CN106397373B - A kind of preparation method of furfuryl group alkyl ether - Google Patents
A kind of preparation method of furfuryl group alkyl ether Download PDFInfo
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- CN106397373B CN106397373B CN201610812312.1A CN201610812312A CN106397373B CN 106397373 B CN106397373 B CN 106397373B CN 201610812312 A CN201610812312 A CN 201610812312A CN 106397373 B CN106397373 B CN 106397373B
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- furfuryl
- alkyl ether
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- -1 furfuryl group alkyl ether Chemical class 0.000 title description 22
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims abstract description 127
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 4
- 150000005215 alkyl ethers Chemical class 0.000 claims abstract 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 6
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 claims description 4
- 229940058352 levulinate Drugs 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 claims 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- 229910006404 SnO 2 Inorganic materials 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 58
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 29
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 24
- 229910052593 corundum Inorganic materials 0.000 description 23
- 229910001845 yogo sapphire Inorganic materials 0.000 description 23
- 235000019441 ethanol Nutrition 0.000 description 12
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 5
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 5
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 5
- 229940035423 ethyl ether Drugs 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- UJEGHEMJVNQWOJ-UHFFFAOYSA-N 1-heptoxyheptane Chemical compound CCCCCCCOCCCCCCC UJEGHEMJVNQWOJ-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种糠醇和一元醇反应得到糠基烷基醚的制备方法。所述制备方法包括如下步骤：在反应釜中将糠醇溶于一元醇中，然后加入催化剂，150‑260℃下反应1至24小时后即可生成糠基烷基醚。所述制备方法工艺简单，易于控制，仅采用无机金属氧化物作为催化剂，不添加有机酸碱或无机酸碱等助催化剂，便于催化剂的分离等操作，有利于大规模工业化生产。The invention discloses a preparation method of furfuryl alkyl ether obtained by reacting furfuryl alcohol and monohydric alcohol. The preparation method includes the following steps: dissolving furfuryl alcohol in monoalcohol in a reaction kettle, then adding a catalyst, and reacting at 150-260° C. for 1 to 24 hours to generate furfuryl alkyl ether. The preparation method is simple in process, easy to control, only uses inorganic metal oxides as catalysts, and does not add cocatalysts such as organic acid-base or inorganic acid-base, which is convenient for operations such as catalyst separation, and is beneficial to large-scale industrial production.
Description
Technical field
The present invention relates to the field of chemical synthesis, react to obtain the system of furfuryl group alkyl ether more particularly to furfuryl alcohol and monohydric alcohol
Preparation Method.
Background technique
Furfuryl group alkyl ether is a kind of important industrial chemicals, it can be used to synthetic drug, be used as food additives, such as adjust
Taste agent, its octane number is very high, may be used as gasoline cetane number improver (US20110035991).Furfuryl group alkyl ether can be with
Generation is directly etherified by furfuryl alcohol and monohydric alcohol, but since the furfuryl group alkyl ether yield there are more side reaction, obtained is very low,
For example, US20110035991 patent research acidic molecular sieve solid acid catalysis furfuryl alcohol and ethyl alcohol etherificate prepare furfuryl group ethylether,
Due to the presence of by-product ethyl levulinate and furfuryl alcohol resin, the furfuryl group ethylether yield of highest 27% is only obtained.Document
(Catalysis Communications 2015,58,76-79) is catalyzed furfuryl alcohol with the acidic molecular sieve ZSM-5 that silica alumina ratio is 25
Furfuryl group ethylether is prepared with ethyl alcohol etherificate, the selectivity of furfuryl group ethylether is only 44.8%.
Preparing the method for furfuryl group alkyl ether at present, that there are yields is low, therefore the shortcomings that high production cost, causes furfuryl group alkyl
Ether it is expensive.
Summary of the invention
Aiming at the problems existing in the prior art, the purpose of the present invention is develop a kind of preparation side of new furfuryl group alkyl ether
Method, wherein using metal oxide as catalyst, catalysis furfuryl alcohol that can be highly selective and unitary is etherified prepares furfuryl group alkane
Base ether effectively prevent or reduces the generation of by-product furfuryl alcohol resin and levulinate.
To achieve the goals above, the technical scheme adopted by the invention is as follows furfuryl alcohol is dissolved in monohydric alcohol in a kettle,
Under the conditions of existing for the catalyst, furfuryl alcohol with unitary is etherified prepares furfuryl group alkyl ether, shown in reaction process following reaction formula 1:
More specifically, the preparation method of furfuryl group alkyl ether according to the present invention includes the following steps:
Furfuryl alcohol is dissolved in monohydric alcohol in a kettle, until the mass percent concentration of the furfuryl alcohol is 1wt to 80wt%,
Then it is added catalyst, the mass ratio of the catalyst and furfuryl alcohol is 0.1:1 to 4:1, is reacted 1 to 24 hour at 150-260 DEG C
Furfuryl group alkyl ether is produced afterwards.Mixture of reaction products passes through Filtration of catalyst, then by way of rectification under vacuum,
Rectification temperature is controlled, unreacted monohydric alcohol is first removed, then improve rectification temperature, collects the furfuryl group alkyl ether of generation, furfuryl alcohol resin
The by-products such as rouge and levulinate can be stayed in kettle and be not distilled out of since boiling point is higher than corresponding furfuryl group alkyl ether.
Wherein, the monohydric alcohol is selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, 2- butanol, n-amyl alcohol, 2- penta
Alcohol, n-hexyl alcohol, 2- hexanol, n-heptanol, 2- enanthol, n-octyl alcohol, sec-n-octyl alcohol.
The concentration of the reaction substrate furfuryl alcohol is preferably 1wt% to 50wt%, further preferred 1wt%, 2wt%,
10wt%, 15wt%, 20wt%, 35wt% or 50wt%.
The catalyst is selected from Al2O3、CeO2、SnO2、SiO2、Fe2O3、TiO2、ZrO2、V2O5、Nb2O5、Cr2O3、MoO2、
WO3、MnO2、RuO2、CoO、NiO、CuO、Ag2O、ZnO、CdO、B2O3One of or it is a variety of.
The reaction temperature is preferably 170 DEG C to 200 DEG C, and the reaction time is preferably 1 to 12 hour, and more preferably 1 to 6 is small
When, most preferably 3 hours.
The preparation method of furfuryl group alkyl ether according to the present invention only with inorganic, metal oxide as catalyst, no
Add the co-catalysts such as organic acids and base or inorganic acid alkali.
Beneficial effect
The preparation method simple process of furfuryl group alkyl ether according to the present invention, it is easily controllable, only with inorganic metal
Object does not add the co-catalysts such as organic acids and base or inorganic acid alkali as catalyst, convenient for the operation such as separation of catalyst, is conducive to
Large-scale industrial production.
Specific embodiment
It tends to form a variety of by-products in the preparation method of furfuryl group alkyl ether, such as passes through ring-opening reaction or condensation
Reaction etc. forms the ester containing ketone group or furfuryl alcohol resin etc., and reaction process is as follows:
Molecular water generation is had after furfuryl alcohol and unitary are etherified, furfuryl group ether, which can further be reacted with the molecular water, generates second
Acyl propionic ester, furfuryl alcohol itself can also occur dehydration polymerization and generate furfuryl alcohol resin.Therefore how to avoid the formation of by-product is very
Important content.The catalyst used in the preparation method of furfuryl group alkyl ether according to the present invention can promote reaction of the invention
It carries out, and adverse effect, suitable catalyst reply levulinate and furfuryl alcohol resin not will cause to reaction yield, purification etc.
Generation show inertia.The preparation method of furfuryl group alkyl ether according to the present invention can be produced using commercially available catalyst
Product, such as Al2O3、CeO2、SnO2、SiO2、Fe2O3、TiO2、ZrO2、V2O5、Nb2O5、Cr2O3、MoO2、WO3、MnO2、RuO2、
CoO、NiO、CuO、Ag2O、ZnO、CdO、B2O3One of or it is a variety of.
The mass ratio of the catalyst and furfuryl alcohol is 0.1:1 to 4:1, if the mass ratio is less than 0.1:1, i.e. catalyst
Deficiency, then reaction speed is low；If the mass ratio is greater than 4:1, i.e. catalyst excess, then reaction is difficult to control and not enough passes through
Ji.
The reaction temperature is 150-260 DEG C, if reaction temperature is too low, is unfavorable for reaction and goes on smoothly, if reaction
Temperature is excessively high, and the requirement to reactor is very high, is unfavorable for being safely operated.
Hereinafter, will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims used in term should not be construed as being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of the appropriate principle for defining term to carry out best interpretations, according to meaning corresponding with technical aspect of the invention and generally
Thought explains.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The range of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.Following embodiment is enumerated only as the example of embodiment of the present invention, not to this hair
Bright composition any restrictions, it will be appreciated by those skilled in the art that modification in the range of without departing from essence and design of the invention
Each fall within protection scope of the present invention.Unless otherwise indicated, the reagent and instrument used in following embodiment is commercially available
Product.
Embodiment 1
In 200ml reaction kettle, 1g furfuryl alcohol is added in 99g methanol, furfuryl alcohol concentration is 1wt%, and 0.5g is added later
Al2O3, react 10 hours at lower 160 DEG C of stirring condition.After the reaction was completed, the product obtained obtains pure after filtering, rectifying separation
Product, gas-chromatography confirm that furfuryl group methyl ether purity is greater than 99%, yield 98%.
Embodiment 2
In addition to 5g furfuryl alcohol to be added in 95g methanol, furfuryl alcohol concentration is other than 5wt%, according to the identical mode system of embodiment 1
Standby furfuryl group methyl ether, yield 97%.
Embodiment 3
In addition to 10g furfuryl alcohol to be added in 95g methanol, furfuryl alcohol concentration is other than 10wt%, according to the identical mode of embodiment 1
Prepare furfuryl group methyl ether, yield 95%.
Embodiment 4
In addition to by 20g furfuryl alcohol be added 80g methanol in, furfuryl alcohol concentration be 20wt% other than, furfuryl alcohol concentration be 20wt% other than,
Furfuryl group methyl ether, yield 93% are prepared according to the identical mode of embodiment 1.
Embodiment 5
In addition to 35g furfuryl alcohol to be added in 65g methanol, furfuryl alcohol concentration is other than 35wt%, according to the identical mode of embodiment 1
Prepare furfuryl group methyl ether, yield 89%.
Embodiment 6
In addition to 50g furfuryl alcohol to be added in 50g methanol, furfuryl alcohol concentration is other than 50wt%, according to the identical mode of embodiment 1
Prepare furfuryl group methyl ether, yield 85%.
Embodiment 7
In 200ml reaction kettle, 15g furfuryl alcohol is added in 85g ethyl alcohol, furfuryl alcohol concentration is 15wt%, and 15g is added later
SnO2, react 20 hours at lower 150 DEG C of stirring condition, yield 85%.
Embodiment 8
Other than setting 160 DEG C for reaction temperature, furfuryl group ether, yield are prepared according to the identical mode of embodiment 7
It is 90%.
Embodiment 9
Other than setting 170 DEG C for reaction temperature, furfuryl group ether, yield are prepared according to the identical mode of embodiment 7
It is 91%.
Embodiment 10
Other than setting 180 DEG C for reaction temperature, furfuryl group ether, yield are prepared according to the identical mode of embodiment 7
It is 93%.
Embodiment 11
Other than setting 200 DEG C for reaction temperature, furfuryl group ether, yield are prepared according to the identical mode of embodiment 7
It is 95%.
Embodiment 12
Other than setting 220 DEG C for reaction temperature, furfuryl group ether, yield are prepared according to the identical mode of embodiment 7
It is 93%.
Embodiment 13
Other than setting 260 DEG C for reaction temperature, furfuryl group ether, yield are prepared according to the identical mode of embodiment 7
It is 94%.
Embodiment 14
In 200ml reaction kettle, 10g furfuryl alcohol is added in 90g methanol, furfuryl alcohol concentration is 10wt%, and 10g is added later
Al2O3, react 8 hours at lower 200 DEG C of stirring condition, furfuryl group methyl ether yield is 88%.
Embodiment 15
Other than replacing methanol with ethyl alcohol, furfuryl group ether, yield 90% are prepared according to the identical mode of embodiment 14.
Embodiment 16
Other than replacing methanol with normal propyl alcohol, furfuryl group positive propyl ether is prepared according to the identical mode of embodiment 14, yield is
91%.
Embodiment 17
Other than replacing methanol with isopropanol, furfuryl group isopropyl ether is prepared according to the identical mode of embodiment 14, yield is
93%.
Embodiment 18
Other than replacing methanol with n-butanol, furfuryl group butyl ether is prepared according to the identical mode of embodiment 14, yield is
89%.
Embodiment 19
Other than replacing methanol with 2- butanol, furfuryl group -2- butyl ether is prepared according to the identical mode of embodiment 14, yield is
92%.
Embodiment 20
Other than replacing methanol with n-amyl alcohol, furfuryl group amyl ether is prepared according to the identical mode of embodiment 14, yield is
92%.
Embodiment 21
Other than replacing methanol with 2- amylalcohol, furfuryl group -2- amyl ether is prepared according to the identical mode of embodiment 14, yield is
93%.
Embodiment 22
Other than replacing methanol with n-hexyl alcohol, furfuryl group hexyl ether is prepared according to the identical mode of embodiment 14, yield is
92%.
Embodiment 23
Other than replacing methanol with 2- hexanol, furfuryl group -2- hexyl ether is prepared according to the identical mode of embodiment 14, yield is
93%.
Embodiment 24
Other than replacing methanol with n-heptanol, furfuryl group heptyl ether is prepared according to the identical mode of embodiment 14, yield is
91%.
Embodiment 25
Other than replacing methanol with 2- enanthol, furfuryl group -2- heptyl ether is prepared according to the identical mode of embodiment 14, yield is
88%.
Embodiment 26
Other than replacing methanol with n-octyl alcohol, furfuryl group octyl ether is prepared according to the identical mode of embodiment 14, yield is
89%.
Embodiment 27
Other than replacing methanol with sec-n-octyl alcohol, furfuryl group -2- octyl ether is prepared according to the identical mode of embodiment 14, yield is
90%.
Embodiment 28
In 200ml reaction kettle, 16g furfuryl alcohol is added in 84g n-butanol, furfuryl alcohol concentration is 16wt%, and 8g is added later
Al2O3, react 10 hours at lower 180 DEG C of stirring condition, furfuryl group butyl ether yield is 92%.
Embodiment 29
In addition to CeO2Replace Al2O3In addition, furfuryl group butyl ether, yield 94% are prepared according to the identical mode of embodiment 28.
Embodiment 30
In addition to SnO2Replace Al2O3In addition, furfuryl group butyl ether, yield 91% are prepared according to the identical mode of embodiment 28.
Embodiment 31
In addition to SiO2Replace Al2O3In addition, furfuryl group butyl ether, yield 90% are prepared according to the identical mode of embodiment 28.
Embodiment 32
In addition to Fe2O3Replace Al2O3In addition, furfuryl group butyl ether is prepared according to the identical mode of embodiment 28, yield is
95%.
Embodiment 33
In addition to TiO2Replace Al2O3In addition, furfuryl group butyl ether, yield 90% are prepared according to the identical mode of embodiment 28.
Embodiment 34
In addition to ZrO2Replace Al2O3In addition, furfuryl group butyl ether, yield 89% are prepared according to the identical mode of embodiment 28.
Embodiment 35
In addition to V2O5Replace Al2O3In addition, furfuryl group butyl ether, yield 88% are prepared according to the identical mode of embodiment 28.
Embodiment 36
In addition to Nb2O5Replace Al2O3In addition, furfuryl group butyl ether is prepared according to the identical mode of embodiment 28, yield is
89%.
Embodiment 37
In addition to Cr2O3Replace Al2O3In addition, furfuryl group butyl ether is prepared according to the identical mode of embodiment 28, yield is
89%.
Embodiment 38
In addition to MoO2Replace Al2O3In addition, furfuryl group butyl ether, yield 88% are prepared according to the identical mode of embodiment 28.
Embodiment 39
In addition to WO3Replace Al2O3In addition, furfuryl group butyl ether, yield 89% are prepared according to the identical mode of embodiment 28.
Embodiment 40
In addition to MnO2Replace Al2O3In addition, furfuryl group butyl ether, yield 87% are prepared according to the identical mode of embodiment 28.
Embodiment 41
In addition to RuO2Replace Al2O3In addition, furfuryl group butyl ether, yield 90% are prepared according to the identical mode of embodiment 28.
Embodiment 42
In addition to replacing Al with CoO2O3In addition, furfuryl group butyl ether, yield 91% are prepared according to the identical mode of embodiment 28.
Embodiment 43
In addition to replacing Al with NiO2O3In addition, furfuryl group butyl ether, yield 89% are prepared according to the identical mode of embodiment 28.
Embodiment 44
In addition to replacing Al with CuO2O3In addition, furfuryl group butyl ether, yield 88% are prepared according to the identical mode of embodiment 28.
Embodiment 45
In addition to Ag2O replaces Al2O3In addition, furfuryl group butyl ether, yield 92% are prepared according to the identical mode of embodiment 28.
Embodiment 46
In addition to replacing Al with ZnO2O3In addition, furfuryl group butyl ether, yield 91% are prepared according to the identical mode of embodiment 28.
Embodiment 47
In addition to replacing Al with CdO2O3In addition, furfuryl group butyl ether, yield 88% are prepared according to the identical mode of embodiment 28.
Embodiment 48
In addition to B2O3Replace Al2O3In addition, furfuryl group butyl ether, yield 88% are prepared according to the identical mode of embodiment 28.
Comparative example 1
In addition to replacing 8g Al with the hydrochloric acid of 3g 37wt%2O3In addition, furfuryl group fourth is prepared according to the identical mode of embodiment 28
Ether, yield 2%.
Comparative example 2
In addition to replacing 8g Al with the 3g concentrated sulfuric acid2O3, other than reaction temperature is adjusted to, according to the identical mode system of embodiment 28
Standby furfuryl group butyl ether, yield 3%.
Comparative example 3
In addition to 3g AlCl3Replace 8g Al2O3, other than reaction temperature is adjusted to, according to the identical mode system of embodiment 28
Standby furfuryl group butyl ether, yield 4%.
Comparative example 4
In addition to 3g AlCl3Replace 8g Al2O3, other than reaction temperature is adjusted to, according to the identical mode system of embodiment 28
Standby furfuryl group butyl ether, yield 4%.
Comparative example 5
In addition to 3g FeCl3Replace 8g Al2O3, other than reaction temperature is adjusted to, according to the identical mode system of embodiment 28
Standby furfuryl group butyl ether, yield 2%.
Comparative example 6
In addition to replacing 8g Al with 4g formic acid2O3, other than reaction temperature is adjusted to, prepared according to the identical mode of embodiment 28
Furfuryl group butyl ether, yield 4%.
Claims (9)
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0037588A1 (en) * | 1980-04-09 | 1981-10-14 | Sumitomo Chemical Company, Limited | Method of preparing furfuryl alcohols |
| US20110035991A1 (en) * | 2007-12-19 | 2011-02-17 | Shell Oil Company | Gasoline composition and process for the preparation of alkylfurfuryl ether |
| CN105348228A (en) * | 2015-09-28 | 2016-02-24 | 李沛轩 | Industrial continuous production method and apparatus for tetrahydrofurfuryl alcohol diethyl ether |
-
2016
- 2016-09-09 CN CN201610812312.1A patent/CN106397373B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0037588A1 (en) * | 1980-04-09 | 1981-10-14 | Sumitomo Chemical Company, Limited | Method of preparing furfuryl alcohols |
| US20110035991A1 (en) * | 2007-12-19 | 2011-02-17 | Shell Oil Company | Gasoline composition and process for the preparation of alkylfurfuryl ether |
| CN105348228A (en) * | 2015-09-28 | 2016-02-24 | 李沛轩 | Industrial continuous production method and apparatus for tetrahydrofurfuryl alcohol diethyl ether |
Non-Patent Citations (2)
| Title |
|---|
| "Graphene Oxide: An Efficient Acid Catalyst for Alcoholysis and Esterification Reactions";Shanhui Zhu et al.;《ChemCatChem》;20140911;第6卷;第3080-3083页 * |
| "Solid acid-catalyzed conversion of furfuryl alcohol to alkyl tetrahydrofurfuryl ether ";Quan Cao et al.;《Catalysis Communications》;20140830;第58卷;第76-79页 * |
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