CN106187752B - A kind of method that near-critical methanol medium intermediary hole molecular sieve catalytic furfural one kettle way prepares methyl ester levulinate - Google Patents

A kind of method that near-critical methanol medium intermediary hole molecular sieve catalytic furfural one kettle way prepares methyl ester levulinate Download PDF

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CN106187752B
CN106187752B CN201610485321.4A CN201610485321A CN106187752B CN 106187752 B CN106187752 B CN 106187752B CN 201610485321 A CN201610485321 A CN 201610485321A CN 106187752 B CN106187752 B CN 106187752B
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sba
furfural
methanol
molecular sieve
methyl ester
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CN106187752A (en
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吕秀阳
阮厚航
吕喜蕾
王立新
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites

Abstract

The invention discloses a kind of methods that Zr-SBA-15 mesopore molecular sieve catalysis furfural one kettle way prepares methyl ester levulinate in near-critical methanol medium.The step of method, is as follows: 1) furfural and methanol being added in the high-temperature high-pressure reaction kettle with stirring, Zr-SBA-15 mesopore molecular sieve is then added, wherein the Si/Zr molar ratio of the Zr-SBA-15 mesopore molecular sieve is 5-100；2) stirring is opened, is heated to 200~280 DEG C, 1~16h of one pot reaction time；3) it after reaction, is cooled to room temperature, filters, filtrate obtains methyl ester levulinate product, methanol reuse after distilling；Filter residue obtains Zr-SBA-15 mesopore molecular sieve, is cleaned with methanol, reuse after drying and roasting.The present invention has simple process, process green, at low cost, has good industrial applications prospect.

Description

A kind of near-critical methanol medium intermediary hole molecular sieve catalytic furfural one kettle way prepares acetyl The method of methyl propionate
Technical field
The present invention relates to the method that furfural prepares methyl ester levulinate, Zr- in especially a kind of near-critical methanol medium The method that SBA-15 mesopore molecular sieve catalysis furfural one kettle way prepares methyl ester levulinate.
Background technique
Biomass is a kind of important renewable resource, from biomass resource prepare chemicals or fuel at An important channel of energy crisis is solved for various countries, wherein lignocellulosic based biomass is since its yield is big, it is wide etc. to be distributed Feature receives significant attention.
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.
Mainly have 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 optimization 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 is prepared with metal salt catalyst furfuryl alcohol alcoholysis, wherein Al2(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.) it uses 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 C5 such as X carbohydrates in a methanol medium.ACS Sustainable Chemistry& Engineering.2013,1 (12): 1593-1599.) from furfural, in Pt/Al2O3It is catalyzed with Amberlyst-70, H2 Under the conditions of, the yield that one kettle way prepares methyl ester levulinate is up to 23%；There are the hydrogen of high energy consumption density cleaning for reaction The problems such as gas, methyl ester levulinate yield is low, it is difficult to industrialize.
Furfural (molecular formula: C5H4O2, CAS No.:98-01-1) and 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, is hydrolyzed, is dehydrated It is made with distillation；It can also be prepared with big wheat husk, sorghum stalk, corncob etc. is hydrolyzed；There are mainly two types of sides for industrial manufacture furfural Method: pressurization is suitble to be mass produced, and by raw material and dilute sulfuric acid boiling under elevated pressure, takes reaction out of with high pressure or superheated steam and produces Object obtains alditol finished product after being fractionated；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.
SBA-15 (Santa Barbara Amorphous) is the one kind for belonging to mesopore molecular sieve, its synthesis is in recent years Come the important Chemical Engineering Technology of another item risen, before the fields such as catalysis, separation, biology and nano material are widely used Scape, and the advantages such as its hydrothermal stability height are that the subjects such as catalysis, adsorbing separation and Advanced Inorganic material have opened up new research Field.
Molecular sieve is to utilize sol-gel, emulsification or micro emulsion, microwave hydrothermal and water using surfactant as template The inorganic material synthetic method such as thermal method is existed by a kind of aperture that the interface interaction assembling between organic matter and inorganic matter generates Between 0.4-30nm, even aperture distribution, size can regulate and control the inorganic porous material for having sieving actoion to substance.SBA points Sub- sieve catalyst has meso-hole structure, has biggish specific surface area (up to 2500m2/ g) and pore volume is (up to 2.25cm3/ g), have a uniform channel diameter distribution, aperture can modulation, wall thickness and hydrothermal stability is very high.SBA molecular sieve catalytic Agent has been applied to the fields such as catalysis, separation, biology and nano material, is also used as solid acid catalyst carrier；SBA-15 is situated between Porous molecular sieve has biggish aperture (maximum up to 30nm), thicker hole wall (wall thickness is up to 6.4nm), preferable hydrothermal stability The advantages that, modified SBA-15 molecular sieve catalyst be mainly used for catalyst oxidation reaction, catalytic hydrogenation, polymerization, condensation reaction, Alkylated reaction, isomerization reaction, catalytic cracking, photocatalysis and thermal decomposition etc..Zr-SBA-15 mesopore molecular sieve is logical It crosses and adulterates zirconium in SBA-15 mesopore molecular sieve to improve mesoporous point of a kind of modification of the surface acidity of SBA-15 and catalytic activity Son sieve.
Summary of the invention
The object of the present invention is to provide Zr-SBA-15 mesopore molecular sieves in a kind of near-critical methanol medium to be catalyzed one pot of furfural The step of method that method prepares methyl ester levulinate, method, is as follows:
1) mass ratio of addition furfural and methanol in the high-temperature high-pressure reaction kettle with stirring, furfural and methanol is 1:5- Then Zr-SBA-15 mesopore molecular sieve is added in 1:60, the mass ratio of furfural and Zr-SBA-15 mesopore molecular sieve is 10:1-1:1, Wherein the Si/Zr molar ratio of the Zr-SBA-15 mesopore molecular sieve is 5-100；
2) stirring is opened, is heated to 200~280 DEG C, 1~16h of one pot reaction time；
3) it after reaction, is cooled to room temperature, filters, filtrate obtains methyl ester levulinate product after distilling, and methanol returns With；Filter residue obtains Zr-SBA-15 mesopore molecular sieve, is cleaned with methanol, reuse after drying and roasting.
Zr-SBA-15 mesopore molecular sieve described in this patent step 1), Si/Zr molar ratio are preferably 10-40；Step 1) furfural and methanol quality described in are than being preferably 1:10-1:30；Furfural described in step 1) and Zr-SBA-15 are mesoporous The mass ratio of molecular sieve is preferably 5:1-2:1；One pot reaction temperature described in step 2) is preferably 230~270 DEG C.Step 2) one pot reaction is in vapour and consolidates in two-phase, saturated vapor pressure of the reaction pressure close to methanol under reaction temperature.Step 3) Intermediary hole regenerating molecular sieve condition is to roast 4h at 550 DEG C.
The present invention is from furfural, and Zr-SBA-15 mesopore molecular sieve is catalyzed furfural one kettle way in near-critical methanol medium Methyl ester levulinate is prepared, reaction equation is as follows:
The invention has the following advantages that
1. original two steps reaction (furfural catalytic hydrogenation and the alcoholysis of furfuryl alcohol acid catalysis) is combined together, realizes and closely face In boundary's METHANOL MEDIUM, Zr-SBA-15 mesopore molecular sieve catalysis furfural one kettle way prepare methyl ester levulinate, simple process；
2. methanol had both been used as reaction medium or had been used as hydrogen supply agent, not the hydrogen of high energy consumption density cleaning, process safety Reliably；
3. using cheap base metal solid catalyst, product separation is simple, and catalyst reclaiming is easy, and repetition makes It is good with performance, it is easy to accomplish fixed bed continuous operation；
4. the yield of good reaction selectivity, methyl ester levulinate reaches as high as 42.5%.
In short, the present invention has simple process, process green, at low cost, there is good industrial applications prospect.
Detailed description of the invention
Attached drawing 1 is that Zr-SBA-15 mesopore molecular sieve catalysis furfural one kettle way prepares acetyl in a kind of near-critical methanol medium The process flow chart of methyl propionate.
Specific embodiment
Zr-SBA-15-X mesopore molecular sieve is used in the present invention, wherein X indicates Si/Zr molar ratio.Using hydrothermal synthesis Method, be prepared for respectively Si/Zr molar ratio be 5,10,20,40,60,100 Zr-SBA-15, be denoted as respectively Zr-SBA-15-5, Zr-SBA-15-10, Zr-SBA-15-20, Zr-SBA-15-40, Zr-SBA-15-60, Zr-SBA-15-100 were specifically prepared Journey is as follows.
The detailed process of Zr-SBA-15-5 catalyst preparation: weighing the dense HCl of 35.52g and be dissolved in 189g deionized water, It is denoted as 1.6M hydrochloric acid solution, 6g P123 is weighed and is added in hydrochloric acid solution, is made it dissolve in 40 DEG C of stirred in water bath 3h, then The ZrOCl of 12.75g TEOS and 3.944g is added2·8H2O, molar ratio n (TEOS): n (ZrOCl of raw material2·8H2It O) is 5, Continue stirring for 24 hours, transfers the solution into the stainless steel hydrothermal reaction kettle with teflon lined, and in 100 DEG C of baking oven Middle standing crystallization is for 24 hours.It takes out hydrothermal reaction kettle to be cooled to room temperature, filters, wash to neutrality, sample is then put in 100 DEG C Drying for 24 hours, is not roasted sample in baking oven.Sample will not be roasted to be put into Muffle furnace, be warming up to the rate of 4 DEG C/min 550 DEG C of roasting 6h, calcined product are Zr-SBA-15-5.
The detailed process of Zr-SBA-15-10 catalyst preparation: weighing the dense HCl of 35.52g and be dissolved in 189g deionized water, It is denoted as 1.6M hydrochloric acid solution, 6g P123 is weighed and is added in hydrochloric acid solution, is made it dissolve in 40 DEG C of stirred in water bath 3h, then The ZrOCl of 12.75g TEOS and 1.972g is added2·8H2O, molar ratio n (TEOS): n (ZrOCl of raw material2·8H2It O) is 10, Continue stirring for 24 hours, transfers the solution into the stainless steel hydrothermal reaction kettle with teflon lined, and in 100 DEG C of baking oven Middle standing crystallization is for 24 hours.It takes out hydrothermal reaction kettle to be cooled to room temperature, filters, wash to neutrality, sample is then put in 100 DEG C Drying for 24 hours, is not roasted sample in baking oven.Sample will not be roasted to be put into Muffle furnace, be warming up to the rate of 4 DEG C/min 550 DEG C of roasting 6h, calcined product are Zr-SBA-15-10.
The detailed process of Zr-SBA-15-20 catalyst preparation: weighing the dense HCl of 35.52g and be dissolved in 189g deionized water, It is denoted as 1.6M hydrochloric acid solution, 6g P123 is weighed and is added in hydrochloric acid solution, is made it dissolve in 40 DEG C of stirred in water bath 3h, then The ZrOCl of 12.75g TEOS and 0.986g is added2·8H2O, molar ratio n (TEOS): n (ZrOCl of raw material2·8H2It O) is 20, Continue stirring for 24 hours, transfers the solution into the stainless steel hydrothermal reaction kettle with teflon lined, and in 100 DEG C of baking oven Middle standing crystallization is for 24 hours.It takes out hydrothermal reaction kettle to be cooled to room temperature, filters, wash to neutrality, sample is then put in 100 DEG C Drying for 24 hours, is not roasted sample in baking oven.Sample will not be roasted to be put into Muffle furnace, be warming up to the rate of 4 DEG C/min 550 DEG C of roasting 6h, calcined product are Zr-SBA-15-20.
The detailed process of Zr-SBA-15-40 catalyst preparation: weighing the dense HCl of 35.52g and be dissolved in 189g deionized water, It is denoted as 1.6M hydrochloric acid solution, 6g P123 is weighed and is added in hydrochloric acid solution, is made it dissolve in 40 DEG C of stirred in water bath 3h, then The ZrOCl of 12.75g TEOS and 0.493g is added2·8H2O, molar ratio n (TEOS): n (ZrOCl of raw material2·8H2It O) is 40, Continue stirring for 24 hours, transfers the solution into the stainless steel hydrothermal reaction kettle with teflon lined, and in 100 DEG C of baking oven Middle standing crystallization is for 24 hours.It takes out hydrothermal reaction kettle to be cooled to room temperature, filters, wash to neutrality, sample is then put in 100 DEG C Drying for 24 hours, is not roasted sample in baking oven.Sample will not be roasted to be put into Muffle furnace, be warming up to the rate of 4 DEG C/min 550 DEG C of roasting 6h, calcined product are Zr-SBA-15-40.
The detailed process of Zr-SBA-15-60 catalyst preparation: weighing the dense HCl of 35.52g and be dissolved in 189g deionized water, It is denoted as 1.6M hydrochloric acid solution, 6g P123 is weighed and is added in hydrochloric acid solution, is made it dissolve in 40 DEG C of stirred in water bath 3h, then The ZrOCl of 12.75g TEOS and 0.328g is added2·8H2O, molar ratio n (TEOS): n (ZrOCl of raw material2·8H2It O) is 60, Continue stirring for 24 hours, transfers the solution into the stainless steel hydrothermal reaction kettle with teflon lined, and in 100 DEG C of baking oven Middle standing crystallization is for 24 hours.It takes out hydrothermal reaction kettle to be cooled to room temperature, filters, wash to neutrality, sample is then put in 100 DEG C Drying for 24 hours, is not roasted sample in baking oven.Sample will not be roasted to be put into Muffle furnace, be warming up to the rate of 4 DEG C/min 550 DEG C of roasting 6h, calcined product are Zr-SBA-15-60.
The detailed process of Zr-SBA-15-100 catalyst preparation: it weighs the dense HCl of 35.52g and is dissolved in 189g deionized water In, it is denoted as 1.6M hydrochloric acid solution, 6g P123 is weighed and is added in hydrochloric acid solution, is made it dissolve in 40 DEG C of stirred in water bath 3h, so The ZrOCl of 12.75g TEOS and 0.197g are added afterwards2·8H2O, molar ratio n (TEOS): n (ZrOCl of raw material2·8H2O) it is 100, continue stirring for 24 hours, transfers the solution into the stainless steel hydrothermal reaction kettle with teflon lined, and at 100 DEG C Crystallization is stood for 24 hours in baking oven.It takes out hydrothermal reaction kettle to be cooled to room temperature, filters, wash to neutrality, sample is then put in 100 DEG C baking oven in it is dry for 24 hours, do not roasted sample.Sample will not be roasted to be put into Muffle furnace, be heated up with the rate of 4 DEG C/min To 550 DEG C of roasting 6h, calcined product is Zr-SBA-15-100.
The yield of methyl ester levulinate is molar yield in following embodiment, and calculation formula is as follows:
Embodiment 1
As shown in Figure 1,60g furfural and 300g methanol, methanol is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Mass ratio with furfural is 1:5, then addition 30g Zr-SBA-15-10, and the mass ratio of furfural and Zr-SBA-15-10 are 2: 1；Stirring is opened, is heated to 280 DEG C, one pot reaction 1h；After reaction, it is cooled to room temperature, filters, filtrate is (after sampling It is analyzed through GC, the molar yield of methyl ester levulinate is that methyl ester levulinate product 18.8%) is obtained after distilling, and methanol returns With；Filter residue obtains Zr-SBA-15-10 mesopore molecular sieve, is cleaned with methanol, reuse after drying and roasting.
Embodiment 2
30g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:10, being then added 10g Zr-SBA-15-20, the mass ratio of furfural and Zr-SBA-15-20 are 3:1；Stirring is opened, is heated 270 DEG C are warming up to, one pot reaction 6h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, acetyl The molar yield of methyl propionate is that methyl ester levulinate product, methanol reuse 35.4%) are obtained after distilling；Filter residue obtains Zr- SBA-15-20 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 3
15g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:20, being then added 3g Zr-SBA-15-40, the mass ratio of furfural and Zr-SBA-15-40 are 5:1；Stirring is opened, is heated 260 DEG C are warming up to, one pot reaction 8h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, acetyl The molar yield of methyl propionate is that methyl ester levulinate product, methanol reuse 35.9%) are obtained after distilling；Filter residue obtains Zr- SBA-15-40 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 4
10g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:30, being then added 5g Zr-SBA-15-10, the mass ratio of furfural and Zr-SBA-15-10 are 2:1；Stirring is opened, is heated 250 DEG C are warming up to, one pot reaction 10h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, acetyl The molar yield of methyl propionate is that methyl ester levulinate product, methanol reuse 41.6%) are obtained after distilling；Filter residue obtains Zr- SBA-15-10 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 5
7.5g furfural and 300g methanol, the matter of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Amount ratio is 1:40, then addition 2.5g Zr-SBA-15-20, and the mass ratio of furfural and Zr-SBA-15-20 are 3:1；Stirring is opened, 240 DEG C are heated to, one pot reaction 12h；After reaction, it is cooled to room temperature, filters, filtrate (it is analyzed after sampling through GC, The molar yield of methyl ester levulinate is that methyl ester levulinate product, methanol reuse 40.6%) are obtained after distilling；Filter residue obtains Zr-SBA-15-20 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 6
6g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:50, being then added 1.2g Zr-SBA-15-40, the mass ratio of furfural and Zr-SBA-15-40 are 5:1；Stirring is opened, is added Heat is warming up to 230 DEG C, reacts 13h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, levulic acid The molar yield of methyl esters is that methyl ester levulinate product, methanol reuse 36.5%) are obtained after distilling；Filter residue obtains Zr-SBA- 15-40 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 7
5g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:60, being then added 2.5g Zr-SBA-15-5, the mass ratio of furfural and Zr-SBA-15-5 are 2:1；Stirring is opened, is heated 220 DEG C are warming up to, one pot reaction 14h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, acetyl The molar yield of methyl propionate is that methyl ester levulinate product, methanol reuse 30.4%) are obtained after distilling；Filter residue obtains Zr- SBA-15-5 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 8
It carries out reusing experiment three times using the Zr-SBA-15-5 mesoporous molecular sieve catalyst of reuse in embodiment 7, He operates and condition is the same as embodiment 7.The molar yield of first time reuse methyl ester levulinate is 30.3%；Second of reuse acetyl The molar yield of methyl propionate is 30.3%；The molar yield of third time reuse methyl ester levulinate is 30.1%.
Embodiment 9
30g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:10, being then added 10g Zr-SBA-15-10, the mass ratio of furfural and Zr-SBA-15-10 are 3:1；Stirring is opened, is heated 200 DEG C are warming up to, one pot reaction 16h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, acetyl The molar yield of methyl propionate is that methyl ester levulinate product, methanol reuse 17.5%) are obtained after distilling；Filter residue obtains Zr- SBA-15-10 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 10
15g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:20, being then added 3g Zr-SBA-15-20, the mass ratio of furfural and Zr-SBA-15-20 are 5:1；Stirring is opened, is heated 230 DEG C are warming up to, one pot reaction 12h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, acetyl The molar yield of methyl propionate is that methyl ester levulinate product, methanol reuse 34.2%) are obtained after distilling；Filter residue obtains Zr- SBA-15-20 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 11
10g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:30, being then added 5g Zr-SBA-15-40, the mass ratio of furfural and Zr-SBA-15-40 are 2:1；Stirring is opened, is heated 250 DEG C are warming up to, one pot reaction 10h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, acetyl The molar yield of methyl propionate is that methyl ester levulinate product, methanol reuse 40.5%) are obtained after distilling；Filter residue obtains Zr- SBA-15-40 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 12
30g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:10, being then added 10g Zr-SBA-15-60, the mass ratio of furfural and Zr-SBA-15-60 are 3:1；Stirring is opened, is heated 270 DEG C are warming up to, 6h is reacted；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, levulic acid first The molar yield of ester is that methyl ester levulinate product, methanol reuse 35.6%) are obtained after distilling；Filter residue obtains Zr-SBA-15- 60 mesopore molecular sieves are cleaned, reuse after drying and roasting with methanol.
Embodiment 13
It carries out reusing experiment three times using the Zr-SBA-15-60 mesoporous molecular sieve catalyst of reuse in embodiment 12, Other operations and condition are the same as embodiment 12.The molar yield of first time reuse methyl ester levulinate is 35.5%；Second of reuse The molar yield of methyl ester levulinate is 35.4%；The molar yield of third time reuse methyl ester levulinate is 35.3%.
Embodiment 14
15g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:20, being then added 3g Zr-SBA-15-100, the mass ratio of furfural and Zr-SBA-15-100 are 5:1；Stirring is opened, is added Heat is warming up to 230 DEG C, one pot reaction 12h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, second The molar yield of acyl methyl propionate is that methyl ester levulinate product, methanol reuse 29.2%) are obtained after distilling；Filter residue obtains Zr-SBA-15-100 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 15
Reuse three times using the Zr-SBA-15-100 mesoporous molecular sieve catalyst of reuse in embodiment 14 real It tests, other operations and condition are the same as embodiment 12.The molar yield of first time reuse methyl ester levulinate is 29%；Second of reuse The molar yield of methyl ester levulinate is 29%；The molar yield of third time reuse methyl ester levulinate is 28.8%.
Embodiment 16
10g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:30, being then added 10g Zr-SBA-15-10, the mass ratio of furfural and Zr-SBA-15-10 are 1:1；Stirring is opened, is heated 270 DEG C are warming up to, one pot reaction 10h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, acetyl The molar yield of methyl propionate is that methyl ester levulinate product, methanol reuse 40.7%) are obtained after distilling；Filter residue obtains Zr- SBA-15-10 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 17
30g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:10, being then added 15g Zr-SBA-15-20, the mass ratio of furfural and Zr-SBA-15-20 are 2:1；Stirring is opened, is heated 270 DEG C are warming up to, one pot reaction 10h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, acetyl The molar yield of methyl propionate is that methyl ester levulinate product, methanol reuse 42.5%) are obtained after distilling；Filter residue obtains Zr- SBA-15-20 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 18
It carries out reusing experiment three times using the Zr-SBA-15-20 mesoporous molecular sieve catalyst of reuse in embodiment 17, Other operations and condition are the same as embodiment 12.The molar yield of first time reuse methyl ester levulinate is 42.4%；Second of reuse The molar yield of methyl ester levulinate is 42.2%；The molar yield of third time reuse methyl ester levulinate is 42.2%.
Embodiment 19
15g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:20, being then added 5g Zr-SBA-15-40, the mass ratio of furfural and Zr-SBA-15-40 are 3:1；Stirring is opened, is heated 230 DEG C are warming up to, one pot reaction 14h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, acetyl The molar yield of methyl propionate is that methyl ester levulinate product, methanol reuse 40.1%) are obtained after distilling；Filter residue obtains Zr- SBA-15-40 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 20
10g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:30, being then added 2g Zr-SBA-15-10, the mass ratio of furfural and Zr-SBA-15-10 are 5:1；Stirring is opened, is heated 250 DEG C are warming up to, one pot reaction 12h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, acetyl The molar yield of methyl propionate is that methyl ester levulinate product, methanol reuse 39.7%) are obtained after distilling；Filter residue obtains Zr- SBA-15-10 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 21
30g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:10, being then added 3.75g Zr-SBA-15-20, the mass ratio of furfural and Zr-SBA-15-20 are 8:1；Stirring is opened, is added Heat is warming up to 270 DEG C, one pot reaction 8h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, second The molar yield of acyl methyl propionate is that methyl ester levulinate product, methanol reuse 33.1%) are obtained after distilling；Filter residue obtains Zr-SBA-15-20 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 22
15g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:20, being then added 1.5g Zr-SBA-15-40, the mass ratio of furfural and Zr-SBA-15-40 are 10:1；Stirring is opened, is added Heat is warming up to 230 DEG C, one pot reaction 12h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, second The molar yield of acyl methyl propionate is that methyl ester levulinate product, methanol reuse 30.4%) are obtained after distilling；Filter residue obtains Zr-SBA-15-40 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 23
10g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:30, being then added 3.33g Zr-SBA-15-10, the mass ratio of furfural and Zr-SBA-15-10 are 3:1；Stirring is opened, is added Heat is warming up to 250 DEG C, one pot reaction 10h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, second The molar yield of acyl methyl propionate is that methyl ester levulinate product, methanol reuse 39.5%) are obtained after distilling；Filter residue obtains Zr-SBA-15-10 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 24
It carries out reusing experiment three times using the Zr-SBA-15-10 mesoporous molecular sieve catalyst of reuse in embodiment 23, Other operations and condition are the same as embodiment 23.The molar yield of first time reuse methyl ester levulinate is 39.3%；Second of reuse The molar yield of methyl ester levulinate is 39.2%；The molar yield of third time reuse methyl ester levulinate is 39.1%.
Embodiment 25
15g furfural and 300g methanol, the quality of methanol and furfural is added in high-temperature high-pressure reaction kettle of the 500mL with stirring Than for 1:20, being then added 5g Zr-SBA-15-40, the mass ratio of furfural and Zr-SBA-15-40 are 3:1；Stirring is opened, is heated 270 DEG C are warming up to, one pot reaction 8h；After reaction, it is cooled to room temperature, filters, filtrate (is analyzed after sampling through GC, acetyl The molar yield of methyl propionate is that methyl ester levulinate product, methanol reuse 38.1%) are obtained after distilling；Filter residue obtains Zr- SBA-15-40 mesopore molecular sieve is cleaned, reuse after drying and roasting with methanol.
Embodiment 26
It carries out reusing experiment three times using the Zr-SBA-15-40 mesoporous molecular sieve catalyst of reuse in embodiment 25, Other operations and condition are the same as embodiment 25.The molar yield of first time reuse methyl ester levulinate is 38.0%；Second of reuse The molar yield of methyl ester levulinate is 37.9%；The molar yield of third time reuse methyl ester levulinate is 37.7%.

Claims (5)

1. Zr-SBA-15 mesopore molecular sieve catalysis furfural one kettle way prepares methyl ester levulinate in a kind of near-critical methanol medium Method, which is characterized in that the step of method is as follows:
1) mass ratio of addition furfural and methanol in the high-temperature high-pressure reaction kettle with stirring, furfural and methanol is 1:5-1:60, Then the mass ratio of addition Zr-SBA-15 mesopore molecular sieve, furfural and Zr-SBA-15 mesopore molecular sieve is 10:1-1:1, wherein The Si/Zr molar ratio of the Zr-SBA-15 mesopore molecular sieve is 5-100；
2) stirring is opened, is heated to 200~280 DEG C, 1~16h of one pot reaction time；
3) it after reaction, is cooled to room temperature, filters, filtrate obtains methyl ester levulinate product, methanol reuse after distilling；Filter Slag obtains Zr-SBA-15 mesopore molecular sieve, is cleaned with methanol, reuse after drying and roasting.
2. Zr-SBA-15 mesopore molecular sieve is catalyzed one pot of furfural in a kind of near-critical methanol medium according to claim 1 The method that method prepares methyl ester levulinate, it is characterised in that Zr-SBA-15 mesopore molecular sieve, Si/Zr described in step 1) Molar ratio is 10-40.
3. Zr-SBA-15 mesopore molecular sieve is catalyzed one pot of furfural in a kind of near-critical methanol medium according to claim 1 The method that method prepares methyl ester levulinate, it is characterised in that furfural described in step 1) and methanol quality ratio are 1:10-1:30.
4. Zr-SBA-15 mesopore molecular sieve is catalyzed one pot of furfural in a kind of near-critical methanol medium according to claim 1 The method that method prepares methyl ester levulinate, it is characterised in that furfural described in step 1) and Zr-SBA-15 mesopore molecular sieve Mass ratio is 5:1-2:1.
5. Zr-SBA-15 mesopore molecular sieve is catalyzed one pot of furfural in a kind of near-critical methanol medium according to claim 1 The method that method prepares methyl ester levulinate, it is characterised in that one pot reaction temperature described in step 2) is 230~270 DEG C.
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