CN116178314A - Method for improving storage and transportation stability of 5-hydroxymethylfurfural - Google Patents
Method for improving storage and transportation stability of 5-hydroxymethylfurfural Download PDFInfo
- Publication number
- CN116178314A CN116178314A CN202111435506.1A CN202111435506A CN116178314A CN 116178314 A CN116178314 A CN 116178314A CN 202111435506 A CN202111435506 A CN 202111435506A CN 116178314 A CN116178314 A CN 116178314A
- Authority
- CN
- China
- Prior art keywords
- hmf
- hydroxymethylfurfural
- compound
- storage
- changed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 172
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000003860 storage Methods 0.000 title claims abstract description 45
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 35
- -1 alcohol compound Chemical group 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 16
- 150000002989 phenols Chemical class 0.000 claims abstract description 13
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 11
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 12
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 7
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 7
- 150000002736 metal compounds Chemical class 0.000 claims description 7
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 7
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 5
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 claims description 4
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 4
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical compound CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims description 4
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 4
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 4
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 claims description 2
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 claims description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 2
- PQOSNJHBSNZITJ-UHFFFAOYSA-N 3-methyl-3-heptanol Chemical compound CCCCC(C)(O)CC PQOSNJHBSNZITJ-UHFFFAOYSA-N 0.000 claims description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 2
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 description 28
- 238000005286 illumination Methods 0.000 description 18
- 238000004321 preservation Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 238000001514 detection method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 230000010355 oscillation Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 3
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 3
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021655 trace metal ion Inorganic materials 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SFBLKWGYRDDITM-UHFFFAOYSA-J [Ti+4].[O-]S([O-])=O.[O-]S([O-])=O Chemical compound [Ti+4].[O-]S([O-])=O.[O-]S([O-])=O SFBLKWGYRDDITM-UHFFFAOYSA-J 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001284 azanium sulfanide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 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 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
Abstract
The application discloses a method for improving storage and transportation stability of 5-hydroxymethylfurfural, which comprises the following steps: in the pH value range of 5-8, the storage and transportation stability of the 5-hydroxymethylfurfural is improved through a reducing environment; wherein the reducing environment comprises: adding a trace amount of a reducing substance A or adding a reducing substance B and a trace amount of metal ions; the reducing substance A comprises an SO-containing substance 4 2‑ 、HSO 3 ‑ At least one of a class of compounds and a class of phenol compounds; the reducing substance B is an alcohol compound. The method eliminates free radical substances in the 5-hydroxymethylfurfural storage solution/solid or prevents free radicals from generating, prevents side reactions such as polymerization or decomposition of the 5-hydroxymethylfurfural, and achieves the purpose of prolonging the storage and transportation time of the 5-hydroxymethylfurfural. The invention has practical application value for the storage and transportation of 5-hydroxymethylfurfural.
Description
Technical Field
The application relates to a method for improving storage and transportation stability of 5-hydroxymethylfurfural, and belongs to the technical field of biomass chemical industry.
Background
The 5-Hydroxymethylfurfural (HMF) is one of research hotspots of biological-based chemicals for recent 20 years, and can be widely applied to the fields of medicines, pesticides, fragrances, chemical industry and the like. HMF is an important bio-based platform compound and is expected to become a large amount of chemical raw materials in the future, but HMF is unstable and is easy to chemically change in the storage and transportation processes, so that the subsequent application is directly affected. The instability of HMF is mainly caused by aldehyde group, hydroxymethyl and furan ring double bond, and contains trace impurities and free radical generated by nonuniform cleavage of covalent bond, so that the HMF is easy to generate side reactions such as polymerization or degradation. Therefore, a method needs to be searched to improve the stability of HMF during storage and transportation, so as to avoid HMF degradation, polymerization, discoloration, precipitation, caking and other consequences caused by impurities contained in the HMF, storage time, storage temperature, insolation condition, shaking condition and the like. The related protection formula and applicable conditions are not reported at present.
Disclosure of Invention
According to one aspect of the application, a method for improving storage and transportation stability of 5-hydroxymethylfurfural is provided, and the method utilizes the self-reducibility of a trace of reducing compound or forms a reducing environment under the catalysis of a trace of metal ions, eliminates free radical substances in a 5-Hydroxymethylfurfural (HMF) storage solution/solid, prevents side reactions such as polymerization or decomposition of HMF and the like, and achieves the aim of improving storage and transportation stability of HMF.
The method utilizes the self-reducibility of trace reducing compounds or forms a reducing environment under the catalysis of trace metal ions, eliminates free radical substances in HMF storage solution/solid or prevents free radicals from generating, prevents HMF from generating side reactions such as polymerization or decomposition, and achieves the aim of prolonging the storage and transportation time of HMF. The method has practical application value for storing and transporting the HMF.
The main principle of the invention is to utilize the reducibility of compounds such as potassium hydrogen sulfite, 2-tertiary butyl-6-methylphenol and the like, alcohol and Fe 2+ The reducing environment formed by the plasma metal ions protects aldehyde groups in the HMF from oxidation and degradation, quenches free radicals generated by the HMF due to comprehensive factors such as visible light, heating, vibration, impurities and the like, and prevents polymerization, discoloration, agglomeration and the like of the HMF.
The method for improving the storage and transportation stability of the 5-hydroxymethylfurfural comprises the following steps: in the pH value range of 5-8, the storage and transportation stability of the 5-hydroxymethylfurfural is improved through a reducing environment;
wherein the reducing environment comprises: adding a micro-reducing substance A or adding a reducing substance B and a trace amount of metal ions;
the reducing substance A comprisesContaining SO 4 2- 、HSO 3 - At least one of a class of compounds and a class of phenol compounds;
the reducing substance B is an alcohol compound.
As a specific embodiment, the method for improving the storage and transportation stability of the 5-hydroxymethylfurfural comprises the following steps: in a certain pH value range, the stability of the 5-hydroxymethylfurfural in the storage and transportation processes is improved by adding a trace amount of reducing substances A or adding a trace amount of reducing substances B and a trace amount of metal ions with a catalytic function;
wherein the reducing substance A comprises an SO-containing substance 4 2- 、HSO 3 - At least one of a class compound and a phenol class compound;
wherein the reducing substance B is an alcohol compound.
As one specific embodiment, when the reducing substance A is a substance containing SO 4 2- In the case of the class of compounds, the metal is a reducing metal such as iron, tin, cerium, titanium, and the like.
Optionally, the SO-containing agent 4 2- The class compound comprises at least one of ferrous sulfate, stannous sulfate, cerium sulfate and titanium sulfite; the HSO-containing 3 - The class of compounds includes at least one of sodium bisulfite, potassium bisulfite, and ammonium bisulfite.
Optionally, the phenol compound comprises at least one of 2, 6-di-tert-butyl-p-cresol (BHT), 2-tert-butyl-6-methylphenol, 4-Methoxyphenol (MEHQ), tert-butylhydroquinone (TBHQ), butyl Hydroxy Anisole (BHA), and 2, 4-dimethyl-6-tert-butylphenol.
Optionally, the SO-containing agent 4 2- 、HSO 3 - When the class compound is added singly, the addition amount is 20-500 ppm; when the phenol compound is added singly, the addition amount is 20-400 ppm; the SO-containing 4 2- 、HSO 3 - When the phenolic compound and the phenolic compound are mixed and added, the adding amount is 20-300 ppm.
Alternatively, the process may be carried out in a single-stage,the SO-containing 4 2- 、HSO 3 - The addition amount of the class compound is 50-500 ppm.
Optionally, the SO-containing agent 4 2- 、HSO 3 - The upper limit of the adding amount of the class compound is selected from 30ppm, 50ppm, 60ppm, 100ppm, 150ppm, 200ppm, 400ppm or 500ppm; the lower limit is selected from 20ppm, 30ppm, 50ppm, 60ppm, 100ppm, 150ppm, 200ppm or 400ppm.
Optionally, the SO-containing agent 4 2- 、HSO 3 - The total amount of the mixed addition of the phenolic compound and the phenolic compound is any value of 20ppm, 30ppm, 60ppm, 200ppm and 300ppm and any point value between the range values formed between any two.
Optionally, the alcohol compound includes at least one of a C1-C8 alcohol.
Alternatively, the alcohol compound is a monohydric alcohol compound, preferably a monohydric alcohol of C1-C8.
Optionally, the C1-C8 alcohol comprises at least one of methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, n-pentanol, tert-pentanol, sec-pentanol, n-hexanol, 2-hexanol, 3-hexanol, 2-ethylhexanol, 4-methyl-2-pentanol, n-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-methyl-3-heptanol, 2-ethylhexanol.
Optionally, the metal of the metal ion comprises at least one of Cu, ag, fe, pb, pt, au, sn, ru, rh, co, ce, ti, mo, zr.
Optionally, the metal ion is derived from a metal compound.
Optionally, the anion in the metal compound is at least one of sulfate radical, acetate radical, phosphate (hydrogen) radical and oxalate radical.
Optionally, the mass ratio of the alcohol compound to the metal compound is 10:1-1000:1.
Optionally, the upper mass ratio of the alcohol compound to the metal compound is selected from 15:1, 16:1, 20:1, 50:1, 100:1, 150:1, 200:1, 500:1 or 1000:1; the lower limit is selected from 10:1, 15:1, 16:1, 20:1, 50:1, 100:1, 150:1, 200:1, or 500:1.
Optionally, the addition amount of the alcohol compound is 0.01-0.1% of the mass of the 5-hydroxymethylfurfural.
Optionally, the upper limit of the percentage of the mass of the alcohol compound added is selected from 0.05% or 0.1% of the mass of the 5-hydroxymethylfurfural; the lower limit is selected from 0.01% or 0.05%.
Optionally, the storage and transportation temperature range of the 5-hydroxymethylfurfural is-50-70 ℃.
Optionally, the pH value range of the 5-hydroxymethylfurfural is 5-8, and when the storage and transportation temperature range T is-50 ℃ or less and 10 ℃ or less, the shelf life T of the 5-hydroxymethylfurfural is 24-36 months or less; when the storage and transportation temperature range is more than 10 and less than or equal to 40 ℃, the shelf life T of the 5-hydroxymethylfurfural is more than or equal to 10 and less than 24 months; when the storage and transportation temperature range is 40-70 ℃, the shelf life T of the 5-hydroxymethylfurfural is 5-10 months.
The illumination intensity of the storage and transportation of the 5-hydroxymethylfurfural is 0-100000 lx.
The related 5-hydroxymethylfurfural can be stirred in a vortex type, a convection type and a horizontal oscillation type in the storage and transportation process.
As a specific embodiment, the methods described herein can extend the storage time of 5-hydroxymethylfurfural by at least a factor of 2.5 times or more as compared to a regimen without the addition of reducing substances.
As used herein, "C1-C8" refers to the number of carbon atoms in the alcohol compound.
Storage and transportation as described herein includes storage and transportation.
The beneficial effects that this application can produce include:
(1) The invention provides a novel method for improving the stability of 5-hydroxymethylfurfural in the storage and transportation processes;
(2) The content of the added reducing substances and metal ions is low, and the cost is low;
(3) The method provided by the invention can obviously improve the stability of the 5-hydroxymethylfurfural.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
In view of the fact that there is no special solution for improving stability in the process of storing and transporting 5-hydroxymethylfurfural, the inventor of the present invention has made extensive studies and practical use, and has proposed the technical scheme of the present invention, which mainly uses the self-reducibility of trace reducing compounds such as ferrous sulfate, sulfite and phenols, or forms a reducing environment with alcohol under the catalysis of very trace metal ions such as Cu, ag, fe, pb, pt, au, sn, ru, rh, co, ce, ti, mo, zr, etc., to eliminate free radical substances in the 5-Hydroxymethylfurfural (HMF) storage solution/solid, prevent side reactions such as HMF polymerization or decomposition, etc., so as to improve HMF storage and transportation stability and prolong the shelf life of HMF.
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise indicated, both the starting materials and the catalysts in the examples of the present application were purchased commercially.
The HMF purity and absorbance ratio were measured/calculated in the same manner as in example 1 in the examples of the present application.
Example 1
1kg of 5-Hydroxymethylfurfural (HMF) with the purity of 99.95% is placed in a white plastic bucket, the pH value of the bucket is measured to be 8.0, 200ppm of ferrous sulfate is added, the bucket is sealed after uniform mixing, the bucket is placed in a constant temperature box at 40 ℃ for storage, a small lamp is kept to be always on in the incubator, and the light intensity in the bucket is measured to be 10lx by an illuminometer. Standing for 10 months, and performing high performance liquid chromatography (C) 18 Reverse phase chromatographic column separation, ultraviolet detector 278nm wavelength detection, methanol and trifluoroacetic acid aqueous solution elution) to calculate the product purity, the maximum time for which the HMF purity is measured unchanged is 10.0 months, and the sample purity is 99.95%. The sample preparation method comprises the following steps: accurately weighing 0.1g HMF, dissolving in 1L deionized water, and preparingThe concentration of the prepared sample is 0.1g/L, the HMF concentration is determined by adopting an external standard method through analysis by a high performance liquid chromatograph, the sample injection amount is 10 mu L, and the purity of the HMF sample is calculated according to the following formula:
the colored impurities in the HMF preparation process have strong absorption at 426nm, and the absorption value (OD) of the HMF sample at 426nm wavelength is measured 426nm ) The change judges whether the sample changes color or not so as to store and transport the OD of the sample at a certain time t 426nm t And the initial time t 0 OD of sample 426nm t0 Ratio OD 426nm t /OD 426nm t0 Indicating a magnitude of discoloration, greater than 1.05 indicates significant discoloration. OD after 7.5 months of standing 426nm t /OD 426nm t0 The ratio was 1.008, the discoloration was not significant. HMF purity was 99.89% after 10 months of standing and OD 426nm t /OD 426nm t0 The ratio was 1.022.
Example 2
1kg of HMF with the purity of 99.97% is placed in a white plastic bucket, the pH value of the HMF is measured to be 5.2, 200ppm of ammonium bisulfide is added, the HMF is sealed after being uniformly mixed, the HMF is oscillated at the rotating speed of 200rpm in a constant temperature shaking table at 50 ℃, a small lamp is kept to be always on in the shaking table, and the light intensity in the bucket is measured to be 25lx by an illuminometer. The HMF purity was measured every 15 days by the method of example 1 after 10 months of standing, and the maximum time in which the HMF purity was not changed was measured to be 7 months, and the sample purity was 99.97%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.012.
Example 3
The HMF preservation method used in this example was the same as that of example 2 except that the reducing agent was changed to 2, 6-di-t-butyl-p-cresol (BHT), the stirring mode was changed to 30 times/horizontal oscillation, the illumination intensity was changed to 10lx, and the temperature was changed to 50 ℃. The maximum time for which the HMF purity was not changed was measured to be 8.0 months, and the sample purity was 99.97%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.002.
Example 4
1kg of the product has a purity of 9998% HMF was placed in a white plastic bucket, the pH value was measured to be 6.0, 400ppm tert-butylhydroquinone (TBHQ) was added, the mixture was mixed uniformly, sealed, placed in a 45-incubator, kept at rest, and a small lamp was kept in the incubator to be always on, and the light intensity was measured to be 10lx by a illuminometer. Other operations and detection methods were the same as in example 1. The maximum time for which the HMF purity was not changed was measured to be 9.5 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.004.
Example 5
1kg of 5-Hydroxymethylfurfural (HMF) with the purity of 99.98% is placed in a white plastic bucket, the pH value of the bucket is measured to be 6.0, 50ppm of ferrous sulfate and 150ppm of BHT are added, 20mL/s convection stirring is carried out by a rib circulating pump after the bucket is uniformly mixed, the bucket is stored in a constant temperature cabinet at 45 ℃, and the light intensity in the bucket is measured to be 10lx by an illuminometer. Other operations and detection methods were the same as in example 1. The maximum time for which the HMF purity was not changed was measured to be 8.5 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.005.
Example 6
The method of preserving HMF used in this example was the same as that of example 3 except that the amount of BHT as a reducing agent was changed to 100ppm and 100ppm of sodium bisulphite was added thereto, and the preserving process was not stirred. The maximum time for which the HMF purity was not changed was measured to be 9.0 months, and the HMF sample purity was 99.97%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.003.
Example 7
The method of preserving HMF used in this example was the same as that of example 1 except that the reducing agent was changed to 100ppm potassium hydrogen sulfite and 100ppm Butyl Hydroxy Anisole (BHA), the stirring mode was 200rpm rotational speed vortex stirring, the preserving temperature was changed to 50℃and the illumination intensity was changed to 25lx. The maximum time for which the HMF purity was not changed was measured to be 8.0 months, and the HMF sample purity was 99.95%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.008.
TABLE 1 HMF maximum shelf life test data Table for examples 1-7
Example 8
The HMF preservation method used in this example was the same as example 1 except that the reducing agent was changed to 50ppm sodium bisulphite, the stirring mode was 30 times/min horizontal oscillation, the preservation temperature was changed to 10 ℃, and the illumination intensity was changed to 10000lx by changing the glass with strong light transmittance and increasing the number of lamps. The maximum time for which the HMF purity was not changed was measured to be 24.0 months, and the HMF sample purity was 99.95%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.007.
Example 9
1kg of HMF with the purity of 99.97% is placed in a white plastic bucket, the pH value of the HMF is measured to be 5.2, 500ppm of sodium bisulphite is added, and the HMF is mixed uniformly and then placed in an ultralow temperature refrigerator at-50 ℃ for storage, wherein the illumination intensity is 0lx. Other operations and detection methods were the same as in example 1. The maximum time for which the HMF purity was not changed was measured to be 36.0 months, and the HMF sample purity was 99.97%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.000.
Example 10
The HMF preservation method used in this example was the same as that used in example 4, except that the reducing agent was changed to 400ppm BHT, the preservation temperature was changed to 15℃and the illumination intensity was changed to 100 lx. The maximum time for which the HMF purity was not changed was measured to be 19.5 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.009.
Example 11
1kg of HMF with the purity of 99.97% is placed in a glass jar, the pH value of the HMF is measured to be 5.2, 20ppm of Tertiary Butyl Hydroquinone (TBHQ) is added, the HMF is mixed uniformly, then the HMF is placed in a constant temperature box at 40 ℃ for storage, the illumination intensity is 100000lx, illumination is not carried out at night, and the day-night alternation time is set to be 12:12. Other operations and detection methods were the same as in example 1. The maximum time for which the HMF purity was not changed was measured to be 10.0 months, and the HMF sample purity was 99.97%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.014.
Example 12
The HMF preservation method used in this example was the same as that used in example 10, except that the reducing agent was changed to 50ppm of ferrous sulfate and 10ppm of BHT, the preservation temperature was changed to 70℃and the illumination intensity was changed to 10000lx. The maximum time for which the HMF purity was not changed was measured to be 5.0 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.018.
Comparative example 1
The HMF preservation method used in this example was the same as that used in example 12, except that no reducing agent was added. The maximum time for which the HMF purity was not changed was measured to be 2.0 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio is 1.019; after 5.0 months of standing, the HMF sample became 90.21% pure and OD 426nm t /OD 426nm t0 The ratio was 1.063.
Example 13
The procedure and test method were the same as in example 9, except that the reducing agent was changed to 10ppm sodium bisulphite and 10ppm BHT. The maximum time for which the HMF purity was not changed was measured to be 32.0 months, and the HMF sample purity was 99.97%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.002.
TABLE 2 longest shelf life test data sheet for HMF of examples 8-13 and comparative example 1
Example 14
The HMF preservation method used in this example was the same as that of example 1 except that the reducing agent combination was changed to 1g of methanol (0.1% of the mass of HMF sample) and 0.1g of titanium sulfate, and the illumination intensity was changed to 0lx. The maximum time for which the HMF purity was not changed was measured to be 10.0 months, and the HMF sample purity was 99.95%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.003. The HMF sample purity was 99.93% and OD at 10.5 months of storage time 426nm t /OD 426nm t0 The ratio was 1.008.
Example 15
1kg of HMF with the purity of 99.98% is placed in a white plastic bucket, the pH value of the HMF is measured to be 6.0, 1g of methanol and 0.05g of silver acetate are added into the HMF, the mixture is uniformly mixed and sealed, the HMF is placed in a constant temperature tank at 50 ℃ for standing and storage, and the HMF is irradiated by outdoor sunlight in summer, wherein the illumination intensity is 100000lx. Other operations and detection methods were the same as in example 1. The maximum time for which the HMF purity was not changed was measured to be 8.5 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.015.
Example 16
The method of preserving HMF used in this example was the same as that of example 15 except that the reducing agent combination was changed to 0.5g of methanol (0.05% of the mass of HMF sample) and 0.05g of stannous oxalate, the stirring mode was changed to 60 times/horizontal oscillation mode, the preserving temperature was changed to 45℃and the illumination intensity was set to 1000 lx. The maximum time for which the HMF purity was not changed was measured to be 8.0 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.006.
Example 17
1kg of HMF with the purity of 99.97% is placed in a white plastic bucket, the pH value of the HMF is measured to be 5.2, 0.5g of isopropanol and 0.03g of titanium sulfate are added into the HMF, the mixture is uniformly mixed, the light is closed and sealed, the HMF is stored in a constant temperature shaking table at 45 ℃, the rotating speed is set to be 200rpm (vortex type oscillation), and the illumination intensity is set to be 0lx. Other operations and detection methods were the same as in example 1. The maximum time for which the HMF purity was not changed was measured to be 9.0 months, and the HMF sample purity was 99.97%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.004.
Example 18
The procedure and test method were the same as in example 15, except that the reducing agent combination was changed to 0.5g of n-butanol (0.05% of the mass of the HMF sample) and 0.05g of cobalt phosphate, the storage temperature was changed to 60℃and the light intensity was set to 10lx. The maximum time for which the HMF purity was not changed was measured to be 7.5 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.008.
Example 19
The method of preserving HMF used in this example was the same as that of example 17 except that the reducing agent combination was changed to 0.1g of 1-octanol (0.01% of the mass of HMF sample) and 0.01g of cuprous acetate, and the preserving temperature was changed to 70℃and the light intensity was 100000lx. The maximum time for which the HMF purity was not changed was measured to be 5.0 months, and the HMF sample purity was 99.97%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.018.
Example 20
The procedure and test method were the same as in example 15, except that the reducing agent combination was changed to 1g of 2-ethylhexanol and 0.001g of stannous sulfate, and the light intensity was set to 0lx. The maximum time for which the HMF purity was not changed was measured to be 9.0 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.006.
Comparative example 2
The procedure and test procedures used in this example were the same as those used in example 20, except that the reducing agent combination was changed to only 0.001g of stannous sulfate. The maximum time for which the HMF purity was not changed was measured to be 4.5 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.030.
TABLE 3 maximum shelf life test data sheet for HMF of examples 14-20
Example 21
The HMF preservation method used in this example was the same as that used in example 15, except that the combination of the reducing agent was changed to 1g of methanol and 0.1g of titanium sulfate, the temperature was changed to-50℃and the illumination intensity was set to 0lx. The maximum time for which the HMF purity was not changed was measured to be 36.0 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.004.
Example 22
The HMF preservation method used in this example was the same as that used in example 15, except that the reducing agent combination was changed to 1g of methanol and 0.05g of titanium sulfate, the temperature was changed to-20℃and the stirring mode was changed to 60 horizontal oscillations per minute. The maximum time for which the HMF purity was not changed was measured to be 30.5 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.020.
Example 23
The HMF preservation method used in this example was the same as that of example 21, except that the temperature was changed to 10 ℃ and the illumination intensity was 10000lx. The maximum time for which the HMF purity was not changed was measured to be 24.0 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.006.
Example 24
1kg of HMF with purity of 99.98% was placed in a glass jar, the pH value was measured to be 6.0, 0.1g of isopropyl alcohol and 0.01g of cobalt phosphate were added as a combination of reducing agents, and after mixing uniformly, the mixture was sealed and stored in a constant temperature shaker at 20℃at 200rpm (vortex type) and the illumination intensity was 10000lx. Other operations and detection methods were the same as in example 1. The maximum time for which the HMF purity was not changed was measured to be 15.0 months, and the HMF sample purity was 99.97%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.005.
Example 25
The method of preserving HMF used in this example was the same as that of example 21 except that the combination of reducing agent was changed to 0.1g of n-butanol and 0.01g of cobalt phosphate, the preserving temperature was changed to 50℃and the illumination intensity was set to 10lx. The maximum time for which the HMF purity was not changed was measured to be 7.5 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.008.
Example 26
The method of preserving HMF used in this example was the same as that of example 21 except that the combination of reducing agent was changed to 0.1g of 1-octanol and 0.001g of tin acetate, the preserving temperature was changed to 70℃and the illumination intensity was set to 100000lx, and the stirring mode was changed to 60 times/min horizontal oscillation. Measurement of HMThe maximum time that F purity was unchanged was 5.0 months, and HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.023.
Example 27
The procedure and test method were the same as in example 21, except that the reducing agent combination was changed to 1g of 2-ethylhexanol and 0.01g of stannous oxalate, and the storage temperature was changed to 40 ℃. The maximum time for which the HMF purity was not changed was measured to be 10.0 months, and the HMF sample purity was 99.98%. OD (optical density) 426nm t /OD 426nm t0 The ratio was 1.004.
TABLE 4 maximum shelf life test data sheet for HMF of examples 21-27
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 improving storage and transportation stability of 5-hydroxymethylfurfural, which is characterized by comprising the following steps: in the pH value range of 5-8, the storage and transportation stability of the 5-hydroxymethylfurfural is improved through a reducing environment;
wherein the reducing environment comprises: adding a trace amount of a reducing substance A or adding a reducing substance B and a trace amount of metal ions;
the reducing substance A comprises an SO-containing substance 4 2- 、HSO 3 - At least one of a class of compounds and a class of phenol compounds;
the reducing substance B is an alcohol compound.
2. The method of claim 1, wherein the SO-containing gas is 4 2- 、HSO 3 - The class compound comprises at least one of ferrous sulfate, stannous sulfate, cerous sulfate, titanium sulfate, sodium bisulfate, potassium bisulfate and ammonium bisulfate.
3. The method of claim 1, wherein the phenolic compound comprises at least one of 2, 6-di-tert-butyl-p-cresol, 2-tert-butyl-6-methylphenol, 4-methoxyphenol, tert-butylhydroquinone, butylhydroxyanisole, 2, 4-dimethyl-6-tert-butylphenol.
4. The method of claim 1, wherein the SO-containing gas is 4 2- 、HSO 3 - The independent adding amount of the class compound is 20-500 ppm; the independent adding amount of the phenol compound is 20-400 ppm; the SO-containing 4 2- 、HSO 3 - The total mixed addition amount of the phenolic compound and the phenolic compound is 20-300 ppm;
preferably, the SO-containing agent 4 2- 、HSO 3 - The total amount of the mixed addition of the phenolic compound and the phenolic compound is 30-300 ppm.
5. The method according to claim 1, characterized in that: the alcohol compound comprises at least one of alcohols of C1-C8;
preferably, the C1-C8 alcohol comprises at least one of methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, n-pentanol, tert-pentanol, sec-pentanol, n-hexanol, 2-hexanol, 3-hexanol, 2-ethylhexanol, 4-methyl-2-pentanol, n-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-methyl-3-heptanol, 2-ethylhexanol.
6. The method of claim 1, wherein the metal of the metal ion comprises at least one of Cu, ag, fe, pb, pt, au, sn, ru, rh, co, ce, ti, mo, zr.
7. The method of claim 1 or 6, wherein the metal ions are derived from a metal compound;
preferably, the anion in the metal compound is at least one of sulfate, acetate, phosphate (hydrogen) and oxalate.
8. The method according to claim 1, 5 or 6, wherein the mass ratio of the alcohol compound to the metal compound is 10:1 to 1000:1.
9. The method according to claim 1 or 5, wherein the addition amount of the alcohol compound is 0.01-0.1% of the mass of the 5-hydroxymethylfurfural.
10. The method according to claim 1, wherein the pH value of the 5-hydroxymethylfurfural is 5-8, and the shelf life T of the 5-hydroxymethylfurfural is 24-36 months when the storage and transportation temperature range T is-50-10 ℃; when the storage and transportation temperature range is more than 10 and less than or equal to 40 ℃, the shelf life T of the 5-hydroxymethylfurfural is more than or equal to 10 and less than 24 months; when the storage and transportation temperature range is 40-70 ℃, the shelf life T of the 5-hydroxymethylfurfural is 5-10 months.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111435506.1A CN116178314A (en) | 2021-11-29 | 2021-11-29 | Method for improving storage and transportation stability of 5-hydroxymethylfurfural |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111435506.1A CN116178314A (en) | 2021-11-29 | 2021-11-29 | Method for improving storage and transportation stability of 5-hydroxymethylfurfural |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116178314A true CN116178314A (en) | 2023-05-30 |
Family
ID=86438918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111435506.1A Pending CN116178314A (en) | 2021-11-29 | 2021-11-29 | Method for improving storage and transportation stability of 5-hydroxymethylfurfural |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116178314A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU387986A1 (en) * | 1971-07-09 | 1973-06-22 | Архангельский ордена Трудового Красного Знамени лесотехнический институт В. В. Куйбышева | METHOD OF STABILIZATION OF FURFUROL |
| CN105007913A (en) * | 2013-03-14 | 2015-10-28 | 阿彻丹尼尔斯米德兰德公司 | Process for making HMF from sugars with reduced byproduct formation, and improved stability HMF compositions |
| EP3401312A1 (en) * | 2017-05-08 | 2018-11-14 | AVALON Industries AG | Method for stabilisation of hydroxymethylfurfural (hmf) |
| CN110407778A (en) * | 2018-04-27 | 2019-11-05 | 中国石油化工股份有限公司 | A kind of storage method of 5 hydroxymethyl furfural, the alcoholic solution of 5 hydroxymethyl furfural and the composition containing 5 hydroxymethyl furfural |
-
2021
- 2021-11-29 CN CN202111435506.1A patent/CN116178314A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU387986A1 (en) * | 1971-07-09 | 1973-06-22 | Архангельский ордена Трудового Красного Знамени лесотехнический институт В. В. Куйбышева | METHOD OF STABILIZATION OF FURFUROL |
| CN105007913A (en) * | 2013-03-14 | 2015-10-28 | 阿彻丹尼尔斯米德兰德公司 | Process for making HMF from sugars with reduced byproduct formation, and improved stability HMF compositions |
| EP3401312A1 (en) * | 2017-05-08 | 2018-11-14 | AVALON Industries AG | Method for stabilisation of hydroxymethylfurfural (hmf) |
| CN110407778A (en) * | 2018-04-27 | 2019-11-05 | 中国石油化工股份有限公司 | A kind of storage method of 5 hydroxymethyl furfural, the alcoholic solution of 5 hydroxymethyl furfural and the composition containing 5 hydroxymethyl furfural |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Simic et al. | Free radical reduction of ferricytochrome-c | |
| EP2166875B1 (en) | Method for removing odor from vinegar | |
| WO2006041216A1 (en) | Sweetener composition | |
| CN116178314A (en) | Method for improving storage and transportation stability of 5-hydroxymethylfurfural | |
| JP2023550724A (en) | Use of carboxylate compounds as absorbents for carbon dioxide capture | |
| CN107307069A (en) | 1- methyl cyclopropenes preparation and preparation and application for fruits and vegetables flower freshness | |
| TWI329632B (en) | Process for the production of acetic acid | |
| Blackadder et al. | 567. The kinetics of the rearrangement and oxidation of hydrazobenzene in solution. Part II. The catalysed oxidation | |
| KR101935245B1 (en) | Novel Oxygen Scavenging Film and a Composition for Packaging Comprising the Same | |
| KR970002901B1 (en) | Method for stabilizing rhodium compound | |
| Veglia et al. | . beta.-Cyclodextrin effects on the photo-Fries rearrangement of aromatic alkyl esters | |
| CN110479371A (en) | A kind of preparation method and application of ligand/plant photochemical catalyst | |
| CN112374980B (en) | Eutectic ionic liquid and application thereof | |
| CN112806387B (en) | Preparation method of iodine-containing disinfectant with stable component content | |
| Ogata et al. | Further studies on the preparation of terephthalic acid from phthalic or benzoic acid | |
| CN109912643B (en) | Method for controlling feeding amount of acid remover in condensation reaction process of methyl tin mercaptide | |
| Rao | Radiolysis of ascorbic acid in aqueous solution by gamma radiation | |
| WO2016186122A1 (en) | Polyester resin | |
| Merrigan et al. | Effects of Experimental Parameters on the (n, γ)-Activated Reactions of Bromine with Liquid Cyclohexane | |
| Cardwell et al. | Gas Chromatography of volatile metal dialkyldithiophosphates | |
| CN104086574A (en) | Preparation method and storage method of 1-methyl cyclopropene lithium | |
| JP2010126466A (en) | Method for producing phenol | |
| Berkesi et al. | Influence of the alkyl-chain on the symmetry and structural changes of Zn4O (RCO2) 6 complexes in film phase—An FT-IR study | |
| Wood | Carbon isotope effects in the decarboxylation of oxaloacetic acid. Part 1.—Studies using 136 C | |
| CN111838616A (en) | Preservation method of spicy materials with peppers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |