CN107385211A - A kind of band side chain long-chain fat acidic group imidazoline extractant and its preparation method and application - Google Patents
A kind of band side chain long-chain fat acidic group imidazoline extractant and its preparation method and application Download PDFInfo
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- CN107385211A CN107385211A CN201710639776.1A CN201710639776A CN107385211A CN 107385211 A CN107385211 A CN 107385211A CN 201710639776 A CN201710639776 A CN 201710639776A CN 107385211 A CN107385211 A CN 107385211A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/36—Heterocyclic compounds
- C22B3/362—Heterocyclic compounds of a single type
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D233/08—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms
- C07D233/12—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of band side chain long-chain fat acidic group imidazoline extractant and its preparation method and application, the imidazoline extractant includes multiple N atoms and alkyl group of drawing money on credit, its preparation method is, at ambient pressure, carboxylic acid and polyethylene polyamine are reacted under solid catalyst effect, after the completion of reaction, separation of solid and liquid recovery solid catalyst, the complete raw material of unreacted is recovered by distillation in liquid mixture, produces；The preparation method has the advantages such as reaction condition is gentle, catalyst is reusable, equipment investment and operating cost are low；Imidazoline extractant is used for the extraction of the anion such as tungstenic, molybdenum, vanadium, has loading capacity high, and the split-phase time is short, the features such as extracting and be stripped function admirable, there is good prospects for commercial application.
Description
Technical field
The present invention relates to a kind of imidazolinium compounds, more particularly to a kind of band side chain long-chain fat acidic group imidazoline extraction
Agent, and in particular to one kind utilizes solid catalyst one-step synthesis band side chain using long chained fatty carboxylic acid and polyethylene polyamine as raw material
The method of long-chain fat acidic group imidazoline and the extraction with side chain 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 technology
The history of imidazoline surfactant existing 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, foaming
And emulsifiability, especially with extremely low toxicity, low irritant and good biological degradability to skin and eyes, daily
Chemical industry, weaving, printing and dyeing, inhibition etc. have broad application prospects.
The synthetic method of existing imidazoline after carboxylic acid and polyamines dehydrating condensation, closed loop mainly by generating imidazoline, also
Carboxylate and eyeball class and polyamines reaction imidazoline can be used.The preparation of imidazoline can use vacuum method【" 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
With extensive, but it must carry out in an inert atmosphere, toluene or dimethylbenzene etc. can be selected in azeotropic agent【" the carboxymethyl of 2 one hendecane agent one
The synthesis and application of the hydroxyethyl imidazole quinolines of one N mono- ", 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 is difficult to control, and reactant is easily oxidized during pyroreaction, is produced
Product color is deep, and of poor quality, the polyamines of recovery is difficult to recycle.And the Solvent method time is general longer (10h), energy consumption compared with
Greatly, make its industrialization more difficult, but solvent method is not high to equipment requirement, and reaction is relatively steady, safety, and product is in N2Be not easy under protection by
Oxidation, product degree of oxidation is low, quality is good.Add for example active A1 of suitable catalyst2O3, CaO, metal Sn, SnO2、ZnCl2、ZnO
Deng【ToshiehikaK., AkioK., Imidazolinederivative, JPpat., 7511917 (clear 50 1 11917)
(1975)】, the reaction time can be shortened, reduce reaction temperature, improve product quality and yield.
Solvent extraction technology has very extensive application in metallurgy, chemical industry, nuclear fuel, biological medicine, environmental protection etc..
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 in 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 the moon with anionic metal
Ion, anionic metal are extracted in organic phase, and it is extracted and back extraction ability is relevant with the power of extractant alkalescence.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 in the presence of catalyst and obtain, 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 to be used for the auric report of extract and separate in the prior art
【" synthesis of 2- (2- benzylthios ethyl)-N- aminoethyl imidazolines and its research applied in Au (III) extract and separate ", leaf
Wen Yu, Henan science, June nineteen ninety, the second phase of volume nine)】, but also not on imidazolines derivative as tungstenic,
The relevant report of the basic extractant of the anion of molybdenum or vanadium.
The content of the invention
The defects of exchange capacity is low, the split-phase time is longer, back extraction is more difficult, this hair be present for extractants such as existing N235
First bright purpose is to be to provide a kind of imidazolinium compounds with long branched chain structure and rich in amido, and it is as alkali
Property extractant have the advantages that capacity is big, the split-phase time is short, back extraction ability is excellent.
For the shortcomings of process conditions are harsh, cost is high in the building-up process of existing imidazolines be present, this
Another purpose of invention be to provide a kind of simple step, mild condition, be easy to purification ＆ isolation prepare the band side chain
The method of long-chain fat acidic group imidazoline.
Third object of the present invention be to provide it is a kind of with side chain long-chain fat acidic group imidazoline as extractant
Using particularly suitable for the extraction of the anion of tungstenic, molybdenum or vanadium, big with loading capacity, the split-phase time is short, extraction and back extraction
Ability good characteristics.
In order to realize above-mentioned technical purpose, the invention provides a kind of band side chain long-chain fat acidic group imidazoline extractant,
With the structure of formula 1：
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.
The band side chain long-chain fat acidic group imidazoline extractant of the present invention is simultaneously comprising multiple N such as primary amine, secondary amine and tertiary amines
Atom, H can be combined+, therefore it shows stronger extracting power and bigger saturated capacity, while it includes long chain branch
Alkyl, there is more preferable lipophile, phase separation ability can be improved, shorten the split-phase time.
Present invention also offers the preparation method with side chain long-chain fat acidic group imidazoline extractant, this method is in normal pressure
Under, by the carboxylic acid of formula 2 and the polyethylene polyamine of formula 3 under solid catalyst effect, reacted at 160 DEG C~220 DEG C, reaction is completed
Afterwards, separation of solid and liquid recovery solid catalyst, liquid mixture are recovered by distillation the complete raw material of unreacted, produced；
Wherein,
N is 4~10；
M is 4~10；
P is 1~3.
The mol ratio of preferable scheme, the carboxylic acid of formula 2 and the polyethylene polyamine of formula 3 is 1:1~6.Pass through appropriate excessive more second
Alkene polyamines makes carboxylic acid fully react complete, the product separation after being advantageous to.
Preferable scheme, the quality of the solid catalyst for the carboxylic acid of formula 2 and the polyethylene polyamine gross mass of formula 3 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, using water caused by water knockout drum separation reaction in the course of reaction.
More preferably scheme, the time of the reaction is 4~10 hours.
Present invention also offers a kind of application with side chain long-chain fat acidic group imidazoline extractant, it is applied to extraction
At least one of tungstenic anion in water solution system, anion containing molybdenum, anion containing vanadium.
Preferable scheme, using containing the organic phase with side chain long-chain fat acidic group imidazoline extractant, be 6~12 to pH,
Temperature is that at least one of the tungstenic anion in 5~40 DEG C of water solution system, anion containing molybdenum, anion containing vanadium are extracted
Take, extraction organic phase is stripped using alkali 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 side chain long-chain fat acidic group imidazoline extractant
The concentration of chain fatty acid based imidazolines extractant is 1~50%.
The band side chain long-chain fat acidic group imidazoline extractant of the present invention preferably first uses inorganic acid in extraction process
Be acidified, this is basic anionic resin than more conventional acidification step, belong to it will be appreciated by those skilled in the art that model
Farmland.
The extraction of the present invention and back extraction process are typically carried out at room temperature, and split-phase is functional in extraction process, profit
Interface is clear.
Including containing the organic phase with side chain long-chain fat acidic group imidazoline extractant for the present invention is commonly used in the art dilute
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 the back extraction process of the present invention, which can use sodium hydroxide or ammoniacal liquor,
It is specifically chosen).
The mistake for extracting tungstate ion in the basic conditions with side chain long-chain fat acidic group imidazoline extractant of the present invention
Journey：Including being acidified, extracting, being stripped and regenerating (exemplified by extracting tungstate ion)；
Acidifying：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 represents extractant, and HX represents inorganic acid used during acidifying.
Extraction process is the anion exchange procedures of acid ion and metal oxygen-containing acid ion；Stripping process is to utilize pH
Rise, when destroying the ammonium salt that generation amine is formed, 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 jumpizations
Work Co., Ltd etc..
The synthetic route with side chain long-chain fat acidic group imidazoline extractant of the present invention：
Compared with the prior art, the advantageous effects that technical scheme is brought：
1) present invention's has special molecular structure with side chain long-chain fat acidic group imidazoline extractant, can wrap simultaneously
Containing primary amine, secondary amine and tertiary amine, it can improve its extracting power and capacity, and shorten the split-phase time with alkyl group of drawing money on credit.
2) reaction condition is gentle in the preparation process with side chain long-chain fat acidic group imidazoline extractant of the invention, reaction
Time is short, and imidazoline products quality is good.
3) solid catalyst is used in the preparation process with side chain long-chain fat acidic group imidazoline extractant of the invention, its
With higher catalytic activity, and possess certain acid strength and hydrophobicity, moisture-stable, avoid inactivating, it is reusable, prolong
The service life of catalyst is grown.
4) solid catalyst is used in the preparation process with side chain long-chain fat acidic group imidazoline extractant of the invention,
Reaction terminates rear and reactant and product is in two phases of solid-liquid, is easy to separate product with catalyst, to obtain high-purity
Product.
5) without equipment corrosion and environment in the preparation process with side chain long-chain fat acidic group imidazoline extractant of the invention
The problems such as pollution, low is required to equipment corrosion resistance, technological process is short, and production process is environmentally friendly, equipment investment and operation
Expense is low, and the water entrainer in water knockout drum can recycle, and section has lacked the dosage of water entrainer, reduces the production cost of product.
6) extraction for being applied to tungsten, molybdenum, vanadium anion with side chain long-chain fat acidic group imidazoline extractant of the invention, its
Loading capacity is high, and the split-phase time is short, and it is extracted and back extraction function admirable.
Brief description of the drawings
【Fig. 1】For WO in embodiment 123Extraction isotherm.
【Fig. 2】For the extraction isotherm of V in embodiment 15.
Embodiment
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 agitator, reflux condensing tube, thermometer, water knockout drum 500mL three-necked flasks in, add the different of 1.0mol
Octanoic acid, 1.2mol diethylenetriamines, appropriate nickel oxide solid catalyst.Heated with oil bath, start agitator, carried out normal
Pressure is heated to reflux stirring reaction, when question response reaches design temperature, starts timing.Reaction is respectively in 160 DEG C of reactions 3 of reaction temperature
Hour, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction terminates, after separation of solid and liquid, washing is distilled off excessive anti-
Answer raw material and reclaim except the complete raw material of unreacted is separated, that is, obtain long chain fatty acids base imidazoline.The long-chain fat acidic group miaow
The yield of oxazoline is：93.2%.
Embodiment 2：
Equipped with agitator, reflux condensing tube, thermometer, water knockout drum 500mL three-necked flasks in, add the different of 0.5mol
Hexadecylic acid, 3.0mol diethylenetriamines, the nickel oxide catalyst of recovery.Heated with oil bath, start agitator, carried out normal
Pressure is heated to reflux stirring reaction, when question response reaches design temperature, starts timing.Reaction is respectively in 160 DEG C of reactions 3 of reaction temperature
Hour, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction terminates, after separation of solid and liquid, washing is distilled off excessive anti-
Answer raw material and reclaim except the complete raw material of unreacted is separated, that is, obtain long chain fatty acids base imidazoline.The long-chain fat acidic group miaow
The yield of oxazoline is：94.3%.
Embodiment 3：
Equipped with agitator, reflux condensing tube, thermometer, water knockout drum 500mL three-necked flasks in, add the different of 0.5mol
Stearic acid, 3.0mol diethylenetriamines, appropriate cobalt oxide catalyst.Heated with oil bath, start agitator, carried out normal pressure and add
Hot return stirring reaction, when question response reaches design temperature, starts timing.Reaction is small in 160 DEG C of reactions 3 of reaction temperature respectively
When, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction terminates, after separation of solid and liquid, excessive reaction is distilled off in washing
Raw material and reclaim remove the complete raw material of Fraction collection unreacted, that is, obtain long chain fatty acids base imidazoline.The long-chain fat acidic group
The yield of imidazoline is：92.6%.
Embodiment 4：
Equipped with agitator, reflux condensing tube, thermometer, water knockout drum 500mL three-necked flasks in, add the different of 0.5mol
Stearic acid, 3.0mol diethylenetriamines, the cobalt oxide catalyst of recovery.Heated with oil bath, start agitator, carry out normal pressure
Stirring reaction is heated to reflux, when question response reaches design temperature, starts timing.Reaction is small in 160 DEG C of reactions 3 of reaction temperature respectively
When, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction terminates, after separation of solid and liquid, excessive reaction is distilled off in washing
Raw material is simultaneously reclaimed except the complete raw material of unreacted is separated, that is, obtains long chain fatty acids base imidazoline.The long-chain fat acidic group imidazoles
The yield of quinoline is：94.3%.
Embodiment 5：
Equipped with agitator, reflux condensing tube, thermometer, water knockout drum 500mL three-necked flasks in, add the different of 1.0mol
Octanoic acid, 1.2mol triethylene tetramines, appropriate nickel oxide solid catalyst.Heated with oil bath, start agitator, carried out normal
Pressure is heated to reflux stirring reaction, when question response reaches design temperature, starts timing.Reaction is respectively in 160 DEG C of reactions 3 of reaction temperature
Hour, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction terminates, after separation of solid and liquid, washing is distilled off excessive anti-
Answer raw material and reclaim except the complete raw material of unreacted is separated, that is, obtain long chain fatty acids base imidazoline.The long-chain fat acidic group miaow
The yield of oxazoline is：95.3%.
Embodiment 6：
Equipped with agitator, reflux condensing tube, thermometer, water knockout drum 500mL three-necked flasks in, add the different of 1.0mol
Octanoic acid, 1.2mol TEPAs, appropriate nickel oxide solid catalyst.Heated with oil bath, start agitator, carried out normal
Pressure is heated to reflux stirring reaction, when question response reaches design temperature, starts timing.Reaction is respectively in 160 DEG C of reactions 3 of reaction temperature
Hour, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction terminates, after separation of solid and liquid, washing is distilled off excessive anti-
Answer raw material and reclaim except the complete raw material of unreacted is separated, that is, obtain long chain fatty acids base imidazoline.The long-chain fat acidic group miaow
The yield of oxazoline is：93.8%.
Embodiment 7：
Equipped with agitator, reflux condensing tube, thermometer 500mL three-necked flasks in, add 0.5mol isomery 16
Acid, 3.0mol TEPAs.The nickel oxide solid catalyst of recovery, is heated with oil bath, starts agitator, carries out normal pressure
Stirring reaction is heated to reflux, when question response reaches design temperature, starts timing.Reaction is small in 120 DEG C of reactions 3 of reaction temperature respectively
When, 140 DEG C are reacted 3 hours, and 160 DEG C are reacted 3 hours.After reaction terminates, excessive reaction raw materials and recovery is distilled off in washing
Except the complete raw material of unreacted is separated, that is, obtain long chain fatty acids amides derivative.The receipts of the long chain fatty acids amides derivative
Rate is：95.2%.
Embodiment 8：
Equipped with agitator, reflux condensing tube, thermometer, water knockout drum 500mL three-necked flasks in, add the different of 0.5mol
Stearic acid, 3.0mol diethylenetriamines, the cobalt oxide catalyst of recovery.Heated with oil bath, start agitator, carry out normal pressure
Stirring reaction is heated to reflux, when question response reaches design temperature, starts timing.Reaction is small in 160 DEG C of reactions 3 of reaction temperature respectively
When, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction terminates, after separation of solid and liquid, excessive reaction is distilled off in washing
Raw material is simultaneously reclaimed except the complete raw material of unreacted is separated, that is, obtains long chain fatty acids base imidazoline.The long-chain fat acidic group imidazoles
The yield of quinoline is：93.8%.
Embodiment 9：
Equipped with agitator, reflux condensing tube, thermometer, water knockout drum 500mL three-necked flasks in, add the different of 0.5mol
Stearic acid, 3.0mol diethylenetriamines, load nickel oxide catalyst.Heated with oil bath, start agitator, carried out normal pressure and add
Hot return stirring reaction, when question response reaches design temperature, starts timing.Reaction is small in 160 DEG C of reactions 3 of reaction temperature respectively
When, 180 DEG C are reacted 3 hours, and 200 DEG C are reacted 3 hours.After reaction terminates, after separation of solid and liquid, excessive reaction is distilled off in washing
Raw material and reclaim separate the complete raw material of unreacted, that is, obtain long chain fatty acids base imidazoline.The long-chain fat acidic group imidazoline
Yield be：94.2%.
Embodiment 10：
Aqueous phase liquid：The actual feed liquid of industry, feed liquid concentration containing tungstic acid are：116.25g·L-1, pH 13.34；
Organic phase：Configuration numbering is respectively five kinds of 1~5 different organic phases of composition, 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 derive
Isooctanol+sulfonated kerosene of the volume fraction of thing extractant+25%, long chain fatty acids made from the example 4 of No. 3 30% volume fractions
Isooctanol+sulfonated kerosene of the volume fraction of amide derivatives extractant+25%, length made from the example 4 of No. 4 40% volume fractions
Isooctanol+sulfonated kerosene of the volume fraction of chain fatty acid amide derivatives extractant+25%, the example 4 of No. 5 50% volume fractions
Isooctanol+sulfonated kerosene of the obtained volume fraction of long chain fatty acids amides derivative extractant+25%.Experiment extraction used
Agent belongs to new amine extractant, it is therefore desirable to acidification.Acidization 0.6molL-1Sulfuric acid with O/A2:1 is carried out
Acidifying.
Extraction：Above-mentioned five kinds of organic phases respectively with feed liquid at 25 DEG C (O/A) 1 compared with:1st, incorporation time 10min, shake
Leaching extraction experimental result is as shown in table 1 below under the conditions of swinging frequency 200r/min.
Influence of the extractant of the various concentrations of table 1 to tungsten extraction yield
| Organic phase is numbered | 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 with the volume fraction increase of organic phase, the single-stage extraction rate of tungsten also increases as, split-phase
Time also extends.Meanwhile find that this is due to the increasing of extractant ratio as organic phase concentration increases in experimentation
Add, profit split-phase effect is deteriorated.
Embodiment 11：
Aqueous phase liquid：The actual 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, 1~6 is ordered as according to this from low to high；
Organic phase：The volume integral of long chain fatty acids amides derivative extractant+25% made from the example 4 of 40% volume fraction
Several isooctanol+sulfonated kerosenes.
Extraction：Above-mentioned organic phase is being in a ratio of 1 with adjusting pH feed liquid with sulfuric acid respectively:Single-stage extraction is carried out under conditions of 1
Take, 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 aqueous phase pH tungsten extraction yields of table 2
| Aqueous phase is numbered | 1 | 2 | 3 | 4 | 5 | 6 |
| Aqueous 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 as the reduction of material liquid pH, the single-stage extraction rate of tungsten gently reduce first, after drastically decline, pH is
When 12, extraction yield, which declines, to tend to be steady, pH increases backward, and extraction yield change 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.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, the moon can not be carried out
Ion exchange extracting power weakens.
Embodiment 12：
Aqueous phase liquid：The actual 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：The volume integral of long chain fatty acids amides derivative extractant+25% made from the example 4 of 40% volume fraction
Several isooctanol+sulfonated kerosenes.
Extraction：Organic phase is 8.27,25 DEG C, compared to (O/A) 1 in material liquid pH:2nd, 25 DEG C, incorporation time 10min, vibration
Contacted under conditions of being carried out under frequency 200r/min the same terms with more parts of fresh feed liquids, until organic phase saturation.It is real
Result is tested to be illustrated in fig. 1 shown below.
It can be seen from the saturation extraction isotherm in Fig. 1, the extraction of 40% (volume fraction) long chain fatty acids amides derivative
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, containing WO3 109.03g·L-1
Strip liquor：Using ammoniacal liquor as strip liquor, it is respectively 1~6 that concentration configures numbering from low to high.
Back extraction：Above-mentioned organic phase respectively with strip liquor compared with (O/A) 1:2nd, 25 DEG C, incorporation time 10min, frequency of oscillation
Back extraction experiment is carried out under 200r/min the same terms.Experimental result such as table 3 below.
Influence of the strip liquor of the various concentrations of table 3 to tungsten back extraction ratio
| Strip liquor is numbered | 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 substantially rises, when ammonia concn is
0.5mol·L-1When, back extraction ratio is only 35%, increase ammonia concn to 1.0molL-1When, back extraction ratio rises very rapidly up to 75%
Left and right, continue to increase ammonia concn, increase 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 lengthening after ammonia concn raises.When back extraction, ammonia concn reaches 3molL-1, have in raffinate
Floccule separates out.The reason for analysis is likely to occur floccule is probably that the tungstate ion in strip liquor is combined life with ammonium ion
Into wolframic acid crystalline ammonium.
Embodiment 14：
Aqueous phase liquid：The vanadic anhydride and sodium molybdate predominantly dissolved with sodium hydroxide, wherein molybdenum concentration are
101.37g/L, vanadium concentration are about 9.53g/L, pH 8.21.
Organic phase：Configuration numbering is respectively five kinds of 1~5 different organic phases of composition, 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 derive
Isooctanol+sulfonated kerosene of the volume fraction of thing extractant+20%, long chain fatty acids made from the example 4 of No. 3 20% volume fractions
Isooctanol+sulfonated kerosene of the volume fraction of amide derivatives extractant+20%, length made from the example 4 of No. 4 25% volume fractions
Isooctanol+sulfonated kerosene of the volume fraction of chain fatty acid amide derivatives extractant+20%, the example 4 of No. 5 30% volume fractions
Isooctanol+sulfonated kerosene of the obtained volume fraction of long chain fatty acids amides derivative extractant+20%.Experiment extraction used
Agent belongs to new amine extractant, it is therefore desirable to acidification.Acidization 0.6molL-1Sulfuric acid with O/A2:1 is carried out
Acidifying.
Extraction：Above-mentioned five kinds of organic phases respectively with feed liquid at 25 DEG C (O/A) 1 compared with:1st, incorporation time 10min, shake
Leaching extraction experimental result is as shown in table 4 below under the conditions of swinging frequency 200r/min.
Influence of the extractant of the various concentrations of table 4 to Mo, V extraction yield
| Organic phase is numbered | 1 | 2 | 3 | 4 | 5 |
| Mo extraction yield (%) | 15.49 | 17.85 | 16.39 | 38.39 | 45.46 |
| V extraction yield (%) | 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：The volume integral of long chain fatty acids amides derivative extractant+20% made from the example 4 of 20% volume fraction
Several isooctanol+sulfonated kerosenes.
Extraction：Organic phase is 8.21,25 DEG C, compared to (O/A) 1 in material liquid pH:1st, 25 DEG C, incorporation time 10min, vibration
Contacted under conditions of being carried out under frequency 200r/min the same terms with more parts of fresh feed liquids, until organic phase saturation.It is real
Result is tested to be illustrated in fig. 2 shown below.
It can be seen from the saturation extraction isotherm in Fig. 2, the extraction of 20% (volume fraction) long chain fatty acids amides derivative
Agent has very strong effect of extracting and higher saturated capacity to the oxygen-containing acid ion of vanadium under this condition, reaches after extracting four times
Balance, extraction saturated capacity is 20.23gL-1。
Embodiment 16：
Aqueous phase liquid：The actual feed liquid of industry, feed liquid concentration containing tungstic acid are：116.25g·L-1, pH 13.34；
Organic phase：Configure the volume integral of long chain fatty acids amides derivative extractant+25% made from the example 5 of volume fraction
Several isooctanol+sulfonated kerosenes, test extractant used and belong to new amine extractant, it is therefore desirable to acidification.Acidifying
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:1st, incorporation time 10min, shake
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 profit circle
Face.
Claims (10)
- A kind of 1. band side chain long-chain fat acidic group imidazoline extractant, it is characterised in that：With the structure of formula 1：Wherein,N is 4~10；M is 4~10；P is 1~3.
- 2. the preparation method with side chain long-chain fat acidic group imidazoline extractant described in claim 1, it is characterised in that：Normal Pressure, by the carboxylic acid of formula 2 and the polyethylene polyamine of formula 3 under solid catalyst effect, reacted at 160 DEG C~220 DEG C, reaction is completed Afterwards, separation of solid and liquid recovery solid catalyst, liquid mixture are recovered by distillation the complete raw material of unreacted, produced；Wherein,N is 4~10；M is 4~10；P is 1~3.
- 3. the preparation method according to claim 2 with side chain long-chain fat acidic group imidazoline extractant, it is characterised in that： The mol ratio of the carboxylic acid of formula 2 and the polyethylene polyamine of formula 3 is 1:1~6.
- 4. the preparation method with side chain long-chain fat acidic group imidazoline extractant according to Claims 2 or 3, its feature exist In：The quality of the solid catalyst is the 1%~5% of the carboxylic acid of formula 2 and the polyethylene polyamine gross mass of formula 3.
- 5. the preparation method according to claim 4 with side chain long-chain fat acidic group imidazoline extractant, it is characterised in that： The solid catalyst is at least one of nickel oxide, cobalt oxide, carried catalyst containing nickel oxide and/or cobalt oxide.
- 6. the preparation method with side chain long-chain fat acidic group imidazoline extractant according to claim 2,3 or 5, its feature It is：Using water caused by water knockout drum separation reaction in the course of reaction.
- 7. the preparation method with side chain long-chain fat acidic group imidazoline extractant according to claim 2,3 or 5, its feature It is：The time of the reaction is 4~10 hours.
- 8. the application with side chain long-chain fat acidic group imidazoline extractant described in claim 1, it is characterised in that：Applied to extraction At least one of tungstenic anion in aqueous system, anion containing molybdenum, anion containing vanadium.
- 9. the application according to claim 8 with side chain long-chain fat acidic group imidazoline extractant, it is characterised in that：Using It is 6~12 to pH, the aqueous liquid that temperature is 5~40 DEG C containing the organic phase with side chain long-chain fat acidic group imidazoline extractant At least one of tungstenic anion in system, anion containing molybdenum, anion containing vanadium are extracted, and extraction organic phase is anti-using alkali lye Extraction, obtains the enrichment solution of at least one of tungstenic anion, anion containing molybdenum, anion containing vanadium.
- 10. the application according to claim 9 with side chain long-chain fat acidic group imidazoline extractant, it is characterised in that：Institute State containing the side chain long-chain fat acidic group imidazoline extractant containing band in the organic phase with side chain long-chain fat acidic group imidazoline extractant Concentration be 1~50%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109022797A (en) * | 2018-08-24 | 2018-12-18 | 肇庆市珈旺环境技术研究院 | A method of separating and recovering molybdenum and vanadium for the mixing amine extractant of molybdenum vanadium separation and from dead catalyst |
| CN109868363A (en) * | 2019-04-04 | 2019-06-11 | 中南大学 | The method of extraction and separation tungsten from molybdate solution |
| 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 |
| CN115094251A (en) * | 2022-07-06 | 2022-09-23 | 中国原子能科学研究院 | Method for separating molybdenum-99 as radioactive fission product |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340744A (en) * | 1980-03-13 | 1982-07-20 | Basf Aktiengesellschaft | Preparation of imidazoles |
| SU1109368A1 (en) * | 1982-01-05 | 1984-08-23 | Уфимский Нефтяной Институт | Process for isolating high-molecular aromatic hydrocarbons from hydrocarbon mixtures |
| CN101723899A (en) * | 2008-10-27 | 2010-06-09 | 西安万德化工有限公司 | Imidazoline derivative and preparation method thereof as well as petroleum refining auxiliary agent containing compound |
| CN102190454A (en) * | 2010-03-12 | 2011-09-21 | 中国科学院金属研究所 | Doped all organic corrosion inhibitor for steel bar in concrete |
| CN102603640A (en) * | 2011-01-20 | 2012-07-25 | 天津瓦同化学品有限公司 | Synthesis method of hydroxyl(amino) ethyl alkyl imidazoline surfactant |
| CN103588710A (en) * | 2013-10-17 | 2014-02-19 | 中国石油化工股份有限公司 | Method for synthesizing imidazoline compound by microwave |
-
2017
- 2017-07-31 CN CN201710639776.1A patent/CN107385211B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340744A (en) * | 1980-03-13 | 1982-07-20 | Basf Aktiengesellschaft | Preparation of imidazoles |
| SU1109368A1 (en) * | 1982-01-05 | 1984-08-23 | Уфимский Нефтяной Институт | Process for isolating high-molecular aromatic hydrocarbons from hydrocarbon mixtures |
| CN101723899A (en) * | 2008-10-27 | 2010-06-09 | 西安万德化工有限公司 | Imidazoline derivative and preparation method thereof as well as petroleum refining auxiliary agent containing compound |
| CN102190454A (en) * | 2010-03-12 | 2011-09-21 | 中国科学院金属研究所 | Doped all organic corrosion inhibitor for steel bar in concrete |
| CN102603640A (en) * | 2011-01-20 | 2012-07-25 | 天津瓦同化学品有限公司 | Synthesis method of hydroxyl(amino) ethyl alkyl imidazoline surfactant |
| CN103588710A (en) * | 2013-10-17 | 2014-02-19 | 中国石油化工股份有限公司 | Method for synthesizing imidazoline compound by microwave |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109022797A (en) * | 2018-08-24 | 2018-12-18 | 肇庆市珈旺环境技术研究院 | A method of separating and recovering molybdenum and vanadium for the mixing amine extractant of molybdenum vanadium separation and from dead catalyst |
| CN109022797B (en) * | 2018-08-24 | 2020-07-07 | 肇庆市珈旺环境技术研究院 | Mixed amine extractant for molybdenum-vanadium separation and method for separating and recovering molybdenum and vanadium from waste catalyst |
| CN109868363A (en) * | 2019-04-04 | 2019-06-11 | 中南大学 | The method of extraction and separation tungsten from molybdate solution |
| 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 |
| CN115094251A (en) * | 2022-07-06 | 2022-09-23 | 中国原子能科学研究院 | Method for separating molybdenum-99 as radioactive fission product |
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