CN109651318A - A kind of preparation method of δ-valerolactone - Google Patents
A kind of preparation method of δ-valerolactone Download PDFInfo
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- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The present invention relates to a kind of preparation methods of δ-valerolactone.The preparation method include: alkyl acetate and propylene oxide in the presence of a catalyst, isomery addition cyclization occurs, a step obtains δ-valerolactone, wherein the catalyst is loaded catalyst, and carrier is aluminium oxide, and active component is lithium phosphate.The raw materials technology is easy to get, and reaction step is simple, and environmental pollution is small, and yield is high, and product is easily purified, and is suitble to industrialized production.
Description
Technical field
The present invention relates to a kind of preparation methods of δ-valerolactone, belong to the field of organic synthesis.
Background technique
δ-valerolactone also known as 1,5- valerolactone, delta- valerolactone, tetrahydro -2H-2- pyranone, tetrahydro coumalin, four
Hydrogen counmalin, English name are δ-Valerolactone, and abbreviation title is generally DVL, is analogous in a kind of ring of caprolactone
Ester type compound, molecular weight 100.12, boiling point are 230 DEG C, molecular formula C5H8O2, it is at room temperature colourless transparent liquid.Specifically
Structural formula is as follows.
δ-valerolactone is a kind of multiduty chemical intermediate, and is applied to different fields, is mainly used in ink, applies
Caprolactone is replaced above feed additives, valerolactone replaces the ink and coating ratio that caprolactone is used in ink, coating additive produces
Only there is Viscosity-reducing good, the noncondensing advantage of low temperature with the product that caprolactone produces.
It can be additionally used for synthesis 5- bromine valeric acid and oligomeric peptide etc.；In pharmaceuticals industry, it to be used for synthesizing pyran pyrimidine, cyclenes
Ether, Cilostazol, witting reagent and Epothifone anticarcinogen；Can also be used in equal polyester and polyactide etc. can degrade height
Molecular material and fragrance such as jasmine lactone and battery industry electrolyte etc..
Industrially mainly by cyclopentanone Baeyer-Villiger oxidation reaction or 1,5- pentanediol occur for δ-valerolactone
Dehydrogenation reaction occurs to obtain.Wherein cyclopentanone is limited to petroleum chemicals, raw material sources in Baeyer-Villiger oxidation reaction
It is narrow；And in reacting using peroxide such as benzoyl hydroperoxide, anhydrous peroxyacetic acid, acetaldehyde list peracetic acid ester etc. to cyclopentanone into
Row oxidation, since the byproduct organic acids that organic peroxyization acid is expensive and reaction generates later pollute environment, post-processing is needed
The alkaline reagents such as a large amount of sodium carbonate are wanted, production cost is undoubtedly increased.Additionally due to the presence of peroxide, in reaction process
If maloperation occurs, it is likely that will lead to catastrophic effect, therefore prepare valerolactone not using Baeyer-Villiger method
Industrially it is used widely.The pair of the method for δ-valerolactone in the reaction product is generated by raw material dehydrogenation of 1,5- pentanediol
The positive valeric acid of product has corrosion to reactor, increases the input cost of consersion unit, and product separation is difficult.
As it can be seen that existing method cannot be to meeting the needs of industrial production high-quality δ-valerolactone.Therefore it needs to seek one
Kind be suitable for the preparation method of the δ-valerolactone of industrialized production, for solve in the prior art product yield is low, raw material sources by
Limit be not easy to obtain and expensive and reaction condition it is sensitive be difficult to control, the problems such as safety coefficient is low.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for manufacturing δ-valerolactone, and this method raw material is cheap and easy to get, right
Environmental pollution is small, at low cost, and is not related to easily causing the raw material of security risk in technique.
To achieve the above object, the technical solution adopted by the present invention is that:
Isomery addition occurs in the presence of a catalyst for a kind of preparation method of δ-valerolactone, alkyl acetate and propylene oxide
Cyclization, a step obtain δ-valerolactone.Wherein, the catalyst is loaded catalyst, and carrier is aluminium oxide, active group
It is divided into lithium phosphate.Preferably, catalyst of the present invention is prepared using the precipitation method, and carrier is that surface uses layered double hydroxide
(LDHs) aluminium oxide modified, active component is lithium phosphate.
The reaction equation of the reaction is shown below:
Wherein R is alkyl, is generally selected from C1-C6 straight chained alkyl or C3-C6 branched alkyl.
In embodiment of the present invention, reaction gained alkylol (ROH) is the Main By product of this method, by-product separation
When, the boiling point of the alkylol (ROH) differs bigger with δ-valerolactone, and the two is more easily separated.Therefore in currently preferred implementation
In scheme, R is selected from one of methyl, ethyl and propyl or a variety of, i.e. R is C1~C3 alkyl.
In some embodiments of the present invention, the molar ratio of the alkyl acetate in this method and propylene oxide is (0.1
~100): 1, preferably (0.1~50): 1, more preferable (0.1~10): 1, more preferred (1~2): 1, further preferably (1.01~
1.05): 1, i.e., alkyl acetate is micro- is in excess in propylene oxide.
In some embodiments of the present invention, the reaction temperature used in this method for 150~350 DEG C, preferably 180~
250 DEG C, reaction pressure is 0~1MPa (gauge pressure), preferably 0~0.5MPa.
In some embodiments of the present invention, the treating capacity of catalyst is 1~10g propylene oxide/(g is urged in this method
Agent hour), preferably 2~5g propylene oxide/(g catalyst hour).
Cyclization in this method is balanced reaction, in some embodiments of the present invention, in order to further speed up
Reaction rate, driving a reaction carry out, and reduce separation costs, are conducive to improve product yield and purity, preferably in catalytic rectifying tower
It carries out, so that reaction and separating step are combined into one, product can constantly be removed reaction system by when production, and quick separating is simultaneously
Reaction is promoted to carry out to the right.
In some embodiments of the present invention, the reflux ratio of the used catalytic rectifying tower of this method is 0.1~10.
In some embodiments of the present invention, catalytic rectifying tower include rectifying section, the catalysis that is connected with rectifying pars infrasegmentalis
Conversion zone, the stripping section being connected with catalyst reaction section lower part, and the tower reactor being connected with stripping pars infrasegmentalis.Of the invention some
In embodiment, general filler tower structure or board-like tower structure is can be used in catalytic rectifying tower, and present invention preferably employs packed towers
Structure.In some embodiments, the Catalyst packing that this method uses is in the conversion zone of catalytic rectifying tower, catalytic rectifying tower
Rectifying section, be filled with filler, such as θ ring in stripping section.In some embodiments of the present invention, the reactant in this method
Material in the middle part of catalytic rectifying tower by feeding, by further cyclization after catalyst generation isomery addition in catalyst reaction section
Generate δ-valerolactone.Above-mentioned cyclization carry out simultaneously, react generation alkylol (ROH) gasified after enter catalytic distillation
The rectifying section of tower is enriched with, and tower top continuously produces low-boiling point alcohol；The δ-valerolactone of hardly possible volatilization is enriched with through the stripping section of catalytic rectifying tower
Into tower reactor, is continuously produced by tower reactor and obtain δ-valerolactone product.In some embodiments of the present invention, to catalytic distillation
The heating of tower tower reactor carries out catalytic distillation.In other embodiments of the invention, the catalyst reaction section of catalytic rectifying tower is added
Heat carries out catalytic distillation.In some preferred embodiments, the tower body periphery of catalytic rectifying tower is coated with collet for this
Catalytic rectifying tower is heated or is kept the temperature, and wherein heating method is to the catalytic rectifying tower conversion zone and/or stripping section
The collet of tower body periphery, the collet and stripping section periphery that are more preferably filled with the tower body periphery of catalyst is heated.
In some embodiments of the present invention, for lithium phosphate supported catalyst, carrier is the catalyst that this method uses
Surface uses the aluminium oxide of layered double hydroxide (LDHs) modification.
Further, in the catalyst active component lithium phosphate mass content 0.1~60%, preferably 10~
50%, more preferable 20~40%.
Further, bimetallic is aluminium and the divalent gold of divalent metal M, the metal M in the double-metal hydroxide
Belong to ion and is selected from Mg2+、Ca2+、Ni2+、Zn2+、Mn2+、Fe2+、Ti2+、Co2+、Zr2+And one of bivalent rare earth ion or more
Kind, preferably Mg2+、Ca2+、Zn2+, more preferable Mg2+。
Preferably, the preparation of the catalyst uses the common precipitation method, specific preparation process are as follows: first prepare phosphoric acid
Sodium water solution (mass concentration such as 0.01-1mol/L, further 0.1-0.5mol/L) and water lithium chloride solution (mass concentration example
Such as 0.01-1mol/L, further 0.1-0.5mol/L), then carrier is placed in sodium phosphate aqueous solution, after sufficiently shaking up,
Be placed in water-bath constant temperature oscillator in processing 10~for 24 hours, during which keep bath temperature at 50-80 DEG C, preferably from about 70 DEG C or so.Concussion
Rate is such as 130~140r/min.Then it keeps the temperature and continues to shake, water lithium chloride solution (lithium chloride and phosphorus is added dropwise
The molar ratio of sour sodium is (2~4): 1, it is further (3.01~3.05): 1), control rate of addition make within a certain period of time (l~
It 5h) adds, during dropwise addition, continues to shake certain time (5~10h) in this temperature, filtering, gained sample is placed in concentrated ammonia liquor
In, it after sufficiently shaking up, is placed in water-bath constant temperature oscillator and handles 5~10h, during which keep bath temperature at 20-40 DEG C, preferably from about
30 DEG C or so.Concussion rate is such as 130~140r/min.Filtering, gained sample are washed with deionized 3-5 times at normal temperature
Afterwards, then at 100-150 DEG C, at preferably from about 120 DEG C after drying, 5-18 is roasted then at 300-400 DEG C, such as at 320 DEG C
Hour, preferably from about 8h, granulation formation obtains catalyst.
Preferably, the carrier be using surface in situ growth method, synthesis through MAl-LDHs surface in situ growth modification and
Modified aluminium oxide.Specific preparation process is for example as follows: by Al2O3It is placed in pressure after mixing with alkaline substance solution
In kettle (self-generated pressure kettle), at 70-100 DEG C, 10-48h is kept under the conditions of preferably 80-95 DEG C, preferably from about 90 DEG C, preferably 18~
Then the nitrate M (NO of divalent metal M is added in 30h3)2Aqueous solution, and it is warming up to 110-150 DEG C, it is preferably 120-140 DEG C, excellent
About 130 DEG C of choosing keeps 10-48h, after preferably 18~30h, wash by deionized water, be dried (such as 90-140 DEG C, it is excellent
Under the conditions of about 120 DEG C of choosing) after, then (such as at 400-600 DEG C, such as 4-20 is small under the conditions of preferably from about 450 DEG C for calcination process
When, preferably from about 8h).
Wherein the M in the catalyst carrier is divalent metal, and the bivalent metal ion of M is selected from Mg2+、Ca2+、Ni2+、
Zn2+、Mn2+、Fe2+、Ti2+、Co2+、Zr2+And one of bivalent rare earth ion or a variety of, preferably Mg2+、Ca2+、Zn2+, more excellent
Select Mg2+.Metal ions M and the molar ratio of Al are 1~50:100, preferably 1-20:100, more preferable 2~8:100.
It prepares alkaline matter used in carrier and is selected from alkali metal hydroxide, alkali carbonate, alkaline-earth metal hydroxide
Object, alkaline earth metal carbonate and ammonia one or more aqueous solution or organic base such as organic amine (including trimethylamine, triethylamine,
One of tri-n-butylamine, urea, dimethylformamide and tetramethylammonium hydroxide are a variety of), preferably sodium hydroxide, potassium hydroxide,
Potassium carbonate, sodium carbonate, trimethylamine, triethylamine, tetramethylammonium hydroxide and urea one or more, more preferable urea.
Further, the molar ratio of the alkaline matter and bivalent metal ion M are 1:1~10, preferably 1:4~6.
Catalyst carrier of the invention is since surface has carried out LDHs modification, can shape after heat treatment processes by roasting etc.
At cellular structure more abundant, this is conducive to obtain the high-dispersion loading type catalyst with good physical structure property, separately
Outside, the regular layer structure that LDHs class material has is distributed its surface acidic-basic property center site in orderly shape, repairs by LDHs
The Al of decorations2O3When as catalyst carrier, is conducive to active component in its surface Development pattern, selective absorption and consolidates
It carries, to obtain having the supported catalyst of specific dispersion load performance, and the carrier preparation after LDHs is modified is urged
Agent is prepared in the reaction of δ-valerolactone for alkyl acetate and propylene oxide, due to the reasonable layout in soda acid site, acid
Property site and basic site can be catalyzed alkyl acetate and propylene oxide isomerized products and addition reaction occurs, acidic site can be simultaneously
Catalytic transesterification cyclization, and then obtain δ-valerolactone.Related specific reaction process is as follows.
Using method described in this patent, alkyl acetate and propylene oxide efficiently can be converted to δ-valerolactone,
Reaction conversion ratio can achieve 99.9%, and selectivity is not less than 95.0% (in terms of propylene oxide).
The beneficial effect of preparation method of the present invention is mainly reflected in:
1) as shown in table 1, reaction raw materials of the invention are from a wealth of sources, cheap and easy to get, and entire reaction process is to environment dirt
It contaminates small；
1. the method for the present invention of table and art methods cost of material compare
| Method | Raw material | Price (yuan/ton) | Other |
| The application | Ethyl acetate | 4500 | Conventional reagent is easy to buy |
| The application | Propylene oxide | 12000 | Conventional reagent is easy to buy |
| The prior art | Cyclopentanone | >20000 | Market is in short supply |
| The prior art | 1,5- pentanediol | >20000 | Market is in short supply |
2) reaction process reaction condition of the invention is mild, is easily manipulated, and largely avoided due to danger such as peroxide
Material bring security risk；
3) the δ-valerolactone yield prepared using the method for the present invention is high, and product is easy to separate and purify, is suitble to industry metaplasia
It produces.
Detailed description of the invention:
Fig. 1 is carrier (b) and Al before roasting in embodiment 12O3(a) XRD diffraction spectrogram.
●: Al2O3Characteristic diffraction peak；
☆: MgAl-LDHs characteristic diffraction peak.
The nucleus magnetic hydrogen spectrum of the δ-valerolactone prepared in Fig. 2 embodiment 1.
The gas phase spectrogram of the δ-valerolactone prepared in Fig. 3 embodiment 1.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, it should be noted that embodiment is not constituted to this
Invent the limitation of claimed range.
Primary raw material source according to the present invention is as follows:
Methyl acetate, ethyl acetate, propyl acetate, propylene oxide, sodium phosphate, lithium chloride, concentrated ammonia liquor: Chinese medicines group chemistry
Reagent Co., Ltd；
Acidic alumina porcelain ball: Dalian Hai Xin；
The test equipment that the present embodiment uses are as follows: XRD uses Shimazu XRD-6000 type powder x-ray diffraction, core
Magnetic is tested using Bruker AV300, and 50mg sample is dissolved in the CDCl of 0.5mL3In, GC is tested using Agilent7820, sample
Using 3 times of chromatography methanol dilution, HP-5 capillary chromatographic column (5%Phenyl Methyl Siloxan, 30m × 0.32mm are used
× 0.25 μm), fid detector.Sample injector and detector temperature are 280 DEG C；Column temperature is controlled using temperature programming: column temperature is initial
100 DEG C are kept for 2 minutes, and 20 DEG C/min is warming up to 250 DEG C, are kept for 0.5 minute.Column pressure 8.5868psi, flow velocity 1.5mL/min,
Residence time 1.6837 minutes.Sample volume: 0.2 μ L.
Specifically, the material modified by MgAl-LDHs the spy of MgAl-LDHs will nearby occur in 12 °, 24 °
Levy diffraction maximum.
Embodiment 1
The preparation of catalyst:
Weigh the Al of 102g2O3(1mol), by the aqueous solution of urea (CO (NH of itself and 100ml2)2: 0.005mol) mixing is
After even in merging 2L self-generated pressure kettle, kept for 24 hours under the conditions of 90 DEG C, then, the Mg (NO of 700ml is added3)2(0.02mol) water
Solution, and 130 DEG C are warming up to, it after keeping for 24 hours, is washed by deionized water, after being dried under the conditions of 120 DEG C, then 450
Calcination process 8h is under the conditions of DEG C to get the alumina composite material LDHs-Al arrived by LDHs modification2O3。
The aqueous solution for preparing certain density sodium phosphate (wherein the amount of sodium phosphate substance is 0.1mol), then will be on 100g
State the LDHs-Al of preparation2O3It is placed in sodium phosphate aqueous solution, after sufficiently shaking up, is placed in water-bath constant temperature oscillator and handles for 24 hours,
Period keeps bath temperature at 70 DEG C or so, and concussion rate is 130~140r/min.Then it keeps the temperature and continues to shake,
Water lithium chloride solution (wherein the amount of sodium phosphate substance is 0.24mol, and the molar ratio of lithium chloride and sodium phosphate is 3.01:1) is added dropwise,
Control rate of addition adds in 1.5h, during dropwise addition, continues to shake 7.5h in this temperature, filtering, gained sample is placed in dense
In ammonium hydroxide, after sufficiently shaking up, it is placed in water-bath constant temperature oscillator and handles 7.5h, during which keep bath temperature at 30 DEG C or so, shake
Swinging rate is such as 130~140r/min.Filtering, after gained sample is washed with deionized 3~5 times at normal temperature, then about
At 120 DEG C after drying, 8h is then roasted at 320 DEG C, granulation formation obtains catalyst 126.51g, active component phosphoric acid
Lithium load capacity is 21.96%.
Carrier XRD diffraction spectrogram before roasting in embodiment 1 is as shown in Figure 1, display forms MgAl-LDHs.
The preparation of δ-valerolactone:
The synthetic reaction of δ-valerolactone carries out in the catalytic rectifying tower for being filled with catalyst, wherein catalytic rectifying tower internal diameter
25mm, length 1000mm；Catalytic rectifying tower conversion zone loading catalyst, rectifying section and stripping section load filler θ ring.
Keeping catalytic rectifying tower conversion zone jacket temperature is 250 DEG C, and methyl acetate and propylene oxide are connected by feed pump
Continuous to enter, oxypropylene liquid air speed WHSV=2.0g/gcat/h, methyl acetate and propylene oxide molar ratio are 1.01:1,
The reflux ratio of catalytic rectifying tower is 0.1, and using feeding in tower, tower top continuously produces the low-boiling compounds such as methanol, and tower reactor is continuous
Obtain the reaction solution containing δ-valerolactone.
Backlash sampling carries out GC analysis after reaction carries out 1h to reaction solution and is reacted into stable state, wherein reaction conversion
Rate reaches 99.9%, and δ-valerolactone selectively reaches 95.8%, and wherein δ-valerolactone G/C content reaches 99.8% in reaction solution, instead
It answers liquid not have to further purification, can be used as product use.
Product use gas-chromatography and nuclear-magnetism confirm its structure for δ-valerolactone, it is specific as Figure 2-3.
Nuclear magnetic spectrogram data are as follows:
1H NMR(300MHz,CDCl3, TMS is internal standard): 1.849~1.935 (m, 4H ,-CH2CH2), 2.547~
2.581(t,2H,-CH2- CO-), 4.338~4.365 (t, 2H ,-O-CH2-)。
Embodiment 2
The preparation of catalyst:
With embodiment 1, the difference is that alkaline matter CO (NH2)2Dosage is 0.014mol, Mg (NO3)2Dosage is
0.08mol, sodium phosphate dosage are 0.58mol, and lithium chloride dosage is 1.77mol, and the catalyst of preparation is 166.53g, active group
Dividing lithium phosphate load capacity is 39.95%.
The preparation of δ-valerolactone:
Reactor and catalyst loading pattern, loadings are the same as embodiment 1.
It keeps catalytic rectifying tower conversion zone and stripping section jacket temperature is 250 DEG C, ethyl acetate and propylene oxide are led to
It crosses feed pump to continuously enter, oxypropylene liquid air speed WHSV=5.0g/gcat/h, ethyl acetate and propylene oxide molar ratio
For 1.05:1, the reflux ratio of catalytic rectifying tower is 10, and using feeding in tower, tower top continuously produces the low-boiling compounds such as ethyl alcohol,
Tower reactor is continuously available the reaction solution containing δ-valerolactone.
Backlash sampling carries out GC analysis to reaction solution, and reaction enters stable state after carrying out 1.5h, wherein reaction conversion ratio
Reach 99.9%, δ-valerolactone selectively reaches 95.1%, and wherein δ-valerolactone G/C content reaches 99.7% in reaction solution, with real
Example 1 is applied, reaction solution does not have to further purification, can be used as product use.
Product uses nuclear-magnetism to confirm its structure for δ-valerolactone.
Spectral data is as follows:
1H NMR (300MHz, CDCl3, TMS is internal standard): 1.846~1.934 (m, 4H ,-CH2CH2), 2.546~
2.583(t,2H,-CH2- CO-), 4.335~4.362 (t, 2H ,-O-CH2-)。
Embodiment 3
The preparation of catalyst:
With embodiment 1, the difference is that alkaline matter CO (NH2)2Dosage is 0.01mol, Mg (NO3)2Dosage is 0.05mol,
Sodium phosphate dosage is 0.39mol, and lithium chloride dosage is 1.18mol, and the catalyst of preparation is 145.07g, active component lithium phosphate
Load capacity is 31.07%.
The preparation of δ-valerolactone:
Reactor and catalyst loading pattern, loadings are the same as embodiment 1.
It keeps catalytic rectifying tower conversion zone and stripping section jacket temperature is 215 DEG C, propyl acetate and propylene oxide are led to
It crosses feed pump to continuously enter, oxypropylene liquid air speed WHSV=3.0g/gcat/h, methyl acetate and propylene oxide molar ratio
For 1.03:1, the reflux ratio of catalytic rectifying tower is 5, and using feeding in tower, tower top continuously produces the low-boiling compounds such as propyl alcohol, tower
Kettle is continuously available the reaction solution containing δ-valerolactone.
Backlash sampling carries out GC analysis to reaction solution, and reaction enters stable state after carrying out 1.5h, wherein reaction conversion ratio
Reach 99.9%, δ-valerolactone selectively reaches 95.9%, and wherein δ-valerolactone G/C content reaches 99.6% in reaction solution, with real
Example 1 is applied, reaction solution does not have to further purification, can be used as product use.
Product uses nuclear-magnetism to confirm its structure for δ-valerolactone.
Spectral data is as follows:
1H NMR (300MHz, CDCl3, TMS is internal standard): 1.842~1.931 (m, 4H ,-CH2CH2), 2.542~
2.576(t,2H,-CH2- CO-), 4.336~4.361 (t, 2H ,-O-CH2-)。
Embodiment 4
The preparation of catalyst:
With embodiment 1, the difference is that alkaline matter CO (NH2)2Dosage is 0.02mol, Mg (NO3)2Dosage is 0.08mol,
Sodium phosphate dosage is 0.40mol, and lithium chloride dosage is 1.22mol, and the catalyst of preparation is 146.11g, active component lithium phosphate
Load capacity is 31.56%.
The preparation of δ-valerolactone:
Reactor, catalyst loading pattern and loadings are with embodiment 1, and operating process is the same as embodiment 2.
Backlash sampling carries out GC analysis to reaction solution, and reaction enters stable state after carrying out 2h, and wherein reaction conversion ratio reaches
To 99.9%, δ-valerolactone selectively reaches 95.0%, and wherein δ-valerolactone G/C content reaches 99.6% in reaction solution, with implementation
Example 1, reaction solution do not have to further purification, can be used as product use.
Product uses nuclear-magnetism method to confirm its structure for δ-valerolactone.
Spectral data is as follows:
1H NMR (300MHz, CDCl3, TMS is internal standard): 1.849~1.935 (m, 4H ,-CH2CH2), 2.548~
2.581(t,2H,-CH2- CO-), 4.337~4.365 (t, 2H ,-O-CH2-)。
Embodiment 5
The preparation of catalyst:
With embodiment 1, the difference is that alkaline matter CO (NH2)2Dosage is 0.0034mol, Mg (NO3)2Dosage is
0.02mol, sodium phosphate dosage are 0.22mol, and lithium chloride dosage is 0.67mol, and the catalyst of preparation is 124.94g, active group
Dividing lithium phosphate load capacity is 19.96%.
The preparation of δ-valerolactone:
Reactor, catalyst loading pattern and loadings are with embodiment 1, and (liquid hourly space velocity (LHSV) of such as raw material adds for operating process
The conditions such as hot temperature, catalytic rectifying tower reflux ratio) with embodiment 3.
Backlash sampling carries out GC analysis to reaction solution, and reaction enters stable state after carrying out 2h, and wherein reaction conversion ratio reaches
To 99.9%, δ-valerolactone selectively reaches 95.3%, and wherein δ-valerolactone G/C content reaches 99.6% in reaction solution, with implementation
Example 1, reaction solution do not have to further purification, can be used as product use.
Product uses nuclear-magnetism method to confirm its structure for δ-valerolactone.
Spectral data is as follows:
1H NMR (300MHz, CDCl3, TMS is internal standard): 1.849~1.935 (m, 4H ,-CH2CH2), 2.547~
2.580(t,2H,-CH2- CO-), 4.338~4.364 (t, 2H ,-O-CH2-)。
Embodiment 6
The preparation of catalyst:
With embodiment 1, the difference is that alkaline matter CO (NH2)2Dosage is 0.016mol, Mg (NO3)2Dosage is
0.08mol, sodium phosphate dosage are 0.59mol, and lithium chloride dosage is 1.77mol, and the catalyst of preparation is 168.15g, active group
Dividing lithium phosphate load capacity is 40.53%.
The preparation of δ-valerolactone:
Reactor, catalyst loading pattern and loadings are with embodiment 1, and operating process is the same as embodiment 1.
Backlash sampling carries out GC analysis to reaction solution, and reaction enters stable state after carrying out 2.5h, wherein reaction conversion ratio
Reach 99.9%, δ-valerolactone selectively reaches 95.1%, and wherein δ-valerolactone G/C content reaches 99.8% in reaction solution, with real
Example 1 is applied, reaction solution does not have to further purification, can be used as product use.
Product uses nuclear-magnetism method to confirm its structure for δ-valerolactone.
Spectral data is as follows:
1H NMR (300MHz, CDCl3, TMS is internal standard): 1.848~1.935 (m, 4H ,-CH2CH2), 2.547~
2.581(t,2H,-CH2- CO-), 4.338~4.364 (t, 2H ,-O-CH2-)。
Embodiment 7
The preparation of catalyst:
Preparation process is with embodiment 1, the difference is that by Mg (NO3)2It is substituted for Ca (NO3)2, the catalyst of preparation is to obtain
Catalyst 127.85g, active component lithium phosphate load capacity are 21.73%.
The preparation of δ-valerolactone:
Reactor, catalyst loading pattern and loadings are with embodiment 1, and operating process is the same as embodiment 1.
Backlash sampling carries out GC analysis to reaction solution, and reaction enters stable state after carrying out 2.5h, wherein reaction conversion ratio
Reach 99.9%, δ-valerolactone selectively reaches 95.6%, and wherein δ-valerolactone G/C content reaches 99.4% in reaction solution, with real
Example 1 is applied, reaction solution does not have to further purification, can be used as product use.
Product uses nuclear-magnetism method to confirm its structure for δ-valerolactone.
Spectral data is as follows:
1H NMR (300MHz, CDCl3, TMS is internal standard): 1.846~1.933 (m, 4H ,-CH2CH2), 2.544~
2.579(t,2H,-CH2- CO-), 4.336~4.362 (t, 2H ,-O-CH2-)。
Embodiment 8
The preparation of catalyst:
Preparation process is with embodiment 2, the difference is that by Zn (NO3)2It is substituted for Ca (NO3)2, the catalyst of preparation is
168.70g, estimated activity component lithium phosphate load capacity are 39.44%.
The preparation of δ-valerolactone:
Reactor, catalyst loading pattern and loadings are with embodiment 2, and operating process is the same as embodiment 2.
Backlash sampling carries out GC analysis to reaction solution, and reaction enters stable state after carrying out 4.5h, wherein reaction conversion ratio
Reach 99.9%, δ-valerolactone selectively reaches 94.9%, and wherein δ-valerolactone G/C content reaches 99.3% in reaction solution, with real
Example 2 is applied, reaction solution does not have to further purification, can be used as product use.
Product uses nuclear-magnetism method to confirm its structure for δ-valerolactone.
Spectral data is as follows:
1H NMR (300MHz, CDCl3, TMS is internal standard): 1.848~1.935 (m, 4H ,-CH2CH2), 2.542~
2.577(t,2H,-CH2- CO-), 4.338~4.363 (t, 2H ,-O-CH2-)。
Claims (12)
1. a kind of preparation method of δ-valerolactone, which is characterized in that alkyl acetate and propylene oxide in the presence of a catalyst, are sent out
Raw isomery addition cyclization, a step obtain δ-valerolactone, wherein the catalyst is loaded catalyst, and carrier is oxygen
Change aluminium, active component is lithium phosphate.
2. the method according to claim 1, wherein the molar ratio of the alkyl acetate and propylene oxide is
1~2:1, preferably 1.01~1.05:1.
3. method according to claim 1 or 2, which is characterized in that the reaction temperature is 150~350 DEG C, preferably
180~250 DEG C, reaction pressure is 0~1MPa, preferably 0~0.5MPa.
4. method according to claim 1-3, which is characterized in that the reaction in catalytic rectifying tower into
Row；Preferably, the reflux ratio of the catalytic rectifying tower is 0.1~10.
5. according to the method described in claim 4, it is characterized in that, the treating capacity of the catalyst be 1~10g propylene oxide/
(g catalyst hour), preferably 2~5g propylene oxide/(g catalyst hour).
6. according to the method described in claim 5, it is characterized in that, the tower body periphery of the catalytic rectifying tower is coated with collet；
Preferably, the tower body periphery collet that catalyst is filled in the catalytic rectifying tower is heated.
7. method according to claim 1 to 6, which is characterized in that the catalyst, the carrier are table
Face uses the aluminium oxide of layered double hydroxide (LDHs) modification.
8. the method according to the description of claim 7 is characterized in that the quality of active component lithium phosphate contains in the catalyst
Amount 0.1~60%, preferably 10~50%, more preferable 20~40% is based on catalyst total amount.
9. the method according to the description of claim 7 is characterized in that bimetallic is aluminium and divalent in the double-metal hydroxide
The bivalent metal ion of metal M, the divalent metal M are selected from Mg2+、Ca2+、Ni2+、Zn2+、Mn2+、Fe2+、Ti2+、Co2+、Zr2+With
And one of bivalent rare earth ion or a variety of, preferably Mg2+、Ca2+And Zn2+One of or a variety of, more preferable Mg2+。
10. the method according to any one of claim 7-9, which is characterized in that the carrier is prepared by following steps:
By Al2O3It is placed in autoclave pressure after being mixed with alkaline substance solution, at 70-100 DEG C, preferably 80-95 DEG C, more preferable 90 DEG C of items
10-48h, preferably 18~30h are kept under part；Then, the nitrate M (NO of divalent metal M is added3)2Aqueous solution, and be warming up to
110-150 DEG C, preferably 120-140 DEG C more preferable 130 DEG C, keep 10-48h, after preferably 18~30h, by water washing, drying
After processing, calcination process.
11. according to the method described in claim 10, it is characterized in that, the molar ratio of the divalent metal M and Al is 1~50:
100, preferably 1-20:100, more preferable 2~8:100；And/or
The molar ratio of the alkaline matter and divalent metal M is 1:1~10, preferably 1:4~6；And/or
Alkaline matter be selected from alkali metal hydroxide, alkali carbonate, alkaline earth metal hydroxide, alkaline earth metal carbonate and
Ammonia it is one or more；Or it is selected from organic base such as organic amine, it preferably is selected from trimethylamine, triethylamine, tri-n-butylamine, urea, dimethyl acyl
One of amine and tetramethylammonium hydroxide are a variety of；The more preferable sodium hydroxide of the alkaline matter, potassium hydroxide, potassium carbonate,
Sodium carbonate, trimethylamine, triethylamine, tetramethylammonium hydroxide and urea one or more, further preferred urea.
12. according to the method described in claim 10, it is characterized in that, the preparation process of the catalyst includes following step
It is rapid: carrier being placed in sodium phosphate aqueous solution processing 10~for 24 hours, 50-80 DEG C is during which maintained the temperature at, lithium chloride is then added
The molar ratio of aqueous solution, preferably lithium chloride and sodium phosphate is (2~4): 1, gained sample is placed in concentrated ammonia liquor, and 5~10h is handled,
Period maintains the temperature at 20-40 DEG C, and drying is washed in filtering, and roasting obtains catalyst.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327907A (en) * | 2019-04-22 | 2019-10-15 | 北京化工大学 | A kind of efficient regenerating anthraquinone degradation products catalyst and preparation method thereof |
| CN114044763A (en) * | 2022-01-13 | 2022-02-15 | 山东国邦药业有限公司 | Method for synthesizing gamma-butyrolactone |
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|---|---|---|---|---|
| GB740993A (en) * | 1953-03-18 | 1955-11-23 | Distillers Co Yeast Ltd | Production of gamma-lactones |
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2018
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB740993A (en) * | 1953-03-18 | 1955-11-23 | Distillers Co Yeast Ltd | Production of gamma-lactones |
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| D.F.SRANKO ET AL.: "Radiation induced topotactic [2+2] dimerisation of acrylate derivatives among the layers of a café layered double hydroxide followed by IR spectrooscopy", 《JOURNAL OF MOLECULAR STRUCTURE》 * |
| 马卫华等: "磷酸锂催化剂上环氧丙烷异构化制烯丙醇的研究", 《工业催化》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327907A (en) * | 2019-04-22 | 2019-10-15 | 北京化工大学 | A kind of efficient regenerating anthraquinone degradation products catalyst and preparation method thereof |
| CN114044763A (en) * | 2022-01-13 | 2022-02-15 | 山东国邦药业有限公司 | Method for synthesizing gamma-butyrolactone |
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