CN103073526A - 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 the preparation of fuel field, be specifically related to a kind of 2, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-.
Background technology
For a long time, human main fossil energy such as coal, oil, Sweet natural gas acquisition fuel and the fuel dope of relying on.Yet, along with the day by day minimizing of world's fossil energy reserve, substitute traditional fossil energy in the urgent need to seeking a kind of new substitute energy.In the renewable energy source of developing, biomass energy is all closely similar with fossil energy on chemical molecular formation, energy utilization form, is the most promising petrochemical industry substitute energy.Biomass resource can be prepared numerous platform chemicals such 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 the production furans take it as raw material, alkanes and levulinate class I liquid I fuel.
Hydroxymethylfurfuraethers ethers is a kind of important furfuran compound, owing to have high energy density, water insoluble, nonhygroscopic in air, be difficult for oxidation and hydrolysis, can improve the advantages such as octane value, make it to be suitable for acting as a fuel or fuel dope.Patent CN 102161918A discloses that the 5-alkoxymethylfurfuralethers ethers acts as a fuel or the purposes of fuel dope.Patent CN 101809010A provides a kind of method for preparing the 5 hydroxymethyl furfural ether mixture, the method is by making raw material or HMF and the alcohol mixture reaction that contains hexose in the presence of an acidic catalyst, patent CN 101827833A provides the method for the mixture of preparation furfural and 5-(alkoxy methyl) furfural derivatives, and the method contains C by making
5And C
6The raw material of sugar reacts in the presence of an acidic catalyst with alcohol, again with the mixture hydrogenation of the furfural that generates and 5-(alkoxy methyl) furfural and/or etherificate so that the aldehyde functional group of furfural and 5-(alkoxy methyl) furfural all is converted into alkoxy methyl functional group or methyl functional group.Patent CN101821248 provides the method for preparation 2-(alkoxy methyl) furans (or mixture of this class furans) that 5-replaces, and method is to react in the presence of pure and mild catalyst system by starting material and the hydrogen that comprises the furfural that at least a 5-replaces.
Contain a furan nucleus in the hydroxymethylfurfuraethers ethers, if the furan nucleus hydrogenation in the hydroxymethylfurfuraethers ethers is generated the tetrahydrofuran derivatives material that replaces, then can greatly increase its energy density, can make it more appropriate to act as a fuel or fuel dope, yet because furan nucleus is stable aromatic nucleus, the difficulty that is 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 the patent report.
Summary of the invention
The invention provides a kind of 2, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-, this preparation method can be reduced into the tetrahydrofuran (THF) ring structure with the furan ring structure in the 5 hydroxymethyl furfural with higher transformation efficiency, the product that forming energy density is higher.
A kind of 2, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-comprises:
(1) under the condition of the first catalyzer and hydrogen existence, the aqueous solution and pure mixed occurrence etherificate reduction reaction with 5 hydroxymethyl furfural or 5 hydroxymethyl furfural after reacting completely, obtain liquid intermediate product;
(2) under the condition that the second catalyzer and hydrogen exist, the liquid intermediate product generation hydrogenation reaction that step (1) is obtained, after reacting completely, it is described 2 that aftertreatment obtains, the dibasic tetrahydrofuran derivatives mixture of 5-;
Described the first catalyzer is comprised 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 dehydrated into an acidic catalyst of ether for the energy catalytic alcohol;
Described the second catalyzer is the metal catalyst of energy catalysis furan nucleus generation hydrogenation.
Among the present invention, under the condition of the co-catalysis of described heterogeneous catalyst for etherification and heterogeneous hydrogenation catalyst, etherificate and acetalation occur respectively in the hydroxyl on the 5 hydroxymethyl furfural and aldehyde radical and raw alcohol, and 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 the 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 the 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 a among Pd, Pt, Ir, Rh, Fe, Cu and the 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 the step (1), dehydration formation ether occurs 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, act as a fuel or the requirement of fuel dope to satisfy, described heterogeneous catalyst for etherification is preferably at least a in ion exchange resin, solid super-strong acid and the molecular sieve, the heterogeneous catalyst for etherification low price of these several classes, obtain easily, and have higher catalytic activity.
In the step (2), described the second catalyzer be for being converted into furan ring structure the catalyzer of tetrahydrofuran (THF) ring structure, and as preferably, described the second catalyzer is gac or Al
2O
3The metal catalyst of load; The active ingredient of this metal catalyst is at least a among Ni, Pd, Ir, Rh and the Os, and the charge capacity of this metal catalyst is 0.01%～10%, and in this charge capacity scope, described the second catalyzer can keep higher catalytic activity.
In described the second catalyzer, active ingredient can evenly distribute or non-uniform Distribution on carrier, is preferably eggshell type and distributes, when adopting this kind distribution, catalytic activity when the 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 the 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 a 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 molar ratio of alcohol, and preferred 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 the step (2) is all carried out in tank reactor;
Obtain described liquid intermediate product after catalyzer was removed in the process centrifugation after reaction in the step (1) was finished.Described tank reactor is autoclave, after the first step reaction is finished, should add again autoclave by the liquid state intermediate product, proceed the second step reaction, after the second step reaction is finished, 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 ℃, 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, and is 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 wherein active ingredient, and the molar ratio of active ingredient and 5 hydroxymethyl furfural is 1: 1～1: 1 * 10
6, preferred 1: 1～1: 1 * 10
4
The consumption of the heterogeneous catalyst for etherification in the first catalyzer is pressed tradable H in the 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 wherein active ingredient, 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 the step (2) is carried out in the fixed-bed reactor of two series connection continuously;
Described the first catalyzer and the second catalyzer are individually fixed on the fixed-bed reactor of described two series connection;
The aqueous solution of described 5 hydroxymethyl furfural or 5 hydroxymethyl furfural with alcohol mix after, under the conveying of hydrogen stream, flow through successively two fixed-bed reactor and react;
The ratio of the aqueous solution of described 5 hydroxymethyl furfural or 5 hydroxymethyl furfural and alcohol with 5 hydroxymethyl furfural and the molar ratio of total alcohol count 1: 1～1: 1000, preferred 1: 1～1: 200; The liquid hourly space velocity of fixed-bed reactor is 1～800, and is preferred 5～100, and hydrogen is 1: 1～2000: 1 with the liquid volume ratio, and preferred 10: 1～1500: 1, when adopting fixed-bed reactor, reaction can be carried out continuously, is more applicable for suitability for industrialized production.
When 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 ℃, and reaction pressure is 0.1～15MPa, preferred 1～10MPa;
The reaction conditions of step (2) is as follows: temperature of reaction is 40～300 ℃, and reaction pressure is 0.1～15MPa, preferred 1～10MPa.
Compare with prior art, 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 advantages such as raw alcohol is easy to separate have good industrial prospect;
(2) metal catalyst of the preferred eggshell type distribution of the present invention is used for the preparation of product, because the active ingredient of metal catalyst only is dispersed on the outside surface of carrier, the catalytic activity of unit load amount catalyzer is higher than the catalytic activity of the catalyzer that even type distributes, thereby can reduce the use cost of catalyzer; Can eliminate simultaneously the restriction of internal diffusion in the reaction process, reduce the degree of degree of depth side reaction, improve the work-ing life of catalyzer.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention is not limited thereto.
Embodiment 1:
5 hydroxymethyl furfural is mixed with the molar ratio of ethanol with 1: 8, under the conveying of hydrogen stream successively by two fixed-bed reactor that catalyzer is housed, temperature of reaction all is 120 ℃, 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.The content of 5 hydroxymethyl furfural adopts high performance liquid chromatography (HPLC) to measure before and after the reaction, 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 of target product/reaction) * 100%
The measurement result of reaction is as shown in table 1.
The reaction assay result of 5 hydroxymethyl furfural and ethanol in the table 1 continous way fixed-bed reactor
Catalyzer in the table makes by method well known to those skilled in the art, and wherein the manufacturer of Amberlyst-15 and Amberlyst-131 is U.S. Rhom and Hass.
In the 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
2Be the selectivity of 5-ethoxyl methyl tetrahydrofuran-2-methanol, the structure of 5-ethoxyl methyl tetrahydrofuran-2-methanol is as follows:
S
3Be the selectivity of 2-(diethoxymethyl)-5-ethoxyl methyl tetrahydrofuran (THF), the structure of 2-(diethoxymethyl)-5-ethoxyl methyl tetrahydrofuran (THF) is as follows:
S
4Be 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 1: 10 volume ratio 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 ℃, reaction pressure is 5MPa, the temperature of reaction of reactor II is 150 ℃, 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, the 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 the table 2 continous way fixed-bed reactor
Catalyzer in the table makes by method well known to those skilled in the art, and wherein the manufacturer of Amberlyst-70 and Amberlyst-15 is U.S. Rhom and Hass.
In the 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
6Be the selectivity of 5-(butoxymethyl) tetrahydrofuran-2-methanol, the structure of 5-(butoxymethyl) tetrahydrofuran-2-methanol is as follows:
S
7Be the selectivity of 2-butoxymethyl-5-(dibutoxy methyl) tetrahydrofuran (THF), the structure of 2-butoxymethyl-5-(dibutoxy methyl) tetrahydrofuran (THF) is as follows:
S
8Be the selectivity of 5-(dibutoxy methyl) tetrahydrofuran-2-methanol, the structure of 5-(dibutoxy methyl) tetrahydrofuran-2-methanol is as follows:
Embodiment 3:
Adding 50g mass percentage concentration is 80% the 5 hydroxymethyl furfural aqueous solution in the 250ml autoclave, 2.4mol the 2-propyl alcohol, add heterogeneous catalyst for etherification as shown in table 3 and hydrogenation catalyst (the first step), the amount of the heterogeneous catalyst for etherification of adding is pressed tradable H in the catalyzer
+Meter, H
+With the molar ratio of 5 hydroxymethyl furfural be 1: 100, the amount of the hydrogenation catalyst that adds is by wherein active ingredient, with the molar ratio of 5 hydroxymethyl furfural be 1: 1000, it is 100 ℃ in temperature, hydrogen pressure is to react 4h under the 5MPa, the liquid product of gained and catalyzer are after centrifugation, again add in the autoclave, add hydrogenation catalyst (second step) as shown in table 3, the add-on of hydrogenation catalyst is by wherein active ingredient, with the molar ratio of the 5 hydroxymethyl furfural of initial adding be 1: 1000, be 100 ℃ in temperature, hydrogen pressure is to react 4h under the 5MPa, and the liquid product of gained and catalyzer are through centrifugation, raw material 2-propyl 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 (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 the table makes by method well known to those skilled in the art, and wherein the manufacturer of Amberlyst-36 and Amberlyst-15 is U.S. Rhom and Hass.
In the 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
10Be the selectivity of 5-(isopropoxy methyl) tetrahydrofuran-2-methanol, the structure of 5-(isopropoxy methyl) tetrahydrofuran-2-methanol is as follows:
S
11Be 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
12Be the selectivity of 5-(diisopropoxy methyl) tetrahydrofuran-2-methanol, the structure of 5-(diisopropoxy methyl) tetrahydrofuran-2-methanol is as follows:
Claims (10)
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 and pure mixed occurrence etherificate reduction reaction with 5 hydroxymethyl furfural or 5 hydroxymethyl furfural after reacting completely, obtain liquid intermediate product;
(2) under the condition that the second catalyzer and hydrogen exist, the liquid intermediate product generation hydrogenation reaction that step (1) is obtained, after reacting completely, it is described 2 that aftertreatment obtains, the dibasic tetrahydrofuran derivatives mixture of 5-;
Described the first catalyzer is comprised 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 dehydrated into an acidic catalyst of ether for the energy catalytic alcohol;
Described the second catalyzer is the metal catalyst of energy catalysis furan nucleus generation hydrogenation.
2. according to claim 12, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-is characterized in that, described heterogeneous hydrogenation catalyst is Al
2O
3The metal catalyst of load;
The active ingredient of described metal catalyst is at least a among Pd, Pt, Ir, Rh, Fe, Cu and the Co, and charge capacity is 0.01%～10%.
3. according to claim 12, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-is characterized in that, in the step (1), described heterogeneous catalyst for etherification is at least a in ion exchange resin, solid super-strong acid and the molecular sieve.
4. according to claim 12, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-is characterized in that, described the second catalyzer is gac or Al
2O
3The metal catalyst of load; The active ingredient of described metal catalyst is at least a among Ni, Pd, Ir, Rh and the Os, and charge capacity is 0.01%～10%.
5. 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%.
6. 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 a 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, the 2-dimethyl-1-propyl alcohol.
7. each is described 2 according to claim 1～6, and the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-is characterized in that, the reaction in step (1) and the step (2) is all carried out in tank reactor;
After removing described the first catalyzer through centrifugation afterwards, reacting completely in the step (1) obtain described liquid intermediate product;
Described liquid intermediate product returns the reaction of carrying out in the tank reactor in the step (2) again.
8. according to claim 72, 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 ℃, and reaction pressure is 0.1～15MPa, and the reaction times is 0.1～72h.
9. each is described 2 according to claim 1～6, and the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-is characterized in that, the reaction in step (1) and the step (2) is carried out in the fixed-bed reactor of two series connection continuously;
Described the first catalyzer and the second catalyzer are individually fixed on the fixed-bed reactor of described two series connection;
The aqueous solution of described 5 hydroxymethyl furfural or 5 hydroxymethyl furfural with alcohol mix after, under the conveying of hydrogen stream, flow through successively two fixed-bed reactor and react.
10. according to claim 92, the preparation method of the dibasic tetrahydrofuran derivatives mixture of 5-is characterized in that,
In the step (1), temperature of reaction is 40～250 ℃, and reaction pressure is 0.1～15MPa;
In the step (2), temperature of reaction is 40～300 ℃, and reaction pressure is 0.1～15MPa.
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| WO2014064318A1 (en) * | 2012-10-25 | 2014-05-01 | Consejo Superior De Investigaciones Científicas (Csic) | Catalyst and catalytic process for the etherification/reduction of furfuryl derivatives to tetrahydrofurfuryl ethers |
| CN105461666A (en) * | 2016-01-07 | 2016-04-06 | 华东师范大学 | Preparation method of 2-substituted tetrahydrofuran compounds |
| WO2018029202A1 (en) * | 2016-08-12 | 2018-02-15 | Henkel Ag & Co. Kgaa | New anionic surfactants and detergents and cleaning agents containing same |
| CN111201221A (en) * | 2017-10-11 | 2020-05-26 | 三菱瓦斯化学株式会社 | Method for producing 2, 5-bis (aminomethyl) tetrahydrofuran |
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| CN103073526B (en) | 2014-12-03 |
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