CN105884616B - A kind of technique that furfural two step method continuously prepares methyl ester levulinate - Google Patents
A kind of technique that furfural two step method continuously prepares methyl ester levulinate Download PDFInfo
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- CN105884616B CN105884616B CN201610331782.6A CN201610331782A CN105884616B CN 105884616 B CN105884616 B CN 105884616B CN 201610331782 A CN201610331782 A CN 201610331782A CN 105884616 B CN105884616 B CN 105884616B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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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
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
Abstract
The invention discloses a kind of techniques that furfural two step method continuously prepares methyl ester levulinate.The step of technique, is as follows：1) supported non-precious metal catalyst is filled in situ plus in hydrogen fixed bed reactors, the filled solid acid catalyst in acid catalysis alcoholysis fixed bed reactors；2) furfural is dissolved in isopropanol and forms homogeneous phase solution, solution is pressurizeed by metering pump 1, preheater 1 is continuously added to react in add in-place hydrogen fixed bed reactors after preheating；3) reaction solution is detached through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating；4) reaction solution is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product.It is big that this technique realizes methyl ester levulinate continuous production, treating capacity, and long-play catalytic activity is stable, product yield high, is suitble to heavy industrialization application, has good industrial applications foreground.
Description
Technical field
The present invention relates to the technique that furfural continuously prepares methyl ester levulinate, especially a kind of furfural two step method is continuously prepared
The technique of methyl ester levulinate.
Background technology
Biomass is a kind of important renewable resource, and important chemical industry platform chemicals have been prepared using biomass resource
Through as the important research topic of chemical field.China's biomass annual output is more than 2,100,000,000 tons, and wherein agricultural stalk is more than 700,000,000
Ton, tree growth law are more than 1,400,000,000 tons.Biomass components are mainly cellulose, hemicellulose and lignin, and the content of three accounts for
90% or more of biomass total amount；Wherein, furfural is that hemicellulose sets out most important primary product.
Methyl ester levulinate (molecular formula：C6H10O3, CAS No.：624-45-3) it is short-chain aliphatic ester, it is one
The important organic chemicals of class can be directly used as fragrance, food additives, gasoline additive and biological liquid fuel etc., knot
Structure formula is as shown below.
Methyl ester levulinate structural formula
Mainly there are three by the approach of Production of Levulinic Acid from Biomass methyl esters：Levulic acid esterification, furfuryl alcohol alcoholysis, furfural are urged
Change and adds hydrogen combination alcoholysis.
Levulic acid is esterified approach：It is fairly simple that levulic acid esterification prepares methyl ester levulinate, (the Song such as Song D
D,An S,Sun Y,Efficient conversion of levulinic acid or furfuryl alcohol into
alkyl levulinates catalyzed by heteropoly acid and ZrO2bifunctionalized
organosilica nanotubes.Journal of Catalysis,2016,333:184-199.) use heteropoly acid catalysis second
Acyl propionic acid prepares methyl ester levulinate, wherein 12.1PW12/ZrO2The methyl ester levulinate of-Si (Et) Si-NTs1.0 optimizations is received
Rate is 99.8%.
Furfuryl alcohol alcoholysis approach：There are many research that furfuryl alcohol alcoholysis prepares methyl ester levulinate, (the Huang Y such as Huang Y B
B,Yang T,Zhou M C,Microwave-assisted alcoholysis of furfural alcohol into
Alkyl levulinates catalyzed by metal salts.Green Chemistry, 2016,18 (6):1516-
1523.) it has studied and methyl ester levulinate, wherein Al is prepared with metal salt catalyst furfuryl alcohol alcoholysis2(SO4)3The levulic acid first of optimization
Ester yield is 80.6%；(Hu X, Wester, Hof R J M, Wu L, the Upgrading biomass-derived such as Hu X
furans via acid-catalysis/hydrogenation:the remarkable difference between
water and methanol as the solvent.Green Chemistry,2015,17(1):219-224.) use
Amberlyst-70 catalysis furfuryl alcohol alcoholysis prepares methyl ester levulinate, and methyl ester levulinate yield is 93%.
Furfural catalytic hydrogenation combination alcoholysis approach：Furfural directly prepares methyl ester levulinate research seldom, at present only Hu
(Hu X, Song Y, the Wu L.One-pot synthesis of levulinic acid/ester from such as X
C5carbohydrates in a methanol medium.ACS Sustainable Chemistry&
Engineering.2013,1(12):1593-1599.) from furfural, in Pt/Al2O3It is catalyzed with Amberlyst-70, H2Item
Under part, the yield that one kettle way prepares methyl ester levulinate is up to 23%；It reacts there are the hydrogen of high energy consumption density cleaning,
The problems such as methyl ester levulinate yield is low, it is difficult to industrialize.
Furfural (molecular formula：C5H4O2, CAS No.：98-01-1) it is a kind of important platform point in biomass transformation process
Son, it is the most important derivative of furans ring system, and chemical property is active, can by aoxidize, be condensed etc. reactions produce it is numerous
Derivative is widely used in the industry such as synthetic plastic, medicine, pesticide；Furfural is acted on by pentose and diluted acid, through hydrolyzing, being dehydrated
It is made with distillation；Also it can use and hydrolyze the preparations such as big wheat husk, sorghum stalk, corncob；There are mainly two types of sides for industrial manufacture furfural
Method：Pressurization is suitble to mass produce, and by raw material and dilute sulfuric acid boiling under elevated pressure, reaction production is taken out of with high pressure or superheated steam
Object obtains alditol finished product after being fractionated into；Non-pressure process is to boil the inorganic salts such as raw material and salt and dilute sulfuric acid altogether, and steam chaff simultaneously
Aldehyde.China is main furfural production state in the world, and annual output is up to 300,000 tons, in recent years due to the pressure of outlet, the price of furfural
It persistently drops, therefore furfural deep process technology is most important for the survival and development of furfural production enterprise.
The conversion process of furfural is lacked ripe continuous reaction process and is had become extensive profit based on high-temperature high-voltage reaction
With the bottleneck of furfural, there is presently no the technique report for preparing methyl ester levulinate from furfural, the present invention from furfural,
It proposes furfural add in-place hydrogen and the reaction of two step of furfuryl alcohol acid catalysis alcoholysis continuously prepares the technique of methyl ester levulinate, reaction equation is such as
Under：
The present invention has the following advantages：
1. first step original position hydrogenation reaction is used as hydrogen supply agent using isopropanol, external offer hydrogen source is not needed, process safety,
The hydrogen of high energy consumption density cleaning is not needed simultaneously；
2. being operated continuously using fixed bed, hydrogenation reaction and acid catalysis alcoholysis reaction in situ all uses solid catalyst, point
It is easy from recycling, inexpensive (using non-precious metal catalyst), long-play catalytic activity is stablized；
3. the yield of good reaction selectivity, methyl ester levulinate reaches as high as 88.6%.
In short, this technique realizes, methyl ester levulinate continuous production, treating capacity are big, and long-play catalytic activity is steady
Fixed, product yield high is suitble to heavy industrialization application, has good industrial applications foreground.
Invention content
The present invention provides the technique that a kind of furfural two step method continuously prepares methyl ester levulinate, processing step is as follows：
1) supported non-precious metal catalyst is filled in situ plus in hydrogen fixed bed reactors, in acid catalysis alcoholysis fixed bed
Filled solid acid catalyst in reactor；
2) furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 10~50%, solution
It is continuously added to react in add in-place hydrogen fixed bed reactors after preheating by the pressurization of metering pump 1, preheater 1, wherein add in-place hydrogen
Fixed bed reactors reaction temperature is 150~210 DEG C, and reaction time is 10~60min, reactor pressure 5MPa；
3) reaction solution is detached through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution, the wherein matter of furfuryl alcohol with methanol
It is 10~50% to measure score, and solution pressurizes through metering pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed reaction after preheating
It is reacted in device, wherein acid catalysis alcoholysis fixed bed reaction temperature is 110~170 DEG C, and reaction time is 10~40min, instead
It is 5MPa to answer device pressure；
4) reaction solution is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product.
Supported non-precious metal catalyst described in this patent step 1) is Cu/Al2O3、Cu/SiO2、Ni/Al2O3、Ni/
SiO2、Ni/C、Cu/MgO-Al2O3、Cu-Ni/Al2O3、Cu-Ni/ZrO2、Cu-Ni/SiO2、Cu-Ni/MgO-Al2O3；Step 1)
Described in solid acid catalyst be HZSM-5, SO3H-SBA-15、Amberlyst-15、Amberlyst-21、Amberlyst-
70；Furfural described in step 2) and the mass fraction of furfural is preferably 15~30% in the homogeneous phase solution of isopropanol；Step 2)
Described in reaction temperature be preferably 170~190 DEG C；Furfuryl alcohol described in step 3) and in the homogeneous phase solution of methanol furfuryl alcohol matter
It is preferably 15~30% to measure score；Reaction temperature described in step 3) is preferably 130~150 DEG C.
Add in-place hydrogen fixed bed reactors and acid catalysis alcoholysis fixed bed reactors are compressive reaction, and pressure control exists
5MPa, by counterbalance valve 1 and 2 pressure controls；Destilling tower 1,2,3 is all air-distillation.
What 1 tower top of destilling tower came out is the mixed liquor of isopropanol and acetone, through the further distillation separation of rectifying column 3, tower top
By-product acetone is obtained, bottom of tower obtains isopropanol can be with reuse；What 2 tower top of destilling tower came out is methanol, can be with reuse.
Description of the drawings
Attached drawing 1 is the process flow chart that a kind of furfural two step method continuously prepares methyl ester levulinate.
Specific implementation mode
Supported non-precious metal catalyst in the present invention used in add in-place hydrogen is prepared using coprecipitation or infusion process.It urges
Detailed process prepared by agent is as follows：
Cu/Al2O3、Cu/MgO-Al2O3、Cu-Ni/Al2O3、Cu-Ni/ZrO2、Cu-Ni/MgO-Al2O3、Ni/Al2O3Specifically
Preparation process is as follows：According to the ratio shared by each component in required catalyst, certain stoicheiometry (activearm is first prepared
Point cation and carrier cation mass ratio) solution, be denoted as solution A.Prepare sodium hydroxide and sodium carbonate mixture, note
For solution B.Solution A and B are slowly dropped to simultaneously in the conical flask containing deionized water, obtain forming uniform precipitation,
Supported non-precious metal catalyst is obtained after being filtered, washed, drying, restore calcining, hydrogen reducing；The mass fraction of copper, nickel
It is 20%.
Cu-Ni/SiO2、Cu/SiO2、Ni/SiO2, Ni/C prepared using infusion process, the specific implementation method of infusion process is first
Certain density nitrate solution is prepared, quantitative carrier is then added and carries out incipient impregnation, through ultrasound, standing, drying, is gone back
Original calcining obtains supported non-precious metal catalyst after hydrogen reducing, copper, nickel mass fraction be 20%.
Catalyst activity component good dispersion degree that is simple by coprecipitation and preparation catalyst process, obtaining.
The solid acid Amberlyst-70 that acid catalysis alcoholysis reaction uses in the present invention is bought in the limited public affairs of Beijing Tao Shi films
Department, Amberlyst-15, Amberlyst-21 purchase are bought in Sigma-Aldrich, HZSM-5 in Nankai University
Catalyst plant；SO3H-SBA-15 makes by oneself.
SO3The specific preparation process of H-SBA-15 is as follows：With P123 (the polyethylene glycol glycerine-embedding aggressiveness of polyethylene glycol)
For template, ethyl orthosilicate (TEOS) is main silicon source, and trimethoxy-propyl sulfydryl silicon (MPTMS) with functional group is
Part silicon source synthesizes under strong oxidized water heat condition, will dissolve in deionized water P123, and be stirred at room temperature, and be added
30min is stirred after concentrated hydrochloric acid, ethyl orthosilicate is added, and be stirred at room temperature.Add MPTMS and hydrogen peroxide, with hydrochloric acid and
The mixed solution of ethyl alcohol washes repeatedly 2 times, removes template P123, SO is dried under vacuum to obtain3H-SBA-15。
Quantitative analysis is carried out using GC-FID in the present invention, concrete analysis condition is as follows：Chromatographic column is Agilent HP-5
Capillary column (30m × 0.32mm × 0.25 μm), injector temperature：0℃；Sample size：1μL；FID detects temperature：320℃；Program
Heating：30 DEG C are kept for 4 minutes, are warming up to 140 DEG C later with the rate of 10 DEG C/min, and then 20 DEG C/min rises to 300 DEG C and keeps 2
Minute.
The yield of this patent is the molar yield on the basis of furfural.Calculation formula is as follows：
Embodiment 1
As shown in Figure 1, filling Cu/MgO-Al in situ plus in hydrogen fixed bed reactors2O3, in acid catalysis alcoholysis fixed bed
Amberlyst-21 is filled in reactor；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural
It is 10%, solution is pressurizeed by metering pump 1, preheater 1 is continuously added to react in add in-place hydrogen fixed bed reactors after preheating,
Middle add in-place hydrogen fixed bed reactors reaction temperature is 150 DEG C, reaction time 60min, reactor pressure 5MPa；Instead
It answers liquid to be flowed out through counterbalance valve 1, is detached through rectifying column 1, bottom of tower obtains furfuryl alcohol and methanol and be mixed to form homogeneous phase solution, wherein furfuryl alcohol
Mass fraction is 10%, and solution pressurizes through metering pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed reactors after preheating
Middle reaction, wherein acid catalysis alcoholysis fixed bed reaction temperature are 110 DEG C, reaction time 40min, and reactor pressure is
5MPa；Reaction solution is flowed out through counterbalance valve 2, is detached through rectifying column 2, bottom of tower obtains methyl ester levulinate product, after stable
Sampling, the molar yield of methyl ester levulinate product are 71.3%, continuous operation for 24 hours after, mole of methyl ester levulinate product
Yield is 71.2%, and yield is not decreased obviously.
Embodiment 2
Fill Cu/MgO-Al in situ plus in hydrogen fixed bed reactors2O3, filled out in acid catalysis alcoholysis fixed bed reactors
Fill Amberlyst-70；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 15%, solution
It is continuously added to react in add in-place hydrogen fixed bed reactors after preheating by the pressurization of metering pump 1, preheater 1, wherein add in-place hydrogen
Fixed bed reactors reaction temperature is 170 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution is through back pressure
Valve 1 flows out, and is detached through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
15%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 150 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 88.6%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 88.4%,
Yield is not decreased obviously.
Embodiment 3
Fill Cu/MgO-Al in situ plus in hydrogen fixed bed reactors2O3, filled out in acid catalysis alcoholysis fixed bed reactors
Fill Amberlyst-70；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 20%, solution
It is continuously added to react in add in-place hydrogen fixed bed reactors after preheating by the pressurization of metering pump 1, preheater 1, wherein add in-place hydrogen
Fixed bed reactors reaction temperature is 170 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution is through back pressure
Valve 1 flows out, and is detached through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
20%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 130 DEG C, reaction time 30min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 85.4%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 85.2%,
Yield is not decreased obviously.
Embodiment 4
Fill Cu/MgO-Al in situ plus in hydrogen fixed bed reactors2O3, filled out in acid catalysis alcoholysis fixed bed reactors
Fill Amberlyst-15；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 30%, solution
It is continuously added to react in add in-place hydrogen fixed bed reactors after preheating by the pressurization of metering pump 1, preheater 1, wherein add in-place hydrogen
Fixed bed reactors reaction temperature is 190 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution is through back pressure
Valve 1 flows out, and is detached through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
30%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 81.3%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 81.2%,
Yield is not decreased obviously.
Embodiment 5
Fill Cu/MgO-Al in situ plus in hydrogen fixed bed reactors2O3, filled out in acid catalysis alcoholysis fixed bed reactors
Fill Amberlyst-70；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 40%, solution
It is continuously added to react in add in-place hydrogen fixed bed reactors after preheating by the pressurization of metering pump 1, preheater 1, wherein add in-place hydrogen
Fixed bed reactors reaction temperature is 190 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution is through back pressure
Valve 1 flows out, and is detached through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
40%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 150 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 72.7%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 72.5%,
Yield is not decreased obviously.
Embodiment 6
Fill Cu/MgO-Al in situ plus in hydrogen fixed bed reactors2O3, filled out in acid catalysis alcoholysis fixed bed reactors
Fill SO3H-SBA-15；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 50%, solution
It is continuously added to react in add in-place hydrogen fixed bed reactors after preheating by the pressurization of metering pump 1, preheater 1, wherein add in-place hydrogen
Fixed bed reactors reaction temperature is 210 DEG C, reaction time 10min, reactor pressure 5MPa；Reaction solution is through back pressure
Valve 1 flows out, and is detached through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
50%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 170 DEG C, reaction time 10min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 62.4%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 62.3%,
Yield is not decreased obviously.
Embodiment 7
Fill Cu-Ni/MgO-Al in situ plus in hydrogen fixed bed reactors2O3, in acid catalysis alcoholysis fixed bed reactors
Fill HZSM-5；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 15%, and solution passes through
The pressurization of metering pump 1, preheater 1 are continuously added to react in add in-place hydrogen fixed bed reactors after preheating, and wherein add in-place hydrogen is fixed
Bed reactor reaction temperature is 170 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution is through counterbalance valve 1
Outflow is detached through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
30%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 170 DEG C, reaction time 10min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 75.2%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 75.1%,
Yield is not decreased obviously.
Embodiment 8
Fill Cu-Ni/MgO-Al in situ plus in hydrogen fixed bed reactors2O3, in acid catalysis alcoholysis fixed bed reactors
Fill SO3H-SBA-15；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 30%, molten
Liquid is pressurizeed by metering pump 1, preheater 1 is continuously added to react in add in-place hydrogen fixed bed reactors after preheating, wherein add in-place
Hydrogen fixed bed reactors reaction temperature is 190 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution is through the back of the body
Pressure valve 1 flows out, and is detached through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution, the wherein mass fraction of furfuryl alcohol with methanol
It is 15%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating,
Middle acid catalysis alcoholysis fixed bed reaction temperature is 150 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution
It flows out through counterbalance valve 2, is detached through rectifying column 2, bottom of tower obtains methyl ester levulinate product, sampled after stable, levulinic
The molar yield of sour methyl esters product be 75.7%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is
75.4%, yield is not decreased obviously.
Embodiment 9
Fill Cu-Ni/SiO in situ plus in hydrogen fixed bed reactors2, filled in acid catalysis alcoholysis fixed bed reactors
Amberlyst-21；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 15%, and solution is logical
It is continuously added to react in add in-place hydrogen fixed bed reactors after crossing the pressurization of metering pump 1, the preheating of preheater 1, wherein add in-place hydrogen is solid
Fixed bed reactor reaction temperature is 170 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
1 outflow, detaches through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
30%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 45.6%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 45.5%,
Yield is not decreased obviously.
Embodiment 10
Fill Cu-Ni/SiO in situ plus in hydrogen fixed bed reactors2, filled in acid catalysis alcoholysis fixed bed reactors
Amberlyst-15；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 30%, and solution is logical
It is continuously added to react in add in-place hydrogen fixed bed reactors after crossing the pressurization of metering pump 1, the preheating of preheater 1, wherein add in-place hydrogen is solid
Fixed bed reactor reaction temperature is 190 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
1 outflow, detaches through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
15%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 46.4%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 46.2%,
Yield is not decreased obviously.
Embodiment 11
Fill Cu-Ni/Al in situ plus in hydrogen fixed bed reactors2O3, filled in acid catalysis alcoholysis fixed bed reactors
HZSM-5；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 15%, and solution passes through metering
1 pressurization of pump, preheater 1 are continuously added to react in add in-place hydrogen fixed bed reactors after preheating, and wherein add in-place hydrogen fixed bed is anti-
It is 170 DEG C, reaction time 40min, reactor pressure 5MPa to answer device reaction temperature；Reaction solution is flowed out through counterbalance valve 1,
It is detached through rectifying column 1, bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the wherein mass fraction of furfuryl alcohol is 30%, molten
Liquid pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein acid catalysis
Alcoholysis fixed bed reaction temperature is 130 DEG C, reaction time 30min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
2 outflows, detach through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, methyl ester levulinate production
The molar yield of product is 46.7%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 46.5%, and yield does not have
It decreased significantly.
Embodiment 12
Fill Cu-Ni/Al in situ plus in hydrogen fixed bed reactors2O3, filled in acid catalysis alcoholysis fixed bed reactors
Amberlyst-15；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 30%, and solution is logical
It is continuously added to react in add in-place hydrogen fixed bed reactors after crossing the pressurization of metering pump 1, the preheating of preheater 1, wherein add in-place hydrogen is solid
Fixed bed reactor reaction temperature is 190 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
1 outflow, detaches through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
15%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 56.7%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 56.3%,
Yield is not decreased obviously.
Embodiment 13
Fill Cu-Ni/ZrO in situ plus in hydrogen fixed bed reactors2, filled in acid catalysis alcoholysis fixed bed reactors
Amberlyst-70；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 15%, and solution is logical
It is continuously added to react in add in-place hydrogen fixed bed reactors after crossing the pressurization of metering pump 1, the preheating of preheater 1, wherein add in-place hydrogen is solid
Fixed bed reactor reaction temperature is 170 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
1 outflow, detaches through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
30%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 170 DEG C, reaction time 10min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 51.3%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 51.2%,
Yield is not decreased obviously.
Embodiment 14
Fill Cu-Ni/ZrO in situ plus in hydrogen fixed bed reactors2, filled in acid catalysis alcoholysis fixed bed reactors
HZSM-5；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 30%, and solution passes through metering
1 pressurization of pump, preheater 1 are continuously added to react in add in-place hydrogen fixed bed reactors after preheating, and wherein add in-place hydrogen fixed bed is anti-
It is 190 DEG C, reaction time 20min, reactor pressure 5MPa to answer device reaction temperature；Reaction solution is flowed out through counterbalance valve 1,
It is detached through rectifying column 1, bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the wherein mass fraction of furfuryl alcohol is 15%, molten
Liquid pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein acid catalysis
Alcoholysis fixed bed reaction temperature is 170 DEG C, reaction time 10min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
2 outflows, detach through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, methyl ester levulinate production
The molar yield of product is 47.5%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 47.2%, and yield does not have
It decreased significantly.
Embodiment 15
Fill Cu/Al in situ plus in hydrogen fixed bed reactors2O3, filled in acid catalysis alcoholysis fixed bed reactors
Amberlyst-21；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 15%, and solution is logical
It is continuously added to react in add in-place hydrogen fixed bed reactors after crossing the pressurization of metering pump 1, the preheating of preheater 1, wherein add in-place hydrogen is solid
Fixed bed reactor reaction temperature is 170 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
1 outflow, detaches through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
30%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 32.4%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 32.2%,
Yield is not decreased obviously.
Embodiment 16
Fill Cu/Al in situ plus in hydrogen fixed bed reactors2O3, filled in acid catalysis alcoholysis fixed bed reactors
SO3H-SBA-15；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 30%, and solution is logical
It is continuously added to react in add in-place hydrogen fixed bed reactors after crossing the pressurization of metering pump 1, the preheating of preheater 1, wherein add in-place hydrogen is solid
Fixed bed reactor reaction temperature is 190 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
1 outflow, detaches through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
15%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 150 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 39.8%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 39.6%,
Yield is not decreased obviously.
Embodiment 17
Fill Cu/SiO in situ plus in hydrogen fixed bed reactors2, filled in acid catalysis alcoholysis fixed bed reactors
Amberlyst-70；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 15%, and solution is logical
It is continuously added to react in add in-place hydrogen fixed bed reactors after crossing the pressurization of metering pump 1, the preheating of preheater 1, wherein add in-place hydrogen is solid
Fixed bed reactor reaction temperature is 170 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
1 outflow, detaches through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
30%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 150 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 28.9%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 28.6%,
Yield is not decreased obviously.
Embodiment 18
Fill Cu/SiO in situ plus in hydrogen fixed bed reactors2, filled in acid catalysis alcoholysis fixed bed reactors
HZSM-5；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 30%, and solution passes through metering
1 pressurization of pump, preheater 1 are continuously added to react in add in-place hydrogen fixed bed reactors after preheating, and wherein add in-place hydrogen fixed bed is anti-
It is 190 DEG C, reaction time 20min, reactor pressure 5MPa to answer device reaction temperature；Reaction solution is flowed out through counterbalance valve 1,
It is detached through rectifying column 1, bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the wherein mass fraction of furfuryl alcohol is 15%, molten
Liquid pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein acid catalysis
Alcoholysis fixed bed reaction temperature is 170 DEG C, reaction time 10min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
2 outflows, detach through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, methyl ester levulinate production
The molar yield of product is 21.3%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 21.1%, and yield does not have
It decreased significantly.
Embodiment 19
Fill Ni/Al in situ plus in hydrogen fixed bed reactors2O3, filled in acid catalysis alcoholysis fixed bed reactors
SO3H-SBA-15；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 15%, and solution is logical
It is continuously added to react in add in-place hydrogen fixed bed reactors after crossing the pressurization of metering pump 1, the preheating of preheater 1, wherein add in-place hydrogen is solid
Fixed bed reactor reaction temperature is 170 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
1 outflow, detaches through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
30%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 150 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 28.9%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 28.6%,
Yield is not decreased obviously.
Embodiment 20
Fill Ni/Al in situ plus in hydrogen fixed bed reactors2O3, filled in acid catalysis alcoholysis fixed bed reactors
Amberlyst-70；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 30%, and solution is logical
It is continuously added to react in add in-place hydrogen fixed bed reactors after crossing the pressurization of metering pump 1, the preheating of preheater 1, wherein add in-place hydrogen is solid
Fixed bed reactor reaction temperature is 190 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
1 outflow, detaches through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
15%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 130 DEG C, reaction time 30min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 28.4%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 28.2%,
Yield is not decreased obviously.
Embodiment 21
Fill Ni/SiO in situ plus in hydrogen fixed bed reactors2, filled in acid catalysis alcoholysis fixed bed reactors
SO3H-SBA-15；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 15%, and solution is logical
It is continuously added to react in add in-place hydrogen fixed bed reactors after crossing the pressurization of metering pump 1, the preheating of preheater 1, wherein add in-place hydrogen is solid
Fixed bed reactor reaction temperature is 170 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
1 outflow, detaches through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
30%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 170 DEG C, reaction time 10min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 17.8%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 17.7%,
Yield is not decreased obviously.
Embodiment 22
Fill Ni/SiO in situ plus in hydrogen fixed bed reactors2, filled in acid catalysis alcoholysis fixed bed reactors
Amberlyst-21；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 30%, and solution is logical
It is continuously added to react in add in-place hydrogen fixed bed reactors after crossing the pressurization of metering pump 1, the preheating of preheater 1, wherein add in-place hydrogen is solid
Fixed bed reactor reaction temperature is 190 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
1 outflow, detaches through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
15%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 19.2%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 19.1%,
Yield is not decreased obviously.
Embodiment 23
Ni/C is filled in situ plus in hydrogen fixed bed reactors, is filled in acid catalysis alcoholysis fixed bed reactors
Amberlyst-15；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 15%, and solution is logical
It is continuously added to react in add in-place hydrogen fixed bed reactors after crossing the pressurization of metering pump 1, the preheating of preheater 1, wherein add in-place hydrogen is solid
Fixed bed reactor reaction temperature is 170 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
1 outflow, detaches through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
30%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C, reaction time 40min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 16.5%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 16.4%,
Yield is not decreased obviously.
Embodiment 24
Ni/C is filled in situ plus in hydrogen fixed bed reactors, is filled in acid catalysis alcoholysis fixed bed reactors
Amberlyst-70；Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 30%, and solution is logical
It is continuously added to react in add in-place hydrogen fixed bed reactors after crossing the pressurization of metering pump 1, the preheating of preheater 1, wherein add in-place hydrogen is solid
Fixed bed reactor reaction temperature is 190 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution is through counterbalance valve
1 outflow, detaches through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution with methanol, and the mass fraction of wherein furfuryl alcohol is
15%, solution pressurizes through metering pump 2, preheater 2 is continuously added to react in acid catalysis alcoholysis fixed bed reactors after preheating, wherein
Acid catalysis alcoholysis fixed bed reaction temperature is 150 DEG C, reaction time 20min, reactor pressure 5MPa；Reaction solution passes through
Counterbalance valve 2 flows out, and is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product, sampled after stable, levulic acid
The molar yield of methyl esters product is 20.4%, continuous operation for 24 hours after, the molar yield of methyl ester levulinate product is 20.3%,
Yield is not decreased obviously.
Claims (6)
1. a kind of technique that furfural two step method continuously prepares methyl ester levulinate, which is characterized in that the step of technique is as follows：
1）Supported non-precious metal catalyst is filled in situ plus in hydrogen fixed bed reactors, in acid catalysis alcoholysis fixed bed reaction
Filled solid acid catalyst in device；The solid acid catalyst is HZSM-5, SO3H-SBA-15、Amberlyst-15、
Amberlyst-21、Amberlyst-70；
2）Furfural is dissolved in isopropanol and forms homogeneous phase solution, wherein the mass fraction of furfural is 10 ~ 50%, and homogeneous phase solution is logical
It is continuously added to react in add in-place hydrogen fixed bed reactors after crossing the pressurization of metering pump 1, the preheating of preheater 1, wherein add in-place hydrogen is solid
Fixed bed reactor reaction temperature is 150 ~ 210 DEG C, and reaction time is 10 ~ 60 min, and reactor pressure is 5 MPa；
3）Reaction solution is detached through rectifying column 1, and bottom of tower obtains furfuryl alcohol and is mixed to form homogeneous phase solution, the wherein quality of furfuryl alcohol point with methanol
Number is 10 ~ 50%, which pressurizes through metering pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed reaction after preheating
It is reacted in device, wherein acid catalysis alcoholysis fixed bed reaction temperature is 110 ~ 170 DEG C, and reaction time is 10 ~ 40 min, reaction
Device pressure is 5 MPa；
4）Reaction solution is detached through rectifying column 2, and bottom of tower obtains methyl ester levulinate product.
2. the technique that a kind of furfural two step method according to claim 1 continuously prepares methyl ester levulinate, it is characterised in that
Step 1）Described in supported non-precious metal catalyst be Cu/Al2O3、Cu/SiO2、Ni/Al2O3、Ni/SiO2、Ni/C、 Cu/
MgO-Al2O3、Cu-Ni/Al2O3、Cu-Ni/ZrO2、Cu-Ni/SiO2 、Cu-Ni/MgO-Al2O3。
3. a kind of technique that furfural two step method continuously prepares methyl ester levulinate according to claim 1, it is characterised in that step
Rapid 2）Described in furfural and isopropanol homogeneous phase solution in furfural mass fraction be 15 ~ 30%.
4. a kind of technique that furfural two step method continuously prepares methyl ester levulinate according to claim 1, it is characterised in that step
Rapid 2）Described in reaction temperature be 170 ~ 190 °C.
5. a kind of technique that furfural two step method continuously prepares methyl ester levulinate according to claim 1, it is characterised in that step
Rapid 3）Described in furfuryl alcohol and methanol homogeneous phase solution in furfuryl alcohol mass fraction be 15 ~ 30%.
6. a kind of technique that furfural two step method continuously prepares methyl ester levulinate according to claim 1, it is characterised in that step
Rapid 3）Described in reaction temperature be 130 ~ 150 °C.
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| WO2003085071A1 (en) * | 2002-04-01 | 2003-10-16 | E.I. Du Pont De Nemours And Company | Preparation of levulinic acid esters and formic acid esters from biomass and olefins |
| CN102030646A (en) * | 2010-11-18 | 2011-04-27 | 郑州大学 | Direct transformation process of ethyl levulinate by hydrolysis of cellulose materials |
| CN103012334A (en) * | 2013-01-11 | 2013-04-03 | 中国科学技术大学 | Method for preparing gamma-valerolactone with high selectivity under mild condition |
| CN103360255A (en) * | 2013-08-01 | 2013-10-23 | 郑州大学 | Method for preparation of ethyl levulinate from furfural residues |
| CN105399705A (en) * | 2015-12-28 | 2016-03-16 | 中国石油大学(北京) | Method for preparing furfuryl alcohol by using hydrogen transfer reaction |
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| WO2003085071A1 (en) * | 2002-04-01 | 2003-10-16 | E.I. Du Pont De Nemours And Company | Preparation of levulinic acid esters and formic acid esters from biomass and olefins |
| CN102030646A (en) * | 2010-11-18 | 2011-04-27 | 郑州大学 | Direct transformation process of ethyl levulinate by hydrolysis of cellulose materials |
| CN103012334A (en) * | 2013-01-11 | 2013-04-03 | 中国科学技术大学 | Method for preparing gamma-valerolactone with high selectivity under mild condition |
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