CN103121929A - Method for producing 4-hexene-3-one by dehydration of 4-hydroxyl-3-hexanone - Google Patents
Method for producing 4-hexene-3-one by dehydration of 4-hydroxyl-3-hexanone Download PDFInfo
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- CN103121929A CN103121929A CN2011103669659A CN201110366965A CN103121929A CN 103121929 A CN103121929 A CN 103121929A CN 2011103669659 A CN2011103669659 A CN 2011103669659A CN 201110366965 A CN201110366965 A CN 201110366965A CN 103121929 A CN103121929 A CN 103121929A
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Abstract
The invention relates to a method for producing 4-hexene-3-one by dehydration of 4-hydroxyl-3-hexanone and mainly solves the problem that catalysts are low in activity, high in reaction temperature and low in space velocity in the prior art. The 4-hydroxyl-3-hexanone is used as material to contact with catalyst at the reaction temperature of 200 DEG C-400 DEG C at weight hourly space velocity of 0.5-15 hours-1 relative to the 4-hydroxyl-3-hexanone so as to generate 4-hexene-3-one. The catalyst is molecular sieve ZSM-11 (zeolite socony mobil-11). The problem is solved well by the application of the technical scheme. The method is applicable to industrial production of 4-hexene-3-one by 4-hydroxyl-3-hexanone.
Description
Technical field
The present invention relates to the method for a kind of 4-hydroxyl-3-hexanone Dehydration 4-hexene-3-one.
Background technology
4-hexene-3-one (CAS:2497-21-4) is a kind of spices (Chinese GB 2760-2007) of uniqueness, is mainly used in allocating the food flavours such as old nurse, butter, horseradish, and is of many uses.
The oxy-compound dehydration reaction is under catalyzer exists, the reaction that hydroxyl on two atoms close in reactant molecule and hydrogen atom are sloughed with the form of water.Contain lone-pair electron on Sauerstoffatom due to hydroxyl, therefore can with proton (H
+) combination, form oxonium ion, due to positively charged on Sauerstoffatom, make it to become strong electron-withdrawing group, make the C-O key easily from solution.Whole dehydration reaction comprises: generate protonated oxonium salt (R-OH
2 +), oxonium salt dissociates into carbonium ion lentamente, gets rid of very soon a hydrogen ion and form alkene from carbonium ion, and β-elimination reaction has namely occured.At alpha-alcohol ketone Dehydration α, in the reaction of beta unsaturated ketone, due to the impact of carbonyl, make Alpha-hydroxy form the oxonium ion difficulty, cause the more difficult generation of reaction.
4-hydroxyl-3-hexanone (the third acyloin) catalytic dehydration mainly generates 4-hexene-3-one, 2-Methyl-1-pentene-two kinds of 3-ketone isomer, and 5-hexene-3-one, two kinds of isomer of cyclopropyl ethyl ketone are subjected to the more difficult formation of thermodynamical restriction, react as follows.
Document EP 406676 discloses the method for Alpha-hydroxy isobutyric acid methyl esters (MOB) Dehydration methyl methacrylate (MM).Document DE3632530 discloses the employing solid acid catalyst, generates α, beta unsaturated ketone by the alpha-alcohol ketone dehydration.Low (air speed was lower than 5 hours but the method exists temperature of reaction high (temperature of reaction is over 300 ℃), air speed
-1) and the shortcoming of poor catalyst activity.
Summary of the invention
Technical problem to be solved by this invention is that in conventional art, temperature of reaction is high, air speed is low and the problem of poor catalyst activity, and the method for a kind of new 4-hydroxyl-3-hexanone Dehydration 4-hexene-3-one is provided.The method has good catalyst activity, temperature of reaction is low and air speed is high characteristics.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for a kind of 4-hydroxyl-3-hexanone Dehydration 4-hexene-3-one, take 4-hydroxyl-3-hexanone as raw material, be 200～400 ℃ in temperature of reaction, be 0.5～15 hour with respect to 4-hydroxyl-3-hexanone liquid mass air speed
-1Under condition, reaction raw materials contacts with catalyzer and generates the 4-hexene-3-one; Wherein catalyzer used is binderless ZSM-5-11 molecular sieve.
In technique scheme, the SiO of binderless ZSM-5-11 molecular sieve
2/ Al
2O
3=20～200.The temperature of reaction preferable range is 250～350 ℃, is 1～10 hour with respect to 4-hydroxyl-3-hexanone liquid mass air speed preferable range
-1
Binderless ZSM-5 in the present invention-11 molecular sieve prepares as follows: a) to be selected from least a as the silicon source in diatomite, water glass, silicon sol or the White Carbon black, to be selected from least a as the aluminium source in sodium metaaluminate, Tai-Ace S 150 or aluminum nitrate, add aqueous sodium hydroxide solution to mix, pinch even, moulding, drying obtains presoma I.Precursor I Raw is 1～20Na according to molar ratio computing
2O: Al
2O
3: 20～200SiO
2B) with precursor I in containing the cationic aqueous solution steam of TBuA, processed 2～25 days under 100～200 ℃ of conditions, products therefrom obtains binderless ZSM-5-11 molecular sieve through washing, Template removal, ammonia exchange, roasting; The weight ratio of the cationic aqueous solution of TBuA and presoma I is 0.5～10, the cationic aqueous solution mass concentration 5～80% of TBuA.
In technique scheme, can add or not add extrusion aid in the kneaded and formed process of precursor I, extrusion aid is selected from least a in field mountain valley with clumps of trees and bamboo powder or starch, and the consumption of extrusion aid is 1～10% of presoma I weight.At least a in the preferred Tetrabutyl amonium bromide of TBuA positively charged ion, tetrabutylammonium chloride, tetrabutylammonium iodide or TBAH.Precursor I preferably processed 5～20 days under 130～180 ℃ of conditions, formed binderless ZSM-5-11 molecular sieve.
Binderless ZSM-5 in the present invention-11 molecular sieve also can prepare as follows: a) to be selected from least a as the silicon source in diatomite, water glass, silicon sol or the White Carbon black, to be selected from least a as the aluminium source in sodium metaaluminate, Tai-Ace S 150 or aluminum nitrate, add SiO
2/ Al
2O
3=20～300 ZSM-11 molecular sieve powder adds aqueous sodium hydroxide solution to mix, pinch even, moulding, drying obtains presoma I.Wherein by weight percentage, the weight percent that the ZSM-11 molecular sieve accounts for precursor I is 0.5～90%, and the raw material in precursor I outside the ZSM-11 molecular sieve powder is counted 0～15Na according to weight ratio
2O: 0～6Al
2O
3: 100SiO
2B) with precursor I in containing the cationic aqueous solution steam of TBuA, processed 1～15 day under 100～200 ℃ of conditions, products therefrom obtains binderless ZSM-5-11 molecular sieve through washing, Template removal, ammonia exchange, roasting; The weight ratio of the cationic aqueous solution of TBuA and presoma I is 0.5～10, the cationic aqueous solution mass concentration 5～80% of TBuA.
In technique scheme, ZSM-11 molecular sieve powder SiO
2/ Al
2O
3Preferred 40～150, by weight percentage, the weight percent that the ZSM-11 molecular sieve accounts for precursor I is preferably 1～60%.Can add or not add extrusion aid in the kneaded and formed process of precursor I, extrusion aid is selected from least a in field mountain valley with clumps of trees and bamboo powder, starch, and the consumption of extrusion aid is 1～10% of presoma I weight.At least a in the preferred Tetrabutyl amonium bromide of TBuA positively charged ion or TBAH.Precursor I preferably processed 2～10 days under 120～180 ℃ of conditions, formed binderless ZSM-5-11.
Zeolite molecular sieve has unique performance, is widely used in catalytic field.General synthetic zeolite molecular sieve is Powdered, is very restricted in catalytic applications, as catalyzer, must first with zeolite powder molecular sieve and binding agent moulding, make catalyzer have certain macro-size.So operation causes the zeolite molecular sieve effective surface area to reduce, and simultaneously, binding agent has stopped up the duct of zeolite molecular sieve to a certain extent, makes the diffusion of reactant be subject to impact.The present invention is by adopting binderless ZSM-5-11 molecular sieve as catalyzer, and not only available effective surface area is large, and catalytic active site is many; And having abundant pore structure, the duct is open, has eliminated to a certain extent the impact of diffusion, and catalyzer can be used more effectively; Avoided simultaneously the binding agent moulding to stop up the shortcoming of molecular sieve pore passage, binderless ZSM-5-11 molecular sieve pore passage is unimpeded, is beneficial to the diffusion of reactant and product, and therefore the formation of carbon distribution in the inhibited reaction process have better catalytic performance.So employing the inventive method, under lower temperature of reaction, higher air speed condition, temperature of reaction is 290 ℃, is 6 hours with respect to 4-hydroxyl-3-hexanone liquid mass air speed
-1, 4-hydroxyl-3-hexanone transformation efficiency is that the selectivity of 100.0%, 4-hexene-3-one reaches 97.0%, has obtained technique effect preferably.
Description of drawings
Fig. 1 is the XRD spectra of [embodiment 1] synthetic binderless ZSM-5-11 molecular sieve.
In Fig. 1, X-ray diffracting spectrum is 23.0,23.9, and there is strong diffraction peak at 7.9,8.8 and 45.1 degree places, illustrate that this zeolite has the MEL topological framework, are the ZSM-11 zeolites.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Take 7.4 gram silicon sol (SiO
2Weight content 40%), then add sodium metaaluminate, 40% aqueous sodium hydroxide solution, make mol ratio be: 6.36Na
2O: Al
2O
3: 80.22SiO
2, and add entry and mix, pinch even and extruded moulding.100 ℃ of dryings are 1 hour afterwards, pelletizing.The mixture that adds in advance 2 gram Tetrabutyl amonium bromides and 10 gram distilled water in reactor, mixture top placement stainless (steel) wire is placed in the molecular sieve after moulding on stainless (steel) wire sealed reactor.Reactor is carried out gas-solid at 150 ℃ to be processed 10 days mutually.Product takes out by washing, 120 ℃ of dryings and removed template in 5 hours 550 ℃ of roastings after 10 hours, and the XRD characterization result of sample is seen Fig. 1.Afterwards with resulting materials at 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
The performance evaluation of catalyzer is carried out on atmospheric fixed bed reaction unit, and the employing internal diameter is the stainless steel reactor of 10 millimeters, and the loadings of catalyzer is 10 milliliters, and temperature of reaction is 270 ℃, and the liquid air speed is 5 hours
-1, react under normal pressure.HP 6890 gas-chromatographies, hydrogen flame detector, HP-6 kapillary pillar (60m * 0.25mm * 0.25 μ m) are adopted in the reaction product analysis.Reaction result sees Table 1.
[embodiment 2]
Take 7.4 gram silicon sol (SiO
2Weight content 40%), then add sodium metaaluminate, 40% aqueous sodium hydroxide solution, make mol ratio be: 8Na
2O: Al
2O
3: 100SiO
2, and add entry and mix, pinch even and extruded moulding.120 ℃ of dryings are 1 hour afterwards, pelletizing.The mixture that adds in advance 2 gram TBAH and 10 gram distilled water in reactor, mixture top placement stainless (steel) wire is placed in the molecular sieve after moulding on stainless (steel) wire sealed reactor.Reactor is carried out gas-solid at 170 ℃ to be processed 5 days mutually.Product takes out by washing, 120 ℃ of dryings and removed template in 5 hours 550 ℃ of roastings after 10 hours.Afterwards with resulting materials at 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction conditions and the results are shown in Table 1.
[embodiment 3]
Take 7.4 gram silicon sol (SiO
2Weight content 40%), then add sodium metaaluminate, 40% aqueous sodium hydroxide solution, make mol ratio be: 4Na
2O: Al
2O
3: 60SiO
2, and add entry and mix, pinch even and extruded moulding.120 ℃ of dryings are 2 hours afterwards, pelletizing.The mixture that adds in advance 7 gram TBAH and 10 gram distilled water in reactor, mixture top placement stainless (steel) wire is placed in the molecular sieve after moulding on stainless (steel) wire sealed reactor.Reactor is carried out gas-solid at 180 ℃ to be processed 3 days mutually.Product takes out by washing, 120 ℃ of dryings and removed template in 5 hours 550 ℃ of roastings after 10 hours.Afterwards with resulting materials at 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction conditions and the results are shown in Table 1.
[embodiment 4]
Take 7.4 gram silicon sol (SiO
2Weight content 40%), then add sodium metaaluminate, 40% aqueous sodium hydroxide solution, make mol ratio be: 11Na
2O: Al
2O
3: 150SiO
2, and add entry and mix, pinch even and extruded moulding.120 ℃ of dryings are 3 hours afterwards, pelletizing.The mixture that adds in advance 10 gram TBAH and 20 gram distilled water in reactor, mixture top placement stainless (steel) wire is placed in the molecular sieve after moulding on stainless (steel) wire sealed reactor.Reactor is carried out gas-solid at 130 ℃ to be processed 20 days mutually.Product takes out by washing, 120 ℃ of dryings and removed template in 5 hours 550 ℃ of roastings after 10 hours.Afterwards with resulting materials at 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction conditions and the results are shown in Table 1.
[embodiment 5]
Take 50 gram SiO
2/ Al
2O
3Mol ratio is 40 ZSM-11 molecular sieve, adds 100 gram silicon sol (SiO
2Weight content 40%), then add 4 gram sodium metaaluminates, then add 2 gram sodium hydroxide, and add entry and mix, pinch even and extruded moulding.120 ℃ of dryings are 10 hours afterwards, pelletizing.The mixture that adds in advance 25 gram four butyl bromation amines and 100 gram distilled water in reactor, mixture top placement stainless (steel) wire is placed in the molecular sieve after moulding on stainless (steel) wire sealed reactor.Reactor is carried out gas-solid at 150 ℃ to be processed 6 days mutually.Product takes out by washing, 120 ℃ of dryings and removed template in 5 hours 550 ℃ of roastings after 10 hours.Afterwards with resulting materials at 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction conditions and the results are shown in Table 1.
[embodiment 6]
Take 40 gram SiO
2/ Al
2O
3Mol ratio is 80 ZSM-11 molecular sieve, adds 100 gram silicon sol (SiO
2Weight content 40%), then add 2 gram sodium metaaluminates, then add 2 gram sodium hydroxide, and add entry and mix, pinch even and extruded moulding.120 ℃ of dryings are 10 hours afterwards, pelletizing.The mixture that adds in advance 25 gram tetrabutylammonium hydroxide amine and 100 gram distilled water in reactor, mixture top placement stainless (steel) wire is placed in the molecular sieve after moulding on stainless (steel) wire sealed reactor.Reactor is carried out gas-solid at 170 ℃ to be processed 5 days mutually.Product takes out by washing, 120 ℃ of dryings and removed template in 5 hours 550 ℃ of roastings after 10 hours.Afterwards with resulting materials at 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction conditions and the results are shown in Table 1.
[embodiment 7]
Take 15 gram SiO
2/ Al
2O
3Mol ratio is 120 ZSM-11 molecular sieve, adds 100 gram silicon sol (SiO
2Weight content 40%), then add 2 gram sodium metaaluminates, then add 2.4 gram sodium hydroxide, and add entry and mix, pinch even and extruded moulding.120 ℃ of dryings are 10 hours afterwards, pelletizing.The mixture that adds in advance 15 gram tetrabutylammonium hydroxide amine and 100 gram distilled water in reactor, mixture top placement stainless (steel) wire is placed in the molecular sieve after moulding on stainless (steel) wire sealed reactor.Reactor is carried out gas-solid at 170 ℃ to be processed 3 days mutually.Product takes out by washing, 120 ℃ of dryings and removed template in 5 hours 550 ℃ of roastings after 10 hours.Afterwards with resulting materials at 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction conditions and the results are shown in Table 1.
[embodiment 8]
Take 15 gram SiO
2/ Al
2O
3Mol ratio is 150 ZSM-11 molecular sieve, adds 100 gram silicon sol (SiO
2Weight content 40%), then add 2 gram sodium metaaluminates, then add 3 gram sodium hydroxide, and add entry and mix, pinch even and extruded moulding.120 ℃ of dryings are 10 hours afterwards, pelletizing.The mixture that adds in advance 20 gram tetrabutylammonium hydroxide amine and 100 gram distilled water in reactor, mixture top placement stainless (steel) wire is placed in the molecular sieve after moulding on stainless (steel) wire sealed reactor.Reactor is carried out gas-solid at 130 ℃ to be processed 10 days mutually.Product takes out by washing, 120 ℃ of dryings and removed template in 5 hours 550 ℃ of roastings after 10 hours.Afterwards with resulting materials at 80 ℃ with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times, wash 2 times, 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction conditions and the results are shown in Table 1.
[Comparative Examples 1]
With NaZSM-11 molecular screen primary powder (SiO
2/ Al
2O
3Mol ratio is 70) removed template in 5 hours 550 ℃ of roastings.Resulting materials, is washed 2 times with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times at 80 ℃, and 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction conditions and the results are shown in Table 1.
[Comparative Examples 2]
With NaZSM-11 molecular screen primary powder (SiO
2/ Al
2O
3Mol ratio is 70) mix with 1: 0.3 part by weight with boehmite.Add 0.5 mol/L salpeter solution and field mountain valley with clumps of trees and bamboo powder in mixture, pinch even and extruded moulding, in 120 ℃ of dryings 10 hours, 550 ℃ of roastings 5 hours.Resulting materials, is washed 2 times with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times at 80 ℃, and 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
By the performance of each step evaluate catalysts of [embodiment 1], reaction conditions and the results are shown in Table 1.
[Comparative Examples 3]
With NaZSM-11 molecular screen primary powder (SiO
2/ Al
2O
3Mol ratio is 70) and silicon sol (SiO
2 Content 40%) mix with 1: 0.75 part by weight.Add field mountain valley with clumps of trees and bamboo powder in mixture, pinch even and extruded moulding, in 120 ℃ of dryings 10 hours, 550 ℃ of roastings 5 hours.Resulting materials, is washed 2 times with the aqueous ammonium nitrate solutions of 10% weight content exchange 3 times at 80 ℃, and 120 ℃ of dryings 10 hours 550 ℃ of roastings 5 hours, obtain catalyzer.
Table 1
*: contain isomer
Claims (3)
1. the method for 4-hydroxyl-3-hexanone Dehydration 4-hexene-3-one, take 4-hydroxyl-3-hexanone as raw material, being 200～400 ℃ in temperature of reaction, is under 0.5～15 hour-1 condition with respect to 4-hydroxyl-3-hexanone liquid mass air speed, and reaction raw materials contacts with catalyzer and generates the 4-hexene-3-one; Catalyzer binderless ZSM-5-11 molecular sieve used wherein.
2. the method for 4-hydroxyl-3-hexanone Dehydration 4-hexene-3-one according to claim 1 is characterized in that the SiO of binderless ZSM-5-11 molecular sieve
2/ Al
2O
3=20～200.
3. the method for 4-hydroxyl-3-hexanone Dehydration 4-hexene-3-one according to claim 1, is characterized in that temperature of reaction is 250～350 ℃, is 1～10 hour-1 with respect to 4-hydroxyl-3-hexanone liquid mass air speed.
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Cited By (1)
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