CN111994931A - Method for recycling desorption liquid of aluminum-loaded fluorine-removing chelating resin - Google Patents
Method for recycling desorption liquid of aluminum-loaded fluorine-removing chelating resin Download PDFInfo
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- 238000003795 desorption Methods 0.000 title claims abstract description 94
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 75
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229920001429 chelating resin Polymers 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 title claims abstract description 29
- 238000004064 recycling Methods 0.000 title claims abstract description 23
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 77
- 238000001556 precipitation Methods 0.000 claims abstract description 69
- 239000011737 fluorine Substances 0.000 claims abstract description 68
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 65
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 53
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 17
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical compound NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 95
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000010413 mother solution Substances 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 51
- 239000011734 sodium Substances 0.000 description 35
- 229910052708 sodium Inorganic materials 0.000 description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 16
- 229910001610 cryolite Inorganic materials 0.000 description 16
- 238000011084 recovery Methods 0.000 description 16
- 238000006115 defluorination reaction Methods 0.000 description 15
- 230000001276 controlling effect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 7
- 229910020834 NaAlF4 Inorganic materials 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000004673 fluoride salts Chemical class 0.000 description 3
- -1 fluorine ions Chemical class 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910020239 KAlF4 Inorganic materials 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 208000004042 dental fluorosis Diseases 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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- 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
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
- C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a desorption liquid recycling method of aluminum-loaded fluorine-removing chelating resin, belonging to the field of wastewater treatment and comprising the following steps: step 1: mixing a desorbent with the aluminum-loaded fluorine-removing chelating resin for desorption, and controlling the liquid-solid ratio of the desorbent to the aluminum-loaded fluorine-removing chelating resin to be 2-10L/kg to obtain a desorption solution; step 2: adding a hydrofluoric acid solution and a hydrochloric acid solution into the desorption solution obtained in the step 1 to obtain a mixed precipitation solution, and performing precipitation reaction to obtain a precipitation mother solution and a precipitation product; aiming at the problems in the prior art, the invention aims to provide a desorption liquid recycling method of aluminum-loaded fluorine removal chelating resin, which recycles fluorine in the desorption liquid in the form of fluoroaluminate products so as to solve the problems of fluorine pollution and fluorine waste caused by difficult recycling of the desorption liquid in the prior art.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a desorption liquid recycling method of aluminum-loaded fluorine-removing chelating resin.
Background
Fluoride salts are important chemical raw materials, and due to the annual over-exploitation, fluoride salts (especially fluorite) have faced a severe shortage situation. In the production and use processes of fluoride salt. A large amount of fluorine-containing wastewater is generated. Excessive fluorine in water can cause acute poisoning of a human body or dental fluorosis and fluorosis diseases and the like. The high-concentration fluorine-containing wastewater is mainly treated by a chemical precipitation method and a flocculation precipitation method. The method has the advantages of simple operation, convenient treatment, low cost and good effect, but the sludge generated by precipitation has high water content and is difficult to settle and dewater, and the concentration of fluorine ions in the effluent can not stably reach the standard. In the face of the increasingly strict national discharge standard requirements, an efficient and economic fluorine-containing wastewater deep purification technology is urgently required to be developed.
Adsorption and ion exchange are commonly used for advanced treatment of fluorine-containing wastewater. However, the traditional ion exchange resin and adsorbent have weak fluorine selective adsorption, small adsorption capacity and poor treatment effect on industrial fluorine-containing wastewater. According to the metal ion Al3+And F-The super coordination ability between Al and Al is provided3+Loaded on chelating resin, and then the loaded chelating resin is utilized to selectively adsorb fluorine ions in water, thereby achieving the purpose of deep purification. The aluminum-loaded chelate resin has strong fluorine adsorption selectivity, good stability and large adsorption capacity, and is a fluorine-containing wastewater deep adsorbent with great potential. However, after desorption of the resin, Al was found3+Will be in contact with F-Simultaneously, the desorption liquid is desorbed into the desorption liquid, so that the desorption liquid is difficult to treat or recycle. Al coexists in the desorption solution3+And F-If the desorption liquid is improperly treated, new fluorine pollution and waste of valuable fluorine resources in the water body can be caused.
Therefore, from the aspects of avoiding fluorine pollution and recycling fluorine resources, how to properly treat desorption liquid of the aluminum-loaded chelating fluorine-removing resin becomes a key for further popularization and application of the aluminum-loaded chelating resin fluorine-removing technology.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a desorption liquid recycling method of aluminum-loaded fluorine removal chelating resin, which recycles fluorine in the desorption liquid in the form of fluoroaluminate products so as to solve the problems of fluorine pollution and fluorine waste caused by difficult recycling of the desorption liquid in the prior art.
In order to realize the purpose, the invention adopts the technical scheme that:
a desorption liquid recycling method of aluminum-loaded fluorine-removing chelating resin comprises the following steps:
step 1: mixing a desorbent with the aluminum-loaded fluorine-removing chelating resin for desorption, and controlling the liquid-solid ratio of the desorbent to the aluminum-loaded fluorine-removing chelating resin to be 2-10L/kg to obtain a desorption solution;
step 2: and (3) adding a hydrofluoric acid solution and a hydrochloric acid solution into the desorption solution obtained in the step (1) to obtain a mixed precipitation solution, and performing precipitation reaction to obtain a precipitation mother liquor and a precipitation product.
Further, the method also comprises the step 3: and dehydrating and drying the obtained precipitation product to obtain the fluoroaluminate product.
Further, the desorbent in the step 1 is sodium hydroxide solution or potassium hydroxide solution, and the concentration of the desorbent is 2-5 mol/L.
Further, the aluminum-loaded fluorine removal chelating resin in the step 1 is iminodiacetic acid type resin or aminophosphonic acid type resin; wherein the main chain of the iminodiacetic acid type aluminum-loaded fluorine-removing chelating resin is of a polystyrene structure or a polyacrylic acid structure, and the main chain is connected with a functional group with a structure shown in a formula (I):
the main chain of the amino phosphoric acid type aluminum-loaded fluorine removal chelating resin is of a polystyrene structure or a polyacrylic acid structure, and the main chain is connected with a functional group with a structure of a formula (II):
further, the desorption time of the desorbent and the aluminum-loaded fluorine removal chelating resin is 10-60 min.
Further, in the desorption solution obtained in the step 1, F-Concentration of 3-20g/L, Al3+Concentration of 4-25g/L, F-With Al3+The molar concentration ratio of (A) is 0.8-2.0: 1, pH is 11.0-14.0.
Further, the mass concentration of the hydrofluoric acid solution in the step 2 is 400g/L of 300-.
Further, adjusting the hydrofluoric acid solution added in the step 2 to F in the mixed precipitation solution-With Al3+The molar ratio is 5.0-6.0: 1.
further, the hydrochloric acid solution added in the step 2 is adjusted to the pH value of the mixed precipitation solution between 4.0 and 6.0.
Further, the precipitation reaction time in the step 2 is 20-60 min.
The invention has the beneficial effects that: (1) the invention provides a method for recycling desorption liquid of aluminum-loaded fluorine-removing chelating resin, which obtains high-concentration F through controlling the volume and concentration of the desorption liquid-With Al3+Adding hydrofluoric acid solution and hydrochloric acid solution into the desorption solution to control F during reaction-With Al3+The molar concentration ratio and the reaction pH value are recovered to obtain a high molecular ratio fluoroaluminate product, so that the resource utilization of fluorine and aluminum in imbibition is realized, fluorine pollution is avoided, and a new solution idea is provided for desorption solution treatment of aluminum-loaded fluorine removal chelating resin;
(2) compared with the prior art, the fluoride ion concentration in the desorption liquid is reduced to about 400mg/L from 3-20g/L after the treatment by the method, the recovery rate of fluorine in the desorption liquid reaches 87-99 percent, and the purity of the fluoroaluminate product is higher than 98 percent; the molecular ratio (Na/Al) of the obtained sodium fluoroaluminate product is higher than 2.7, the product quality meets the requirement of GB/T4291-.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a flow chart of a process for recycling desorption solution of the chelating resin for removing fluorine by carrying aluminum in the invention;
FIG. 2 is XRD patterns of products obtained in example 1(a) and comparative example 2(b) of the present invention.
Detailed Description
For a better understanding of the present invention, embodiments of the present invention are described in detail below with reference to examples, but those skilled in the art will understand that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
The invention provides a desorption liquid recycling method of aluminum-loaded fluorine-removing chelating resin, which comprises the following steps:
a) mixing a desorbent with the aluminum-loaded fluorine-removing chelating resin, and controlling the liquid-solid ratio of the desorbent to the aluminum-loaded fluorine-removing chelating resin to be 2-10L/kg to obtain a desorption solution;
b) and adding a hydrochloric acid solution and a hydrofluoric acid solution into the desorption solution to obtain a mixed precipitation solution, and performing precipitation reaction to obtain a precipitation mother liquor and a precipitation product.
The aluminum-carrying fluorine-removing chelating resin is iminodiacetic acid resin or aminophosphonic acid resin.
The purpose of the step a) is to desorb fluorine in the aluminum-loaded fluorine-removing chelating resin into a desorption solution by using a desorbent, and the desorption rate is ensured to be higher than 90% and the concentration of fluorine ions in the desorption solution is ensured to be higher than 2g/L by controlling the liquid-solid ratio of the desorbent to the aluminum-loaded fluorine-removing chelating resin.
If the liquid-solid ratio of the desorbent to the aluminum-loaded defluorination chelating resin is lower than 2L/kg, the desorption rate is lower than 90 percent; if the liquid-solid ratio of the desorbent to the aluminum-loaded fluorine removal chelating resin is higher than 10L/kg, the fluoride ion concentration in the desorbent is lower than 2 g/L. Too high or too low a liquid-to-solid ratio will result in a lower recovery of desorbed liquid fluorine in step b).
The main chain of the iminodiacetic acid type aluminum-loaded fluorine-removing chelating resin is of a polystyrene structure or a polyacrylic acid structure, and the main chain is connected with a functional group with a structure shown in a formula (I):
al of the aluminum-loaded defluorinated chelating resin of iminodiacetic acid type after the treatment of the step a)3+And F-Entering a desorption solution, and changing the functional group into a group shown in a formula (i):
the main chain of the amino phosphoric acid type aluminum-loaded fluorine removal chelating resin is of a polystyrene structure or a polyacrylic acid structure, and the main chain is connected with a functional group with a structure of a formula (II):
after the treatment of step a), the Al of the amino phosphoric acid type aluminum-loaded defluorination chelating resin3+And F-Entering a desorption solution, and changing the functional group into a group shown in a formula (ii):
in the step a), the desorbent is sodium hydroxide solution or potassium hydroxide solution, and the concentration of the desorbent is 2-5 mol/L. If the concentration of the desorbent is less than 2mol/L, the desorption rate of fluorine is less than 90%, and if the concentration of the desorbent is more than 5mol/L, alkali is wasted. If the desorption is not carried out by alkali and is carried out by acid, the desorption rate of fluorine is lower than 70 percent.
In the step a), the mixed desorption time of the desorbent and the aluminum-loaded fluorine removal chelating resin is 10-60 min.
In step a)In the desorption solution, the concentration of F-is 3-20g/L, and Al is3+Concentration of 4-25g/L, F-and Al3+The molar concentration ratio of (A) is 0.8-2.0: 1, pH is 11.0-14.0.
The purpose of the step b) is to utilize hydrofluoric acid solution and hydrochloric acid solution to remove F and Al in desorption solution3+Converted into fluoroaluminate precipitate. When the desorbent is sodium hydroxide solution, the fluoroaluminate precipitation component is Na3AlF6. The chemical reaction involved in step b) is represented by formula (III):
6F-+3Na++Al3+→Na3AlF6and ↓ (III).
When the desorbent is potassium hydroxide solution, the fluoroaluminate precipitation component is K3AlF6. The chemical reaction involved in step b) is represented by formula (IV):
6F-+3K++Al3+→K3AlF6and ↓ (IV).
According to the formulae (III) and (IV), the precipitation reaction is intended to give Na3AlF6And K3AlF6In step b), it is necessary to adjust F-and Al in the mixed precipitation solution3+In a molar ratio of 5.0 to 6.0: 1, F-and Al can be adjusted by adding hydrofluoric acid solution into desorption solution3+Purpose of molar ratio.
Due to Al in the desorption liquid3+The molar concentration ratio of F-to F-is 0.8-2.0: 1, if Al is not increased3+In molar ratio to F-, the following reactions (V) and (VI) or (V) and (VII) will take place and the precipitated product will be Al (OH)3、NaAlF4Or and Al (OH)3、KAlF4At the moment, the components and the purity of the precipitated product can not meet the national standard requirements, and the precipitated product is difficult to be reused as a product:
Al3++3OH-→Al(OH)3formula ↓ (V);
4F-+Na++Al3+→NaAlF4formula ↓ (VI);
4F-+K++Al3+→KAlF4formula (VII).
In the step b), the pH value of the mixed precipitation solution is 4.0-6.0, and the purpose of regulating the pH value can be realized by adding a hydrochloric acid solution into the desorption solution.
If the pH of the mixed precipitate is above 6.0, reaction (V) will be carried out simultaneously with reaction (III) or reaction (IV) and Al (OH) will be present in the precipitate3Resulting in a decrease in purity. If the pH of the mixed precipitation liquid is less than 4.0, the fluoroaluminate solubility increases, resulting in a decrease in the fluorine recovery rate.
In the step b), the mass concentration of the hydrofluoric acid solution is 400g/L, and the mass concentration of the hydrochloric acid solution is 350g/L, wherein the hydrofluoric acid solution is 300-400 g/L. The concentration of the hydrofluoric acid and the hydrochloric acid solution is not too low, so that the excessive accumulation of the mixed precipitation liquid is avoided.
In the step b), the precipitation reaction time is 20-60 min.
A desorption liquid recycling method of aluminum-loaded fluorine-removing chelating resin further comprises the following steps:
c) and dehydrating and drying the precipitation product to obtain the fluoroaluminate product.
The precipitated product can be dehydrated through centrifugation or filter pressing, and then is recycled as a product after being dried at high temperature or normal temperature. According to the difference of recycling requirements, the precipitated product can also be directly recycled without dehydration and drying.
For the sake of clarity, the following examples are given in detail. Unless otherwise specifically stated, each of the operation steps involved in the following examples of the present invention was carried out at room temperature.
Example 1:
the aluminum-loaded fluorine-removing chelating resin and the desorption solution thereof are processed according to the process flow chart shown in FIG. 1, and the specific processing steps comprise:
adding 0.5L and 2mol/L sodium hydroxide solution into 50g of aluminum-loaded defluorination D751 resin (iminodiacetic acid type), controlling the liquid-solid ratio of the sodium hydroxide solution to the aluminum-loaded defluorination chelating resin to be 10L/kg, and stirring for 10min to react to obtain desorption solution; pH of desorption solution is 12.8, F-Concentration is 3508mg/L, Al3+Concentration of 5042mg/L, F-With Al3+Has a molar concentration ratio of 0.99:1, and is fed to a desorption solution23.3mL of 400g/L hydrofluoric acid (8854mg F) was added-) Adjusting F in the mixed precipitation solution-With Al3+Is 6.0: 1, adding 350g/L hydrochloric acid, adjusting the pH value of the mixed precipitation solution to 4.0, and controlling the precipitation reaction time to be 20min to obtain precipitation mother liquor and a precipitation product. And (4) centrifugally dewatering the precipitated product and drying the precipitated product at 80 ℃ for 24 hours to obtain a sodium fluoroaluminate product.
The experimental result shows that the residual fluorine concentration of the mixed precipitation solution is 401.8mg/L, the recovery rate of fluorine in the desorption solution is 87.6 percent, and the comprehensive recovery rate of fluorine is 97.9 percent (8854mg F of added hydrofluoric acid)-A merge calculation). The sodium fluoroaluminate product contains Na as main component3AlF6(see figure 2(a)), the dry weight is 19.1g, the molecular ratio (Na/Al molar ratio) is 2.82, the purity reaches 98.4 percent, the contents of Na, Al, F and the like meet the quality requirement of GB/T4291-2007 cryolite, and the cryolite can be recycled.
Example 2:
the aluminum-loaded fluorine-removing chelating resin and the desorption solution thereof are processed according to the process flow chart shown in FIG. 1, and the specific processing steps comprise:
adding 0.25L and 3mol/L sodium hydroxide solution into 50g of aluminum-loaded defluorination D751 resin (iminodiacetic acid type), controlling the liquid-solid ratio of the sodium hydroxide solution to the aluminum-loaded defluorination chelating resin to be 5L/kg, and stirring for reaction for 25min to obtain desorption solution; pH of desorption solution is 13.0, F-The concentration is 6579mg/L, Al3+The concentration is 10965mg/L, F-With Al3+In a molar ratio of 0.85: 1, adding 24.0mL of 350g/L hydrofluoric acid (7980mg F) to the desorption solution-) Adjusting F in the mixed precipitation solution-With Al3+Is 5.0: 1, adding 300g/L hydrochloric acid, adjusting the pH value of the mixed precipitation solution to 5.0, and controlling the precipitation reaction time to be 25min to obtain precipitation mother liquor and a precipitation product. And (4) centrifugally dewatering the precipitated product and drying the precipitated product at 90 ℃ for 20 hours to obtain a sodium fluoroaluminate product.
The experimental result shows that the residual fluorine concentration of the mixed precipitation solution is 415.1mg/L, the recovery rate of the fluorine in the desorption solution is 92.9 percent, and the comprehensive recovery rate of the fluorine is 98.8 percent (7980mg F of the added hydrofluoric acid-A merge calculation). The sodium fluoroaluminate product contains Na as main component3AlF617.5g of dry weight, 2.84 of molecular ratio (Na/Al molar ratio), 98.1 percent of purity, and the contents of Na, Al, F and the like meet the quality requirement of GB/T4291-2007 cryolite and can be recycled.
Example 3:
the aluminum-loaded fluorine-removing chelating resin and the desorption solution thereof are processed according to the process flow chart shown in FIG. 1, and the specific processing steps comprise:
adding 0.5L and 5mol/L sodium hydroxide solution into 50g of aluminum-loaded defluorination D751 resin (iminodiacetic acid type), controlling the liquid-solid ratio of the sodium hydroxide solution to the aluminum-loaded defluorination chelating resin to be 10L/kg, and stirring for reacting for 18min to obtain desorption solution; pH of desorption solution is 13.6, F-Concentration 3623mg/L, Al3+The concentration is 5112mg/L, F-With Al3+With a molar concentration ratio of 1.01:1, 27.7mL of 300g/L hydrofluoric acid (7894mg F)-) Adjusting F in the mixed precipitation solution-With Al3+In a molar ratio of 5.4: 1, adding 250g/L hydrochloric acid, adjusting the pH value of the mixed precipitation solution to 6.0, and controlling the precipitation reaction time to be 20min to obtain a precipitation mother solution and a precipitation product. And (4) centrifugally dewatering the precipitated product and drying the precipitated product at 100 ℃ for 15 hours to obtain a sodium fluoroaluminate product.
The experimental result shows that the residual fluorine concentration of the mixed precipitation solution is 387.7mg/L, the recovery rate of the fluorine in the desorption solution is 88.4 percent, and the comprehensive recovery rate of the fluorine is 97.8 percent (7894mg F of additional hydrofluoric acid-A merge calculation). The sodium fluoroaluminate product contains Na as main component3AlF617.4g of dry weight, 2.80 of molecular ratio (Na/Al molar ratio), 98.2 percent of purity, and the contents of Na, Al, F and the like meet the quality requirement of GB/T4291-2007 cryolite and can be recycled.
Example 4:
the aluminum-loaded fluorine-removing chelating resin and the desorption solution thereof are processed according to the process flow chart shown in FIG. 1, and the specific processing steps comprise:
adding 0.1L and 5mol/L sodium hydroxide solution into 50g of aluminum-loaded defluorination D412 resin (amino phosphoric acid type), controlling the liquid-solid ratio of the sodium hydroxide solution to the aluminum-loaded defluorination chelating resin to be 2L/kg, and stirring for reaction for 60min to obtain desorption solution; pH of desorption solution is 13.4, F-At a concentration of17550mg/L，Al3+The concentration is 24200mg/L, F-With Al3+With a molar concentration ratio of 1.03:1, 22.3mL of 400g/L hydrofluoric acid (8474mg F)-) Adjusting F in the mixed precipitation solution-With Al3+Is 6.0: 1, adding 350g/L hydrochloric acid, adjusting the pH value of the mixed precipitation solution to 4.0, and controlling the precipitation reaction time to be 60min to obtain precipitation mother liquor and precipitation products. And centrifugally dewatering the precipitate product and drying the precipitate product at 75 ℃ for 26 hours to obtain a sodium fluoroaluminate product.
The experimental result shows that the residual fluorine concentration of the mixed precipitation solution is 426.4mg/L, the recovery rate of the fluorine in the desorption solution is 96.8 percent, and the comprehensive recovery rate of the fluorine is 99.4 percent (8474mg F of additional hydrofluoric acid-A merge calculation). The sodium fluoroaluminate product contains Na as main component3AlF618.7g of dry weight, 2.79 of molecular ratio (Na/Al molar ratio), 98.1 percent of purity, and the contents of Na, Al, F and the like meet the quality requirement of GB/T4291-2007 cryolite and can be recycled.
Example 5:
the aluminum-loaded fluorine-removing chelating resin and the desorption solution thereof are processed according to the process flow chart shown in FIG. 1, and the specific processing steps comprise:
adding 0.5L and 2mol/L potassium hydroxide solution into 50g of aluminum-loaded defluorination D751 resin (iminodiacetic acid type), controlling the liquid-solid ratio of the sodium hydroxide solution to the aluminum-loaded defluorination chelating resin to be 10L/kg, and stirring for 10min to react to obtain desorption solution; pH of desorption solution is 12.5, F-Concentration of 3459mg/L, Al3+The concentration is 5025mg/L, F-With Al3+With a molar concentration ratio of 0.98:1, 23.4mL of 400g/L hydrofluoric acid (8892mg F)-) Adjusting F in the mixed precipitation solution-With Al3+Is 6.0: 1, adding 350g/L hydrochloric acid, adjusting the pH value of the mixed precipitation solution to 4.0, and controlling the precipitation reaction time to be 20min to obtain precipitation mother liquor and a precipitation product. And (4) centrifugally dewatering the precipitated product and drying the precipitated product at 80 ℃ for 24 hours to obtain a sodium fluoroaluminate product.
The experimental result shows that the residual fluorine concentration of the mixed precipitation solution is 429.9mg/L, the recovery rate of the fluorine in the desorption solution is 86.5 percent, and the comprehensive recovery rate of the fluorine is 97.8 percent (8892mg F of hydrofluoric acid added-A merge calculation). The main component of the potassium fluoroaluminate product is K3AlF623.5g of dry weight, 2.73 of molecular ratio (K/Al molar ratio), 98.0 percent of purity, and the contents of K, Al, F and the like which meet the requirements of QB/DFD 4294-.
Comparative example 1:
the difference from example 1 is that no hydrofluoric acid solution was added to the desorption solution.
The experimental result shows that the main component of the sodium fluoroaluminate product is Al (OH)3And NaAlF4The molecular ratio (Na/Al molar ratio) is 0.71, and the contents of Na, Al, F and the like do not meet the quality requirement of GB/T4291-2007 cryolite and can not be recycled.
Comparative example 2:
the difference from example 1 is that 14.0mL of 400g/L hydrofluoric acid (5320mg F) was added to the desorption solution-) Adjusting F in the mixed precipitation solution-With Al3+Is 4.0: 1.
the experimental result shows that the main component of the sodium fluoroaluminate product is NaAlF4(see FIG. 2(b)), and a small amount of Al (OH)3And Na3AlF6The molecular ratio (Na/Al molar ratio) is 1.28, the contents of Na, Al, F and the like do not meet the quality requirement of GB/T4291-2007 cryolite, and the cryolite can not be recycled.
Comparative example 3:
the difference from example 1 is that 350g/L hydrochloric acid was added to adjust the pH of the mixed precipitate to 7.5.
The experimental result shows that the main component of the sodium fluoroaluminate product is Na3AlF6And Al (OH)3The molecular ratio (Na/Al molar ratio) is 1.82, the contents of Na, Al, F and the like do not meet the quality requirement of GB/T4291-2007 cryolite, and the cryolite can not be recycled.
Comparative example 4:
the difference from the example 1 is that 1000mL of 2mol/L sodium hydroxide solution is added into 50g of aluminum-supported defluorination D751 resin (iminodiacetic acid type), and the liquid-solid ratio of the sodium hydroxide solution to the aluminum-supported defluorination chelating resin is controlled to be 20L/kg; f in desorption liquid-1759mg/L of Al3+At a concentration of 2538mg/L。
The experimental result shows that the residual fluorine concentration of the mixed precipitation liquid is 399.2mg/L, and compared with the example 1, the recovery rate of the fluorine in the desorption liquid is reduced to 76.3 percent due to the increase of the volume of the mixed precipitation liquid.
Comparative example 5:
the difference from example 1 is that 500mL of 0.5mol/L sodium hydroxide solution was added to 50g of the aluminum-supported defluorinated D751 resin (iminodiacetic acid form); f in desorption liquid-The concentration is 2748mg/L, Al3+The concentration was 3872mg/L, and 17.9mL of 400g/L hydrofluoric acid (6802mg F) was added to the desorption solution-) Adjusting F in the mixed precipitation solution-With Al3+Is 6.0: 1. the dry weight of the sodium fluoroaluminate product is 14.6 g.
The experimental result shows that compared with the example 1, the fluorine desorption amount of the aluminum-loaded fluorine removal chelating resin is reduced by 21.7 percent, and the product recovery amount is reduced by 23.5 percent.
Combining example 1 and comparative examples 1-2, it can be seen that F in the mixed precipitation solution can be controlled without adding hydrofluoric acid solution-With Al3+The main component of the sodium fluoroaluminate product is Al (OH)3And NaAlF4And does not meet the recycling requirement.
As can be seen by combining example 1 with comparative example 3, the sodium fluoroaluminate product had a major component of Al (OH) if the pH of the mixed precipitate was not controlled by adding a hydrochloric acid solution3、NaAlF4And Na3AlF6And does not meet the recycling requirement.
Combining example 1 with comparative example 4, it can be seen that if the liquid-to-solid ratio of desorbent to aluminum-loaded defluorination chelating resin is not controlled, F in the desorbent can be caused-And Al3+The concentration decreases and the fluorine recovery rate decreases.
It can be seen from the combination of example 1 and comparative example 5 that if the concentration of the desorbent is not controlled, the desorption rate of fluorine on the resin is reduced, and F in the desorption solution-And Al3+The concentration is reduced, and the recovery amount of the fluoroaluminate product is reduced.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. 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 the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.
Claims (10)
1. A method for recycling desorption liquid of aluminum-loaded fluorine-removing chelating resin is characterized by comprising the following steps:
step 1: mixing a desorbent with the aluminum-loaded fluorine-removing chelating resin for desorption, and controlling the liquid-solid ratio of the desorbent to the aluminum-loaded fluorine-removing chelating resin to be 2-10L/kg to obtain a desorption solution;
step 2: and (3) adding a hydrofluoric acid solution and a hydrochloric acid solution into the desorption solution obtained in the step (1) to obtain a mixed precipitation solution, and performing precipitation reaction to obtain a precipitation mother liquor and a precipitation product.
2. The method for recycling the desorption solution of the aluminum-loaded fluorine removal chelating resin according to claim 1, further comprising the step 3: and dehydrating and drying the obtained precipitation product to obtain the fluoroaluminate product.
3. The method as claimed in claim 1, wherein the desorbent used in step 1 is sodium hydroxide solution or potassium hydroxide solution with a concentration of 2-5 mol/L.
4. The method for recycling the desorption solution of the chelating resin for removing fluorine loaded with aluminum according to claim 1, wherein the chelating resin for removing fluorine loaded with aluminum in step 1 is iminodiacetic acid type resin or aminophosphonic acid type resin; wherein the main chain of the iminodiacetic acid type aluminum-loaded fluorine-removing chelating resin is of a polystyrene structure or a polyacrylic acid structure, and the main chain is connected with a functional group with a structure shown in a formula (I):
the main chain of the amino phosphoric acid type aluminum-loaded fluorine removal chelating resin is of a polystyrene structure or a polyacrylic acid structure, and the main chain is connected with a functional group with a structure of a formula (II):
5. the method of claim 1, wherein the desorption time of the desorbent from the chelating resin for removing fluorine from aluminum carrier is 10-60 min.
6. The method for recycling the desorption solution of the aluminum-loaded fluorine-removing chelating resin as claimed in claim 1, wherein F is the desorption solution obtained in the step 1-Concentration of 3-20g/L, Al3+Concentration of 4-25g/L, F-With Al3+The molar concentration ratio of (A) is 0.8-2.0: 1, pH is 11.0-14.0.
7. The method as claimed in claim 1, wherein the mass concentration of the hydrofluoric acid solution in step 2 is 400g/L and the mass concentration of the hydrochloric acid solution is 350g/L, respectively.
8. The method for recycling the desorption solution of the chelating resin for removing fluorine loaded with aluminum as claimed in claim 1, wherein the hydrofluoric acid solution added in the step 2 is adjusted to F in the mixed precipitation solution-With Al3+The molar ratio is 5.0-6.0: 1.
9. the method as claimed in claim 1, wherein the hydrochloric acid solution added in step 2 is adjusted to pH 4.0-6.0.
10. The method for recycling the desorption solution of the aluminum-loaded fluorine removal chelating resin as claimed in claim 1, wherein the precipitation reaction time in the step 2 is 20-60 min.
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| CN113003650A (en) * | 2021-04-17 | 2021-06-22 | 江苏国创新材料研究中心有限公司 | Preparation method and process of efficient defluorinating resin |
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