecting agent that the embodiment of the present invention is provided can obtain excellent In the flotation effect of the prior art.
Embodiment 3
By weight, 50 parts of sulfonation tall oils, 10 parts of ricinoleic acids, 5 parts of Salicyl Hydroximic Acids and 5 parts of diesel oil are weighed, 20min is mixed at room temperature, 10 parts of foaming agent octanols are then added, continues stirring 20min and obtains a homogeneous mixture.By 20 parts Sodium hydroxide is dissolved in 100 parts of water, is then slowly added into said mixture, and reaction is stirred evenly in 35 DEG C of conditions 60min makes its abundant saponification, obtains a kind of Scheelite Flotation collecting agent.
Use Scheelite Flotation collecting agent that the embodiment of the present invention 3 provided in the prior art using enuatrol as collecting The technical solution of agent carries out contrast test:Selected sample ore WO3Grade is 0.51%, and pH values of pulp 9.5~10.0 is adjusted with sodium carbonate, Then waterglass 3000g/t is added and inhibits gangue, then the impact of performance comparison of the two is as follows:
What selection was provided using enuatrol as the optimum implementation of collecting agent and the embodiment of the present invention 3 in the prior art Scheelite collecting agent carries out flotation effect comparison, and particular technique effect can be as shown in table 3:
Table 3
As can be seen from Table 3:Scheelite Flotation is carried out under 15 DEG C of cryogenic conditions, the embodiment of the present invention 3 is provided white The WO obtained after tungsten ore collecting agent one roughing3Grade obtains after being higher than the prior art using enuatrol as collecting agent one roughing WO3Grade, WO3Operation recovery is far above the prior art.Therefore, under cryogenic, provided using the embodiment of the present invention Scheelite collecting agent carry out Scheelite Flotation can obtain grade be higher than the prior art white tungsten rough concentrate, and scheelite return Yield is also above the prior art;As it can be seen that under cryogenic, the scheelite collecting agent that the embodiment of the present invention is provided can obtain Better than the flotation effect of the prior art.
The flotation effect contrast test of the embodiment of the present invention 3 at different temperatures
The scheelite collecting agent that embodiment 3 using the present invention is provided is respectively at 10 DEG C, 12 DEG C, 15 DEG C, 20 DEG C and 25 The contrast test of one roughing is carried out at DEG C, specific flotation effect is as shown in table 4:
Table 4
As can be seen from Table 4:Under 12~25 DEG C of different temperatures, the scheelite that the embodiment of the present invention 3 is provided is caught Receiving agent can obtain excellent flotation effect.
To sum up, the embodiment of the present invention has good low temperature resistant selectivity and collecting performance, either in normal temperature condition It is lower that excellent flotation effect still can be obtained under the conditions of low temperature (12~20 DEG C);One is being carried out using the scheelite collecting agent After secondary roughing, obtained white tungsten rough concentrate grade and tungsten operation recovery are obviously improved than existing collecting agent, because This is with good market popularization value.
Comparative example 1
This comparative example difference from example 1 is that, prepare in raw material, sulfonation unsaturated fatty acid replaces with oil Acid, other are same as Example 1.
Certain middle-low grade Scheelite Flotation is tested:Selected sample ore WO3Grade is 0.39%, and ore pulp is adjusted using sodium carbonate PH9.5~10.0, inhibitor waterglass dosage 3000g/t, collector dosage 800g/t, 15 DEG C of flotation temperature, through one roughing It can get WO3The tungsten rough concentrate that grade is 4.56%, operation recovery 83.65%.
Comparative example 2
This comparative example difference from example 1 is that, prepare in raw material, hydroxy fatty acid replaces with linoleic acid, He is same as Example 1.
Certain middle-low grade Scheelite Flotation is tested:Selected sample ore WO3Grade is 0.39%, and ore pulp is adjusted using sodium carbonate PH9.5~10.0, inhibitor waterglass dosage 3000g/t, collector dosage 800g/t, 15 DEG C of flotation temperature, through one roughing It can get WO3The tungsten rough concentrate that grade is 4.94%, operation recovery 84.07%.
Comparative example 3
This comparative example difference from example 1 is that, prepare in raw material, hydroximic acid replaces with styryl phosphonic acid, He is same as Example 1.
Certain middle-low grade Scheelite Flotation is tested:Selected sample ore WO3Grade is 0.39%, and ore pulp is adjusted using sodium carbonate PH9.5~10.0, inhibitor waterglass dosage 3000g/t, collector dosage 800g/t, 15 DEG C of flotation temperature, through one roughing It can get WO3The tungsten rough concentrate that grade is 4.87%, operation recovery 83.59%.
Comparative example 4
This comparative example difference from example 1 is that, prepare in raw material, diesel oil replaces with kerosene, other with reality It is identical to apply example 1.
Certain middle-low grade Scheelite Flotation is tested:Selected sample ore WO3Grade is 0.39%, and ore pulp is adjusted using sodium carbonate PH9.5~10.0, inhibitor waterglass dosage 3000g/t, collector dosage 800g/t, 15 DEG C of flotation temperature, through one roughing It can get WO3The tungsten rough concentrate that grade is 4.98%, operation recovery 84.26%.
Comparative example 5
This comparative example difference from example 1 is that, prepare in raw material, foaming agent replace with 2# oil, other with Embodiment 1 is identical.
Certain middle-low grade Scheelite Flotation is tested:Selected sample ore WO3Grade is 0.39%, and ore pulp is adjusted using sodium carbonate PH9.5~10.0, inhibitor waterglass dosage 3000g/t, collector dosage 800g/t, 15 DEG C of flotation temperature, through one roughing It can get WO3The tungsten rough concentrate that grade is 4.76%, operation recovery 84.03%.
Comparative example 6
This comparative example difference from example 1 is that, in preparation method, the temperature of saponification is 80 DEG C, saponification The time of reaction is 20min, other are same as Example 1.
Certain middle-low grade Scheelite Flotation is tested:Selected sample ore WO3Grade is 0.39%, and ore pulp is adjusted using sodium carbonate PH9.5~10.0, inhibitor waterglass dosage 3000g/t, collector dosage 800g/t, 15 DEG C of flotation temperature, through one roughing It can get WO3The tungsten rough concentrate that grade is 5.06%, operation recovery 84.74%.
Comparative example 7
This comparative example difference from example 1 is that, prepare in raw material, do not contain sulfonation unsaturated fatty acid, He is same as Example 1.
Certain middle-low grade Scheelite Flotation is tested:Selected sample ore WO3Grade is 0.39%, and ore pulp is adjusted using sodium carbonate PH9.5~10.0, inhibitor waterglass dosage 3000g/t, collector dosage 800g/t, 15 DEG C of flotation temperature, through one roughing It can get WO3The tungsten rough concentrate that grade is 4.17%, operation recovery 66.98%.
Comparative example 8
This comparative example difference from example 1 is that, prepare in raw material, do not contain hydroxy fatty acid, other with Embodiment 1 is identical.
Certain middle-low grade Scheelite Flotation is tested:Selected sample ore WO3Grade is 0.39%, and ore pulp is adjusted using sodium carbonate PH9.5~10.0, inhibitor waterglass dosage 3000g/t, collector dosage 800g/t, 15 DEG C of flotation temperature, through one roughing It can get WO3The tungsten rough concentrate that grade is 5.12%, operation recovery 84.37%.
Comparative example 9
This comparative example difference from example 1 is that, prepare in raw material, do not contain hydroximic acid, other with implementation Example 1 is identical.
Certain middle-low grade Scheelite Flotation is tested:Selected sample ore WO3Grade is 0.39%, and ore pulp is adjusted using sodium carbonate PH9.5~10.0, inhibitor waterglass dosage 3000g/t, collector dosage 800g/t, 15 DEG C of flotation temperature, through one roughing It can get WO3The tungsten rough concentrate that grade is 5.05%, operation recovery 84.51%.
Comparative example 10
This comparative example difference from example 1 is that, prepare in raw material, do not contain diesel oil, other with embodiment 1 It is identical.
Certain middle-low grade Scheelite Flotation is tested:Selected sample ore WO3Grade is 0.39%, and ore pulp is adjusted using sodium carbonate PH9.5~10.0, inhibitor waterglass dosage 3000g/t, collector dosage 800g/t, 15 DEG C of flotation temperature, through one roughing It can get WO3The tungsten rough concentrate that grade is 4.87%, operation recovery 82.67%.
Comparative example 11
This comparative example difference from example 1 is that, prepare in raw material, do not contain foaming agent, other with implementation Example 1 is identical.
Certain middle-low grade Scheelite Flotation is tested:Selected sample ore WO3Grade is 0.39%, and ore pulp is adjusted using sodium carbonate PH9.5~10.0, inhibitor waterglass dosage 3000g/t, collector dosage 800g/t, 15 DEG C of flotation temperature, through one roughing It can get WO3The tungsten rough concentrate that grade is 5.07%, operation recovery 75.39%.
The Scheelite Flotation collecting agent of the present invention is used for Scheelite Flotation, and low temperature resistant good, selectivity is good, and collecting ability is strong, The white tungsten rough concentrate compared with high-grade and higher recovery can be obtained.The preparation method of the Scheelite Flotation collecting agent of the present invention, Have the advantages that raw material sources are extensive, preparation process is simple, Scheelite Flotation collecting agent solubility property obtained is good, collecting power By force, selectivity, lower temperature resistance are good, especially resistance to 12~20 DEG C of flotation at low temperature, can effectively improve beneficiating technology index, economy effect It is beneficial notable, there is good market promotion prospect.
The present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, but the present invention is not It is confined to above-mentioned detailed process equipment and technological process, that is, does not mean that the present invention has to rely on above-mentioned detailed process equipment and work Skill flow could be implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to product of the present invention The equivalence replacement of each raw material and the addition of auxiliary element, the selection of concrete mode etc., all fall within protection scope of the present invention and public affairs Within the scope of opening.

Claims (10)

1. a kind of Scheelite Flotation collecting agent, which is characterized in that by weight, it includes following components to prepare raw material:
2. Scheelite Flotation collecting agent according to claim 1, which is characterized in that the sulfonation unsaturated fatty acid is sulphur Carburetion acid and/or sulfonation tall oil.
3. Scheelite Flotation collecting agent according to claim 1 or 2, which is characterized in that the sulfonation unsaturated fatty acid By weight, including 40~60 parts of unsaturated fatty acid and 6~10 parts of sulfonated reagent.
4. Scheelite Flotation collecting agent according to claim 3, which is characterized in that the unsaturated fatty acid be oleic acid, One kind in linoleic acid and tall oil or at least two mixture.
5. Scheelite Flotation collecting agent according to claim 3, which is characterized in that the sulfonated reagent be the concentrated sulfuric acid and/ Or sulfurous acid.
6. the Scheelite Flotation collecting agent according to one of claim 1-5, which is characterized in that the hydroxy fatty acid is hydroxyl Based oleic acid and/or ricinoleic acid.
7. the Scheelite Flotation collecting agent according to one of claim 1-6, which is characterized in that the hydroximic acid is benzene first hydroxyl Oxime acid, naphthalene hydroximic acid and one kind in Salicyl Hydroximic Acid or at least two mixture.
8. the Scheelite Flotation collecting agent according to one of claim 1-7, which is characterized in that the diesel oil is -10# diesel oil And/or -20# diesel oil;
Preferably, the foaming agent is terpenic oil, MIBC and one kind in octanol class foaming agent or at least two mixture.
9. a kind of preparation method of such as claim 1-8 any one of them Scheelite Flotation collecting agents, which is characterized in that described Preparation method includes the following steps:
1) by weight, the hydroxy fatty acid of 10~20 parts of addition, 5~10 into 40~60 parts of sulfonation unsaturated fatty acid The hydroximic acid, 5~10 parts of diesel oil and 5~10 parts of foaming agent of part, are uniformly mixing to obtain compounding mixture;
2) lye is added in the compounding mixture obtained to step 1), stirs through saponification, obtains the Scheelite Flotation and catch Receive agent.
10. preparation method according to claim 9, which is characterized in that in step 1), the sulfonation unsaturated fatty acid is It prepares in accordance with the following methods:By weight, 40~60 parts of unsaturated fatty acid is weighed, 6~10 parts of sulfonation examination is added Agent is heated to 30~90 DEG C of stirrings fully 2~4h of reaction, sulfonation unsaturated fatty acid is obtained after cooling;
Preferably, in step 2), the weight part ratio of the lye and the compounding mixture is (1~5):1;
Preferably, in step 2), the lye is a kind of aqueous solution of alkali in sodium hydroxide, sodium bicarbonate and sodium carbonate;
Preferably, in step 2), the temperature of the saponification is 30~45 DEG C, time of the saponification is 45~ 90min。
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