CN105439836A - Method for preparing 2,5-hexanedione under catalysis of solid acid - Google Patents
Method for preparing 2,5-hexanedione under catalysis of solid acid Download PDFInfo
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Abstract
The invention provides a method for preparing 2,5-hexanedione under the catalysis of solid acid. The method comprises the following steps: adding an organic solvent with weak polarity, a solid acid catalyst and distilled water into a raw material 2,5-dimethylfuran and carrying out a reaction at a temperature of 80 to 200 DEG C for 1 to 12 h; quenching a reaction system so as to allow the temperature of the system to rapidly drop to normal temperature, taking out a reaction solution, then subjecting the reaction solution to filtering or centrifugation, drying the solid catalyst and recovering the dried solid catalyst; and collecting an organic phase, subjecting the obtained organic phase to reduced-pressure distillation and removing the organic solvent so as to obtain 2,5-hexanedione. The method provided by the invention has the advantages of easiness in separation and no pollution.
Description
Technical field
The invention belongs to a kind of method adopting solid acid molecular sieve to do catalyst preparing 2,5-hexanedione.
Background technology
In recent years, 2,5-hexanedione receives increasing concern as a kind of important chemical intermediate.At present, mainly be used as synthetic resins, nitro spray paint, the high boiling solvent of tinting material, printing-ink etc., leather tanning agent, thiofide and sterilant, medicine material, also can be applicable to sterilant, the various fields such as foodstuff additive, spices, plating are sprayed paint, photograph medicament.
The preparation method of 2,5-hexanedione is numerous, is main usually to be hydrolyzed 2,5-dimethyl furan.2,5-dimethyl furan be hydrolyzed to acid catalyzed process, suitable acid catalyst is selected to be the key that it is effectively hydrolyzed, wherein mineral acid example hydrochloric acid, phosphoric acid or phosphoric acid hydrolysis are prepared comparatively common, but these mineral acids are homogeneous catalysis systems, reaction system and reaction product are not easily separated, easily cause environmental pollution.
Summary of the invention
The object of the present invention is to provide a kind of easily separated, free of contamination 2,5-solid acid catalysis prepare the method for 2,5-hexanedione.
Zeolite molecular sieve is a kind of poromerics being widely used in petrochemical complex, it has strongly-acid, good hydrothermal stability, nontoxicity and the easier advantage such as to reclaim from solution, there is good selective activization in chemical reaction, become a kind of an acidic catalyst of industrially widespread use.Molecular sieve is as solid acid catalyst, and its catalysis derives from the acidic site with catalytic activity that solid surface exists, and molecular sieve itself has uniformly, microvoid structure, the bond area of this acidic site also increased.2,5-dimethyl furan molecular dimension is little, directly enters the micropore of solid acid molecular sieve in the process of reaction.The outer surface acidity of molecular sieve is less on catalytic hydrolysis reaction impact, and hydrolysis reaction mainly occurs in the active sites in molecular sieve pore passage.Patent of the present invention have employed solid acid molecular sieve catalyst hydrolysis 2,5-dimethyl furan, and introduces the organic solvent of low-pole in the reaction, makes reactants dissolved in organic solvent, improves productive rate and the yield of reaction.
Preparation method of the present invention comprises the steps:
(1) in raw material 2,5-dimethyl furan, add weakly polar organic solvent, solid acid catalyst, distilled water, temperature of reaction is 80-200 DEG C, and the reaction times is 1-12 hour;
(2) after reaction terminates, reaction system quenched, system temperature is down to normal temperature rapidly, takes out reaction solution, and by reacting liquid filtering or centrifugation, solid catalyst is dried, and reclaims; Collect organic phase, by the organic phase underpressure distillation obtained, remove organic solvent, obtain product 2,5-hexanedione.The qualitative analysis of product is characterized by nuclear magnetic spectrum and obtains.
As described in step (1), weakly polar organic solvent comprises: toluene, mibk, hexanaphthene or ethyl acetate;
Solid acid catalyst as described in step (1) comprises: (silica alumina ratio is 5-50 to ZSM-5 zeolite molecular sieve, best than being 15-20), (silica alumina ratio is 5-70 to H beta molecular sieve, best than being 20-25), (silica alumina ratio is 0.1-40 to SAPO-11 molecular sieve, best than being 0.1-10), USY molecular sieve (silica alumina ratio is 1-50, best than being 1-15);
As described in step (1), the volume ratio of 2,5-dimethyl furans and distilled water is 1:0.1-0.5;
As described in step (1), the volume ratio of 2,5-dimethyl furans and weakly polar organic solvent is 1:5-20;
As described in step (1), the volume of 2,5-dimethyl furans and the mass ratio of solid acid catalyst are 1mL:0.5-2g.
The present invention first proposed and adopts solid acid molecular sieve catalyst hydrolysis 2,5-dimethyl furan to prepare 2,5-hexanedione, and this is a kind of easy and simple to handle, method that efficient economy is green.The present invention has selected several different molecular sieve as catalyzer, select several solvent as the extraction agent in system, in 80-200 DEG C of temperature range, in the little the reaction time of 1-12, investigate 2,5-dimethyl furan highly selective is converted into the reaction result of 2,5-hexanedione.
The present invention has investigated differing molecular sieve catalyst, different solvents, reaction times, temperature of reaction and reaction mass proportioning to the impact of 2,5-hexanedione yield.First different molecular sieve catalysts has been investigated.The mechanism of furan nucleus fracture is the aromaticity that the protonation of Sauerstoffatom destroys furan nucleus.The stability of ring fracture depends on the substituent type in local.The alkyl derivative of furans is then easier to destroyed aromaticity, makes 2,5-dimethyl furan have hydrolysis rate faster.In fact, the hydrolysis rate of 2,5-dimethyl furan even can arrive 5000 times of furans.The hydrolysis of 2,5-dimethyl furan is acid catalyzed process, selects suitable acid catalyst to be the key that 2,5-dimethyl furan is effectively hydrolyzed.Solid acid molecular sieve has uniform bore road structure, larger acidic site bond area, and the features such as easily separated recovery, this patent selects four kinds of different molecular sieves as 2, the acid catalyst of 5-dimethyl furan, such as, ZSM-5 zeolite molecular sieve, H beta molecular sieve, SAPO-11 molecular sieve, USY molecular sieve.The vesicular structure of molecular sieve can hold a lot of positively charged ion, as H
+, Na
+, K
+, Mg
2+deng.What these positively charged ions were loose is combined in molecular sieve surface, and they can be discharged in the aqueous solution and show different catalytic performances.The size of 2,5-dimethyl furan molecule is little, directly enters the micropore of solid acid molecular sieve in the process of reaction.The outer surface acidity of molecular sieve is less on catalytic hydrolysis reaction impact, and hydrolysis reaction mainly occurs in the acid active sites in molecular sieve pore passage.The silica alumina ratio of molecular sieve can be strong the character affecting its acid.When the silica alumina ratio of ZSM-5 zeolite molecular sieve be less than 5, the silica alumina ratio of H beta molecular sieve is less than 5, the silica alumina ratio of SAPO-11 molecular sieve is less than 0.1, the silica alumina ratio of USY molecular sieve is less than 1 time, the product 2 obtained, 5-hexanedione output is lower, this be due to silica alumina ratio lower time, the acidity of acidic site is too weak effectively can not promote that 2,5-dimethyl furan is hydrolyzed.Along with silica alumina ratio is higher, total acid content reduces, and acidic site reduces, the acid grow of Single locus.When the silica alumina ratio of ZSM-5 zeolite molecular sieve be greater than 50, the silica alumina ratio of H beta molecular sieve is greater than 70, the silica alumina ratio of SAPO-11 molecular sieve is greater than 40, the silica alumina ratio of USY molecular sieve is greater than 50 time, the quantity of acidic site can not make raw material 2 less, 5-dimethyl furan complete hydrolysis, product 2, the 5-hexanedione yield obtained is low.Therefore, when the scope of the scope of an acidic catalyst ZSM-5 zeolite molecular sieve silica alumina ratio to be the scope of 5-50, H beta molecular sieve silica alumina ratio be 5-70, SAPO-11 molecular sieve silica alumina ratio is 0.1-40, the scope of USY molecular sieve silica alumina ratio is 1-50,2 can be hydrolyzed by efficient catalytic, 5-dimethyl furan prepares 2,5-hexanedione.And for the add-on of catalyzer, when 2, when the volume of 5-dimethyl furan and the mass ratio of acid catalyst are greater than 1mL:2g, adding of a large amount of solid acid catalyst, although catalysis positive reaction target product can be generated, product can be caused can not to migrate out pore passage structure in time simultaneously, be trapped in molecular sieve pore passage and continue to have an effect with acidic site, cause the product generated to decompose further, cause serious side reaction, the yield of product declines.When the volume of 2,5-dimethyl furan and the mass ratio of acid catalyst are less than 1mL:0.5g, the add-on calculating molecular sieve due to solid is very few, causes raw material 2,5-dimethyl furan with acidic site fully in conjunction with conversion, can not obtain target product yield low.Therefore, when the volume of 2,5-dimethyl furan and the mass ratio of acid catalyst are between 1mL:0.5-2g, catalyzer can efficient catalytic raw material 2,5-dimethyl furan, obtains high product yield.In sum, the catalyzer applied in 2,5-dimethyl furan hydrolysis preparation feedback is solid acid molecular sieve catalyst, and it is more easily separated at product, environmental pollution is less, in the development in future, have huge potentiality.
Then, the impact that different organic solvents is hydrolyzed 2,5-dimethyl furan is investigated.Select the object of organic solvent, on the one hand, in order to the acidic site making raw material 2,5-dimethyl furan can touch molecular sieve better, the present invention has selected different organic solvent dissolution raw materials; On the other hand, the existence of organic solvent can be hydrolyzed the product generated by situ extracting raw material, effectively can avoid product 2,5-hexanedione generation side reaction like this, ensure that the purity of product.Target product 2,5-hexanedione is a kind of low-pole compound, according to the similar principle mixed, selects weakly polar organic solvent to be more suitable for the separation preparation of this product compared to polar solvent.Weakly polar organic solvent is a kind of environmentally friendly solvent, is used as the medium much having chemical reaction.Multiple weakly polar organic solvent has been selected, as hexanaphthene, toluene, mibk, methylene dichloride, ethyl acetate etc. in the present invention.Product 2,5-hexanedione partition ratio in these organic solvents is all greater than 1.0.Experimental data shows, in these solvents, toluene and mibk catalytic effect are very well, this is because product 2,5-hexanedione has good solvability in toluene and mibk.In particular, because mibk contains ketone group, so best to the effect of extracting of 2,5-hexanedione, the output of the finished product is also up to 98%.But, when 2, when the volume ratio of 5-dimethyl furan and weakly polar organic solvent is greater than 1:20, the transformation efficiency of raw material can decline, this is because a large amount of organic solvents exists, raw material mass transfer is in organic solvent hindered, and causes raw material 2,5-dimethyl furan can not fully contact generation with acid and transforms completely; And the volume ratio of 2,5-dimethyl furans and weakly polar organic solvent is when being less than 1:5, because the add-on of organic solvent is very few, can not extraction product completely, product can continue to contact with mineral acid, side reaction occurs, can not prepare target product with high yield.Therefore, when raw material 2,5-dimethyl furan and weakly polar organic solvent volume ratio are between 1:5-20,2,5-dimethyl furan can efficient high place of production preparing product 2,5-hexanedione.
In addition, the hydrolytic process due to 2,5-dimethyl furan needs the participation of water, adds a certain amount of distilled water in system of the present invention.When the volume ratio of 2,5-dimethyl furan and distilled water is less than 1:0.1, be not enough to provide 2,5-dimethyl furan be hydrolyzed required for water molecules, thus hydrolysis reaction can not carry out completely, and this just constrains the conversion of raw material, causes the decline of product yield; When 2, when the volume ratio of 5-dimethyl furan and distilled water is greater than 1:0.5, the yield of product 2,5-hexanedione also can reduce, and this is because solid acid molecular sieve has stronger water-absorbent, when adding a large amount of water, water molecules can occupy the pore passage structure of molecular sieve, causes 2,5-dimethyl furan molecule not to be combined by the acidic site well in duct, raw material can not transform completely, and the product yield obtained is low.So, when the volume ratio of 2,5-dimethyl furan and distilled water is between 1:0.1-0.5,2,5-dimethyl furan can synthesize 2,5-hexanedione efficiently.
The reaction conditions of the present invention's hydrolysis is temperature of reaction is 80-200 DEG C, and the reaction times is 1-12 hour, and the determination of reaction conditions needs the feature of association reaction and the performance synthesis of catalyzer to consider.Experimental result shows, reaction starts, 2, the yield of 5-hexanedione is lower, and along with the reaction times was increased to 12 hours from 1 hour, molecular sieve is inside and outside constantly to carry out with the effect of mass transmitting of organic solvent, raw material 2,5-dimethyl furan constantly contacts hydrolysis with the acidic site in molecular sieve pore passage structure, and the yield of 2,5-hexanedione continues to increase, time to 12 hours, raw material 2,5-dimethyl furan completes conversion substantially, and the transformation efficiency of raw material now reaches maximum 87%.Continue prolongation when reacted more than 12 hours, transformation efficiency and the product yield of raw material have a declining tendency.Temperature of reaction is elevated to 200 DEG C from 80 DEG C, and the transformation efficiency of 2,5-dimethyl furan raises gradually, and the yield of 2,5-hexanedione is also in rising.This is because 2,5-dimethyl furan exists β-protonated and α-protonated two kinds of routes in hydrolytic process, β-protonated can obtain 2,5-hexanedione product, and α-protonated route finally obtains by product, due to the activation energy (E of β-protonated
a=20kcal/mol) higher than the activation energy (E of α-protonated
a=17kcal/mol), therefore, the higher meeting of temperature makes reaction tend to β-protonated route, so be elevated to 200 DEG C of periods at 80 DEG C, the transformation efficiency of raw material and selectivity of product all can increase.When temperature reaches 200 DEG C, the transformation efficiency of raw material 2,5-dimethyl furan reaches maximum 90%, and now the yield of 2,5-hexanediones also reaches maximum 88%.But when temperature of reaction is more than 200 DEG C, the yield of product has no raising, has on the contrary and slightly declines.Major cause is above 200 DEG C can cause serious side reaction, and 2,5-hexanediones of generation may be impelled to be decomposed into other micromolecular compounds further, thus causes the yield of 2,5-hexanedione to reduce.
According to above-mentioned great many of experiments, the proportioning of the different solid acid molecular sieves investigated, different organic solvents, differential responses thing can be determined, and the various experiment parameter such as different time and different temperature of reaction, all can catalysis efficiently 2,5-dimethyl furan hydrolysis preparation 2,5-hexanedione.
The present invention has following advantage:
(1) the present invention selects solid acid catalyst, 2 are realized in weakly polar organic solvent, 5-dimethyl furan hydrolysis preparation 2,5-hexanedione, this reaction make use of the porous advantage of molecular sieve and the characteristic of bigger serface, and molecular sieve fully can contact with raw material, its Hole bottom cavity blast suppresses the polymerization of product simultaneously, main reaction can fully be carried out, and reaction after product is easy to be separated with catalyzer, operates comparatively simple.And molecular sieve is nontoxic can not to environment.
(2) adopt organic solvent in the reaction, for whole reaction is carried out creating favourable reaction environment, suppress the generation of side reaction simultaneously.After product generates, situ extracting, in organic solvent, significantly improves selectivity and the productive rate of reaction, also reduces the separating difficulty of reactant and product.The transformation efficiency of 2,5-dimethyl furan reaches as high as 85%, and yield is more than 79%.
(3) whole reaction process, simple to operate, safe and reliable, and reaction conditions is gentle, can not produce pollute environment.
Accompanying drawing explanation
Fig. 1 is the response path of the present invention 2,5-dimethyl furan synthesis 2,5-hexanedione.
Fig. 2 is embodiment 1 product
13cNMR collection of illustrative plates.
Fig. 3 is embodiment 1 product
1hNMR collection of illustrative plates.
Embodiment
Embodiment 1:
1ml2,5-dimethyl furan is joined in container, then adds 12ml mibk, 0.2ml deionized water and 0.8gH beta molecular sieve (silica alumina ratio is 20), mix.Container is placed in 180 DEG C of isothermal reactors, constantly stirs, react 5 hours.After reaction terminates, ice bath put into by container, and reaction is quenched, and system temperature is dropped rapidly to room temperature.Take out reaction product, centrifugation organic phase and solid catalyst, collect organic phase, reclaim catalyzer.By the organic phase underpressure distillation obtained, remove organic solvent, obtain product (see accompanying drawing 2 and 3).The transformation efficiency of raw material and the yield of product are measured by GC-External Standard method and obtain, and the purity of product is obtained by liquid chromatogram measuring.The transformation efficiency of result display 2,5-dimethyl furan is 85%, and the purity of product is the yield of 92%, 5-hexanedione is 81%.
Embodiment 2:
First 1ml raw material 2,5-dimethyl furan is joined in container, then add 10ml mibk, 0.8gUSY molecular sieve (silica alumina ratio is 5), 0.1ml deionized water.Put into reactor after mixing, stir, 180 DEG C of isothermal reactions 5 hours.Reaction completes, and reaction product is placed in low temperature and quenches, and makes temperature be down to normal temperature rapidly.Centrifugation afterwards, reclaims catalyzer, collects organic phase, by the organic phase underpressure distillation obtained, removes organic solvent, obtains product.The transformation efficiency of raw material and the yield of product are measured by GC-External Standard method and obtain, and the purity of product is obtained by liquid chromatogram measuring.The transformation efficiency of result display raw material 2,5-dimethyl furan is 85%, and the purity of product is the yield of 90%, 2,5-hexanedione is 78%.
Embodiment 3:
To in container, add successively: 1ml2,5-dimethyl furan, 12ml mibk, 0.1ml deionized water, 1.2gZSM-5 zeolite molecular sieve (silica alumina ratio is 20), and Homogeneous phase mixing.Container is placed in isothermal reactor, 200 DEG C of reactions 5 hours.System is made to be dropped rapidly to normal temperature after reaction terminates.By reaction soln, solid phase organic phase is separated, and reclaims catalyzer, collects organic phase.Underpressure distillation is carried out to organic phase, to remove organic solvent, obtains product.The transformation efficiency of raw material and the yield of product are measured by GC-External Standard method and obtain, and the purity of product is obtained by liquid chromatogram measuring.The transformation efficiency of result display raw material 2,5-dimethyl furan is 82%, and the purity of product is the yield of 92%, 2,5-hexanedione is 75%.
Embodiment 4:
1ml2,5-dimethyl furan is joined in container, then adds 12ml toluene, 0.8gH beta molecular sieve (silica alumina ratio is 20) and 0.2ml deionized water, mix.Container is placed in 160 DEG C of isothermal reactors, constantly stirs, react 5 hours.After reaction terminates, ice bath put into by container, and reaction is quenched, and system temperature is dropped rapidly to room temperature.Take out reaction product, centrifugation organic phase and solid catalyst, reclaim catalyzer, collect organic phase.Underpressure distillation is carried out to organic phase, to remove organic solvent, obtains target product.The transformation efficiency of raw material and the yield of product are measured by GC-External Standard method and obtain, and the purity of product is obtained by liquid chromatogram measuring.The transformation efficiency of result display raw material 2,5-dimethyl furan is 86%, and the purity of product is the yield of 91%, 2,5-hexanedione is 82%.
Embodiment 5:
First 1ml raw material 2,5-dimethyl furan is joined in container, then add 10ml mibk, 0.1ml deionized water and 1.5gSAPO-11 molecular sieve (silica alumina ratio is 1).Put into reactor after mixing, stir, 200 DEG C of isothermal reactions 12 hours.Reaction completes, and reaction product is placed in low temperature and quenches, and makes temperature be down to normal temperature rapidly.Centrifugation afterwards, reclaims catalyzer, collects organic phase, and carries out underpressure distillation to it, to remove organic solvent, obtain target product.The transformation efficiency of raw material and the yield of product are measured by GC-External Standard method and obtain, and the purity of product is obtained by liquid chromatogram measuring.The transformation efficiency of result display raw material 2,5-dimethyl furan is 82%, and the purity of product is the yield of 90%, 2,5-hexanedione is 77%.
Embodiment 6:
To in container, add successively: 1ml2,5-dimethyl furan, 12ml ethyl acetate, 1.5gUSY molecular sieve (silica alumina ratio is 20), 0.5ml deionized water, and Homogeneous phase mixing.Container is placed in isothermal reactor, under the condition stirred, with 180 DEG C of steady temperatures, reacts 5 hours.After reaction terminates, container is placed in low temperature environment, makes system be dropped rapidly to normal temperature.By reaction soln, solid phase organic phase is separated, and reclaims solid phase, retains organic phase, and carries out underpressure distillation to it, can obtain target product.The transformation efficiency of raw material and the yield of product are measured by GC-External Standard method and obtain, and the purity of product is obtained by liquid chromatogram measuring.The transformation efficiency of result display raw material 2,5-dimethyl furan is 87%, and the purity of product is the yield of 92%, 2,5-hexanedione is 83%.
Embodiment 7:
To in container, add successively: 1ml2,5-dimethyl furan, 15mL toluene, 0.5gH beta molecular sieve (silica alumina ratio is 25), 0.3ml deionized water, and Homogeneous phase mixing.Container is placed in isothermal reactor, under the condition stirred, with 200 DEG C of steady temperatures, reacts 1 hour.After reaction terminates, container is placed in low temperature environment, makes system be dropped rapidly to normal temperature.By reaction soln, solid phase organic phase is separated, and reclaims solid acid molecular sieve, retains organic phase, and carries out underpressure distillation to it, can obtain target product.The transformation efficiency of raw material and the yield of product are measured by GC-External Standard method and obtain, and the purity of product is obtained by liquid chromatogram measuring.The transformation efficiency of result display raw material 2,5-dimethyl furan is 84%, and the purity of product is the yield of 94%, 2,5-hexanedione is 80%.
Embodiment 8:
1ml2,5-dimethyl furan is joined in container, then adds 10ml toluene, 0.2ml deionized water and 1.0gZSM-5 zeolite molecular sieve (silica alumina ratio is 20), mix.Container is placed in 200 DEG C of isothermal reactors, constantly stirs, react 3 hours.After reaction terminates, ice bath put into by container, and reaction is quenched, and system temperature is dropped rapidly to room temperature.Take out reaction product, centrifugation organic phase and solid catalyst, reclaim catalyzer, collect organic phase.Underpressure distillation is carried out to organic phase, can target product be obtained.The transformation efficiency of raw material and the yield of product are measured by GC-External Standard method and obtain, and the purity of product is obtained by liquid chromatogram measuring.The transformation efficiency of result display 2,5-dimethyl furan is 80%, and the purity of product is the yield of 90%, 2,5-hexanedione is 75%.
Embodiment 9:
First 1ml raw material 2,5-dimethyl furan is joined in container, then add 15ml mibk, 0.1ml deionized water and 1.0gZSM-5 zeolite molecular sieve (silica alumina ratio is 20).Put into reactor after mixing, stir, 200 DEG C of isothermal reactions 12 hours.Reaction completes, and reaction product is placed in low temperature and quenches, and makes temperature be down to normal temperature rapidly.Centrifugation afterwards, reclaims solid acid, collects organic phase, and carries out underpressure distillation to it, can obtain target product.The transformation efficiency of raw material and the yield of product are measured by GC-External Standard method and obtain, and the purity of product is obtained by liquid chromatogram measuring.The transformation efficiency of result display raw material 2,5-dimethyl furan is 79%, and the purity of product is the yield of 92%, 2,5-hexanedione is 75%.
Embodiment 10:
First 1ml raw material 2,5-dimethyl furan is joined in container, then adds 8ml mibk, 1.0gZSM-5 zeolite molecular sieve (silica alumina ratio is 20), 0.1ml deionized water.Put into reactor after mixing, stir, 180 DEG C of isothermal reactions 8 hours.Reaction completes, and reaction product is placed in low temperature and quenches, and makes temperature be down to normal temperature rapidly.Centrifugation afterwards, reclaims solid acid molecular sieve, collects organic phase, carries out underpressure distillation, can obtain target product to it.The transformation efficiency of raw material and the yield of product are measured by GC-External Standard method and obtain, and the purity of product is obtained by liquid chromatogram measuring.The transformation efficiency of result display raw material 2,5-dimethyl furan is 79%, and the purity of product is the yield of 90%, 2,5-hexanedione is 75%.
Embodiment 11:
1ml2,5-dimethyl furan is joined in container, then adds 10ml hexanaphthene, 0.2ml deionized water and 1.2H beta molecular sieve (silica alumina ratio is 20), mix.Container is placed in 140 DEG C of isothermal reactors, constantly stirs, react 7 hours.After reaction terminates, ice bath put into by container, and reaction is quenched, and system temperature is dropped rapidly to room temperature.Take out reaction product, centrifugation organic phase and solid catalyst, reclaim catalyzer, collect organic phase, and underpressure distillation is carried out to it, can target product be obtained.The transformation efficiency of raw material and the yield of product are measured by GC-External Standard method and obtain, and the purity of product is obtained by liquid chromatogram measuring.The transformation efficiency of result display raw material 2,5-dimethyl furan is 84%, and the purity of product is the yield of 95%, 2,5-hexanedione is 80%.
Embodiment 12:
To in container, add successively: 1.5ml2,5-dimethyl furan, 20mL methylene dichloride, 0.8gUSY molecular sieve (silica alumina ratio is 20), 0.1ml deionized water, and Homogeneous phase mixing.Container is placed in isothermal reactor, under the condition stirred, with 180 DEG C of steady temperatures, reacts 5 hours.After reaction terminates, container is placed in low temperature environment, makes system be dropped rapidly to normal temperature.By reaction soln, solid phase organic phase is separated, and reclaims solid acid catalyst, retains organic phase, and carries out underpressure distillation to it, to remove organic solvent, obtain target product.The transformation efficiency of raw material and the yield of product are measured by GC-External Standard method and obtain, and the purity of product is obtained by liquid chromatogram measuring.The transformation efficiency of result display raw material 2,5-dimethyl furan is 85%, and the purity of product is the yield of 93%, 2,5-hexanedione is 79%.
Claims (8)
1. a solid acid catalysis prepares the method for 2,5-hexanedione, it is characterized in that comprising the steps:
(1) in raw material 2,5-dimethyl furan, add weakly polar organic solvent, solid acid catalyst, distilled water, temperature of reaction is 80-200 DEG C, and the reaction times is 1-12 hour;
(2) after reaction terminates, reaction system quenched, system temperature is down to normal temperature rapidly, takes out reaction solution, and by reacting liquid filtering or centrifugation, solid catalyst is dried, and reclaims; Collect organic phase, by the organic phase underpressure distillation obtained, remove organic solvent, obtain product 2,5-hexanedione; The qualitative analysis of product is characterized by nuclear magnetic spectrum and obtains.
2. a kind of solid acid catalysis as claimed in claim 1 prepares the method for 2,5-hexanedione, it is characterized in that step (1) described weakly polar organic solvent comprises: toluene, mibk, hexanaphthene or ethyl acetate.
3. a kind of solid acid catalysis as claimed in claim 1 prepares the method for 2,5-hexanedione, it is characterized in that the solid acid catalyst described in step (1) comprises ZSM-5 zeolite molecular sieve, H beta molecular sieve, SAPO-11 molecular sieve or USY molecular sieve.
4. a kind of solid acid catalysis as claimed in claim 3 prepares 2, the method of 5-hexanedione, it is characterized in that the silica alumina ratio of described ZSM-5 zeolite molecular sieve is 5-50,, H beta molecular sieve silica alumina ratio be 5-70, the silica alumina ratio of SAPO-11 molecular sieve is 0.1-40, and the silica alumina ratio of USY molecular sieve is 1-505.
5. a kind of solid acid catalysis as claimed in claim 4 prepares 2, the method of 5-hexanedione, is characterized in that the silica alumina ratio of silica alumina ratio 15-20, H beta molecular sieve of described ZSM-5 zeolite molecular sieve be the silica alumina ratio of 20-25, SAPO-11 molecular sieve is 0.1-10, the silica alumina ratio of USY molecular sieve is 1-15.
6. a kind of solid acid catalysis as claimed in claim 1 prepares the method for 2,5-hexanedione, it is characterized in that the volume ratio of 2,5-dimethyl furans described in step (1) and distilled water is 1:0.1-0.5.
7. a kind of solid acid catalysis as claimed in claim 1 prepares the method for 2,5-hexanedione, it is characterized in that the volume ratio of described 2, the 5-dimethyl furans of step (1) and weakly polar organic solvent is 1:5-20.
8. a kind of solid acid catalysis as claimed in claim 1 prepares the method for 2,5-hexanedione, it is characterized in that the volume of described 2, the 5-dimethyl furans of step (1) and the mass ratio of solid acid catalyst are 1mL:0.5-2g.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510918512.0A CN105439836B (en) | 2015-12-11 | 2015-12-11 | A kind of method that solid acid catalysis prepares 2,5 acetyl butyryls |
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| CN201510918512.0A CN105439836B (en) | 2015-12-11 | 2015-12-11 | A kind of method that solid acid catalysis prepares 2,5 acetyl butyryls |
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| CN105439836A true CN105439836A (en) | 2016-03-30 |
| CN105439836B CN105439836B (en) | 2017-07-25 |
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| CN201510918512.0A Active CN105439836B (en) | 2015-12-11 | 2015-12-11 | A kind of method that solid acid catalysis prepares 2,5 acetyl butyryls |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022242730A1 (en) * | 2021-05-21 | 2022-11-24 | 中国石油化工股份有限公司 | Method for preparing 2, 5-hexanedione by catalyzing and converting biomass by one-pot synthesis |
| US11608317B2 (en) | 2021-03-16 | 2023-03-21 | Chevron Phillips Chemical Company, Lp | Two-step synthesis of pyrrole compounds from furan compounds |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA376066A (en) * | 1938-08-30 | J. Toussaint Walter | Acetonylacetone | |
| CN101423467A (en) * | 2008-11-14 | 2009-05-06 | 河北科技大学 | Method for synthesizing 2,5-acetonyl acetone |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA376066A (en) * | 1938-08-30 | J. Toussaint Walter | Acetonylacetone | |
| CN101423467A (en) * | 2008-11-14 | 2009-05-06 | 河北科技大学 | Method for synthesizing 2,5-acetonyl acetone |
Non-Patent Citations (1)
| Title |
|---|
| YUE ZHANG ET AL: "Clean synthesis process of 2,5-hexanedione", 《ADANCED MATERIALS RESEARCH》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11608317B2 (en) | 2021-03-16 | 2023-03-21 | Chevron Phillips Chemical Company, Lp | Two-step synthesis of pyrrole compounds from furan compounds |
| WO2022242730A1 (en) * | 2021-05-21 | 2022-11-24 | 中国石油化工股份有限公司 | Method for preparing 2, 5-hexanedione by catalyzing and converting biomass by one-pot synthesis |
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| CN105439836B (en) | 2017-07-25 |
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