CN108927292A - A kind of amino phosphine acid compounds and its preparation method and application - Google Patents
A kind of amino phosphine acid compounds and its preparation method and application Download PDFInfo
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- CN108927292A CN108927292A CN201710372697.9A CN201710372697A CN108927292A CN 108927292 A CN108927292 A CN 108927292A CN 201710372697 A CN201710372697 A CN 201710372697A CN 108927292 A CN108927292 A CN 108927292A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/014—Organic compounds containing phosphorus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION 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
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
- B03D2203/06—Phosphate ores
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Abstract
The invention discloses a kind of amino phosphine acid compounds, the general formula of the compound is（）It is shown.The invention also discloses the amino phosphine acids compounds process for production thereof, the amino phosphine acid compounds are by 3,7- dimethyl -2,6- zinn diene aldehyde, aniline or aniline containing substituent group and phosphorous acid carry out Mannich reaction under the action of acidic catalyst and are prepared.Amino phosphine acid compounds of the present invention may be used as the flotation collector of ilmenite, bauxite, fluorite ore, Rare Earth Mine or collophane, has the characteristics that good, the water-soluble strong and good dispersion of selectivity, can improve 2 ~ 16 percentage points of flotation recovery rate.Preparation method of the present invention uses one-pot synthesis method, and operation is easily controllable, product yield is high, easy to industrialized production.
Description
Technical field
The invention belongs to mineral floating fields, are related to a kind of amino phosphine acid compounds, the invention further relates to its preparation sides
Method and the application in ilmenite, bauxite, Rare Earth Mine, fluorite ore or phosphate rock floating.
Background technique
Oleic acid and its modified product are most common beneficiation collecting agent in oxide ore flotation technique, Chinese patent document
（Publication number：CN102921537A）It the use of oleic acid is collecting agent in limonite flotation agent, method for floating and floatation system, it can
Effectively improve the grade of iron ore concentrate；Chinese patent document（Publication number：CN101585016）Low grade fluorite and barite flotation
Using oleic acid as collecting agent in separation method, waterglass is that siliceous and calcareous mineral inhibitor carries out FLOTATION SEPARATION；China discloses special
Sharp document（Publication number：CN101712014A）In Multicategory-impurity single fluorite ore dressing method respectively with alkaline oleic acid, in
Property oleic acid and acid oleic acid segmentation flotation plurality of impurities single type fluorite ore；Chinese patent document（Publication number：
CN101648157B）Flotation is carried out by collecting agent of sulphation oleate soap in a kind of beneficiation method of black and white tungsten mineral；It is Chinese public
Open patent document（Publication number：CN102962144A）It is used in a kind of efficient selective collecting agent of bauxite and preparation method thereof
The oleic acid that saponification degree is 50% is that collecting agent carries out bauxite flotation；Chinese patent document（Publication number：
CN102716811A）Cotton oil acid and rape oil acid bulk flotation are used in water-soluble weathering phosphorite mineral froth flotation collector
Separate weathering phosphorus ash mine.
Oleic acid has many advantages, such as that collecting ability is strong and price is lower as flotation collector, but its disadvantage it is also obvious that
Selectivity is not high, and freezing tolerance is lower, and having put long can be layered, and water-soluble at normal temperature and dispersibility is poor, therefore, it is necessary to
Collecting agent is emulsified, or heat treatment is carried out to flotation pulp, heating flotation not only increases energy consumption, but also to production operation and
Management is made troubles.The shortcomings that for oleic acid, develops efficient flotation collector and is of great significance to the development and utilization of mining industry.
Phosphonic acid base has stronger polarity in organic phosphine acid compounds, is a kind of efficient beneficiation collecting agent, organic phosphine
Sour collecting agent has good sorting, arranges in pairs or groups, can successfully separate valuable mineral with gangue mine with effective inhibitor.China
Patent document（Publication number：CN1047462A）Hydroxyl-alkyl -1 1- is used in beach placer in the optimum flotation of zircon,
1- two banks are as zircon collecting agent；Chinese patent document（Publication number：CN1063627A）Disclose α-nitroso phosphine
Acid esters is used as pyrite collecting agent；Chinese patent document（Publication number：CN102500462A）Selective milling-coarse grain weight
It combines styryl phosphonic acid with hydroximic acid in choosing-fine particles flotation rutile roughing technology and is used as rutile collecting agent；It is Chinese public
Open patent document（Publication number：CN103613614A）A kind of Alpha-hydroxy unsaturated alkyl phosphinic acid compounds and its preparation and application side
A kind of novel organic phosphonic compound for multi mineral collecting agent is disclosed in method.These organic phosphonic compounds are used as floating
Collecting agent, good sorting are selected, but these preparation of compounds are complicated, synthesis yield is lower, and in preparation process to environment
Pollute larger, somebody is used as collecting agent, effect with above-mentioned organic phosphonic compound in the mines such as ilmenite, bauxite, phosphorus ore
Unobvious, selectivity is poor.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of novel amino phosphine acid compounds, the changes
Closing object may be used as the flotation collector of ilmenite, bauxite, Rare Earth Mine, fluorite ore or phosphorus ore, and the sorting of mineral can be improved
Property, realize efficiently separating for target minreal and gangue mineral.
Another object of the present invention is to provide the preparation methods of above-mentioned amino phosphine acid compounds.
Purposes it is also another object of the present invention to provide above-mentioned amino phosphine acid compounds as flotation collector.
The purpose of the present invention is to achieve the following.The present invention is a kind of amino phosphine acid compounds, feature
It is, structure such as formula（I）It is shown：
Wherein：R is H, F, Cl, Br or C1~6Alkyl；
Substituent R is H in preferred embodiment.
The application method of the amino phosphine acid compounds, may be used as ilmenite, bauxite, Rare Earth Mine, fluorite ore
Or phosphorite flotation collector.
Amino phosphine acid compounds of the present invention can be prepared using following methods：Aniline is added in a kettle
Or aniline, phosphorous acid solution and acidic catalyst containing substituent group, the temperature of reaction system is risen to 80 DEG C ~ 100 DEG C（It is preferred that 85
DEG C ~ 95 DEG C, most preferably 90 DEG C）, 3,7- dimethyl -2,6- zinn diene aldehyde is slowly added dropwise at such a temperature, it will be anti-after being added dropwise
The temperature of system is answered to be increased to 110 DEG C ~ 160 DEG C（It is preferred that 120 DEG C ~ 150 DEG C, most preferably 130 DEG C）, 1 ~ 4 is reacted at such a temperature
Hour（It is preferred that reaction 1 ~ 2 hour, most preferably react 1.5 hours）, white solid is obtained after cooling to obtain the final product.
Acidic catalyst used in synthetic reaction of the present invention can be inorganic acid compound or organic acid compound.
Preferred inorganic acid compound catalyst is hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid or phosphoric acid；Most preferred acidic catalyst is neighbour
Phthalic acid.Preferred organic acid compound catalyst is oxalic acid, citric acid, tartaric acid, hydroxyacetic acid, phthalic acid, ammonia
Base sulfonic acid, p-methyl benzenesulfonic acid.Each raw material 3,7- dimethyl -2,6- zinn diene aldehyde, aniline are reacted in synthetic reaction or containing substituent group
Aniline, phosphorous acid and acidic catalyst molar ratio be 1:1~2:1~3:0.02~0.08.3,7- diformazan most preferably in scheme
The molar ratio of base -2,6- zinn diene aldehyde, aniline or aniline containing substituent group, phosphorous acid and acidic catalyst is 1:1:1:0.05.
Amino phosphine acid compounds provided by the invention have benzene ring structure, amino structure, branched structure and multiple carbon carbon
Double bond is a kind of completely new organic phosphonic compound.Disclosed organic phosphonic compound is also to be used as ilmenite, alumina for the first time
Mine, Rare Earth Mine, fluorite ore or phosphorite flotation collector can be to a variety of gold due to having phosphonic acid base and amino simultaneously in compound
Belong to ion and generates chelation, it is higher to the sorting of valuable mineral, warming operation is not needed in flotation.Amino of the invention
Phosphonic acids compounds can be used for ilmenite, bauxite, Rare Earth Mine, fluorite ore or phosphorite flotation collector.
Compared with current technology, beneficial effects of the present invention：One kind is obtained for the first time contains benzene ring structure, amino knot simultaneously
The organic phospho acid of structure, branched structure and multiple carbon-carbon double bond structures.Organic phospho acid group has chela to metal ion in compound
Cooperation is used, and amino can play synergistic effect with phosphonic acid base in structure, increases the collecting ability to target minreal；Multiple carbon in structure
Carbon double bond can improve the dispersibility in its hydrophily and floatation process.The compound is as flotation collector, good water solubility, dispersion
Property it is strong, use process is convenient；The selectivity and collecting performance having had simultaneously.The preparation method use of the compounds of this invention can adopt
With one-pot synthesis method, operation is easily controllable, product yield is high, and easy to industrialized production, cost is relatively low and will not generation environment
Pollution.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of 1- anilino- -2,7- methyl -2,6- octadienyl -1- phosphonic acids.
Fig. 2 is the mass spectrogram of 1- anilino- -2,7- methyl -2,6- octadienyl -1- phosphonic acids.
Fig. 3 is the flotation process of 1- anilino- -2,7- methyl -2,6- octadienyl -1- phosphonic acids flotation ilmenite mine
Figure.
Fig. 4 is the flotation process figure of 1- anilino- -2,7- methyl -2,6- octadienyl -1- phosphonic acids flotation fluorite ore.
Specific embodiment
The present invention is further illustrated by following embodiment, but is not restricted by the embodiments.All numbers in embodiment
Quality is unless otherwise specified referred both to percentage.
Embodiment 1, a kind of amino phosphine acid compounds, the general formula of the compound are（I）It is shown：
Wherein：R is H, F, Cl or Br.
Preparation method includes the following steps：Aniline or the aniline containing substituent group, phosphorous acid solution are added in a kettle
And acidic catalyst, the temperature of reaction system is risen to 80 DEG C, 3,7- dimethyl -2,6- octadiene is slowly added dropwise at such a temperature
The temperature of reaction system is increased to 110 DEG C after being added dropwise, reacted at such a temperature by aldehyde, obtains white solid i.e. after cooling
?.Reaction time is 1 hour.Acidic catalyst used in reaction is in hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid or phosphoric acid
It is a kind of；Reaction raw materials 3,7- dimethyl -2,6- zinn diene aldehyde, aniline or aniline, phosphorous acid and acidic catalyst containing substituent group
Molar ratio be 1:1:1:0.02.Amino is used in the floatation process of ilmenite, bauxite, Rare Earth Mine, fluorite ore or phosphorus ore
Phosphonic acids compounds are as flotation collector.
Embodiment 2, a kind of amino phosphine acid compounds, the general formula of the compound are（I）It is shown：
Wherein：R is C1~6Alkyl.
Preparation method includes the following steps：Aniline or the aniline containing substituent group, phosphorous acid solution are added in a kettle
And acidic catalyst, the temperature of reaction system is risen to 100 DEG C, 3,7- dimethyl -2,6- pungent two is slowly added dropwise at such a temperature
The temperature of reaction system is increased to 160 DEG C after being added dropwise, reacted at such a temperature by olefine aldehydr, obtains white solid after cooling
To obtain the final product.Reaction time is 4 hours.Acidic catalyst used in reaction is selected from oxalic acid, citric acid, tartaric acid, hydroxyacetic acid, neighbour
Phthalic acid, sulfamic acid or p-methyl benzenesulfonic acid.Reaction raw materials 3,7- dimethyl -2,6- zinn diene aldehyde, aniline contain substituent group
Aniline, phosphorous acid and acidic catalyst molar ratio be 1: 2: 3: 0.08.In ilmenite, bauxite, Rare Earth Mine, fluorite
Use amino phosphine acid compounds as flotation collector in the floatation process of mine or phosphorus ore.
Embodiment 3, a kind of amino phosphine acid compounds, the general formula of the compound are（I）It is shown：
Wherein：R is H.
Preparation method includes the following steps：Aniline or the aniline containing substituent group, phosphorous acid solution are added in a kettle
And acidic catalyst, the temperature of reaction system is risen to 90 DEG C, 3,7- dimethyl -2,6- octadiene is slowly added dropwise at such a temperature
The temperature of reaction system is increased to 130 DEG C after being added dropwise, reacted at such a temperature by aldehyde, obtains white solid i.e. after cooling
?.Reaction time is 1.5 hours.Acidic catalyst used in reaction is selected from oxalic acid, citric acid, tartaric acid, hydroxyacetic acid, neighbour
Phthalic acid, sulfamic acid or p-methyl benzenesulfonic acid.Reaction raw materials 3,7- dimethyl -2,6- zinn diene aldehyde, aniline contain substituent group
Aniline, phosphorous acid and acidic catalyst molar ratio be 1:1:1:0.05.Ilmenite, bauxite, Rare Earth Mine, fluorite ore or
Use amino phosphine acid compounds as flotation collector in the floatation process of phosphorus ore.
Embodiment 3：The preparation of 1- anilino- -2,7- methyl -2,6- octadienyl -1- phosphonic acids
93 parts of aniline, 166 parts of phosphorous acid solutions are added in the reaction kettle with stirring（Concentration is 50%）With 8.3 parts of adjacent benzene two
The temperature of reaction system is risen to 90 DEG C by formic acid, is at such a temperature added to 152 parts of 3,7- dimethyl -2,6- zinn diene aldehydes
In reaction kettle, after addition, the temperature of reaction system is risen to 130 DEG C, reacts 1.5 hours at such a temperature, obtains white
Solid is required collecting agent OP, yield 83%.Its map is referring to Fig. 1 and 2.
Embodiment 4：The preparation of 1- anilino- -2,7- methyl -2,6- octadienyl -1- phosphonic acids
93 parts of aniline, 166 parts of phosphorous acid solutions are added in the reaction kettle with stirring（Concentration is 50%）It, will be anti-with 4 parts of hydrochloric acid
It answers the temperature of system to rise to 90 DEG C, 152 parts of 3,7- dimethyl -2,6- zinn diene aldehydes is added in reaction kettle at such a temperature,
After addition, the temperature of reaction system is risen to 130 DEG C, is reacted 1.5 hours at such a temperature, obtaining white solid is institute
Need collecting agent OP, yield 73%.
Embodiment 5：Application of the collecting agent in ilmenite flotation
Ilmenite sample ore comes from Xuan Tai factory of Sichuan Pan Gang group, head grade TiO218.56%, -200 mesh account for -33%, and water is added to size mixing
It is 30% to pulp density, 1kg/t sulfuric acid, 0.3kg/t xanthate, 0.05kg/t98# oil is added and carries out floatation desulphurization, is added
0.8kg/ sulfuric acid, collecting agent OP2.8kg/t carry out ilmenite roughing, and primary cleaning adds sulfuric acid to enter 0.3kg/t, and recleaning is added
Sulfuric acid 0.2kg/t.Flotation process figure is shown in Fig. 3.Collecting agent OP of the present invention and industrially common collecting agent MOH flotation comparison are real
It tests and the results are shown in Table 1.Seen from table 1, collecting agent OP of the present invention improves the flotation recovery rate of ilmenite than existing collecting agent MOH
9.43%.
1 collecting agent flotation ilmenite comparing result of table
| Collecting agent type | Ilmenite concentrate yield/% | TiO2Grade/% | TiO2The rate of recovery/% |
| OP | 32.21 | 48.12 | 83.30 |
| MOH | 28.52 | 48.07 | 73.87 |
Embodiment 6：Collecting agent is applied in fluorite flotation
CaF in the fluorite green ore of Zhejiang2Fluorite ore ore grinding to -200 mesh will be accounted for -65% using ore mill by grade 36.20%,
Adding water to size mixing to pulp density is 30%, and 1.5kg/t sodium carbonate, 0.5kg/t waterglass, 0.6kg/t collecting agent OP, room temperature is added
For 10 DEG C or so progress float tests, flotation process figure is shown in Fig. 4.Collecting agent OP of the present invention is floating with common collecting agent oleic acid
Test result is selected to be shown in Table 2.It is higher than conventional collecting agent oleic acid by flotation recovery rate of the visible collecting agent OP of table 2 to fluorite ore
15.37%
2 collecting agent flotation fluorite ore comparing result of table
| Collecting agent type | Rough concentrate yield/% | CaF2Grade/% | CaF2The rate of recovery/% |
| Enuatrol | 30.12 | 81.69 | 67.97 |
| Collecting agent OP | 37.10 | 81.32 | 83.34 |
Claims (10)
1. a kind of amino phosphine acid compounds, which is characterized in that the general formula of the compound is（I）It is shown：
Wherein：R is H, F, Cl, Br or C1~6Alkyl.
2. a kind of preparation method of amino phosphine acid compounds as described in claim 1, which is characterized in that including following step
Suddenly：Aniline or aniline, phosphorous acid solution and acidic catalyst containing substituent group are added in a kettle, by the temperature of reaction system
80 DEG C ~ 100 DEG C are risen to, 3,7- dimethyl -2,6- zinn diene aldehyde is slowly added dropwise at such a temperature, by reaction system after being added dropwise
Temperature be increased to 110 DEG C ~ 160 DEG C, react at such a temperature, obtain white solid after cooling to obtain the final product.
3. the preparation method of amino phosphine acid compounds according to claim 2, which is characterized in that the reaction time is 1 ~ 4
Hour.
4. the preparation method of amino phosphine acid compounds according to claim 2, which is characterized in that acid used in reaction
Property catalyst be inorganic acid compound or organic acid compound.
5. the preparation method of amino phosphine acid compounds according to claim 2 or 4, which is characterized in that described is inorganic
Acid compound is selected from hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid or phosphoric acid；The organic acid compound is selected from oxalic acid, citric acid, wine
Stone acid, hydroxyacetic acid, phthalic acid, sulfamic acid or p-methyl benzenesulfonic acid.
6. the preparation method of amino phosphine acid compounds according to claim 2, which is characterized in that reaction raw materials 3,7- bis-
The molar ratio of methyl -2,6- zinn diene aldehyde, aniline or aniline containing substituent group, phosphorous acid and acidic catalyst is 1:1~2:1~3:
0.02 ~ 0.08, preferred molar ratio is 1:1:1:0.05.
7. the preparation method of amino phosphine acid compounds according to claim 2, which is characterized in that the temperature of reaction system
It is 120 DEG C ~ 150 DEG C, preferable reaction temperature is 130 DEG C.
8. the preparation method of amino phosphine acid compounds according to claim 2 or 3, which is characterized in that the reaction time 1
~ 2 hours, the preferred reaction time was 1.5 hours.
9. method described in any one of amino phosphine acid compounds described in claim 1 or claim 2-8 is made
Purposes of the amino phosphine acid compounds as flotation collector.
10. purposes according to claim 9, it is characterised in that：The purposes is in ilmenite, bauxite, Rare Earth Mine, fluorite
Use amino phosphine acid compounds as flotation collector in the floatation process of mine or phosphorus ore.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111068926A (en) * | 2019-11-12 | 2020-04-28 | 中南大学 | Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent and preparation method and application thereof |
| CN111468306A (en) * | 2020-05-26 | 2020-07-31 | 河南天鸿选矿科技有限公司 | Fluorite ore flotation collecting agent |
| CN111482278A (en) * | 2020-06-03 | 2020-08-04 | 广东省资源综合利用研究所 | Copper oxide ore flotation method |
| CN112791859A (en) * | 2020-12-21 | 2021-05-14 | 湖南新田岭钨业有限公司 | Application of phosphoric acid amino acid compound |
| CN112808463A (en) * | 2020-12-30 | 2021-05-18 | 中南大学 | Medicament and method for flotation separation of iron-titanium ore and iron-containing gangue |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111068926A (en) * | 2019-11-12 | 2020-04-28 | 中南大学 | Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent and preparation method and application thereof |
| CN111468306A (en) * | 2020-05-26 | 2020-07-31 | 河南天鸿选矿科技有限公司 | Fluorite ore flotation collecting agent |
| CN111482278A (en) * | 2020-06-03 | 2020-08-04 | 广东省资源综合利用研究所 | Copper oxide ore flotation method |
| CN111482278B (en) * | 2020-06-03 | 2022-03-22 | 广东省资源综合利用研究所 | Copper oxide ore flotation method |
| CN112791859A (en) * | 2020-12-21 | 2021-05-14 | 湖南新田岭钨业有限公司 | Application of phosphoric acid amino acid compound |
| CN112808463A (en) * | 2020-12-30 | 2021-05-18 | 中南大学 | Medicament and method for flotation separation of iron-titanium ore and iron-containing gangue |
| CN112808463B (en) * | 2020-12-30 | 2022-06-21 | 中南大学 | Medicament and method for flotation separation of iron-titanium ore and iron-containing gangue |
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