CN115724765B - Method for purifying aromatic hydroxamic in aromatic hydroxamic extractant - Google Patents
Method for purifying aromatic hydroxamic in aromatic hydroxamic extractant Download PDFInfo
- Publication number
- CN115724765B CN115724765B CN202110989604.3A CN202110989604A CN115724765B CN 115724765 B CN115724765 B CN 115724765B CN 202110989604 A CN202110989604 A CN 202110989604A CN 115724765 B CN115724765 B CN 115724765B
- Authority
- CN
- China
- Prior art keywords
- aromatic hydroxamic
- aromatic
- organic phase
- extractant
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000012074 organic phase Substances 0.000 claims abstract description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 20
- 239000002244 precipitate Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000012071 phase Substances 0.000 claims abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 26
- 238000004821 distillation Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005191 phase separation Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000007792 addition Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 23
- 238000000605 extraction Methods 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 238000011160 research Methods 0.000 abstract description 7
- 238000012512 characterization method Methods 0.000 abstract description 3
- 239000004480 active ingredient Substances 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 150000002923 oximes Chemical class 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- JWLRQNQOJOZVOX-UHFFFAOYSA-N 2-(N-hydroxy-C-methylcarbonimidoyl)-4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C(C(C)=NO)=C1 JWLRQNQOJOZVOX-UHFFFAOYSA-N 0.000 description 1
- JWLRQNQOJOZVOX-NBVRZTHBSA-N 2-[(E)-N-hydroxy-C-methylcarbonimidoyl]-4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C(=C1)C(\C)=N\O JWLRQNQOJOZVOX-NBVRZTHBSA-N 0.000 description 1
- MJUVQSGLWOGIOB-GHRIWEEISA-N 2-[(E)-hydroxyiminomethyl]-4-nonylphenol Chemical compound [H]\C(=N/O)C1=CC(CCCCCCCCC)=CC=C1O MJUVQSGLWOGIOB-GHRIWEEISA-N 0.000 description 1
- GZIPTYFZCAFRFL-UHFFFAOYSA-N 2-[N-hydroxy-C-(2-hydroxy-5-nonylphenyl)carbonimidoyl]-4-nonylphenol Chemical compound OC1=C(C=C(C=C1)CCCCCCCCC)C(=NO)C1=C(C=CC(=C1)CCCCCCCCC)O GZIPTYFZCAFRFL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a purification method of aromatic hydroxamic in an aromatic hydroxamic extractant, which comprises the following steps: 1) Adding sodium hydroxide into the aromatic hydroxamic extraction agent to form colloidal precipitate, and separating from the diluent; 2) Adding hexane into the precipitate, mixing, standing, separating upper hexane layer, repeating until hexane is colorless, and removing liquid phase; 3) Adding hexane into the residual precipitate, adding low-concentration inorganic acid, and fully mixing to obtain free aromatic hydroxamic; 4) Fully mixing the free aromatic hydroxamic and the low-concentration inorganic acid, separating phases, and repeating the above processes for a plurality of times until the organic phase is clear; 5) Fully mixing and phase-separating the pickled aromatic hydroxamic and deionized water for a plurality of times, and removing free inorganic acid in an organic phase; 6) And distilling the separated organic phase to obtain the purified aromatic hydroxamic. The aromatic hydroxamic with higher purity can be obtained through the purification treatment of the invention, and is used for experimental research and characterization with higher requirement on the purity of the organic phase.
Description
Technical Field
The invention belongs to the technical field of extraction and separation, and relates to a purification method of an aromatic hydroxamic extraction agent.
Background
In order to meet the requirements of clean and efficient extraction and green development of the current mineral resources, a wet smelting technology for extracting metals such as copper, nickel and the like from low-grade refractory ore dressing by adopting a leaching-extraction-electrodeposition method is one of important methods for industrially producing copper and nickel. Among them, solvent extraction is a key step in wet smelting, and the extractant plays an important role in the extraction process. The hydroximic extractant is one of the most widely used extractants in the industry at present, has the characteristics of high extraction efficiency, excellent selectivity, stable structure and the like, and plays an indispensable important role in the field of metal separation of copper, nickel, cobalt and the like. Common hydroxamic extraction agents mainly include LIX63 (5, 8-diethyl-7-hydroxy-dodecane-6-oxime), LIX84 (1- (2-hydroxy-5-nonylphenyl) ethanone oxime), LIX860 (2-hydroxy-5-nonylbenzaldehyde oxime), ACORGA P50 (2-hydroxybenzaldehyde oxime), and the like.
However, in the current process of synthesizing hydroxamic, the purity of the obtained product is generally 80% -95%, and the hydroxamic with the purity of more than 95% is not yet seen. Commercial hydroxamic extractant products in the market mostly take hydroxamic as an active ingredient, and high-voltage lightning kerosene and the like are added as a mixture of hydrocarbon diluents, and the extractants have good effects in the fields of nonferrous metal smelting, circuit board ammonia immersion liquid copper recovery, electroplating wastewater extraction, heavy metal recovery and the like. However, in experimental studies, some of the study methods are as follows: electrochemical working stations, extract structure characterization and the like have higher requirements on the purity of an organic phase, and components such as diluents except for effective components contained in industrial extractants can interfere with experimental results.
In view of the above, there is a need for purification of an aromatic hydroxamic in an aromatic hydroxamic extractant to obtain an aromatic hydroxamic for extraction with high purity required for experimental investigation.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a method for purifying an aromatic hydroxamic in an aromatic hydroxamic extraction agent, which can separate an active ingredient in the aromatic hydroxamic extraction agent from other impurity components such as diluents and modifiers to improve the purity of the aromatic hydroxamic as an extraction agent.
In order to achieve the above object, the present invention provides a method for purifying an aromatic hydroxamic in an aromatic hydroxamic extractant, comprising the steps of:
(1) Precipitation: adding 5-40g/L sodium hydroxide solution into the aromatic hydroxamic extractant to form colloidal precipitate of the aromatic hydroxamic in the aromatic hydroxamic extractant, and separating the colloidal precipitate from the diluent in the aromatic hydroxamic extractant, wherein the volume ratio of the sodium hydroxide solution to the aromatic hydroxamic extractant is 1:0.5-1:5;
(2) Washing and precipitating: adding hexane into the precipitate, fully shaking and mixing, standing, and separating and removing hexane on the upper layer after standing; then repeating the washing process for 1-20 times until hexane is colorless, and discarding hexane; wherein the volume ratio of hexane to the aromatic hydroxamic extractant is 1:0.1-1:10;
(3) And (3) redissolving: adding hexane into the residual precipitate, and then adding an inorganic acid solution with the volume percentage concentration of 10-40% and fully mixing to obtain an organic phase containing free aromatic hydroxamic acid, wherein the volume ratio of hexane to the aromatic hydroxamic acid extractant is 1:0.1-1:10, and the volume ratio of the inorganic acid solution to the aromatic hydroxamic acid extractant is 1:1-10:1;
(4) Acid washing: fully mixing an organic phase containing free aromatic hydroxamic and an inorganic acid solution with the volume percentage concentration of 10-40% according to the volume ratio of 1:1-1:10, separating phases, taking the organic phase after the phases are separated, discarding the aqueous phase, and repeating the process for 1-10 times until the organic phase is clear;
(5) Washing: fully mixing the pickled aromatic hydroxamic and deionized water according to the volume ratio of 1:0.5-1:5, standing for phase separation to obtain an organic phase and a water phase, discarding the water phase, and reserving the organic phase to remove free inorganic acid in the organic phase;
(6) And (3) distilling: distilling the organic phase after phase separation in the step (5), wherein the distillation temperature in the first stage is 65-75 ℃, collecting the target product hexane in the stage when the temperature rises to a certain temperature and is kept unchanged, and finishing the distillation in the stage when the temperature continues to rise; the second stage distillation temperature is 95-105 ℃, when the temperature rises to a certain temperature and is kept unchanged, the target product water of the stage is collected, and when the temperature continues to rise, the distillation of the stage is finished. After the distillation of water and hexane is completed, the distillation is stopped, and the remaining liquid phase is purified aromatic hydroxamic.
Further, the aromatic hydroxamic has a structure according to formula (I):
wherein R represents alkyl, and the number of carbon atoms is 1-12; r' represents a hydrogen atom or a methyl group.
It is to be noted that when R 'is a hydrogen atom, it is called an aldoxime (also called a aldoxime), and when R' is a methyl group, it is called a ketoxime (also called a ketoxime).
Further, the inorganic acid is sulfuric acid or hydrochloric acid
Still further, the method for adding the inorganic acid in the step (3) comprises the following steps: the inorganic acid with a certain volume is measured by a measuring cylinder, then slowly added by a dropper for 1-20 times, stirred by a glass stirring rod for 0.5-30min after each addition, and then added next time.
Further, in the step (5), the number of repetitions of the phase separation by mixing the aromatic hydroxamic and deionized water is 1 to 10.
Still further, the step (5) is followed by the following steps: centrifuging the organic phase at 4-60deg.C and 1000-10000r/min for 1-120min, collecting the upper clear organic phase, and distilling in step (6).
In the purification process of the aromatic hydroxamic in the aromatic hydroxamic extractant provided by the invention, firstly, sodium hydroxide and the aromatic hydroxamic are used for precipitation, and the reaction formula (1) is as follows:
HL+NaOH→NaL↓+H 2 o (wherein HL represents an aromatic hydroxamic acid) (1)
The precipitate is then washed with hexane to remove impurity components, such as diluents, from the precipitate.
And then hexane is used as a solvent, and the precipitate is reconverted into an organic phase containing liquid aromatic hydroxamic acid in a mode of adding organic acid, wherein the reaction formula (2) is as follows:
NaL+H + →HL+Na + (2)
and then distilling the organic phase to remove hexane and water in the organic phase to obtain the aromatic hydroxamic with higher purity.
The invention adds low concentration inorganic acid, which releases a large amount of heat in the acid adding process, and adds inorganic acid a little times and slowly to prevent the solution from overheating and make the inorganic acid fully contact with the sediment, thereby obtaining more free oxime as much as possible and preventing the free oxime from being separated from the water phase due to emulsification.
The invention limits the distillation temperature, and the separation of the hydroxamic and hexane and water can be strictly controlled by the distillation temperature, so that the purity of the aromatic hydroxamic is improved as much as possible.
The beneficial effects of the invention are as follows:
according to the purification method of the aromatic hydroxamic in the aromatic hydroxamic extractant, the aromatic hydroxamic is purified by methods such as precipitation separation and distillation, so that the relatively pure aromatic hydroxamic is obtained, the laboratory scientific research standard is met, the interference of components, such as diluents except effective components, contained in the industrial extractant on scientific research results is reduced, and the method can be used for experimental research and characterization research with relatively high requirements on the purity of an organic phase. The preparation process disclosed by the invention is simple to operate, easy to control conditions and low in cost, is suitable for large-scale purification of the extractant, and has a wide application value.
Drawings
Fig. 1 is a process flow diagram of a method for purifying an aromatic hydroxamic in an aromatic hydroxamic extractant according to the present invention.
FIG. 2A is a nuclear magnetic resonance hydrogen spectrum of the pre-purification extractant Mextral 84H in example 1.
FIG. 2B is a nuclear magnetic resonance hydrogen spectrum of the purified extractant Mextral 84H of example 1.
FIG. 3A is a nuclear magnetic resonance hydrogen spectrum of the pre-purification extractant Mextral 860H in example 2.
FIG. 3B is a nuclear magnetic resonance hydrogen spectrum of the purified extractant Mextral 860H of example 2.
Detailed Description
The invention is further illustrated by the following examples, which are not meant to limit the scope of the invention.
A process flow diagram of the present invention is shown in fig. 1.
The reagents used in the invention are all commercial products.
The metal extractants Mextral 84H, mextral 860H were all purchased from Chongqing Kangpu chemical industries, inc.
Example 1
The Mextral 84H metal extractant is compounded by taking ketoxime (2-hydroxy-5-nonylphenyl ketoxime) as an active ingredient and adding a surfactant, a modifier and the like.
The specific procedure for purification of ketoxime in extractant Mextral 84H is shown in fig. 1:
(1) Separating effective components
To 50mL of the extractant Mextral 84H was added 40mL of 25g/L sodium hydroxide solution to form a colloidal precipitate of 2-hydroxy-5-nonylphenyl ethanone oxime which was separated from the diluent 260# sulphonated kerosene.
(2) Washing the precipitate
Adding 10mL of hexane into the precipitate, fully shaking and mixing, standing, separating and removing hexane at the upper layer after standing, repeating for 5 times until hexane is colorless, and removing hexane at the upper layer liquid phase;
(3) Obtaining the free oxime
10mL of hexane was added to the remaining precipitate, followed by 5 additions of 80mL of 25% dilute sulfuric acid, 15-20mL each, with the first 3 precipitation reactions and the second 2 acid washes to give the free aromatic hydroxamic. After each addition, the mixture was stirred with a glass stirring bar for 2min, and then the next addition was performed.
(4) Phase separation
The free aromatic hydroxamic is thoroughly mixed with 20mL of 25% dilute sulfuric acid and then phase separated, and the above procedure is repeated 5-10 times until the organic phase is clear.
(5) Washing
The organic phase containing the aromatic hydroxamic acid was rinsed with 20mL of deionized water, 5-10 total times, to remove free acid.
(6) Distillation
The remaining organic phase was distilled at 68℃with hexane collected, water collected at 100℃and distilled off after continued increase in temperature, and the remaining liquid phase was purified aromatic hydroxamic acid.
Example 2
This embodiment differs from embodiment 1 in that: the purified extractant is Mextral 860H (active ingredient 2-hydroxy-5-dodecanesalicylaldoxime), after step (5), the organic phase is required to be centrifuged at 4 ℃ and 8000r/min for 5min, and after centrifugation, the upper clear organic phase is taken and distilled in step (6). The other steps were the same as in example 1.
Since the organic phase and the aqueous phase of the active ingredient in Mextral 84H are well separated, and the organic phase and the aqueous phase of the active ingredient in Mextral 860H are poorly separated, a partial precipitate, which is a component that is not reduced to free oxime, is also mixed in the organic phase, and the precipitate cannot be completely reacted with the inorganic acid due to the nature of Mextral 860H itself, resulting in the case of residual partial precipitation, thus adding a centrifugation step to enhance the separation effect.
Therefore, whether to add a centrifugation step or not is judged according to the separation effect of the organic phase and the water phase in different aromatic hydroxamic extraction agents, and the centrifugation condition is determined.
Nuclear magnetic resonance was performed on the active ingredients before and after purification of the extractant Mextral 84H, mextral H in example 1 and example 2, and the peak areas of the peaks in the active ingredients before and after purification were compared, and the results are shown in FIG. 2A, FIG. 2B, FIG. 3A, and FIG. 3B.
As shown in fig. 2A, in the nuclear magnetic resonance hydrogen spectrum of unpurified Mextral 84H, the chemical shifts δ9.13 and δ11.27 are H of phenolic hydroxy-OH and H of oxime hydroxy-c=noh, respectively; in the nmr hydrogen spectrum of Mextral 84H after purification as shown in fig. 2B, the chemical shifts δ9.30 and δ11.35 are H of phenolic hydroxyl-OH and H of oxime hydroxyl-c=noh, respectively, and the results are not greatly different before and after purification, and the purification process does not affect the active ingredients of the extractant.
As shown in fig. 3A, in the nuclear magnetic resonance hydrogen spectrum of unpurified Mextral 860H, chemical shifts δ1.97 and δ8.27 are H of phenolic hydroxy-OH and H of oxime hydroxy-c=noh, respectively; in the nmr hydrogen spectrum of Mextral 860H after purification as shown in fig. 3B, the chemical shifts δ1.97 and δ8.24 are H of phenolic hydroxyl-OH and H of oxime hydroxyl-c=noh, respectively, and the results are not greatly different before and after purification, and the purification process does not affect the active ingredients of the extractant.
The nuclear magnetic resonance hydrogen spectrogram shows the number of atoms in the same environment, the larger the peak area is, the more atoms are in the environment, and the larger the peak area corresponding to the larger number of atoms in the same environment is due to the influence of impurities before purification; the content of impurities after purification is lower, the number of atoms in the same environment is reduced, and the corresponding peak area is reduced, so that the purification is purer.
As can be seen from comparison of fig. 2A, fig. 2B, fig. 3A and fig. 3B, the peak areas of the peaks in the nmr hydrogen spectrum of the active ingredient in the purified extractant are reduced compared with those before purification, which indicates that the active ingredient in the purified extractant is purer, and the purer active ingredient has lower interference to experimental results in scientific research. The purification method provided by the invention does not influence the structure of active ingredients, and can purify the commercialized extractant with lower purity into ingredients with higher purity so as to meet scientific research requirements.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (5)
1. A method for purifying an aromatic hydroxamic acid in an aromatic hydroxamic acid extractant, comprising the steps of:
(1) Precipitation: adding 5-40g/L sodium hydroxide solution into the aromatic hydroxamic extractant to form colloidal precipitate of the aromatic hydroxamic in the aromatic hydroxamic extractant, and separating the colloidal precipitate from the diluent in the aromatic hydroxamic extractant, wherein the volume ratio of the sodium hydroxide solution to the aromatic hydroxamic extractant is 1:0.5-1:5;
(2) Washing and precipitating: adding hexane into the precipitate, fully shaking and mixing, standing, and separating and removing hexane on the upper layer after standing; then repeating the washing process for 1-20 times until hexane is colorless, and discarding hexane; wherein the volume ratio of hexane to the aromatic hydroxamic extractant is 1:0.1-1:10;
(3) And (3) redissolving: adding hexane into the residual precipitate, and then adding an inorganic acid solution with the volume percentage concentration of 10-40% and fully mixing to obtain an organic phase containing free aromatic hydroxamic acid, wherein the volume ratio of hexane to the aromatic hydroxamic acid extractant is 1:0.1-1:10, and the volume ratio of the inorganic acid solution to the aromatic hydroxamic acid extractant is 1:1-10:1;
(4) Acid washing: fully mixing an organic phase containing free aromatic hydroxamic and an inorganic acid solution with the volume percentage concentration of 10-40% according to the volume ratio of 1:1-1:10, separating phases, taking the organic phase after the phases are separated, discarding the aqueous phase, and repeating the process for 1-10 times until the organic phase is clear;
(5) Washing: fully mixing the pickled aromatic hydroxamic and deionized water according to the volume ratio of 1:0.5-1:5, standing for phase separation to obtain an organic phase and a water phase, discarding the water phase, and reserving the organic phase to remove free inorganic acid in the organic phase;
(6) And (3) distilling: distilling the organic phase after phase separation in the step (5), wherein the distillation temperature in the first stage is 65-75 ℃, collecting the target product hexane in the stage when the temperature rises to a certain temperature and is kept unchanged, and finishing the distillation in the stage when the temperature continues to rise; the second stage distillation temperature is 95-105 ℃, when the temperature rises to a certain temperature and is kept unchanged, the target product water of the stage is collected, and when the temperature continues to rise, the distillation of the stage is finished; after the distillation of water and hexane is completed, stopping the distillation, wherein the residual liquid phase is purified aromatic hydroxamic;
the structure of the aromatic hydroxamic is shown as a formula (I):
wherein R represents alkyl, and the number of carbon atoms is 1-12; r' represents a hydrogen atom or a methyl group.
2. The method for purifying an aromatic hydroxamic acid in an aromatic hydroxamic acid extractor according to claim 1, wherein the mineral acid in step (3) is sulfuric acid or hydrochloric acid.
3. The method for purifying an aromatic hydroxamic acid in an aromatic hydroxamic acid according to claim 1, wherein the method for adding the inorganic acid in the step (3) comprises: the inorganic acid with a certain volume is measured by a measuring cylinder, then slowly added by a dropper for 1-20 times, stirred by a glass stirring rod for 0.5-30min after each addition, and then added next time.
4. The method for purifying an aromatic hydroxamic acid according to claim 1, wherein the step (5) is carried out in a manner such that the number of repetitions of the phase separation by mixing the aromatic hydroxamic acid with deionized water is 1 to 10.
5. The method for purifying an aromatic hydroxamic acid in an aromatic hydroxamic acid extractant according to claim 1, wherein the step (5) is followed by the step of: centrifuging the organic phase at 4-60deg.C and 1000-10000r/min for 1-120min, collecting the upper clear organic phase, and distilling in step (6).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110989604.3A CN115724765B (en) | 2021-08-26 | 2021-08-26 | Method for purifying aromatic hydroxamic in aromatic hydroxamic extractant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110989604.3A CN115724765B (en) | 2021-08-26 | 2021-08-26 | Method for purifying aromatic hydroxamic in aromatic hydroxamic extractant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115724765A CN115724765A (en) | 2023-03-03 |
| CN115724765B true CN115724765B (en) | 2024-02-20 |
Family
ID=85290033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110989604.3A Active CN115724765B (en) | 2021-08-26 | 2021-08-26 | Method for purifying aromatic hydroxamic in aromatic hydroxamic extractant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115724765B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103320612A (en) * | 2013-06-26 | 2013-09-25 | 中国科学院过程工程研究所 | Tungsten-molybdenum separation method for extracting solution containing tungsten-molybdenum acid salt employing serotonin-hydroximic extractant |
| CN110205492A (en) * | 2019-07-03 | 2019-09-06 | 内蒙古科技大学 | Reduce the method and its application of hydroxyl oxime extractant nitrification degradation |
-
2021
- 2021-08-26 CN CN202110989604.3A patent/CN115724765B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103320612A (en) * | 2013-06-26 | 2013-09-25 | 中国科学院过程工程研究所 | Tungsten-molybdenum separation method for extracting solution containing tungsten-molybdenum acid salt employing serotonin-hydroximic extractant |
| CN110205492A (en) * | 2019-07-03 | 2019-09-06 | 内蒙古科技大学 | Reduce the method and its application of hydroxyl oxime extractant nitrification degradation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115724765A (en) | 2023-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6556685B2 (en) | Platinum extractant, platinum extraction method, and platinum recovery method | |
| EP1115891A1 (en) | Process for extracting and recovering copper | |
| CN112981139B (en) | Hydrophobic eutectic solvent for separating nickel and cobalt ions, preparation method thereof and method for separating nickel and cobalt ions | |
| CN112320860B (en) | Method for purifying nickel sulfate | |
| CA2400673A1 (en) | Process for recovery of metals from metal-containing ores | |
| CN106906369A (en) | The technique that a kind of utilization synergic solvent extraction technology reclaims copper, zinc, nickel, cadmium from heavy metal wastewater thereby | |
| KR910001610B1 (en) | Callium complexes and solvent extration of gallium | |
| JP2017165995A (en) | Method for refining scandium | |
| CN115724765B (en) | Method for purifying aromatic hydroxamic in aromatic hydroxamic extractant | |
| CN114436997A (en) | Amide ionic liquid, synthesis method thereof and application thereof in gold extraction and separation | |
| CN112501445A (en) | Method for preparing battery-grade nickel-cobalt-manganese | |
| CN113736995A (en) | Application of carboxylic acid compound as extracting agent and metal ion extraction method | |
| CN115161481A (en) | Method for recovering waste nickel catalyst | |
| CN111961849B (en) | Method for extracting and separating scandium | |
| US4194905A (en) | Solvent-extraction process for recovery and separation of metal values | |
| US3878286A (en) | Process for recovering copper from aqueous solutions | |
| KR102067606B1 (en) | A method for separation and recovery of Nd(III) and Dy(III) from nitrate leach solution of spent mobile phone camera module | |
| KR930007139B1 (en) | Process for the recovery of gallium from basic solution | |
| US5993757A (en) | Reoximation of metal extraction circuit organics | |
| JPS60245736A (en) | Method for recovering gallium | |
| RU2260068C1 (en) | Method of extraction of arsenic (+5) from acid sulfate solutions | |
| US3449246A (en) | Liquid ion exchange separation of iron from copper-iron ore mixtures | |
| EP2942409B1 (en) | Valuable-metal extraction method | |
| KISHIKO et al. | Regeneration of Degraded Extractant by Sodium Hydroxide Activated Clay and Evaluation of Its Performances in Copper Solvent Extraction | |
| CN114196827A (en) | Method for separating nickel and lithium and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |