CN108976183A - A method of by preparation by furfural gas phase hydrogenation for gamma-valerolactone - Google Patents
A method of by preparation by furfural gas phase hydrogenation for gamma-valerolactone Download PDFInfo
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- CN108976183A CN108976183A CN201811176306.7A CN201811176306A CN108976183A CN 108976183 A CN108976183 A CN 108976183A CN 201811176306 A CN201811176306 A CN 201811176306A CN 108976183 A CN108976183 A CN 108976183A
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- valerolactone
- gamma
- furfural
- hydrogenation
- gas phase
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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
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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Abstract
The invention discloses a kind of by preparation by furfural gas phase hydrogenation for the method for gamma-valerolactone, it is carried out on fixed bed reactors, raw material furfural enters catalyst bed after preheating in vaporizer with hydrogen together, and furfural hydrogenation, hydration synthesis levulic acid are carried out under metal/solid acid catalyst effect；Levulic acid further adds hydrogen to obtain gamma-valerolactone without isolation, and reaction solution obtains liquid product after gas-liquid separation, condensation, liquid product enters rectifying column, by rectifying, isolated gamma-valerolactone sterling after collecting, hydrogen is recycled, and product purity is high, is suitble to industrialized production.Avoid the separation of intermediate acetyl propionic acid, energy saving；In addition, using gas phase continuous processing, treating capacity is big.
Description
Technical field
The present invention relates to a kind of by preparation by furfural gas phase hydrogenation for the method for gamma-valerolactone, be using cheap furfural as raw material,
It is carried out under metal/solid acid catalyst effect plus hydrogen, hydration synthesis levulic acid, levulic acid further adds hydrogen without isolation
Gamma-valerolactone is obtained, the further isolated product gamma-valerolactone of rectifying has been expanded the route of synthesis of gamma-valerolactone, belonged to
Technical field of fine.
Background technique
Gamma-valerolactone is a kind of important biomass platform chemicals, is had broad application prospects.Gamma-valerolactone has
Fruit flavor, and it is nontoxic, it can be used as food additives；Fuel additive is also served as, or for synthesizing valerate, butyl ketone, fourth
Alkene and long-chain olefin etc., these compounds have higher calorific value, can be used as GOOD TASTE fuel.In addition, gamma-valerolactone is also
Adipic acid can be obtained by carboxylation reaction, and adipic acid is the precursor of synthetic nylon, which achieves from cellulose to
The synthetic route of nylon and so-called " biomass-based nylon ".
In general, gamma-valerolactone is to be hydrolyzed to obtain levulic acid (ester) by cellulose, levulic acid (ester) plus hydrogen cyclisation system
?.The method is primarily present following problems: 1, separating acetylpropionic acid is difficult from biomass hydrolysate, and the separation of levulic acid needs
Consume big energy；2, reaction step is more, complicated for operation, at high cost.Furfural is a kind of important derivatives of hemicellulose,
If one-step method realizes the preparation of gamma-valerolactone from furfural, the above problem can be well solved.There is researcher
(Angew.Chem.Int.Ed., 2013,52,8022-8025) is mixed using B acid and Zr-Beta molecular sieve using 2- butanol as hydrogen source
Conjunction object is catalyst, and hydrogen is added by way of transfer hydrogenation, one step of furfural is made to be converted to gamma-valerolactone, is a green economy
Route.But there are the separation problems of mixed catalyst for the method, and using 2- butanol as hydrogen source, can generate pair during the reaction
The problem of product.The Chinese patent application of Publication No. CN104557801A discloses one kind and urges in multi-function metal/solid acid
In agent, product continues without isolation after furfural hydrogenation hydrolysis plus hydrogen obtains gamma-valerolactone, and furfural conversion ratio reaches 100%,
Gamma-valerolactone selectivity is up to 80% or more.The technique does not have intermediate steps, is not required to carry out other complex operations processing, operation
Simply, process is short, at low cost, and process green reduces the human operation loss of pilot process.But the process is caldron process,
Treating capacity is smaller, in addition, the technique uses a large amount of solvents (mass ratio of solvent and furfural is up to 33), there are solvents to use, returns
Harvest this it is high the problems such as.
Summary of the invention
Goal of the invention: for overcome the deficiencies in the prior art, the present invention provides one kind by preparation by furfural gas phase hydrogenation for γ-
The method of valerolactone, on fixed bed reactors, using furfural as raw material, one step of gas phase hydrogenation on metal/solid acid catalyst
Gamma-valerolactone is obtained, the further isolated product gamma-valerolactone of rectifying, selectivity of product is high, not only overcomes still reaction
The problem of needing using a large amount of solvents, moreover, continuous process has big unit time feed throughput, yield and purity is high
Advantage has good technique application value.
Technical solution:
In order to achieve the above-mentioned object of the invention, the application uses following technical scheme:
A method of it by preparation by furfural gas phase hydrogenation for gamma-valerolactone, is carried out on fixed bed reactors, is by raw material chaff
Aldehyde enters catalyst bed after preheating in vaporizer with hydrogen together, carries out hydrogenation reaction, reaction solution under the action of catalyst
After gas-liquid separation, condensation, liquid product is obtained, liquid product mainly contains gamma-valerolactone (yield > 90%), other by-products
Including 2- methylfuran, furfuryl alcohol, tetrahydrofurfuryl alcohol etc., liquid product enters rectifying column after collecting, by atmospheric distillation, decompression essence
It evaporates, finally obtains the gamma-valerolactone product of purification, hydrogen is recycled.
Metal/the solid acid catalyst prepares (J.Catal., 2011,277,1-13) using equi-volume impregnating,
It is the SiO using copper oxide as active component2、Al2O3, ZSM-5, H β, HY molecular sieve be carrier, and doped with auxiliary agent, auxiliary agent is
ZnO、Fe2O3、Al2O3、ZrO2One or both of (preferably, auxiliary agent is ZnO, only lists in the embodiment below and help
The case where agent is ZnO, but auxiliary agent is Fe2O3、Al2O3、ZrO2When can also implement the invention！)；The quality hundred of active component copper oxide
Score is 10~50%, and the mass percent of carrier is 45~90%, and the mass percent of auxiliary agent is 0~15%.Copper oxide with
And the precursor of auxiliary agent is metal nitrate.
In above-mentioned technical proposal, hydrogenation conditions are as follows: 0.1~3.0MPa of hydrogenation pressure, and hydrogenation reaction temperature is 200
~300 DEG C, the molar ratio of hydrogen and furfural is 1.0~20:1, and the feed volume air speed of furfural is 0.1~1.0h-1。
In above-mentioned technical proposal, the operating condition of the rectifying column are as follows: atmospheric distillation, 50~100 DEG C of bottom temperature, decompression
Rectifying pressure is -0.05~-0.1MPa, and bottom temperature is 50 DEG C~200 DEG C.
The preparation by furfural gas phase hydrogenation that the present invention uses has the advantages that for gamma-valerolactone method
(1) furfural single step reaction obtains gamma-valerolactone, avoids the separation of intermediate acetyl propionic acid, energy saving, hydrogenation
Liquid passes through simple distillation operation, and the gamma-valerolactone product of high-purity can be obtained；
(2) continuous processing is used, treating capacity is big, and it is at low cost, it is suitble to industrialized production；
(3) reaction process greatly reduces use, the cost recovery of solvent without using solvent；
(4) catalyst life is long, stable operation 1000h or more.
Specific embodiment
Below in conjunction with specific embodiment to further illustrate the technical scheme of the present invention.
Metal/solid acid catalyst bibliography (J.Catal., 2011,277,1-13) preparation, specific preparation process is such as
Under:
(1) load capacity for pressing CuO and auxiliary agent, calculates the quality of copper nitrate and metal promoter nitrate, is dissolved in pure water
In, matched liquor capacity is the Kong Rong of carrier, and the metal promoter nitrate is zinc nitrate, ferric nitrate, aluminum nitrate, zirconium nitrate
One or both of；
(2) 50.0g carrier is weighed, is uniformly dripped on carrier with the solution of above-mentioned CuO and auxiliary agent, carrier just absorbs whole
Solution carries out incipient impregnation, and dip time is for 24 hours；
(3) in 120 DEG C of dry 12h, 400 DEG C of roasting 4h are later to get final catalyst.
Embodiment 1
20.0g CuO-ZnO/ZSM-5 catalyst, the catalyst are packed into the reaction tube flat-temperature zone of fixed bed reactors
CuO load capacity is that 30%, ZnO load capacity is 5%, remaining is carrier.
Catalyst is in the lower 250 DEG C of reduction 4h of hydrogen atmosphere.Hydrogen and furfural are that 10:1 enters reactor in molar ratio, add hydrogen
Pressure is normal pressure, and hydrogenation reaction temperature is 250 DEG C, and the feed volume air speed of furfural is 0.2h-1.Material after reaction is through gas-liquid point
After device, the fresh air of vapor phase hydrogen and supplement enters in hydrogenator together.Liquid product enters rectifying column, first often
Pressure distillation obtains 2- methylfuran and 2- methyltetrahydrofuran product, then rectification under vacuum, and pressure is -0.095MPa, obtains product
Gamma-valerolactone.
The liquid product that hydrogenator outlet is collected is analyzed, the conversion ratio of furfural reaches 99.5%, gamma-valerolactone selection
Property 90.4%, 2- methylfuran 5.5%, 2- of selectivity methyltetrahydrofuran selectivity 2.1%, other products be tetrahydrofurfuryl alcohol,
Furfuryl alcohol etc..Isolated gamma-valerolactone purity >=99.5% of rectifying column.
The catalyst of embodiment 1-9 is as shown in table 1, using procatalyst in the lower 250 DEG C of reduction 4h of hydrogen atmosphere.
Table 1
In above-mentioned table 1, the load capacity for only embodying copper oxide is 30wt%, and the load capacity of auxiliary agent is 5%, the load of carrier
Amount is the situation of surplus.The mass percent that inventor has also investigated copper oxide in fact is 10~50%, the quality percentage of auxiliary agent
The case where number is 0~15%, and the load capacity of carrier vector is the head and the tail endpoint in the numberical range of surplus, but because in table 1
The situation of each component load capacity is optimum condition, therefore table 1 only lists the situation, and experiment condition hereafter is according to the condition
Under examined.
The reaction condition of embodiment 1-9 is as shown in table 2:
Table 2
The operable hydrogenation conditions of institute of the invention are as follows: 0.1~3.0MPa of hydrogenation pressure, hydrogenation reaction temperature are
200~300 DEG C, the molar ratio of hydrogen and furfural is 1.0~20:1, and the feed volume air speed of furfural is 0.1~1.0h-1.Rectifying
The operating condition of tower are as follows: atmospheric distillation, 50~100 DEG C of bottom temperature, rectification under vacuum pressure is -0.05~-0.1MPa, tower reactor temperature
Degree is 50 DEG C~200 DEG C.
Table 2 only enumerates: 0.1~0.5MPa of hydrogenation pressure, and hydrogenation reaction temperature is 230-270 DEG C, hydrogen and furfural
Molar ratio is 5:1-15:1, and the feed volume air speed of furfural is 0.2h-1, rectification under vacuum pressure is the reaction condition of -0.095MPa,
It is because more preferably experiment effect can be obtained under the reaction condition of table 2.Reaction product obtained by embodiment 1-9 is as shown in table 3:
Table 3
From the data in table 3, it can be seen that the catalyst that embodiment 2 uses is Cu-ZnO/SiO2, SiO2Support acidity is very weak, generates and produces
Object is based on 2- methylfuran, other carriers are the molecular sieve of highly acid, and the product of generation is based on penta lactones.
Embodiment 10
By the identical reaction process condition of embodiment 1, the long period stability examination of CuO-ZnO/ZSM-5 catalyst is carried out
It tests.The liquid product for collecting hydrogenator outlet is analyzed, and analysis the results are shown in Table 4.
The stability test result of 4 furfuraldehyde hydrogenation catalyst of table
From the data in table 4, it can be seen that CuO-ZnO/ZSM-5 catalyst is with good stability, after the continuous 1000h of catalyst,
Furfural conversion ratio is still maintained at 97% or more, and γ-penta lactones selectively up to 88.5%, which has good industry
Application prospect.
Claims (6)
1. it is a kind of by preparation by furfural gas phase hydrogenation for the method for gamma-valerolactone, carried out on fixed bed reactors, raw material furfural and hydrogen
Gas enters catalyst bed after preheating in vaporizer together, carries out furfural hydrogenation, water under metal/solid acid catalyst effect
Synthesis levulic acid；Levulic acid further adds hydrogen to obtain gamma-valerolactone without isolation, and reaction solution is through gas-liquid separation, condensation
Afterwards, liquid product is obtained, liquid product enters rectifying column after collecting, by rectifying, isolated gamma-valerolactone sterling, hydrogen
It is recycled.
2. it is described in claim 1 by preparation by furfural gas phase hydrogenation for the method for gamma-valerolactone, which is characterized in that metal/solid acid
Catalyst is prepared using equi-volume impregnating, is the SiO using copper oxide as active component2、Al2O3, ZSM-5, H β, HY molecular sieve be
Carrier, and doped with auxiliary agent, auxiliary agent ZnO, Fe2O3、Al2O3、ZrO2One or both of.
3. it is as claimed in claim 2 by preparation by furfural gas phase hydrogenation for the method for gamma-valerolactone, it is characterised in that active component oxidation
The mass percent of copper is 10 ~ 50%, and the mass percent of carrier is 45 ~ 90%, and the mass percent of auxiliary agent is 0 ~ 15%.
4. it is described in claim 1 by preparation by furfural gas phase hydrogenation for the method for gamma-valerolactone, it is characterised in that the catalyst
Hydrogen reducing need to be used before use in reactor, reduction temperature is 200 ~ 300 DEG C, and the recovery time is 2 ~ 8 h.
5. it is described in claim 1 by preparation by furfural gas phase hydrogenation for the method for gamma-valerolactone, which is characterized in that hydrogenation reaction item
Part is as follows: 0.1 ~ 3.0 MPa of hydrogenation pressure, and hydrogenation reaction temperature is 200 ~ 300 DEG C, and the molar ratio of hydrogen and furfural is 1.0 ~
20:1, the feed volume air speed of furfural are 0.1 ~ 1.0 h-1。
6. it is described in claim 1 by preparation by furfural gas phase hydrogenation for the method for gamma-valerolactone, which is characterized in that the behaviour of rectifying column
Make condition are as follows: atmospheric distillation, 50 ~ 100 DEG C of bottom temperature, rectification under vacuum pressure is -0.05 ~ -0.1 MPa, bottom temperature 50
℃~200℃。
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| Application Number | Priority Date | Filing Date | Title |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563674A (en) * | 2019-07-25 | 2019-12-13 | 宏业生物科技股份有限公司 | Device and method for preparing furfuryl alcohol |
| CN112694459A (en) * | 2020-12-08 | 2021-04-23 | 中科合成油技术有限公司 | Method for continuously preparing gamma-valerolactone from furfuryl alcohol by one-step method |
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|---|---|---|---|---|
| US20120302767A1 (en) * | 2011-05-25 | 2012-11-29 | Dumesic James A | PRODUCTION OF LEVULINIC ACID, FURFURAL, AND GAMMA VALEROLACTONE FROM C5 and C6 CARBOHYDRATES IN MONO- AND BIPHASIC SYSTEMS USING GAMMA- VALEROLACTONE AS A SOLVENT |
| CN103917532A (en) * | 2011-11-03 | 2014-07-09 | 赫多特普索化工设备公司 | Process for the production of hydrocarbons |
| CN104557801A (en) * | 2014-10-31 | 2015-04-29 | 华东理工大学 | Method for preparing gamma-valerolactone from furfural on metal/solid acid catalyst |
| CN105148923A (en) * | 2015-10-10 | 2015-12-16 | 中国科学院山西煤炭化学研究所 | Preparation method for Cu-based hydrogenation catalyst |
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2018
- 2018-10-10 CN CN201811176306.7A patent/CN108976183B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120302767A1 (en) * | 2011-05-25 | 2012-11-29 | Dumesic James A | PRODUCTION OF LEVULINIC ACID, FURFURAL, AND GAMMA VALEROLACTONE FROM C5 and C6 CARBOHYDRATES IN MONO- AND BIPHASIC SYSTEMS USING GAMMA- VALEROLACTONE AS A SOLVENT |
| CN103917532A (en) * | 2011-11-03 | 2014-07-09 | 赫多特普索化工设备公司 | Process for the production of hydrocarbons |
| CN104557801A (en) * | 2014-10-31 | 2015-04-29 | 华东理工大学 | Method for preparing gamma-valerolactone from furfural on metal/solid acid catalyst |
| CN105148923A (en) * | 2015-10-10 | 2015-12-16 | 中国科学院山西煤炭化学研究所 | Preparation method for Cu-based hydrogenation catalyst |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563674A (en) * | 2019-07-25 | 2019-12-13 | 宏业生物科技股份有限公司 | Device and method for preparing furfuryl alcohol |
| CN110563674B (en) * | 2019-07-25 | 2023-05-05 | 宏业生物科技股份有限公司 | Device and method for preparing furfuryl alcohol |
| CN112694459A (en) * | 2020-12-08 | 2021-04-23 | 中科合成油技术有限公司 | Method for continuously preparing gamma-valerolactone from furfuryl alcohol by one-step method |
| CN112694459B (en) * | 2020-12-08 | 2022-09-02 | 中科合成油技术股份有限公司 | Method for continuously preparing gamma-valerolactone from furfuryl alcohol by one-step method |
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