CN105439836B - A kind of method that solid acid catalysis prepares 2,5 acetyl butyryls - Google Patents
A kind of method that solid acid catalysis prepares 2,5 acetyl butyryls Download PDFInfo
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Abstract
A kind of method that solid acid catalysis prepares 2,5 acetyl butyryls is, into the dimethyl furan of raw material 2,5, to add weakly polar organic solvent, solid acid catalyst, and distilled water, reaction temperature is 80 200 DEG C, and the reaction time is 1 12 hours；Reaction system is quenched, system temperature is rapidly decreased to normal temperature, take out reaction solution, by reacting liquid filtering or centrifugation, solid catalyst drying is reclaimed；Organic phase is collected, by obtained organic phase vacuum distillation, organic solvent is removed, obtains the acetyl butyryl of product 2,5.The present invention has easily separated, free of contamination advantage.
Description
Technical field
The invention belongs to a kind of method that use solid acid molecular sieve does catalyst preparation 2,5- acetyl butyryls.
Background technology
In recent years, 2,5- acetyl butyryls are received more and more attention as a kind of important chemical intermediate.At present, it is main
It is used as the high boiling solvent of synthetic resin, nitro spray painting, colouring agent, printing-ink etc., leather tanning agent, the vulcanization of rubber promotees
Enter agent and insecticide, medicine material, can also be applied to insecticide, food additives, spices, plating spray painting, photograph medicament etc.
Various fields.
The preparation method of 2,5- acetyl butyryls is numerous, generally to hydrolyze based on 2,5- dimethyl furans.2,5- dimethyl furans
Be hydrolyzed to acid catalyzed process, it is the key that it is effectively hydrolyzed, wherein mineral acid such as hydrochloric acid, phosphorus to select appropriate acid catalyst
Acid or phosphoric acid hydrolysis are relatively conventional to prepare, but these mineral acids are homogeneous catalysis system, reaction system and reaction product
It is not readily separated, easily causes environmental pollution.
The content of the invention
It is an object of the invention to provide one kind is easily separated, free of contamination 2,5- solid acid catalysis prepares 2,5- acetyl butyryls
Method.
Zeolite molecular sieve is a kind of poromerics for being widely used in petrochemical industry, and it has highly acid, good hydro-thermal
Stability, nontoxicity and the advantages of be easier to reclaim from solution, have good selective activization in chemical reaction, make its into
For a kind of industrially wide variety of acidic catalyst.Molecular sieve is as solid acid catalyst, and its catalysis is from solid
There is the acidic site of catalytic activity present on body surface face, and molecular sieve has uniform, microcellular structure in itself, and this also increases
The bond area of big acidic site.2,5- dimethyl furan molecular dimensions are small, and solid acid is directly entered during reaction
The micropore of molecular sieve.The outer surface acidity of molecular sieve influences smaller to catalytic hydrolysis reaction, and hydrolysis occurs mainly in molecule
In active sites in sieve aperture road.Patent of the present invention employ solid acid molecular sieve catalyst hydrolysis 2,5- dimethyl furans, and
The organic solvent of low pole is introduced in reaction so that reactant dissolves the yield and yield for improving reaction in organic solvent.
The preparation method of the present invention comprises the following steps：
(1) to raw material 2, in 5- dimethyl furans, weakly polar organic solvent, solid acid catalyst, distilled water, reaction are added
Temperature is 80-200 DEG C, and the reaction time is 1-12 hours；
(2) after reaction terminates, reaction system is quenched, system temperature is rapidly decreased to normal temperature, reaction solution is taken out, by reaction solution
Filtering is centrifuged, solid catalyst drying, is reclaimed；Organic phase is collected, by obtained organic phase vacuum distillation, removal has
Machine solvent, obtains product 2,5- acetyl butyryls.The qualitative analysis of product is characterized by nuclear magnetic spectrum and obtained.
As step (1) described weakly polar organic solvent includes：Toluene, methylisobutylketone, hexamethylene or ethyl acetate；
Solid acid catalyst as described in step (1) includes：(silica alumina ratio is 5-50 to ZSM-5 zeolite molecular sieve, and optimal ratio is
15-20), H beta molecular sieves (silica alumina ratio is 5-70, optimal ratio be 20-25), (silica alumina ratio is 0.1-40 to SAPO-11 molecular sieves, most
Good ratio is 0.1-10), USY molecular sieve (silica alumina ratio is 1-50, optimal than being 1-15)；
Volume ratio such as step (1) the 2,5- dimethyl furans and distilled water is 1：0.1-0.5；
Volume ratio such as step (1) the 2,5- dimethyl furans and weakly polar organic solvent is 1：5-20；
If the volume of step (1) the 2,5- dimethyl furans and the mass ratio of solid acid catalyst are 1mL：0.5-2g.
Present invention firstly provides using solid acid molecular sieve catalyst hydrolysis 2,5- dimethyl furans prepare 2,5- oneself two
Ketone, this is a kind of green method of easy to operate, high-efficiency and economic.The present invention has selected several different molecular sieves as catalysis
Agent, has selected several solvents as the extractant in system, in 80-200 DEG C of temperature range, is examined in the small the reaction times of 1-12
The reaction result that 2,5- dimethyl furan high selectivities are converted into 2,5- acetyl butyryls is examined.
The present invention has investigated different molecular sieve catalyst, different solvents, reaction time, reaction temperature and reaction mass proportioning
Influence to 2,5- acetyl butyryl yields.Different molecular sieve catalysts are primarily looked at.The mechanism of furan nucleus fracture is oxygen atom
Protonation destroy the armaticity of furan nucleus.The stability of ring fracture depends on the type of local substituent.Furans
Alkyl derivative is then easier to destroyed armaticity so that 2,5- dimethyl furans have faster hydrolysis rate.In fact, 2,5-
The hydrolysis rate of dimethyl furan even can reach 5000 times of furans.The hydrolysis of 2,5- dimethyl furans is acid catalyzed mistake
Journey, it is the key that 2,5- dimethyl furans are effectively hydrolyzed to select suitable acid catalyst.Solid acid molecular sieve has uniform bore road
Structure, larger acidic site bond area, and the features such as easily separated recovery, this patent is from four kinds of different molecular sieve conducts
The acid catalyst of 2,5- dimethyl furans, for example, ZSM-5 zeolite molecular sieve, H beta molecular sieves, SAPO-11 molecular sieves, USY points
Son sieve.The loose structure of molecular sieve can accommodate many cations, such as H+、Na+、K+、Mg2+Deng.The loose combination of these cations
In molecular sieve surface, they, which can be discharged into the aqueous solution, shows different catalytic performances.The size of 2,5- dimethyl furan molecules
It is small, the micropore of solid acid molecular sieve is directly entered during reaction.The outer surface acidity of molecular sieve is to catalytic hydrolysis reaction
Influence is smaller, and hydrolysis is occurred mainly in the acid active sites in molecular sieve pore passage.The silica alumina ratio of molecular sieve can be strong
Influence its sour property.When the silica alumina ratio that the silica alumina ratio of ZSM-5 zeolite molecular sieve is less than 5, H beta molecular sieves is less than 5, SAPO-
When the silica alumina ratio of 11 molecular sieves is less than the 0.1, silica alumina ratio of USY molecular sieve and is less than 1, obtained product 2,5- acetyl butyryls yield compared with
Low, when this is due to that silica alumina ratio is relatively low, acid too weak 2, the 5- dimethyl furans that can not effectively facilitate of acidic site are hydrolyzed.With
Silica alumina ratio is higher, and total acid content reduction, acidic site is reduced, and the acid of Single locus becomes strong.When the sial of ZSM-5 zeolite molecular sieve
The silica alumina ratio for being more than 70, SAPO-11 molecular sieves than the silica alumina ratio more than 50, H beta molecular sieves is more than the sial of 40, USY molecular sieve
During than more than 50, the quantity of acidic site can not make raw material 2 less, 5- dimethyl furan complete hydrolysis, the product 2 of acquisition, 5- oneself
Diketone yield is low.Therefore, the scope of acidic catalyst ZSM-5 zeolite molecular sieve silica alumina ratio is 5-50, H beta molecular sieve silica alumina ratio
Scope when being that the scope of 5-70, SAPO-11 molecular sieve silica alumina ratio is that 0.1-40, the scope of USY molecular sieve silica alumina ratio are 1-50,
2,5- acetyl butyryls can be prepared with efficient catalytic hydrolysis 2,5- dimethyl furans.And for the addition of catalyst, when 2,5- diformazans
The volume of base furans and the mass ratio of acid catalyst are more than 1mL：During 2g, the addition of a large amount of solid acid catalysts, although can urge
Change positive reaction generation target product, but simultaneously product can be caused to be transferred out of pore passage structure in time, be trapped in molecular sieve pores
Continue to have an effect with acidic site in road, cause the product of generation further to decompose, cause serious side reaction, the receipts of product
Rate declines.When the volume of 2,5- dimethyl furans and the mass ratio of acid catalyst are less than 1mL：During 0.5g, due to solid point counting
The addition of sieve is very few, causes raw material 2, and 5- dimethyl furans can not fully be combined conversion with acidic site, obtain target product
Yield is low.Therefore, the volume of 2,5- dimethyl furans and the mass ratio of acid catalyst are in 1mL：When between 0.5-2g, catalyst can
With efficient catalytic raw material 2,5- dimethyl furans obtain high product yield.In summary, hydrolyze and make in 2,5- dimethyl furans
The catalyst applied in standby reaction is solid acid molecular sieve catalyst, and it is product is more easily separated, environmental pollution is smaller, not
There are huge potentiality in the development come.
Then, the influence that different organic solvents are hydrolyzed to 2,5- dimethyl furans is investigated.From the purpose of organic solvent,
On the one hand, in order that raw material 2,5- dimethyl furans can better contact with the acidic site of molecular sieve, the present invention has been selected not
Same organic solvent dissolving raw material；On the other hand, the presence of organic solvent can hydrolyze the product of generation with situ extracting raw material, this
Sample is it is possible to prevente effectively from side reaction occurs for product 2,5- acetyl butyryls, it is ensured that the purity of product.Target product 2,5- acetyl butyryls are
A kind of low pole compound, according to the similar principle mixed, is more suitable for from weakly polar organic solvent compared to polar solvent
It is prepared by the separation of the product.Weakly polar organic solvent is a kind of environmentally friendly solvent, is used as Jie for much having chemical reaction
Matter.A variety of weakly polar organic solvents, such as hexamethylene, toluene, methylisobutylketone, dichloromethane, acetic acid second have been selected in the present invention
Ester etc..Product 2,5- acetyl butyryls distribution coefficient in these organic solvents is all higher than 1.0.Experimental data shows, in these solvents
Middle toluene and methylisobutylketone catalytic effect is fine, because product 2,5- acetyl butyryls have very in toluene and methylisobutylketone
Good dissolubility.In particular, because methylisobutylketone contains ketone group, thus it is best to the effect of extracting of 2,5- acetyl butyryls, most
The yield of finished product is also up to 98%.But, when the volume ratio of 2,5- dimethyl furans and weakly polar organic solvent is more than 1:20
When, the conversion ratio of raw material can decline, and this is due to that substantial amounts of organic solvent is present, and the mass transfer of raw material in organic solvent is hindered
Hinder, cause raw material 2,5- dimethyl furans can not fully contact generation conversion completely with acid；And 2,5- dimethyl furans and weak pole
Property organic solvent volume ratio be less than 1:When 5, because the addition of organic solvent is very few, it is impossible to extract product, product meeting completely
Continuation is contacted with inorganic acid, occurs side reaction, it is impossible to prepare target product in high yield.Therefore, raw material 2,5- dimethyl furans
It is 1 with weakly polar organic solvent volume ratio:When between 5-20,2,5- dimethyl furans can the efficiently high place of production prepare product 2,
5- acetyl butyryls.
Added further, since the hydrolytic process of 2,5- dimethyl furans is needed in the participation of water, system of the invention
A certain amount of distilled water.When the volume ratio of 2,5- dimethyl furans and distilled water is less than 1：When 0.1, offer 2,5- diformazans are not enough to
Hydrone required for the hydrolysis of base furans, thus hydrolysis can not carry out completely, this just constrains the conversion of raw material, causes production
The decline of thing yield；When the volume ratio of 2,5- dimethyl furans and distilled water is more than 1：When 0.5, product 2, the yield of 5- acetyl butyryls
Also it can reduce, this is due to that solid acid molecular sieve has stronger water imbibition, and when adding substantial amounts of water, hydrone can occupy molecule
The pore passage structure of sieve, causes 2,5- dimethyl furans molecule to be combined well with the acidic site in duct, raw material can not
Conversion completely, obtained product yield is low.So, when the volume ratio of 2,5- dimethyl furans and distilled water is 1：0.1-0.5 it
Between when, 2,5- dimethyl furans can be efficiently synthesized 2,5- acetyl butyryls.
The reaction condition that the present invention is hydrolyzed is that reaction temperature is 80-200 DEG C, and the reaction time is 1-12 hours, reaction condition
Determination is the characteristics of need association reaction and the performance synthesis of catalyst considers.Test result indicates that, reaction starts, 2,5- oneself two
The yield of ketone is relatively low, as the reaction time increased to 12 hours from 1 hour, and the inside and outside effect of mass transmitting with organic solvent of molecular sieve is not
Disconnected to carry out, raw material 2,5- dimethyl furans and the acidic site in molecular sieve pore passage structure constantly contact hydrolysis, 2,5- oneself
The yield of diketone continues to increase, and when to 12 hours, raw material 2,5- dimethyl furans are basically completed conversion, raw material now
Conversion ratio reaches maximum 87%.Continue to extend more than 12 hours between when reacted, the conversion ratio and product yield of raw material have decline
Trend.Reaction temperature is increased to 200 DEG C from 80 DEG C, and the conversion ratio of 2,5- dimethyl furans gradually rises, 2,5- acetyl butyryls
Yield is also in rise.Because there are two kinds of roads of β-protonation and α-protonation in hydrolytic process in 2,5- dimethyl furans
Line, β-protonation can obtain 2,5- acetyl butyryl products, and α-protonation route finally gives accessory substance, due to β-protonation
Activation energy (Ea=20kcal/mol) it is higher than the activation energy (E of α-protonationa=17kcal/mol), therefore, temperature is higher to be made instead
β-protonation route should be tended to, so being increased to 200 DEG C of periods at 80 DEG C, the conversion ratio and selectivity of product of raw material can all increase
Plus.When temperature reaches 200 DEG C, raw material 2, the conversion ratio of 5- dimethyl furans reaches maximum 90%, now 2,5- acetyl butyryls
Yield also reaches maximum 88%.But, when reaction temperature is more than 200 DEG C, the yield of product has no raising, under having slightly on the contrary
Drop.Main cause is to cause serious side reaction more than 200 DEG C, and 2, the 5- acetyl butyryls of generation may be promoted further to decompose
For other micromolecular compounds, so that causing the yield of 2,5- acetyl butyryls reduces.
According to above-mentioned many experiments, it may be determined that the different solid acid molecular sieves of investigation, different organic solvents, difference are anti-
Answer the proportioning of thing, and the various experiment parameters such as different time and different reaction temperatures, it can efficiently be catalyzed 2,5-
Dimethyl furan hydrolysis prepares 2,5- acetyl butyryls.
The present invention has following advantage：
(1) present invention selects solid acid catalyst, and 2,5- dimethyl furans hydrolysis system is realized in weakly polar organic solvent
Standby 2,5- acetyl butyryls, this reaction make use of the porous advantage of molecular sieve and the characteristic of bigger serface, and molecular sieve can be with original
Material fully contact, while its Hole bottom cavity blast suppresses the polymerization of product so that main reaction can be carried out fully, product and catalysis after reaction
Agent is easily isolated, and is operated relatively simple.And molecular sieve is nontoxic to be polluted to environment.
(2) organic solvent is used in the reaction, is that whole reaction carries out creating favourable reaction environment, while suppressing secondary anti-
The generation answered.After product is generated, situ extracting is into organic solvent, hence it is evident that improves the selectivity and yield of reaction, also reduces
The separating difficulty of reactant and product.The conversion ratio of 2,5- dimethyl furans reaches as high as 85%, and yield is more than 79%.
(3) whole course of reaction, simple to operate, safe and reliable, and reaction condition is gentle, will not produce pollution to environment.
Brief description of the drawings
Fig. 1 is the response path that 2,5- dimethyl furans of the present invention synthesize 2,5- acetyl butyryls.
Fig. 2 is the product of embodiment 113C NMR spectras.
Fig. 3 is the product of embodiment 11H NMR spectras.
Embodiment
Embodiment 1：
By 1ml2,5- dimethyl furans are added in container, are subsequently added into 12ml methylisobutylketones, 0.2ml deionized waters
With 0.8g H beta molecular sieves (silica alumina ratio is 20), it is well mixed.Container is placed in 180 DEG C of isothermal reactors, is stirred continuously,
Reaction 5 hours.After reaction terminates, container is put into ice bath, quenches reaction, and system temperature is dropped rapidly to room temperature.Take out anti-
Product is answered, organic phase and solid catalyst is centrifuged, organic phase is collected, catalyst is reclaimed.Obtained organic phase is depressurized and steamed
Evaporate, remove organic solvent, obtain product (see accompanying drawing 2 and 3).The conversion ratio of raw material and the yield of product are by GC-External Standard method
Measure is obtained, and the purity of product is obtained by liquid chromatogram measuring.As a result the conversion ratio for showing 2,5- dimethyl furans is 85%, production
The purity of thing is that the yield of 92%, 5- acetyl butyryls is 81%.
Embodiment 2：
First by 1ml raw materials 2,5- dimethyl furans are added in container, are subsequently added into 10ml methylisobutylketones, 0.8g USY
Molecular sieve (silica alumina ratio is 5), 0.1ml deionized waters.It is put into reactor, stirs after well mixed, 180 DEG C of isothermal reactions 5 is small
When.Reaction is completed, and reaction product is placed in low temperature and quenched, temperature is rapidly decreased to normal temperature.Centrifuge afterwards, reclaim catalysis
Agent, collects organic phase, by obtained organic phase vacuum distillation, removes organic solvent, obtains product.The conversion ratio and product of raw material
Yield by GC-External Standard method determine obtain, the purity of product is obtained by liquid chromatogram measuring.As a result raw material 2,5- is shown
The conversion ratio of dimethyl furan is 85%, and the purity of product is 90%, and the yield of 2,5- acetyl butyryls is 78%.
Embodiment 3：
Into container, sequentially add：1ml2,5- dimethyl furan, 12ml methylisobutylketones, 0.1ml deionized waters,
1.2gZSM-5 zeolite molecular sieves (silica alumina ratio is 20), and uniformly mix.Container is placed in isothermal reactor, in 200 DEG C of reactions
5 hours.Reaction makes system be dropped rapidly to normal temperature after terminating.By reaction solution, catalyst is reclaimed in the organic phase separation of solid phase, is received
Collect organic phase.Vacuum distillation is carried out to organic phase, to remove organic solvent, product is obtained.The conversion ratio of raw material and the receipts of product
Rate is determined by GC-External Standard method and obtained, and the purity of product is obtained by liquid chromatogram measuring.As a result raw material 2,5- diformazans are shown
The conversion ratio of base furans is 82%, and the purity of product is 92%, and the yield of 2,5- acetyl butyryls is 75%.
Embodiment 4：
By 1ml2,5- dimethyl furans are added in container, are subsequently added into 12ml toluene, 0.8g H beta molecular sieve (sial
20) and 0.2ml deionized waters than, to be well mixed.Container is placed in 160 DEG C of isothermal reactors, is stirred continuously, reaction 5 is small
When.After reaction terminates, container is put into ice bath, quenches reaction, and system temperature is dropped rapidly to room temperature.Take out reaction product,
Organic phase and solid catalyst are centrifuged, catalyst is reclaimed, organic phase is collected.Vacuum distillation is carried out to organic phase, to remove
Organic solvent, obtains target product.The conversion ratio of raw material and the yield of product are determined by GC-External Standard method to be obtained, product
Purity is obtained by liquid chromatogram measuring.As a result raw material 2 is shown, the conversion ratio of 5- dimethyl furans is 86%, and the purity of product is
91%, the yield of 2,5- acetyl butyryls is 82%.
Embodiment 5：
First by 1ml raw materials 2,5- dimethyl furans are added in container, are subsequently added into 10ml methylisobutylketones, 0.1ml and are gone
Ionized water and 1.5g SAPO-11 molecular sieves (silica alumina ratio is 1).It is put into reactor, stirs after well mixed, 200 DEG C of constant temperature is anti-
Answer 12 hours.Reaction is completed, and reaction product is placed in low temperature and quenched, temperature is rapidly decreased to normal temperature.Centrifuge, return afterwards
Catalyst is received, organic phase is collected, and vacuum distillation is carried out to it, to remove organic solvent, target product is obtained.The conversion of raw material
The yield of rate and product is determined by GC-External Standard method and obtained, and the purity of product is obtained by liquid chromatogram measuring.As a result show
Raw material 2, the conversion ratio of 5- dimethyl furans is 82%, and the purity of product is 90%, and the yield of 2,5- acetyl butyryls is 77%.
Embodiment 6：
Into container, sequentially add：1ml2,5- dimethyl furan, 12ml ethyl acetate, 1.5g USY molecular sieve (sial
Than for 20), 0.5ml deionized waters, and uniformly mix.Container is placed in isothermal reactor, under conditions of stirring, with 180
DEG C steady temperature, reacts 5 hours.Container is placed in low temperature environment by reaction after terminating, and system is dropped rapidly to normal temperature.Will be anti-
Solution is answered, the organic phase separation of solid phase reclaims solid phase, retains organic phase, and carries out vacuum distillation to it, can obtain target product.
The conversion ratio of raw material and the yield of product are determined by GC-External Standard method to be obtained, and the purity of product is obtained by liquid chromatogram measuring
Arrive.As a result raw material 2 is shown, the conversion ratio of 5- dimethyl furans is 87%, the purity of product is 92%, the yield of 2,5- acetyl butyryls
For 83%.
Embodiment 7：
Into container, sequentially add：1ml2,5- dimethyl furan, 15mL toluene, (silica alumina ratio is 0.5g H beta molecular sieves
25), 0.3ml deionized waters, and uniformly mix.Container is placed in isothermal reactor, under conditions of stirring, with 200 DEG C of perseverances
Constant temperature degree, reacts 1 hour.Container is placed in low temperature environment by reaction after terminating, and system is dropped rapidly to normal temperature.It will react molten
Solid acid molecular sieve is reclaimed in liquid, the organic phase separation of solid phase, retains organic phase, and carries out vacuum distillation to it, can obtain target production
Product.The conversion ratio of raw material and the yield of product are determined by GC-External Standard method to be obtained, and the purity of product is by liquid chromatogram measuring
Obtain.As a result raw material 2 is shown, the conversion ratio of 5- dimethyl furans is 84%, the purity of product is 94%, the receipts of 2,5- acetyl butyryls
Rate is 80%.
Embodiment 8：
By 1ml2,5- dimethyl furans are added in container, are subsequently added into 10ml toluene, 0.2ml deionized waters and 1.0g
ZSM-5 zeolite molecular sieve (silica alumina ratio is 20), is well mixed.Container is placed in 200 DEG C of isothermal reactors, is stirred continuously, instead
Answer 3 hours.After reaction terminates, container is put into ice bath, quenches reaction, and system temperature is dropped rapidly to room temperature.Take out reaction
Product, centrifuges organic phase and solid catalyst, reclaims catalyst, collects organic phase.Vacuum distillation is carried out to organic phase, can
Obtain target product.The conversion ratio of raw material and the yield of product are determined by GC-External Standard method to be obtained, and the purity of product is by liquid
Phase chromatographic determination is obtained.As a result the conversion ratio for showing 2,5- dimethyl furans is 80%, and the purity of product is 90%, 2,5- oneself two
The yield of ketone is 75%.
Embodiment 9：
First by 1ml raw materials 2,5- dimethyl furans are added in container, are subsequently added into 15ml methylisobutylketones, 0.1ml and are gone
Ionized water and 1.0g ZSM-5 zeolites molecular sieve (silica alumina ratio is 20).It is put into reactor, stirs, 200 DEG C of perseverances after well mixed
Temperature reaction 12 hours.Reaction is completed, and reaction product is placed in low temperature and quenched, temperature is rapidly decreased to normal temperature.Centrifugation point afterwards
From, solid acid is reclaimed, organic phase is collected, and vacuum distillation is carried out to it, it can obtain target product.The conversion ratio and product of raw material
Yield by GC-External Standard method determine obtain, the purity of product is obtained by liquid chromatogram measuring.As a result raw material 2,5- is shown
The conversion ratio of dimethyl furan is 79%, and the purity of product is 92%, and the yield of 2,5- acetyl butyryls is 75%.
Embodiment 10：
First by 1ml raw materials 2,5- dimethyl furans are added in container, are subsequently added into 8ml methylisobutylketones, 1.0gZSM-5
Zeolite molecular sieve (silica alumina ratio is 20), 0.1ml deionized waters,.It is put into reactor, stirs after well mixed, 180 DEG C of constant temperature is anti-
Answer 8 hours.Reaction is completed, and reaction product is placed in low temperature and quenched, temperature is rapidly decreased to normal temperature.Centrifuge, return afterwards
Solid acid molecular sieve is received, organic phase is collected, vacuum distillation is carried out to it, target product is can obtain.The conversion ratio and product of raw material
Yield by GC-External Standard method determine obtain, the purity of product is obtained by liquid chromatogram measuring.As a result raw material 2,5- is shown
The conversion ratio of dimethyl furan is 79%, and the purity of product is 90%, and the yield of 2,5- acetyl butyryls is 75%.
Embodiment 11：
By 1ml2,5- dimethyl furans are added in container, be subsequently added into 10ml hexamethylenes, 0.2ml deionized waters and
1.2H beta molecular sieves (silica alumina ratio is 20), are well mixed.Container is placed in 140 DEG C of isothermal reactors, is stirred continuously, reaction 7
Hour.After reaction terminates, container is put into ice bath, quenches reaction, and system temperature is dropped rapidly to room temperature.Take out reaction production
Thing, centrifuges organic phase and solid catalyst, reclaims catalyst, collects organic phase, and carries out vacuum distillation to it, can obtain
Target product.The conversion ratio of raw material and the yield of product are determined by GC-External Standard method to be obtained, and the purity of product is by liquid phase color
Spectrum measure is obtained.As a result show raw material 2, the conversion ratio of 5- dimethyl furans is 84%, the purity of product is 95%, 2,5- oneself two
The yield of ketone is 80%.
Embodiment 12：
Into container, sequentially add：1.5ml2,5- dimethyl furan, 20mL dichloromethane, 0.8gUSY molecular sieve (sial
Than for 20), 0.1ml deionized waters, and uniformly mix.Container is placed in isothermal reactor, under conditions of stirring, with 180
DEG C steady temperature, reacts 5 hours.Container is placed in low temperature environment by reaction after terminating, and system is dropped rapidly to normal temperature.Will be anti-
Solution is answered, the organic phase separation of solid phase reclaims solid acid catalyst, retains organic phase, and carries out vacuum distillation to it, has to remove
Machine solvent, obtains target product.The conversion ratio of raw material and the yield of product are determined by GC-External Standard method and obtained, product it is pure
Degree is obtained by liquid chromatogram measuring.As a result raw material 2 is shown, the conversion ratio of 5- dimethyl furans is 85%, and the purity of product is
93%, the yield of 2,5- acetyl butyryls is 79%.
Claims (6)
1. a kind of method that solid acid catalysis prepares 2.5- acetyl butyryls, it is characterised in that comprise the following steps：
（1）Into raw material 2.5- dimethyl furans, weakly polar organic solvent, solid acid catalyst, distilled water, reaction temperature are added
For 80-200 DEG C, the reaction time is 1-12 hours；
（2）After reaction terminates, reaction system is quenched, system temperature is rapidly decreased to normal temperature, reaction solution is taken out, by reacting liquid filtering
Or centrifuge, solid catalyst drying is reclaimed；Organic phase is collected, obtained organic phase vacuum distillation is removed organic molten
Agent, obtains product 2, and 5- acetyl butyryls, the qualitative analysis of product is obtained by nuclear magnetic spectrum sign；
Step（1）The weakly polar organic solvent is toluene, methylisobutylketone, hexamethylene or ethyl acetate；
Step（1）Described solid acid catalyst is ZSM-5 zeolite molecular sieve, H beta molecular sieves, SAPO-11 molecular sieves or USY
Molecular sieve.
2. the method that a kind of solid acid catalysis as claimed in claim 1 prepares 2.5- acetyl butyryls, it is characterised in that described
The silica alumina ratio of ZSM-5 zeolite molecular sieve is 5-50, and the silica alumina ratio of H beta molecular sieves is 5-70, the silica alumina ratio of SAPO-11 molecular sieves
For 0.1-40, the silica alumina ratio of USY molecular sieve is 1-50.
3. the method that a kind of solid acid catalysis as claimed in claim 2 prepares 2.5- acetyl butyryls, it is characterised in that described
The silica alumina ratio of silica alumina ratio 15-20, H beta molecular sieve of ZSM-5 zeolite molecular sieve is the silica alumina ratio of 20-25, SAPO-11 molecular sieve
It is 1-15 for 0.1-10, USY molecular sieve silica alumina ratio.
4. the method that a kind of solid acid catalysis as claimed in claim 1 prepares 2.5- acetyl butyryls, it is characterised in that step（1）Institute
The 2.5- dimethyl furans and the volume ratio of distilled water stated are 1：0.1-0.5.
5. the method that a kind of solid acid catalysis as claimed in claim 1 prepares 2.5- acetyl butyryls, it is characterised in that step（1）Institute
The volume ratio for stating 2.5- dimethyl furans and weakly polar organic solvent is 1：5-20 .
6. the method that a kind of solid acid catalysis as claimed in claim 1 prepares 2.5- acetyl butyryls, it is characterised in that step（1）Institute
It is 1 mL to state the volume of 2.5- dimethyl furans and the mass ratio of solid acid catalyst：0.5-2 g.
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