CN111977676A - Preparation and purification of Al30Method for morphological polymerization of aluminum - Google Patents
Preparation and purification of Al30Method for morphological polymerization of aluminum Download PDFInfo
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- CN111977676A CN111977676A CN202010682750.7A CN202010682750A CN111977676A CN 111977676 A CN111977676 A CN 111977676A CN 202010682750 A CN202010682750 A CN 202010682750A CN 111977676 A CN111977676 A CN 111977676A
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 24
- 238000000746 purification Methods 0.000 title claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 5
- 238000006116 polymerization reaction Methods 0.000 title abstract description 6
- 230000000877 morphologic effect Effects 0.000 title abstract description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 26
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 24
- 238000001556 precipitation Methods 0.000 claims abstract description 19
- 238000006073 displacement reaction Methods 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000000706 filtrate Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 229910001422 barium ion Inorganic materials 0.000 claims description 9
- 239000012452 mother liquor Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 7
- 239000010413 mother solution Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 7
- 239000004021 humic acid Substances 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000000701 coagulant Substances 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000002452 interceptive effect Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- ZBJWWKFMHOAPNS-UHFFFAOYSA-N loretin Chemical compound C1=CN=C2C(O)=C(I)C=C(S(O)(=O)=O)C2=C1 ZBJWWKFMHOAPNS-UHFFFAOYSA-N 0.000 description 1
- 229950010248 loretin Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/46—Purification of aluminium oxide, aluminium hydroxide or aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to the technical field of aluminum polymer purification, and particularly discloses a method for preparing and purifying Al30Process for morphological polymerization of aluminum using benzoic acid pairs containing Al and Al in the mesomeric state30The polyaluminium chloride solution is treated to complex and decompose the medium polymeric Al, benzoic acid is removed by an extracting agent, and the Al is treated by a precipitating agent containing sulfate radicals and a displacing agent containing barium ions30Carrying out precipitation displacement, separating and purifying to obtain purified Al30And (5) producing the product. The invention solves the problems of intermediate-aggregation Al and Al in the process of precipitation and replacement30The technical problem that cannot be distinguished is Al30Provides a new solution.
Description
Technical Field
The invention relates to the technical field of aluminum polymer purification, in particular to preparation and purification of Al30A method of forming a polymeric aluminum.
Background
Al30(Al2O8Al28(OH)56(H2O)26 18+) Is an important nanometer discovered in 2000The metastable polymer grade, which has a particle size of about 2nm and 18 positive charges, is the aluminum form with the largest degree of polymerization known at present.
Due to Al30Has more positive charges, larger molecular size and higher stability compared with the traditional aluminum salt and Al13The coagulant has better adaptability to temperature and pH value, thus being a novel nano coagulant with potential excellent coagulation performance. The study shows that Al30In the process of removing turbidity, humic acid, heavy metal pollution (such as arsenic) and the like, the method has the advantages of good stability, small using amount, wide pH value application range, strong applicability to organic matter removal and the like, and has wide development prospect in the field of water treatment. However, these findings were all obtained in the case where a plurality of aluminum forms coexist, and Al is30The content can only reach 70 to 80 percent, and only roughly thought that the coagulation effect is mainly attributed to Al30The function of (1). Al (Al)a、AlbThe existence of the morphologies will interfere with the accuracy of the research results. Thus, Al30The purification work of (2) is gradually attracting attention.
Some of the researchers have conducted Al30The purification work of (1). Al which is currently available30The separation and purification methods comprise gel permeation chromatography, sulfate radical precipitation, selenate radical precipitation and the like, but have the defects of complex operation and low yield, and cannot be popularized in practical application. In addition to this, based on the existing para-Al13The present inventors also compared the precipitation displacement and organic solvent precipitation methods for Al30The purification effect of (2) was found that the former could not be achieved for Al13And Al30The latter has the problems of high cost, low efficiency, environmental pollution and the like, and can not realize the separation of Al30Large scale purification. Therefore, a convenient and efficient Al is developed30The purification method is a problem to be solved at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for preparing and purifying Al30A method of forming a polymeric aluminum.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
the invention provides a method for preparing and purifying Al30Method of morphologically polymerizing aluminum with Al30Using polyaluminium chloride solution with content of above 70% as mother liquor, firstly utilizing benzoic acid to treat Al contained in the mother liquorbPerforming complex decomposition, filtering to remove precipitate, extracting the obtained filtrate (first filtrate) with extractant to remove benzoic acid, and performing Al-ion exchange with precipitant containing sulfate radical and displacer containing barium ion30Carrying out precipitation displacement, separating and purifying to obtain purified Al30And (5) producing the product.
Al according to the inventionbRefers to the moderately hydrolyzed polymeric form of Al, in the form of Al13Is the most important component.
Further, Al contained in the mother liquor is treated with benzoic acidbThe specific operation of the complex decomposition is as follows: to the mother liquor was added an excess of benzoic acid solid.
The "excess" refers to the benzoic acid solids relative to AlbIn an excessive state.
And further, adding a benzoic acid solid, stirring, and reacting for 2-4 h.
Further, the extractant is any one of ethyl ether, ethyl acetate and chloroform. In the specific embodiment of the invention, diethyl ether is taken as an extracting agent as an illustrative example.
In one embodiment of the present invention, by way of illustration, the filtrate is extracted 1-5 times, preferably 3 times, with ethyl ether: the filtrate was extracted at a ratio of 1: 3.
Further, Al is precipitated by sulfate radical-containing precipitant and barium ion-containing displacer30The specific method for carrying out precipitation and replacement comprises the following steps: adding sulfate or its solution into the filtrate, reacting to obtain precipitate, cleaning the precipitate, air drying, adding barium ion solution to perform precipitation displacement, reacting, and filtering to obtain filtrate (second filtrate), i.e. purified Al30And (5) producing the product.
Preferably, when the sulfate is added, the molar ratio of the sulfate ion to aluminum in the filtrate is 0.5:1 to 2:1, more preferably 1: 1. And after the addition, stirring and reacting for 10-48 h, preferably 24 h.
Preferably, when the barium ion solution is added, the molar ratio of barium ions to sulfate ions is 0.5:1 to 2:1, more preferably 1: 1. And after the addition, stirring and reacting for 1-4 h, preferably 3 h.
In one embodiment of the invention, the sulfate salt is, illustratively, Na2SO4The barium ion solution is Ba (NO)3)2And (3) solution.
Preferably, the filtration after the complex decomposition and the filtration after the precipitation and the replacement are performed by using a filter membrane or a filter paper having a pore size of not more than 0.45. mu.m.
In one embodiment of the present invention, as an illustration, the mother liquor is prepared by the following steps: adding Al with the alkalinity of 2.2 and the mol/L of 0.113The predominantly PAC solution was heated at 95 ℃ for 48 h.
More specifically, the present invention provides a method for preparing and purifying Al30The specific application of the method for morphological polymerization of aluminum is embodied as a method for forming high-Al aluminum30Polyaluminium chloride solution (PAC-Al) content30) Middle Al30The purification method of (1), the purification method comprising:
step one, to PAC-Al30Adding excessive benzoic acid into the solution, and stirring at normal temperature to obtain a main interfering substance Al13Is gradually complexed and decomposed into Al monomer;
step two, filtering the solution obtained in the step one by using a membrane, performing liquid-phase extraction on the filtered solution by using ether, repeating the step three times, and removing impurity benzoic acid;
step three, adding Na into the solution obtained in the step two2SO4As a precipitant, stirring to obtain Al30-(SO4)nPrecipitating;
step four, cleaning the precipitate obtained in the step three, and adding Ba (NO)3)2Stirring the solution as a displacer to obtain high-purity Al30And (3) solution.
The raw materials or reagents involved in the invention are all common commercial products, and the operations involved are all routine operations in the field unless otherwise specified.
The above-described preferred conditions may be combined with each other to obtain a specific embodiment, in accordance with common knowledge in the art.
The invention has the beneficial effects that:
according to the invention, a large number of objective experimental researches show that benzoic acid can be Al13The main component of the medium polymeric Al (main interfering component) is complexly decomposed into low polymeric Al or Al monomer, but not high polymeric Al (such as Al)30) Constituting an influence. The invention therefore proposes a process for preparing and purifying Al30Method for morphological polymerization of aluminum by using benzoic acid pairs containing Al and Al in a mesomeric state30The polyaluminium chloride solution is treated to complex and decompose the mesomeric Al, thereby solving the problems of the mesomeric Al and the Al during the precipitation and replacement30The technical problem that cannot be distinguished is Al30Provides a new solution for the separation and purification of Al30Lays a foundation for further research and application.
Al prepared and purified by the method of the invention30Product, Al30The purity can reach 90%. The detection proves that the yield of the method can reach more than 70%. The method is simple to operate and has good application and popularization prospects.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present disclosure and together with the description, serve to explain the principles of the disclosure.
FIG. 1 shows benzoic acid as the main interfering substance Al13Decomposition time profile of (a).
FIG. 2 is Al30-(SO4)nScanning electron micrograph (c).
FIG. 3 is Al30-(SO4)nX-ray diffraction pattern of (a).
FIG. 4 shows purified Al30Of (2) a solid27Nuclear magnetic resonance spectrum of Al.
FIG. 5 shows AlCl3、Al13、Al30The effect of removing turbidity.
FIG. 6 shows AlCl3、Al13、Al30High performance liquid chromatogram of the residual humic acid after coagulation.
Detailed Description
In order that the above objects, features and advantages of the present disclosure may be more clearly understood, aspects of the present disclosure will be further described below. It should be noted that the embodiments and features of the embodiments of the present disclosure may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure, but the present disclosure may be practiced in other ways than those described herein; it is to be understood that the embodiments disclosed in the specification are only a few embodiments of the present disclosure, and not all embodiments.
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
The invention provides a method for purifying Al by combining organic matter complexation decomposition-ether extraction-precipitation replacement30Mainly by benzoic acid on the main interfering substance Al13Decomposing, removing benzoic acid impurity by liquid phase extraction with diethyl ether, and precipitating to remove Al30And (5) purifying the morphology.
Example 1
The true bookExamples are provided to illustrate the preparation and purification of Al according to the invention30The method for morphologically polymerizing aluminum comprises the following specific steps:
1) adding Al with the alkalinity of 2.2 and the mol/L of 0.113PAC solutions based on PAC (denoted PAC-Al)13) Heating at 95 deg.C for 48h to obtain PAC-Al30And (3) solution.
2) PAC-Al in step 1)30Adding excessive benzoic acid solid into the solution, stirring for reaction for 2h, and filtering with a 0.45 μm filter membrane to obtain filtrate.
3) The filtrate obtained in the step 2) is mixed with ethyl ether according to the volume ratio: the filtrate was extracted 3 times at a ratio of 1:3 to remove benzoic acid as an impurity.
4) In the solution obtained in step 3) according to SO4 2-Na is added in the proportion of 1.0/Al2SO4Stirring and reacting for 24 hours to obtain Al30-(SO4)nWashing the precipitate with ethanol, air drying, adding Ba (NO)3)2The solution was displaced and stirred for 3 h. Filtering with 0.45 μm filter membrane to obtain filtrate, i.e. purified Al30And (5) producing the product.
Example 2
To further illustrate the invention, high purity Al is obtained30The product is characterized in a series of characteristics.
To observe benzoic acid vs. Al13In benzoic acid and PAC-Al30In the reaction process, solutions are taken at the reaction time of 0h, 0.5h, 1h, 1.5h, 2h, 3h and 6h respectively for precipitation and replacement, the form of aluminum is characterized by using a Ferron method, and the change condition of each component is shown in figure 1.
Al in FIG. 1aRepresents Al monomer, AlbRepresents Al13，AlcRepresents Al30。
As the reaction proceeds, Al13The content is reduced from 15 percent to 2 percent, and Al30The content is increased from 84% to 96%, and the content of Al monomer is basically unchanged. Shows Al13Gradually decomposed by benzoic acid into Al monomer and removed by precipitation, Al30The content is thus significantly increased.
Obtained by carrying out step 4) of example 1Al of (2)30-(SO4)nAnd (3) carrying out characterization after the solid is dried, wherein the characterization method comprises the following steps: scanning electron microscope, X-ray diffraction; final purified Al30Freeze drying the solution and making solid27And detecting the nuclear magnetic resonance of Al.
Al30-(SO4)nThe scanning electron microscope is shown in FIG. 2:
from FIG. 2, it can be seen that needle-like crystal clusters are formed, indicating that Al having a higher purity is obtained30-(SO4)nAnd its morphology and long-strip shape of Al30The molecular structures are consistent to some extent.
Al30-(SO4)nThe X-ray diffraction pattern is shown in FIG. 3:
by comparison, the XRD pattern after the purification by benzoic acid has a clearer crystal structure and is compared with the pure Al obtained by the previous researchers30-(SO4)nThe XRD spectrum has very close peak shape, and Al is laterally reacted30The purity of (2).
Purification of Al30Of (2) a solid27The Al NMR spectrum is shown in FIG. 4:
70ppm and 7-12ppm of Al30The signal peak of (1), generally 70ppm, was regarded as Al30The characteristic peak of the crystal is-Keggin-Al13Middle AlO4Chemical shift of (d). The peak is clearly seen at 70ppm in the spectrogram, which proves that Al30The content is greatly improved.
From the above test results, it can be seen that the method provided by the present invention can obtain high purity Al30。
Example 3
To verify the purified Al30For the removal effect of pollutants, water samples with different turbidity and humic acid content and AlCl are prepared3And Al13The two coagulants were compared and subjected to coagulation experiments.
The water distribution parameters are as follows:
1) turbidity: mixing SiO2Dispersing in water to make the turbidity of raw water reach 10NTU and 50NTU respectively;
2) humic acid: humic acid was dissolved in water to make the TOC of the raw water 3 mg/L.
Both types of NaHCO were dissolved in 5mmol/L water3And NaNO3Acting as a pH buffer and simulating the ionic strength in natural water.
Adding a coagulant according to the target adding amount, wherein the coagulant adding gradient of a turbidity experiment is 0, 5, 10, 20, 30, 40, 50, 80, 110, 140, 170, 200 and 240 mu mol/L, and the optimal adding amount of Al is selected in a humic acid experimentT110. mu. mol/L. And after the coagulant is added, quickly stirring for 90s, slowly stirring for 10min, standing for 30min, and taking the supernatant for relevant characterization.
As is clear from FIG. 5, under the medium alkaline condition, Al was removed from the turbidity30The method has the advantages of excellent removal effect and capability of achieving 90% of turbidity removal rate at a low dosage. And Al13And AlCl3Under certain specific conditions (such as Al)13At pH 7, AlCl3At pH 9 and lower dosages) were all subject to varying degrees of failure.
FIG. 6 is a high performance liquid chromatogram of humic acid remaining after coagulation, and it can be found that Al is an organic substance having a molecular weight of Da 1000 to 300030Has relatively obvious removal advantage, which indicates that Al30The organic matters with large molecular weight are easier to adsorb and complex, and are finally removed by flocculation and precipitation.
The foregoing are merely exemplary embodiments of the present disclosure, which enable those skilled in the art to understand or practice the present disclosure. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the disclosure. Thus, the present disclosure is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. Preparation and purification of Al30A method for morphologically polymerizing aluminum, characterized in that Al is used30Using the polyaluminium chloride solution with the content of more than 70 percent as mother solution, and firstly utilizing benzoic acid to reactAl contained in the mother liquorbPerforming complex decomposition, filtering to remove precipitate, extracting the obtained filtrate with extractant to remove benzoic acid, and performing Al-ion exchange with precipitant containing sulfate radical and displacer containing barium ion30Carrying out precipitation displacement, separating and purifying to obtain purified Al30And (5) producing the product.
2. The method according to claim 1, wherein Al contained in the mother liquor is treated with benzoic acidbThe specific operation of the complex decomposition is as follows: to the mother liquor was added an excess of benzoic acid solid.
3. The method according to claim 2, wherein the benzoic acid solid is added and then stirred for reaction for 2-4 h.
4. A process according to any one of claims 1 to 3, wherein the extractant is diethyl ether.
5. The method as claimed in claim 4, wherein the filtrate is extracted 1-5 times with ethyl ether as extractant, each time with ethyl ether: the filtrate was extracted at a ratio of 1: 3.
6. The method according to any one of claims 1 to 3, wherein the specific method for carrying out precipitation displacement is as follows: adding sulfate or its solution into the filtrate, reacting to obtain precipitate, cleaning the precipitate, air drying, adding barium ion solution to perform precipitation displacement, reacting, and filtering to obtain filtrate, i.e. purified Al30And (5) producing the product.
7. The method of claim 6, wherein when sulfate is added, the molar ratio of sulfate ions to aluminum in the filtrate is 0.5:1 to 2: 1;
and/or when the barium ion solution is added, the molar ratio of the barium ions to the sulfate ions is 0.5: 1-2: 1.
8. The method of claim 7, wherein the sulfate salt is Na2SO4The barium ion solution is Ba (NO)3)2And (3) solution.
9. The method as claimed in claim 6, wherein the filtration after the complex decomposition and the precipitation displacement are performed by using a filter membrane or a filter paper having a pore size of not more than 0.45 μm.
10. The method according to claim 1, wherein the mother liquor is prepared by: adding Al with the alkalinity of 2.2 and the mol/L of 0.113The predominantly PAC solution was heated at 95 ℃ for 48 h.
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| CN202010682750.7A CN111977676A (en) | 2020-07-15 | 2020-07-15 | Preparation and purification of Al30Method for morphological polymerization of aluminum |
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| CN202010682750.7A CN111977676A (en) | 2020-07-15 | 2020-07-15 | Preparation and purification of Al30Method for morphological polymerization of aluminum |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796283A (en) * | 2004-12-24 | 2006-07-05 | 中国科学院生态环境研究中心 | Method and technique for preparing Nano type sol of polyaluminium chloride in high purity |
| CN1915830A (en) * | 2006-09-07 | 2007-02-21 | 中国科学院生态环境研究中心 | Method for purifying Al13 in high yield |
| CN102965506A (en) * | 2012-12-14 | 2013-03-13 | 葛新芳 | Method for removing aluminum from rare earth solution by benzoate precipitation method |
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| CN1796283A (en) * | 2004-12-24 | 2006-07-05 | 中国科学院生态环境研究中心 | Method and technique for preparing Nano type sol of polyaluminium chloride in high purity |
| CN1915830A (en) * | 2006-09-07 | 2007-02-21 | 中国科学院生态环境研究中心 | Method for purifying Al13 in high yield |
| CN102965506A (en) * | 2012-12-14 | 2013-03-13 | 葛新芳 | Method for removing aluminum from rare earth solution by benzoate precipitation method |
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| CHANGQING YE ET AL.: "Formation of Al30 from aqueous polyaluminum chloride under high temperature: Role of Al13 aggregates", 《COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS》 * |
| LIBING LIU ET AL.: "Efficient purification of Al30 by organic complexation method", 《JOURNAL OF ENVIRONMENTAL SCIENCES》 * |
| 吴珍等著: "《新型高分子铝盐混凝剂制备及应用 2019年9月第1版》", 30 September 2019, 北京工业大学出版社 * |
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