CN105032427B - A kind of preparation method of 2,5 dimethyl furan - Google Patents
A kind of preparation method of 2,5 dimethyl furan Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of 2,5 dimethyl furans on supported non-precious metal catalyst.It is being on the non-precious metal catalyst of carrier with activated carbon, silica, aluminum oxide, using batch still or fixed bed reactors, the efficient hydrogenolysis of 5 hydroxymethylfurfurals can be converted into 2,5 dimethyl furans under the conditions of relatively mild.In 0.1 5.0 MPa hydrogen pressures, 100 250oAt a temperature of C, using activated carbon as carrier, in fixed bed reactors, the highest yield of 2,5 dimethyl furans can be stablized 80 hours and be basically unchanged up to 95%.Using this technology, by using non-precious metal catalyst, reaction cost is reduced, while on fixed bed reactors, the catalyst shows longer service life, has potential prospects for commercial application.
Description
Technical field
This patent is related to a kind of biomass derivatives 5 hydroxymethyl furfural hydrogenolysis suitable for fixed bed reactors and prepares 2,
The preparation method of 5- dimethyl furans, belong to biomass catalyzing conversion and field of chemical engineering.
Background technology
With the increasingly reduction of fossil energy reserves on the earth, exploitation regenerative resource turns into the task of top priority.Biomass is made
For a kind of reproducible green energy resource, with its low stain, it is widely distributed, total amount is abundant the advantages that more and more by people's
Concern.5 hydroxymethyl furfural（5-hydroxymethylfurfural, HMF）It is a kind of very potential biomass platform
Compound, it can be dehydrated and be made by glucose and fructose, its hydroformylation product solution 2,5- dimethyl furans（2,5-dimethylfuran,
DMF）As a kind of reproducible liquid biomass fuels and additive, compared with ethanol, there is higher energy density, higher
Boiling point and octane number（Octane number：119）, and it is not miscible with water the features such as, therefore have great application prospect.But current
Often there is the problems such as cost is higher, catalyst life is short in production process, limit applications of the DMF in actual production.Therefore,
The cost of catalyst is reduced, selectivity height is developed and can be particularly important with quantity-produced process route.
At present, DMF is prepared mainly under the catalytic action of noble metal by fructose and HMF hydrogenolysis.Dumesic seminars open
Send out a kind of diphasic system and be used for fructose preparation DMF, first using HCl as catalyst, fructose is dehydrated generation HMF, then with Cu:
Ru/C is catalyst, obtains DMF, yield 71%, but the process and dehydration liquid be present need to purifying and the influence of chlorion
（Nature [J].2007,447,982）.Thananatthanachon seminars develop prepares DMF in formic acid system, with
HMF is substrate in HCOOH, H2SO4, Pd/C and tetrahydrofuran (THF) it is existing under the conditions of, DMF yields up to 95%, using fructose as
Substrate, yield is up to 51% (Angew.Chem.Int.Ed [J] .2010,49,6616).Chidambaram seminars develop
DMF preparation in ionic liquid, first using glucose as raw material, phosphomolybdic acid (12-MPA) is catalyst, and acetonitrile is auxiliary agent, from
Sub- liquid chlorine -1- ethyl-3-methylimidazoles（EMIMCl）Or chlorination -1- butyl -3- methylimidazoles（BMIMCl）In be made
HMF, then using Pd/C as catalyst, acetonitrile is auxiliary agent, and HMF is hydrogenated with EMIMCl, is selectively 32% to DMF, but from
Sub- liquid building-up process is complicated, expensive, is still only applicable to the use of laboratory scale at present（Green Chem.[J]
.2010,12,1253）.Ancestral's bright red et al. develops Ru/Co3O4Catalyst is used for HMF hydrogenolysis and prepares DMF, relatively relatively mild
Under the conditions of（130oC, 0.7MPa）, DMF yield is up to 93.4%（Appl. Catal. B Environ.[J].2014,
146,244）.
In summary, it is most of to use noble metal catalyst in the system of existing literature report, cause costly.
Nearest Fu Yao etc.（Chinese patent：CN 103554066 A）Using Ni-W load bimetallic catalyst realize HMF efficiently,
The conversion of high selectivity prepares DMF.But the preparation method temperature and pressure are higher, have higher requirement to consersion unit, together
When add power consumption.
The design philosophy of the present invention is exploitation non-precious metal catalyst, under gentle reaction condition, passes through batch still
DMF is prepared with fixed bed reactors high-efficiency and continuous, DMF selectivity is more than 95%, not only significantly reduces reaction cost and right
The requirement of equipment, and the prospect with industrial applications
The content of the invention
It is an object of the invention to provide a kind of 2,5- dimethyl furans are prepared by raw material hydrogenolysis of 5 hydroxymethyl furfural
Catalyst.The active component of the catalyst mainly includes：Catalyst carrier is used as using activated carbon, silica, alundum (Al2O3)；
By the one or more in carrier loaded base metal Fe, Co, Ni, Cu, wherein it is preferred that in Co, Ni bimetallic active
The heart.Wherein, the carrier such as activated carbon disperses metal height, metal active position is more exposed, and absorption is anti-during the course of the reaction
Answer thing.This high performance deoxidation hydrogenation catalyst is also applied for the deoxidation hydrogenation reaction of other furan derivatives.
The present invention is achieved by the following technical solutions：
Reacted using batch reactor or continous way fixed bed reactors, with different boiling organic solvent, as methanol,
One or more in ethanol, tetrahydrofuran, valerolactone, alkyl phenol, Isosorbide-5-Nitrae-dioxane are as reaction dissolvent, with mass fraction
0.1-50% 5 hydroxymethyl furfural or 5- methylols furfuryl alcohol solution is as reaction raw materials, and reaction temperature is 100-250 DEG C, pressure
Reaction prepares 2,5- dimethyl furans under the conditions of power is 0.1-5MPa.Used catalyst is load type metal catalyst, including group
Divide A and component B：（Ⅰ）Component A is a small amount of for the one or more in the iron of lower valency, cobalt, nickel, copper after the zeroth order of load or reduction
The hydrogenation sites of metal, the mass fraction that metal accounts for carrier are 0.1-30%, its preparation method be coprecipitation, infusion process,
In-situ reducing deposition-precipitation method, it is carried on component B；（Ⅱ）Component B is the carriers such as activated carbon, silica, alundum (Al2O3).
Optimization, catalyst Ni-Co/C,
Optimization, wherein Ni content is 1-10%, and Co content is 2-30%,
Optimization, preparation method is excessive infusion process, and the process includes：
1) according to certain calculating ratio, the mixed solution of excessive cobalt salt, nickel salt is configured, carrier is added and is impregnated,
Obtain impregnation product；
2) impregnation product is dried, obtains the presoma of loaded catalyst；
3) by gained sample at 100-500 DEG C in H2Or H2Reductase 12-6 hours in/Ar gaseous mixture, is obtained required
Catalyst.
The reaction can be carried out in batch reactor or continous way fixed bed.It is anti-according to continous way fixed bed
Should, its reaction condition is：Hydrogen Vapor Pressure 0.1-5MPa, hydrogen flow rate 20-100ml/min, 100-250 DEG C of reaction temperature, raw material
The concentration of liquid is 0.1-50wt%, volume space velocity 0.1-10ml/h.Reacted according to batch still, its condition is：Hydrogen Vapor Pressure
0.1-5MPa, 100-250 DEG C of reaction temperature, the concentration of material liquid is 2-20wt%, reaction time 1-24h.
Specific embodiment：
Fixed bed reaction：
First by catalyst tabletting and 40-60 mesh particles are ground into, by gained sample in 100-500oIn H under C2Or H2/Ar
Gaseous mixture in reductase 12-6 hours, obtain required catalyst.Then it is anti-0.4-2.0 g catalyst to be loaded into stainless steel tubular type
Device is answered, remainder is filled with 40-60 mesh quartz sand to reduce dead volume.Reaction tube is put into reacting furnace fix and hunt leak it is whole
Individual device, Hydrogen Vapor Pressure rise to 0.1-5MPa.Controlling reaction temperature is 100-250oC, gas flow rate 20-100ml/min, 5-
The mass fraction 0.1-50% of hydroxymethylfurfural（Solvent：Methanol, ethanol, tetrahydrofuran, valerolactone, alkyl phenol, 1,4- dioxies six
Ring）, substrate solution injects with liquid phase pump, air speed 0.1-10ml/h, and reaction solution, through condensation, flows after bed after gas-liquid separation
Enter reservoir, take out tank liquid at regular intervals and analyze.
Batch still reacts：
Using mass fraction 2-20% 5 hydroxymethyl furfural or 5- methylol furfuryl alcohol solutions as reaction raw materials（Solvent：First
Alcohol, ethanol, tetrahydrofuran, valerolactone, alkyl phenol, 1,4- dioxane）10ml inputs carry 50ml polytetrafluoroethylliner liners
Intermittent high-pressure reactor, that is, it is 2-20% to control substrate mass concentration, adds above-mentioned load type metal catalyst 0.02-
1.0g, in 100-250oC, 0.1-5MPa hydrogen are depressed, high-speed stirred, are reacted 4-30h, are obtained DMF.
Illustrate technical scheme, but protection scope of the present invention not limited to this with example below.Brief description of the drawings
Accompanying drawing 1 is the yield of 2,5- dimethyl furans in fixed bed reactors in embodiment 6 with the result of time.
Accompanying drawing 2 is the yield of 2,5- dimethyl furans in fixed bed reactors in embodiment 7 with the result of time.
Embodiment 1：
With reference to above-mentioned excessive infusion process, a certain proportion of nickel nitrate, cobalt nitrate, activated carbon and 60ml deionized waters are mixed
Uniformly, so as to get mixture in nickel account for carrier mass fraction be 3%, cobalt account for carrier mass fraction be 15%, this is mixed
Thing impregnates 12h, obtained impregnation product then is placed in into 200 under 200r/min mechanical agitationoDried in C baking oven
12h, by after drying product sieve, it is 40-60 purpose products to obtain particle size, that is, obtain using activated carbon as carrier nickel-
Co catalysts presoma；By it is above-mentioned using activated carbon be the nickel-cobalt catalyst precursor of carrier in H2/ Ar (10%/90%) is mixed
Reduced under the conditions of gas, condition is：With 3oC/min speed heating heating, reduction temperature is from 20oC rises to 450oC, keep
2h, hydrogen-argon-mixed flow are 40ml/min.The nickel-cobalt catalyst using activated carbon as carrier is obtained after reduction.
Embodiment 2-3：
Scheme according to embodiment 1 obtains the nickel-cobalt catalyst using activated carbon as carrier, as different from Example 1
The mass fraction that nickel accounts for carrier in using activated carbon as the nickel-cobalt catalyst of carrier is respectively 6%, 8%.Catalyst in embodiment
Composition, is shown in Table 1.
Embodiment 4-5：
Scheme according to embodiment 1 obtains catalyst, and it is silica to change catalyst carrier as different from Example 1
And alundum (Al2O3).Catalyst composition in embodiment, is shown in Table 1.
Table 1
| Embodiment | The content of nickel（%） | The content of cobalt（%） | Carrier |
| Embodiment 1 | 3 | 15 | Activated carbon |
| Embodiment 2 | 6 | 15 | Activated carbon |
| Embodiment 3 | 8 | 15 | Activated carbon |
| Embodiment 4 | 3 | 15 | SiO2 |
| Embodiment 5 | 3 | 15 | Al2O3 |
Embodiment 6：
12.5g 5 hydroxymethyl furfurals are dissolved in the solution for being made into that concentration of substrate is 2.8% in 500ml tetrahydrofurans, upper
Under the 3%Ni-15%Co-C catalyst actions for stating the preparation of embodiment 1, a successive reaction, reaction temperature 120 is fixedoC, hydrogen
To press as 1.0 MPa, hydrogen flowing quantity 60ml/min, air speed 7.2ml/h, 5 hydroxymethyl furfural converts completely in course of reaction, and 2,
More than 90%, yield is basically unchanged the yield of 5- dimethyl furans for 80 hours（See accompanying drawing 1）
Embodiment 7：
2,5- dimethyl furans are prepared according to the technical scheme of embodiment 6, the difference is that using concentration of substrate to be replaced for 5%
2.8% concentration of substrate in embodiment 6,5 hydroxymethyl furfural converts completely in course of reaction, and the yield of 2,5- dimethyl furans exists
More than 90%, and successive reaction 50 hours, yield is basically unchanged（See accompanying drawing 2）.
Embodiment 8-15：
Batch still catalyst activity is evaluated：0.3g 5 hydroxymethyl furfurals are dissolved in 10ml tetrahydrofurans, using embodiment
1 catalyst, in 50ml batch still, reaction pressure 0.7-3MPa, temperature 120-150oUnder conditions of C, reaction
24h, yield reaction the results are shown in Table 2.
Table 2
Embodiment 16：
Scheme according to embodiment 1 prepares catalyst, changes catalyst metals center as different from Example 1 and is respectively
（1）Iron and cobalt,（2）Copper and cobalt,（3）Iron,（4）Nickel（5）Cobalt,（6）Copper, it is respectively 5%Fe/20%Co-C, 5%Cu/ to obtain catalyst
20%Co-C、20%Fe-C、10%Ni-C、20%Co-C、15%Cu-C。
Above-mentioned catalyst is subjected to activity rating according to the reaction condition of batch still in embodiment 8, the results are shown in Table 3.
Table 3
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Protection scope of the present invention should be defined by the protection domain of claims.
Claims (5)
1. a kind of method that 5 hydroxymethyl furfural hydrogenolysis prepares 2,5- dimethyl furans, using supported non-precious metal catalyst,
Substrate is the organic solution of 5 hydroxymethyl furfural, and reactor is fixed bed reactors or intermittent kettle reactor；The base metal
The mass fraction that metal ingredient accounts for carrier in catalyst is 0.1-30%, and the metal ingredient is iron, one kind in nickel, copper, institute
The carrier for stating supported non-precious metal catalyst is activated carbon, alundum (Al2O3), silica.
2. according to the method for claim 1, it is characterised in that the carrier of the supported non-precious metal catalyst is activity
Charcoal.
3. according to the method for claim 1, it is characterised in that the organic solution of 5 hydroxymethyl furfural is 5 hydroxymethyl furfural
Methanol, ethanol, tetrahydrofuran, valerolactone, alkyl phenol, one or more of solution in 1,4- dioxane.
4. according to the method for claim 1, it is characterised in that the condition of fixed bed reactors is：Hydrogen Vapor Pressure 0.1-
5MPa, hydrogen flow rate 20-100ml/min, 100-250 DEG C of reaction temperature, the concentration of material liquid are 0.1-50wt%, volume space velocity
For 0.1-10ml/h.
5. according to the method for claim 1, it is characterised in that the condition of batch reactor is：Hydrogen Vapor Pressure 0.1-5MPa,
100-250 DEG C of reaction temperature, the concentration of material liquid is 2-20wt%, reaction time 1-24h.
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| CN105597771B (en) * | 2016-03-01 | 2018-05-29 | 中国科学技术大学 | A kind of preparation method of hydrogenolysis catalyst and 2,5- dimethyl furans |
| CN105903481A (en) * | 2016-04-27 | 2016-08-31 | 中国科学院合肥物质科学研究院 | Sulfonyl-functionalized carbon-based metal catalyst and application thereof |
| CN106279075B (en) * | 2016-08-15 | 2018-08-28 | 中国石油大学(北京) | A method of catalysis 5 hydroxymethyl furfural prepares 2,5- dimethyl furans |
| CN106861754B (en) * | 2017-03-02 | 2019-02-12 | 贵州大学 | A kind of modified Pd/C is directly catalyzed the method that carbohydrate prepares 2,5- dimethyl furan |
| CN107398276B (en) * | 2017-07-11 | 2020-02-14 | 中国科学院广州能源研究所 | Catalyst for preparing 2, 5-dimethylfuran by catalyzing selective hydrodeoxygenation of 5-hydroxymethylfurfural and preparation method |
| CN108047174A (en) * | 2017-12-19 | 2018-05-18 | 厦门大学 | The preparation method of one kind 2,5- dimethyl furans |
| CN109364922B (en) * | 2018-11-06 | 2021-08-10 | 中国科学院广州能源研究所 | Biomass carbon-based material high-load nano metal catalyst and preparation method and application thereof |
| CN109503525B (en) * | 2018-12-01 | 2022-03-22 | 烟台大学 | Method for preparing 2, 5-dimethylfuran by hydrogenation of 5-hydroxymethylfurfural |
| CN109678821B (en) * | 2019-01-25 | 2022-08-23 | 沈阳科技学院 | Method for preparing 2, 5-dimethylfuran by catalyzing 5-hydroxymethylfurfural through hydrogenation under normal pressure gas phase |
| CN113117706B (en) * | 2019-12-31 | 2024-04-12 | 中国石油化工股份有限公司 | Metal modified ruthenium-based catalyst and method for preparing 2, 5-furan dicarboxylic acid by catalysis of metal modified ruthenium-based catalyst |
| CN111875566B (en) * | 2020-08-21 | 2022-11-29 | 湖南师范大学 | Method for preparing 2, 5-dimethylfuran |
| CN112892537A (en) * | 2021-01-25 | 2021-06-04 | 大连理工大学 | Preparation method and application of easily-recycled high-selectivity furfural hydrogenation catalyst |
| CN113292519B (en) * | 2021-06-04 | 2023-03-14 | 云南大学 | Magnetic gold-cobalt composite catalyst and preparation method and application thereof |
| CN113773284A (en) * | 2021-09-16 | 2021-12-10 | 厦门大学 | Method for preparing 2, 5-dihydroxymethyl tetrahydrofuran by hydrogenation of 5-hydroxymethylfurfural |
| CN113979837B (en) * | 2021-09-30 | 2024-09-27 | 华东理工大学 | Application of cobalt-based catalyst in hydrogenolysis reaction of biomass and derivative thereof |
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| CN103554066B (en) * | 2013-11-13 | 2016-01-20 | 中国科学技术大学 | A kind of preparation method of 2,5-dimethyl furan |
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