CN106145078A - Method for synthesizing neodymium phosphate solution and synthesized neodymium phosphate solution - Google Patents
Method for synthesizing neodymium phosphate solution and synthesized neodymium phosphate solution Download PDFInfo
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- CN106145078A CN106145078A CN201510142593.XA CN201510142593A CN106145078A CN 106145078 A CN106145078 A CN 106145078A CN 201510142593 A CN201510142593 A CN 201510142593A CN 106145078 A CN106145078 A CN 106145078A
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- solution
- phosphate
- metal halide
- neodymium
- phosphoric acid
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- DZNFWGVDYGAMJB-UHFFFAOYSA-K neodymium(3+);phosphate Chemical compound [Nd+3].[O-]P([O-])([O-])=O DZNFWGVDYGAMJB-UHFFFAOYSA-K 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 65
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 97
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- -1 phosphate ester Chemical class 0.000 claims abstract description 37
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 35
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 35
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 30
- 239000010452 phosphate Substances 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 19
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims description 50
- 239000003054 catalyst Substances 0.000 claims description 47
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 41
- 235000021317 phosphate Nutrition 0.000 claims description 32
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 28
- 150000002910 rare earth metals Chemical class 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 18
- 230000000694 effects Effects 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 12
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 150000005309 metal halides Chemical class 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- 150000001924 cycloalkanes Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 4
- DBLHYLDWZSNRBI-UHFFFAOYSA-N N=NC=NN.N=NC=NN.P(=O)(O)(O)O Chemical compound N=NC=NN.N=NC=NN.P(=O)(O)(O)O DBLHYLDWZSNRBI-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 18
- 229920001971 elastomer Polymers 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000005060 rubber Substances 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000003292 glue Substances 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 229920003051 synthetic elastomer Polymers 0.000 abstract description 3
- 239000005061 synthetic rubber Substances 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 230000032683 aging Effects 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 229910000159 nickel phosphate Inorganic materials 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000037048 polymerization activity Effects 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 229910052779 Neodymium Inorganic materials 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 5
- KWKDMHWAAVTQSZ-UHFFFAOYSA-N neodymium phosphoric acid Chemical compound [Nd].P(O)(O)(O)=O KWKDMHWAAVTQSZ-UHFFFAOYSA-N 0.000 description 5
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HCIQUGMKXQZZMG-UHFFFAOYSA-N ethyl hexyl hydrogen phosphate Chemical compound CCCCCCOP(O)(=O)OCC HCIQUGMKXQZZMG-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A method for synthesizing a neodymium phosphate solution and the synthesized neodymium phosphate solution, the method comprises the following steps: preparing a metal halide salt into a saturated metal halide salt aqueous solution; mixing acidic phosphate with an organic solvent to obtain a phosphate solution, wherein the volume ratio of the acidic phosphate to the organic solvent is 1: 2-1: 20; adding neodymium oxide solid powder into a phosphate solution, stirring to obtain a turbid solution, and heating to 20-50 ℃; adding the saturated metal halide salt aqueous solution into the turbid solution, heating and stirring, adding a molecular sieve, reacting for 20-90 minutes at 20-70 ℃, standing and layering after the reaction is finished, separating to obtain an oil phase which is a neodymium phosphate solution, wherein the molar ratio of the metal halide salt to the acidic phosphate ester is controlled to be 1: 5-1: 50. the neodymium phosphate solution contains a small amount of phosphoric acid non-rare earth metal salt, so that the viscosity of the glue solution can be reduced in the polymerization catalysis process of the synthetic rubber, and the production loss is reduced; the molecular weight distribution of the synthetic rubber is widened, and the processability of the rubber is improved.
Description
Technical field
The present invention relates to the synthetic method of a kind of neodymium phosphate solution, particularly relate to a kind of with saturated metal halide
Solution is the method for the synthesis neodymium phosphate solution of catalyst, belongs to compou nd synthesis technical field.
Background technology
Neodymium phosphate catalyst combines differently with other components, is aged, can be as olefin polymerization catalysis.
Neodymium phosphate for the research work of olefin polymerization catalysis at eighties of last century the seventies it has been reported that phosphorus used
Acid neodymium catalyst is solid phosphoric acid neodymium catalyst.
In " rare earth catalyst synthetic rubber collected works " " different coordinating group rare earth compounds gather at isoprene
Catalysis activity in conjunction " (Science Press, 1980, ground by Changchun applied chemistry institute of the Chinese Academy of Sciences the 4th
Study carefully room) in sketched the preparation method of neodymium phosphate catalyst, its product is solid phosphoric acid neodymium catalyst.This is solid
Body catalyst is insoluble in alkane, aromatic solvent, and its preparation method is: make neodymia and hydrochloric acid reaction, preparation
The neodymium chloride aqueous solution;Phosphate is mixed with ethanol, adds ammoniacal liquor saponification;Add in sodium phosphate saponification liquor
Entering the neodymium chloride aqueous solution, reaction afterproduct is neodymium phosphate (powder or floccule), sedimentation, separation, filtration
Obtain solid phosphoric acid neodymium;Solid phosphoric acid neodymium with ethanol wash, sedimentation, separate, filter, in triplicate or with
On;Gained solid phosphoric acid neodymium is dried, and makes ethanol volatilize completely.Neodymium phosphate catalyst prepared by the method is
Solid, neodymium phosphate dry run is loaded down with trivial details, and production process produces substantial amounts of ethanol aqueous waste solution, it is impossible to be repeated several times
Utilizing, product is insoluble in alkane solvent, aromatic hydrocarbons, dissolves in alkane solvent after adding alkyl aluminum, but many groups
Divided catalyst ageing process can be subject to bigger restriction.
United States Patent (USP) US6838534, US7157533, US7056998 each provide a kind of neodymium phosphate
Preparation method, it is essentially identical with above-mentioned method, is all to use neodymia and hydrochloric acid reaction to prepare neodymium chloride
Solution, is then respectively adopted di-(2-ethylhexyl)phosphoric acid ester and acetone, di-(2-ethylhexyl)phosphoric acid
Ester and acetone, di-(2-ethylhexyl)phosphoric acid ester and acetone react, and prepare neodymium phosphate solid and urge
Agent.
The experimental technique of prior art (publication number CN101778853A) is the invention of Rhodia of France
Disclosed technology, but in CN101778853A, mention rare-earth organophosphate solution in organic solvent
Preparation method, accelerator used i.e. catalyst is selected from water, nitric acid, hydrochloric acid, acetic acid, formic acid and propionic acid
And the rare-earth salts of these acid.In patent CN101778853A, the catalyst used in embodiment 5 is chlorination
The neodymium aqueous solution, is rare earth metal halide salt.
Patent CN101778853A discloses the concrete inventory of its method and reaction temperature and time.
And patent CN101778853A is not all mentioned the impact on reaction system for the water content.This method prepares
Neodymium phosphate solution viscosity is higher, and residual solid content and residual acid comparision contents are high, the neodymium phosphate solution of gained
Also need to filter, washing repeatedly, the step such as distillation can be only used for rubber polymerization and uses.
Content of the invention
The preparation method and the obtained neodymium phosphate that it is an object of the invention to provide a kind of neodymium phosphate solution are molten
Liquid, single with the neodymium phosphate solution composition solving prepared by art methods, gathering as elastomeric
Close the defect that can not effectively reduce gelatin viscosity in catalytic process.
For achieving the above object, the present invention proposes a kind of method synthesizing neodymium phosphate solution, comprises the following steps:
Step 1: metal halide salt is made saturated metal halide saline solution, with described saturated metal halide
Saline solution is catalyst;
Step 2: acid phosphoric acid ester and organic solvent are mixed to get phosphate ester solution, described acid phosphoric acid ester
Volume ratio with organic solvent is 1:2-1:20, and described organic solvent is linear paraffin or cycloalkane or aromatic hydrocarbons;
Step 3: neodymia pressed powder is joined stirring in phosphate ester solution and obtains turbid solution, and heat
To 20-50 DEG C, described neodymia is 1:6 with the mol ratio of described acid phosphoric acid ester;
Step 4: described saturated metal halide saline solution is joined in described turbid solution, heating stirring,
Adding molecular sieve, reacting 20-90 minute at 20-70 DEG C, reaction terminates rear static layering, isolated
Oil phase, described oil phase is neodymium phosphate solution, the mol ratio control of described metal halide salt and described acid phosphoric acid ester
It is made as 1:5-1:50.
Wherein, described metal halide salt is non-rare earth metal halide salt, and described non-rare earth metal halide salt is selected from
Nickel chloride, iron chloride, cobalt chloride or titanium chloride, this metallic element has catalytic action to alkene or alkadienes.
Wherein, a small amount of nickel, iron, cobalt, titanium can generate organic phosphate and be present in neodymium phosphate solution, should
Nickel, iron, cobalt, the organic phosphate of titanium play the effect in activated centre in the course of the polymerization process, improve product
Processed and applied performance.
Wherein, in step 3, described be heated to 20-50 DEG C for turbid solution catalyst addition before preheating temperature
Degree, can make reaction accelerate and make reaction more complete.
Wherein, step 4 adds described molecular sieve to remove the water that reaction generates, make catalyst system and catalyzing meet reaction
Demanding kinetics.
Wherein, described acid phosphoric acid ester is acid organo phosphates, it is preferred that described acid organo phosphates
For (RO)2POOH, R (RO) POOH or R2POOH, described R are alkyl or its isomers of 2-13 carbon, more
Goodly, described acid organo phosphates is di-(2-ethylhexyl)phosphoric acid ester, 2-ethylhexyl phosphoric acid 2-second
One or more in base hexyl ester and methyl acid phosphate diformazan fat in heptan.
Wherein, described organic solvent is hexane, heptane, one or more in carbon six oil.
Wherein, in described step 1, it is will to carry 0-6 that metal halide salt is made saturated metal halide saline solution
Saturated nickel chloride aqueous solution made by the nickel chloride of the individual crystallization water, and described saturated nickel chloride aqueous solution is 20-50 DEG C
Saturated nickel chloride aqueous solution.
It is preferred that also include step 5: reaction terminates rear static layering, and lower floor is aqueous metal halogenation salt solution
Solution, recycling.
And, for achieving the above object, the present invention also proposes a kind of neodymium phosphate solution, is closed by above-mentioned method
Becoming, the chemical formula of described neodymium phosphate is NdD3, D represents acid phosphoric acid ester, and described acid phosphoric acid ester is acidity
Organophosphorus ester.This neodymium phosphate solution contains a small amount of Metal organophosphates, described Metal organophosphates
Chemical formula is MDn, M represents metal, and D represents acid phosphoric acid ester, and n represents the number of the organophosphorus ester containing
Amount, described acid phosphoric acid ester is acid organo phosphates.
Invention effect:
The method of the present invention is during synthesis neodymium phosphate solution, and catalyst choice is non-rare earth metal halogen
Changing the saturated solution of salt, a small amount of saturated non-rare earth metal halide salt can react with acid phosphoric acid ester, generation
A small amount of non-rare earth metal salt of phosphoric acid, and the non-rare earth metal salt of phosphoric acid has polymerization activity equally, the side of the present invention
The neodymium phosphate solution of method synthesis contains the non-rare earth metal salt of a small amount of phosphoric acid, is urging as elastomeric polymerization
There is its specific effect during change, be in particular in: during polymerization, reduce gelatin viscosity, subtract
Few energy loss;Elastomeric molecular weight distribution is made to broaden, at the premium properties possessing original rare-earth rubber
Outside, improve the processing characteristics of rubber.
The especially present invention selects saturated nickel chloride aqueous solution, a small amount of saturated nickel chloride aqueous solution can and acid
Phosphate reacts, and a small amount of nickel phosphate of generation has polymerization activity equally, the phosphoric acid of the method synthesis of the present invention
In neodymium solution contain a small amount of nickel phosphate, as elastomeric polymerization catalyzed during, it is possible to decrease glue glue
Degree, reduces energy loss;Make elastomeric molecular weight distribution broaden, possess the excellent of original rare-earth rubber
Outside optimum energy, improve the processing characteristics of rubber.
Water content in reaction system directly affects the carrying out of this reaction, makes reaction slack-off or terminates, this
While the saturated nickel chloride aqueous solution of bright middle use ensures catalytic action, the water content in control reaction system,
A small amount of nickel chloride and phosphate additionally can be made to react, meet the requirement of its reaction power.Use saturated nickel chloride
The aqueous solution, as catalyst, has its special role and meaning.
Use the method for the present invention, course of reaction adds dehydrating agent (such as molecular sieve, silica gel), removes
The water that dereaction generates, its object is to water content in control course of reaction, makes catalyst system and catalyzing meet reaction dynamic
Mechanical requirements, reaction generates the neodymium phosphate solution that product is containing a small amount of nickel phosphate, is new bimetallic catalyst,
Can be used for rubber synthesis;In addition, reaction system water content is fewer, the reaction speed of this reaction is faster, reaction
Carry out is more thorough;Finally, the water content controlling reaction system can make the viscous of product neodymium phosphate solution
Degree reduces, and can directly utilize.
Neodymium phosphate solution prepared by the method for the present invention can be urged as causing alkene, the rare earth of diene polymerization
Major catalyst in change system, as elastomeric polymerization catalyzed during can effectively reduce gelatin viscosity,
Having, product polymerization activity is high, production technology is simple, production cost is low.And, in delaminating process
The aqueous phase that arrives can be with safety dumping after processing, and Reusability.In this method course of reaction pollution-free
Thing discharges, and does not results in environmental pollution.
The product of method provided by the present invention is neodymium phosphate solution, can be as initiation alkene, diene polymerization
Rare-earth catalysis system in major catalyst;This product can dissolve each other with alkane, aromatic hydrocarbons equal solvent arbitrary proportion,
Optional more and aging more freely in multicomponent catalyst ageing process.
Metal halide salt of the present invention is non-rare earth metal halide salt, and described non-rare earth metal halide salt is selected from
Nickel chloride, iron chloride, cobalt chloride, titanium chloride, this metallic element has catalytic action to alkene or alkadienes,
A small amount of nickel, iron, cobalt, titanium can generate organic phosphate and be present in neodymium phosphate solution, this nickel, iron, cobalt,
The organic phosphate of titanium plays the effect in activated centre in the course of the polymerization process, improves the processed and applied performance of product.
Brief description
The structural representation of the process units that Fig. 1 is used by embodiment 1.
Wherein, reference:
1-the first charging aperture
2-nickel chloride solution kettle
3-the second charging aperture
4-reactor
5-drain hole
6-the 3rd charging aperture
7-the 4th charging aperture
Detailed description of the invention
The present invention is by with neodymia as raw material, and with non-rare earth metal halide salt as catalyst, synthesis obtains phosphorus
Acid neodymium solution.
Present invention firstly provides a kind of method synthesizing neodymium phosphate solution, it comprises the following steps:
Step 1: metal halide salt is made saturated metal halide saline solution, with described saturated metal halide
Saline solution is catalyst;
Step 2: acid phosphoric acid ester and organic solvent are mixed to get phosphate ester solution, described acid phosphoric acid ester
Volume ratio with organic solvent is 1:2-1:20, and described organic solvent is linear paraffin or cycloalkane or aromatic hydrocarbons;
Step 3: neodymia pressed powder is joined stirring in phosphate ester solution and obtains turbid solution, and heat
To 20-50 DEG C, described neodymia is 1:6 with the mol ratio of described acid phosphoric acid ester;
Step 4: described saturated metal halide saline solution is joined in described turbid solution, heating stirring,
Adding molecular sieve, reacting 20-90 minute at 20-70 DEG C, reaction terminates rear static layering, isolated
Oil phase, described oil phase is neodymium phosphate solution, the mol ratio control of described metal halide salt and described acid phosphoric acid ester
It is made as 1:5-1:50.
It is preferred that also include step 5: reaction terminates rear static layering, and lower floor is aqueous metal halogenation salt solution
Solution, recycling.
Wherein, described metal halide salt is non-rare earth metal halide salt, and described non-rare earth metal halide salt is selected from
Nickel chloride, iron chloride, cobalt chloride or titanium chloride, this metallic element has catalytic action to alkene or alkadienes.
Wherein, a small amount of nickel, iron, cobalt, titanium can generate organic phosphate and be present in neodymium phosphate solution, should
Nickel, iron, cobalt, the organic phosphate of titanium play the effect in activated centre in the course of the polymerization process, improve product
Processed and applied performance.
Wherein, in step 3, described be heated to 20-50 DEG C for turbid solution catalyst addition before preheating temperature
Degree, can make reaction accelerate and make reaction more complete.
Wherein, step 4 adds described molecular sieve to remove the water that reaction generates, make catalyst system and catalyzing meet reaction
Demanding kinetics.
Wherein, in described step 1, it is will to carry 0-6 that metal halide salt is made saturated metal halide saline solution
Saturated nickel chloride aqueous solution made by the nickel chloride of the individual crystallization water, and described saturated nickel chloride aqueous solution is 20-50 DEG C
Saturated nickel chloride aqueous solution.
In the above-mentioned methods, the acid phosphoric acid ester being used can be acid organo phosphates;Preferably, should
Acid organo phosphates is (RO)2POOH, R (RO) POOH or R2POOH etc., wherein, R is 2-13 carbon
Alkyl or its isomers.It is highly preferred that acid organo phosphates is di-(2-ethylhexyl)phosphoric acid ester, 2-
One or more in ethylhexyl phosphoric acid 2-ethylhexyl and methyl acid phosphate diformazan fat in heptan etc..
In the above-mentioned methods, the organic solvent being used can be alkane or cycloalkane or aromatic hydrocarbons etc., is preferably
Linear paraffin or cycloalkane etc.;It is highly preferred that above-mentioned organic solvent is in hexane, heptane, carbon six oil etc.
One or more.
The neodymium phosphate solution being obtained by said method, can be mutual with arbitrary proportion with alkane, aromatic hydrocarbons equal solvent
Molten, optional more, aging more freely in multicomponent catalyst ageing process.At isolated oil
Aqueous phase obtained during phase is the aqueous solution of nickel chloride, can reuse, it is to avoid environmental pollution.
Present invention also offers a kind of neodymium phosphate solution, it is by above-mentioned method synthesis, this neodymium phosphate
Chemical formula is NdD3, wherein D represents acid phosphoric acid ester, for example acid organo phosphates, this neodymium phosphate solution
Containing a small amount of Metal organophosphates, the chemical formula of described Metal organophosphates is MDn, M represents metal,
D represents acid phosphoric acid ester, and n represents the quantity of the organophosphorus ester containing, and described acid phosphoric acid ester is that acidity has
Machine phosphate.
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, existing to this
Bright technical scheme carries out described further below, but it is not intended that to the present invention can the restriction of practical range.
Embodiment 1
Present embodiments providing a kind of method synthesizing neodymium phosphate solution, it is to use the production dress shown in Fig. 1
Putting and carrying out, the method comprises the following steps:
1st, six water nickel chlorides are configured to saturated nickel chloride aqueous solution in nickel chloride solution kettle 2;
2nd, in reactor 4, add carbon six oil 840kg by the first charging aperture 1, be subsequently adding 2-ethyl hexyl
Base phosphoric acid 2-ethylhexyl 150kg, molecular sieve 5kg, heating stirring 5min;
3rd, in reactor 4, add neodymia pressed powder 25kg by the 3rd charging aperture 6, stir 5min;
4th, the saturated nickel chloride aqueous solution in nickel chloride solution kettle 2 is joined reaction by the second charging aperture 3
Reacting in kettle 4, the addition of saturated nickel chloride aqueous solution is 5L, and reaction temperature control is 35-50 DEG C,
Reaction time control is 90min;
5th, after reaction completes, stop the stirring in reactor 4, stand 30min, treat material layering in kettle,
By drain hole 5 by lower floor's aqueous phase output, join in nickel chloride solution kettle 2 through the 4th charging aperture 7, stay
In reactor 4 for oil phase, this oil phase is neodymium phosphate solution, can be exported by drain hole 5, should
Neodymium phosphate solution can preserve under nitrogen protection in products pot for a long time.
Conclusion: saturated nickel chloride solution plays the effect of catalyst in the reaction of synthesis neodymium phosphate solution.
Embodiment 2
The saturated nickel chloride solution of the present embodiment checking synthesizes its catalysis in neodymium phosphate solution methods in embodiment 1 and makees
With this checking test comprises the following steps:
1st, in reactor 4, add carbon six oil 840kg by the first charging aperture 1, be subsequently adding 2-ethyl hexyl
Base phosphoric acid 2-ethylhexyl 150kg, adds molecular sieve 5kg, heating stirring 5min;
2nd, in reactor 4, add neodymia pressed powder 25kg by the 3rd charging aperture 6, stir 5min;
Being 50-55 DEG C by the control of mixed solution temperature, stir 60min, there is not any reaction in neodymia;
3rd, six water nickel chlorides are configured to saturated nickel chloride aqueous solution in nickel chloride solution kettle 2;
4th, the saturated nickel chloride aqueous solution in nickel chloride solution kettle 2 is joined reaction by the second charging aperture 3
Reacting in kettle 4, the addition of saturated nickel chloride aqueous solution is 5L, and reaction temperature control is 50-55 DEG C,
Reaction time control is 60min, and neodymia starts reaction, and reaction solution is light blue purple;
5th, after reaction completes, stop the stirring in reactor 4, stand 30min, treat material layering in kettle,
By drain hole 5 by lower floor's aqueous phase output, join in nickel chloride solution kettle 2 through the 4th charging aperture 7, stay
In reactor 4 for oil phase, this oil phase is neodymium phosphate solution, can be exported by drain hole 5.
Conclusion: saturated nickel chloride solution plays the effect of catalyst in the reaction of synthesis neodymium phosphate solution.
Embodiment 3
Present embodiments providing a kind of method synthesizing neodymium phosphate solution, it is to use the production dress shown in Fig. 1
Putting and carrying out, the method comprises the following steps:
1st, six water titanium chlorides are configured to saturated titanium chloride aqueous solution in titanium chloride solution kettle 2;
2nd, in reactor 4, add carbon six oil 840kg by the first charging aperture 1, be subsequently adding 2-ethyl hexyl
Base phosphoric acid 2-ethylhexyl 150kg, molecular sieve 5kg, heating stirring 5min;
3rd, in reactor 4, add neodymia pressed powder 25kg by the 3rd charging aperture 6, stir 5min,
Being 20-50 DEG C by the control of mixed solution temperature, stir 60min, there is not any reaction in neodymia;
4th, the saturated titanium chloride aqueous solution in titanium chloride solution kettle 2 is joined reaction by the second charging aperture 3
Reacting in kettle 4, the addition of saturated titanium chloride aqueous solution is 5L, and reaction temperature control is 20-70 DEG C,
Reaction time control is 20min;
5th, after reaction completes, stop the stirring in reactor 4, stand 30min, treat material layering in kettle,
By drain hole 5 by lower floor's aqueous phase output, join in titanium chloride solution kettle 2 through the 4th charging aperture 7, stay
In reactor 4 for oil phase, this oil phase is neodymium phosphate solution, can be exported by drain hole 5, should
Neodymium phosphate solution can preserve under nitrogen protection in products pot for a long time.
Conclusion: saturated titanium chloride solution plays the effect of catalyst in the reaction of synthesis neodymium phosphate solution.
In addition, iron chloride, cobalt chloride can be applied equally in above-described embodiment 1-3.
Embodiment 4
Carrying out activity rating to the neodymium phosphate solution of embodiment 1 preparation, wherein, catalyst is in embodiment 1
Rare earth catalyst.
Activity rating method: use batch solution polymerization technique synthesizing rare-earth butadiene rubber to evaluate, specifically
Method is: adds 2100mL carbon six oil in polymeric kettle, then adds 5.74mol butadiene in polymeric kettle,
Stir, and temperature of charge is maintained at 35-50 DEG C in making polymeric kettle, pressure≤0.4MPa in kettle, carbon six
Oil, butadiene adition process require to use N2Protection, it is to avoid ingress of air, oxygen gas and water etc.;To catalyst
2.87 × 10 are added in charge pipe-4mol NdD3/5.74×10-3molDIBAL-H/1.0×10-3molEASC;Make
It is pressed into the catalyst in catalyst addition tube in reactor with N2, by the N2 ftercompction of reactor pressure extremely
0.45-0.50MPa;Control jacket of polymerization coolant-temperature gage is 60-80 DEG C, discharges material after reacting 4 hours;
In kettle, material boils 40 minutes in boiling water, takes out material mill (control of mill temperature is 120 DEG C)
On press dry after, obtain rare earth polybutadiene rubber, weigh.Obtain dry glue 290g.
Catalyst: this catalyst system and catalyzing includes NdD3, DIBAL-H and EASC tri-kinds of components, wherein NdD3For reality
Execute the catalyst that example 1 provides.
Polymerization technique uses batch solution polymerization, and reactor uses 5L polymerization reaction kettle, and agitating mode uses anchor
Formula stirs, and agitation revolution is 100r/min, and fourth oil concentration is 12g/100mL, and polymerization reaction time is
3.5-4.5h, polymeric reaction temperature is 60-120 DEG C, and polymerization pressure is 0.3-0.8MPa.
Activity evaluation display polymerization reaction monomer conversion ratio reaches 94%, and product Mooney is 44.2.
Evaluation and test conclusion: use NdD3It for major catalyst, is catalyzed with DIBAL-H and EASC composition ternary RE
System, can cause polymerizing butadiene, synthesizing rare-earth butadiene rubber, and result shows, uses the present invention to prepare
Neodymium phosphate solution is major catalyst, and activity is good, and monomer conversion reaches more than 90%.
The effect of the present invention:
The method of the present invention is during synthesis neodymium phosphate solution, and catalyst choice is non-rare earth metal halogen
Changing the saturated solution of salt, a small amount of saturated non-rare earth metal halide salt can react with acid phosphoric acid ester, generation
A small amount of non-rare earth metal salt of phosphoric acid, and the non-rare earth metal salt of phosphoric acid has polymerization activity equally, the side of the present invention
The neodymium phosphate solution of method synthesis contains the non-rare earth metal salt of a small amount of phosphoric acid, is urging as elastomeric polymerization
There is its specific effect during change, be in particular in: during being polymerized again, reduce gelatin viscosity, subtract
Few production is lost;Elastomeric molecular weight distribution is made to broaden, at the premium properties possessing original rare-earth rubber
Outside, improve the processing characteristics of rubber.
The especially present invention selects saturated nickel chloride aqueous solution, a small amount of saturated nickel chloride aqueous solution can and acid
Phosphate reacts, and a small amount of nickel phosphate of generation has polymerization activity equally, the phosphoric acid of the method synthesis of the present invention
In neodymium solution contain a small amount of nickel phosphate, as elastomeric polymerization catalyzed during, it is possible to decrease glue glue
Degree, reduces and produces loss;Make elastomeric molecular weight distribution broaden, possess the excellent of original rare-earth rubber
Outside optimum energy, improve the processing characteristics of rubber.
Water content in reaction system directly affects the carrying out of this reaction, makes reaction slack-off or terminates, this
While the saturated nickel chloride aqueous solution of bright middle use ensures catalytic action, the water content in control reaction system,
A small amount of nickel chloride and phosphate additionally can be made to react, meet the requirement of its reaction power.Use saturated nickel chloride
The aqueous solution, as catalyst, has its special role and meaning.
Use the method for the present invention, course of reaction adds dehydrating agent (such as molecular sieve, silica gel), removes
The water that dereaction generates, its object is to water content in control course of reaction, makes catalyst system and catalyzing meet reaction dynamic
Mechanical requirements.
Neodymium phosphate solution prepared by the method for the present invention as elastomeric polymerization catalyzed during can have
Effect reduces gelatin viscosity, and product polymerization activity is high, production technology is simple, production cost is low, environmental protection having
The feature such as pollution-free.
Compared with prior art, the method for synthesis neodymium phosphate solution provided by the present invention has the advantage that
Neodymium phosphate catalyst synthesized by preparation method of the prior art is solid, and reaction is to make at ethanol or acetone
By lower generation neodymium phosphate precipitation, this precipitation is insoluble in alkane, aromatic solvent;And method provided by the present invention
Product be neodymium phosphate solution, and the product obtained by the method for the present invention can be with alkane, aromatic hydrocarbons equal solvent
Arbitrary proportion dissolves each other, optional more and aging more freely in multicomponent catalyst ageing process;
In addition, method provided by the present invention will not produce the acetone or alcohol aqueous solution in preparation process, no
Relating to product repeatedly to wash, be dried, production technology is substantially simple, and production cost is low, and, it had been layered
The nickel chloride aqueous solution obtaining in journey, can reuse, not result in environmental pollution.
Certainly, the present invention also can have other various embodiments, in the feelings without departing substantially from present invention spirit and essence thereof
Under condition, those of ordinary skill in the art can make various corresponding change according to the present invention and deform, but this
A little corresponding changes and deformation all should belong to the protection domain of the claims in the present invention.
Claims (14)
1. the method synthesizing neodymium phosphate solution, it is characterised in that comprise the following steps:
Step 1: metal halide salt is made saturated metal halide saline solution, with described saturated metal halide
Saline solution is catalyst;
Step 2: acid phosphoric acid ester and organic solvent are mixed to get phosphate ester solution, described acid phosphoric acid ester
Volume ratio with organic solvent is 1:2-1:20, and described organic solvent is linear paraffin or cycloalkane or aromatic hydrocarbons;
Step 3: by neodymia pressed powder, join stirring in phosphate ester solution and obtain turbid solution, and add
Heat arrives 20-50 DEG C, and described neodymia is 1:6 with the mol ratio of described acid phosphoric acid ester;
Step 4: described saturated metal halide saline solution is joined in described turbid solution, heating stirring,
Adding molecular sieve, reacting 20-90 minute at 20-70 DEG C, reaction terminates rear static layering, isolated
Oil phase, described oil phase is neodymium phosphate solution, the mol ratio control of described metal halide salt and described acid phosphoric acid ester
It is made as 1:5-1:50.
2. method according to claim 1, it is characterised in that described metal halide salt is non-rare earth gold
Belong to halide salt.
3. method according to claim 2, it is characterised in that described non-rare earth metal halide salt is selected from
Nickel chloride, iron chloride, cobalt chloride or titanium chloride.
4. method according to claim 3, it is characterised in that a small amount of nickel, iron, cobalt, titanium generate
Organic phosphate is present in neodymium phosphate solution, and this nickel, iron, cobalt, the organic phosphate of titanium are in polymerization process
In play the effect in activated centre, improve the processed and applied performance of product.
5. method according to claim 1, it is characterised in that in step 3, described is heated to 20-50 DEG C
For preheating temperature before catalyst addition for the turbid solution.
6. method according to claim 1, it is characterised in that add described molecular sieve to remove in step 4
The water that dereaction generates.
7. method according to claim 1, it is characterised in that described acid phosphoric acid ester is acid organic
Phosphate.
8. method according to claim 7, it is characterised in that described acid organo phosphates is
(RO)2POOH, R (RO) POOH or R2POOH, described R are alkyl or its isomers of 2-13 carbon.
9. method according to claim 8, it is characterised in that described acid organo phosphates is two (2-
Ethylhexyl) phosphate, in 2-ethylhexyl phosphoric acid 2-ethylhexyl and methyl acid phosphate diformazan fat in heptan one
Plant or several.
10. method according to claim 1, it is characterised in that described organic solvent is hexane, heptan
One or more in alkane, carbon six oil.
11. methods according to claim 1, it is characterised in that in described step 1, by metal halogen
Change salt making saturated metal halide saline solution is that the nickel chloride with 0-6 the crystallization water is made saturated nickel chloride
The aqueous solution.
12. methods according to claim 11, it is characterised in that described saturated nickel chloride aqueous solution is
The saturated nickel chloride aqueous solution of 20-50 DEG C.
13. methods according to claim 1, it is characterised in that also include step 5: reaction terminates
Rear static layering, lower floor is the aqueous metal halide salt aqueous solution, recycling.
14. 1 kinds of neodymium phosphate solution, it is characterised in that by the method according to any one of claim 1-13
Synthesis, the chemical formula of described neodymium phosphate is NdD3, D represents acid phosphoric acid ester, and described acid phosphoric acid ester is acid
Property organophosphorus ester, this neodymium phosphate solution contains a small amount of Metal organophosphates, described Metal organophosphates
Chemical formula be MDn, M represents metal, and D represents acid phosphoric acid ester, and n represents the organophosphorus ester containing
Quantity, described acid phosphoric acid ester is acid organo phosphates.
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