CN116120264A - Method for regulating and controlling particle size of 2, 5-furandicarboxylic acid crystal - Google Patents
Method for regulating and controlling particle size of 2, 5-furandicarboxylic acid crystal Download PDFInfo
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- CN116120264A CN116120264A CN202111342653.4A CN202111342653A CN116120264A CN 116120264 A CN116120264 A CN 116120264A CN 202111342653 A CN202111342653 A CN 202111342653A CN 116120264 A CN116120264 A CN 116120264A
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- Prior art keywords
- metal
- furandicarboxylic acid
- organic solvent
- solvent
- crystallization
- Prior art date
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- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 86
- 239000013078 crystal Substances 0.000 title claims abstract description 68
- 239000002245 particle Substances 0.000 title claims abstract description 34
- 230000001276 controlling effect Effects 0.000 title claims abstract description 13
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 56
- 230000008025 crystallization Effects 0.000 claims abstract description 53
- 239000002270 dispersing agent Substances 0.000 claims abstract description 33
- 239000002667 nucleating agent Substances 0.000 claims abstract description 29
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 51
- 239000002904 solvent Substances 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 34
- 239000003960 organic solvent Substances 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 12
- -1 N-diethylformamide Chemical compound 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 150000003462 sulfoxides Chemical class 0.000 claims description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910001510 metal chloride Inorganic materials 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- JGOJQVLHSPGMOC-UHFFFAOYSA-N triethyl stiborite Chemical compound [Sb+3].CC[O-].CC[O-].CC[O-] JGOJQVLHSPGMOC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 3
- YLHUPYSUKYAIBW-UHFFFAOYSA-N 1-acetylpyrrolidin-2-one Chemical compound CC(=O)N1CCCC1=O YLHUPYSUKYAIBW-UHFFFAOYSA-N 0.000 claims description 3
- LOWMYOWHQMKBTM-UHFFFAOYSA-N 1-butylsulfinylbutane Chemical compound CCCCS(=O)CCCC LOWMYOWHQMKBTM-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- QAZYYQMPRQKMAC-FDGPNNRMSA-L calcium;(z)-4-oxopent-2-en-2-olate Chemical compound [Ca+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O QAZYYQMPRQKMAC-FDGPNNRMSA-L 0.000 claims description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 3
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 claims description 3
- 229960003966 nicotinamide Drugs 0.000 claims description 3
- 235000005152 nicotinamide Nutrition 0.000 claims description 3
- 239000011570 nicotinamide Substances 0.000 claims description 3
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 3
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- AVBJHQDHVYGQLS-AWEZNQCLSA-N (2s)-2-(dodecanoylamino)pentanedioic acid Chemical compound CCCCCCCCCCCC(=O)N[C@H](C(O)=O)CCC(O)=O AVBJHQDHVYGQLS-AWEZNQCLSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims 1
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- 238000010899 nucleation Methods 0.000 description 33
- 230000006911 nucleation Effects 0.000 description 33
- 239000000203 mixture Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 17
- 239000000843 powder Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 11
- 229960000583 acetic acid Drugs 0.000 description 7
- 238000007792 addition Methods 0.000 description 7
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 5
- 230000009471 action Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KZRXPHCVIMWWDS-AWEZNQCLSA-N (4S)-4-amino-5-dodecanoyloxy-5-oxopentanoic acid Chemical compound CCCCCCCCCCCC(=O)OC(=O)[C@@H](N)CCC(O)=O KZRXPHCVIMWWDS-AWEZNQCLSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940071085 lauroyl glutamate Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QAXZWHGWYSJAEI-UHFFFAOYSA-N n,n-dimethylformamide;ethanol Chemical compound CCO.CN(C)C=O QAXZWHGWYSJAEI-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/08—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by cooling of the solution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Furan Compounds (AREA)
Abstract
The application discloses a method for regulating and controlling the grain size of 2, 5-furandicarboxylic acid crystals, which comprises the steps of adding an auxiliary agent into a raw material containing 2, 5-furandicarboxylic acid, and regulating the types and the content of the auxiliary agent by combining with technological parameters such as crystallization temperature and the like to obtain 2, 5-furandicarboxylic acid crystals with a certain grain size range; wherein the auxiliary agent comprises at least one of a dispersing agent and a nucleating agent; the 2, 5-furandicarboxylic acid crystals have a controllable average particle diameter d 50 20-2000 μm. The method can effectively control the grain size of the 2, 5-furandicarboxylic acid crystal, meets the grain size control requirement in the subsequent application, and has practical application value.
Description
Technical Field
The application relates to a method for regulating and controlling the grain size of 2, 5-furandicarboxylic acid crystals, belonging to the technical field of organic chemical crystallization.
Background
2, 5-furandicarboxylic acid (FDCA) as the only rigid aromatic ring bio-based platform compound known at present can be used for synthesizing polyester with glycol, such as polyethylene 2, 5-furandicarboxylic acid glycol (PEF), and polyamide with diamine, and is green and environment-friendly due to bio-based materials and better than petroleum-based polyester in some properties, so FDCA has obvious advantages in the synthesis of high polymer materials, and has been developed as petroleum-based alternative chemical monomers. At present, the method for purifying FDCA has been studied more, but the particle size is less, and the particle size has influence on mass transfer, dissolution, reaction rate and the like in the synthesis process of polyester and polyamide, and crystals with smaller particle size can float on a reaction solution or adhere to the wall of a reaction kettle and a paddle, so that the reaction is incomplete, the yield is reduced, and meanwhile, more impurities and poor chromaticity are caused. The study of purification of FDCA by crystallization in water has been reported (JP 2017190316A), but the crystalline form of FDCA recrystallized in water is flaky and irregular (US 20210332021A 1), the crystal cracks are more likely to break, larger crystals are not likely to grow, and the particle size of the product is difficult to control. In the glacial acetic acid system, the FDCA crystal has small particle size and narrow controllable range (US 20210332021A 1), and the crystals are secondarily nucleated during low-temperature crystallization, and have irregular shape and low transparency, so that the method for regulating and controlling the particle size of the FDCA crystal is searched, and the method has important practical application value for meeting the requirements of downstream application on products with different particle sizes.
Disclosure of Invention
According to one aspect of the present application, there is provided a method of controlling the particle size of 2, 5-furandicarboxylic acid crystals, the method comprising: heating 2, 5-furandicarboxylic acid, adding adjuvants such as dispersing agent and/or nucleating agent, and regulating crystallization process of 2, 5-furandicarboxylic acid in solution by crystallization process such as crystallization temperature change to obtain average particle diameter d 50 2, 5-furandicarboxylic acid crystals of 20 to 2000 μm. The invention can effectively control the grain size of 2, 5-furandicarboxylic acid crystal, meets the grain size control requirement in the subsequent application, and has practical application value.
The method for regulating and controlling the particle size of 2, 5-furandicarboxylic acid crystals comprises the steps of adding an auxiliary agent into a raw material containing 2, 5-furandicarboxylic acid, heating, and crystallizing at a controlled temperature to obtain 2, 5-furandicarboxylic acid crystals with a certain particle size range;
wherein the auxiliary agent comprises at least one of a dispersing agent and a nucleating agent;
the average particle diameter d of the 2, 5-furandicarboxylic acid crystals 50 20-2000 μm.
Alternatively, the average particle diameter d of the 2, 5-furandicarboxylic acid crystals 50 Any value or range between any of 20 μm, 35.6 μm, 78.8 μm, 85.1 μm, 91.4 μm, 127.8 μm, 157.5 μm, 352.4 μm, 425.8 μm, 438.5 μm, 511.6 μm, 618.4 μm, 801.4 μm, 824.5 μm, 855.7 μm, 884.5 μm, 914.6 μm, 925.7 μm, 1148.2 μm, 1240 μm, 1272.5 μm, 1305.8 μm, 1522.1 μm, 1614.2 μm, 2000 μm.
Optionally, the raw materials further comprise a solvent; the mass concentration of the 2, 5-furandicarboxylic acid in the solvent is 0.3-60%.
Optionally, the upper mass concentration of the 2, 5-furandicarboxylic acid in the solvent is selected from 5%, 10%, 15%, 20%, 25%, 35%, 40%, 50% or 60%; the lower limit is selected from 0.3%, 5%, 10%, 15%, 20%, 25%, 35%, 40% or 50%.
Optionally, the solvent includes at least one of water and an organic solvent a.
Optionally, the organic solvent a includes at least one of amide organic solvent, pyrrolidone organic solvent, sulfoxide organic solvent, acetic acid, methanol, ethanol, acetone, and acetonitrile.
Optionally, the solvent comprises at least one of water, an amide organic solvent, a pyrrolidone organic solvent and a sulfoxide organic solvent; as a specific embodiment, the solvent may further include at least one of acetic acid, methanol, ethanol, acetone, and acetonitrile with a volume content of not more than 90%.
Optionally, the amide-based organic solvent comprises at least one of N, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide and nicotinamide.
Optionally, the pyrrolidone type organic solvent comprises at least one of N-methyl pyrrolidone, 1-ethyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone and N-octyl pyrrolidone.
Optionally, the sulfoxide organic solvent comprises at least one of thionyl chloride, dimethyl sulfoxide and dibutyl sulfoxide.
Optionally, the solvent does not contain the organic solvent B or contains the organic solvent B with the volume fraction of not more than 90%.
Optionally, the organic solvent B includes at least one of acetic acid, methanol, ethanol, acetone, acetonitrile.
Optionally, the dispersing agent comprises at least one of polyethylene glycol, ethylene glycol, glycerol, linear sodium alkylbenzenesulfonate (LAS), sodium fatty alcohol polyoxyethylene ether sulfate (AES), ammonium fatty alcohol polyoxyethylene ether sulfate (AESA), sodium lauryl sulfate (SDS), and lauroyl glutamic acid.
Optionally, the raw materials further comprise a solvent; the addition amount of the dispersing agent is 0-5% of the mass of the solvent.
Optionally, the addition amount of the dispersing agent is 0.001-5% of the mass of the solvent.
Optionally, the dispersant is added in an amount such that the upper limit of the mass of the solvent is selected from 0.1%, 0.5%, 1%, 2%, 3% or 5%; the lower limit is selected from 0.001%, 0.1%, 0.5%, 1%, 2% or 3%. Optionally, the nucleating agent is selected from metal-containing compounds; the metal comprises at least one of calcium, zinc, germanium, antimony, tin, titanium, and antimony.
Optionally, the metal-containing compound includes at least one of a metal inorganic salt, a metal oxide, and a metal organic compound.
Optionally, the metal inorganic salt is selected from at least one of metal chloride, metal acetate and metal carbonate.
Optionally, the metal chloride comprises at least one of calcium chloride, zinc chloride, germanium chloride, antimony trichloride, tin tetrachloride, titanium tetrachloride.
Optionally, the acetate of the metal comprises at least one of calcium acetate, zinc acetate, antimony acetate, and tin acetate.
Optionally, the metal oxide includes at least one of calcium oxide, zinc oxide, germanium oxide, antimony trioxide, antimony pentoxide, tin dioxide, stannous oxide, titanium monoxide, titanium dioxide.
Optionally, the metal organic compound comprises at least one of antimony ethoxide and calcium acetylacetonate.
Optionally, the nucleating agent is added in an amount of 0 to 1000ppm.
Optionally, the addition amount of the nucleating agent is 15ppm to 1000ppm.
Optionally, the upper limit of the addition amount of the nucleating agent is selected from 10ppm, 15ppm, 30ppm, 50ppm, 100ppm, 200ppm, 300ppm, 500ppm, 800ppm or 1000ppm; the lower limit is selected from 0ppm, 5ppm, 10ppm, 15ppm, 30ppm, 50ppm, 100ppm, 200ppm, 300ppm, 500ppm or 800ppm.
Optionally, the method comprises: adding a nucleating agent and/or a dispersing agent into a raw material containing 2, 5-furandicarboxylic acid, and cooling and crystallizing under the conditions of stirring at 0-1200 rpm and stirring at II to obtain 2, 5-furandicarboxylic acid crystals.
Optionally, the heating method includes: adding dispersant and/or nucleating agent into raw material containing 2, 5-furandicarboxylic acid, heating at 80-190 deg.C, stirring at 0-1200 rpm for 0.5-3 h.
As a specific embodiment, the stirring rate I is 0 to 1200rpm, and the stirring rate I is 0 when stirring is not performed.
As one specific embodiment, the method comprises the following steps: and adding a nucleating agent and/or a dispersing agent into a raw material containing 2, 5-furandicarboxylic acid, stirring the raw material I under the condition of not stirring or being lower than 1200rpm, and cooling and crystallizing under the condition of not stirring or being lower than 300rpm under the condition of stirring II to obtain 2, 5-furandicarboxylic acid crystals.
Optionally, the temperature of the heating (constant temperature) is 80-190 ℃.
Alternatively, the stirring II is carried out at a rate of 0 to 30rpm, 30 to 60rpm, 60 to 300rpm.
As one specific embodiment, the method comprises:
adding 2, 5-furandicarboxylic acid into a solvent, then adding a dispersing agent and/or a nucleating agent, heating (constant temperature treatment at a certain temperature), and crystallizing at a controlled temperature to obtain 2, 5-furandicarboxylic acid crystals.
As a specific implementation manner, the temperature-controlled crystallization is to cool to a certain temperature for constant-temperature crystallization; preferably, the cooling is performed at a cooling rate.
Optionally, the heating conditions are: the temperature is 80-190 ℃ and the time is 0.5-5 h.
Optionally, the heating time is 0.5-3 h.
Optionally, the heating time is 1.5-3 hours.
Optionally, during the heating, the upper temperature limit is selected from 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃ or 190 ℃; the lower limit is selected from 80 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or 160 ℃.
Optionally, during the heating, the upper time limit is selected from 1.5h, 2h, 3h or 5h; the lower limit is selected from 1h, 1.5h, 2h or 3h.
Optionally, the stirring speed of the stirring I is 60-1200 rpm.
Optionally, the upper limit of the stirring speed of the stirring I is selected from 100rpm, 150rpm, 200rpm, 300rpm, 600rpm, 1000rpm or 1200rpm; the lower limit is selected from 60rpm, 100rpm, 150rpm, 200rpm, 300rpm, 600rpm or 1000rpm.
Optionally, the stirring time of the stirring step I is 0.5-3 h.
Optionally, the nucleation time in the crystallization process is 1s to 120s.
Optionally, the upper time limit for nucleation during the crystallization is selected from 2s, 3s, 4s, 5s, 8s, 7s, 10s, 12s, 16s, 18s, 20s, 25s, 30s, 38s, 50s, 100s or 120s; the lower limit is selected from 1s, 2s, 3s, 4s, 5s, 8s, 7s, 10s, 12s, 16s, 18s, 20s, 25s, 30s, 38s, 50s or 100s.
Optionally, the conditions of the temperature-controlled crystallization include: the cooling rate of the temperature-controlled crystallization is 0.5-15 ℃/min, and the crystallization temperature of the temperature-controlled crystallization is 4-70 ℃;
the crystallization time of the temperature-controlled crystallization is 0.5-72 hours.
Optionally, the stirring II rate is 0 to 300rpm.
As a specific embodiment, the stirring rate II is 0 to 300rpm, and the stirring rate II is 0 when stirring is not performed.
Optionally, the upper limit of the cooling rate of the temperature-controlled crystallization is selected from 1 ℃/min, 5 ℃/min, 10 ℃/min or 15 ℃/min; the lower limit is selected from 0.5deg.C/min, 1deg.C/min, 5deg.C/min or 10deg.C/min.
Optionally, the upper crystallization temperature limit of the temperature-controlled crystallization is selected from 10 ℃, 20 ℃, 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ or 70 ℃; the lower limit is selected from 4 ℃, 10 ℃, 20 ℃, 25 ℃, 30 ℃, 40 ℃, 50 ℃ or 60 ℃.
Optionally, the upper crystallization time limit of the temperature-controlled crystallization is selected from 1h, 2h, 5h, 6h, 18h, 20h, 48h or 72h; the lower limit is selected from 0.5h, 1h, 2h, 5h, 6h, 18h, 20h or 48h.
Optionally, the upper speed limit of the stirring II is selected from 50rpm, 100rpm, 150rpm, 200rpm, 250rpm or 300rpm; the lower limit is selected from 30rpm, 50rpm, 100rpm, 150rpm, 200rpm or 250rpm.
The invention mainly aims to provide a method for regulating and controlling the grain size of 2, 5-furandicarboxylic acid crystals, so as to realize the regulation and control of the grain size of the 2, 5-furandicarboxylic acid crystals and meet the requirements of downstream application on products with different grain sizes.
In order to achieve the above object, the present invention adopts the technical scheme that: 2, 5-furandicarboxylic acid is added into a solvent, nucleation auxiliary agents and/or dispersing agents are added, the nucleation auxiliary agents are helpful for forming crystal nuclei of the 2, 5-furandicarboxylic acid, the crystallization speed is accelerated, the dispersing agents regulate and control the collision probability and uniformity between 2, 5-furandicarboxylic acid molecules or with the crystal nuclei, and the activity of the 2, 5-furandicarboxylic acid molecules can be effectively realized by controlling the crystallization temperature in combination. The average particle diameter d can be obtained by combining the particle diameter regulating and controlling method 50 2, 5-furandicarboxylic acid crystals of 20 to 2000 μm.
In the present invention, the average crystal grain size d of 2, 5-furandicarboxylic acid 50 The controllable range is 20-2000 mu m.
As a specific implementation mode, in the scheme provided by the application, when FDCA is not completely dissolved, undissolved parts can become crystal nuclei, and FDCA is secondarily nucleated in the cooling process, but collision probability among the crystal nuclei can be increased when the quantity of the crystal nuclei is large, and the crystal particles are small in particle size and are easy to aggregate.
The beneficial effects that this application can produce include:
(1) The nucleation time of the 2, 5-furandicarboxylic acid can be shortened and the crystallization time can be shortened by adding the nucleating agent.
(2) The invention can regulate the collision probability and uniformity between 2, 5-furandicarboxylic acid molecules or between the 2, 5-furandicarboxylic acid molecules and crystal nucleus by adding the dispersing agent, thereby being beneficial to the formation of large-particle-size crystals.
(3) The 2, 5-furandicarboxylic acid crystal grain size obtained by the invention has the advantages of wide adjustable range, good controllability and strong practicability.
Drawings
FIG. 1 is a graph showing the crystal size distribution of 2, 5-furandicarboxylic acid prepared in example 5 of the present invention.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Measurement of particle diameter in examples of the present application was performed by a laser particle sizer (HELOS-OASIS, new Patag, germany) to measure the average particle diameter d 50 The particle size is indicated.
The 5'15 "in the tables of the examples represents 5 minutes and 15 seconds, 15s represents 15 seconds, and the like.
According to one embodiment of the present application, the method for controlling the particle size of 2, 5-furandicarboxylic acid crystals comprises: adding 2, 5-furandicarboxylic acid into solvent, and under the regulation and control action of nucleating agent and/or dispersing agent and other auxiliary agents, combining and controlling crystallization temperature to obtain average grain size d 50 2, 5-furandicarboxylic acid crystal with 20-2000 mu mA body.
The mass concentration of the 2, 5-furandicarboxylic acid in the solvent is 0.3-60%.
The solvents involved include organic solvents, water and mixtures of the two.
The organic solvent includes amide organic solvents such as N, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide and nicotinamide; pyrrolidone organic solvents including N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, and N-octylpyrrolidone; comprises sulfoxide organic solvents such as thionyl chloride, dimethyl sulfoxide, dibutyl sulfoxide and the like.
The solvent may contain 0 to 90% by volume of a solvent such as acetic acid, methanol, ethanol, acetone, acetonitrile, etc.
The nucleating agents include, but are not limited to, chlorides, acetates, carbonates, oxides of metals including calcium, zinc, germanium, antimony, tin, titanium, etc.; and also comprises organic compounds composed of metals such as calcium, zinc, germanium, tin, antimony and the like.
Further, the metal chlorides involved include calcium chloride, zinc chloride, germanium chloride, antimony trichloride, tin tetrachloride, titanium tetrachloride, and the like.
Further, the acetates involved include calcium acetate, zinc acetate, antimony acetate, tin acetate, and the like.
Further, the oxide concerned includes calcium oxide, zinc oxide, germanium oxide, antimony trioxide, antimony pentoxide, tin dioxide, stannous oxide, titanium monoxide, titanium dioxide, and the like.
Further, the organic compound composed of the metal includes antimony ethoxide, calcium acetylacetonate, and the like.
The dispersants involved include, but are not limited to, polyethylene glycol 200, ethylene glycol 400, glycerol, sodium Linear Alkylbenzenesulfonate (LAS), sodium fatty alcohol polyoxyethylene ether sulfate (AES), ammonium fatty alcohol polyoxyethylene ether sulfate (AESA), sodium lauryl sulfate (SDS), lauroyl glutamate.
The addition amount of the related auxiliary agent is 0-1000 ppm, and the addition amount of the dispersant is 0-5% of the mass of the solvent.
The heating condition of the 2, 5-furandicarboxylic acid is 80-190 ℃, after adding the auxiliary agent and/or the dispersing agent, stirring for 0.5-3 h, cooling and crystallizing at the speed of 0.5-15 ℃/min, cooling to 4-70 ℃, and recrystallizing for 0.5-72 h.
The stirring speed in the heating process is 0-1200 rpm.
The stirring speed in the crystallization process is 0-300 rpm.
Example 1
Weighing 40g of FDCA powder, adding the powder with the purity of 99.5% into 100g of dimethyl sulfoxide (DMSO), adding no nucleating agent, adding 0.1g of sodium lauryl sulfate (SDS), heating to 140 ℃ in a high-pressure reaction kettle at constant temperature for 1.5h (stirring in the heating process), cooling to 50 ℃ at a cooling rate of 5 ℃/min, crystallizing at constant temperature for 1h (stirring in the crystallizing process), and measuring the average grain diameter d of the crystals by a laser particle analyzer after crystallization is completed 50 91.4 μm. The nucleation time is based on the time at which nuclei are observed on a hot stage polarization microscope. The nucleation time was 5 minutes 15 seconds.
Example 2
The procedure of example 1 was followed except that 100ppm of zinc chloride was added thereto to obtain an average crystal grain size d 50 78.8 μm. The nucleation time was 25s.
Example 3
The procedure of example 1 was followed except that 1000ppm of zinc chloride was added thereto to obtain a mean particle diameter d 50 35.6 μm. The nucleation time was 8s.
Example 4
10g of FDCA powder is weighed, the purity is 99.5%, 100g of 90% acetic acid aqueous solution is added, 50ppm of zinc acetate nucleating agent is added, the mixture is heated to 160 ℃ in a high-pressure reaction kettle at constant temperature for 1.5 hours (stirring is not carried out in the heating process), the mixture is cooled to 50 ℃ at constant temperature for 6 hours (stirring rate in the crystallization process is 30 rpm) at a cooling rate of 5 ℃ per minute, and the average grain diameter d of the crystals is measured according to the method of the example 1 50 The nucleation time was 20s at 511.6. Mu.m.
Example 5
60g of FDCA powder is weighed out and purified99.9% of the total weight, 100g N-methylpyrrolidone (NMP) was added, 200ppm of an antimony trioxide nucleating agent was added, a dispersing agent was not added, the mixture was heated at a constant temperature of 190℃for 3 hours in a high-pressure reactor (no stirring during the heating), and the mixture was cooled to 50℃at a cooling rate of 5℃per minute and crystallized at a constant temperature for 6 hours (no stirring during the crystallization), and the average crystal grain diameter d was measured by the method of example 1 50 For 678.4 μm (see FIG. 1), the nucleation time was 14s.
Example 6
20g of FDCA powder was weighed, 99.9% pure, 100g of DMF-ethanol solution (60:40, m/m) was added, 50ppm of titanium dioxide nucleating agent was added, the mixture was heated at constant temperature up to 80℃for 3 hours (heating stirring rate: 300 rpm) in a high-pressure reaction vessel, and the mixture was cooled down to 50℃at constant temperature at a cooling rate of 5℃per minute for 6 hours (crystallization process was not stirred), and the average crystal grain diameter d was measured by the method of example 1 50 The nucleation time was 1 minute and zero 8 seconds at 824.5 μm.
Example 7
0.3g of FDCA powder with the purity of 99.9% is weighed, 100g of water is added, 50ppm of antimony ethoxide nucleating agent is added, the mixture is heated in a high-pressure reaction kettle to 150 ℃ at constant temperature for 2 hours (the heating stirring rate is 300 rpm), the mixture is cooled to 10 ℃ at a cooling rate of 15 ℃/min for 0.5 hour (the stirring rate in the crystallization process is 300 rpm), and the average grain diameter d of the crystals is measured according to the method of example 1 50 20 μm and nucleation time of 12s.
Table 1 experimental data for examples 1 to 7 are as follows
Comparative example 1
50g of FDCA powder was weighed, 99.5% pure, added to 100g of DMSO without any nucleating agent or dispersing agent, heated at a constant temperature of 150℃for 2 hours (heating stirring rotation speed 300 rpm) in a high-pressure reaction vessel, cooled to 60℃at a cooling rate of 1℃per minute, and crystallized at a constant temperature for 1 hour (crystallization process was not stirred), and the average crystal particle diameter d was measured by the method of example 1 50 18.5 μm, nucleation time was 18 minutes 44 seconds.
Example 8
50g of FDCA powder is weighed, the purity is 99.5%, 100g of DMSO is added, 50ppm of calcium chloride nucleating agent is added, the mixture is heated to 150 ℃ in a high-pressure reaction kettle at constant temperature for 2 hours (the heating stirring rotating speed is 300 rpm), the mixture is cooled to 60 ℃ at a cooling rate of 1 ℃/min and is crystallized at constant temperature for 1 hour (the crystallization process is not stirred), and the average grain diameter d of the crystals is measured according to the method of the example 1 50 157.5 μm, nucleation time of 3 minutes 20 seconds.
Example 9
The procedure of example 8 was followed to determine the average crystal particle diameter d by the procedure of example 1, except that polyethylene glycol 200 was further added in an amount of 0.001% by mass of the solvent, the crystallization temperature was changed to 25℃and the crystallization time was changed to 20 hours 50 925.7 μm. The nucleation time was 3 minutes 25 seconds.
Example 10
The procedure of example 9 was followed to obtain a crystal average particle diameter d by the method of example 1, except that the dispersant was changed to polyethylene glycol 200 having a solvent mass% in the same manner as described in example 9 50 1240 μm. The nucleation time was 3 minutes 58 seconds.
Example 11
The procedure of example 9 was followed to obtain a crystal average particle diameter d by the method of example 1, except that the dispersant was changed to polyethylene glycol 200 having a solvent mass% of 5% in the method of this example 50 1522.1 μm. The nucleation time was 5 minutes 16 seconds.
Example 12
20g of FDCA powder is weighed, the purity is 99.5%, 100g of DMF (90:10) is added into DMSO, polyethylene glycol 200 dispersant with the solvent mass of 3% is added, the mixture is heated to the constant temperature of 120 ℃ in a high-pressure reaction kettle for 2 hours (the heating stirring rotation speed is 300 rpm), the mixture is cooled to the constant temperature of 30 ℃ at the cooling rate of 1 ℃/min for 72 hours (the crystallization process is not stirred), and the average grain diameter d of the crystals is measured according to the method of the example 1 50 The nucleation time was 2000 μm and 4 minutes 48 seconds.
Example 13
The procedure of example 12 is followed except that the dispersant is changed to sodium lauryl sulfate (SDS) having a solvent mass% in accordance with the FDCA crystallization methodExample 1 measurement of average Crystal particle diameter d 50 1614.2 μm. The nucleation time was 3 minutes 50 seconds.
Example 14
20g of FDCA powder with the purity of 99.5% is weighed, added into 100g N-methyl pyrrolidone (NMP), added with fatty alcohol polyoxyethylene ether sodium sulfate (AES) dispersant with the solvent mass of 1%, heated to the constant temperature of 120 ℃ in a high-pressure reaction kettle for 2 hours (the heating stirring rotation speed of 300 rpm), cooled to the constant temperature of 40 ℃ at the cooling rate of 1 ℃/min for 48 hours (the crystallization process is not stirred), and the average grain diameter d of the crystals is measured according to the method of the example 1 50 The nucleation time was 1148.2 μm and 11 seconds of 4 minutes.
Table 2 Experimental data for comparative example 1, examples 8-14 are as follows
Example 15
15g of FDCA powder is weighed, the purity is 99.5%, the powder is added into 100g of DMSO solvent, 15ppm of calcium chloride nucleating agent and SDS dispersant accounting for 1% of the mass of the solvent are added, the mixture is heated to 80 ℃ for 2 hours at constant temperature, the stirring speed is 600rpm in the heating process, the mixture is cooled to 20 ℃ at constant temperature at a cooling speed of 1 ℃/min for 18 hours (crystallization stirring speed is 30 rpm), and the average grain diameter d of the crystals is measured according to the method of the example 1 50 At 438.5 μm, the nucleation time was 2s.
Example 16
The procedure of example 15 was followed except that the heating temperature was changed to 130℃in the same manner as in example 15 to obtain the average crystal grain size d by the method of example 1 50 855.7 μm. The nucleation time was 8s.
Example 17
The procedure of example 15 was followed except that the heating temperature was changed to 190℃in the same manner as in example 15 to obtain the average crystal grain size d by the method of example 1 50 1305.8 μm. The nucleation time was 120s.
Example 18
Weighing 15g FDCA powder with purity of 99.5%, adding into 100g DMF solvent, adding15ppm of calcium chloride nucleating agent and SDS dispersant with 1% of solvent mass, heating to 120 ℃ for 2 hours at constant temperature, cooling to 30 ℃ at a cooling rate of 1 ℃/min without stirring, crystallizing for 18 hours at constant temperature (crystallization stirring rate of 30 rpm), and measuring the average grain diameter d of the crystals according to the method of example 1 50 801.4 μm, nucleation time was 5s.
Example 19
The procedure of example 18 was followed to determine the average crystal grain size d by the method of example 1, except that the stirring rate during heating was changed to 60rpm 50 884.5 μm. The nucleation time was 7s.
Example 20
The procedure of example 18 is followed except that the stirring rate during heating is changed to 1200rpm, thereby obtaining an average crystal grain size d 50 914.6 μm. The nucleation time was 10s.
Table 3 experimental data for examples 15-20 are as follows
Example 21
Weighing 5g of FDCA powder, adding the powder with the purity of 99.5% into 100g of 70% acetic acid aqueous solvent with the mass concentration, adding 15ppm of antimony acetate nucleating agent and 0.5% SDS dispersing agent with the mass concentration, heating to 160 ℃ and keeping the temperature for 2 hours, heating at the stirring rate of 600rpm, cooling to 4 ℃ at the cooling rate of 15 ℃/min, crystallizing at the constant temperature for 5 hours (crystallization stirring rate of 30 rpm), and measuring the average grain diameter d of the crystals according to the method of the example 1 50 The nucleation time was 15s at 85.1. Mu.m.
Example 22
The procedure of example 21 was followed to determine the average crystal particle diameter d by the method of example 1, except that the cooling rate was changed to 0.5℃per minute and the crystallization temperature was changed to 40℃in the FDCA crystallization method used in this example 50 425.8 μm. The nucleation time was 18s.
Example 23
The FDCA crystallization method employed in this example removes the rate of coolingThe average grain diameter d of the crystals was measured by the method of example 1, except that the crystallization temperature was changed to 70℃at 5℃per minute, which was the same as in example 21 50 352.4 μm. The nucleation time was 38s.
Example 24
The procedure of example 22 was followed except that the cooling rate was changed to 10℃per minute and the stirring rate was changed to 300rpm in the FDCA crystallization method used in this example, to obtain the average crystal grain size d by the method of example 1 50 127.8 μm. The nucleation time was 7s.
Example 25
The procedure of example 22 was followed to determine the average crystal grain size d by the procedure of example 1, except that the stirring rate during the crystallization was changed to 0rpm and the crystallization time was changed to 48 hours 50 1272.5 μm. The nucleation time was 29s.
Example 26
The procedure of example 22 was followed to determine the average crystal grain size d by the procedure of example 1, except that the stirring rate during the crystallization was changed to 0rpm and the crystallization time was changed to 72 hours 50 2000. Mu.m. The nucleation time was 29s.
Table 4 experimental data for examples 21 to 26 are as follows
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the present invention.
Throughout this disclosure, where a composition is described as having, comprising, or including a particular component, or where a process is described as having, comprising, or including a particular process step, it is contemplated that the composition of the teachings of the present invention also consist essentially of, or consist of, the recited component, and that the process of the teachings of the present invention also consist essentially of, or consist of, the recited process step.
It should be understood that the order of steps or order in which a particular action is performed is not critical, as long as the present teachings remain operable. Furthermore, two or more steps or actions may be performed simultaneously. While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A method for regulating and controlling the grain size of 2, 5-furandicarboxylic acid crystals is characterized in that the method comprises the steps of adding an auxiliary agent into a raw material containing 2, 5-furandicarboxylic acid, heating, and crystallizing at a controlled temperature to obtain 2, 5-furandicarboxylic acid crystals with a certain grain size range;
wherein the auxiliary agent comprises at least one of a dispersing agent and a nucleating agent;
the average particle diameter d of the 2, 5-furandicarboxylic acid crystals 50 20-2000 μm.
2. The method of claim 1, wherein the feedstock further comprises a solvent; the mass concentration of the 2, 5-furandicarboxylic acid in the solvent is 0.3-60%.
3. The method according to claim 2, wherein the solvent comprises at least one of water, organic solvent a;
preferably, the organic solvent A comprises an amide organic solvent, a pyrrolidone organic solvent and a sulfoxide organic solvent;
preferably, the amide-based organic solvent comprises at least one of N, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide and nicotinamide;
preferably, the pyrrolidone type organic solvent comprises at least one of N-methyl pyrrolidone, 1-ethyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone and N-octyl pyrrolidone;
preferably, the sulfoxide organic solvent comprises at least one of thionyl chloride, dimethyl sulfoxide and dibutyl sulfoxide.
4. A method according to claim 3, wherein the solvent does not contain organic solvent B or contains organic solvent B in a volume fraction of not more than 90%;
preferably, the organic solvent B includes at least one of acetic acid, methanol, ethanol, acetone, acetonitrile.
5. The method of claim 1, wherein the dispersant comprises at least one of polyethylene glycol, ethylene glycol, glycerol, sodium linear alkyl benzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, ammonium fatty alcohol polyoxyethylene ether sulfate, sodium lauryl sulfate, lauroyl glutamic acid.
6. The method according to claim 1 or 5, wherein the dispersant is added in an amount of 0 to 5% by mass of the solvent;
preferably, the dispersant is added in an amount of 0.001 to 5% by mass of the solvent.
7. The method of claim 1, wherein the nucleating agent is selected from the group consisting of metal-containing compounds; the metal comprises at least one of calcium, zinc, germanium, antimony, tin, titanium and antimony;
the metal-containing compound comprises at least one of a metal inorganic salt, a metal oxide and a metal organic compound;
preferably, the metal inorganic salt is selected from at least one of metal chloride, metal acetate and metal carbonate;
preferably, the metal chloride comprises at least one of calcium chloride, zinc chloride, germanium chloride, antimony trichloride, tin tetrachloride and titanium tetrachloride;
preferably, the acetate of the metal comprises at least one of calcium acetate, zinc acetate, antimony acetate and tin acetate;
preferably, the metal oxide comprises at least one of calcium oxide, zinc oxide, germanium oxide, antimony trioxide, antimony pentoxide, tin dioxide, stannous oxide, titanium monoxide, titanium dioxide;
preferably, the metal organic compound comprises at least one of antimony ethoxide and calcium acetylacetonate.
8. The method according to claim 1 or 7, wherein the nucleating agent is added in an amount of 0 to 1000ppm;
preferably, the nucleating agent is added in an amount of 15ppm to 1000ppm.
9. The method of claim 1, wherein the heating method comprises: adding dispersant and/or nucleating agent into raw material containing 2, 5-furandicarboxylic acid, heating at 80-190 deg.C, stirring at 0-1200 rpm for 0.5-3 h.
10. The method of claim 1, wherein the conditions for temperature controlled crystallization include: the cooling rate of the temperature-controlled crystallization is 0.5-15 ℃/min, the crystallization temperature of the temperature-controlled crystallization is 4-70 ℃, the stirring II rate is 0-300 rpm, and the crystallization time is 0.5-72 hours.
Priority Applications (1)
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| JP2017190316A (en) * | 2016-04-15 | 2017-10-19 | 三菱ケミカル株式会社 | Method of purifying 2,5-furandicarboxylic acid |
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