CN109053642A - A kind of method that Mineral salts-glucose acid system is catalyzed fructose converting 5 hydroxymethyl furfural - Google Patents
A kind of method that Mineral salts-glucose acid system is catalyzed fructose converting 5 hydroxymethyl furfural Download PDFInfo
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- fructose
- hydroxymethyl furfural
- reaction
- gluconic acid
- mineral salts
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- 239000005715 Fructose Substances 0.000 title claims abstract description 60
- 229930091371 Fructose Natural products 0.000 title claims abstract description 57
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 title claims abstract description 57
- 239000002253 acid Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000008103 glucose Substances 0.000 title claims abstract description 15
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 12
- 239000011707 mineral Substances 0.000 title claims abstract description 12
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims description 44
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims description 29
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims abstract description 59
- 235000012208 gluconic acid Nutrition 0.000 claims abstract description 57
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000174 gluconic acid Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 230000018044 dehydration Effects 0.000 claims abstract description 23
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010850 salt effect Methods 0.000 claims abstract description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 16
- 239000001110 calcium chloride Substances 0.000 claims description 16
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 235000010755 mineral Nutrition 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 235000009754 Vitis X bourquina Nutrition 0.000 claims description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 claims description 2
- 240000006365 Vitis vinifera Species 0.000 claims description 2
- 235000014787 Vitis vinifera Nutrition 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 11
- 238000007171 acid catalysis Methods 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- -1 aldehyde radical Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 235000021433 fructose syrup Nutrition 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- FXLJDRXREUZRIC-BAOOBMCLSA-N (3s,4r,5r)-1,3,4,5,6-pentahydroxyhexan-2-one;hydrate Chemical compound O.OC[C@@H](O)[C@@H](O)[C@H](O)C(=O)CO FXLJDRXREUZRIC-BAOOBMCLSA-N 0.000 description 1
- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 description 1
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 1
- 108091022917 Gluconate dehydratase Proteins 0.000 description 1
- PCSKKIUURRTAEM-UHFFFAOYSA-N HMF acid Natural products OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- OFMTVAFQBCXDFR-UHFFFAOYSA-K calcium;lithium;trichloride Chemical compound [Li+].[Cl-].[Cl-].[Cl-].[Ca+2] OFMTVAFQBCXDFR-UHFFFAOYSA-K 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods that Mineral salts-glucose acid system is catalyzed fructose converting HMF.This method improves the hydrogen ion dissociation constant of gluconic acid by salt effect, so that the acidity that fructose dehydration prepares HMF can be catalyzed by reaching, realizes and prepares HMF by gluconic acid catalysis fructose.The present invention extends the catalyst type that fructose dehydration prepares HMF, reduces the corrosion impact to reaction unit, while high conversion rate, HMF selectivity are high, gluconic acid and inorganic salts can be recycled recycling.
Description
Technical field
The present invention relates to chemical reaction technologies, in particular to enhance the hydrogen ion degree of ionization of gluconic acid by salt effect,
To improve the effect that catalysis fructose dehydration prepares 5 hydroxymethyl furfural.
Background technique
The energy and widely used chemical products that the mankind depend on for existence and development are mainly by fossil fuel
Processing obtains.Fossil fuel inevitably moves towards failure as non-renewable resources.Biomass is as a kind of renewable, storage
Amount is enriched and the resource of low pollution, it can not only serve as fuel use, but also can be converted into chemical intermediate to close
At various chemicals and liquid fuel.In biomass conversion, it is dehydrated using C6 carbohydrate as reactant and generates 5 hydroxymethyl furfural
(5-HMF) is one of the hot spot of research.5-HMF have furan ring structure, aldehyde radical, hydroxyl and conjugated diene, can by hydrolysis,
The means such as selective oxidation plus hydrogen, esterification obtain a series of derivative, such as 2,5-furandaldehyde, levulic acid, 2,5-
Furandicarboxylic acid etc., these derivatives are suffered from fields such as medicine, fuel and plastics industries and are widely applied.
Currently, HMF is mainly in acid condition by carbohydrate (fructose, glucose, sucrose etc. and its polysaccharide formed)
Selectively dewatering and obtain, wherein the difficulty for producing HMF as raw material using fructose is smaller and easily obtains higher yield.By right
Fructose is found during being dehydrated the Techno-Economic Analysis of HMF preparation: cost of material proportion in HMF preparation is very big.
Therefore, we have developed enzymatically aoxidized to obtain gluconic acid and fructose mixed solution, then by cheap raw material fructose syrup
In the process (ZL201610212019.1) of acid-catalyzed dehydration coproduction HMF and gluconic acid.But in this process, gluconic acid
It is weak organic acid, pKa is only 3.6.Since it is acid weaker, the effect of catalysis fructose dehydration can not be played, needs to add big
The inorganic acid of amount is dehydrated to be catalyzed fructose.The addition of inorganic acid not only increases cost, while also to the anticorrosive of reaction unit
More stringent requirements are proposed.
For just having had research before the catalyst system catalysis fructose preparation 5-HMF of gluconic acid, Kuster etc. is with second
Acid is used as catalyst, the yield about 58% of 5-HMF when acetic acid (pKa=4.74) is as catalyst reaction 20min；El Hajj etc. with
Oxalic acid (pKa=1.23) is used as catalyst, and 130min is reacted at 135-142 DEG C, and fructose converting rate is the yield of 61%, 5-HMF
About 34%；Zhang Xiudong etc. reacts 20min at 150 DEG C in DMSO/ aqueous systems using xylonic (pKa=3.65) as catalyst, can
To obtain the yield of 5-HMF as 69.8%；Liu Shulan etc. is with citric acid (pKa1=3.13) it is used as catalyst, is reacted at 140 DEG C
400min, the yield of available 5-HMF are about 40%；Li Tiancheng etc. using the mixed acid of maleic acid and hydrochloric acid as catalyst, from
Sub- liquid can urged as reaction dissolvent and medium under microwave-assisted with super low concentration catalyzing cellulose hydrolysis at glucose
Change gluconate dehydratase and prepare 5-HMF, the yield of available 5-HMF is 29.13%.It is also proved: being depended merely on from side by example above
The less hydrogen ion that organic monoacid self-ionization comes out, when being catalyzed fructose dehydration catalyst, to generally require higher reaction temperature
(200 DEG C or so), longer reaction time are spent, and the lower simultaneous selection of the yield of 5-HMF is not high.
Summary of the invention
The present invention utilizes salt effect principle, strengthens the degree of ionization of gluconic acid by addition inorganic salts, so that de- in fructose
Water can be carried out with high selectivity when reacting with high conversion, HMF.
The technical solution adopted by the invention is as follows:
A kind of method that Mineral salts-glucose acid system is catalyzed fructose converting 5 hydroxymethyl furfural, in gluconic acid-fructose mixing
Inorganic salts are added in solution, hydrogen ion concentration in gluconic acid degree of ionization and reaction system is improved by salt effect, is catalyzed fructose
Dehydration conversion 5 hydroxymethyl furfural.
Wherein, the inorganic salts used in the present invention are sodium chloride, potassium chloride, sodium bromide, lithium chloride, calcium chloride, chlorination
Zinc, magnesium sulfate, lithium bromide, potassium bromide etc.；It is preferred that salt is calcium chloride.
Wherein, the inorganic salts dosage being added in the present invention is 1-30wt%.
Wherein, gluconic acid catalyst concn is 5-200g/L in Mineral salts-glucose acid system of the invention.
Wherein, fructose dehydration prepares the reaction of 5 hydroxymethyl furfural in the present invention, and it is anti-that reaction system can be single water
System is answered, water/organic solvent two-phase reaction system is also possible to.Wherein organic solvent can be tetrahydrofuran, 2- methyl tetrahydro
Furans, dimethyl carbonate, methylisobutylketone, n-butanol, sec-butyl alcohol, butanone etc..
Wherein, fructose dehydration prepares the reaction of 5 hydroxymethyl furfural in the present invention, and reaction temperature is 100-170 DEG C；Instead
It should be carried out in oil bath, microwave-assisted or micro passage reaction；Reaction time is 1-10min.
Wherein, 5 hydroxymethyl furfural water phase yield determination of the invention is by high performance liquid chromatography outer marking quantitative analysis side
Method；5 hydroxymethyl furfural organic phase yield determination is by gas-chromatography uantitative analytical method.
The present invention utilizes salt effect principle, in gluconic acid system, strengthens the electricity of gluconic acid by addition inorganic salts
From degree, enable the gluconic acid obtained by fructose syrup enzymatic oxidation with the fructose in fructose mixed solution in gluconic acid
Catalysis under high conversion, prepare HMF with high selectivity；Meanwhile and since gluconic acid is substituted as corrosivity such as inorganic acids
Stronger acid, it is possible to reduce the corrosion to reactor；Finally, HMF can be removed by organic extractant phase after dehydration,
The mixed liquor of gluconic acid and inorganic salts can be to recycle gluconic acid after simple separation.
The utility model has the advantages that
The present invention utilizes salt effect principle, and gluconic acid is expanded in fructose dehydration preparation HMF system, high fructose can be obtained
Conversion ratio, high HMF selectivity；Meanwhile being substituted by gluconic acid as the stronger acid of the corrosivity such as inorganic acid, it is possible to reduce to reaction
The corrosion of device；Finally, HMF can be removed by organic extractant phase after dehydration, gluconic acid and inorganic salts can be carried out
Recycling and reusing.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, content described in embodiment is merely to illustrate
The present invention, without the present invention described in detail in claims should will not be limited.
Influence of the different gluconic acid concentration of embodiment 1 to reaction result
Different amounts of gluconic acid is weighed respectively and 1g fructose is settled to 10mL volumetric flask respectively, obtains the grape of various concentration
The mixed solution of saccharic acid and 10% fructose.1mL is taken to have mixed solution of the different glucose acid for catalyst in four respectively
In the microwave tube of 10mL.150 DEG C on microwave reactor, reaction 10min.It is anti-by gas phase, liquid chromatogram difference quantitative analysis
Answer the various products in liquid.
Water phase detection method are as follows: Agilent high performance liquid chromatography (HPLC 1260) is equipped with Bio-Rad Aminex HPX-
87H chromatographic column and ultraviolet and show poor dual detector, mobile phase is the dilute sulfuric acid of 5mM, flow velocity 0.6mL/min, column temperature 35
DEG C, the temperature of Composition distribution is 35 DEG C, and sample volume is 10 μ L；Organic phase detection method are as follows: Shimadzu gas chromatograph (GC-
It 2010Plus) is equipped with Restek Rtx-VMS caplillary, using He as carrier gas, flow velocity is 0.43 mL/min, initial column
Temperature is 40 DEG C (stopping 5min), and heating rate is 7.5 DEG C/min, and terminating column temperature is 240 DEG C (stopping 15min), and sample volume is 1 μ
L.The standard curve for being all made of external standard method foundation calculates the amount of each product.Reaction result such as table 1；
Influence of the different gluconic acid concentration of table 1 to fructose dehydration
By data in table 1 it is found that the pH difference of the gluconic acid solution of various concentration and less (2.0 or so), but this is right
It is inadequate for fructose dehydration, therefore fructose converting rate is lower；But the selectivity for preparing HMF to fructose dehydration influences
It is unobvious.As gluconic acid concentration increases, pH is gradually decreased, and fructose dehydration conversion ratio is also gradually increased.Therefore, single from raising
The concentration of gluconic acid sets out to improve hydrogen ion degree of ionization and cannot achieve.
The influence that 2 salt effect of embodiment changes gluconic acid solution pH
10g fructose, 21.78g gluconic acid (gluconic acid solution of 50%wt) is claimed to be settled in the volumetric flask of 100mL with water
100mL obtains 10% fructose, the gluconic acid mixed liquor of 106g/L.Weigh respectively 1.000g NaCl, NaBr, KCl, LiCl,
CaCl2、ZnCl2Etc. different inorganic salts in 10mL volumetric flask mixed liquor dissolution, be settled to 10mL.Measure pH such as table 2:
Influence of the different inorganic salts of table 2 to gluconic acid degree of ionization
| Salt type | Nothing | NaCl | NaBr | KCl | LiCl | CaCl2 | ZnCl2 |
| pH | 2.03 | 1.53 | 1.67 | 1.86 | 1.46 | 1.07 | 1.21 |
By 2 data of table it is found that the degree of ionization of gluconic acid can be obviously increased after 10% inorganic salts are added, to make in system
Hydrogen ion concentration increases, pH value decline.It is added in the weak electrolyte solution as gluconic acid not identical as weak electrolyte
When strong electrolyte (the various inorganic salts) of ion, since effects of ion total concentration increases, the mutual restraining function enhancing of interionic,
So that the chance that the hydrogen ion of gluconic acid dissociation forms molecule in conjunction with gluconic acid radical ion reduces, to make gluconic acid
Molecular concentration reduces, and hydrogen ion concentration increases accordingly, and the pH value for showing as solution reduces.
Influence of the different salt ions of embodiment 3 to gluconic acid catalysis fructose dehydrating effect
10g fructose, 21.78g gluconic acid (gluconic acid solution of 50%wt) is claimed to be settled in the volumetric flask of 100mL with water
100mL obtains 10% fructose, the gluconic acid mixed liquor of 108.9g/l.Weigh 0.100g NaCl, NaBr, KCl, LiCl,
CaCl2、ZnCl2Respectively in the microwave tube of ten 10mL, it is separately added into 1mL mixed liquor；The 2- butanone for adding 4mL, in microwave
150 DEG C on reactor, react 10min.Obtain result such as chart 3:
Facilitation of the different inorganic salts of table 3 to gluconic acid catalysis fructose dehydration
As shown in Table 2, different inorganic salts influence gluconic acid hydrogen ion ionization effect different, and then show in table 3
For to catalysis fructose dehydration prepare HMF influence it is also not identical.Wherein calcium chloride has preferable effect, and fructose converting rate reaches
100%, HMF yield also reaches 89.78%.
Influence of the 4 various concentration calcium chloride of embodiment to gluconic acid catalysis fructose dehydration result
0.100g, 0.050 g, 0.010 g CaCl are weighed respectively2In the microwave tube of three 10mL, it is separately added into 1mL example
The organic acid configured in three-fructose mixed liquor；The methylisobutylketone of 4mL is added, 150 DEG C on microwave reactor, reaction
10min.Obtain result such as table 4:
Influence of the 4 various concentration calcium chloride of table to gluconic acid catalysis fructose dehydration result
As seen from the results in Table 4: the influence using various concentration calcium chloride to gluconic acid catalysis fructose dehydration is little,
To accomplish 90% or more conversion ratio, the selectivity of HMF is also 85% or so.
The reaction result of embodiment 5 different calcium chloride concentrations, differential responses time on micro passage reaction
Weigh the gluconic acid solution of calcium chloride 2g and 5g, fructose 10g, gluconic acid 21.78g(50%wt) in the capacity of 100mL
With water be settled to 100mL in bottle, obtain 10% fructose, the gluconic acid of 108.9g/l, 2% or 5% calcium chloride mixing
Liquid, organic phase are dimethyl carbonate, and two-phase charge ratio is 1:4, by charging rate adjusting reaction time, respectively 150 DEG C,
4min, 6min, 8min, reaction result such as chart 5 are reacted at 160 DEG C, 170 DEG C；
5 calcium chloride of table promotes reaction result of the gluconic acid catalysis fructose dehydration on micro passage reaction to ring
Compared with microwave reaction, microchannel plate should be easier to realize serialization, also do not need additional microwave device, be easier in work
Implement in industry.As shown in Table 5, compared with microwave reaction, the Efficient Conversion of fructose should be also may be implemented in microchannel plate, but needs
It is carried out at higher temperature.Such as: 2% calcium chloride can be converted completely with 170 DEG C of promotion gluconic acid catalysis fructose, the yield of HMF
Reach 96.83%.
The separation and recovery of gluconic acid in 6 gluconic acids of embodiment-calcium chloride solution
In example 5 2% calcium chloride is taken to promote gluconic acid in 170 DEG C of fructose converting reaction solution 100mL of catalysis, through two-phase laminated flow,
20mL aqueous phase solution is obtained, concentrated sulfuric acid 0.5mL is added, generates white calcium sulfate precipitation.Water phase is detected through liquid phase, and gluconic acid returns
Yield is 96%.
Claims (7)
1. a kind of method that Mineral salts-glucose acid system is catalyzed fructose converting 5 hydroxymethyl furfural, it is characterised in that: in grape
Inorganic salts are added in saccharic acid-fructose mixed solution system, gluconic acid hydrogen ion concentration are improved by salt effect, catalysis fructose is de-
Water Efficient Conversion 5 hydroxymethyl furfural.
2. the method that Mineral salts-glucose acid system according to claim 1 is catalyzed fructose converting 5 hydroxymethyl furfural,
Be characterized in that: used inorganic salts are sodium chloride, potassium chloride, sodium bromide, potassium bromide, lithium chloride, calcium chloride, magnesium chloride, chlorine
Change zinc, magnesium sulfate, lithium bromide, preferably salt is calcium chloride.
3. the method that Mineral salts-glucose acid system according to claim 1 is catalyzed fructose converting 5 hydroxymethyl furfural,
Be characterized in that: the additional amount of the inorganic salts is 1-30wt%.
4. the method that Mineral salts-glucose acid system according to claim 1 is catalyzed fructose converting 5 hydroxymethyl furfural,
Be characterized in that: the gluconic acid concentration is 5-200g/L.
5. the method that Mineral salts-glucose acid system according to claim 1 is catalyzed fructose converting 5 hydroxymethyl furfural,
Be characterized in that: the reaction system can be single water reaction system, be also possible to water/organic solvent two-phase reaction system.
6. the method that Mineral salts-glucose acid system according to claim 1 is catalyzed fructose converting 5 hydroxymethyl furfural,
Be characterized in that: the fructose dehydration prepares the reaction of 5 hydroxymethyl furfural, and reaction temperature is 100-170 DEG C；Reaction oil bath,
It is carried out in microwave-assisted or micro passage reaction；Reaction time is 1-10min.
7. the method that Mineral salts-glucose acid system according to claim 5 is catalyzed fructose converting 5 hydroxymethyl furfural,
Be characterized in that: organic solvent include but is not limited to tetrahydrofuran, 2- methyltetrahydrofuran, dimethyl carbonate, methyl iso-butyl ketone (MIBK),
N-butanol, sec-butyl alcohol, butanone.
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