CN112430192A - Dialkylamino phenoxyacetic acid precipitator and preparation method and application thereof - Google Patents
Dialkylamino phenoxyacetic acid precipitator and preparation method and application thereof Download PDFInfo
- Publication number
- CN112430192A CN112430192A CN202011328467.0A CN202011328467A CN112430192A CN 112430192 A CN112430192 A CN 112430192A CN 202011328467 A CN202011328467 A CN 202011328467A CN 112430192 A CN112430192 A CN 112430192A
- Authority
- CN
- China
- Prior art keywords
- precipitator
- rare earth
- acid
- ion
- phenoxyacetic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 Dialkylamino phenoxyacetic acid Chemical compound 0.000 title claims abstract description 72
- 239000012716 precipitator Substances 0.000 title claims abstract description 66
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxy-acetic acid Natural products OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 100
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 35
- 125000004663 dialkyl amino group Chemical group 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002244 precipitate Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 9
- 238000010828 elution Methods 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 238000007127 saponification reaction Methods 0.000 claims description 18
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 15
- HZQYAEDFCYEQMF-UHFFFAOYSA-N (4-aminophenyl) hydrogen carbonate Chemical compound NC1=CC=C(OC(O)=O)C=C1 HZQYAEDFCYEQMF-UHFFFAOYSA-N 0.000 claims description 13
- LOVPHSMOAVXQIH-UHFFFAOYSA-N (4-nitrophenyl) hydrogen carbonate Chemical compound OC(=O)OC1=CC=C([N+]([O-])=O)C=C1 LOVPHSMOAVXQIH-UHFFFAOYSA-N 0.000 claims description 11
- 150000007522 mineralic acids Chemical class 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- 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 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 238000005804 alkylation reaction Methods 0.000 claims description 6
- 150000008282 halocarbons Chemical class 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims 1
- RJOJUSXNYCILHH-UHFFFAOYSA-N gadolinium(3+) Chemical compound [Gd+3] RJOJUSXNYCILHH-UHFFFAOYSA-N 0.000 claims 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 claims 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims 1
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 48
- 238000011068 loading method Methods 0.000 abstract description 4
- MMDSMWGHQSXYMV-UHFFFAOYSA-N 3-methyl-2-phenoxynonanoic acid Chemical compound CCCCCCC(C)C(C(O)=O)OC1=CC=CC=C1 MMDSMWGHQSXYMV-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 230000001376 precipitating effect Effects 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 7
- 239000001099 ammonium carbonate Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 230000020477 pH reduction Effects 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- AMVRSHNTGTWNLY-UHFFFAOYSA-N 2-amino-2-phenoxyacetic acid Chemical compound OC(=O)C(N)OC1=CC=CC=C1 AMVRSHNTGTWNLY-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000002479 acid--base titration Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 239000002168 alkylating agent Substances 0.000 description 3
- 229940100198 alkylating agent Drugs 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 2
- AYMUQTNXKPEMLM-UHFFFAOYSA-N 1-bromononane Chemical compound CCCCCCCCCBr AYMUQTNXKPEMLM-UHFFFAOYSA-N 0.000 description 2
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 2
- QJGFNGJJRGJYJQ-UHFFFAOYSA-N (4-nitrophenyl) ethaneperoxoate Chemical compound CC(=O)OOC1=CC=C([N+]([O-])=O)C=C1 QJGFNGJJRGJYJQ-UHFFFAOYSA-N 0.000 description 1
- GIFGMEWQGDEWKB-UHFFFAOYSA-N 2-(4-aminophenoxy)acetic acid Chemical compound NC1=CC=C(OCC(O)=O)C=C1 GIFGMEWQGDEWKB-UHFFFAOYSA-N 0.000 description 1
- AVDLFIONKHGQAP-UHFFFAOYSA-N 4-nitrophenoxyacetic acid Chemical compound OC(=O)COC1=CC=C([N+]([O-])=O)C=C1 AVDLFIONKHGQAP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006959 Williamson synthesis reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of rare earth resource recovery, and particularly relates to a dialkyl amino phenoxyacetic acid precipitator and a preparation method and application thereof. The dialkyl amino phenoxyacetic acid precipitator provided by the invention has a chemical structure shown in formula (I), wherein R1 and R2 are independently selected from C6～C12Alkyl group of (1). Compared with the existing industrial application precipitator, the dialkyl amino phenoxyacetic acid precipitator provided by the invention has higher precipitation capacity, high precipitation efficiency and larger precipitation particles, and is beneficial to separation of rare earth precipitation and a water phase; in addition, the water phase residue of the precipitator is low, and the precipitator can be repeatedly used, so that the economic cost is saved, and the production efficiency is improved. Precipitate with other existing alkyl phenoxy carboxylic acidsCompared with the reagent (such as sec-octyl phenoxyacetic acid), the precipitator provided by the invention has two coordination sites of O and N, so that more rare earth ions can be adsorbed, the saturated loading capacity of the precipitator at the equilibrium is obviously higher, the required dosage is less, and the process cost can be saved.
Description
Technical Field
The invention belongs to the field of rare earth resource recovery, and particularly relates to a dialkyl amino phenoxyacetic acid precipitator and a preparation method and application thereof.
Background
The ionic rare earth ore is a rare earth ore which is special in China and is rich in medium and heavy rare earth elements. The chemical precipitation method is widely applied to industry for enriching rare earth elements in ionic rare earth ore leachate, and commonly used precipitating agents comprise oxalic acid, ammonium bicarbonate, magnesium oxide, calcium oxide and the like. The precipitant has large processing capacity and simple operation process, but has more problems, such as higher price of the oxalic acid precipitant, high oxalic acid residue in the precipitation mother liquor, higher toxicity and easy environmental pollution; the precipitator cannot be recycled, so that the economic cost is high; the tail liquid has ammonia nitrogen pollution and is difficult to treat; the more important problems are small size of the precipitate, long aging period and difficult solid-liquid separation.
Therefore, it is necessary to develop a new precipitant to realize the efficient and economical enrichment of rare earth.
Disclosure of Invention
In view of the above, the present invention provides a dialkylamino phenoxyacetic acid precipitant, and a preparation method and an application thereof, and the dialkylamino phenoxyacetic acid precipitant provided by the present invention is applied to the enrichment of low-concentration rare earth, which can shorten the precipitation period, improve the enrichment rate, and can realize the reuse of the precipitant.
The invention provides a dialkyl amino phenoxyacetic acid precipitator, which has a chemical structure shown in a formula (I):
wherein R1 and R2 are independently selected from C6～C12Alkyl group of (1).
Preferably, the dialkylaminophenoxyacetic acid precipitator is one or more of compounds shown in formulas (I-1) to (I-4):
the invention provides a preparation method of a dialkyl amino phenoxyacetic acid precipitator, which comprises the following steps:
a) mixing p-nitrophenol, sodium haloacetate, alkali, alcohol and water, heating and refluxing for reaction to obtain p-nitrophenoxycarboxylate;
b) carrying out hydrogenation reduction on the p-nitrophenoxy carboxylate to obtain p-aminophenoxy carboxylate;
c) reacting the p-aminophenoxy carboxylate with halogenated hydrocarbon to carry out alkylation reaction, and then acidifying the reaction product to obtain a dialkyl amino phenoxyacetic acid precipitator with the structure shown in the formula (I);
wherein R1 and R2 are independently selected from C6～C12Alkyl group of (1).
Preferably, in the step a), the reaction temperature is 90-110 ℃; the reaction time is 0.5-6 h.
The invention provides a method for enriching rare earth, which comprises the following steps:
A) after the dialkyl amino phenoxyacetic acid precipitator in the technical scheme or the dialkyl amino phenoxyacetic acid precipitator prepared by the preparation method in the technical scheme is saponified, the dialkyl amino phenoxyacetic acid precipitator is mixed with feed liquid containing rare earth ions, and solid-liquid separation is carried out to obtain a precipitate;
B) and eluting the precipitate with inorganic acid solution to obtain rare earth enriched solution and regenerated dialkylaminophenoxyacetic acid precipitant.
Preferably, in step a), the saponification mode is as follows: saponifying the dialkylaminophenoxyacetic acid precipitator and hydroxide in water;
the hydroxide is ammonia monohydrate; by NH3The mass ratio of the ammonia monohydrate to the dialkyl amino phenoxyacetic acid precipitator is (0.01-0.3): 1.
preferably, in the step a), the rare earth ions contained in the feed liquid include one or more of lanthanum ions, cerium ions, praseodymium ions, neodymium ions, samarium ions, europium ions, gadolinium ions, terbium ions, dysprosium ions, holmium ions, erbium ions, thulium ions, ytterbium ions, lutetium ions, scandium ions and yttrium ions; the total concentration of rare earth ions in the feed liquid is 0.05-50 g/L; the pH value of the feed liquid is 5-7.
Preferably, in step B), the acid in the inorganic acid solution comprises one or more of hydrochloric acid, nitric acid and sulfuric acid; the concentration of the inorganic acid solution is 0.5-12 mol/L.
Preferably, in the step B), the elution temperature is 50-130 ℃.
The invention provides a saponification precipitator which has a chemical structure shown in a formula (II):
wherein R1 and R2 are independently selected from C6～C12Alkyl groups of (a); m is the residue remaining after removal of-OH from the hydroxide.
Compared with the prior art, the invention provides a dialkyl amino phenoxyacetic acid precipitator and a preparation method and application thereof. The dialkyl amino phenoxyacetic acid precipitator provided by the invention has a chemical structure shown in formula (I), wherein R1 and R2 are independently selected from C6～C12Alkyl group of (1). Compared with the existing industrial application precipitator (such as ammonium bicarbonate and ammonium carbonate), the dialkyl amino phenoxyacetic acid precipitator provided by the invention has higher precipitation capacity, high precipitation efficiency and larger precipitation particles, and is beneficial to separation of rare earth precipitation and a water phase; in addition, the water phase residue of the precipitator is low, and the precipitator can be repeatedly used, so that the economic cost is saved, and the production efficiency is improved. Compared with other existing alkyl phenoxy carboxylic acid precipitants (such as sec-octyl phenoxy acetic acid), the precipitant provided by the invention has two coordination sites of O and N, so that more rare earth ions can be adsorbed, the saturated loading capacity of the precipitant is obviously higher in balance, the required dosage is less, and the process can be savedAnd (4) cost.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a dialkyl amino phenoxyacetic acid precipitator, which has a chemical structure shown in a formula (I):
wherein R1 and R2 are independently selected from C6～C12More specifically may be C6Alkyl radical, C7Alkyl radical, C8Alkyl radical, C9Alkyl radical, C10Alkyl radical, C11Alkyl or C12An alkyl group.
In the invention, the dialkylaminophenoxyacetic acid precipitant can be specifically one or more of the compounds shown in formulas (I-1) to (I-4):
the invention also provides a preparation method of the dialkyl amino phenoxyacetic acid precipitator, which comprises the following steps:
a) mixing p-nitrophenol, sodium haloacetate, alkali, alcohol and water, heating and refluxing for reaction to obtain p-nitrophenoxycarboxylate;
b) carrying out hydrogenation reduction on the p-nitrophenoxy carboxylate to obtain p-aminophenoxy carboxylate;
c) reacting the p-aminophenoxy carboxylate with halogenated hydrocarbon to carry out alkylation reaction, and then acidifying the reaction product to obtain a dialkyl amino phenoxyacetic acid precipitator with the structure shown in the formula (I);
wherein R1 and R2 are independently selected from C6～C12More specifically may be C6Alkyl radical, C7Alkyl radical, C8Alkyl radical, C9Alkyl radical, C10Alkyl radical, C11Alkyl or C12An alkyl group.
In the preparation method provided by the invention, the p-nitrophenol, the sodium haloacetate, the alkali, the alcohol and the water are firstly mixed. Wherein the sodium haloacetate is preferably sodium chloroacetate; the base is preferably sodium hydroxide; the alcohol includes, but is not limited to, one or more of ethanol, propanol, isopropanol, and butanol, preferably ethanol for economical reasons; the molar ratio of the p-nitrophenol to the sodium haloacetate is preferably 1: (1-2), specifically 1: 1.5; the molar ratio of the p-nitrophenol to the base is preferably 1: (0.5-2), specifically 1: 1; the dosage ratio of the p-nitrophenol to the alcohol is preferably 0.1 mol: (20-100) mL, specifically 0.1 mol: 50 mL; the dosage ratio of the p-nitrophenol to the water is preferably 0.1 mol: (20-100) mL, specifically 0.1 mol: 50 mL; preferably, a certain amount of catalyst is further added into a mixed system consisting of the p-nitrophenol, the sodium haloacetate, the alkali, the alcohol and the water, the catalyst is preferably KI, and the dosage ratio of the catalyst to the p-nitrophenol is preferably (0.1-0.5) g: 0.1mol, in particular 0.2 g: 0.1 mol. In the present invention, the specific process of mixing is preferably as follows: mixing p-nitrophenol, alcohol and water, mixing with alkali, and finally mixing with sodium haloacetate and catalyst.
In the preparation method provided by the invention, after the materials are uniformly mixed, heating and refluxing are carried out to carry out Williamson reaction. Wherein the reaction temperature is preferably 90-110 ℃, and specifically can be 90 ℃, 95 ℃, 100 ℃, 105 ℃ or 110 ℃; the reaction time is preferably 0.5-6 h, and specifically can be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6 h. After the reaction is finished, removing alcohol in the reaction product to obtain the p-nitrophenoxy carboxylate product. Among them, the alcohol removal method is preferably rotary evaporation.
In the preparation method provided by the invention, after the p-nitrophenoxycarboxylate is obtained, the p-nitrophenoxycarboxylate is subjected to hydrogenation reduction. In the present invention, the specific steps of the hydrogenation reduction preferably include: firstly, mixing p-nitrophenoxycarboxylate, a catalyst and a solvent, then heating a mixed system to a reaction temperature, and introducing hydrogen into the mixed system to perform a reduction reaction. The catalyst is preferably a Pd/C catalyst, and the Pd loading amount of the Pd/C catalyst is preferably 5-15 wt.%, and specifically can be 10 wt.%; the solvent is preferably ethanol; the dosage ratio of the catalyst to p-nitrophenol serving as a raw material for preparing the p-nitrophenoxy carboxylate is preferably (1-10) mg: 0.1mol, in particular 5 mg: 0.1 mol; the reaction temperature is preferably 60-90 ℃, and specifically can be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃; the time of the reduction reaction is preferably 2-8 h, and specifically can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 6h, 7h or 8 h. And after the hydrogenation reduction is finished, carrying out solid-liquid separation on the obtained reduction product and removing the solvent by rotary evaporation to obtain the p-aminophenoxy carboxylate.
In the preparation method provided by the invention, after the p-aminophenoxy carboxylate is obtained, alkylation reaction is carried out on the p-aminophenoxy carboxylate. In the present invention, the specific steps of the alkylation reaction preferably include: mixing and reacting p-aminophenoxy carboxylate, alkali metal hydroxide, halogenated hydrocarbon and a solvent. Wherein the alkali metal hydroxide includes, but is not limited to, sodium hydroxide; the halogenated hydrocarbon is selected according to the R1 and R2 substituents of the dialkylaminophenoxyacetic acid precipitant to be produced, including but not limited to one or more of 1-bromohexane, 1-bromooctane, 1-bromononane, and 1-bromododecane; the solvent is preferably ethanol; the molar ratio of the alkali metal hydroxide to p-nitrophenol serving as a raw material for preparing the p-aminophenoxy carboxylate is preferably (0.5-2): 1, specifically 1: 1; the molar ratio of the halogenated hydrocarbon to p-nitrophenol serving as a raw material for preparing the p-aminophenoxy carboxylate is preferably (1-3): 1, specifically 2: 1; the temperature of the mixing reaction is preferably 60-90 ℃, and specifically can be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃; the mixing reaction time is preferably 4-8 h, and specifically can be 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h or 8 h.
In the preparation method provided by the invention, after the alkylation reaction is finished, the reaction product is acidified. Wherein, the acid solution used for acidification includes but is not limited to one or more of hydrochloric acid solution, sulfuric acid solution, nitric acid solution and phosphoric acid solution, and is preferably hydrochloric acid solution for economic reasons; the concentration of the acid liquor is preferably 0.5-12 mol/L, and specifically can be 0.5mol/L, 1mol/L, 2mol/L, 4mol/L, 6mol/L, 8mol/L, 10mol/L and 12 mol/L; the acidification temperature is preferably 15-35 ℃, and specifically can be 25 ℃ (room temperature); the pH value of the final point of acidification is preferably 1-3, and specifically can be 2. After the acidification is finished, performing rotary evaporation, water washing and drying on the acidification product to obtain the dialkyl amino phenoxyacetic acid precipitator with the structure shown in the formula (I).
Compared with the existing industrial application precipitator (such as ammonium bicarbonate and ammonium carbonate), the dialkyl amino phenoxyacetic acid precipitator provided by the invention has higher precipitation capacity, high precipitation efficiency and larger precipitation particles, and is beneficial to separation of rare earth precipitation and a water phase; in addition, the water phase residue of the precipitator is low, and the precipitator can be repeatedly used, so that the economic cost is saved, and the production efficiency is improved. Compared with other existing alkyl phenoxy carboxylic acid precipitants (such as sec-octyl phenoxy acetic acid), the precipitant provided by the invention has two coordination sites of O and N, so that more rare earth ions can be adsorbed, the saturated loading capacity of the precipitant is obviously higher during balance, the required dosage is less, and the process cost can be saved.
The invention also provides a method for enriching rare earth, which comprises the following steps:
A) after the dialkyl amino phenoxyacetic acid precipitator in the technical scheme or the dialkyl amino phenoxyacetic acid precipitator prepared by the preparation method in the technical scheme is saponified, the dialkyl amino phenoxyacetic acid precipitator is mixed with feed liquid containing rare earth ions, and solid-liquid separation is carried out to obtain a precipitate;
B) and eluting the precipitate with inorganic acid solution to obtain rare earth enriched solution and regenerated dialkylaminophenoxyacetic acid precipitant.
In the enrichment method provided by the invention, the precipitant is firstly saponified, and the specific mode is preferably as follows: and (3) carrying out saponification reaction on the dialkyl amino phenoxyacetic acid precipitator and hydroxide in water. Wherein, the hydroxide includes but is not limited to one or more of sodium hydroxide, potassium hydroxide and ammonium monohydrate, and is preferably ammonium monohydrate for economic reasons; by NH3The mass ratio of the ammonium monohydrate to the dialkylaminophenoxyacetic acid precipitator is preferably (0.01-0.3): 1, specifically 0.01:1, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1 or 0.3: 1; the temperature of the saponification reaction is preferably 15-35 ℃, and specifically can be 25 ℃ (room temperature); the time of the saponification reaction is preferably 10-60 min, and specifically may be 10min, 20min, 30min, 40min, 50min or 60 min. And obtaining the saponification precipitator after the saponification is finished.
In the enrichment method provided by the invention, after the saponification precipitator is obtained, the saponification precipitator is mixed with the feed liquid containing rare earth ions. The rare earth ions contained in the feed liquid include but are not limited to one or more of lanthanum ions, cerium ions, praseodymium ions, neodymium ions, samarium ions, europium ions, gadolinium ions, terbium ions, dysprosium ions, holmium ions, erbium ions, thulium ions, ytterbium ions, lutetium ions, scandium ions and yttrium ions; the total concentration of rare earth ions in the feed liquid is preferably 0.05-50 g/L, and specifically can be 0.05g/L, 1g/L, 2g/L, 2.3g/L, 3g/L, 5g/L, 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L or 50 g/L; the pH value of the feed liquid is preferably 5-7, and specifically can be 5, 5.5, 6, 6.5 or 7; the dosage ratio of the saponification precipitating agent to the feed liquid calculated by the dialkyl amino phenoxy acetic acid precipitating agent is preferably 33.5 g: (0.5-5) L, specifically 33.5 g: 0.5L, 33.5 g: 1L, 33.5 g: 1.5L, 33.5 g: 2L, 33.5 g: 2.5L, 33.5 g: 3L, 33.5 g: 3.5L, 33.5 g: 4L, 33.5 g: 4.5L or 33.5 g: 5L; the mixing temperature is preferably 15-35 ℃, and specifically can be 25 ℃ (room temperature); the mixing time is preferably 1-10 min, and specifically can be 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10 min. And after the mixing is finished, carrying out solid-liquid separation to obtain a precipitate enriched with rare earth ions.
In the enrichment method provided by the invention, after the precipitate is obtained, the precipitate is eluted by using an inorganic acid solution. Wherein the acid in the inorganic acid solution includes but is not limited to one or more of hydrochloric acid, nitric acid and sulfuric acid; the concentration of the inorganic acid solution is preferably 0.5-12 mol/L, and specifically can be 0.5mol/L, 1mol/L, 2mol/L, 4mol/L, 6mol/L, 8mol/L, 10mol/L and 12 mol/L; the temperature of the elution is preferably 50-130 ℃, and specifically can be 50 ℃, 80 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃. In the elution process, the rare earth ions in the precipitate gradually enter into the acid liquor, and finally the rare earth enrichment solution and the regenerated dialkylaminophenoxyacetic acid precipitant are obtained.
The enrichment method provided by the invention enriches the rare earth ions in the feed liquid by using the saponified precipitator, has the advantages of short precipitation period, high enrichment rate, realization of the reuse of the precipitator and very good market prospect.
The invention also provides a saponification precipitating agent which has a chemical structure shown in a formula (II):
wherein R1 and R2 are independently selected from C6～C12Alkyl groups of (a); m is the residue remaining after removal of-OH from the hydroxide, including but not limited to NH4 +。
The saponification precipitating agent provided by the invention is a saponification product of a dialkyl amino phenoxyacetic acid precipitating agent with a structure shown in a formula (II), can be used for precipitating and enriching rare earth ions in rare earth-containing feed liquid, and has a very good market application prospect.
For the sake of clarity, the following examples are given in detail.
In the following examples and comparative examples, characterization was performed by the method for chemical analysis of rare earth metals and compounds thereof-determination of total amount of rare earth GB/T14635-. The precipitation rate P, the elution rate St and the total enrichment rate E (total) are calculated as follows: the concentrations of the rare earth ions in the water phase before and after precipitation are respectively C0 and C1, and the volumes are respectively V0 and V1; assuming that the concentration and volume of the rare earth ions in the water phase after elution are Cst and Vst respectively, then:
precipitation rate:
elution rate:
the total enrichment ratio is as follows:
example 1
The precipitator is 4-N, N-dihexylamino phenoxyacetic acid, namely, R1 is hexyl and R2 is hexyl in the formula (I), and the chemical structure of the precipitator is shown in the formula (I-1):
the preparation method of the 4-N, N-dihexylamino phenoxyacetic acid comprises the following steps:
a three-neck flask is filled with 0.1mol of p-nitrophenol, 100mL of a mixed solvent of ethanol and water in a volume ratio of 1:1, 0.1mol of sodium hydroxide is added, and the mixture is stirred and dissolved. Then 0.15mol of sodium chloroacetate and 0.2g of KI are added, the mixture is heated to 110 ℃, and the condensation reflux reaction is carried out for 0.5 h. After the reaction is finished, cooling to room temperature, evaporating the solvent, and washing with water to obtain the p-nitrophenoxyacetate.
And mixing the p-nitrophenyloxy acetate, 5mg of a commercially available 10 wt.% Pd/C catalyst and 100mL of an ethanol solvent, controlling the reaction temperature to be 70 ℃, circularly introducing hydrogen, reacting for 4 hours, cooling to room temperature, performing solid-liquid separation, and performing rotary evaporation to remove the ethanol solvent to obtain the p-aminophenoxyacetate.
Mixing p-aminophenoxy carboxylate, 0.1mol of sodium hydroxide, 0.2mol of 1-bromohexane and 100mL of ethanol solvent, controlling the reaction temperature at 75 ℃, reacting for 6 hours, cooling to room temperature after the reaction is finished, acidifying with inorganic acid, then removing the ethanol solvent by rotary evaporation, washing with water, and drying to obtain the 4-N, N-dihexylamino phenoxyacetic acid precipitator.
The results of acid-base titration and nuclear magnetic resonance instrument characterization show that: the purity of the 4-N, N-dihexylamino phenoxyacetic acid prepared by the embodiment is more than 95%, and the total preparation yield is more than 90%.
The rare earth enrichment steps are as follows:
1) and (3) saponification of a precipitator: diluting 25 wt.% of commercial ammonia water 6.8g to 25mL with deionized water, mixing with 33.5g of 4-N, N-dihexylamino phenoxyacetic acid at room temperature, stirring and reacting for 30min to obtain a saponification precipitant.
2) Precipitation reaction: taking 2.0L of rare earth feed liquid, wherein the total rare earth content is 2.3g/L, and the mass ratio (calculated by oxides) of each rare earth element is 27.5 percent of La, 2.5 percent of Ce, 5.86 percent of Pr, 21.7 percent of Nd, 5.12 percent of Sm, 0.35 percent of Eu, 4.76 percent of Gd, 0.7 percent of Tb, 3.77 percent of Dy, 0.63 percent of Ho, 1.98 percent of Er, 0.29 percent of Tm, 1.79 percent of Yb, 0.26 percent of Lu and 22.9 percent of Y. Adjusting pH to 6, adding saponification precipitant, stirring rapidly for 5min, precipitating completely, and performing solid-liquid separation to obtain solid precipitate.
3) And (3) elution: eluting the solid precipitate with 6mol/L hydrochloric acid at 50 deg.C to make rare earth enter into acid solution, and regenerating precipitant.
The result shows that the time of the rare earth precipitation for complete sedimentation is 5min, the precipitation rate of the rare earth obtained by the precipitation reaction is 98.2 percent, the elution rate in the elution process is 95.8 percent, and the total enrichment rate of the rare earth is 94.0 percent; the residual amount of precipitant in the solution was 10.3 ppm.
Example 2
The precipitator is 4-N, N-dioctyl amino phenoxyacetic acid, namely, R1 is octyl in the formula (I), R2 is octyl, and the chemical structure is specifically shown in the formula (I-2):
4-N, N-Dioctylaminophenoxyacetic acid was prepared according to example 1, except that the alkylating agent used was 1-bromooctane.
Acid-base titration and nuclear magnetic resonance characterization are carried out, and the results show that: the purity of the 4-N, N-dioctyl amino phenoxyacetic acid prepared by the embodiment is more than 95 percent, and the total preparation yield is more than 87 percent.
The rare earth enrichment step was performed in accordance with example 1, except that the amount of the 4-N, N-dioctylaminophenoxyacetic acid precipitant was 39.1g and the elution temperature was 80 ℃.
The results show that the precipitation rate of the rare earth obtained by the precipitation reaction is 99.0 percent, the elution rate in the elution process is 96.8 percent, and the total enrichment rate of the rare earth is 95.8 percent; the residual amount of precipitant in the solution was 8.6 ppm.
Example 3
The precipitator is 4- (N-dodecyl-N-nonyl amino) phenoxyacetic acid, namely, in the formula (I), R1 is dodecyl, R2 is nonyl, and the chemical structure of the precipitator is shown as the formula (I-3):
4- (N-dodecyl-N-nonylamino) phenoxyacetic acid was prepared according to the method described in example 1, except that the alkylating agents used were 1-bromononane and 1-bromododecane, in a molar ratio of 1:1.
Acid-base titration and nuclear magnetic resonance characterization are carried out, and the results show that: the purity of the 4- (N-dodecyl-N-nonyl amino) phenoxyacetic acid prepared by the embodiment is more than 95 percent, and the total preparation yield is more than 85 percent.
The rare earth enrichment step was performed in accordance with example 1, except that the amount of the 4- (N-dodecyl-N-nonylamino) phenoxyacetic acid precipitant was 46.1g and the elution temperature was 100 ℃.
The results show that the precipitation rate of the rare earth obtained by the precipitation reaction is 99.5 percent, the elution rate in the elution process is 97.7 percent, and the total enrichment rate of the rare earth is 97.4 percent; the residual amount of precipitant in the solution was 7.5 ppm.
Example 4
The precipitator is 4-N, N-didodecyl amino phenoxyacetic acid, namely, R1 is dodecyl in formula (I), R2 is dodecyl, and the chemical structure is specifically shown in formula (I-4):
4-N, N-Didodecyl amino phenoxy acetic acid was prepared according to example 1, except that the alkylating agent used was 1-bromododecane.
Acid-base titration and nuclear magnetic resonance characterization are carried out, and the results show that: the purity of the 4-N, N-didodecyl amino phenoxy acetic acid prepared in this example is more than 94%, and the total preparation yield is more than 85%.
The rare earth enrichment step was performed in accordance with example 1, except that the amount of the 4-N, N-didodecyl aminophenoxyacetic acid precipitant was 50.4g and the elution temperature was 130 ℃.
The results show that the precipitation rate of the rare earth obtained by the precipitation reaction is 97.0 percent, the elution rate in the elution process is 98.1 percent, and the total enrichment rate of the rare earth is 95.2 percent; the residual amount of precipitant in the solution was 3.2 ppm.
Example 5
Rare earth enrichment was performed using 4-N, N-dihexylamino phenoxyacetic acid prepared in example 1 as a precipitant, and the specific rare earth enrichment procedure was as described in example 1 except that the amount of commercially available ammonia water was adjusted to 40.2 g.
The results show that the precipitation rate of the rare earth obtained by the precipitation reaction is 99.4 percent, the elution rate in the elution process is 96.2 percent, and the total enrichment rate of the rare earth is 95.6 percent; the residual amount of precipitant in the solution was 15.7 ppm.
Example 6
The 4-N, N-dihexylamino phenoxyacetic acid prepared in the example 1 is used as a precipitator for rare earth enrichment, and the specific rare earth enrichment step refers to the example 1, and is different in that the pH value of the rare earth feed liquid is adjusted to 5.
The results show that the precipitation rate of the rare earth obtained by the precipitation reaction is 97.8 percent, the elution rate in the elution process is 96.0 percent, and the total enrichment rate of the rare earth is 93.9 percent; the residual amount of precipitant in the solution was 9.8 ppm.
Example 7
The 4-N, N-dihexylamino phenoxyacetic acid prepared in the example 1 is used as a precipitator for rare earth enrichment, and the specific rare earth enrichment step refers to the example 1, and is different in that the pH value of the rare earth feed liquid is adjusted to 7.
The results show that the precipitation rate of the rare earth obtained by the precipitation reaction is 98.6 percent, the elution rate in the elution process is 96.7 percent, and the total enrichment rate of the rare earth is 95.4 percent; the residual amount of precipitant in the solution was 10.5 ppm.
Example 8
Rare earth enrichment is carried out by adopting the 4-N, N-dihexylamino phenoxyacetic acid prepared in the example 1 as a precipitator, and the specific rare earth enrichment step refers to the example 1, and the difference is that the concentration of hydrochloric acid used for elution is adjusted to be 0.5 mol/L.
The results show that the precipitation rate of the rare earth obtained by the precipitation reaction is 98.2 percent, the elution rate in the elution process is 90.3 percent, and the total enrichment rate of the rare earth is 88.7 percent; the residual amount of precipitant in the solution was 10.3 ppm.
Example 9
Rare earth enrichment is carried out by adopting the 4-N, N-dihexylamino phenoxyacetic acid prepared in the example 1 as a precipitator, and the specific rare earth enrichment step refers to the example 1, and the difference is that the concentration of hydrochloric acid used for elution is adjusted to be 12 mol/L.
The results show that the precipitation rate of the rare earth obtained by the precipitation reaction is 98.2 percent, the elution rate in the elution process is 99.8 percent, and the total enrichment rate of the rare earth is 98 percent; the residual amount of precipitant in the solution was 10.3 ppm.
Example 10
The 4-N, N-dihexylamino phenoxyacetic acid prepared in the example 1 is used as a precipitator to carry out rare earth enrichment, and the specific rare earth enrichment step refers to the example 1, wherein the difference is that the elution temperature is adjusted to be 100 ℃.
The results show that the precipitation rate of the rare earth obtained by the precipitation reaction is 98.2 percent, the elution rate in the elution process is 94.6 percent, and the total enrichment rate of the rare earth is 92.8 percent; the residual amount of precipitant in the solution was 10.3 ppm.
Example 11
The 4-N, N-dihexylamino phenoxyacetic acid prepared in the example 1 is used as a precipitator to carry out rare earth enrichment, and the specific rare earth enrichment step refers to the example 1, which is different in that the elution temperature is adjusted to 130 ℃.
The results show that the precipitation rate of the rare earth obtained by the precipitation reaction is 98.2 percent, the elution rate in the elution process is 96.2 percent, and the total enrichment rate of the rare earth is 94.5 percent; the residual amount of precipitant in the solution was 10.3 ppm.
Comparative example 1
Taking the typical industrial precipitant ammonium bicarbonate as a reference, the rare earth enrichment steps are as follows:
precipitation reaction: taking 2.0L of rare earth feed liquid, wherein the total rare earth content is 2.3g/L, the mass proportion of each rare earth element is the same as that in example 1, adjusting the pH to be 6, adding 7.9g of ammonium bicarbonate solid, stirring, and carrying out solid-liquid separation after complete precipitation reaction to obtain solid precipitate.
And (3) elution: and eluting the rare earth precipitate by using 6mol/L hydrochloric acid solution to make the rare earth enter the hydrochloric acid solution.
The results show that in the present example, the time for the rare earth precipitation to completely settle is 30min, the solid-liquid separation is difficult, and the precipitation rate of the rare earth is 96.5%.
Comparative example 2
Rare earth enrichment was performed using 4-N, N-dihexylamino phenoxyacetic acid prepared in example 1 as a precipitant, and the specific rare earth enrichment procedure was as described in example 1 except that the amount of commercially available ammonia water was adjusted to 0.34 g.
The results show that the precipitation rate of the rare earth obtained by the precipitation reaction is 24.5 percent, the elution rate in the elution process is 99.7 percent, and the total enrichment rate of the rare earth is 24.4 percent; the residual amount of precipitant in the solution was 13.4 ppm.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A dialkylaminophenoxyacetic acid precipitant having a chemical structure represented by formula (I):
wherein R1 and R2 are independently selected from C6～C12Alkyl group of (1).
2. The dialkylaminophenoxyacetic acid precipitant according to claim 1, wherein the dialkylaminophenoxyacetic acid precipitant is one or more compounds having a structure represented by formula (I-1) to formula (I-4):
3. a preparation method of a dialkyl amino phenoxyacetic acid precipitator is characterized by comprising the following steps:
a) mixing p-nitrophenol, sodium haloacetate, alkali, alcohol and water, heating and refluxing for reaction to obtain p-nitrophenoxycarboxylate;
b) carrying out hydrogenation reduction on the p-nitrophenoxy carboxylate to obtain p-aminophenoxy carboxylate;
c) reacting the p-aminophenoxy carboxylate with halogenated hydrocarbon to carry out alkylation reaction, and then acidifying the reaction product to obtain a dialkyl amino phenoxyacetic acid precipitator with the structure shown in the formula (I);
wherein R1 and R2 are independently selected from C6～C12Alkyl group of (1).
4. The preparation method according to claim 3, wherein the reaction temperature in step a) is 90-110 ℃; the reaction time is 0.5-6 h.
5. A method for enriching rare earth is characterized by comprising the following steps:
A) saponifying the dialkylaminophenoxyacetic acid precipitator according to any one of claims 1 to 2 or the dialkylaminophenoxyacetic acid precipitator prepared by the preparation method according to any one of claims 3 to 4, mixing the saponified product with a feed liquid containing rare earth ions, and performing solid-liquid separation to obtain a precipitate;
B) and eluting the precipitate with inorganic acid solution to obtain rare earth enriched solution and regenerated dialkylaminophenoxyacetic acid precipitant.
6. The method according to claim 5, wherein in step A), the saponification is performed by: saponifying the dialkylaminophenoxyacetic acid precipitator and hydroxide in water;
the hydroxide is ammonia monohydrate; by NH3The mass ratio of the ammonia monohydrate to the dialkyl amino phenoxyacetic acid precipitator is (0.01-0.3): 1.
7. the method according to claim 5, wherein in step A), the rare earth ions contained in the feed liquid comprise one or more of lanthanum ion, cerium ion, praseodymium ion, neodymium ion, samarium ion, europium ion, gadolinium ion, terbium ion, dysprosium ion, holmium ion, erbium ion, thulium ion, ytterbium ion, lutetium ion, scandium ion and yttrium ion; the total concentration of rare earth ions in the feed liquid is 0.05-50 g/L; the pH value of the feed liquid is 5-7.
8. The method according to claim 5, wherein in step B), the acid in the inorganic acid solution comprises one or more of hydrochloric acid, nitric acid and sulfuric acid; the concentration of the inorganic acid solution is 0.5-12 mol/L.
9. The method according to claim 5, wherein the temperature of the elution in the step B) is 50-130 ℃.
10. A saponification precipitant characterized by having a chemical structure represented by formula (II):
wherein R1 and R2 are independently selected from C6～C12Alkyl groups of (a); m is the residue remaining after removal of-OH from the hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011328467.0A CN112430192A (en) | 2020-11-24 | 2020-11-24 | Dialkylamino phenoxyacetic acid precipitator and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011328467.0A CN112430192A (en) | 2020-11-24 | 2020-11-24 | Dialkylamino phenoxyacetic acid precipitator and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112430192A true CN112430192A (en) | 2021-03-02 |
Family
ID=74693957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011328467.0A Pending CN112430192A (en) | 2020-11-24 | 2020-11-24 | Dialkylamino phenoxyacetic acid precipitator and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112430192A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106702180A (en) * | 2015-07-29 | 2017-05-24 | 王艳良 | Scandium element extraction method |
| CN107628955A (en) * | 2017-09-04 | 2018-01-26 | 中国石油集团长城钻探工程有限公司钻井液公司 | Water-base drilling fluid amido inhibitor, water base drilling fluid system and preparation method |
| CN111020188A (en) * | 2019-12-04 | 2020-04-17 | 厦门稀土材料研究所 | Extracting agent and preparation method and application thereof |
| RU2726519C1 (en) * | 2019-12-09 | 2020-07-14 | Акционерное общество "Радиевый институт имени В.Г. Хлопина" | Extraction mixture for extracting tpe and rare earth from highly active raffinate of oat grain processing and method of its application |
-
2020
- 2020-11-24 CN CN202011328467.0A patent/CN112430192A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106702180A (en) * | 2015-07-29 | 2017-05-24 | 王艳良 | Scandium element extraction method |
| CN107628955A (en) * | 2017-09-04 | 2018-01-26 | 中国石油集团长城钻探工程有限公司钻井液公司 | Water-base drilling fluid amido inhibitor, water base drilling fluid system and preparation method |
| CN111020188A (en) * | 2019-12-04 | 2020-04-17 | 厦门稀土材料研究所 | Extracting agent and preparation method and application thereof |
| RU2726519C1 (en) * | 2019-12-09 | 2020-07-14 | Акционерное общество "Радиевый институт имени В.Г. Хлопина" | Extraction mixture for extracting tpe and rare earth from highly active raffinate of oat grain processing and method of its application |
Non-Patent Citations (1)
| Title |
|---|
| 申令生, 水利电力出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101798627B (en) | Method for precipitating rare earth | |
| CN103374652B (en) | Method for comprehensively recycling rare earth and fluorine in process of treating bastnaesite | |
| CN112575188B (en) | Dialkyl amino phenoxyacetic acid extracting agent, preparation method and application thereof | |
| US10697042B2 (en) | Methods and composition for sequential isolation of rare earth elements | |
| CN104928504B (en) | A kind of recovery method of aluminium scrap silicon middle rare earth | |
| US20190032172A1 (en) | Making mineral salts from various sources | |
| CN105087924B (en) | A kind of leaching agent and its leaching method for reinforced leaching ion type rareearth ore | |
| CN104928475A (en) | Recycling method of rare earth-containing aluminum silicon waste material | |
| CN110699546B (en) | Extracting agent and preparation method and application thereof | |
| CN111440946B (en) | Rare earth extraction method for realizing recycling of magnesium bicarbonate | |
| CN112430192A (en) | Dialkylamino phenoxyacetic acid precipitator and preparation method and application thereof | |
| CN100387524C (en) | Method of preparing rare earth fluoride from rare earth oxide | |
| JP5905592B2 (en) | Rare earth element separation method and separation apparatus | |
| CN114180613B (en) | Method for preparing rare earth oxide by recycling ammonia and carbon and application of rare earth oxide | |
| CN105861831A (en) | Method for precipitation recycling of rare earth from rare earth salt solution | |
| CN116621847A (en) | Desulfurization and denitrification agent and application thereof | |
| EP3342886B1 (en) | Useful method for separating light rare earth elements and heavy rare earth elements | |
| CN115441029A (en) | Vanadium electrolyte and preparation method and application thereof | |
| KR20190109082A (en) | Recovery method rare earth elements from waste RE:YAG crystal | |
| CN105861828B (en) | A kind of rare earth complex chemical compound containing rare earth hydrate and rare earth carbonate and preparation method thereof | |
| CN113444883B (en) | Mixed extracting agent and method for enriching rare earth by using same | |
| CN110438351A (en) | A kind of rare earth impurities separation method | |
| CN112250110A (en) | Preparation method of ammonium metavanadate without wastewater discharge | |
| WO2021000721A1 (en) | Method for saponifying rare-earth organic extractant | |
| CN113462910B (en) | Enrichment method of rare earth ions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220606 Address after: 361000 new industrial zone, Changting Economic Development Zone, Longyan City, Fujian Province Applicant after: FUJIAN CHANGTING GOLDEN DRAGON RARE-EARTH Co.,Ltd. Address before: 361027 Ke Jing she, Haicang District, Xiamen City, Fujian Province Applicant before: XIAMEN TUNGSTEN Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210302 |
|
| RJ01 | Rejection of invention patent application after publication |