CN103073526B - Preparation method of 2, 5-disubstituted tetrahydrofuran mixture - Google Patents
Preparation method of 2, 5-disubstituted tetrahydrofuran mixture Download PDFInfo
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Abstract
The invention discloses a preparation method of a 2, 5-disubstituted tetrahydrofuran mixture. The preparation method comprises the following steps: under the condition of existence of a multi-phase etherification catalyst, a multi-phase hydrogenation catalyst and hydrogen, 5-hydroxymethylfurfural or 5-hydroxymethylfurfural water solution and alcohol are mixed to achieve etherification reduction reaction to obtain a liquid intermediate product; and then the liquid intermediate product is subject to hydrogenation reaction under the action of a second catalyst so as to obtain the 2, 5-disubstituted tetrahydrofuran mixture. The preparation method achieves transformation from 5-hydroxymethylfurfural to the target product through the two-step process to obtain the 2, 5-disubstituted tetrahydrofuran mixture which can serve as a potential fuel or a fuel additive.
Description
Technical field
The invention belongs to preparation of fuel field, be specifically related to the preparation method of the dibasic tetrahydrofuran derivatives mixture of a kind of 2,5-.
Background technology
For a long time, the mankind mainly rely on fossil energy as coal, oil, Sweet natural gas acquisition fuel and fuel dope.But, along with the minimizing day by day of world's fossil energy reserve, substitute traditional fossil energy in the urgent need to finding a kind of new substitute energy.In the renewable energy source of developing, biomass energy is all closely similar with fossil energy in chemical molecular formation, energy utilization form, is the most promising petrochemical industry substitute energy.Biomass resource can be prepared numerous platform chemicals as ethanol, 1,3-PD, furfural, 5 hydroxymethyl furfural, levulinic acid etc. by physics, chemistry or biochemical method.Wherein 5 hydroxymethyl furfural (5-HM) is considered to a kind of very important hardware and software platform compound, can production furans taking it as raw material, alkanes and levulinate class I liquid I fuel.
Hydroxymethylfurfuraethers ethers is a kind of important furfuran compound, owing to having high energy density, water insoluble, nonhygroscopic in air, and not oxidizable and hydrolysis, can improve the advantages such as octane value, makes it to be suitable for as fuel or fuel dope.Patent CN 102161918A discloses the purposes of 5-alkoxymethylfurfuralethers ethers as fuel or fuel dope.Patent CN 101809010A provides a kind of method of preparing 5 hydroxymethyl furfural ether mixture, the method by making the raw material or the HMF that contain hexose react with alcohol mixture under the existence of an acidic catalyst, patent CN 101827833A provides the method for the mixture of preparing furfural and 5-(alkoxy methyl) furfural derivatives, and the method is by making containing C
5and C
6the raw material of sugar reacts under the existence of an acidic catalyst with alcohol, then by the furfural of generation and the mixture hydrogenation of 5-(alkoxy methyl) furfural and/or etherificate so that the aldehyde functional group of furfural and 5-(alkoxy methyl) furfural is all converted into alkoxy methyl functional group or methyl functional group.Patent CN101821248 provides the method for 2-(alkoxy methyl) furans (or mixture of this class furans) of preparation 5-replacement, and method is that the starting material of the furfural by comprising at least one 5-replacement react under alcohol and catalyst system existence with hydrogen.
In hydroxymethylfurfuraethers ethers, contain a furan nucleus, if the furan nucleus hydrogenation in hydroxymethylfurfuraethers ethers is generated to the tetrahydrofuran derivatives material replacing, can greatly increase its energy density, can make it more appropriate to as fuel or fuel dope, but because furan nucleus is stable aromatic nucleus, the difficulty being reduced is far longer than carbonyl, and the transformation efficiency of reduction reaction is generally lower.Can be used as potential fuel or fuel dope 2, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-yet there are no patent report.
Summary of the invention
The preparation method who the invention provides the dibasic tetrahydrofuran derivatives mixture of a kind of 2,5-, this preparation method can be reduced into tetrahydrofuran (THF) ring structure by the furan ring structure in 5 hydroxymethyl furfural with higher transformation efficiency, the product that forming energy density is higher.
The preparation method of the dibasic tetrahydrofuran derivatives mixture of a kind of 2,5-, comprising:
(1) under the condition of the first catalyzer and hydrogen existence, the aqueous solution of 5 hydroxymethyl furfural or 5 hydroxymethyl furfural is mixed with alcohol etherificate reduction reaction occurs, after reacting completely, obtain liquid intermediate product;
(2) under the condition of the second catalyzer and hydrogen existence, the liquid intermediate product generation hydrogenation reaction that step (1) is obtained, after reacting completely, 2 described in aftertreatment obtains, the dibasic tetrahydrofuran derivatives mixture of 5-;
The first described catalyzer is made up of heterogeneous catalyst for etherification and heterogeneous hydrogenation catalyst;
Described heterogeneous hydrogenation catalyst is the metal catalyst of energy catalytic hydrogenolysis alkoxy-functional;
Described heterogeneous catalyst for etherification is an acidic catalyst that energy catalytic alcohol is dehydrated into ether;
The second described catalyzer is the metal catalyst of energy catalysis furan nucleus generation hydrogenation.
In the present invention, under the condition of the co-catalysis of described heterogeneous catalyst for etherification and heterogeneous hydrogenation catalyst, there is respectively etherificate and acetalation in the hydroxyl on 5 hydroxymethyl furfural and aldehyde radical and raw alcohol, some alkoxy-functional hydrogenolysis, obtains liquid intermediate product subsequently; Then under the catalysis of the second catalyzer, furan nucleus in the further liquid towards intermediate product of hydrogen carries out hydrogenating reduction, make furan nucleus change into tetrahydrofuran (THF) ring, obtained 2 high conversion, the dibasic tetrahydrofuran derivatives mixture of 5-, such mixture can be used as potential fuel or fuel dope.
In step (1), described heterogeneous hydrogenation catalyst be can catalytic hydrogenolysis the catalyzer of some alkoxy-functional, as preferably, this heterogeneous hydrogenation catalyst is Al
2o
3the metal catalyst of load, the active ingredient of this metal catalyst is at least one in Pd, Pt, Ir, Rh, Fe, Cu and Co, and wherein, the charge capacity of this metal catalyst is 0.01%～10%, these catalyst activity are higher, and can buy from the market easily.
In step (1), there is dehydration formation ether in act as the catalysis aldehyde or alcohol and alcohol of described heterogeneous catalyst for etherification.Can improve the energy density of product by etherification reaction, to meet as the requirement of fuel or fuel dope, described heterogeneous catalyst for etherification is preferably at least one in ion exchange resin, solid super-strong acid and molecular sieve, the heterogeneous catalyst for etherification low price of these several classes, easily obtain, and there is higher catalytic activity.
In step (2), the second described catalyzer is the catalyzer that furan ring structure can be converted into tetrahydrofuran (THF) ring structure, and as preferably, the second described catalyzer is gac or Al
2o
3the metal catalyst of load; The active ingredient of this metal catalyst is at least one in Ni, Pd, Ir, Rh and Os, and the charge capacity of this metal catalyst is 0.01%～10%, and within the scope of this charge capacity, the second described catalyzer can keep higher catalytic activity.
In the second described catalyzer, active ingredient can be uniformly distributed or non-uniform Distribution on carrier, is preferably eggshell type and distributes, while adopting this kind of distribution, the catalytic activity when catalytic activity of unit load amount catalyzer distributes than even type is high, thereby can reduce the use cost of catalyzer.
Commercially available 5 hydroxymethyl furfural can be directly used in invention, re-uses after also can be water-soluble, and as preferably, in the described 5 hydroxymethyl furfural aqueous solution, the mass percent concentration of 5 hydroxymethyl furfural is greater than 60%.
Described alcohol is monohydroxy-alcohol, be preferably methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 2-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl-1-butanol and 2, at least one in 2-dimethyl-1-propyl alcohol, these alcohol are cheap and easy to get, and are easy to occur etherification reaction.
As preferably, described 5 hydroxymethyl furfural is 1: 1～1: 1000 with the amount of substance ratio of alcohol, and preferably 1: 1～1: 200, wherein, the consumption of alcohol was larger, and productive rate is higher, but the increase of the consumption of alcohol can cause cost to increase.
As preferably, the reaction in step (1) and step (2) is all carried out in tank reactor;
After completing, reaction in step (1) obtains described liquid intermediate product after catalyzer is removed in centrifugation.Described tank reactor is autoclave, after the first step has been reacted, this liquid state intermediate product is added to autoclave again, proceed second step reaction, after second step has reacted, remove solid-state catalyzer through centrifugation, and then remove alcohol through distillation method and can obtain final product.When adopting tank reactor to react, reaction can be carried out more fully, and reaction yield is higher.
Step (1) is identical, specific as follows with the reaction conditions of step (2): temperature of reaction is 40～250 DEG C, and reaction pressure is 0.1～15MPa, be preferably 1～10MPa, the reaction times is 0.1～72h, is preferably 0.5-24h, wherein, reaction pressure is larger, and the concentration of hydrogen is just higher, and speed of reaction is just faster, but, pressure is higher, also higher to the requirement of tank reactor, can cause cost to rise accordingly.
Wherein, the consumption of the heterogeneous hydrogenation catalyst in the first catalyzer is by active ingredient wherein, and active ingredient is 1: 1～1: 1 × 10 with the amount of substance ratio of 5 hydroxymethyl furfural
6, preferably 1: 1～1: 1 × 10
4.
The consumption of the heterogeneous catalyst for etherification in the first catalyzer is pressed tradable H in catalyzer
+meter, tradable H
+with the ratio of the amount of substance of 5 hydroxymethyl furfural be 1: 0.1～1: 1 × 10
4, be preferably 1: 1～1: 100.
The consumption of the second catalyzer is by active ingredient wherein, and the ratio of the amount of substance of active ingredient and 5 hydroxymethyl furfural is 1: 1～1: 1 × 10
6, be preferably 1: 1～1: 1 × 10
4.
As preferably, the reaction in step (1) and step (2) is carried out continuously in the fixed-bed reactor of two series connection;
The first described catalyzer and the second catalyzer are individually fixed on the fixed-bed reactor of two described series connection;
After described 5 hydroxymethyl furfural or the aqueous solution of 5 hydroxymethyl furfural mix with alcohol, under the conveying of hydrogen stream, flow through successively two fixed-bed reactor and react;
The ratio of described 5 hydroxymethyl furfural or the aqueous solution of 5 hydroxymethyl furfural and alcohol with 5 hydroxymethyl furfural and the amount of substance ratio of total alcohol count 1: 1～1: 1000, preferably 1: 1～1: 200; The liquid hourly space velocity of fixed-bed reactor is 1～800, preferably 5～100, and hydrogen is 1: 1～2000: 1 with liquid volume ratio, preferably 10: 1～1500: 1, while adopting fixed-bed reactor, reaction can be carried out continuously, is more applicable for suitability for industrialized production.
In carrying out in the fixed-bed reactor of the continuous flow of two series connection, as preferably, the reaction conditions of step (1) is as follows: temperature of reaction is 40～250 DEG C, and reaction pressure is 0.1～15MPa, preferably 1～10MPa;
The reaction conditions of step (2) is as follows: temperature of reaction is 40～300 DEG C, and reaction pressure is 0.1～15MPa, preferably 1～10MPa.
Compared with the existing technology, beneficial effect of the present invention is embodied in:
(1) the present invention prepares the method for the dibasic tetrahydrofuran derivatives mixture of 2,5-, has simple to operately, and product yield is high, and product and the advantage such as raw alcohol is easy to separate, have good industrial prospect;
(2) metal catalyst that the preferred eggshell type of the present invention distributes is for the preparation of product, because the active ingredient of metal catalyst is only dispersed on the outside surface of carrier, the catalytic activity of the catalyzer that the catalytic activity of unit load amount catalyzer distributes than even type is high, thereby can reduce the use cost of catalyzer; Can eliminate the restriction of internal diffusion in reaction process, reduce the degree of degree of depth side reaction, improve the work-ing life of catalyzer simultaneously.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited thereto.
Embodiment 1:
By 5 hydroxymethyl furfural and ethanol with the amount of substance of 1: 8 than mixing, under the conveying of hydrogen stream successively by two fixed-bed reactor that catalyzer is housed, temperature of reaction is all 120 DEG C, reaction pressure is 4MPa, the volume ratio of hydrogen and liquid is 50: 1, after certain reaction times (TOS), collects the product that reactor II flows out, feed ethanol adopts distillation method to remove, and measures the selectivity of 5 hydroxymethyl furfural transformation efficiency and product.Before and after reaction, the content of 5 hydroxymethyl furfural adopts high performance liquid chromatography (HPLC) to measure, and the quantitative and qualitative analysis of product adopts column chromatography and LC-MS technology (LC-MS).Primary product is respectively 2 through Mass Spectrometric Identification, two (ethoxyl methyl) tetrahydrofuran (THF)s (molecular weight 188) of 5-, 5-ethoxyl methyl tetrahydrofuran-2-methanol (molecular weight 160), 2-(diethoxymethyl)-5-ethoxyl methyl tetrahydrofuran (THF) (molecular weight 232), 5-(diethoxymethyl) tetrahydrofuran-2-methanol (molecular weight 204), the optionally calculation formula of the transformation efficiency of raw material and target product is as follows:
Transformation efficiency=(the 5 hydroxymethyl furfural amount in the 5 hydroxymethyl furfural amount/charging of reaction) × 100%
Selectivity=(the 5 hydroxymethyl furfural amount of the amount/reaction of target product) × 100%
The measurement result of reaction is as shown in table 1.
The reaction assay result of 5 hydroxymethyl furfural and ethanol in table 1 continous way fixed-bed reactor
Catalyzer in table makes by method well known to those skilled in the art, and wherein the manufacturer of Amberlyst-15 and Amberlyst-131 is Rhom and Hass of the U.S..
In table 1, S
1be the selectivity of two (ethoxyl methyl) tetrahydrofuran (THF)s of 2,5-, the structure of two (ethoxyl methyl) tetrahydrofuran (THF)s of 2,5-is as follows:
S
2for the selectivity of 5-ethoxyl methyl tetrahydrofuran-2-methanol, the structure of 5-ethoxyl methyl tetrahydrofuran-2-methanol is as follows:
S
3for the selectivity of 2-(diethoxymethyl)-5-ethoxyl methyl tetrahydrofuran (THF), the structure of 2-(diethoxymethyl)-5-ethoxyl methyl tetrahydrofuran (THF) is as follows:
S
4for the selectivity of 5-(diethoxymethyl) tetrahydrofuran-2-methanol, the structure of 5-(diethoxymethyl) tetrahydrofuran-2-methanol is as follows:
Embodiment 2:
5 hydroxymethyl furfural is mixed with the volume ratio of 1: 10 with n-butyl alcohol, under the conveying of hydrogen stream successively by two fixed-bed reactor that catalyzer is housed, the temperature of reaction of reactor I is 130 DEG C, reaction pressure is 5MPa, the temperature of reaction of reactor II is 150 DEG C, reaction pressure is 6MPa, the volume ratio of hydrogen and liquid is 50: 1, after certain reaction times (TOS), collect the product that reactor II flows out, raw material n-butyl alcohol adopts distillation method to remove, and measures the selectivity of 5 hydroxymethyl furfural transformation efficiency and product.Primary product is respectively 2 through Mass Spectrometric Identification, two (butoxymethyl) tetrahydrofuran (THF)s (molecular weight 244) of 5-, 5-(butoxymethyl) tetrahydrofuran-2-methanol (molecular weight 188), 2-butoxymethyl-5-(dibutoxy methyl) tetrahydrofuran (THF) (molecular weight 316), 5-(dibutoxy methyl) tetrahydrofuran-2-methanol (molecular weight 260).The optionally calculation formula of the quantitative and qualitative analysis method of product and the transformation efficiency of raw material and target product is the same.Measurement result is as shown in table 2.
The reaction assay result of 5 hydroxymethyl furfural and n-butyl alcohol in table 2 continous way fixed-bed reactor
Catalyzer in table makes by method well known to those skilled in the art, and wherein the manufacturer of Amberlyst-70 and Amberlyst-15 is Rhom and Hass of the U.S..
In table 2, S
5be the selectivity of two (butoxymethyl) tetrahydrofuran (THF)s of 2,5-, the structure of two (butoxymethyl) tetrahydrofuran (THF)s of 2,5-is as follows:
S
6for the selectivity of 5-(butoxymethyl) tetrahydrofuran-2-methanol, the structure of 5-(butoxymethyl) tetrahydrofuran-2-methanol is as follows:
S
7for the selectivity of 2-butoxymethyl-5-(dibutoxy methyl) tetrahydrofuran (THF), the structure of 2-butoxymethyl-5-(dibutoxy methyl) tetrahydrofuran (THF) is as follows:
S
8for the selectivity of 5-(dibutoxy methyl) tetrahydrofuran-2-methanol, the structure of 5-(dibutoxy methyl) tetrahydrofuran-2-methanol is as follows:
Embodiment 3:
In 250ml autoclave, adding 50g mass percentage concentration is 80% the 5 hydroxymethyl furfural aqueous solution, the 2-propyl alcohol of 2.4mol, add heterogeneous catalyst for etherification as shown in table 3 and hydrogenation catalyst (the first step), the amount of the heterogeneous catalyst for etherification adding is by tradable H in catalyzer
+meter, H
+with the amount of substance ratio of 5 hydroxymethyl furfural be 1: 100, the amount of the hydrogenation catalyst adding is by active ingredient wherein, with the amount of substance ratio of 5 hydroxymethyl furfural be 1: 1000, it is 100 DEG C in temperature, hydrogen pressure is to react 4h under 5MPa, the liquid product of gained and catalyzer are after centrifugation, again add in autoclave, add hydrogenation catalyst as shown in table 3 (second step), the add-on of hydrogenation catalyst is by active ingredient wherein, with the amount of substance ratio of the initial 5 hydroxymethyl furfural adding be 1: 1000, it is 100 DEG C in temperature, hydrogen pressure is to react 4h under 5MPa, the liquid product of gained and catalyzer are through centrifugation, raw material 2-propyl alcohol adopts distillation method to remove, measure the selectivity of 5 hydroxymethyl furfural transformation efficiency and product.Primary product is respectively 2 through Mass Spectrometric Identification, two (isopropoxy methyl) tetrahydrofuran (THF)s (molecular weight 216) of 5-, 5-(isopropoxy methyl) tetrahydrofuran-2-methanol (molecular weight 174), 2-diisopropoxy methyl-5-(isopropoxy methyl) tetrahydrofuran (THF) (molecular weight 274), 5-(diisopropoxy methyl) tetrahydrofuran-2-methanol (molecular weight 232).The optionally calculation formula of the quantitative and qualitative analysis method of product and the transformation efficiency of raw material and target product is the same.Measurement result is as shown in table 3.
The reaction assay result of 5 hydroxymethyl furfural and 2-propyl alcohol in table 3 tank reactor
Catalyzer in table makes by method well known to those skilled in the art, and wherein the manufacturer of Amberlyst-36 and Amberlyst-15 is Rhom and Hass of the U.S..
In table 3, S
9be the selectivity of two (isopropoxy methyl) tetrahydrofuran (THF)s of 2,5-, the structure of two (isopropoxy methyl) tetrahydrofuran (THF)s of 2,5-is as follows:
S
10for the selectivity of 5-(isopropoxy methyl) tetrahydrofuran-2-methanol, the structure of 5-(isopropoxy methyl) tetrahydrofuran-2-methanol is as follows:
S
11for the selectivity of 2-diisopropoxy methyl-5-(isopropoxy methyl) tetrahydrofuran (THF), the structure of 2-diisopropoxy methyl-5-(isopropoxy methyl) tetrahydrofuran (THF) is as follows:
S
12for the selectivity of 5-(diisopropoxy methyl) tetrahydrofuran-2-methanol, the structure of 5-(diisopropoxy methyl) tetrahydrofuran-2-methanol is as follows:
Claims (7)
1. one kind 2, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-, is characterized in that, comprising:
(1) under the condition of the first catalyzer and hydrogen existence, the aqueous solution of 5 hydroxymethyl furfural or 5 hydroxymethyl furfural is mixed with alcohol etherificate reduction reaction occurs, after reacting completely, obtain liquid intermediate product;
(2) under the condition of the second catalyzer and hydrogen existence, the liquid intermediate product generation hydrogenation reaction that step (1) is obtained, after reacting completely, 2 described in aftertreatment obtains, the dibasic tetrahydrofuran derivatives mixture of 5-;
The first described catalyzer is made up of heterogeneous catalyst for etherification and heterogeneous hydrogenation catalyst;
Described heterogeneous hydrogenation catalyst is Al
2o
3the metal catalyst of load;
The active ingredient of described metal catalyst is at least one in Pd, Pt, Ir, Rh, Fe, Cu and Co, and charge capacity is 0.01%～10%
Described heterogeneous catalyst for etherification is at least one in ion exchange resin, solid super-strong acid and molecular sieve;
The second described catalyzer is gac or Al
2o
3the metal catalyst of load; The active ingredient of described metal catalyst is at least one in Ni, Pd, Ir, Rh and Os, and charge capacity is 0.01%～10%.
2. according to claim 12, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-, is characterized in that, in the aqueous solution of described 5 hydroxymethyl furfural, the mass percent concentration of 5 hydroxymethyl furfural is greater than 60%.
3. according to claim 12, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-, it is characterized in that, described alcohol is at least one in methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 2-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl-1-butanol and 2,2-dimethyl-1-propyl alcohol.
4. according to 2 described in claim 1～3 any one, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-, is characterized in that, the reaction in step (1) and step (2) is all carried out in tank reactor;
Reacting completely in step (1) obtains described liquid intermediate product afterwards after the first described catalyzer is removed in centrifugation;
Described liquid intermediate product returns and in tank reactor, carries out the reaction in step (2).
5. according to claim 42, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-, is characterized in that, in step (1) and step (2), temperature of reaction is 40～250 DEG C, and reaction pressure is 0.1～15MPa, and the reaction times is 0.1～72h.
6. according to 2 described in claim 1～3 any one, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-, is characterized in that, the reaction in step (1) and step (2) is carried out continuously in the fixed-bed reactor of two series connection;
The first described catalyzer and the second catalyzer are individually fixed on the fixed-bed reactor of two described series connection;
After described 5 hydroxymethyl furfural or the aqueous solution of 5 hydroxymethyl furfural mix with alcohol, under the conveying of hydrogen stream, flow through successively two fixed-bed reactor and react.
7. according to claim 62, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-, is characterized in that,
In step (1), temperature of reaction is 40～250 DEG C, and reaction pressure is 0.1～15MPa;
In step (2), temperature of reaction is 40～300 DEG C, and reaction pressure is 0.1～15MPa.
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| ES2462872B1 (en) * | 2012-10-25 | 2015-03-10 | Consejo Superior Investigacion | Catalyst and catalytic process for the etherification / reduction of furfuryl derivatives to tetrahydro-furfuryl ethers |
| CN105461666B (en) * | 2016-01-07 | 2018-03-13 | 华东师范大学 | A kind of preparation method of 2 substituted tetrahydrofuran class compound |
| DE102016009798A1 (en) * | 2016-08-12 | 2018-02-15 | Henkel Ag & Co. Kgaa | New anionic surfactants and detergents and cleaners containing them |
| WO2019073987A1 (en) * | 2017-10-11 | 2019-04-18 | 三菱瓦斯化学株式会社 | Method for producing 2,5-bis (aminomethyl) tetrahydrofuran |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101809010A (en) * | 2007-09-07 | 2010-08-18 | 福兰尼克斯科技公司 | hydroxymethylfurfural ethers from sugars or hmf and mixed alcohols |
| CN101821248A (en) * | 2007-09-07 | 2010-09-01 | 福兰尼克斯科技公司 | 5-substituted 2-(alkoxymethyl)furans |
| CN101827833A (en) * | 2007-09-07 | 2010-09-08 | 福兰尼克斯科技公司 | Mixture of furfural and 5-(alkoxymethyl)furfural derivatives from sugars and alcohols |
| CN102177146A (en) * | 2008-10-30 | 2011-09-07 | 阿彻丹尼尔斯米德兰德公司 | Reduction of HMF ethers with metal catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101809010A (en) * | 2007-09-07 | 2010-08-18 | 福兰尼克斯科技公司 | hydroxymethylfurfural ethers from sugars or hmf and mixed alcohols |
| CN101821248A (en) * | 2007-09-07 | 2010-09-01 | 福兰尼克斯科技公司 | 5-substituted 2-(alkoxymethyl)furans |
| CN101827833A (en) * | 2007-09-07 | 2010-09-08 | 福兰尼克斯科技公司 | Mixture of furfural and 5-(alkoxymethyl)furfural derivatives from sugars and alcohols |
| CN102177146A (en) * | 2008-10-30 | 2011-09-07 | 阿彻丹尼尔斯米德兰德公司 | Reduction of HMF ethers with metal catalyst |
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