CN107385211B - A kind of band branch long-chain fat acidic group imidazoline extractant and its preparation method and application - Google Patents
A kind of band branch long-chain fat acidic group imidazoline extractant and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of band branch long-chain fat acidic group imidazoline extractants and its preparation method and application, the imidazoline extractant includes multiple N atoms and alkyl group of drawing money on credit, preparation method is, under normal pressure, carboxylic acid and polyethylene polyamine are reacted under solid catalyst effect, after the reaction was completed, are separated by solid-liquid separation recycling solid catalyst, liquid mixture be recovered by distillation the complete raw material of unreacted to get；The preparation method has the advantages that reaction condition is mild, catalyst is reusable, equipment investment and operating cost are low etc.；The features such as extraction of the imidazoline extractant for anion such as tungstenic, molybdenum, vanadium has loading capacity high, and the split-phase time is short, extraction and back extraction function admirable, there is good prospects for commercial application.
Description
Technical field
The present invention relates to a kind of imidazolinium compounds, in particular to a kind of band branch long-chain fat acidic group imidazoline extraction
Agent, and in particular to one kind utilizes solid catalyst one-step synthesis band branch using long chained fatty carboxylic acid and polyethylene polyamine as raw material
The method of long-chain fat acidic group imidazoline and extraction with branch long-chain fat acidic group imidazoline as the anion of tungstenic, molybdenum or vanadium
The application of agent is taken, belonging to has fine chemistry industry and field of hydrometallurgy.
Background technique
Imidazoline surfactant has the history of decades, there is multiple kinds based on cationic and both sexes class,
Imidazoline is imidazoline surface-active intermediate.Due to imidazoline surface-active excellent combination property, there are good decontamination, blistering
And emulsifiability, especially with extremely low toxicity, to the low irritant and good biological degradability of skin and eyes, daily
Chemical industry, weaving, printing and dyeing, inhibition etc. have broad application prospects.
The synthetic method of existing imidazoline is mainly by generating imidazoline after carboxylic acid and polyamines dehydrating condensation, closed loop, also
Imidazoline can be reacted with polyamines with carboxylate and eyeball class.Vacuum method can be used in the preparation of imidazoline【" dihydroxy ethyl imidazoline sun from
The synthesis of sub- surfactant ", Shi Zhen, Yang Weiguo, chemistry world, 1994,1：14-15】Or solvent method【" higher aliphatic amido
The synthesis of alkyl imidazoline ", Ma Xiaomei etc., Speciality Petrochemicals, 1996,5：25-27】Dehydration.Solvent method dehydration experiment room makes
It with extensive, but must carry out in an inert atmosphere, toluene or dimethylbenzene etc. can be selected in azeotropic agent【" 2 one hendecane agent, one carboxymethyl
The synthesis and application of one N, mono- hydroxyethyl imidazole quinoline ", Liu Yongshan etc., Liaoning chemical industry, 1994,2：49-50】.Vacuum method is generally work
Industry production is used, but high to equipment sealing requirements, and vacuum degree is not easy to control, and reactant is easily oxidized when pyroreaction, production
Product color is deep, and of poor quality, the polyamines of recycling is difficult to recycle.And the Solvent method time is generally longer (10h), energy consumption compared with
Greatly, make its industrialization more difficult, but solvent method is not high to equipment requirement, reaction is relatively steady, safe, and product is in N2Be not easy under protection by
Oxidation, product degree of oxidation are low, high-quality.Suitable catalyst such as activity A1 is added2O3, CaO, metal Sn, SnO2、ZnCl2、ZnO
Deng【ToshiehikaK., (clear 50 1 11917) AkioK., Imidazolinederivative, JPpat., 7511917
(1975)】, the reaction time can be shortened, reduce reaction temperature, improve product quality and yield.
Solvent extraction technology metallurgy, chemical industry, nuclear fuel, biological medicine, in terms of have very extensive application.?
In extraction process, the extracting power and extraction selectivity of extractant depend mainly on the molecular structure and its property of itself,
Therefore, the quality overwhelming majority of extraction ability depends on the property of extractant itself.Extractant can generally be divided into acid extract
Take agent, Neutral-neutral Extractants, basic extractant and chelating kind of extractants etc..Wherein basic extractant mainly includes the primary of macromolecule
The amine extractants such as amine, secondary amine, tertiary amine, they form amine salt in acidic aqueous solution, and then form network yin with anionic metal
Ion, anionic metal are extracted in organic phase, and extraction and back extraction ability are related with the power of extractant alkalinity.Tungsten, molybdenum,
Usually used extractant is N235, N263, N1923 during vanadium Extraction metallurgy, and the synthesis of these extractants will be in high temperature, height
Pressure, could synthesize to obtain under the effect of the catalyst, and consersion unit requires height, and reaction is complicated, operate difficult grasp, production cost
Height, security context hidden danger are more.There are synthesis imidazoles chela and extractant for the auric report of extraction and separation in the prior art
【" synthesis of 2- (2- benzylthio ethyl)-N- aminoethyl imidazoline and its research applied in Au (III) extraction and separation ", leaf
Wen Yu, Henan science, June nineteen ninety, the second phase of volume nine)】, but not yet about imidazolines derivative as tungstenic,
The relevant report of the basic extractant of the anion of molybdenum or vanadium.
Summary of the invention
The defects of that there are exchange capacities is low, the split-phase time is longer, back extraction is more difficult for extractants such as existing N235, this hair
First bright purpose be to provide it is a kind of with long branched chain structure and be rich in the imidazolinium compounds of amido, be used as alkali
Property extractant have many advantages, such as that capacity is big, the split-phase time is short, back extraction ability is excellent.
The disadvantages of harsh, at high cost for there are process conditions in the synthesis process of existing imidazolines, this
Another purpose of invention be to provide a kind of simple step, mild condition, be easy to purification & isolation prepare the band branch
The method of long-chain fat acidic group imidazoline.
Third object of the present invention be to provide it is a kind of with branch long-chain fat acidic group imidazoline as extractant
Using the extraction of the anion particularly suitable for tungstenic, molybdenum or vanadium has loading capacity big, and the split-phase time is short, extraction and back extraction
Ability good characteristics.
In order to achieve the above technical purposes, the present invention provides a kind of band branch long-chain fat acidic group imidazoline extractant,
With 1 structure of formula：
Wherein,
N is 4~10；
M is 4~10；
P is 1~3；
N, m and p can identical also can be different, n, m and p are positive integer.
Band branch long-chain fat acidic group imidazoline extractant of the invention includes simultaneously multiple N such as primary amine, secondary amine and tertiary amine
Atom can combine H+, therefore it shows stronger extracting power and bigger saturated capacity, while it includes long chain branch
Alkyl has preferably lipophilicity, phase separation ability can be improved, shortens the split-phase time.
The present invention also provides the preparation methods with branch long-chain fat acidic group imidazoline extractant, and this method is in normal pressure
Under, by 2 carboxylic acid of formula and 3 polyethylene polyamine of formula under solid catalyst effect, reacted at 160 DEG C~220 DEG C, reaction is completed
Afterwards, be separated by solid-liquid separation recycling solid catalyst, liquid mixture be recovered by distillation the complete raw material of unreacted to get；
Wherein,
N is 4~10；
M is 4~10；
P is 1~3.
Preferred scheme, the molar ratio of 3 polyethylene polyamine of 2 carboxylic acid of formula and formula are 1:1~6.Pass through appropriate excessive more second
Alkene polyamines makes the abundant fully reacting of carboxylic acid, the product separation after being conducive to.
Preferred scheme, the quality of the solid catalyst be 3 polyethylene polyamine gross mass of 2 carboxylic acid of formula and formula 1%~
5%.
More preferably scheme, the solid catalyst are nickel oxide, cobalt oxide, the carrier containing nickel oxide and/or cobalt oxide
At least one of catalyst.Most preferred solid catalyst is nickel oxide or the carried catalyst containing nickel oxide.
More preferably scheme, the water generated using water segregator separation reaction in the reaction process.
More preferably scheme, the time of the reaction are 4~10 hours.
The present invention also provides a kind of applications with branch long-chain fat acidic group imidazoline extractant, are applied to extraction
At least one of tungstenic anion in water solution system, anion containing molybdenum, anion containing vanadium.
Preferred scheme, using containing the organic phase with branch long-chain fat acidic group imidazoline extractant, be 6~12 to pH,
Temperature is extracted at least one of the tungstenic anion in 5~40 DEG C of water solution system, anion containing molybdenum, anion containing vanadium
It takes, extraction organic phase is stripped using lye, obtains the richness of at least one of tungstenic anion, anion containing molybdenum, anion containing vanadium
Collect solution.
More preferably scheme, it is described containing the branch chain length containing band in the organic phase with branch long-chain fat acidic group imidazoline extractant
The concentration of chain fatty acid based imidazolines extractant is 1~50%.
Band branch long-chain fat acidic group imidazoline extractant of the invention preferably first uses inorganic acid in extraction process
Be acidified, this is the more conventional acidification step of basic anionic resin, belong to it will be appreciated by those skilled in the art that model
Farmland.
Extraction and back extraction process of the invention generally carries out at room temperature, and split-phase is functional in extraction process, grease
Interface is clear.
It is of the invention containing including commonly used in the art dilute in the organic phase with branch long-chain fat acidic group imidazoline extractant
Agent and modification agent, diluent such as sulfonated kerosene, aviation kerosine etc. are released, modification agent is eight carbon alcohol etc..
It (is sodium salt system or ammonium salt system according to solution that sodium hydroxide or ammonium hydroxide, which can be used, in back extraction process of the invention
Specific choice).
The mistake for extracting tungstate ion under alkaline condition with branch long-chain fat acidic group imidazoline extractant of the invention
Journey：Including acidification, extraction, back extraction and regeneration (for extracting tungstate ion)；
Acidification：Q (o)+nHX (a)=QHn+Xn-(a)；
Extraction：QHn+Xn-(o)+n/2WO4 2-(a)=QHn+(WO4 2-)n/2(o)+nX-(a)；
Back extraction：QHn+(WO4 2-)n/2(o)+nNH4OH (a)=Q (o)+n/2 (NH4)2WO4(a)+nH2O；
Regeneration：Q (o)+nHX (a)=QHn+Xn-(a)；
Q indicates that extractant, HX indicate inorganic acid used when acidification.
Extraction process is the anion exchange procedures of acid ion and metal oxygen-containing acid ion；Stripping process is to utilize pH
It increases, when destroying the ammonium salt for generating amine formation, metal oxygen-containing acid ion is stripped.
The carboxylic acid starting material that the present invention uses can directly buy Yushan Hill thing Asia chemical industry Co., Ltd, Rong Cheng jumpization
Work Co., Ltd etc..
Synthetic route with branch long-chain fat acidic group imidazoline extractant of the invention：
Compared with the prior art, technical solution of the present invention bring advantageous effects：
1) of the invention that there is special molecular structure with branch long-chain fat acidic group imidazoline extractant, it can wrap simultaneously
Its extracting power and capacity can be improved with alkyl group of drawing money on credit containing primary amine, secondary amine and tertiary amine, and shortens the split-phase time.
2) reaction condition is mild in the preparation process of the invention with branch long-chain fat acidic group imidazoline extractant, reaction
Time is short, and imidazoline products are high-quality.
3) solid catalyst is used in the preparation process of the invention with branch long-chain fat acidic group imidazoline extractant,
Catalytic activity with higher, and possess certain acid strength and hydrophobicity, moisture-stable avoids inactivating, and it is reusable, prolong
The service life of catalyst is grown.
4) solid catalyst is used in the preparation process of the invention with branch long-chain fat acidic group imidazoline extractant,
Two phases of solid-liquid are in reactant and product after reaction, are easy to separate product with catalyst, to obtain high-purity
Product.
5) without equipment corrosion and environment in the preparation process of the invention with branch long-chain fat acidic group imidazoline extractant
The problems such as pollution, low to the requirement of equipment corrosion resistance, process flow is short, and production process is environmentally friendly, equipment investment and operation
Expense is low, and the water entrainer in water segregator can be recycled, and section has lacked the dosage of water entrainer, reduces the production cost of product.
6) extraction of the invention for being applied to tungsten, molybdenum, vanadium anion with branch long-chain fat acidic group imidazoline extractant,
Loading capacity is high, and the split-phase time is short, extraction and back extraction function admirable.
Detailed description of the invention
【Fig. 1】For WO in embodiment 123Extraction isotherm.
【Fig. 2】For the extraction isotherm of V in embodiment 15.
Specific embodiment
Below with reference to specific embodiment the present invention is described further, but protection scope of the present invention and not only limit
In this.
Embodiment 1：
Equipped with blender, reflux condensing tube, thermometer, water segregator 500mL three-necked flask in, the different of 1.0mol is added
Octanoic acid, 1.2mol diethylenetriamine, suitable nickel oxide solid catalyst.It is heated with oil bath, starts blender, carried out normal
Pressure, which is heated to reflux, to be stirred to react, and when reaching set temperature wait react, starts timing.Reaction reacts 3 at 160 DEG C of reaction temperature respectively
Hour, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction, after separation of solid and liquid, washing is distilled off excessive anti-
It answers raw material and recycles to remove and separate the complete raw material of unreacted to get long-chain fat acidic group imidazoline is arrived.The long-chain fat acidic group miaow
The yield of oxazoline is：93.2%.
Embodiment 2：
Equipped with blender, reflux condensing tube, thermometer, water segregator 500mL three-necked flask in, the different of 0.5mol is added
Hexadecylic acid, 3.0mol diethylenetriamine, the nickel oxide catalyst of recycling.It is heated with oil bath, starts blender, carried out normal
Pressure, which is heated to reflux, to be stirred to react, and when reaching set temperature wait react, starts timing.Reaction reacts 3 at 160 DEG C of reaction temperature respectively
Hour, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction, after separation of solid and liquid, washing is distilled off excessive anti-
It answers raw material and recycles to remove and separate the complete raw material of unreacted to get long-chain fat acidic group imidazoline is arrived.The long-chain fat acidic group miaow
The yield of oxazoline is：94.3%.
Embodiment 3：
Equipped with blender, reflux condensing tube, thermometer, water segregator 500mL three-necked flask in, the different of 0.5mol is added
Stearic acid, 3.0mol diethylenetriamine, appropriate cobalt oxide catalyst.It is heated with oil bath, starts blender, carried out normal pressure and add
Hot return stirring reaction, when reaching set temperature wait react, starts timing.Reaction is small in 160 DEG C of reaction temperature reactions 3 respectively
When, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction, after separation of solid and liquid, excessive reaction is distilled off in washing
Raw material and recycling remove the complete raw material of Fraction collection unreacted to get long-chain fat acidic group imidazoline is arrived.The long-chain fat acidic group
The yield of imidazoline is：92.6%.
Embodiment 4：
Equipped with blender, reflux condensing tube, thermometer, water segregator 500mL three-necked flask in, the different of 0.5mol is added
Stearic acid, 3.0mol diethylenetriamine, the cobalt oxide catalyst of recycling.It is heated with oil bath, starts blender, carry out normal pressure
It is heated to reflux and is stirred to react, when reaching set temperature wait react, start timing.Reaction is small in 160 DEG C of reaction temperature reactions 3 respectively
When, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction, after separation of solid and liquid, excessive reaction is distilled off in washing
Raw material and recycling, which remove, separates the complete raw material of unreacted to get long-chain fat acidic group imidazoline is arrived.The long-chain fat acidic group imidazoles
The yield of quinoline is：94.3%.
Embodiment 5：
Equipped with blender, reflux condensing tube, thermometer, water segregator 500mL three-necked flask in, the different of 1.0mol is added
Octanoic acid, 1.2mol triethylene tetramine, suitable nickel oxide solid catalyst.It is heated with oil bath, starts blender, carried out normal
Pressure, which is heated to reflux, to be stirred to react, and when reaching set temperature wait react, starts timing.Reaction reacts 3 at 160 DEG C of reaction temperature respectively
Hour, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction, after separation of solid and liquid, washing is distilled off excessive anti-
It answers raw material and recycles to remove and separate the complete raw material of unreacted to get long-chain fat acidic group imidazoline is arrived.The long-chain fat acidic group miaow
The yield of oxazoline is：95.3%.
Embodiment 6：
Equipped with blender, reflux condensing tube, thermometer, water segregator 500mL three-necked flask in, the different of 1.0mol is added
Octanoic acid, 1.2mol tetraethylenepentamine, suitable nickel oxide solid catalyst.It is heated with oil bath, starts blender, carried out normal
Pressure, which is heated to reflux, to be stirred to react, and when reaching set temperature wait react, starts timing.Reaction reacts 3 at 160 DEG C of reaction temperature respectively
Hour, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction, after separation of solid and liquid, washing is distilled off excessive anti-
It answers raw material and recycles to remove and separate the complete raw material of unreacted to get long-chain fat acidic group imidazoline is arrived.The long-chain fat acidic group miaow
The yield of oxazoline is：93.8%.
Embodiment 7：
In the 500mL three-necked flask equipped with blender, reflux condensing tube, thermometer, the isomery 16 of 0.5mol is added
Acid, 3.0mol tetraethylenepentamine.The nickel oxide solid catalyst of recycling, is heated with oil bath, starts blender, carries out normal pressure
It is heated to reflux and is stirred to react, when reaching set temperature wait react, start timing.Reaction is small in 120 DEG C of reaction temperature reactions 3 respectively
When, 140 DEG C are reacted 3 hours, and 160 DEG C are reacted 3 hours.After reaction, washing is distilled off excessive reaction raw materials and recycles
Except separating the complete raw material of unreacted to get to long chain fatty acids amides derivative.The receipts of the long chain fatty acids amides derivative
Rate is：95.2%.
Embodiment 8：
Equipped with blender, reflux condensing tube, thermometer, water segregator 500mL three-necked flask in, the different of 0.5mol is added
Stearic acid, 3.0mol diethylenetriamine, the cobalt oxide catalyst of recycling.It is heated with oil bath, starts blender, carry out normal pressure
It is heated to reflux and is stirred to react, when reaching set temperature wait react, start timing.Reaction is small in 160 DEG C of reaction temperature reactions 3 respectively
When, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction, after separation of solid and liquid, excessive reaction is distilled off in washing
Raw material and recycling, which remove, separates the complete raw material of unreacted to get long-chain fat acidic group imidazoline is arrived.The long-chain fat acidic group imidazoles
The yield of quinoline is：93.8%.
Embodiment 9：
Equipped with blender, reflux condensing tube, thermometer, water segregator 500mL three-necked flask in, the different of 0.5mol is added
Stearic acid, 3.0mol diethylenetriamine load nickel oxide catalyst.It is heated with oil bath, starts blender, carried out normal pressure and add
Hot return stirring reaction, when reaching set temperature wait react, starts timing.Reaction is small in 160 DEG C of reaction temperature reactions 3 respectively
When, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction, after separation of solid and liquid, excessive reaction is distilled off in washing
Raw material and recycling separate the complete raw material of unreacted to get long-chain fat acidic group imidazoline is arrived.The long-chain fat acidic group imidazoline
Yield be：94.2%.
Embodiment 10：
Aqueous phase liquid：The practical feed liquid of industry, feed liquid concentration containing tungstic acid are：116.25g·L-1, pH 13.34；
Organic phase：Five kinds of configuration number respectively 1~5 form different organic phases, and the diluent in organic phase is sulphur
Change kerosene, modification agent is isooctanol, long chain fatty acids amides derivative extractant made from the example 4 of No. 1 10% volume fraction+
Isooctanol+sulfonated kerosene of 25% volume fraction, long chain fatty acids amides made from the example 4 of No. 2 20% volume fractions are derivative
Isooctanol+sulfonated kerosene of+25% volume fraction of object extractant, long chain fatty acids made from the example 4 of No. 3 30% volume fractions
Isooctanol+sulfonated kerosene of+25% volume fraction of amide derivatives extractant, it is long made from the example 4 of No. 4 40% volume fractions
Isooctanol+sulfonated kerosene of+25% volume fraction of chain fatty acid amide derivatives extractant, the example 4 of No. 5 50% volume fractions
Isooctanol+sulfonated kerosene of+25% volume fraction of long chain fatty acids amides derivative extractant obtained.Experiment extraction used
Agent belongs to novel amine extractant, it is therefore desirable to acidification.Acidization 0.6molL-1Sulfuric acid with O/A2:1 carries out
Acidification.
Extraction：Above-mentioned five kinds of organic phases respectively with feed liquid at 25 DEG C (O/A) 1 compared with:1, incorporation time 10min, vibration
Leaching extraction experimental result is as shown in table 1 below under the conditions of swinging frequency 200r/min.
Influence of the extractant of 1 various concentration of table to tungsten extraction yield
| Organic phase number | 1 | 2 | 3 | 4 | 5 |
| The extraction yield (%) of tungsten | 4.30 | 10.31 | 31.04 | 62.97 | 69.26 |
| The split-phase time (min) | 1 | 1.8 | 2.5 | 6 | 14 |
As it can be seen from table 1 the volume fraction with organic phase increases, the single-stage extraction rate of tungsten is also increased as, split-phase
Time also extends.Meanwhile finding to increase with organic phase concentration during the experiment, this is because with the increasing of extractant ratio
Add, grease split-phase effect is deteriorated.
Embodiment 11：
Aqueous phase liquid：The practical feed liquid of industry, feed liquid concentration containing tungstic acid are：116.25g·L-1, initial pH is 13.34,
With sulphur acid for adjusting pH, it is ordered as 1~6 according to this from low to high；
Organic phase：+ 25% volume of long chain fatty acids amides derivative extractant made from the example 4 of 40% volume fraction point
Several isooctanol+sulfonated kerosenes.
Extraction：Above-mentioned organic phase is being comparably 1 with the feed liquid of sulfuric acid adjustment pH respectively:Single-stage extraction is carried out under conditions of 1
It takes, extraction time is 5 minutes, and temperature is 25 DEG C, and experimental result is as shown in table 2 below.
The influence of the different water phase pH tungsten extraction yields of table 2
| Water phase number | 1 | 2 | 3 | 4 | 5 | 6 |
| Water phase pH | 8.27 | 9.36 | 10.12 | 11.20 | 12.07 | 13.11 |
| The extraction yield (%) of tungsten | 99.33 | 97.21 | 89.53 | 79.61 | 68.25 | 67.75 |
As shown in Table 2 with the reduction of material liquid pH, the single-stage extraction rate of tungsten gently reduces first, after sharply decline, pH is
When 12, extraction yield decline tends to be steady, and pH increases backward, and extraction yield variation is little.When pH is 8.3 or so, extraction yield is maximum,
Reach 99% or so, and the single-stage extraction rate of tungsten is only less than 67% when pH is 13.It is analyzed according to experiment effect, it is main former
Because being that the amine salt that part long chain fatty acids amides derivative extractant is formed under high ph conditions can hydrolyze, yin can not be carried out
Ion exchange extracting power weakens.
Embodiment 12：
Aqueous phase liquid：The practical feed liquid of industry, feed liquid concentration containing tungstic acid are：116.25g·L-1, initial pH is 13.34,
With sulphur acid for adjusting pH to 8.27.
Organic phase：+ 25% volume of long chain fatty acids amides derivative extractant made from the example 4 of 40% volume fraction point
Several isooctanol+sulfonated kerosenes.
Extraction：Organic phase is 8.27,25 DEG C, is comparing (O/A) 1 in material liquid pH:2,25 DEG C, incorporation time 10min, oscillation
It is contacted under conditions of being carried out under the same terms of frequency 200r/min with more parts of fresh feed liquids, until organic phase is saturated.It is real
Result is tested to be illustrated in fig. 1 shown below.
According to the saturation extraction isotherm in Fig. 1 it is found that 40% (volume fraction) long chain fatty acids amides derivative extracts
Agent has very strong effect of extracting and higher saturated capacity to the oxygen-containing acid ion of tungsten under this condition, has by single-stage extraction
WO in machine phase3Already exceed 107gL-1, extract and reach balance afterwards three times, extraction saturated capacity is 109.03gL-1。
Embodiment 13：
Organic phase：Load organic phases contain WO3 109.03g·L-1
Strip liquor：Using ammonium hydroxide as strip liquor, it is respectively 1~6 that concentration configures number from low to high.
Back extraction：Above-mentioned organic phase respectively with strip liquor compared with (O/A) 1:2,25 DEG C, incorporation time 10min, frequency of oscillation
Back extraction experiment is carried out under the same terms of 200r/min.Experimental result such as the following table 3.
Influence of the strip liquor of 3 various concentration of table to tungsten back extraction ratio
| Strip liquor number | 1 | 2 | 3 | 4 | 5 | 6 |
| Strip liquor concentration (g/L) | 0.5 | 1.0 | 1.5 | 2.0 | 2.5 | 3.0 |
| The counter of tungsten takes rate (%) | 35.36 | 75.73 | 79.06 | 82.15 | 89.52 | 86.18 |
| The split-phase time (min) | 3 | 3 | 5 | 8 | 5 | 5 |
From table 3 it can be seen that gradually rising with ammonia concn, back extraction ratio obviously rises, when ammonia concn is
0.5mol·L-1When, back extraction ratio is only 35%, increases ammonia concn to 1.0molL-1When, back extraction ratio rises very rapidly up to 75%
Left and right, continues growing ammonia concn, increases to 2.5molL-1When, back extraction ratio reaches highest, close to 90%, and when concentration rises
To 3molL-1When, back extraction ratio is slightly declined.Ammonia concn is 0.5molL-1When the split-phase time it is most fast, divided after 3min
Mutually completely, split-phase time extension after ammonia concn increases.When back extraction, ammonia concn reaches 3molL-1, have in raffinate
Floccule is precipitated.The reason of analysis is likely to occur floccule may be that the tungstate ion in strip liquor is given birth in conjunction with ammonium ion
At wolframic acid crystalline ammonium.
Embodiment 14：
Aqueous phase liquid：Predominantly with sodium hydroxide dissolve vanadic anhydride and sodium molybdate, wherein molybdenum concentration be
101.37g/L, vanadium concentration are about 9.53g/L, pH 8.21.
Organic phase：Five kinds of configuration number respectively 1~5 form different organic phases, and the diluent in organic phase is sulphur
Change kerosene, modification agent is isooctanol, long chain fatty acids amides derivative extractant made from the example 4 of No. 1 10% volume fraction+
Isooctanol+sulfonated kerosene of 20% volume fraction, long chain fatty acids amides made from the example 4 of No. 2 15% volume fractions are derivative
Isooctanol+sulfonated kerosene of+20% volume fraction of object extractant, long chain fatty acids made from the example 4 of No. 3 20% volume fractions
Isooctanol+sulfonated kerosene of+20% volume fraction of amide derivatives extractant, it is long made from the example 4 of No. 4 25% volume fractions
Isooctanol+sulfonated kerosene of+20% volume fraction of chain fatty acid amide derivatives extractant, the example 4 of No. 5 30% volume fractions
Isooctanol+sulfonated kerosene of+20% volume fraction of long chain fatty acids amides derivative extractant obtained.Experiment extraction used
Agent belongs to novel amine extractant, it is therefore desirable to acidification.Acidization 0.6molL-1Sulfuric acid with O/A2:1 carries out
Acidification.
Extraction：Above-mentioned five kinds of organic phases respectively with feed liquid at 25 DEG C (O/A) 1 compared with:1, incorporation time 10min, vibration
Leaching extraction experimental result is as shown in table 4 below under the conditions of swinging frequency 200r/min.
Influence of the extractant of 4 various concentration of table to Mo, V extraction yield
| Organic phase number | 1 | 2 | 3 | 4 | 5 |
| The extraction yield (%) of Mo | 15.49 | 17.85 | 16.39 | 38.39 | 45.46 |
| The extraction yield (%) of V | 89.38 | 97.59 | 98.57 | 97.77 | 99.64 |
| The split-phase time (min) | 1 | 1 | 1.5 | 2 | 3 |
Embodiment 15：
Aqueous phase liquid：The vanadic anhydride predominantly dissolved with sodium hydroxide, vanadium concentration is about 9.53g/L, and pH is
8.21。
Organic phase：+ 20% volume of long chain fatty acids amides derivative extractant made from the example 4 of 20% volume fraction point
Several isooctanol+sulfonated kerosenes.
Extraction：Organic phase is 8.21,25 DEG C, is comparing (O/A) 1 in material liquid pH:1,25 DEG C, incorporation time 10min, oscillation
It is contacted under conditions of being carried out under the same terms of frequency 200r/min with more parts of fresh feed liquids, until organic phase is saturated.It is real
Result is tested to be illustrated in fig. 2 shown below.
Saturation extraction isotherm according to fig. 2 is it is found that 20% (volume fraction) long chain fatty acids amides derivative extracts
Agent has very strong effect of extracting and higher saturated capacity to the oxygen-containing acid ion of vanadium under this condition, reaches after extraction four times
Balance, extraction saturated capacity are 20.23gL-1。
Embodiment 16：
Aqueous phase liquid：The practical feed liquid of industry, feed liquid concentration containing tungstic acid are：116.25g·L-1, pH 13.34；
Organic phase：Configure+25% volume of long chain fatty acids amides derivative extractant made from the example 5 of volume fraction point
Several isooctanol+sulfonated kerosenes tests extractant used and belongs to novel amine extractant, it is therefore desirable to acidification.Acidification
Process 0.6molL-1Sulfuric acid with O/A 2:1 is acidified.
Extraction：Above-mentioned five kinds of organic phases respectively with feed liquid at 25 DEG C (O/A) 1 compared with:1, incorporation time 10min, vibration
Leaching extraction under the conditions of frequency 200r/min to be swung to test, extraction results are shown, after 6h, split-phase not yet, without obvious grease circle
Face.
Claims (3)
1. a kind of application with branch long-chain fat acidic group imidazoline extractant, it is characterised in that：Applied to extraction aqueous liquid
At least one of tungstenic anion in system, anion containing molybdenum, anion containing vanadium；
The band branch long-chain fat acidic group imidazoline extractant has 1 structure of formula：
Wherein,
N is 4~10；
M is 4~10；
P is 1~3.
2. the application according to claim 1 with branch long-chain fat acidic group imidazoline extractant, it is characterised in that：Using
Containing the organic phase with branch long-chain fat acidic group imidazoline extractant, the aqueous liquid that pH be 6~12, temperature is 5~40 DEG C
At least one of tungstenic anion in system, anion containing molybdenum, anion containing vanadium are extracted, and extraction organic phase is anti-using lye
Extraction, obtains the enrichment solution of at least one of tungstenic anion, anion containing molybdenum, anion containing vanadium.
3. the application according to claim 2 with branch long-chain fat acidic group imidazoline extractant, it is characterised in that：It is described
Containing in the organic phase with branch long-chain fat acidic group imidazoline extractant containing with branch long-chain fat acidic group imidazoline extractant
Concentration is 1~50%.
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| CN110256353A (en) * | 2019-07-10 | 2019-09-20 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of imidazoline type antirust agent |
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