CN108997275A - A method of primary product distribution in control fructose-ethanol synthesis system - Google Patents
A method of primary product distribution in control fructose-ethanol synthesis system Download PDFInfo
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- CN108997275A CN108997275A CN201810636281.8A CN201810636281A CN108997275A CN 108997275 A CN108997275 A CN 108997275A CN 201810636281 A CN201810636281 A CN 201810636281A CN 108997275 A CN108997275 A CN 108997275A
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 112
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 78
- 239000000047 product Substances 0.000 claims abstract description 67
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 63
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000005715 Fructose Substances 0.000 claims abstract description 52
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract description 52
- 229930091371 Fructose Natural products 0.000 claims abstract description 52
- CCDRPZFMDMKZSZ-UHFFFAOYSA-N 5-(ethoxymethyl)furan-2-carbaldehyde Chemical compound CCOCC1=CC=C(C=O)O1 CCDRPZFMDMKZSZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000006184 cosolvent Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 40
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 239000003456 ion exchange resin Substances 0.000 claims description 24
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 18
- 229910001423 beryllium ion Inorganic materials 0.000 claims description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 2
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 abstract description 55
- 239000006227 byproduct Substances 0.000 abstract description 22
- 238000007086 side reaction Methods 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 description 42
- 239000007788 liquid Substances 0.000 description 32
- 229910001220 stainless steel Inorganic materials 0.000 description 30
- 239000010935 stainless steel Substances 0.000 description 30
- 150000001299 aldehydes Chemical class 0.000 description 17
- 239000005457 ice water Substances 0.000 description 15
- ROAYSRAUMPWBQX-UHFFFAOYSA-N ethanol;sulfuric acid Chemical compound CCO.OS(O)(=O)=O ROAYSRAUMPWBQX-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 235000013399 edible fruits Nutrition 0.000 description 5
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000002816 fuel additive Substances 0.000 description 2
- 239000003864 humus Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- AEMOLEFTQBMNLQ-UHFFFAOYSA-N 3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound OC1OC(C(O)=O)C(O)C(O)C1O AEMOLEFTQBMNLQ-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
- 241000208838 Asteraceae Species 0.000 description 1
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 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 1
- -1 Methyl furfural Chemical compound 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
Abstract
The present invention relates to a kind of methods of primary product distribution in control fructose-ethanol synthesis system, belong to biomass high level conversion technical field.Catalyst and fructose is added in the present invention in alcohol solvent, is added or is not added cosolvent and be uniformly mixed and obtains reaction system, temperature is 140 ~ 180 DEG C, 4 ~ 12h of reaction obtains reaction product under stirring condition；Effectively to control the distribution of 5 hydroxymethyl furfural in reaction product, 5- ethoxymethyl furfural and ethyl levulinate by adjusting the addition type and dosage, reaction temperature and reaction time of cosolvent, reduce side reaction, it avoids generating complicated by-product, realizes the enrichment of simple target product, that is, 5 hydroxymethyl furfural, 5- ethoxymethyl furfural or ethyl levulinate.
Description
Technical field
The present invention relates to a kind of methods of primary product distribution in control fructose-ethanol synthesis system, belong to biomass height
It is worth transformation technology field.
Background technique
5 hydroxymethyl furfural (5-hydroxymethylfurfural, CAS No:67-47-0), referred to as: HMF；It is a kind of
Important chemical intermediate and Novel platform compound, and find after study, application is relatively broad, and it is poly- to can be used for synthesizing function
The fine chemicals such as ester, photoelectric material, medicine.
5- ethoxymethyl furfural (5-Ethoxymethylfurfural, CAS No:1917-65-3), referred to as: EMF；In room
Under the conditions of temperature, exist in the form of oily liquids, there is good oxidation stability and higher 16 octane number, these characteristics to determine
Having determined it can be used as excellent potential alternative fuel or fuel additive.The energy density of EMF is 8.7 kW h/L, close to mark
The energy density (8.8 kW h/L) of quasi- gasoline, much higher than the energy density (6.1 kW h/L) of ethyl alcohol.Meanwhile as
It possesses high oxidation stability and can reduce the discharge of flue dust, oxysulfide and nitrogen oxides fuel, so as to reduce pair
The pollution of environment, therefore be considered as a kind of very potential renewable green New-type fuel.In addition, EMF also has well
Chemical reactivity, can be used as reaction substrate for synthesizing other chemicals for having industrial significance, such as cyclopentenone.
Ethyl levulinate (Ethyl levulinate, CAS No:539-88-8), referred to as: EL；It is not only applicable to molten
The industries such as agent, oil dope, fragrance and plasticizer, also as important medicine and industrial chemicals.In addition, it or one kind are new
The liquid fuel additive of type is widely used in substitute energy source for petroleum field.In short, ethyl levulinate is a kind of potential height
The green bio matter based platform compound of value.
Fructose is a kind of most commonly seen ketohexose, is widely present in honey, in fruit, and almost always same with glucose
When be present in plant, be with compositae plant especially it is more, it is from a wealth of sources, rich reserves, cheap, prepared using fructose as raw material high
The compound of added value is the approach of most research significance and development prospect.And in fructose ethanol synthesis system, it is related to a variety of
Complicated organic reaction relates generally to following reaction: (1) fructose dehydration generates 5 hydroxymethyl furfural；(2) 5 hydroxymethyl furfural and second
Etherified generation 5- ethoxymethyl furfural；(3) 5 hydroxymethyl furfural and the direct open loop of 5- ethoxymethyl furfural generate levulic acid
Ethyl ester；(4) a variety of organic compound polymerizations such as 5 hydroxymethyl furfural generate solvable and insoluble polymer (humus).
Currently, numerous researchers in single fructose ethanol system, utilize acid catalyst to prepare 5- ethoxymethyl chaff
Aldehyde or ethyl levulinate do not provide a kind of reliable control method, although yield is pretty good to promote reaction system
In, the enrichment of simple target product reduces a variety of side reactions and the generation of humus.
Summary of the invention
For the above-mentioned problems of the prior art and deficiency, the present invention provides a kind of control fructose-ethanol synthesis system
The method of middle primary product distribution has by adjusting the addition type and dosage of cosolvent, reaction temperature and reaction time
The distribution of 5 hydroxymethyl furfural, 5- ethoxymethyl furfural and ethyl levulinate, reduces side reaction, keeps away in effect control reaction product
Exempt to generate complicated by-product, realizes simple target product, that is, 5 hydroxymethyl furfural, 5- ethoxymethyl furfural or levulic acid second
The enrichment of ester.
A method of primary product distribution in control fructose-ethanol synthesis system, the specific steps are as follows:
Catalyst and fructose are added in alcohol solvent, is added or is not added cosolvent and be uniformly mixed and obtain reaction system, in temperature
Degree is 140 ~ 180 DEG C, 4 ~ 12h of reaction obtains reaction product under stirring condition；Wherein catalyst be ion exchange resin or sulfuric acid,
Cosolvent is dimethyl sulfoxide or N,N-dimethylformamide；
It is 30 ~ 50%, when reaction temperature is 140 ~ 160 DEG C, the reaction time is 4 ~ 6h when cosolvent accounts for the volume fraction of total solvent,
With molar concentration meter, 5 hydroxymethyl furfural accounts for the 75 ~ 85% of reaction product；
When cosolvent be dimethyl sulfoxide and cosolvent to account for the volume fraction of total solvent be 20 ~ 40%, reaction temperature is 140 ~ 180 DEG C,
When reaction time is 8 ~ 12h, with molar concentration meter, 5- ethoxymethyl furfural accounts for the 65 ~ 80% of reaction product；
When cosolvent is not added, when reaction temperature is 160 ~ 180 DEG C, the reaction time is 6 ~ 10h, with molar concentration meter, levulic acid
Ethyl ester accounts for the 80 ~ 90% of reaction product；
The concentration of fructose is 0.1 ~ 0.5mol/L in step (1) reaction system；
Step (1) ion exchange resin be ion exchange resin Amberlyst-15, reaction system ion exchange resin it is dense
Degree is 5 ~ 20g/L；
The concentration of sulfuric acid is 0.005 ~ 0.02mol/L in step (1) reaction system.
The beneficial effects of the present invention are:
(1) the method for the present invention effectively controls by adjusting the addition type and dosage, reaction temperature and reaction time of cosolvent
The distribution of 5 hydroxymethyl furfural, 5- ethoxymethyl furfural and ethyl levulinate in reaction product reduces side reaction, avoids generating
Complicated by-product realizes the richness of simple target product, that is, 5 hydroxymethyl furfural, 5- ethoxymethyl furfural or ethyl levulinate
Collection；
(2) the method for the present invention can be effectively controlled primary product i.e. 5 hydroxymethyl furfural in reaction product, 5- ethoxymethyl furfural or
The distribution of ethyl levulinate realizes that biomass fructose high level conversion utilizes；
(3) with molar concentration meter, can control by the method for the invention single product 5 hydroxymethyl furfural account for reaction product 75 ~
85%, single product 5- ethoxymethyl furfural account for the 65 ~ 80% of reaction product and single product ethyllevulinate account for reaction product
80 ~ 90%, realize simple target product enrichment.
Specific embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1: a method of primary product (5 hydroxymethyl furfural) distribution, tool in control fructose ethanol synthesis system
Steps are as follows for body:
(1) molar concentration is prepared by solvent of ethyl alcohol as sulfuric acid-ethanol solution of 0.1mol/L, sulfuric acid-ethanol solution is added
Into stainless steel autoclave, sequentially add ethyl alcohol, dimethyl sulfoxide, fructose and be uniformly mixed obtain reaction system；Wherein
It is 40 % that cosolvent dimethyl sulfoxide, which accounts for the volume fraction of total solvent, in reaction system, and the concentration of fructose is 0.2 mol/L, sulfuric acid
Concentration be 0.01mol/L；
(2) under the conditions of temperature is 150 DEG C, stirring rate is 400 r/min, the reaction system of step (1) carries out isothermal reaction
5h obtains reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part liquid
Body calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
The 84.74% of product, 5- ethoxymethyl furfural is answered to account for the 7.24% of reaction product, ethyl levulinate and account for the 0.38% of reaction product,
By-product only accounts for the 7.64% of reaction product.
Embodiment 2: a method of primary product (5 hydroxymethyl furfural) distribution, tool in control fructose ethanol synthesis system
Steps are as follows for body:
(1) ethyl alcohol, N,N-dimethylformamide, fructose and ion exchange resin (Amberlyst-15) are added to stainless steel height
It is uniformly mixed in pressure reaction kettle and obtains reaction system；Wherein cosolvent N,N-dimethylformamide accounts for total solvent in reaction system
Volume fraction is 30%, and the concentration of fructose is 0.2mol/L, and the concentration of ion exchange resin (Amberlyst-15) is 10 g/L；
(2) under the conditions of temperature is 140 DEG C, stirring rate is 600 r/min, the reaction system of step (1) carries out isothermal reaction
6h obtains reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part liquid
Body calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
The 75.67% of product, 5- ethoxymethyl furfural is answered to account for the 13.55% of reaction product, ethyl levulinate and account for reaction product
1.26%, by-product only accounts for the 9.52% of reaction product.
Embodiment 3: a method of primary product (5 hydroxymethyl furfural) distribution, tool in control fructose ethanol synthesis system
Steps are as follows for body:
(1) ethyl alcohol, dimethyl sulfoxide, fructose and ion exchange resin (Amberlyst-15) are added to stainless steel autoclave
In be uniformly mixed obtain reaction system；The volume fraction that wherein cosolvent dimethyl sulfoxide accounts for total solvent in reaction system is 50%, fruit
The concentration of sugar is 0.3mol/L, and the concentration of ion exchange resin (Amberlyst-15) is 15g/L；
(2) under the conditions of temperature is 160 DEG C, stirring rate is 600 r/min, the reaction system of step (1) carries out isothermal reaction
4h obtains reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part liquid
Body calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
The 83.93% of product, 5- ethoxymethyl furfural is answered to account for the 12.69% of reaction product, ethyl levulinate and account for reaction product
0.57%, by-product only accounts for the 2.81% of reaction product.
Comparative example 1:
(1) molar concentration is prepared by solvent of ethyl alcohol as sulfuric acid-ethanol solution of 0.1mol/L, sulfuric acid-ethanol solution is added
Into stainless steel autoclave, sequentially add ethyl alcohol, n,N-Dimethylformamide, fructose and be uniformly mixed obtain reactant
System；The volume fraction that wherein cosolvent n,N-Dimethylformamide accounts for total solvent in reaction system is 10%, and the concentration of fructose is
0.5mol/L, the concentration of sulfuric acid are 0.005mol/L；
(2) under the conditions of temperature is 120 DEG C, stirring rate is 400 r/min, the reaction system of step (1) carries out isothermal reaction
3h obtains reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part liquid
Body calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
5.37 %, the ethyl levulinate for answering the 61.28% of product, 5- ethoxymethyl furfural to account for reaction product account for reaction product
1.18%, by-product only accounts for the 32.17% of reaction product.
Comparative example 2:
(1) ethyl alcohol, N,N-dimethylformamide, fructose and ion exchange resin (Amberlyst-15) are added to stainless steel height
It is uniformly mixed in pressure reaction kettle and obtains reaction system；Wherein cosolvent N,N-dimethylformamide accounts for total solvent in reaction system
Volume fraction is 60%, and the concentration of fructose is 0.5mol/L, and the concentration of ion exchange resin (Amberlyst-15) is 20g/L；
(2) under the conditions of temperature is 170 DEG C, stirring rate is 600 r/min, the reaction system of step (1) carries out isothermal reaction
6h obtains reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part liquid
Body calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
1.17 %, the ethyl levulinate for answering the 69.53% of product, 5- ethoxymethyl furfural to account for reaction product account for reaction product
0.23%, by-product only accounts for 29.07 % of reaction product.
Embodiment 4: a method of primary product (5- ethoxymethyl furfural) distribution in control fructose ethanol synthesis system,
Specific step is as follows:
(1) ethyl alcohol, dimethyl sulfoxide, fructose and ion exchange resin (Amberlyst-15) are added to stainless steel autoclave
In be uniformly mixed obtain reaction system；The volume fraction that wherein cosolvent dimethyl sulfoxide accounts for total solvent in reaction system is 20%, fruit
The concentration of sugar is 0.2mol/L, and the concentration of ion exchange resin (Amberlyst-15) is 10 g/L；
(2) under the conditions of temperature is 140 DEG C, stirring rate is 600 r/min, the reaction system of step (1) carries out isothermal reaction
8h obtains reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part liquid
Body calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
The 8.76% of product, 5- ethoxymethyl furfural is answered to account for the 68.57% of reaction product, ethyl levulinate and account for the 8.17% of reaction product,
By-product only accounts for the 14.50% of reaction product.
Embodiment 5: a method of primary product (5- ethoxymethyl furfural) distribution in control fructose ethanol synthesis system,
Specific step is as follows:
(1) ethyl alcohol, dimethyl sulfoxide, fructose and ion exchange resin (Amberlyst-15) are added to stainless steel autoclave
In be uniformly mixed obtain reaction system；The volume fraction that wherein cosolvent dimethyl sulfoxide accounts for total solvent in reaction system is 30%, fruit
The concentration of sugar is 0.2mol/L, and the concentration of ion exchange resin (Amberlyst-15) is 10g/L；
(2) under the conditions of temperature is 160 DEG C, stirring rate is 600 r/min, the reaction system of step (1) carries out isothermal reaction
12h obtains reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part
Liquid calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
The 4.79% of product, 5- ethoxymethyl furfural is answered to account for the 74.58% of reaction product, ethyl levulinate and account for reaction product
10.26%, by-product only accounts for the 10.37% of reaction product.
Embodiment 6: a method of primary product (5- ethoxymethyl furfural) distribution in control fructose ethanol synthesis system,
Specific step is as follows:
(1) molar concentration is prepared by solvent of ethyl alcohol as sulfuric acid-ethanol solution of 0.1mol/L, sulfuric acid-ethanol solution is added
Into stainless steel autoclave, sequentially add ethyl alcohol, dimethyl sulfoxide, fructose and be uniformly mixed obtain reaction system；Wherein
It is 40% that cosolvent dimethyl sulfoxide, which accounts for the volume fraction of total solvent, in reaction system, and the concentration of fructose is 0.2 mol/L, sulfuric acid
Concentration is 0.01 mol/L；
(2) under the conditions of temperature is 180 DEG C, stirring rate is 400r/min, the reaction system of step (1) carries out isothermal reaction
10h obtains reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part
Liquid calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
The 2.55% of product, 5- ethoxymethyl furfural is answered to account for the 79.61% of reaction product, ethyl levulinate and account for reaction product
13.26%, by-product only accounts for the 4.58% of reaction product.
Comparative example 3:
(1) molar concentration is prepared by solvent of ethyl alcohol as sulfuric acid-ethanol solution of 0.1mol/L, sulfuric acid-ethanol solution is added
Into stainless steel autoclave, sequentially add ethyl alcohol, dimethyl sulfoxide, fructose and be uniformly mixed obtain reaction system；Wherein
It is 15% that cosolvent dimethyl sulfoxide, which accounts for the volume fraction of total solvent, in reaction system, and the concentration of fructose is 0.5mol/L, sulfuric acid it is dense
Degree is 0.05mol/L；
(2) under the conditions of temperature is 200 DEG C, stirring rate is 400r/min, the reaction system of step (1) carries out isothermal reaction 3h
Obtain reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part liquid
Body calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
38.26 %, the ethyl levulinate for answering the 10.28% of product, 5- ethoxymethyl furfural to account for reaction product account for reaction product
35.75%, by-product only accounts for the 15.71% of reaction product.
Comparative example 4:
(1) ethyl alcohol, dimethyl sulfoxide, fructose and ion exchange resin (Amberlyst-15) are added to stainless steel autoclave
In be uniformly mixed obtain reaction system；The volume fraction that wherein cosolvent dimethyl sulfoxide accounts for total solvent in reaction system is 55%, fruit
The concentration of sugar is 0.5mol/L, and the concentration of ion exchange resin (Amberlyst-15) is 15 g/L；
(2) under the conditions of temperature is 120 DEG C, stirring rate is 600 r/min, the reaction system of step (1) carries out isothermal reaction
6h obtains reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part liquid
Body calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
7.86 %, the ethyl levulinate for answering the 65.36% of product, 5- ethoxymethyl furfural to account for reaction product account for reaction product
2.31%, by-product only accounts for the 24.47% of reaction product.
Embodiment 7: a method of primary product (ethyl levulinate) distribution, tool in control fructose ethanol synthesis system
Steps are as follows for body:
(1) molar concentration is prepared by solvent of ethyl alcohol as sulfuric acid-ethanol solution of 0.1mol/L, sulfuric acid-ethanol solution is added
Into stainless steel autoclave, sequentially add ethyl alcohol, fructose and be uniformly mixed obtain reaction system；Wherein in reaction system
The concentration of fructose is 0.2mol/L, and the concentration of sulfuric acid is 0.1mol/L；
(2) under the conditions of temperature is 160 DEG C, stirring rate is 500 r/min, the reaction system of step (1) carries out isothermal reaction
10h obtains reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part
Liquid calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
The 0.15% of product, 5- ethoxymethyl furfural is answered to account for the 1.34% of reaction product, ethyl levulinate and account for the 85.84% of reaction product,
By-product only accounts for the 13.86% of reaction product.
Embodiment 8: a method of primary product (ethyl levulinate) distribution, tool in control fructose ethanol synthesis system
Steps are as follows for body:
(1) ethyl alcohol, fructose and ion exchange resin (Amberlyst-15) are added in stainless steel autoclave and are mixed
It is even to obtain reaction system；Wherein the concentration of fructose is 0.2mol/L, ion exchange resin (Amberlyst-15) in reaction system
Concentration be 10 g/L；
(2) under the conditions of temperature is 180 DEG C, stirring rate is 400 r/min, the reaction system of step (1) carries out isothermal reaction
6h obtains reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part liquid
Body calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
The 0.03% of product, 5- ethoxymethyl furfural is answered to account for the 0.56% of reaction product, ethyl levulinate and account for the 87.95% of reaction product,
By-product only accounts for the 11.46% of reaction product.
Embodiment 9: a method of primary product (ethyl levulinate) distribution, tool in control fructose ethanol synthesis system
Steps are as follows for body:
(1) molar concentration is prepared by solvent of ethyl alcohol as sulfuric acid-ethanol solution of 0.1mol/L, sulfuric acid-ethanol solution is added
Into stainless steel autoclave, sequentially add ethyl alcohol, fructose and be uniformly mixed obtain reaction system；Wherein in reaction system
The concentration of fructose is 0.2 mol/L, and the concentration of sulfuric acid is 0.01 mol/L；
(2) under the conditions of temperature is 170 DEG C, stirring rate is 400r/min, the reaction system of step (1) carries out isothermal reaction 8h
Obtain reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part liquid
Body calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
The 0.01% of product, 5- ethoxymethyl furfural is answered to account for the 2.16% of reaction product, ethyl levulinate and account for the 84.58% of reaction product,
By-product only accounts for the 13.25% of reaction product.
Comparative example 5:
(1) molar concentration is prepared by solvent of ethyl alcohol as sulfuric acid-ethanol solution of 0.1mol/L, sulfuric acid-ethanol solution is added
Into stainless steel autoclave, sequentially add ethyl alcohol, fructose and be uniformly mixed obtain reaction system；Wherein in reaction system
The concentration of fructose is 0.5mol/L, and the concentration of sulfuric acid is 0.05mol/L；
(2) under the conditions of temperature is 150 DEG C, stirring rate is 400r/min, the reaction system of step (1) carries out isothermal reaction 4h
Obtain reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part liquid
Body calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
35.73 %, the ethyl levulinate for answering the 13.26% of product, 5- ethoxymethyl furfural to account for reaction product account for reaction product
45.81%, by-product only accounts for the 5.20% of reaction product.
Comparative example 6:
(1) ethyl alcohol, fructose and ion exchange resin (Amberlyst-15) are added in stainless steel autoclave and are mixed
It is even to obtain reaction system；Wherein the concentration of fructose is 0.5mol/L, ion exchange resin (Amberlyst-15) in reaction system
Concentration be 5g/L；
(2) under the conditions of temperature is 200 DEG C, stirring rate is 600r/min, the reaction system of step (1) carries out isothermal reaction
12h obtains reaction product；After reaction, stainless steel autoclave is placed in ice water and is quickly cooled to room temperature, take part
Liquid calculates target product (5 hydroxymethyl furfural, 5- ethoxymethyl chaff using high performance liquid chromatograph and chromatographic
Aldehyde, ethyl levulinate) yield, specific yield is shown in Table 1；As known from Table 1, with molar concentration meter, 5 hydroxymethyl furfural is accounted for instead
4.36 %, the ethyl levulinate for answering the 2.75% of product, 5- ethoxymethyl furfural to account for reaction product account for the 70.28 of reaction product
%, by-product only account for the 22.61% of reaction product；
1 reaction product yield of table
It is can be seen that from the data of embodiment 1 ~ 3 from 1 reaction product yield data of table as can be seen that fructose ethanol synthesis body
The yield of primary product (5 hydroxymethyl furfural) is 75% ~ 85% in system, and other two primary products (5- ethoxymethyl furfurals
With ethyl levulinate) yield under reduced levels, by-product yield is relatively low, realizes single product 5- methylol
The enrichment of furfural in the reaction system under relatively mild reaction conditions, is conducive to by rationally controlling reaction condition parameter
The generation of 5 hydroxymethyl furfural, and cosolvent is rationally added in system, it accumulates 5 hydroxymethyl furfural in system, weakens
Further with ethyl alcohol reacts, and realizes the enrichment of 5 hydroxymethyl furfural；Comparative example 1 ~ 2 can be seen that the receipts of 5 hydroxymethyl furfural
Rate does not reach higher level, and possible cause is taken more time or is more catalyzed under the concentration of higher fructose
Agent carries out correlated response, it was confirmed that the type and its volume fraction of response parameter and cosolvent are rationally controlled, it could preferably
Controlling 5 hydroxymethyl furfural yield is 75% ~ 85%；
From in the data of embodiment 4 ~ 6 as can be seen that primary product (5- ethoxymethyl furfural) in fructose ethanol synthesis system
Yield is 65% ~ 80%, and the yield of other two primary products (5 hydroxymethyl furfural and ethyl levulinate) is lower
The lower by-product yield of level is relatively low, realizes the enrichment of single product 5- ethoxymethyl furfural in the reaction system, passes through
Rationally control response parameter makes forerunner's product 5 hydroxymethyl furfural further generate 5- ethoxymethyl chaff with ethyl alcohol etherification reaction
Aldehyde, addition cosolvent dimethyl sulfoxide inhibit the further reaction of 5- ethoxymethyl furfural, keep ethyl levulinate yield lower,
And then realize the enrichment of 5- ethoxymethyl furfural；Comparative example 3 ~ 4 is as can be seen that the reaction carried out at 200 DEG C of high temperature, fructose second
In alcohol system, even if being added to a small amount of dimethyl sulfoxide, 35.75% ethyl levulinate is also created, just makes 5- ethoxy in this way
Methyl furfural yield drops to 38.26%；And in system excessive addition dimethyl sulfoxide, the system score of being allowed to reaches 55%, can
To find out that the yield of 5 hydroxymethyl furfural reaches 65.36%, illustrates not convert further to 5- ethoxymethyl furfural, similarly demonstrate,prove
It is real can only more effectively to control the enrichment of 5- ethoxymethyl furfural in rationally control reaction condition；
From the receipts that can be seen that primary product (ethyl levulinate) in fructose ethanol synthesis system in the data of embodiment 7 ~ 9
Rate is 80% ~ 90%, and the yield of other two primary products (5 hydroxymethyl furfural and 5- ethoxymethyl furfural) is lower
Under level, by-product yield is relatively low, realizes the enrichment of single product ethyllevulinate in the reaction system, and fructose exists
It is reacted in straight alcohol system, rationally controls reaction temperature and time, the 5 hydroxymethyl furfural generated and 5- ethoxymethyl can be made
The further Synthesis of furfural is to ethyl levulinate, and high temperature is conducive to the generation of ethyl levulinate, in certain time
Maximized Synthesis inside can be realized, ethyl levulinate can be made preferably to be enriched in the reaction system；Comparative example 5 ~ 6
As can be seen that react 4h at 150 DEG C, there are also part 5 hydroxymethyl furfural and 5- ethoxymethyl furfural do not convert further to
Ethyl levulinate；12h is reacted at 200 DEG C, more by-products will be generated.
Above the embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment party
Formula can also be made without departing from the purpose of the present invention within the knowledge of a person skilled in the art
Various change out.
Claims (4)
1. a kind of method of primary product distribution in control fructose-ethanol synthesis system, which is characterized in that specific step is as follows:
Catalyst and fructose are added in alcohol solvent, is added or is not added cosolvent and be uniformly mixed and obtain reaction system, in temperature
Degree is 140 ~ 180 DEG C, 4 ~ 12h of reaction obtains reaction product under stirring condition；Wherein catalyst be ion exchange resin or sulfuric acid,
Cosolvent is dimethyl sulfoxide or N,N-dimethylformamide；
It is 30 ~ 50%, when reaction temperature is 140 ~ 160 DEG C, the reaction time is 4 ~ 6h when cosolvent accounts for the volume fraction of total solvent,
With molar concentration meter, 5 hydroxymethyl furfural accounts for the 75 ~ 85% of reaction product；
When cosolvent be dimethyl sulfoxide and cosolvent to account for the volume fraction of total solvent be 20 ~ 40%, reaction temperature is 140 ~ 180 DEG C,
When reaction time is 8 ~ 12h, with molar concentration meter, 5- ethoxymethyl furfural accounts for the 65 ~ 80% of reaction product；
When cosolvent is not added, when reaction temperature is 160 ~ 180 DEG C, the reaction time is 6 ~ 10h, with molar concentration meter, levulic acid
Ethyl ester accounts for the 80 ~ 90% of reaction product.
2. controlling the method for primary product distribution in fructose-ethanol synthesis system according to claim 1, it is characterised in that:
The concentration of fructose is 0.1 ~ 0.5mol/L in step (1) reaction system.
3. controlling the method for primary product distribution in fructose-ethanol synthesis system according to claim 1, it is characterised in that:
Step (1) ion exchange resin is ion exchange resin Amberlyst-15, and the concentration of reaction system ion exchange resin is 5
~20g/L。
4. controlling the method for primary product distribution in fructose-ethanol synthesis system according to claim 1, it is characterised in that:
The concentration of sulfuric acid is 0.005 ~ 0.02mol/L in step (1) reaction system.
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