CN105884616A - Technique for continuously preparing methyl levulinate by furfural two-step process - Google Patents
Technique for continuously preparing methyl levulinate by furfural two-step process Download PDFInfo
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- C07C67/00—Preparation of carboxylic acid esters
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- 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
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Abstract
The invention discloses a technique for continuously preparing methyl levulinate by a furfural two-step process. The technique comprises the following steps: 1) filling an in-situ hydrogenation fixed-bed reactor with a supported non-noble metal catalyst, and filling an acid-catalyzed alcoholysis fixed-bed reactor with a solid acid catalyst; 2) dissolving furfural in isopropanol to form a homogeneous solution, pressurizing the solution through a measuring pump 1, preheating the solution through a preheater 1, continuously adding the solution into the in-situ hydrogenation fixed-bed reactor, and reacting; 3) separating the reaction solution by a rectification tower 1, mixing the furfuryl alcohol obtained on the tower bottom with methanol to form a homogeneous solution, pressurizing the solution through a measuring pump 2, preheating the solution through a preheater 2, continuously adding the solution into the acid-catalyzed alcoholysis fixed-bed reactor, and reacting; and 4) separating the reaction solution by a rectification tower 2, and obtaining the methyl levulinate product from the tower bottom. The technique implements continuous production on the methyl levulinate, has the advantages of high treatment capacity, stable long-time operation catalytic activity and high product yield, is suitable for large-scale industrial application, and has favorable industrialization application prospects.
Description
Technical field
The present invention relates to furfural and prepare the technique of methyl ester levulinate, especially a kind of furfural two step method continuously
The technique preparing methyl ester levulinate continuously.
Background technology
Living beings are the renewable resources that a class is important, utilize biomass resource to prepare important chemical industry platform
Compound has become as the research topic that chemical field is important.China's living beings annual production more than 2,100,000,000 tons,
Wherein agricultural stalk more than 700,000,000 tons, tree growth law is more than 1,400,000,000 tons.Biomass components mainly fibre
Dimension element, hemicellulose and lignin, the content of three accounts for more than the 90% of living beings total amount；Wherein, chaff
Aldehyde is that hemicellulose sets out most important primary product.
Methyl ester levulinate (molecular formula: C6H10O3, CAS No.:624-45-3) it is short-chain fat
Fat acid esters, is the important organic chemicals of a class, can be directly used as spices, food additives, gasoline add
Adding agent and biological liquid fuel etc., its structural formula is as shown below.
Methyl ester levulinate structural formula
Three are mainly had: levulic acid esterification, furfuryl alcohol alcohol by the approach of Production of Levulinic Acid from Biomass methyl esters
Solve, furfural catalytic hydrogenation combines alcoholysis.
Levulic acid esterification approach: it is fairly simple that methyl ester levulinate is prepared in levulic acid esterification, Song D
Deng (Song 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
Methyl ester levulinate prepared by levulic acid, wherein 12.1PW12/ZrO2The second that-Si (Et) Si-NTs1.0 optimizes
Acyl methyl propionate yield is 99.8%.
Furfuryl alcohol alcoholysis approach: the research that methyl ester levulinate is prepared in furfuryl alcohol alcoholysis is a lot, Huang Y B etc.
(Huang Y 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.) have studied and prepare methyl ester levulinate, wherein with metal salt catalyst furfuryl alcohol alcoholysis
Al2(SO4)3The methyl ester levulinate yield optimized is 80.6%；(Hu X, Wester, the Hof R J such as Hu X
M,Wu L,Upgrading biomass-derived furans via acid-catalysis/hydrogenation:the
remarkable difference between water and methanol as the solvent.Green
Chemistry, 2015,17 (1): 219-224.) prepare levulic acid with Amberlyst-70 catalysis furfuryl alcohol alcoholysis
Methyl esters, methyl ester levulinate yield is 93%.
Furfural catalytic hydrogenation combines alcoholysis approach: furfural directly prepares methyl ester levulinate research seldom, at present
(Hu X, Song Y, the Wu L.One-pot synthesis of levulinic acid/ester such as only Hu X
from C5carbohydrates in a methanol medium.ACS Sustainable Chemistry&
Engineering.2013,1 (12): 1593-1599.) from furfural, at Pt/Al2O3And Amberlyst-70
Catalysis, H2Under the conditions of, one kettle way is prepared the yield of methyl ester levulinate and is up to 23%；Reaction existence disappears
The hydrogen that consumption high-energy-density is clean, the problems such as methyl ester levulinate yield is low, it is difficult to industrialization.
Furfural (molecular formula: C5H4O2, CAS No.:98-01-1) and it is a kind of in living beings conversion process
Important plateform molecules, it is the most important derivative of furans ring system, and chemical property is active, can pass through
Numerous derivatives is produced in the reaction such as oxidation, condensation, is widely used in synthetic plastic, medicine, agricultural chemicals
Deng industry；Furfural is by pentose and diluted acid effect, through hydrolyzing, be dehydrated and distill and preparing；Also can be with hydrolysis
The preparations such as big wheat husk, jowar stalk, corncob；Industrial manufacture furfural mainly has two kinds of methods: pressurization
It is suitable for large-scale production, by raw material and dilute sulfuric acid boiling under elevated pressure, takes out of instead with high pressure or superheated steam
Answer product, after being fractionated into, obtain alditol finished product；Non-pressure process is the inorganic salts such as raw material and salt and dilute sulfuric acid to be total to
Boil, and steam furfural simultaneously.China is main furfural production state in the world, and annual production reaches 300,000 tons,
In recent years due to the pressure of outlet, the price of furfural persistently drops, and therefore furfural deep process technology is for chaff
The survival and development of aldehyde manufacturing enterprise are most important.
The conversion process of furfural should be main with high temperature high pressure reverse, and lacking ripe continuous reaction process becomes
Utilize the bottleneck of furfural on a large scale, there is presently no the technique report preparing methyl ester levulinate from furfural
Road, the present invention is from furfural, it is proposed that furfural hydrogenation in situ and the reaction of furfuryl alcohol acid catalysis alcoholysis two step are even
The continuous technique preparing methyl ester levulinate, reaction equation is as follows:
The invention have the advantages that
1. first step hydrogenation reaction in situ uses isopropanol as hydrogen supply agent, it is not necessary to outside offer hydrogen source,
Process safety, without the need for the hydrogen that high energy consumption density is clean；
2. using fixed bed continuous operation, hydrogenation reaction and acid catalysis alcoholysis reaction all use solid to urge in situ
Agent, easily, inexpensive (employing non-precious metal catalyst), long-play catalysis activity is steady for separation and recovery
Fixed；
3. good reaction selectivity, the yield of methyl ester levulinate reaches as high as 88.6%.
In a word, this technique achieve methyl ester levulinate produce continuously, treating capacity big, long-play is urged
Change activity stabilized, product yield is high, be suitable for heavy industrialization application, there is good industrial applications
Prospect.
Summary of the invention
The invention provides a kind of furfural two step method and prepare the technique of methyl ester levulinate, processing step continuously
As follows:
1) filling supported non-precious metal catalyst in fixed bed reactors it is hydrogenated with in position, in acid catalysis
Alcoholysis fixed bed reactors are filled solid acid catalyst；
2) furfural is dissolved in isopropanol formation homogeneous phase solution, and wherein the mass fraction of furfural is
10～50%, solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to after preheating be hydrogenated with fixed bed in situ
Reacting in reactor, wherein hydrogenation fixed bed reactors reaction temperature is 150～210 DEG C in situ, and reaction stops
Staying the time is 10～60min, and reactor pressure is 5MPa；
3) reactant liquor separates through rectifying column 1, obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower,
Wherein the mass fraction of furfuryl alcohol is 10～50%, and solution pressurizes through measuring pump 2, preheater 2 connects after preheating
Continuous addition in acid catalysis alcoholysis fixed bed reactors reacts, and wherein acid catalysis alcoholysis fixed bed reaction temperature is
110～170 DEG C, reaction time is 10～40min, and reactor pressure is 5MPa；
4) reactant liquor separates through rectifying column 2, obtains methyl ester levulinate product at the bottom of tower.
This patent 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；Step 1) described in solid acid catalyst be HZSM-5,
SO3H-SBA-15、Amberlyst-15、Amberlyst-21、Amberlyst-70；Step 2) described in
Furfural and isopropanol homogeneous phase solution in the mass fraction of furfural be preferably 15～30%；Step 2) in institute
The reaction temperature stated is preferably 170～190 DEG C；Step 3) described in furfuryl alcohol and the homogeneous phase solution of methyl alcohol
The mass fraction of middle furfuryl alcohol is preferably 15～30%；Step 3) described in reaction temperature be preferably
130～150 DEG C.
Hydrogenation fixed bed reactors and acid catalysis alcoholysis fixed bed reactors are compressive reaction in situ, pressure control
System is at 5MPa, by counterbalance valve 1 and 2 pressure control；Destilling tower 1,2,3 is all air-distillation.
Destilling tower 1 tower top out be the mixed liquor of isopropanol and acetone, distill further through rectifying column 3
Separating, tower top obtains by-product acetone, and obtaining isopropanol at the bottom of tower can be with reuse；Destilling tower 2 tower top is out
It is methyl alcohol, can be with reuse.
Accompanying drawing explanation
Accompanying drawing 1 is the process chart that a kind of furfural two step method prepares methyl ester levulinate continuously.
Detailed description of the invention
Supported non-precious metal catalyst used by situ of the present invention hydrogenation uses coprecipitation
Or prepared by infusion process.Detailed process prepared by catalyst is as follows:
Cu/Al2O3、Cu/MgO-Al2O3、Cu-Ni/Al2O3、Cu-Ni/ZrO2、
Cu-Ni/MgO-Al2O3、Ni/Al2O3Concrete preparation process is as follows: according to required catalysis
Ratio shared by each component in agent, first prepare certain stoicheiometry (active component cation and
The mass ratio of carrier cation) solution, be designated as solution A.Preparation NaOH and sodium carbonate
Mixed solution, is designated as solution B.Solution A is slowly dropped to containing deionization with B simultaneously
In the conical flask of water, obtain forming uniform precipitation, through filtering, wash, be dried, reducing
Supported non-precious metal catalyst is obtained after calcining, hydrogen reducing；Copper, nickel mass fraction equal
It is 20%.
Cu-Ni/SiO2、Cu/SiO2、Ni/SiO2, Ni/C use infusion process prepare, infusion process
Specific implementation method for first to prepare certain density nitrate solution, be subsequently adding quantitative load
Body carries out incipient impregnation, through ultrasonic, stand, be dried, reduce after calcining, hydrogen reducing
To supported non-precious metal catalyst, copper, the mass fraction of nickel are 20%.
Catalyst activity simple by coprecipitation and preparation catalyst process, that obtain
Component good dispersion degree.
The solid acid Amberlyst-70 that in the present invention, acid catalysis alcoholysis reaction uses buys in north
Capital Tao Shi film Co., Ltd, Amberlyst-15, Amberlyst-21 buy in the U.S.
Sigma-Aldrich company, HZSM-5 buys in Catalyst Factory, Nankai Univ；
SO3H-SBA-15 makes by oneself.
SO3The concrete preparation process of H-SBA-15 is as follows: with P123 (polyethylene glycol glycerine
The embedding aggressiveness of-polyethylene glycol) it is template, tetraethyl orthosilicate (TEOS) is main silicon source, tool
Trimethoxy-propyl group sulfydryl silicon (MPTMS) having functional group is part silicon source, at highly acid
Synthesis under hydrothermal condition, just P123 dissolves in deionized water, is stirred at room temperature,
Stir 30min after adding concentrated hydrochloric acid, add tetraethyl orthosilicate, and be stirred at room temperature.Add again
Enter MPTMS and hydrogen peroxide, with the mixed solution repeated washing 2 times of hydrochloric acid and ethanol, remove
Remove template P123, be dried under vacuum to obtain SO3H-SBA-15。
Using GC-FID to carry out quantitative analysis in the present invention, concrete analysis condition is as follows: chromatogram
Post is Agilent HP-5 capillary column (30m × 0.32mm × 0.25 μm), injector temperature:
0℃；Sample size: 1 μ L；FID detects temperature: 320 DEG C；Temperature programming: 30 DEG C keep 4
Minute, afterwards with the ramp of 10 DEG C/min to 140 DEG C, then 20 DEG C/min rises to 300 DEG C
Keep 2 minutes.
The yield of this patent is the molar yield on the basis of furfural.Computing formula is as follows:
Embodiment 1
Cu/MgO-Al is filled as it is shown in figure 1, be hydrogenated with in position in fixed bed reactors2O3, urge in acid
Change and alcoholysis fixed bed reactors are filled Amberlyst-21；Furfural is dissolved in isopropanol formation homogeneous
Solution, wherein the mass fraction of furfural is 10%, and solution is by measuring pump 1 pressurizes, preheater 1 preheats
After be continuously added to be hydrogenated with in fixed bed reactors in situ reaction, wherein hydrogenation fixed bed reactors react in situ
Temperature is 150 DEG C, and reaction time is 60min, and reactor pressure is 5MPa；Reactant liquor is through the back of the body
Pressure valve 1 flows out, and separates through rectifying column 1, obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, its
The mass fraction of middle furfuryl alcohol is 10%, and solution pressurizes through measuring pump 2, preheater 2 is continuously added to after preheating
Reacting in acid catalysis alcoholysis fixed bed reactors, wherein acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C,
Reaction time is 40min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, warp
Rectifying column 2 separates, and obtains methyl ester levulinate product at the bottom of tower, samples, levulic acid after stable
The molar yield of methyl esters product is 71.3%, after continuously running 24h, methyl ester levulinate product mole
Yield is 71.2%, and yield is not decreased obviously.
Embodiment 2
In position Cu/MgO-Al filled by hydrogenation fixed bed reactors2O3, in acid catalysis alcoholysis fixed bed
Reactor is filled Amberlyst-70；Furfural is dissolved in isopropanol formation homogeneous phase solution, wherein chaff
The mass fraction of aldehyde is 15%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to former after preheating
Reacting in the hydrogenation fixed bed reactors of position, wherein hydrogenation fixed bed reactors reaction temperature is 170 DEG C in situ,
Reaction time is 40min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, warp
Rectifying column 1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the quality of furfuryl alcohol is divided
Number is 15%, and solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis after preheating and fixes
Reacting in bed reactor, wherein acid catalysis alcoholysis fixed bed reaction temperature is 150 DEG C, reaction time
For 20min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2,
Obtain methyl ester levulinate product at the bottom of tower, after stable sample, methyl ester levulinate product mole
Yield is 88.6%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 88.4%,
Yield is not decreased obviously.
Embodiment 3
In position Cu/MgO-Al filled by hydrogenation fixed bed reactors2O3, in acid catalysis alcoholysis fixed bed
Reactor is filled Amberlyst-70；Furfural is dissolved in isopropanol formation homogeneous phase solution, wherein chaff
The mass fraction of aldehyde is 20%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to former after preheating
Reacting in the hydrogenation fixed bed reactors of position, wherein hydrogenation fixed bed reactors reaction temperature is 170 DEG C in situ,
Reaction time is 40min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, warp
Rectifying column 1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the quality of furfuryl alcohol is divided
Number is 20%, and solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis after preheating and fixes
Reacting in bed reactor, wherein acid catalysis alcoholysis fixed bed reaction temperature is 130 DEG C, reaction time
For 30min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2,
Obtain methyl ester levulinate product at the bottom of tower, after stable sample, methyl ester levulinate product mole
Yield is 85.4%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 85.2%,
Yield is not decreased obviously.
Embodiment 4
In position Cu/MgO-Al filled by hydrogenation fixed bed reactors2O3, in acid catalysis alcoholysis fixed bed
Reactor is filled Amberlyst-15；Furfural is dissolved in isopropanol formation homogeneous phase solution, wherein chaff
The mass fraction of aldehyde is 30%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to former after preheating
Reacting in the hydrogenation fixed bed reactors of position, wherein hydrogenation fixed bed reactors reaction temperature is 190 DEG C in situ,
Reaction time is 20min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, warp
Rectifying column 1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the quality of furfuryl alcohol is divided
Number is 30%, and solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis after preheating and fixes
Reacting in bed reactor, wherein acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C, reaction time
For 40min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2,
Obtain methyl ester levulinate product at the bottom of tower, after stable sample, methyl ester levulinate product mole
Yield is 81.3%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 81.2%,
Yield is not decreased obviously.
Embodiment 5
In position Cu/MgO-Al filled by hydrogenation fixed bed reactors2O3, in acid catalysis alcoholysis fixed bed
Reactor is filled Amberlyst-70；Furfural is dissolved in isopropanol formation homogeneous phase solution, wherein chaff
The mass fraction of aldehyde is 40%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to former after preheating
Reacting in the hydrogenation fixed bed reactors of position, wherein hydrogenation fixed bed reactors reaction temperature is 190 DEG C in situ,
Reaction time is 20min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, warp
Rectifying column 1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the quality of furfuryl alcohol is divided
Number is 40%, and solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis after preheating and fixes
Reacting in bed reactor, wherein acid catalysis alcoholysis fixed bed reaction temperature is 150 DEG C, reaction time
For 20min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2,
Obtain methyl ester levulinate product at the bottom of tower, after stable sample, methyl ester levulinate product mole
Yield is 72.7%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 72.5%,
Yield is not decreased obviously.
Embodiment 6
In position Cu/MgO-Al filled by hydrogenation fixed bed reactors2O3, in acid catalysis alcoholysis fixed bed
Reactor is filled SO3H-SBA-15；Furfural is dissolved in isopropanol formation homogeneous phase solution, wherein chaff
The mass fraction of aldehyde is 50%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to former after preheating
Reacting in the hydrogenation fixed bed reactors of position, wherein hydrogenation fixed bed reactors reaction temperature is 210 DEG C in situ,
Reaction time is 10min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, warp
Rectifying column 1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the quality of furfuryl alcohol is divided
Number is 50%, and solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis after preheating and fixes
Reacting in bed reactor, wherein acid catalysis alcoholysis fixed bed reaction temperature is 170 DEG C, reaction time
For 10min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2,
Obtain methyl ester levulinate product at the bottom of tower, after stable sample, methyl ester levulinate product mole
Yield is 62.4%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 62.3%,
Yield is not decreased obviously.
Embodiment 7
In position Cu-Ni/MgO-Al filled by hydrogenation fixed bed reactors2O3, fix in acid catalysis alcoholysis
Bed reactor fills HZSM-5；Furfural is dissolved in isopropanol formation homogeneous phase solution, wherein furfural
Mass fraction be 15%, solution is pressurizeed by measuring pump 1, preheater 1 is continuously added in situ after preheating
Reacting in hydrogenation fixed bed reactors, wherein hydrogenation fixed bed reactors reaction temperature is 170 DEG C in situ,
Reaction time is 40min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, warp
Rectifying column 1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the quality of furfuryl alcohol is divided
Number is 30%, and solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis after preheating and fixes
Reacting in bed reactor, wherein acid catalysis alcoholysis fixed bed reaction temperature is 170 DEG C, reaction time
For 10min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2,
Obtain methyl ester levulinate product at the bottom of tower, after stable sample, methyl ester levulinate product mole
Yield is 75.2%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 75.1%,
Yield is not decreased obviously.
Embodiment 8
In position Cu-Ni/MgO-Al filled by hydrogenation fixed bed reactors2O3, fix in acid catalysis alcoholysis
Bed reactor fills SO3H-SBA-15；Furfural is dissolved in isopropanol formation homogeneous phase solution, wherein
The mass fraction of furfural is 30%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to after preheating
Reacting in hydrogenation fixed bed reactors in situ, wherein hydrogenation fixed bed reactors reaction temperature is in situ
190 DEG C, reaction time is 20min, and reactor pressure is 5MPa；Reactant liquor is through counterbalance valve 1
Flow out, separate through rectifying column 1, obtain furfuryl alcohol at the bottom of tower and be mixed to form homogeneous phase solution with methyl alcohol, wherein furfuryl alcohol
Mass fraction be 15%, solution pressurizes through measuring pump 2, preheater 2 preheating after be continuously added to acid catalysis
Reacting in alcoholysis fixed bed reactors, wherein acid catalysis alcoholysis fixed bed reaction temperature is 150 DEG C, reaction
The time of staying is 20min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, through rectifying
Tower 2 separates, and obtains methyl ester levulinate product at the bottom of tower, samples, methyl ester levulinate after stable
The molar yield of product is 75.7%, after running 24h continuously, and the molar yield of methyl ester levulinate product
Being 75.4%, yield is not decreased obviously.
Embodiment 9
In position Cu-Ni/SiO filled by hydrogenation fixed bed reactors2, at acid catalysis alcoholysis fixed bed reaction
Device is filled Amberlyst-21；Furfural is dissolved in isopropanol formation homogeneous phase solution, wherein furfural
Mass fraction is 15%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to add in-place after preheating
Reacting in hydrogen fixed bed reactors, wherein hydrogenation fixed bed reactors reaction temperature is 170 DEG C in situ, instead
Should be 40min the time of staying, reactor pressure be 5MPa；Reactant liquor flows out through counterbalance valve 1, through essence
Evaporate tower 1 to separate, obtain furfuryl alcohol at the bottom of tower and be mixed to form homogeneous phase solution with methyl alcohol, the wherein mass fraction of furfuryl alcohol
Being 30%, solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed after preheating
Reacting in reactor, wherein acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C, and reaction time is
40min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2,
Obtain methyl ester levulinate product at the bottom of tower, after stable sample, methyl ester levulinate product mole
Yield is 45.6%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 45.5%,
Yield is not decreased obviously.
Embodiment 10
In position Cu-Ni/SiO filled by hydrogenation fixed bed reactors2, at acid catalysis alcoholysis fixed bed reaction
Device is filled Amberlyst-15；Furfural is dissolved in isopropanol formation homogeneous phase solution, wherein furfural
Mass fraction is 30%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to add in-place after preheating
Reacting in hydrogen fixed bed reactors, wherein hydrogenation fixed bed reactors reaction temperature is 190 DEG C in situ, instead
Should be 20min the time of staying, reactor pressure be 5MPa；Reactant liquor flows out through counterbalance valve 1, through essence
Evaporate tower 1 to separate, obtain furfuryl alcohol at the bottom of tower and be mixed to form homogeneous phase solution with methyl alcohol, the wherein mass fraction of furfuryl alcohol
Being 15%, solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed after preheating
Reacting in reactor, wherein acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C, and reaction time is
40min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2,
Obtain methyl ester levulinate product at the bottom of tower, after stable sample, methyl ester levulinate product mole
Yield is 46.4%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 46.2%,
Yield is not decreased obviously.
Embodiment 11
In position Cu-Ni/Al filled by hydrogenation fixed bed reactors2O3, at acid catalysis alcoholysis fixed bed reaction
Device is filled HZSM-5；Furfural is dissolved in isopropanol formation homogeneous phase solution, the wherein quality of furfural
Mark is 15%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to after preheating be hydrogenated with in situ admittedly
Reacting in fixed bed reactor, wherein hydrogenation fixed bed reactors reaction temperature is 170 DEG C in situ, and reaction stops
Staying the time is 40min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, through rectifying column
1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the mass fraction of furfuryl alcohol is
30%, it is anti-that solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed after preheating
Answering in device and react, wherein acid catalysis alcoholysis fixed bed reaction temperature is 130 DEG C, and reaction time is 30
Min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2, tower
The end, obtains methyl ester levulinate product, samples after stable, mole receipts of methyl ester levulinate product
Rate is 46.7%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 46.5%, receives
Rate is not decreased obviously.
Embodiment 12
In position Cu-Ni/Al filled by hydrogenation fixed bed reactors2O3, at acid catalysis alcoholysis fixed bed reaction
Device is filled Amberlyst-15；Furfural is dissolved in isopropanol formation homogeneous phase solution, wherein furfural
Mass fraction is 30%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to add in-place after preheating
Reacting in hydrogen fixed bed reactors, wherein hydrogenation fixed bed reactors reaction temperature is 190 DEG C in situ, instead
Should be 20min the time of staying, reactor pressure be 5MPa；Reactant liquor flows out through counterbalance valve 1, through essence
Evaporate tower 1 to separate, obtain furfuryl alcohol at the bottom of tower and be mixed to form homogeneous phase solution with methyl alcohol, the wherein mass fraction of furfuryl alcohol
Being 15%, solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed after preheating
Reacting in reactor, wherein acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C, and reaction time is
40min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2,
Obtain methyl ester levulinate product at the bottom of tower, after stable sample, methyl ester levulinate product mole
Yield is 56.7%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 56.3%,
Yield is not decreased obviously.
Embodiment 13
In position Cu-Ni/ZrO filled by hydrogenation fixed bed reactors2, at acid catalysis alcoholysis fixed bed reaction
Device is filled Amberlyst-70；Furfural is dissolved in isopropanol formation homogeneous phase solution, wherein furfural
Mass fraction is 15%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to add in-place after preheating
Reacting in hydrogen fixed bed reactors, wherein hydrogenation fixed bed reactors reaction temperature is 170 DEG C in situ, instead
Should be 40min the time of staying, reactor pressure be 5MPa；Reactant liquor flows out through counterbalance valve 1, through essence
Evaporate tower 1 to separate, obtain furfuryl alcohol at the bottom of tower and be mixed to form homogeneous phase solution with methyl alcohol, the wherein mass fraction of furfuryl alcohol
Being 30%, solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed after preheating
Reacting in reactor, wherein acid catalysis alcoholysis fixed bed reaction temperature is 170 DEG C, and reaction time is
10min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2,
Obtain methyl ester levulinate product at the bottom of tower, after stable sample, methyl ester levulinate product mole
Yield is 51.3%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 51.2%,
Yield is not decreased obviously.
Embodiment 14
In position Cu-Ni/ZrO filled by hydrogenation fixed bed reactors2, at acid catalysis alcoholysis fixed bed reaction
Device is filled HZSM-5；Furfural is dissolved in isopropanol formation homogeneous phase solution, the wherein quality of furfural
Mark is 30%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to after preheating be hydrogenated with in situ admittedly
Reacting in fixed bed reactor, wherein hydrogenation fixed bed reactors reaction temperature is 190 DEG C in situ, and reaction stops
Staying the time is 20min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, through rectifying column
1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the mass fraction of furfuryl alcohol is
15%, it is anti-that solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed after preheating
Answering in device and react, wherein acid catalysis alcoholysis fixed bed reaction temperature is 170 DEG C, and reaction time is 10
Min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2, tower
The end, obtains methyl ester levulinate product, samples after stable, mole receipts of methyl ester levulinate product
Rate is 47.5%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 47.2%, receives
Rate is not decreased obviously.
Embodiment 15
In position Cu/Al filled by hydrogenation fixed bed reactors2O3, at acid catalysis alcoholysis fixed bed reactors
Middle filling Amberlyst-21；Furfural is dissolved in isopropanol formation homogeneous phase solution, the wherein matter of furfural
Amount mark is 15%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to after preheating be hydrogenated with in situ
Reacting in fixed bed reactors, wherein hydrogenation fixed bed reactors reaction temperature is 170 DEG C in situ, reaction
The time of staying is 40min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, through rectifying
Tower 1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the mass fraction of furfuryl alcohol is
30%, it is anti-that solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed after preheating
Answering in device and react, wherein acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C, and reaction time is 40
Min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2, tower
The end, obtains methyl ester levulinate product, samples after stable, mole receipts of methyl ester levulinate product
Rate is 32.4%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 32.2%, receives
Rate is not decreased obviously.
Embodiment 16
In position Cu/Al filled by hydrogenation fixed bed reactors2O3, at acid catalysis alcoholysis fixed bed reactors
Middle filling SO3H-SBA-15；Furfural is dissolved in isopropanol formation homogeneous phase solution, the wherein matter of furfural
Amount mark is 30%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to after preheating be hydrogenated with in situ
Reacting in fixed bed reactors, wherein hydrogenation fixed bed reactors reaction temperature is 190 DEG C in situ, reaction
The time of staying is 20min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, through rectifying
Tower 1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the mass fraction of furfuryl alcohol is
15%, it is anti-that solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed after preheating
Answering in device and react, wherein acid catalysis alcoholysis fixed bed reaction temperature is 150 DEG C, and reaction time is 20
Min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2, tower
The end, obtains methyl ester levulinate product, samples after stable, mole receipts of methyl ester levulinate product
Rate is 39.8%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 39.6%, receives
Rate is not decreased obviously.
Embodiment 17
In position Cu/SiO filled by hydrogenation fixed bed reactors2, at acid catalysis alcoholysis fixed bed reactors
Middle filling Amberlyst-70；Furfural is dissolved in isopropanol formation homogeneous phase solution, the wherein matter of furfural
Amount mark is 15%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to after preheating be hydrogenated with in situ
Reacting in fixed bed reactors, wherein hydrogenation fixed bed reactors reaction temperature is 170 DEG C in situ, reaction
The time of staying is 40min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, through rectifying
Tower 1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the mass fraction of furfuryl alcohol is
30%, it is anti-that solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed after preheating
Answering in device and react, wherein acid catalysis alcoholysis fixed bed reaction temperature is 150 DEG C, and reaction time is 20
Min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2, tower
The end, obtains methyl ester levulinate product, samples after stable, mole receipts of methyl ester levulinate product
Rate is 28.9%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 28.6%, receives
Rate is not decreased obviously.
Embodiment 18
In position Cu/SiO filled by hydrogenation fixed bed reactors2, at acid catalysis alcoholysis fixed bed reactors
Middle filling HZSM-5；Furfural is dissolved in isopropanol formation homogeneous phase solution, and wherein the quality of furfural is divided
Number is 30%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to original position and is hydrogenated with fixing after preheating
Reacting in bed reactor, wherein hydrogenation fixed bed reactors reaction temperature is 190 DEG C in situ, and reaction stops
Time is 20min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, through rectifying column 1
Separating, obtain furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, wherein the mass fraction of furfuryl alcohol is 15%,
Solution pressurizes through measuring pump 2, preheater 2 is continuously added in acid catalysis alcoholysis fixed bed reactors after preheating
Reaction, wherein acid catalysis alcoholysis fixed bed reaction temperature is 170 DEG C, and reaction time is 10min,
Reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2, obtains at the bottom of tower
Methyl ester levulinate product, samples after stable, and the molar yield of methyl ester levulinate product is
21.3%, after running 24h continuously, the molar yield of methyl ester levulinate product is 21.1%, and yield does not has
It is decreased obviously.
Embodiment 19
In position Ni/Al filled by hydrogenation fixed bed reactors2O3, at acid catalysis alcoholysis fixed bed reactors
Middle filling SO3H-SBA-15；Furfural is dissolved in isopropanol formation homogeneous phase solution, the wherein matter of furfural
Amount mark is 15%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to after preheating be hydrogenated with in situ
Reacting in fixed bed reactors, wherein hydrogenation fixed bed reactors reaction temperature is 170 DEG C in situ, reaction
The time of staying is 40min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, through rectifying
Tower 1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the mass fraction of furfuryl alcohol is
30%, it is anti-that solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed after preheating
Answering in device and react, wherein acid catalysis alcoholysis fixed bed reaction temperature is 150 DEG C, and reaction time is 20
Min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2, tower
The end, obtains methyl ester levulinate product, samples after stable, mole receipts of methyl ester levulinate product
Rate is 28.9%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 28.6%, receives
Rate is not decreased obviously.
Embodiment 20
In position Ni/Al filled by hydrogenation fixed bed reactors2O3, at acid catalysis alcoholysis fixed bed reactors
Middle filling Amberlyst-70；Furfural is dissolved in isopropanol formation homogeneous phase solution, the wherein matter of furfural
Amount mark is 30%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to after preheating be hydrogenated with in situ
Reacting in fixed bed reactors, wherein hydrogenation fixed bed reactors reaction temperature is 190 DEG C in situ, reaction
The time of staying is 20min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, through rectifying
Tower 1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the mass fraction of furfuryl alcohol is
15%, it is anti-that solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed after preheating
Answering in device and react, wherein acid catalysis alcoholysis fixed bed reaction temperature is 130 DEG C, and reaction time is 30
Min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2, tower
The end, obtains methyl ester levulinate product, samples after stable, mole receipts of methyl ester levulinate product
Rate is 28.4%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 28.2%, receives
Rate is not decreased obviously.
Embodiment 21
In position Ni/SiO filled by hydrogenation fixed bed reactors2, at acid catalysis alcoholysis fixed bed reactors
Middle filling SO3H-SBA-15；Furfural is dissolved in isopropanol formation homogeneous phase solution, the wherein matter of furfural
Amount mark is 15%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to after preheating be hydrogenated with in situ
Reacting in fixed bed reactors, wherein hydrogenation fixed bed reactors reaction temperature is 170 DEG C in situ, reaction
The time of staying is 40min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, through rectifying
Tower 1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the mass fraction of furfuryl alcohol is
30%, it is anti-that solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed after preheating
Answering in device and react, wherein acid catalysis alcoholysis fixed bed reaction temperature is 170 DEG C, and reaction time is 10
Min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2, tower
The end, obtains methyl ester levulinate product, samples after stable, mole receipts of methyl ester levulinate product
Rate is 17.8%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 17.7%, receives
Rate is not decreased obviously.
Embodiment 22
In position Ni/SiO filled by hydrogenation fixed bed reactors2, at acid catalysis alcoholysis fixed bed reactors
Middle filling Amberlyst-21；Furfural is dissolved in isopropanol formation homogeneous phase solution, the wherein matter of furfural
Amount mark is 30%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to after preheating be hydrogenated with in situ
Reacting in fixed bed reactors, wherein hydrogenation fixed bed reactors reaction temperature is 190 DEG C in situ, reaction
The time of staying is 20min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, through rectifying
Tower 1 separates, and obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, and wherein the mass fraction of furfuryl alcohol is
15%, it is anti-that solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcoholysis fixed bed after preheating
Answering in device and react, wherein acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C, and reaction time is 40
Min, reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2, tower
The end, obtains methyl ester levulinate product, samples after stable, mole receipts of methyl ester levulinate product
Rate is 19.2%, and after running 24h continuously, the molar yield of methyl ester levulinate product is 19.1%, receives
Rate is not decreased obviously.
Embodiment 23
In position Ni/C filled by hydrogenation fixed bed reactors, fill out in acid catalysis alcoholysis fixed bed reactors
Fill Amberlyst-15；Furfural is dissolved in isopropanol formation homogeneous phase solution, and wherein the quality of furfural is divided
Number is 15%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to original position and is hydrogenated with fixing after preheating
Reacting in bed reactor, wherein hydrogenation fixed bed reactors reaction temperature is 170 DEG C in situ, and reaction stops
Time is 40min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, through rectifying column 1
Separating, obtain furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, wherein the mass fraction of furfuryl alcohol is 30%,
Solution pressurizes through measuring pump 2, preheater 2 is continuously added in acid catalysis alcoholysis fixed bed reactors after preheating
Reaction, wherein acid catalysis alcoholysis fixed bed reaction temperature is 110 DEG C, and reaction time is 40min,
Reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2, obtains at the bottom of tower
Methyl ester levulinate product, samples after stable, and the molar yield of methyl ester levulinate product is
16.5%, after running 24h continuously, the molar yield of methyl ester levulinate product is 16.4%, and yield does not has
It is decreased obviously.
Embodiment 24
In position Ni/C filled by hydrogenation fixed bed reactors, fill out in acid catalysis alcoholysis fixed bed reactors
Fill Amberlyst-70；Furfural is dissolved in isopropanol formation homogeneous phase solution, and wherein the quality of furfural is divided
Number is 30%, and solution is pressurizeed by measuring pump 1, preheater 1 is continuously added to original position and is hydrogenated with fixing after preheating
Reacting in bed reactor, wherein hydrogenation fixed bed reactors reaction temperature is 190 DEG C in situ, and reaction stops
Time is 20min, and reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 1, through rectifying column 1
Separating, obtain furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, wherein the mass fraction of furfuryl alcohol is 15%,
Solution pressurizes through measuring pump 2, preheater 2 is continuously added in acid catalysis alcoholysis fixed bed reactors after preheating
Reaction, wherein acid catalysis alcoholysis fixed bed reaction temperature is 150 DEG C, and reaction time is 20min,
Reactor pressure is 5MPa；Reactant liquor flows out through counterbalance valve 2, separates through rectifying column 2, obtains at the bottom of tower
Methyl ester levulinate product, samples after stable, and the molar yield of methyl ester levulinate product is
20.4%, after running 24h continuously, the molar yield of methyl ester levulinate product is 20.3%, and yield does not has
It is decreased obviously.
Claims (7)
1. the technique that a furfural two step method prepares methyl ester levulinate continuously, it is characterised in that the step of technique is as follows:
1) filling supported non-precious metal catalyst in fixed bed reactors it is hydrogenated with in position, anti-in acid catalysis alcoholysis fixed bed
Answer filling solid acid catalyst in device；
2) furfural is dissolved in isopropanol formation homogeneous phase solution, and wherein the mass fraction of furfural is 10～50%, all mixes
Liquid is pressurizeed by measuring pump 1, preheater 1 is continuously added to after preheating be hydrogenated with in fixed bed reactors reaction, its Central Plains in situ
Position hydrogenation fixed bed reactors reaction temperature is 150～210 DEG C, and reaction time is 10～60min, and reactor pressure is
5MPa；
3) reactant liquor separates through rectifying column 1, obtains furfuryl alcohol and be mixed to form homogeneous phase solution with methyl alcohol at the bottom of tower, the wherein matter of furfuryl alcohol
Amount mark is 10～50%, and this homogeneous phase solution pressurizes through measuring pump 2, preheater 2 is continuously added to acid catalysis alcohol defastening after preheating
Reacting in fixed bed reactor, wherein acid catalysis alcoholysis fixed bed reaction temperature is 110～170 DEG C, and reaction time is 10～40
Min, reactor pressure is 5MPa；
4) reactant liquor separates through rectifying column 2, obtains methyl ester levulinate product at the bottom of tower.
A kind of furfural two step method the most according to claim 1 prepares the technique of methyl ester levulinate continuously, and its feature exists
In 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。
The technique that a kind of furfural two step method prepares methyl ester levulinate continuously, it is characterised in that
Step 1) described in solid acid catalyst be HZSM-5, SO3H-SBA-15、Amberlyst-15、Amberlyst-21、
Amberlyst-70。
The technique that a kind of furfural two step method prepares methyl ester levulinate continuously, it is characterised in that
Step 2) described in furfural and isopropanol homogeneous phase solution in the mass fraction of furfural be 15～30%.
The technique that a kind of furfural two step method prepares methyl ester levulinate continuously, it is characterised in that
Step 2) described in reaction temperature be 170～190 DEG C.
The technique that a kind of furfural two step method prepares methyl ester levulinate continuously, it is characterised in that
Step 3) described in furfuryl alcohol and methyl alcohol homogeneous phase solution in the mass fraction of furfuryl alcohol be 15～30%.
The technique that a kind of furfural two step method prepares methyl ester levulinate continuously, it is characterised in that
Step 3) described in reaction temperature be 130～150 DEG C.
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| WO2018113240A1 (en) * | 2016-12-21 | 2018-06-28 | Rhodia Operations | Process for the preparation of levulinate esters |
| CN108675928A (en) * | 2018-05-25 | 2018-10-19 | 昆明理工大学 | A kind of method that furfural directly prepares levulinate |
| WO2023094511A1 (en) | 2021-11-26 | 2023-06-01 | Basf Se | Process for forming alkyl ester of levulinic acid |
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