CN113277475B - Method for removing metal ions in anhydrous hydrogen fluoride - Google Patents
Method for removing metal ions in anhydrous hydrogen fluoride Download PDFInfo
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- CN113277475B CN113277475B CN202110583376.XA CN202110583376A CN113277475B CN 113277475 B CN113277475 B CN 113277475B CN 202110583376 A CN202110583376 A CN 202110583376A CN 113277475 B CN113277475 B CN 113277475B
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910000040 hydrogen fluoride Inorganic materials 0.000 title claims abstract description 74
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920001429 chelating resin Polymers 0.000 claims abstract description 42
- 238000001179 sorption measurement Methods 0.000 claims abstract description 38
- 238000005260 corrosion Methods 0.000 claims abstract description 29
- 230000007797 corrosion Effects 0.000 claims abstract description 29
- 229920003023 plastic Polymers 0.000 claims abstract description 29
- 239000004033 plastic Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 8
- 238000011049 filling Methods 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims description 60
- 239000011347 resin Substances 0.000 claims description 60
- 238000005406 washing Methods 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 35
- -1 polyethylene terephthalate Polymers 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000002791 soaking Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 12
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 9
- AKYLNDFIHYWREP-UHFFFAOYSA-N 2-ethenyl-1h-triazine-4,6-diamine Chemical compound NC1=CC(N)=NN(C=C)N1 AKYLNDFIHYWREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 238000010894 electron beam technology Methods 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 108010010803 Gelatin Proteins 0.000 claims description 7
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229920000159 gelatin Polymers 0.000 claims description 7
- 239000008273 gelatin Substances 0.000 claims description 7
- 235000019322 gelatine Nutrition 0.000 claims description 7
- 235000011852 gelatine desserts Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000004640 Melamine resin Substances 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 6
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 6
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- 229920006122 polyamide resin Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 4
- 239000012670 alkaline solution Substances 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- 239000013522 chelant Substances 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract 1
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract 1
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- 239000000428 dust Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 239000010436 fluorite Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- WEWFIUPOLKEEJP-UHFFFAOYSA-N triazine-4,6-diamine Chemical compound NC1=CC(N)=NN=N1 WEWFIUPOLKEEJP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
- C01B7/197—Separation; Purification by adsorption
- C01B7/198—Separation; Purification by adsorption by solid ion-exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the chemical industry field, in particular to a method for removing metal ions in anhydrous hydrogen fluoride; comprising the following steps: cleaning filler, filling an adsorption column, adsorbing and removing ions, removing water and the like; the invention adopts the metal ion chelating resin with a special branched structure to adsorb and chelate and remove the metal ions in the hydrogen fluoride raw material solution, and the lone electron pair in N or O atoms on heterocycle contained in the metal ion chelating resin forms a high-efficiency strong coordination bond with the metal ions, so that the aim of removing the metal ions is fulfilled, and the adopted adsorption column is processed by hydrogen fluoride corrosion-resistant plastic, so that the plastic material has good processing formability, is suitable for processing into columnar sections, can resist the strong acidity of hydrogen fluoride, can not generate corrosion phenomenon when the hydrogen fluoride passes through the column, and can not generate chemical reaction with the hydrogen fluoride, thereby ensuring that the hydrogen fluoride passing through the column can not be polluted by the column material, and ensuring the adsorption effect and the quality and purity of products.
Description
Technical Field
The invention belongs to the field of chemical industry, and in particular relates to a method for removing metal ions in anhydrous hydrogen fluoride.
Background
Hydrogen fluoride is the basis of modern fluorine chemical industry, and is the most basic raw material for preparing elemental fluorine, various fluorine refrigerants, new fluorine-containing materials, inorganic fluoride salts, various organic fluorides and the like. Industrial anhydrous hydrogen fluoride is a chemical product with wide application, the appearance is hydrofluoric acid with more than 99% of colorless fuming liquid, and the hydrofluoric acid is easy to gasify under reduced pressure or high temperature. Is mainly used for preparing fluorine salt, fluorohaloalkane, fluororefrigerant, corrosive glass, impregnated wood, electrolytic element fluorine and the like.
CN110656344a discloses a device for removing water from anhydrous hydrogen fluoride, which comprises an electrolytic tank body, an electrolytic tank upper cover, an anode plate, a cathode plate and a separator, wherein an electrolytic cavity is arranged in the electrolytic tank body, the anode plate, the cathode plate and the separator are all positioned in the electrolytic cavity, the anode plate is fixed in the electrolytic tank body and separates the lower space of the electrolytic cavity, the cathode plate is fixed in the electrolytic tank upper cover and extends towards the bottom of the electrolytic cavity, the separator is fixed in the electrolytic tank upper cover and positioned between the anode plate and the cathode plate, and the separator separates the upper space of the electrolytic cavity into an anode air chamber and a cathode air chamber. Through the innovative design of the electrode plate and the electrolytic tank, the continuous water removal treatment of anhydrous hydrogen fluoride is realized, and the removal efficiency is improved. The invention also discloses a method for removing the anhydrous hydrogen fluoride based on the device for removing the anhydrous hydrogen fluoride, which adopts an electrolysis method to remove trace moisture in the anhydrous hydrogen fluoride, can realize continuous treatment, does not need to use oxidizing reagents or adsorbents such as fluorine gas, and has simple and efficient treatment process.
CN106276801B discloses a production facility of anhydrous hydrogen fluoride, which comprises a forklift, a conveying facility, a fluorite storage bin, a cyclone separator, a bag type dust collector, a rotary reaction furnace, a mixed acid tank, a slag storage hopper, a dust collector, a washing tower, a primary cooler, an HF condenser, a rectifying tower and a degassing tower, wherein the forklift, the conveying facility, the fluorite storage bin, the cyclone separator, the bag type dust collector, the rotary reaction furnace, the mixed acid tank, the dust collector, the washing tower, the primary cooler, the HF condenser, the rectifying tower and the degassing tower are sequentially connected, the slag storage hopper is connected with the mixed acid tank, and the HF condenser comprises an HF primary condenser and an HF secondary condenser; the anhydrous hydrogen fluoride production equipment and process has less discharge and can produce higher economic benefit.
CN106276801a discloses a production facility of anhydrous hydrogen fluoride, which comprises a forklift, a conveying device, a fluorite storage bin, a cyclone separator, a bag type dust remover, a rotary reaction furnace, a mixed acid tank, a slag storage hopper, a dust remover, a washing tower, a primary cooler, an HF condenser, a rectifying tower and a degassing tower, wherein the forklift, the conveying device, the fluorite storage bin, the cyclone separator, the bag type dust remover, the rotary reaction furnace, the mixed acid tank, the dust remover, the washing tower, the primary cooler, the HF condenser, the rectifying tower and the degassing tower are sequentially connected, the slag storage hopper is connected with the mixed acid tank, and the HF condenser comprises an HF primary condenser and an HF secondary condenser; the anhydrous hydrogen fluoride production equipment and process has less discharge and can produce higher economic benefit.
In the prior art, a rectification method is generally adopted for removing metal ions in anhydrous hydrogen fluoride, but the method has low impurity removal efficiency and high energy consumption.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for removing metal ions from anhydrous hydrogen fluoride.
A method for removing metal ions in anhydrous hydrogen fluoride comprises the following specific scheme:
washing the filler, repeatedly washing the metal ion chelating resin with hot water at 50-60 ℃ until the water after the resin is soaked is clear, then soaking the resin for 4-6 hours with acid washing, soaking the resin for 30-120 minutes with alkali liquor, washing the resin with pure water until the pH value of the effluent is 7 after the resin is soaked for 30-120 minutes, and drying the resin at 40-80 ℃;
filling an adsorption column, wherein metal ion chelating resin is filled in the adsorption column, and the length-diameter ratio of the column is 300-800:8-12; the adsorption column is characterized by being a corrosion-resistant plastic hollow column;
step three, adsorbing and removing ions, controlling the temperature of the hydrogen fluoride raw material solution to be 15-19 ℃, and enabling the hydrogen fluoride raw material solution to pass through an adsorption column at a flow rate of 5-10BV, so as to complete metal ion removal;
the corrosion-resistant plastic hollow column is formed by processing hydrogen fluoride corrosion-resistant plastic, and the preparation method comprises the following steps:
according to the parts by weight, adding 26.4-38.2 parts of polyethylene terephthalate into 6.4-16.8 parts of perfluoropropyl perfluorovinyl ether and 75.2-96.8 parts of polytetrafluoroethylene, heating to 125-145 ℃ and mixing for 10-30min under heat preservation, adding 10-28 parts of silicon dioxide, and continuing mixing for 5-10min under heat preservation to obtain a fluorocarbon resin mixture; then taking 12-32 parts of polyamide resin, adding 5-12 parts of linear low-density polyethylene and 2-6 parts of hexamethylol melamine resin, heating to 120-140 ℃ at the heating rate of 3-8 ℃/min, preserving heat and mixing for 10-15min, then adding 2-8 parts of carbon nitride micro powder and 0.1-0.8 part of cetyltrimethylammonium chloride, continuing to preserving heat and mixing for 5-10min, adding into fluorocarbon resin mixture, fully mixing for 5-10min, then feeding into a mixing mill, mixing for 3-5min at the temperature of 110-150 ℃, and continuing to mix for 3-5min after standing for 30-60min, thus obtaining the plastic with hydrogen fluoride corrosion resistance.
The preparation method of the metal ion chelating resin comprises the following steps:
according to the parts by weight, 50-70 parts of polystyrene imine diacetic acid group chelating resin is subjected to electron beam radiation by using an electron accelerator, so that active free radicals which can be used for grafting reaction are generated, and the irradiation conditions are as follows: the irradiation voltage is 3-5MeV, the irradiation dose is 15-30kGy, and the dose rate is 5-10kGy/pass; immediately dispersing macroporous adsorption resin into 200-500 parts of toluene after completion, adding 0.3-0.6 part of gelatin and 1.1-3.6 parts of 1-vinyl-3-butylimidazole tetrafluoroborate, 5-15 parts of hexafluorobutyl acrylate, 1-4 parts of 2-vinyl-4, 6-diamino-triazine (CAS: 3194-70-5), 2-4 parts of benzoyl peroxide, controlling the temperature to 70-85 ℃, stirring and carrying out grafting reaction for 120-180min, filtering out resin after completion, washing, soaking in ethanol for 5-10h, and filtering to obtain the metal ion chelating resin.
The mass portion of the hydrofluoric acid for pickling is 3% -5%.
The mass portion of the alkaline washing ammonia water solution is 5% -10%.
The hydrogen fluoride raw material solution is anhydrous hydrogen fluoride.
The said chelate resin is a chelate resin with weak acid iminodiacetic acid group [ -CH 2 N-(CH 2 OOH) 2 ]Such as Dowex A-1, D iaionCR-10, KT-1, D751, D401, D402, D403, etc.
The reaction mechanism is as follows:
the metal ion chelating resin is grafted or copolymerized with 1-vinyl-3-butyl imidazole tetrafluoroborate, hexafluorobutyl acrylate, 2-vinyl-4, 6-diamino-triazine through active free radicals radiated by polystyrene imine diacetic acid group chelating resin electron beams, and functional groups such as tetrafluoroboric acid, hexafluorobutyl, diamino-triazine are grafted on the framework of the chelating resin, wherein the reaction equation is shown as follows:
the invention adopts a metal ion chelate resin with a special branched structure to adsorb and chelate to remove metal ions in hydrogen fluoride raw material solution, the metal ion chelate resin is processed by using active free radicals radiated by polystyrene imine diacetic acid chelate resin electron beams, and is grafted or copolymerized with 1-vinyl-3-butylimidazole tetrafluoroborate, hexafluorobutyl acrylate, 2-vinyl-4, 6-diamino-triazine, and functional groups such as tetrafluoroboric acid, hexafluorobutyl, diamino-triazine, and the like are grafted on the skeleton of the chelate resin.
Drawings
FIG. 1 is a Fourier infrared spectrum of a metal ion chelate resin sample prepared in example 3:
at 1612/1500/1454cm -1 The benzene ring absorption peak of the benzene ring exists nearby and is 2946cm -1 The hydrocarbon expansion absorption peak exists nearby at 1759cm -1 The existence of a telescopic absorption peak of carboxyl carbonyl nearby indicates that the polystyrene imine diacetyl chelating resin participates in the reaction; at 1162/1085cm -1 An antisymmetric stretch/symmetrical stretch absorption peak with carbon-oxygen single bond near 914cm -1 Having fluorocarbon bonds in the vicinityAbsorption peaks, indicating that hexafluorobutyl acrylate is involved in the reaction; at 1653/1561cm -1 A telescopic absorption peak with carbon-nitrogen double bond at 3445/3396/3309cm -1 The presence of an antisymmetric/symmetrical telescopic absorption peak of the nitrogen-hydrogen bond nearby indicates that 2-vinyl-4, 6-diamino-triazine participates in the reaction; at 1037cm -1 The presence of an absorption peak near the boron-fluorine bond indicates that 1-vinyl-3-butylimidazole tetrafluoroborate participates in the reaction.
Detailed Description
The invention is further illustrated by the following examples:
and (3) measuring the content of metal ions in the hydrogen fluoride before and after treatment by adopting an atomic absorption spectrophotometry.
Example 1
A method for removing metal ions in anhydrous hydrogen fluoride comprises the following specific scheme:
washing the filler, repeatedly washing the metal ion chelating resin with hot water at 50 ℃ until the water after the resin is soaked is clear, then soaking for 4 hours with acid washing, soaking for 30 minutes with alkali liquor, washing with pure water until the pH value of the effluent is 7 after the completion, and drying the resin at 40 ℃;
filling an adsorption column, wherein metal ion chelating resin is filled in the adsorption column, and the length-diameter ratio of the column is 300:8; the adsorption column is characterized by being a corrosion-resistant plastic hollow column;
step three, adsorbing and removing ions, controlling the temperature of the hydrogen fluoride raw material solution to be 15 ℃, and passing through an adsorption column at a flow rate of 5BV to finish metal ion removal;
the corrosion-resistant plastic hollow column is formed by processing hydrogen fluoride corrosion-resistant plastic, and the preparation method comprises the following steps:
adding 26.4g of polyethylene terephthalate into 6.4g of perfluoropropyl perfluorovinyl ether and 75.2g of polytetrafluoroethylene, heating to 125 ℃, mixing for 10min at a constant temperature, adding 10g of silicon dioxide, and mixing for 5min at a constant temperature to obtain a fluorocarbon resin mixture; then taking 12g of polyamide resin, adding 5g of linear low-density polyethylene and 2g of hexamethylol melamine resin, heating to 120 ℃ at a heating rate of 3 ℃/min, preserving heat and mixing for 10min, then adding 2g of carbon nitride micro powder and 0.1g of hexadecyl trimethyl ammonium chloride, continuing to preserving heat and mixing for 5min, adding into fluorocarbon resin mixture, fully mixing for 5min, then sending into a mixer, mixing for 3min at a temperature of 110 ℃, standing for 30min, and continuing to mix for 3min to obtain the plastic resistant to hydrogen fluoride corrosion.
The preparation method of the metal ion chelating resin comprises the following steps:
50g of a polystyrene-imine diacetic acid-based chelate resin were subjected to electron beam irradiation using an electron accelerator, so that they produced active radicals usable for the grafting reaction, under irradiation conditions: the irradiation voltage is 3MeV, the irradiation dose is 15gy, and the dose rate is 5gy/pass; immediately dispersing macroporous adsorption resin into 200g of toluene after completion, adding 0.3g of gelatin and 1.1g of 1-vinyl-3-butylimidazole tetrafluoroborate, 5g of hexafluorobutyl acrylate, 1g of 2-vinyl-4, 6-diamino-triazine (CAS: 3194-70-5), 2g of benzoyl peroxide, controlling the temperature to 70 ℃, stirring and grafting for 120min, filtering out resin after completion, washing, soaking in ethanol for 5h, and filtering to obtain the metal ion chelating resin.
The mass percentage content of hydrofluoric acid for pickling is 3%.
The alkaline washing solution contains 5% of ammonia water solution by mass percent.
The hydrogen fluoride raw material solution is anhydrous hydrogen fluoride.
The polystyrene imine diacetic acid group chelating resin is D751 chelating resin.
Example 2
A method for removing metal ions in anhydrous hydrogen fluoride comprises the following specific scheme:
washing the filler, repeatedly washing the metal ion chelating resin with hot water at 55 ℃ until the water after the resin is soaked is clear, then soaking for 5 hours with acid washing, soaking for 60 minutes with alkali liquor, washing with pure water until the pH value of the effluent is 7 after the completion, and drying the resin at 60 ℃;
filling an adsorption column, wherein metal ion chelating resin is filled in the adsorption column, and the length-diameter ratio of the column is 500:10; the adsorption column is characterized by being a corrosion-resistant plastic hollow column;
step three, adsorbing and removing ions, controlling the temperature of the hydrogen fluoride raw material solution to be 17 ℃, and enabling the hydrogen fluoride raw material solution to pass through an adsorption column at a flow rate of 8BV, so as to complete metal ion removal;
the corrosion-resistant plastic hollow column is formed by processing hydrogen fluoride corrosion-resistant plastic, and the preparation method comprises the following steps:
adding 32.4g of polyethylene terephthalate into 12.4g of perfluoropropyl perfluorovinyl ether and 86.2g of polytetrafluoroethylene, heating to 135 ℃, mixing for 20min at a constant temperature, adding 18g of silicon dioxide, and mixing for 8min at a constant temperature to obtain a fluorocarbon resin mixture; then taking 24g of polyamide resin, adding 8g of linear low-density polyethylene and 4g of hexamethylol melamine resin, heating to 130 ℃ at a heating rate of 5 ℃ per minute, preserving heat and mixing for 12min, then adding 5g of carbon nitride micro powder and 0.4g of hexadecyl trimethyl ammonium chloride, continuing to preserving heat and mixing for 8min, adding into fluorocarbon resin mixture, fully mixing for 8min, then sending into a mixer, mixing for 4min at a temperature of 140 ℃, standing for 40min, and continuing to mix for 4min to obtain the plastic resistant to hydrogen fluoride corrosion.
The preparation method of the metal ion chelating resin comprises the following steps:
55g of a polystyrene-imine diacetic acid-based chelate resin was subjected to electron beam irradiation using an electron accelerator to generate active radicals usable for the grafting reaction, under irradiation conditions: the irradiation voltage is 4MeV, the irradiation dose is 20gy, and the dose rate is 8gy/pass; immediately dispersing macroporous adsorption resin into 400g of toluene after completion, adding 0.5g of gelatin and 2.3g of 1-vinyl-3-butylimidazole tetrafluoroborate, 10g of hexafluorobutyl acrylate, 2g of 2-vinyl-4, 6-diamino-triazine (CAS: 3194-70-5), 3g of benzoyl peroxide, controlling the temperature to 77 ℃, stirring and grafting for 140min, filtering out the resin after completion, washing, soaking in ethanol for 7h, and filtering to obtain the metal ion chelating resin.
The mass percentage content of hydrofluoric acid for pickling is 4%.
The alkaline washing water solution is 8% of ammonia water solution in percentage by mass.
The hydrogen fluoride raw material solution is anhydrous hydrogen fluoride.
The polystyrene imine diacetic acid group chelating resin is D403 chelating resin.
Example 3
A method for removing metal ions in anhydrous hydrogen fluoride comprises the following specific scheme:
washing the filler, repeatedly washing the metal ion chelating resin with hot water at 60 ℃ until the water after the resin is soaked is clear, then soaking for 6 hours with acid washing, soaking for 120 minutes with alkali liquor, washing with pure water until the pH value of the effluent is 7 after the completion, and drying the resin at 80 ℃;
filling an adsorption column, wherein metal ion chelating resin is filled in the adsorption column, and the length-diameter ratio of the column is 800:12; the adsorption column is characterized by being a corrosion-resistant plastic hollow column;
step three, adsorbing and removing ions, controlling the temperature of the hydrogen fluoride raw material solution to be 19 ℃, and passing through an adsorption column at a flow rate of 10BV to finish metal ion removal;
the corrosion-resistant plastic hollow column is formed by processing hydrogen fluoride corrosion-resistant plastic, and the preparation method comprises the following steps:
adding 38.2g of polyethylene terephthalate into 16.8g of perfluoropropyl perfluorovinyl ether and 96.8g of polytetrafluoroethylene, heating to 145 ℃, mixing for 30min at a constant temperature, adding 28g of silicon dioxide, and mixing for 10min at a constant temperature to obtain a fluorocarbon resin mixture; then, 32g of polyamide resin is taken, 12g of linear low-density polyethylene and 6g of hexamethylol melamine resin are added, the temperature is raised to 140 ℃ at the heating rate of 8 ℃/min, the mixture is kept for 15min, then 8g of carbon nitride micro powder and 0.8g of hexadecyl trimethyl ammonium chloride are added, the mixture is continuously kept for 10min, the mixture is added into fluorocarbon resin mixture, the mixture is fully mixed for 10min, then the mixture is fed into a mixer, the mixing is carried out for 5min at the temperature of 150 ℃, the mixture is kept still for 60min, and the mixing is continuously carried out for 5min, thus obtaining the plastic with hydrogen fluoride corrosion resistance.
The preparation method of the metal ion chelating resin comprises the following steps:
70g of a polystyrene-imine diacetic acid-based chelate resin were subjected to electron beam irradiation using an electron accelerator, so that it produced active radicals usable for the grafting reaction, under irradiation conditions: the irradiation voltage is 5MeV, the irradiation dose is 30gy, and the dose rate is 10gy/pass; immediately dispersing macroporous adsorption resin into 500g of toluene after completion, adding 0.6g of gelatin and 3.4g of 1-vinyl-3-butylimidazole tetrafluoroborate, 15g of hexafluorobutyl acrylate, 4g of 2-vinyl-4, 6-diamino-triazine and 4g of benzoyl peroxide, controlling the temperature to 85 ℃, stirring and grafting for 180min, filtering out resin after completion, washing, soaking in ethanol for 10h, and filtering to obtain the metal ion chelating resin.
The mass percentage content of hydrofluoric acid for pickling is 5%.
The alkaline washing solution contains 10% of ammonia water solution by mass percent.
The hydrogen fluoride raw material solution is anhydrous hydrogen fluoride.
The polystyrene imine diacetic acid group chelating resin is D402 chelating resin.
The results of the metal ion content measurements of the hydrogen fluoride of the above examples before and after the treatment are shown in the following table:
| calcium (ppb) | Iron (ppb) | Zinc (ppb) | Copper (ppb) | Manganese (ppb) | |
| Before treatment | 680 | 730 | 550 | 410 | 720 |
| Example 1 | 12 | 20 | 9 | 10 | 15 |
| Example 2 | 10 | 17 | 8 | 8 | 13 |
| Example 3 | 9 | 15 | 7 | 6 | 11 |
Comparative example 1
A method for removing metal ions in anhydrous hydrogen fluoride comprises the following specific scheme:
washing the filler, repeatedly washing the metal ion chelating resin with hot water at 50 ℃ until the water after the resin is soaked is clear, then soaking for 4 hours with acid washing, soaking for 30 minutes with alkali liquor, washing with pure water until the pH value of the effluent is 7 after the completion, and drying the resin at 40 ℃;
filling an adsorption column, wherein polystyrene imine diacetic acid group chelating resin is filled in the adsorption column, and the length-diameter ratio of the column is 300:8; the adsorption column is characterized by being a corrosion-resistant plastic hollow column;
step three, adsorbing and removing ions, controlling the temperature of the hydrogen fluoride raw material solution to be 15 ℃, and passing through an adsorption column at a flow rate of 5BV to finish metal ion removal;
the corrosion-resistant plastic hollow column is formed by processing hydrogen fluoride corrosion-resistant plastic, and the preparation method comprises the following steps:
adding 26.4g of polyethylene terephthalate into 6.4g of perfluoropropyl perfluorovinyl ether and 75.2g of polytetrafluoroethylene, heating to 125 ℃, mixing for 10min at a constant temperature, adding 10g of silicon dioxide, and mixing for 5min at a constant temperature to obtain a fluorocarbon resin mixture; then taking 12g of polyamide resin, adding 5g of linear low-density polyethylene and 2g of hexamethylol melamine resin, heating to 120 ℃ at a heating rate of 3 ℃/min, preserving heat and mixing for 10min, then adding 2g of carbon nitride micro powder and 0.1g of hexadecyl trimethyl ammonium chloride, continuing to preserving heat and mixing for 5min, adding into fluorocarbon resin mixture, fully mixing for 5min, then sending into a mixer, mixing for 3min at a temperature of 110 ℃, standing for 30min, and continuing to mix for 3min to obtain the plastic resistant to hydrogen fluoride corrosion.
The mass percentage content of hydrofluoric acid for pickling is 3%.
The hydrogen fluoride raw material solution is anhydrous hydrogen fluoride.
Comparative example 2
A method for removing metal ions in anhydrous hydrogen fluoride comprises the following specific scheme:
washing the filler, repeatedly washing the metal ion chelating resin with hot water at 50 ℃ until the water after the resin is soaked is clear, then soaking for 30min with alkali liquor, washing with pure water until the pH value of the effluent is 7 after the completion, and drying the resin at 40 ℃;
filling an adsorption column, wherein metal ion chelating resin is filled in the adsorption column, and the length-diameter ratio of the column is 300:8; the adsorption column is characterized by being a corrosion-resistant plastic hollow column;
step three, adsorbing and removing ions, controlling the temperature of the hydrogen fluoride raw material solution to be 15 ℃, and passing through an adsorption column at a flow rate of 5BV to finish metal ion removal;
the corrosion-resistant plastic hollow column is formed by processing hydrogen fluoride corrosion-resistant plastic, and the preparation method comprises the following steps:
the preparation method of the metal ion chelating resin comprises the following steps:
50g of a polystyrene-imine diacetic acid-based chelate resin were subjected to electron beam irradiation using an electron accelerator, so that they produced active radicals usable for the grafting reaction, under irradiation conditions: the irradiation voltage is 3MeV, the irradiation dose is 15gy, and the dose rate is 5gy/pass; immediately dispersing macroporous adsorption resin into 200g of toluene after completion, adding 0.3g of gelatin and 1.1g of 1-vinyl-3-butylimidazole tetrafluoroborate, 1g of 2-vinyl-4, 6-diamino-triazine (CAS: 3194-70-5), 2g of benzoyl peroxide, controlling the temperature to 70 ℃, stirring and grafting for 120min, filtering out resin after completion, washing, soaking in ethanol for 5h, and filtering to obtain the metal ion chelating resin.
The alkaline washing solution contains 5% of ammonia water solution by mass percent.
The hydrogen fluoride raw material solution is anhydrous hydrogen fluoride.
Comparative example 3
The preparation method of the metal ion chelating resin comprises the following steps:
50g of a polystyrene-imine diacetic acid-based chelate resin were subjected to electron beam irradiation using an electron accelerator, so that they produced active radicals usable for the grafting reaction, under irradiation conditions: the irradiation voltage is 3MeV, the irradiation dose is 15gy, and the dose rate is 5gy/pass; immediately dispersing macroporous adsorption resin into 200g of toluene after completion, adding 0.3g of gelatin and 1.1g of 1-vinyl-3-butylimidazole tetrafluoroborate, 5g of hexafluorobutyl acrylate and 2g of benzoyl peroxide, stirring and grafting at the temperature of 70 ℃ for 120min, filtering out resin after completion, washing, soaking in ethanol for 5h, and filtering to obtain the metal ion chelating resin.
Other technical scheme is the same as that of the embodiment 1.
The results of the metal ion content measurements of the hydrogen fluoride of the above examples before and after the treatment are shown in the following table:
| calcium (ppb) | Iron (ppb) | Zinc (ppb) | Copper (ppb) | Manganese (ppb) | |
| Before treatment | 680 | 730 | 550 | 410 | 720 |
| Comparative example 1 | 276 | 358 | 321 | 267 | 452 |
| Comparative example 2 | 76 | 114 | 83 | 92 | 127 |
| Comparative example 3 | 58 | 83 | 62 | 68 | 105 |
Claims (4)
1. A method for removing metal ions in anhydrous hydrogen fluoride comprises the following specific scheme: washing the filler, repeatedly washing the metal ion chelating resin with hot water at 50-60 ℃ until the water after the resin is soaked is clear, then soaking the resin for 4-6 hours with acid washing, soaking the resin for 30-120 minutes with alkali liquor, washing the resin with pure water until the pH value of the effluent is 7 after the resin is soaked for 30-120 minutes, and drying the resin at 40-80 ℃; filling an adsorption column, wherein metal ion chelating resin is filled in the adsorption column, and the length-diameter ratio of the column is 300-800:8-12; the adsorption column is characterized by being a corrosion-resistant plastic hollow column; step three, adsorbing and removing ions, controlling the temperature of the hydrogen fluoride raw material solution to be 15-19 ℃, and enabling the hydrogen fluoride raw material solution to pass through an adsorption column at a flow rate of 5-10BV, so as to complete metal ion removal;
the corrosion-resistant plastic hollow column is formed by processing hydrogen fluoride corrosion-resistant plastic, and the preparation method comprises the following steps: according to the parts by weight, adding 26.4-38.2 parts of polyethylene terephthalate into 6.4-16.8 parts of perfluoropropyl perfluorovinyl ether and 75.2-96.8 parts of polytetrafluoroethylene, heating to 125-145 ℃ and mixing for 10-30min under heat preservation, adding 10-28 parts of silicon dioxide, and continuing mixing for 5-10min under heat preservation to obtain a fluorocarbon resin mixture; then taking 12-32 parts of polyamide resin, adding 5-12 parts of linear low-density polyethylene and 2-6 parts of hexamethylol melamine resin, heating to 120-140 ℃ at a heating rate of 3-8 ℃/min, preserving heat and mixing for 10-15min, then adding 2-8 parts of carbon nitride micro powder and 0.1-0.8 part of cetyltrimethylammonium chloride, continuing to preserve heat and mix for 5-10min, adding into fluorocarbon resin mixture, fully mixing for 5-10min, then feeding into a mixing mill, mixing for 3-5min at a temperature of 110-150 ℃, and continuing to mix for 3-5min after standing for 30-60min, thus obtaining the plastic with hydrogen fluoride corrosion resistance;
the preparation method of the metal ion chelating resin comprises the following steps of irradiating 50-70 parts of polystyrene imine diacetic acid based chelating resin with electron beam by using an electron accelerator to generate active free radicals for grafting reaction, wherein the irradiation conditions are as follows: the irradiation voltage is 3-5MeV, the irradiation dose is 15-30kGy, and the dose rate is 5-10kGy/pass; immediately dispersing macroporous adsorption resin into 200-500 parts of toluene after completion, adding 0.3-0.6 part of gelatin and 1.1-3.6 parts of 1-vinyl-3-butylimidazole tetrafluoroborate, 5-15 parts of hexafluorobutyl acrylate, 1-4 parts of 2-vinyl-4, 6-diamino-triazine and 2-4 parts of benzoyl peroxide, controlling the temperature to be 70-85 ℃, stirring and grafting for 120-180min, filtering out the resin after completion, washing cleanly, soaking in ethanol for 5-10h, and filtering to obtain the metal ion chelating resin.
2. A method for removing metal ions from anhydrous hydrogen fluoride as claimed in claim 1, wherein: the mass fraction of hydrofluoric acid for pickling is 3% -5%.
3. A method for removing metal ions from anhydrous hydrogen fluoride as claimed in claim 1, wherein: the alkaline solution is soaked in ammonia water solution with the mass fraction of 5% -10%.
4. A method for removing metal ions from anhydrous hydrogen fluoride as claimed in claim 1, wherein: the hydrogen fluoride raw material solution is anhydrous hydrogen fluoride.
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| US4599175A (en) * | 1983-09-30 | 1986-07-08 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for separating and purifying metallic elements by displacement chromatography |
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| BR102014011473A2 (en) * | 2014-04-29 | 2016-07-12 | José Ferreira De Alcantara | ion exchange sorption chemical process for the removal of fluoride in water for human and industrial consumption |
| CN112778349A (en) * | 2020-12-29 | 2021-05-11 | 浙江博瑞电子科技有限公司 | Refining method of tetra (dimethylamino) hafnium |
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| US4599175A (en) * | 1983-09-30 | 1986-07-08 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for separating and purifying metallic elements by displacement chromatography |
| JP2010285655A (en) * | 2009-06-11 | 2010-12-24 | Kurita Water Ind Ltd | Metal recovering method |
| CN102092684A (en) * | 2011-01-06 | 2011-06-15 | 苏州晶瑞化学有限公司 | Method for preparing electronic grade ultrahigh purity hydrofluoric acid |
| BR102014011473A2 (en) * | 2014-04-29 | 2016-07-12 | José Ferreira De Alcantara | ion exchange sorption chemical process for the removal of fluoride in water for human and industrial consumption |
| WO2016011900A1 (en) * | 2014-07-25 | 2016-01-28 | 南京大学 | Chelating resin adsorbing material and preparation method therefor |
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