CN116726702A - Hydrophobic deep eutectic solvent for extracting and separating boron isotopes and application thereof - Google Patents
Hydrophobic deep eutectic solvent for extracting and separating boron isotopes and application thereof Download PDFInfo
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- CN116726702A CN116726702A CN202310574114.6A CN202310574114A CN116726702A CN 116726702 A CN116726702 A CN 116726702A CN 202310574114 A CN202310574114 A CN 202310574114A CN 116726702 A CN116726702 A CN 116726702A
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- eutectic solvent
- deep eutectic
- hydrogen bond
- boron
- isotope
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 91
- 239000002904 solvent Substances 0.000 title claims abstract description 53
- 230000005496 eutectics Effects 0.000 title claims abstract description 49
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 32
- 239000004327 boric acid Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 alcohol compound Chemical class 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 44
- 238000000605 extraction Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 10
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- 229940035437 1,3-propanediol Drugs 0.000 claims description 6
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical group CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 claims description 6
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical group CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 claims description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical group CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 6
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 6
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical group CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 claims description 4
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Chemical group CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005844 Thymol Substances 0.000 claims description 4
- 229940041616 menthol Drugs 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 229960000790 thymol Drugs 0.000 claims description 4
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 3
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 3
- NCZPCONIKBICGS-UHFFFAOYSA-N 3-(2-ethylhexoxy)propane-1,2-diol Chemical compound CCCCC(CC)COCC(O)CO NCZPCONIKBICGS-UHFFFAOYSA-N 0.000 claims description 3
- MGDNLGRMXPBCOR-UHFFFAOYSA-N bis(2-hydroxyethyl)azanium;dodecanoate Chemical compound OCCNCCO.CCCCCCCCCCCC(O)=O MGDNLGRMXPBCOR-UHFFFAOYSA-N 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- OLBCVFGFOZPWHH-UHFFFAOYSA-N propofol Chemical group CC(C)C1=CC=CC(C(C)C)=C1O OLBCVFGFOZPWHH-UHFFFAOYSA-N 0.000 claims description 3
- 229960004134 propofol Drugs 0.000 claims description 3
- GQPHSXFLIDYJQL-UHFFFAOYSA-N 2,3-dimethyl-4-phenylbutane-1,3-diol Chemical compound OCC(C)C(C)(O)CC1=CC=CC=C1 GQPHSXFLIDYJQL-UHFFFAOYSA-N 0.000 claims description 2
- XUOQMVZDJIZKDB-UHFFFAOYSA-N 2,4-dimethyldodecane-2,4-diol Chemical compound CCCCCCCCC(C)(O)CC(C)(C)O XUOQMVZDJIZKDB-UHFFFAOYSA-N 0.000 claims description 2
- DYWXVYCXQJKOCK-UHFFFAOYSA-N 2-methyl-1-phenylpentane-2,4-diol Chemical compound CC(O)CC(C)(O)CC1=CC=CC=C1 DYWXVYCXQJKOCK-UHFFFAOYSA-N 0.000 claims description 2
- JVZZUPJFERSVRN-UHFFFAOYSA-N 2-methyl-2-propylpropane-1,3-diol Chemical compound CCCC(C)(CO)CO JVZZUPJFERSVRN-UHFFFAOYSA-N 0.000 claims description 2
- IJALWSVNUBBQRA-UHFFFAOYSA-N 4-Isopropyl-3-methylphenol Chemical compound CC(C)C1=CC=C(O)C=C1C IJALWSVNUBBQRA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- CSFUNXXUTSRHPN-UHFFFAOYSA-N undecane-1,3-diol Chemical compound CCCCCCCCC(O)CCO CSFUNXXUTSRHPN-UHFFFAOYSA-N 0.000 claims description 2
- ASLNDVUAZOHADR-UHFFFAOYSA-N 2-butyl-3-methylphenol Chemical group CCCCC1=C(C)C=CC=C1O ASLNDVUAZOHADR-UHFFFAOYSA-N 0.000 claims 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 abstract description 20
- 229910015900 BF3 Inorganic materials 0.000 abstract description 10
- 238000005372 isotope separation Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 4
- 239000008346 aqueous phase Substances 0.000 abstract description 2
- 125000005619 boric acid group Chemical group 0.000 abstract description 2
- 239000003317 industrial substance Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 31
- 239000002994 raw material Substances 0.000 description 21
- 239000000126 substance Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000007547 defect Effects 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 238000004255 ion exchange chromatography Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- ZOXJGFHDIHLPTG-BJUDXGSMSA-N Boron-10 Chemical compound [10B] ZOXJGFHDIHLPTG-BJUDXGSMSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- KUGSJJNCCNSRMM-UHFFFAOYSA-N ethoxyboronic acid Chemical compound CCOB(O)O KUGSJJNCCNSRMM-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NFIVJOSXJDORSP-QMMMGPOBSA-N (2s)-2-amino-3-(4-boronophenyl)propanoic acid Chemical compound OC(=O)[C@@H](N)CC1=CC=C(B(O)O)C=C1 NFIVJOSXJDORSP-QMMMGPOBSA-N 0.000 description 1
- 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
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 235000015511 Liquidambar orientalis Nutrition 0.000 description 1
- 241000862969 Stella Species 0.000 description 1
- 241000736148 Styrax Species 0.000 description 1
- 239000004870 Styrax Substances 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 238000001307 laser spectroscopy Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 108010047303 von Willebrand Factor Proteins 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/22—Separation by extracting
- B01D59/24—Separation by extracting by solvent extraction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a hydrophobic deep eutectic solvent for extracting and separating boron isotopes and application thereof. The hydrophobic deep eutectic solvent comprises a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor comprises a dihydric alcohol compound containing a bishydroxy group, and the hydrogen bond acceptor comprises a compound containing a phenolic hydroxy group and/or a solid monohydric alcohol. The separation provided by the invention 10 In the method of the B isotope, a hydrophobic deep eutectic solvent takes a dihydroxyl-containing dihydric alcohol compound as a hydrogen bond donor, a phenolic hydroxyl-containing compound or solid monohydric alcohol as a hydrogen bond acceptor, and an aqueous phase is boric acid aqueous solution, so that the use of boron trifluoride in the traditional industrial chemical exchange rectification method is avoided, and the problems of high medium toxicity, high equipment investment, high energy consumption, high protection requirement and the like caused by the boron trifluoride are avoided; and has high boron isotope separation factor.
Description
Technical Field
The invention belongs to the technical field of separation, and particularly relates to a hydrophobic deep eutectic solvent for extracting and separating boron isotopes and application thereof.
Background
The industrial production method and research direction of boron isotope separation are mainly focused on a chemical exchange method, and the main technology for separating isotopes by using the chemical method at present comprises the following steps: chemical exchange distillation of gas-liquid systems, liquid-liquid system extraction and solid-liquid system ion exchange chromatography. As the main production method of boron isotopes at present, the chemical rectification method of boron trifluoride diethyl ether (or anisole) belongs to a gas-liquid exchange method, but has the defects of high toxicity of working medium, high equipment investment, high energy consumption, high protection requirement, high cost and the like; the ion exchange chromatography has the advantages of high efficiency, energy saving, high safety and the like, is focused on the research at present, but has the defects of low separation factors and the like to limit the amplification application. The extraction method belongs to liquid-liquid exchange, is easy to amplify, safe, energy-saving, simple and easy to operate, is environment-friendly, has a short process, is an ideal and economical separation method, is widely applied to the field of hydrometallurgy, finds a proper extraction separation system with high separation factors, and is a mass production method for separating boron isotopes with the highest potential and economy.
Boron has 10 B and 11 b two stable isotopes whose natural abundance is approximately 19.7% and 80.3%, respectively. 10 B and 11 the absorption properties of B for neutrons vary greatly, 10 b has a thermal neutron absorption cross section of 3837 target, while 11 B is only 0.005 target. Due to 10 B excellent neutron absorption characteristics, high abundance 10 B is widely used in the nuclear industry and related modern industries and, furthermore, 10 b is used as main ingredient for treating cancerThe essential components have been broken through in theory and application.
At present, separation and enrichment 10 There are 5 main methods of the B isotope: boron trifluoride chemical exchange rectification method, boron trifluoride low-temperature distillation method, ion exchange resin method, laser spectrometry and electromagnetic method, wherein the chemical exchange rectification method and the ion exchange chromatography are the only chemical exchange rectification method really realizing industrial production, which is the method studied by scholars at home and abroad.
Boron isotopes are increasingly used in nuclear power, modern industry, military equipment, medicine and the like, particularly in neutron protection and nuclear power. Currently, in the field of boron isotope separation and application, there have been monopolies in the few countries of the united states, russia, japan, united kingdom, and france. Boron-10 acid production by ceridan, a company of Ceradyne, purchased by 3M in 2014, has been over 40 years old, with boron-10 acid production accounting for over 85% of the world. The company of Stella-chemifa, japan, at the end of year 2000, produced 6 tons of boron-10 (40 tons of boron-10 acids) in japan by the single-family boron isotope separation facility in the tsaoko-tsaojin city; in combination with the company of von Willebrand and Japanese Innovation networks, 6 th 2006, the company of Styrax pharmaceutical (Stella Pharma Co.) has been working with emphasis on boron compounds, particularly those used in boron neutron capture therapy, the first BNCT drug in the world, borofalan [ in 2020 10 B]. With the progress of modern technology, the method has high abundance worldwide 10 B is more and more demanded, and therefore, development and production 10 The B isotope has extremely high economic value and social benefit.
At present, a great deal of industrialized production method is a chemical exchange distillation method, which carries out chemical distillation on boron trifluoride diethyl ether or anisole complex, 11 BF 3 is enriched in the form of gas at the top of the tower, 10 BF 3 enriched in the bottom liquid phase as a complex. The method has the advantages of obvious defects, large equipment investment and large energy consumption, and the boron trifluoride complex is used, so that the protection requirement is high, the boron trifluoride is particularly easy to hydrolyze, and the performance and the corrosion resistance requirement on the equipment are also high, thus being a part of ChinaThe price of the enriched boric acid is always high in places which are difficult to break through, and the method is also a reason for higher production cost. (market price of initial raw material boron trifluoride gas reaches 20 ten thousand yuan/ton), and because boron trifluoride is needed to be used at the end in the form of boron trifluoride during isotopic enrichment, most nuclear power plants are used in the form of enriched boric acid, precious fluorine resource waste is caused by the process of reacting with sodium ethoxide to generate ethyl borate and then hydrolyzing the ethyl borate into boric acid. At present, the ion chromatography has the characteristic of energy conservation, but the separation factor is very low. The extraction method is easy to amplify, easy to produce in large scale and environment-friendly, directly adopts boric acid as a raw material, omits a conversion step of an intermediate compound, and can be more easily converted into other boron-enriched materials by using the enriched boric acid as the raw material, but the most critical problem is that what solvent is selected for extraction, so that the problem to be solved is to provide a hydrophobic deep eutectic solvent for extracting and separating boron isotopes.
Disclosure of Invention
The invention mainly aims to provide a hydrophobic deep eutectic solvent for extracting and separating boron isotopes and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a hydrophobic deep eutectic solvent for extracting and separating boron isotopes, which comprises the following components: a hydrogen bond donor comprising a dihydric alcohol compound comprising a dihydroxy group, and a hydrogen bond acceptor comprising a phenolic hydroxyl group-containing compound and/or a solid monohydric alcohol.
The embodiment of the invention also provides application of the hydrophobic deep eutectic solvent in extraction and separation of boron isotopes.
The embodiment of the invention also provides a method for separating the boric acid from the aqueous solution 10 A method of a B isotope, comprising:
providing the hydrophobic deep eutectic solvent;
and mixing the hydrophobic deep eutectic solvent with boric acid water solution for extraction fromRealizing the following 10 Enrichment of the B isotope.
Compared with the prior art, the invention has the beneficial effects that:
(1) The separation provided by the invention 10 In the method of the B isotope, a dihydroxyl-containing dihydric alcohol compound is used as a hydrogen bond donor, a phenolic hydroxyl-containing compound or solid monohydric alcohol is used as a hydrogen bond acceptor, and the aqueous phase is boric acid aqueous solution, so that the problems of high medium toxicity, high equipment investment, high energy consumption, high protection requirement and the like caused by the traditional industrial chemical exchange rectification method are avoided, and compared with an organic solvent in the traditional solvent extraction method, the deep eutectic solvent has lower toxicity, higher biodegradability and lower cost, so that the deep eutectic solvent is paid attention to the research of environment-friendly solvents;
(2) The boron isotope separation factor of the hydrophobic deep eutectic solvent adopted in the method provided by the invention reaches 1.033, and meets and exceeds the requirement of industrialization;
(3) After the deep eutectic solvent adopted in the invention is loaded with boron, the boron can be regenerated by back extraction with low-concentration alkali solution, so that the damage to equipment and personnel caused by the use of strong acid and strong alkali is avoided;
(4) The deep eutectic solvent can be recycled for a plurality of times, so that resources are saved.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has provided a technical scheme through long-term research and a large amount of practice, mainly by taking a dihydric alcohol compound containing dihydroxyl as a hydrogen bond donor, taking a compound containing phenolic hydroxyl or a solid monohydric alcohol as a hydrogen bond acceptor, mixing the two to form a hydrophobic deep eutectic solvent according to a certain proportion, extracting and separating boron isotopes from boric acid solution, avoiding the use of boron trifluoride, and further avoiding the problems of high medium toxicity, high energy consumption, high protection requirement and the like.
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Specifically, as one aspect of the technical scheme of the invention, the hydrophobic deep eutectic solvent for extracting and separating boron isotopes comprises the following components: a hydrogen bond donor comprising a dihydric alcohol compound comprising a dihydroxy group, and a hydrogen bond acceptor comprising a phenolic hydroxyl group-containing compound and/or a solid monohydric alcohol.
The hydrogen bond donor and acceptor are organic compounds containing hydroxyl, are insoluble in water, are generally solid at normal temperature, and are mixed to lower the melting point to form liquid eutectic solvent.
In some preferred embodiments, the molar ratio of hydrogen bond donor to hydrogen bond acceptor in the hydrophobic deep eutectic solvent is in the range of 1:3 to 3:1.
In some preferred embodiments, the hydrogen bond donor has a structure as shown in formula (I) and/or formula (II):
wherein R is 1 、R 2 And R is 3 Are independently selected from any one of hydrogen, C1-C10 straight chain or branched alkyl, C1-C10 straight chain or branched substituted alkyl, phenyl ether, thiophene, naphthalene, carboxyl and amino.
Further, the hydrogen bond donor includes any one or a combination of two or more of 2-ethyl-1, 3-hexanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2-diaryl-1, 3-propanediol, 2-diethyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 3- (2-ethylhexyloxy) -1, 2-propanediol, salicyl alcohol, diethanolamine lauric acid, 2, 4-dimethyl-2, 4-dodecanediol, 2-methyl-3-benzyl-1, 3-butanediol, 2-benzyl-2, 4-pentanediol, 2-dimethyl-1-benzyl-1, 3-propanediol, 1, 3-undecanediol, and the like, and is not limited thereto.
In some preferred embodiments, the hydrogen bond acceptor includes any one or a combination of two or more of thymol, cresol, 3-methyl-4-isopropylphenol, 6-t-butyl-m-cresol, 2, 3-xylenol, propofol, 4-ethylphenol, menthol, 1-dodecanol, and is not limited thereto.
Another aspect of the embodiments of the present invention also provides an application of the aforementioned hydrophobic deep eutectic solvent in extraction separation of boron isotopes.
In another aspect of embodiments of the invention, there is also provided a method of separating boric acid from an aqueous solution 10 A method of a B isotope, comprising:
providing the hydrophobic deep eutectic solvent;
and mixing the hydrophobic deep eutectic solvent with boric acid water solution, and extracting to obtain 10 Enrichment of the B isotope.
In some preferred embodiments, the concentration of boric acid in the aqueous boric acid solution is from 1 to 30g/L. The aqueous boric acid solution may or may not contain lithium, sodium, potassium, magnesium, or other ions.
In some preferred embodiments, the volume ratio of the hydrophobic deep eutectic solvent to the aqueous boric acid solution is from 1:5 to 5:1.
In some preferred embodiments, the method specifically comprises: mixing the hydrophobic deep eutectic solvent with boric acid water solution, and performing single-stage extraction at 10-40 ℃ to obtain a rich product 10 And B isotope solution.
In some preferred embodiments, the method further comprises: the back extractant is adopted for the enrichment 10 Back-extracting the B isotope solution at 10-40 deg.C to obtain enriched solution 10 B isotope aqueous solution.
Wherein the stripping agent comprises sodium hydroxide aqueous solution.
Further, the concentration of the sodium hydroxide aqueous solution is 0.1-0.5 mol/L.
Further, the stripping agent is rich in 10 The volume ratio of the B isotope solution is1∶3～5∶1。
In some more specific embodiments, the separation from aqueous boric acid 10 The method for the B isotope comprises the following steps:
A. preparing a hydrophobic deep eutectic solvent; the hydrophobic deep eutectic solvent is formed by mixing a hydrogen bond donor and a hydrogen bond acceptor; wherein the hydrogen bond donor is a dihydric alcohol compound containing dihydroxyl, and the hydrogen bond acceptor is a compound containing phenolic hydroxyl or solid monohydric alcohol;
B. and extracting and separating the boron isotope from the boric acid aqueous solution by adopting the deep eutectic solvent.
Further, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor in the deep eutectic solvent is from 1:3 to 3:1.
Further, the aqueous boric acid solution (H 3 BO 3 ) The concentration is 1 g/L-30 g/L, and the solution may or may not contain lithium, sodium, potassium, magnesium and other ions.
Further, in the step B, the volume ratio of the deep eutectic solvent to the boric acid aqueous solution is 1:5-5:1.
Further, the method comprises the steps of: C. back-extracting the boron-rich organic phase with a back-extractant; wherein the back extraction agent is NaOH aqueous solution with the concentration of 0.1 mol/L-0.5 mol/L, and the back extraction ratio is 1:3-5:1.
Further, the operation temperature of the extraction and the back extraction can be 10-40 ℃, namely room temperature.
The technical scheme of the invention is further described in detail below with reference to a plurality of preferred embodiments, the embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
Example 1:
the boric acid aqueous solution is used as raw material liquid, and 0.1938mol/L boric acid is contained. 2, 4-trimethyl-1, 3-pentanediol/thymol is mixed according to the mol ratio of 2:1, the mixed solution is used as deep eutectic solvent, single-stage extraction is carried out at the room temperature of 25 ℃ with the ratio of 1/1, the shaking is carried out for 10min at 300rpm, and raffinate is obtained after standing and phase separation. And measuring the boron content and the boron isotope abundance in the residual liquid, comparing the boron content and the boron isotope abundance with the initial boron content and the initial boron abundance of the raw material liquid, and calculating to obtain the separation factor of the boron isotope of 1.033. The obtained organic phase loaded with boron is back-extracted by 0.40mol/L NaOH, and compared with 1/1 of back-extraction, the single-stage back-extraction rate is 89.12%.
The method for calculating the boron isotope separation factor alpha is shown as follows:
separation factor α= [ c ] 0 α 1 (1+α 1 )-c 1 α 1 (1+α 0 )]/[c 0 α 0 (1+α 1 )-c 1 α 1 (1+α 0 )]
Wherein alpha is a separation factor, alpha 0 Abundance ratio of boron isotope in raw material boric acid water solution 11 B/ 10 B) 4.02008; alpha 1 Is the abundance ratio of boron isotopes in the boric acid aqueous solution in the raffinate 11 B/ 10 B)；c 0 Is the concentration of boron in the raw material liquid and mol/L; c 1 Is the concentration of boric acid in raffinate, mol/L.
Example 2:
the aqueous solution of boric acid is used as raw material liquid, and 0.109mol/L boric acid is contained. Mixing 2-ethyl-1, 3-hexanediol/menthol according to a molar ratio of 3:1, taking the mixed solution as deep eutectic solvent, performing single-stage extraction at the temperature of 25 ℃ at the room temperature of 1/5, oscillating for 10min at 300rpm, standing and phase-separating to obtain raffinate. And measuring the boron content and the boron isotope abundance in the residual liquid, comparing the boron content and the boron isotope abundance with the initial boron content and the initial boron abundance of the raw material liquid, and calculating to obtain the separation factor of the boron isotope as 1.021. The obtained organic phase loaded with boron is back-extracted by 0.40mol/L NaOH, and compared with 1/1 of back-extraction, the single-stage back-extraction rate is 91.32%.
Example 3:
the boric acid aqueous solution is used as raw material liquid, and 0.1938mol/L boric acid is contained. Mixing 3- (2-ethylhexyl oxy) -1, 2-propylene glycol/cresol according to a molar ratio of 1:1, taking the mixed solution as deep eutectic solvent, performing single-stage extraction at the temperature of 25 ℃ at the room temperature of 2/1, oscillating for 10min at 300rpm, standing and phase-separating to obtain raffinate. And measuring the boron content and the boron isotope abundance in the residual liquid, comparing the boron content and the boron isotope abundance with the initial boron content and the initial boron abundance of the raw material liquid, and calculating to obtain the separation factor of the boron isotope of 1.025.
Example 4:
the boric acid aqueous solution is used as raw material liquid, and 0.1938mol/L boric acid is contained. Salicylic acid/2, 3-xylenol is mixed according to the mol ratio of 2:1, the mixed solution is used as deep eutectic solvent, single-stage extraction is carried out at room temperature of 25 ℃ for 10min at the temperature of 1/1, shaking is carried out at 300rpm, and raffinate is obtained after standing and phase separation. And measuring the boron content and the boron isotope abundance in the residual liquid, comparing the boron content and the boron isotope abundance with the initial boron content and the initial boron abundance of the raw material liquid, and calculating to obtain the separation factor of the boron isotope as 1.011.
Example 5:
the aqueous solution of boric acid is used as raw material liquid, which contains 0.478mol/L boric acid. The diethanolamine lauric acid/propofol is mixed according to the mol ratio of 1:3, the mixed solution is used as deep eutectic solvent, single-stage extraction is carried out at the room temperature of 25 ℃ with the ratio of 5/1, shaking is carried out for 10min at 300rpm, and raffinate is obtained after standing and phase separation. And measuring the boron content and the boron isotope abundance in the residual liquid, comparing the boron content and the boron isotope abundance with the initial boron content and the initial boron abundance of the raw material liquid, and calculating to obtain the separation factor of the boron isotope of 1.026.
Example 6:
the boric acid aqueous solution is used as raw material liquid, and 0.1938mol/L boric acid is contained. 2-butyl-2-ethyl-1, 3-propylene glycol/4-ethylphenol is mixed according to a molar ratio of 2:1, the mixed solution is used as deep eutectic solvent, single-stage extraction is carried out at room temperature of 25 ℃ for 10min at room temperature, shaking is carried out at 300rpm, and raffinate is obtained after standing and phase separation. And measuring the boron content and the boron isotope abundance in the residual liquid, comparing the boron content and the boron isotope abundance with the initial boron content and the initial boron abundance of the raw material liquid, and calculating to obtain the separation factor of the boron isotope of 1.020.
Example 7:
the boric acid aqueous solution is used as raw material liquid, and 0.1938mol/L boric acid is contained. 2, 4-trimethyl-1, 3-pentanediol/menthol is mixed according to the mol ratio of 2:1, the mixed solution is used as deep eutectic solvent, single-stage extraction is carried out at the room temperature of 25 ℃ for 10min at the phase ratio of 1/1, shaking is carried out at 300rpm, and raffinate is obtained after standing and phase separation. And measuring the boron content and the boron isotope abundance in the residual liquid, comparing the boron content and the boron isotope abundance with the initial boron content and the initial boron abundance of the raw material liquid, and calculating to obtain the separation factor of the boron isotope of 1.031. The obtained organic phase loaded with boron is back-extracted by 0.12mol/L NaOH, and compared with 1/3 of the back-extraction, the single-stage back-extraction rate is 88.18%.
Example 8:
the boric acid aqueous solution is used as raw material liquid, and 0.1938mol/L boric acid is contained. Mixing l, 3-undecanediol/1-dodecanol according to a molar ratio of 2:1, taking the mixed solution as deep eutectic solvent, performing single-stage extraction at the temperature of 25 ℃ at the room temperature of 1/1, oscillating for 10min at 300rpm, standing and phase-separating to obtain raffinate. And measuring the boron content and the boron isotope abundance in the residual liquid, comparing the boron content and the boron isotope abundance with the initial boron content and the initial boron abundance of the raw material liquid, and calculating to obtain the separation factor of the boron isotope of 1.030.
In the above examples, 2, 4-trimethyl-1, 3-pentanediol and thymol are solid at room temperature, and can not be directly extracted and separated when used alone, and toluene and CCl are required to be added 4 The deep eutectic solvent avoids the use of the traditional diluents, is used as a novel green solvent, and has the characteristics of low volatility, biodegradability, reproducibility, low toxicity, wider electrochemical stability and the like compared with the traditional solvents.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope of the claims are within the scope of the present invention.
Claims (10)
1. A hydrophobic deep eutectic solvent for extraction separation of boron isotopes, comprising a hydrogen bond donor comprising a dihydric alcohol compound comprising a dihydroxy group and a hydrogen bond acceptor comprising a compound comprising a phenolic hydroxy group and/or a solid monohydric alcohol.
2. The hydrophobic deep eutectic solvent of claim 1, wherein: the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1:3-3:1.
3. The hydrophobic deep eutectic solvent of claim 1, wherein: the hydrogen bond donor has a structure as shown in formula (I) and/or formula (II):
wherein R is 1 、R 2 And R is 3 Are independently selected from any one of hydrogen, C1-C10 straight chain or branched alkyl, C1-C10 straight chain or branched substituted alkyl, phenyl ether, thiophene, naphthalene, carboxyl and amino;
preferably, the hydrogen bond donor includes any one or a combination of two or more of 2-ethyl-1, 3-hexanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2-diaryl-1, 3-propanediol, 2-diethyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 3- (2-ethylhexyloxy) -1, 2-propanediol, salicylic acid alcohol, diethanolamine lauric acid, 2, 4-dimethyl-2, 4-dodecanediol, 2-methyl-3-benzyl-1, 3-butanediol, 2-benzyl-2, 4-pentanediol, 2-dimethyl-1-benzyl-1, 3-propanediol, and 1, 3-undecanediol.
4. The hydrophobic deep eutectic solvent of claim 1, wherein: the hydrogen bond acceptor comprises any one or more than two of thymol, cresol, 3-methyl-4-isopropylphenol, 6-tertiary butyl m-cresol, 2, 3-xylenol, propofol, 4-ethylphenol, menthol and 1-dodecanol.
5. Use of the hydrophobic deep eutectic solvent of any one of claims 1-4 for extractive separation of boron isotopes.
6. Separation from aqueous boric acid solution 10 A method of producing a B isotope, comprising:
providing a hydrophobic deep eutectic solvent of any one of claims 1-4;
and mixing the hydrophobic deep eutectic solvent with boric acid water solution for extraction, thereby realizing 10 Enrichment of the B isotope.
7. The method according to claim 6, wherein: the concentration of boric acid in the boric acid aqueous solution is 1-30 g/L.
8. The method according to claim 6, wherein: the volume ratio of the hydrophobic deep eutectic solvent to the boric acid aqueous solution is 1:5-5:1.
9. The method according to claim 6, characterized in that it comprises in particular: mixing the hydrophobic deep eutectic solvent with boric acid water solution, and performing single-stage extraction at 10-40 ℃ to obtain a rich product 10 And B isotope solution.
10. The method as recited in claim 9, further comprising: the back extractant is adopted for the enrichment 10 Back-extracting the B isotope solution at 10-40 deg.C to obtain enriched solution 10 B isotope aqueous solution;
wherein the stripping agent comprises sodium hydroxide aqueous solution; preferably, the concentration of the sodium hydroxide aqueous solution is 0.1-0.5 mol/L; preferably, the stripping agent is rich in 10 The volume ratio of the B isotope solution is 1:3-5:1.
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| CN117244402B (en) * | 2023-11-17 | 2024-02-09 | 西安稀有金属材料研究院有限公司 | Method for extracting and separating boron isotopes |
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