CN103121932A - Catalytic dehydrating preparation method of 4-hexen-3-ketone by 4- hydroxy-3-hexanone - Google Patents
Catalytic dehydrating preparation method of 4-hexen-3-ketone by 4- hydroxy-3-hexanone Download PDFInfo
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Abstract
The invention relates to a catalytic dehydrating preparation method of 4-hexen-3-ketone by 4- hydroxy-3-hexanone and solves problems of low catalytic activity, high reaction temperature and low airspeed in the prior art. The 4- hydroxy-3-hexanone is adopted as a raw material, on conditions that reaction temperature ranges from 200 DEG C to 400 DEG C and the airspeed of 4- hydroxy-3-hexanone liquid quality is 0.5-15 hour -1, the raw material is contacted with a catalyst to form the 4-hexen-3-ketone. The grain diameter of the catalyst is </= 5 micron, the catalyst is provided with zeolite ZSM-11 with mesopores and micropores, and the values of pore volumes of the mesopores and micropores of the zeolite ZSM-11 are 1.5-10. According to the technical scheme, the catalytic dehydrating preparation method solves the problems effectively and can be used in industrial production of 4-hexen-3-ketone by 4- hydroxy-3-hexanone.
Description
Technical field
The present invention relates to a kind of 4-of utilization hydroxyl-3-hexanone catalytic dehydration and prepare the method for 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 shown below.
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 to have in conventional art that temperature of reaction is high, air speed is low and the problem of poor catalyst activity, provides a kind of new 4-hydroxyl-3-hexanone catalytic dehydration that utilizes to prepare the method for 4-hexene-3-one.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: a kind of 4-of utilization hydroxyl-3-hexanone catalytic dehydration prepares the method for 4-hexene-3-one, take 4-hydroxyl-3-hexanone as raw material, being 200～400 ℃ in temperature of reaction, is 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 used catalyst is that crystal grain diameter is≤5 microns, and has simultaneously mesoporous and ZSM-11 zeolite micropore, and the value of described ZSM-11 zeolite intermediary hole pore volume/Micropore volume is 1.5～10.
In technique scheme, the crystal grain diameter preferable range of described ZSM-11 zeolite is 0.1～5 micron, and more preferably scope is 0.1～2 micron.The silica alumina ratio of described ZSM-11 zeolite is 10～500, and preferable range is 20～200.The value preferable range of described ZSM-11 zeolite intermediary hole pore volume/Micropore volume is 2～8.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
The preparation method of ZSM-11 zeolite who has mesoporous and micropore the time used in the present invention is as follows: at first silicon source, aluminium source, alkali source, template, metal-salt, mesoporous pore-forming material, water are mixed plastic, reaction mixture is take molar ratio computing as SiO
2/ Al
2O
3=10～500, H
2O/SiO
2=10～150, Cl
-/ SiO
2=0.01～5, OH
-/ SiO
2=0.001～1, template/SiO
2=0.01～1; Preferable range is SiO
2/ Al
2O
3=20～200, H
2O/SiO
2=30～80, Cl
-/ SiO
2=0.1～1, OH
-/ SiO
2=0.05～0.5, template/SiO
2=0.1～0.5.Add mesoporous pore-forming material in said mixture, under 100～200 ℃ of conditions of crystallization temperature, crystallization 0.5～16 day, crystallized product is after filtration, namely get the described ZSM-11 zeolite that has simultaneously mesoporous and micropore after washing, drying; Wherein, mesoporous pore-forming material and SiO
2Mass ratio be 0.01～20, preferable range is 0.05～10.The silicon source is at least a in tetraethoxy, methyl silicate, water glass, silicon sol or White Carbon black; The aluminium source is at least a in aluminum isopropylate, sodium metaaluminate, Tai-Ace S 150 or aluminum nitrate; Alkali source is at least a in sodium hydroxide, potassium hydroxide or ammoniacal liquor; Template is at least a in Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide or TBAH; Metal-salt is at least a in sodium-chlor or Repone K; Mesoporous pore-forming material is at least a in polyoxyethylene glycol, starch, dextrin, cyclodextrin or Mierocrystalline cellulose.The crystallization temperature preferable range is 120～180 ℃, and the crystallization time preferable range is 1～10 day.
In the inventive method, synthetic size of microcrystal is≤5 microns, ZSM-11 zeolite that have simultaneously mesoporous and micropore, for before the 4-hydroxyl-3-hexanone catalytic dehydration prepares the reaction of 4-hexene-3-one, adopt known ammonium exchange, drying and roasting technology to process.
Have mesoporous the time used in the inventive method and ZSM-11 zeolite micropore, its mesoporous pore diameter range is 2～15 nanometers, and the micropore size scope is 0.5～0.6 nanometer.
In the present invention, whether the synthetic ZSM-11 zeolite of judgement has value mesoporous and that foundation micropore is mesoporous pore volume/Micropore volume simultaneously.Mesoporous pore volume and Micropore volume are to measure by the method for known low temperature nitrogen physical adsorption.
In prior art, the ZSM-11 zeolite generally only contains microvoid structure.The present invention is catalyzer by adopting size of microcrystal for≤5 microns, ZSM-11 zeolite that have simultaneously mesoporous and micropore, because little crystal grain zeolite facies have larger external surface area and higher intracrystalline rate of diffusion than conventional zeolite, all show superior performance improving the utilization ratio of catalyzer, strengthen the macromole conversion capability, reduce deep reaction, improve selectivity and reduce the aspects such as coking and deactivation.In addition, this fine grain ZSM-5-11 zeolite contains a large amount of mesoporous, and these newly-increased mesoporous catalyzer that increased hold burnt ability, have improved the stability of catalyzer.So employing the inventive method, under lower temperature of reaction, higher air speed condition, temperature of reaction is 285 ℃, is 5 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 95.2%, has obtained technique effect preferably.
Description of drawings
Fig. 1 has the XRD spectra of the ZSM-11 zeolite of mesoporous and micropore when synthesizing for [embodiment 1].
Fig. 2 has the SEM photo of the ZSM-11 zeolite of mesoporous and micropore when synthesizing for [embodiment 1].
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.
In Fig. 2, can be found out by the SEM photo, the average crystal grain diameter of this ZSM-11 zeolite is 0.3 micron.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
40% silicon sol, sodium metaaluminate, Tetrabutyl amonium bromide, Repone K, sodium hydroxide and water are mixed, stirred 20 minutes, then add polyoxyethylene glycol (molecular weight is 6000), stirred 20 minutes, in the reactor of packing into, 170 ℃ of crystallization 1 day.The crystallization product chilling, to filter, be washed to the pH value be 8, in 120 ℃ of oven dry 12 hours, makes the ZSM-11 molecular screen primary powder.In reaction mixture, the mol ratio of each raw material is: SiO
2/ Al
2O
3=149.3, H
2O/SiO
2=32.8, KCl/SiO
2=0.6, NaOH/SiO
2=0.08, TBABr/SiO
2=0.12, polyoxyethylene glycol quality/SiO
2Quality=0.1.
Fig. 1 is the XRD spectra of this zeolite, is shown as typical ZSM-11 crystalline phase feature.Fig. 2 is the SEM photo of this zeolite, and average crystal grain diameter is 0.3 micron.This zeolite micropore pore volume is 0.12 centimetre
3/ gram, mesoporous pore volume are 0.38 centimetre
3/ gram, mesoporous pore volume are 3 times of Micropore volume.Synthetic zeolite parameter specifically sees Table 1.
Aqueous ammonium nitrate solution with 10% mass concentration exchanges 3 times under 80 ℃, and aqueous ammonium nitrate solution is 10,120 ℃ of dryings 12 hours with the ratio of the weight of zeolite, and 550 ℃ of roastings 5 hours get 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 285 ℃, 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 2.
[embodiment 2]
40% silicon sol, sodium metaaluminate, Tetrabutyl amonium bromide, sodium-chlor, sodium hydroxide and water are mixed, stirred 20 minutes, then add starch, stirred 20 minutes, in the reactor of packing into, 170 ℃ of crystallization 1 day.The crystallization product chilling, to filter, be washed to the pH value be 8, in 120 ℃ of oven dry 12 hours, makes the ZSM-11 molecular screen primary powder, and average crystal grain diameter is 0.5 micron.In reaction mixture, the mol ratio of each raw material is: SiO
2/ Al
2O
3=149.3, H
2O/SiO
2=32.8, NaCl/SiO
2=0.6, NaOH/SiO
2=0.08, TBABr/SiO
2=0.12, starch/SiO
2Quality=1.Synthetic zeolite parameter specifically sees Table 1.
Synthetic ZSM-11 molecular screen primary powder was processed 4 hours at 80 ℃ with 0.3 mol/L hydrochloric acid, continuous 3 times, obtained HZSM-11.
By the condition evaluating catalyst performance of [embodiment 1], concrete reaction conditions and the results are shown in Table 2.
[embodiment 3]
By each Step By Condition of [embodiment 2], be mesoporous pore-forming material be dextrin, dextrin/SiO
2Quality=5, SiO in synthesizing formula
2/ Al
2O
3=52.3, template adopts TBAH, 120 ℃ of crystallization of crystallization temperature 8 days.Synthetic zeolite parameter specifically sees Table 1.With the exchange of [embodiment 1] ammonium, dry, roasting.
By the condition evaluating catalyst performance of [embodiment 1], concrete reaction conditions and the results are shown in Table 2.
[embodiment 4]
By each Step By Condition of [embodiment 2], be that synthesizing formula Raw, batching proportioning are different.The aluminium source is Tai-Ace S 150, and the silicon source is water glass, and template is TBAH, and mesoporous pore-forming material is cyclodextrin.In reaction mixture, the mol ratio of each raw material is: SiO
2/ Al
2O
3=80.9, H
2O/SiO
2=58.5, NaCl/SiO
2=0.80, NaOH/SiO
2=0.30, TBAOH/SiO
2=0.19, cyclodextrin/SiO
2Quality=8.Synthetic zeolite parameter specifically sees Table 1.With the exchange of [embodiment 1] ammonium, dry, roasting.
By the condition evaluating catalyst performance of [embodiment 1], concrete reaction conditions and the results are shown in Table 2.
[embodiment 5]
By each Step By Condition of [embodiment 1], be that synthesizing formula Raw, batching proportioning are different.The aluminium source is aluminum isopropylate, and the silicon source is tetraethoxy, and template is TBAH.In reaction mixture, the mol ratio of each raw material is: SiO
2/ Al
2O
3=96.1, H
2O/SiO
2=58.52, KCl/SiO
2=0.50, KOH/SiO
2=0.39, TBAOH/SiO
2=0.42.Mesoporous pore-forming material is Mierocrystalline cellulose, Mierocrystalline cellulose/SiO
2Quality=10.Synthetic zeolite parameter specifically sees Table 1.With the exchange of [embodiment 1] ammonium, dry, roasting.
By the condition evaluating catalyst performance of [embodiment 1], concrete reaction conditions and the results are shown in Table 2.
[embodiment 6]
By each Step By Condition of [embodiment 1], be that synthesizing formula Raw, batching proportioning are different.The aluminium source is sodium metaaluminate, and the silicon source is water glass, and template is Tetrabutyl amonium bromide.In reaction mixture, the mol ratio of each raw material is: SiO
2/ Al
2O
3=30.2, H
2O/SiO
2=28.15, KCl/SiO
2=0.50, NaOH/SiO
2=0.39, TBABr/SiO
2=0.19.Mesoporous pore-forming material is polyoxyethylene glycol (molecular weight is 20000), polyoxyethylene glycol/SiO
2Quality=3.Synthetic zeolite parameter specifically sees Table 1.With the exchange of [embodiment 1] ammonium, dry, roasting.
By the condition evaluating catalyst performance of [embodiment 1], concrete reaction conditions and the results are shown in Table 2.
[Comparative Examples 1]
By each Step By Condition of [embodiment 1], just in synthesizing formula, the aluminium source is different, and does not add NaCl.The aluminium source is Tai-Ace S 150.Synthetic zeolite parameter specifically sees Table 1.With the exchange of [embodiment 1] ammonium, dry, roasting.
By the condition evaluating catalyst performance of [embodiment 1], concrete reaction conditions and the results are shown in Table 2.
[Comparative Examples 2]
Each Step By Condition by [embodiment 1] does not just add mesoporous pore-forming material.Synthetic zeolite parameter specifically sees Table 1.With the exchange of [embodiment 1] ammonium, dry, roasting.
By the condition evaluating catalyst performance of [embodiment 1], concrete reaction conditions and the results are shown in Table 2.
[Comparative Examples 3]
Each Step By Condition by [Comparative Examples 1] does not just add mesoporous pore-forming material.Synthetic zeolite parameter specifically sees Table 1.With the exchange of [embodiment 1] ammonium, dry, roasting.
By the condition evaluating catalyst performance of [embodiment 1], concrete reaction conditions and the results are shown in Table 2.
Table 1
Table 2
*: contain isomer
Claims (7)
1. one kind is utilized 4-hydroxyl-3-hexanone catalytic dehydration to prepare the method for 4-hexene-3-one, take 4-hydroxyl-3-hexanone as raw material, is 200～400 ℃ in temperature of reaction, is 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 used catalyst is that crystal grain diameter is≤5 microns, and has simultaneously mesoporous and ZSM-11 zeolite micropore, and the value of described ZSM-11 zeolite intermediary hole pore volume/Micropore volume is 1.5～10.
2. utilize according to claim 1 4-hydroxyl-3-hexanone catalytic dehydration to prepare the method for 4-hexene-3-one, the crystal grain diameter that it is characterized in that described ZSM-11 zeolite is 0.1～5 micron.
3. utilize according to claim 2 4-hydroxyl-3-hexanone catalytic dehydration to prepare the method for 4-hexene-3-one, the crystal grain diameter that it is characterized in that described ZSM-11 zeolite is 0.1～2 micron.
4. utilize according to claim 1 4-hydroxyl-3-hexanone catalytic dehydration to prepare the method for 4-hexene-3-one, it is characterized in that the value of described ZSM-11 zeolite intermediary hole pore volume/Micropore volume is 2～8.
5. utilize according to claim 1 4-hydroxyl-3-hexanone catalytic dehydration to prepare the method for 4-hexene-3-one, it is characterized in that the silica alumina ratio SiO of described ZSM-11 zeolite
2/ Al
2O
3Be 10～500.
6. utilize according to claim 5 4-hydroxyl-3-hexanone catalytic dehydration to prepare the method for 4-hexene-3-one, the silica alumina ratio that it is characterized in that described ZSM-11 zeolite is SiO
2/ Al
2O
3Be 20～200.
7. utilizing according to claim 1 4-hydroxyl-3-hexanone catalytic dehydration to prepare the method for 4-hexene-3-one, it is characterized in that temperature of reaction is 250～350 ℃, is 1～10 hour with respect to 4-hydroxyl-3-hexanone liquid mass air speed
-1
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Citations (3)
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|---|---|---|---|---|
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- 2011-11-18 CN CN201110367376.2A patent/CN103121932B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101121624A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Method for preparing ethylene by ethanol dehydration |
| CN101244971A (en) * | 2008-02-27 | 2008-08-20 | 大连理工大学 | Synthesis method for producing ethylene with high-efficiency dehydration of biological ethyl alcohol |
| CN101941897A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Method for catalyzing and dehydrating 4-hydroxy-3-hexanone |
Non-Patent Citations (1)
| Title |
|---|
| 程晓维等: "黏结剂H-ZSM-5沸石催化剂的改性及其催化稀乙醇脱水", 《石油学报(石油加工)》, 31 October 2008 (2008-10-31), pages 282 - 290 * |
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