CN114105915A - Method for preparing 5-ethoxymethylfurfural by using 5-hydroxymethylfurfural - Google Patents
Method for preparing 5-ethoxymethylfurfural by using 5-hydroxymethylfurfural Download PDFInfo
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 44
- CCDRPZFMDMKZSZ-UHFFFAOYSA-N 5-(ethoxymethyl)furan-2-carbaldehyde Chemical compound CCOCC1=CC=C(C=O)O1 CCDRPZFMDMKZSZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000002808 molecular sieve Substances 0.000 claims abstract description 52
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000006266 etherification reaction Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000446 fuel Substances 0.000 description 8
- 235000006408 oxalic acid Nutrition 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000010306 acid treatment Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L Zinc bromide Inorganic materials Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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Abstract
The invention discloses a method for preparing 5-ethoxymethylfurfural by using 5-hydroxymethylfurfural, which is characterized in that 5-hydroxymethylfurfural and ethanol are used as raw materials and are directly etherified under the action of a catalyst to prepare the 5-ethoxymethylfurfural, and the catalyst is an H-type beta molecular sieve. The method of the invention solves the problems of environmental pollution and equipment corrosion caused by the reaction, and has the advantages of low cost, high conversion rate and high selectivity.
Description
Technical Field
The invention relates to a method for preparing 5-ethoxymethylfurfural by using 5-hydroxymethylfurfural.
Background
With the continuous development of scientific technology, the use of non-renewable fossil fuels is increasing, which leads to the decreasing fuel reserves and the impact on global climate, and it is imperative to replace the current dangerous and non-renewable processes with sustainable, green and environmentally friendly practices, which is of great strategic importance. In the course of future developments, the production of petroleum cannot keep up with the ever increasing demand for fuels and chemicals. Therefore, new synthetic routes and related technologies for producing fuels and chemicals from renewable feedstocks are needed.
5-ethoxymethylfurfural is regarded as an important biomass-based platform compound and has wide application. In recent years, its preparation and application have attracted increasing attention from researchers. The etherification product of 5-Hydroxymethylfurfural (HMF) is 5-Ethoxymethylfurfural (EMF), which is considered to be a high energy density (30.3MJ · L)-1) A promising candidate biofuel product, diesel fuel (33.6 MJ. L)-1) And gasoline (33.1 MJ. L)-1) Compared with the prior art, the biological ethanol is much higher than the biological ethanol (23.5 MJ.L)-1). The characteristics determine that the fuel can be used as a good potential alternative fuel or fuel additive and is expected to play an important role in the alternative energy of the petroleum era. Meanwhile, as a fuel, the high oxidation stability of the fuel can reduce the emission of smoke dust, sulfur oxides and nitrogen oxides, and the fuel has good environmental benefit and is a clean novel biofuel.
However, the current problem is that the production cost of 5-ethoxymethylfurfural is high, thereby limiting the industrial production of 5-ethoxymethylfurfural. On one hand, although the homogeneous liquid phase catalyst can be used for synthesizing 5-ethoxymethylfurfural, the method has the serious problems of environmental pollution, equipment corrosion, difficult recovery and the like, so the method is not suitable for producing 5-ethoxymethylfurfural. On the other hand, the heterogeneous solid acid catalyst developed in the current market generally has the problems of low activity, poor stability, high cost and the like, so that the production cost of the 5-ethoxymethylfurfural is obviously increased. Therefore, the search for a low-cost, high-activity and high-selectivity heterogeneous solid acid catalyst for the production of 5-ethoxymethylfurfural is urgent.
To solve the problemIn view of the above problems, researchers at home and abroad strive to search for a green and environment-friendly production process with good economy. Catalysts such as MCM-41 nanospheres, multi-layered polyoxometallate (niobium molybdate), Zr-SBA-15, ion exchange resins, and the like are reported in the literature. In the invention patent with application publication number CN104628682A, kojiuxia et al uses tert-butyl alcohol as raw material, uses graphene as carrier, connects acidic organic functional group with catalytic activity on the graphene as catalyst to prepare alkoxymethylfurfural, and the yield can reach 40%. In patent application publication No. CN102911141A, Xujie et al used heteropolyacid with Keggin type structure as catalyst to prepare the desired product, and the yield can reach more than 76%. In the patent of invention with application publication No. CN102260229A, Advance et al applied for the fixed bed of lignocellulosic biomass and ZnBr as raw material2With an inorganic acid, or ZnBr2Alcohol solution formed by inorganic acid is used as catalyst, and the method uses inorganic acid and ZnBr2The co-catalysis reaction has the possibility of corroding experimental equipment.
At present, the catalysts used in the reaction are mostly mesoporous solid acids, and related documents such as catalysts MCM-41 (Catalysis Today 175(2011) 435-. In the literature (Applied Catalysis a, General 590(2020)117338), a ZSM-5 molecular sieve with a hierarchical structure is constructed by introducing a mesoporous structure into ZSM-5 through alkali treatment and oxalic acid treatment and adjusting the acidity of ZSM-5, and is used for the etherification reaction of HMF and ethanol, the conversion rate of HMF reaches 97.0%, and the EMF yield reaches 90.6%. The selectivity of 5-ethoxymethylfurfural at high conversion rate of 5-hydroxymethylfurfural still needs to be improved.
Therefore, a heterogeneous solid acid catalyst is sought, the selectivity of the 5-ethoxymethylfurfural under high conversion rate of the catalyst can be obviously improved on the basis of maintaining higher catalytic activity, and the catalyst has great industrial application significance and prospect. The invention uses a heterogeneous catalyst, reduces the corrosion to equipment and greatly improves the selectivity of the reaction.
Disclosure of Invention
The invention aims to provide a method for preparing 5-ethoxymethylfurfural by directly etherifying 5-hydroxymethylfurfural and ethanol, which solves the problems of environmental pollution and equipment corrosivity caused by the reaction and has the advantages of low cost, high conversion rate and high selectivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing 5-ethoxymethylfurfural by using 5-hydroxymethylfurfural is characterized in that 5-hydroxymethylfurfural and ethanol are used as raw materials and are directly etherified under the action of a catalyst to prepare the 5-ethoxymethylfurfural, and the catalyst is an H-type beta molecular sieve.
The H-type beta molecular sieve is a microporous molecular sieve, is high-silicon zeolite with a three-dimensional twelve-membered ring pore structure, has stronger acidity and higher framework stability, and has larger adsorption capacity to water, thereby inhibiting the occurrence of side reactions. The H-type beta molecular sieve can meet the acidity required by the reaction, so that the conversion rate of reactants in the reaction process reaches more than 99 percent and the EMF selectivity is high. And the H-type beta molecular sieve is cheap and easy to obtain, can be repeatedly used and has the advantage of low cost.
Specifically, the method comprises the following steps:
adding 5-hydroxymethylfurfural, ethanol and an H-type beta molecular sieve into an autoclave type reactor, introducing nitrogen to replace air in the reactor, starting stirring and heating, controlling the stirring speed to be 500-1000 r/min and the reaction temperature to be 80-180 ℃ for reaction, and obtaining the target product 5-ethoxymethylfurfural after full reaction. The used catalyst is recycled.
Preferably, the mass amount of the H-type beta molecular sieve is 0.1-50% of the mass amount of the 5-hydroxymethylfurfural, and the molar ratio of the 5-hydroxymethylfurfural to ethanol is 0.001-0.05: 1. The mass usage amount of the H-type beta molecular sieve is more preferably 3-50% of the mass usage amount of the 5-hydroxymethylfurfural, and more preferably 3-10%.
According to the etherification reaction, the reaction temperature is 80-180 ℃, when the reaction time is fixed, the yield of the target product is increased along with the increase of the temperature, and the preferable reaction temperature is 140 ℃.
According to the etherification reaction, when the reaction temperature is constant, the yield of the target product is increased along with the prolonging of the time. However, when the etherification reaction reaches equilibrium and the reaction time continues to be extended, the selectivity of the target product decreases. The reaction time of the reaction is generally 0.5 to 8 hours, and preferably more than 5 hours.
In the present invention, the H-type molecular sieve may be obtained by using a commercially available product, or by treating (e.g., ammonium salt exchange, calcination) a commercially available Na-type β molecular sieve by a conventional method.
The invention relates to an etherification catalyst system with high activity, high selectivity, easy regeneration and low corrosivity, which solves the problems of low yield of a target product 5-ethoxymethylfurfural, difficult catalyst recovery, strong corrosivity of a reaction system and the like in the direct etherification of 5-hydroxymethylfurfural and ethanol.
The invention has the beneficial effects that:
(1) according to the invention, 5-hydroxymethylfurfural and ethanol are used as raw materials for direct etherification, and an H-type beta molecular sieve is used as a catalyst, so that the use of strong corrosive protonic acid is avoided, and the corrosion to equipment is slight;
(2) under mild conditions, the H-type beta molecular sieve realizes the efficient catalysis of the conversion of 5-hydroxymethylfurfural to prepare 5-ethoxymethylfurfural. During the etherification reaction, a molecule of water is generated, and the beta molecular sieve has larger water adsorption capacity, so that the generation of side reaction is inhibited, and the yield of the 5-ethoxymethylfurfural can reach more than 90 percent.
(3) The H-type beta molecular sieve used in the invention is cheap and easy to obtain, can be repeatedly used and has the advantage of low cost.
Drawings
FIG. 1 is a HPLC analysis chart of the product obtained in example 4.
Figure 2 is a low temperature argon desorption isotherm of the beta molecular sieve used in the examples.
FIG. 3 shows the pyridine infrared patterns (Py-IR) at 100 deg.C (lower) and 150 deg.C (upper) for the beta molecular sieves used in the examples.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to the examples.
The beta molecular sieve used in the embodiment of the invention is NKF-6 (beta) molecular sieve of Tianjin south chemical catalyst Co. Wherein the silicon-aluminum ratio of the beta molecular sieve is 25, and the specific surface area is 457.71m2(ii) in terms of/g. The low temperature argon adsorption and desorption isotherms of the beta molecular sieve and the pyridine infrared images (Py-IR) at 100 ℃ (lower) and 150 ℃ (upper) are shown in the second and third figures, respectively.
Example 1
Adding 0.315g of 5-hydroxymethylfurfural, 0.01g of beta molecular sieve and 30mL of ethanol into a stainless steel high-pressure kettle type reactor, introducing nitrogen to replace air in the reactor, starting stirring and heating, reacting for 5 hours at 140 ℃ by mechanical stirring at 1000r/min, immediately immersing the kettle type reactor into cold water to reduce the temperature after the reaction is finished, cooling the temperature of the reactor to the normal temperature, filtering a reaction mixture, collecting filtrate, and analyzing and calculating by using a high performance liquid chromatograph to obtain the target product 5-ethoxymethylfurfural. The conversion rate of the 5-hydroxymethylfurfural can reach 99%, the selectivity of the target product 5-ethoxymethylfurfural is 95%, and other products are EL (ethyl levulinate) and tar substances.
Example 2
The beta molecular sieve catalyst is adopted, the dosage of the catalyst, the reaction temperature and the reaction time of the 5-hydroxymethylfurfural and ethanol are changed, the reaction temperature is 100 ℃, 120 ℃ and 140 ℃, the reaction is required to be carried out in an autoclave, the rest is similar to the example 1, and the specific reaction conditions and the reaction results are listed in the table 1. The figure is an HPLC analysis chart of the product obtained in example 4, wherein the peak with the retention time of 12.643 is the target product 5-ethoxymethylfurfural, and the peak area ratio is 95.8519%.
TABLE 1
Example 9
Adding 0.315g of 5-hydroxymethylfurfural, 0.03g of beta molecular sieve and 30mL of ethanol into a stainless steel autoclave type reactor, introducing nitrogen to replace air in the reactor, starting stirring and heating, and reacting for 5 hours at 140 ℃ by mechanical stirring at 1000 r/min. After each reaction, the catalyst was collected by high speed centrifugation, washed with ethanol, dried at 80 ℃ for 12h, and the experiment was repeated. After the catalyst is used for five times, the activity of the catalyst is not greatly reduced, the conversion rate of 5-HMF in the first reaction is 99.0 percent, and the conversion rate is reduced to 83.70 percent after 5 times of reaction.
Example 10
Acid treatment of the molecular sieve: 2g of beta molecular sieve is put into 40mL of 0.02M oxalic acid, heated and stirred for 1h at 80 ℃, immediately cooled to room temperature in an ice bath after stirring is finished, and the obtained powder is washed to be neutral by deionized water and dried. Adding 0.03g of the treated beta molecular sieve (0.02M), 0.315g of 5-hydroxymethylfurfural and 30mL of ethanol into a stainless steel autoclave type reactor, introducing nitrogen to replace air in the reactor, starting stirring and heating, and reacting for 5 hours at 140 ℃ by mechanical stirring at 1000 r/min. The selectivity of EMF is 91.09% and the conversion rate of 5-HMF is 97.98% as measured by HPLC.
Example 11
Acid treatment of the molecular sieve: 2g of beta molecular sieve is put into 40mL of 0.04M oxalic acid, heated and stirred for 1h at 80 ℃, immediately cooled to room temperature in an ice bath after stirring is finished, and the obtained powder is washed to be neutral by deionized water and dried. Adding 0.03g of the treated beta molecular sieve (0.04M), 0.315g of 5-hydroxymethylfurfural and 30mL of ethanol into a stainless steel autoclave type reactor, introducing nitrogen to replace air in the reactor, starting stirring and heating, and reacting for 5 hours at 140 ℃ by mechanical stirring at 1000 r/min. The selectivity of EMF was 77.86% and the conversion of 5-HMF was 98.83% as determined by HPLC.
Example 12
Acid treatment of the molecular sieve: 2g of beta molecular sieve is put into 40mL of 0.08M oxalic acid, heated and stirred for 1h at 80 ℃, immediately cooled to room temperature in an ice bath after stirring is finished, and the obtained powder is washed to be neutral by deionized water and dried. Adding 0.03g of treated beta molecular sieve (0.08M), 0.315g of 5-hydroxymethylfurfural and 30mL of ethanol into a stainless steel autoclave type reactor, introducing nitrogen to replace air in the reactor, starting stirring and heating, and reacting for 5 hours at 140 ℃ by mechanical stirring at 1000 r/min. HPLC detection gave an EMF selectivity of 63.86% and a conversion of 5-HMF of 98.63%.
Example 13
Acid treatment of the molecular sieve: 2g of beta molecular sieve is put into 40mL of 0.1M oxalic acid, heated and stirred for 1h at 80 ℃, immediately cooled to room temperature in an ice bath after stirring is finished, and the obtained powder is washed to be neutral by deionized water and dried. Adding 0.03g of treated beta molecular sieve (0.1M), 0.315g of 5-hydroxymethylfurfural and 30mL of ethanol into a stainless steel autoclave type reactor, introducing nitrogen to replace air in the reactor, starting stirring and heating, and reacting for 5 hours at 140 ℃ by mechanical stirring at 1000 r/min. The selectivity of EMF was 52.34% and the conversion of 5-HMF was 97.34% as determined by HPLC.
Example 14
Acid-base treatment of the molecular sieve: mixing 100mL of 0.5M NaOH solution and 10mL of CTAB together, processing 5g of beta molecular sieve, heating and stirring at 80 ℃ for 24 hours, immediately placing in an ice bath to cool to room temperature after stirring is finished, washing the powder to be neutral, drying, placing 2g of the molecular sieve subjected to alkali treatment in 40mL of 0.1M oxalic acid, heating and stirring at 80 ℃ for 1 hour, immediately cooling to room temperature in the ice bath after stirring is finished, washing the obtained powder to be neutral by deionized water, and drying. Adding 0.03g of the treated beta molecular sieve, 0.315g of 5-hydroxymethylfurfural and 30mL of ethanol into a stainless steel autoclave type reactor, introducing nitrogen to replace air in the reactor, starting stirring and heating, and reacting for 5 hours at 140 ℃ through mechanical stirring at 1000 r/min. The selectivity of EMF was 32.33% and the conversion of 5-HMF was 60.34% as determined by HPLC.
The beta molecular sieve is used as the catalyst on the surface of the above examples 2, 3, 4 and 5, other reaction conditions are fixed, the dosage of the beta molecular sieve catalyst is adjusted, when the dosage is 0.03g, the best reaction effect is obtained, the dosage of the catalyst is continuously increased, the conversion rate is improved, but the side reaction is accelerated, and the EMF yield of the target product is reduced.
Examples 4, 6 and 7 show that beta molecular sieve is used as a catalyst, other conditions are consistent, and the reaction temperature of the catalytic reaction is changed. As the reaction temperature is lowered, the conversion of 5-HMF is also lowered. This also indicates that temperature increases the activity of the catalyst.
Example 8 is a reaction carried out in the absence of a catalyst at a reaction temperature of 140 ℃ and 1000rmp under autogenous pressure. The reaction was carried out for 8 hours with a conversion of 5-HMF of 4.54%. This indicates that the presence of the catalyst accelerates the etherification reaction.
Examples 10, 11, 12, 13 show that the change in activity of the molecular sieves is not significant after treatment of the beta molecular sieves with oxalic acid, but the selectivity to EMF is reduced. This is probably because the oxalic acid solution causes defects in the molecular sieve framework during the process of adjusting the acidity thereof.
Claims (7)
1. A method for preparing 5-ethoxymethylfurfural by using 5-hydroxymethylfurfural is characterized in that 5-hydroxymethylfurfural and ethanol are used as raw materials and are directly etherified under the action of a catalyst to prepare the 5-ethoxymethylfurfural, and the method is characterized in that: the catalyst is H-type beta molecular sieve.
2. The method of claim 1, wherein: the method comprises the following steps:
adding 5-hydroxymethylfurfural, ethanol and an H-type beta molecular sieve into an autoclave type reactor, introducing nitrogen to replace air in the reactor, starting stirring and heating, controlling the stirring speed to be 500-1000 r/min and the reaction temperature to be 80-180 ℃ for reaction, and obtaining the target product 5-ethoxymethylfurfural after full reaction.
3. The method of claim 2, wherein: the mass amount of the H-type beta molecular sieve is 0.1-50% of that of the 5-hydroxymethylfurfural, and the molar ratio of the 5-hydroxymethylfurfural to ethanol is 0.001-0.05: 1.
4. The method of claim 3, wherein: the mass usage amount of the H-type beta molecular sieve is 3-50% of the mass usage amount of the 5-hydroxymethylfurfural.
5. The method of claim 3, wherein: the mass usage amount of the H-type beta molecular sieve is 3-10% of the mass usage amount of the 5-hydroxymethylfurfural.
6. The method of claim 2, wherein: the reaction temperature of the etherification reaction was 140 ℃.
7. The method of claim 2 or 6, wherein: the reaction time of the etherification reaction is more than 5 hours.
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| CN116217524A (en) * | 2023-02-23 | 2023-06-06 | 中国科学院广州能源研究所 | Method for synthesizing 5-ethoxymethyl furfural by catalyzing biomass or derivative thereof with modified polyurethane sponge carbon |
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