CN105837467A - Preparation method of ketoxime and/or aldoxime - Google Patents
Preparation method of ketoxime and/or aldoxime Download PDFInfo
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- CN105837467A CN105837467A CN201510019541.3A CN201510019541A CN105837467A CN 105837467 A CN105837467 A CN 105837467A CN 201510019541 A CN201510019541 A CN 201510019541A CN 105837467 A CN105837467 A CN 105837467A
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- aldehyde
- ketone
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Abstract
The invention provides a preparation method of ketoxime and/or aldoxime. The method includes a step of performing an ammoximation reaction to ketone and/or aldehyde, ammonia and hydrogen peroxide at 50-200 DEG C in a water solution in the presence of an oximation catalyst without any organic solvent. The method has high conversion rate of ketone and/or aldehyde and high selectivity of ketoxime and/or aldoxime, is simple in subsequent separation and purification, and has great industrial application prospect.
Description
Technical field
The present invention relates to the preparation method of a kind of ketoxime and/or aldoxime.
Background technology
Ketoxime or aldoxime are important industrial chemicals, be widely used at present petrochemical industry, medical treatment,
Multiple field such as medicine and analysis, is also to prepare many amide-type monomers or the intermediate of polymer simultaneously
Raw material.At present, the domestic method preparing ketoxime or aldoxime is mainly oximes method.Specifically, existing
Oximes method is prepared the method for ketoxime or aldoxime and is included in the presence of oximate catalyst, by ketone or aldehyde, ammonia
And hydrogen peroxide carries out Ammoximation reaction in organic solvent, thus generate corresponding ketoxime or aldoxime.Tool
Precursor reactant process is as follows:
When using oximes method to produce ketoxime or aldoxime, there is the advantage that technological process is short, by-product is few,
It it is the prefered method producing amide substance at present.But, although oximes method has many advantages, but
It is to there is also multinomial deficiency, such as Organic substance low, inflammable, explosive owing to adding boiling point in reaction system
As reaction dissolvent, make the temperature of Ammoximation reaction should not control get Tai Gao, usually 60-84 DEG C, this
Sample cannot obtain higher ketone or the conversion ratio of aldehyde and ketoxime or the selectivity of aldoxime first, second increases
Follow-up ketoxime or the equipment investment expense of aldoxime separating-purifying and energy resource consumption.To sum up, need badly at present
Develop a kind of have higher ketone or the conversion ratio of aldehyde and ketoxime or the selective ketoxime of aldoxime and/or
The preparation method of aldoxime.
Summary of the invention
The invention aims to overcome the existing Ammoximation reaction of employing to produce ketoxime and/or aldoxime
Time, there is the defect that relatively low and ketoxime and/or aldoxime the selectivity of conversion ratio of ketone and/or aldehyde is relatively low,
And provide a kind of new ketoxime and/or the preparation method of aldoxime.
The present inventor finds after the further investigation to the mechanism of catalytic reaction of Ammoximation reaction,
Traditional Ammoximation reaction is substantially using organic solvent as reaction medium, and adds the mesh of organic solvent
Primarily to avoid generate ketoxime or aldoxime blocking oximate catalyst duct, affect oximate be catalyzed
Agent activity, but so but limit reaction temperature so that and reaction is only capable of and carries out at a lower temperature,
So that relatively low and ketoxime and/or aldoxime the selectivity of the conversion ratio of ketone and/or aldehyde is relatively low.
And the present inventor abandons the thinking of routine, Ammoximation reaction is placed in without any organic
Solvent and directly using pure water as the system of reaction medium in carry out, reaction temperature is properly increased simultaneously
(control at 50-200 DEG C, be preferably controlled in the fusing point of described ketone and/or ketoxime corresponding to aldehyde and/or aldehyde extremely
Higher than described ketoxime and/or 5-100 DEG C of aldoxime fusing point), obtain the conversion ratio of higher ketone and/or aldehyde
And ketoxime and/or the selectivity of aldoxime.Speculate its reason, it may be possible to due to: using water as reaction medium,
The temperature of Ammoximation reaction can properly increase, and the raising of reaction temperature can make ketoxime or aldoxime
Viscosity reduces, and liquid fluidity strengthens such that it is able to promptly detach from the duct of oximate catalyst
Coming, more preferably, high temperature excites the lateral reactivity of oximate catalyst simultaneously for ketoxime or aldoxime separating effect.Base
In this, complete the present invention.
Specifically, the present invention provides ketoxime and/or the preparation method of aldoxime are included in oximate catalyst
In the presence of and under conditions of without any organic solvent, by ketone and/or aldehyde, ammonia and hydrogen peroxide at aqueous solution
In carry out Ammoximation reaction, and the temperature of described Ammoximation reaction is 50-200 DEG C.
The method using the present invention to provide be obtained in that higher ketone and/or the conversion ratio of aldehyde and ketoxime and/
Or the selectivity of aldoxime.Additionally, the reaction that the preparation method of the ketoxime of present invention offer and/or aldoxime is corresponding
System is heterogeneous system, and later separation purifies simple, obtain after reaction containing water, oil phase and oximate
The product of catalyst (normally solid granule) can enter eddy flow after directly extracting with inert organic solvents
Separator, upper strata isolates the oil phase (extraction phase) containing ketoxime and/or aldoxime, and what lower floor obtained contains
The raffinate phase of oximate catalyst and water is after solid-liquid separation, it is possible to separated with water by oximate catalyst, oxime
Changing catalyst and be cycled to used in Ammoximation reaction, water then enters waste water system.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
Ketoxime that the present invention provides and/or the preparation method of aldoxime be included in the presence of oximate catalyst and
Under conditions of without any organic solvent, ketone and/or aldehyde, ammonia and hydrogen peroxide are carried out ammonia in aqueous
Oximation reaction, and the temperature of described Ammoximation reaction is 50-200 DEG C.
There is no particular limitation to the consumption of water in oxamidinating reaction system for the present invention, can be former according to reaction
The actual amount of material ketone and/or aldehyde reasonably adds joins, as a rule, with the ketone described in 1kg and aldehyde
Total gauge, in described oxamidinating reaction system, the consumption of water can be 2-30kg.Additionally, in order to obtain
Obtain higher ketone and/or the conversion ratio of aldehyde and ketoxime and/or the selectivity of aldoxime, reduce later separation difficulty
And wastewater treatment capacity, and improve reaction efficiency, it is preferable that in terms of the described ketone of 1kg and the gross weight of aldehyde,
In described oxamidinating reaction system, the consumption of water is 5-25kg.It should be noted that when reaction raw materials is only
During ketone, total consumption of described ketone and aldehyde refers to the consumption of ketone；When reaction raw materials is only aldehyde, described ketone and
Total consumption of aldehyde refers to the consumption of aldehyde；When reaction raw materials contains ketone and aldehyde simultaneously, described ketone and aldehyde total
Consumption refers to total consumption of ketone and aldehyde.
The ketoxime provided according to the present invention and/or the preparation method of aldoxime, the temperature of described Ammoximation reaction
For 50-200 DEG C, the fusing point of the most described ketone and/or ketoxime corresponding to aldehyde and/or aldehyde is to higher than described ketone
Oxime and/or 5-100 DEG C of aldoxime fusing point, when controlling the temperature of Ammoximation reaction in above-mentioned preferred scope
Time interior, be more beneficial for the carrying out of reaction such that it is able to significantly more improve ketone and/or the conversion ratio of aldehyde and
Ketoxime and/or the selectivity of aldoxime.Additionally, the pressure of described Ammoximation reaction can be 0.1-0.5MPa,
It is preferably 0.3-0.45MPa.In the present invention, described pressure each means absolute pressure.Described oximes
Extending of response time is conducive to reaction-ure conversion-age and the raising of product yield, but the response time
The long amplitude improving reaction-ure conversion-age and product yield is the most inconspicuous, therefore, from every side
Combined factors consider, the time of described Ammoximation reaction is preferably 10-300 minute, more preferably
30-120 minute.
Described hydrogen peroxide can add with the form of gaseous hydrogen peroxide, it is also possible to the form of hydrogen peroxide
Add, preferably add with the form of hydrogen peroxide, be so more beneficial for the carrying out of operation and be more beneficial for each thing
The accurate adjustment of proportioning between matter.There is no particular limitation to the concentration of described hydrogen peroxide for the present invention, permissible
Reasonably select according to practical situation, for example, it is possible to for commercially available concentration be 27.5 weight %, 50
Weight % or the hydrogen peroxide of 70 weight %.It should be noted that when described hydrogen peroxide is with the shape of hydrogen peroxide
Formula adds fashionable, and in oxamidinating reaction system, the above-mentioned consumption of water includes the content of water in hydrogen peroxide.
Main the theing improvement is that of the present invention is not added with any Organic substance during Ammoximation reaction
As reaction dissolvent, and only with pure water as reaction dissolvent, and correspondingly improve the temperature of Ammoximation reaction
Degree, and the consumption of various reaction raw materials can be all the conventional selection of this area.Such as, with 1mol's
Described ketone and total gauge of aldehyde, the consumption of described hydrogen peroxide can be 1-1.5mol, is preferably
1-1.25mol.With described ketone and total gauge of aldehyde of 1mol, the consumption of described ammonia can be 1-1.5mol,
It is preferably 1-1.25mol.
The kind of described ketone can be the conventional selection of this area, for example, it is possible to be 3-20 for carbon number
Aliphatic ketone and/or carbon number be the aromatic ketone of 8-25, preferably carbon number be the fat of 4-10
Fat race ketone and/or carbon number are the aromatic ketone of 8-13.Specifically, carbon number is the fat of 4-10
The example of race's ketone includes but not limited to: at least one in butanone, heptanone, pentanone, Ketohexamethylene etc..Carbon
Atomic number is that the example of the aromatic ketone of 8-13 includes but not limited to: 1-Phenylethanone., propiophenone, hexichol first
At least one in ketone etc..Additionally, it is ready availability from raw material and Ammoximation reaction product widespread popularity
Angle considers, and described ketone is particularly preferably at least one of butanone, 1-Phenylethanone. and Ketohexamethylene.
The kind of described aldehyde can be the conventional selection of this area, for example, it is possible to be 3-20 for carbon number
Aliphatic aldehyde and/or carbon number be the aromatic aldehyde of 7-24, preferably carbon number be the fat of 4-10
Fat race aldehyde and/or carbon number are the aromatic aldehyde of 7-15.Specifically, carbon number is the fat of 4-10
The example of race's aldehyde includes but not limited to: at least one in butyraldehyde, octanal, dimethyl propionic aldehyde etc..Carbon is former
Subnumber is that the example of the aromatic aldehyde of 7-15 includes but not limited to: benzaldehyde, hyacinthin, cinnamaldehyde
At least one in Deng.Additionally, and the angle of Ammoximation reaction product widespread popularity ready availability from raw material
Degree considers, and described aldehyde is particularly preferably at least one in butyraldehyde, octanal and hyacinthin.
Described Ammoximation reaction needs to carry out in the presence of oximate catalyst.The kind of described oximate catalyst
Class can be the conventional selection of this area, such as, typically titanium-silicon molecular sieve catalyst, is preferably
The HTS (such as TS-1) with MFI structure, the HTS (TS-2) with MEL structure,
There is at least one in the HTS (Ti-β) of BETA structure.Additionally, with 100 weight portions
Described ketone and total gauge of aldehyde, the consumption of described oximate catalyst can be 10-50 weight portion, excellent
Elect 25-40 weight portion as.
The concrete form of described titanium-silicon molecular sieve catalyst is had no particular limits by the present invention, can basis
Concrete reaction formation selects, for example, it is possible to be unformed HTS, it is also possible to for becoming
The titanium-silicon molecular sieve catalyst of type.For the ease of between titanium-silicon molecular sieve catalyst and Ammoximation reaction product
Separation, described titanium-silicon molecular sieve catalyst is preferably the titanium-silicon molecular sieve catalyst of molding.Described molding
Titanium-silicon molecular sieve catalyst generally comprise HTS and carrier, wherein, with the titanium silicon molecule of molding
On the basis of the gross weight of sieve catalyst, the content of described carrier can be 40-90 weight %, is preferably
50-80 weight %；The content of described HTS can be 10-60 weight %, preferably 20-50 weight
Amount %.
The present invention without particular/special requirement, can be conventional various to the carrier of described titanium-silicon molecular sieve catalyst
The carrier of preformed catalyst, such as, can be heat-resistant inorganic oxide and/or the silicate of porous.Specifically,
Described carrier can be such as aluminium oxide, silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide,
In at least one in beryllium oxide and clay, preferably aluminium oxide, silicon oxide, magnesium oxide and zirconium oxide
At least one.
Additionally, described titanium-silicon molecular sieve catalyst is commercially available, it is also possible to according to people in the art
The known various methods of member prepare.Such as, titanium-silicon molecular sieve catalyst TS-1 is referred to [Cy
clohexaneOxidation Catalyzed by Titanium Silicalite(TS-1)with Hydrogen
PeroxideJournal of Natural Gas Chemistry 2001,10 (4): 295-307] in disclosed side
Method prepares, it is also possible to preparing with reference to the method disclosed in CN101279959A, therefore not to repeat here.
The reaction system provided due to the present invention is heterogeneous system, therefore, in order to make reaction raw materials and oxime
Changing catalyst and can carry out being fully contacted mass transfer, described Ammoximation reaction preferably enters under conditions of stirring
OK.The degree of described stirring is to realize whole reaction system mix homogeneously, to reach the abundant mass transfer of reactant
It is as the criterion, these those skilled in the art can be known, will not repeat at this.Additionally, in order to make reaction
Raw ketone and/or aldehyde, hydrogen peroxide, ammonia etc. can reach to be fully contacted mass transfer reaction, described ketoxime and/
Or the preparation method of aldoxime preferably employs pressure outer circulation continuous charging formula and feeds.Wherein, circulating load
Should be fully contacted mass transfer with realization, load is properly as the criterion.
Additionally, the ketoxime that provides of the present invention and/or the preparation method of aldoxime also include by described oximes instead
The product answered is separated into containing ketoxime and/or the oil phase of aldoxime and contains oximate catalyst and the aqueous phase of water,
Then from aqueous phase, isolate oximate catalyst, and described oximate catalyst is cycled to used in described oximes
Reaction.Wherein, the product of described Ammoximation reaction is separated into containing ketoxime and/or the oil phase of aldoxime and
Aqueous phase containing oximate catalyst and water such as can be carried out in cyclone separator and/or decanter.According to
A kind of detailed description of the invention of the present invention, extracts the product organic solvent of described Ammoximation reaction
Taking, ketoxime and/or aldoxime are dissolved in organic solvent, and oximate catalyst and water are insoluble in organic solvent, thus
Obtain the oil phase (extraction phase) containing ketoxime and/or aldoxime and the aqueous phase (extraction containing oximate catalyst and water
Remaining phase).Described organic solvent can be at least one in hexamethylene, toluene, dimethylbenzene etc..From water
The method typically solid-liquid separation of oximate catalyst is isolated in mutually, specifically can be at decanter, film
The equipment such as filter are carried out.Additionally, in order to reduce the water content in oil phase further, the present invention provides
Ketoxime and/or the preparation method of aldoxime also include that described oil phase carries out in decanter decantation to be separated, with
It is further separated out the water of remnants.
According to a kind of detailed description of the invention of the present invention, the preparation method of described ketoxime and/or aldoxime includes
Ketone and/or aldehyde, ammonia, hydrogen peroxide, the extra water added and oximate catalyst are sent into Ammoximation reaction device
In carry out Ammoximation reaction, and product is sent in cyclone separator and decanter and separates,
To the oil phase containing ketoxime and/or aldoxime and containing oximate catalyst and the aqueous phase of water, and will urge containing oximate
The aqueous phase of agent and water returns to continue on for Ammoximation reaction to Ammoximation reaction device.
Hereinafter will be described the present invention by embodiment.
Oximate catalyst used in following example and comparative example is HTS (TS-1) catalyst,
It presses document [Cy clohexaneOxidation Catalyzed by Titanium Silicalite (TS-1) with
Hydrogen PeroxideJournal of Natural Gas Chemistry 2001,10 (4): 295-307] in
Page 296 methods described by 9-24 row prepare, and wherein, the content of titanium oxide is 2.5 weight %.
In following example and comparative example, the selectivity of ketone or the conversion ratio of aldehyde and ketoxime or aldoxime according to
Below equation is calculated, and wherein, ω % is that ketone or ketoxime, aldehyde or aldoxime in light phase component, reaction are miscellaneous
The weight/mass percentage composition of matter, α is ketone and the molal weight ratio of ketoxime or aldehyde or the molal weight of aldoxime
Ratio.
Wherein, the weight/mass percentage composition of ketone or ketoxime, aldehyde or aldoxime, reaction impurities uses gas chromatogram (island
Tianjin GC14B, DB-1 capillary column 30m × 0.25mm × 0.25 μm) analyze obtain.
Embodiment 1
The present embodiment is used for ketoxime and/or the preparation method of aldoxime that the present invention provides is described.
Prepare diacetylmonoxime in the present inventive method.First by 100.00 tons of water, 3.00 tons of oximate catalyst
(TS-1) adding in Ammoximation reaction device, then by butanone, ammonia, hydrogen peroxide, (concentration is 27.5 weight
%) being continuously introduced in Ammoximation reaction device by pump, wherein, the flow of above-mentioned several materials is followed successively by
5000kg/h、1358kg/h、10131kg/h.The temperature of reaction system is controlled at 60-70 DEG C, pressure
Controlling at 0.3-0.4MPa, the material time of staying in Ammoximation reaction device is 70 minutes, is contained
There are diacetylmonoxime and the product of oximate catalyst (TS-1).Urge obtain containing diacetylmonoxime and oximate
The product of agent (TS-1) is continuously introduced in cyclone separator and decanter and separates, with by light
Phase component separates with heavy phase component, and wherein, light phase component is the oil phase containing diacetylmonoxime, and heavy phase component is
Aqueous phase containing oximate catalyst (TS-1).Light phase component sends rearrangement or refined, and heavy phase component is through again
After secondary cyclonic separation, oximate catalyst (TS-1) and major part water are recycled back in Ammoximation reaction device,
A small amount of water is sent to waste water treatment and reclamation operation.By analysis and calculate understand, the conversion ratio of butanone is
99.95%, the selectivity of diacetylmonoxime is 99.86%.
Embodiment 2
The present embodiment is used for ketoxime and/or the preparation method of aldoxime that the present invention provides is described.
Prepare diacetylmonoxime in the present inventive method.First by 100.00 tons of water, 3.00 tons of oximate catalyst
(TS-1) adding in Ammoximation reaction device, then by butanone, ammonia, hydrogen peroxide, (concentration is 27.5 weight
%) being continuously introduced in Ammoximation reaction device by pump, wherein, the flow of above-mentioned several materials is followed successively by
10500kg/h、2720kg/h、20700kg/h.The temperature of reaction system is controlled at 55-60 DEG C, pressure
Controlling at 0.35-0.45MPa, the material time of staying in Ammoximation reaction device is 80 minutes, obtains
Containing diacetylmonoxime and the product of oximate catalyst (TS-1).By obtain containing diacetylmonoxime and oximate
The product of catalyst (TS-1) is continuously introduced in cyclone separator and decanter and separates, to incite somebody to action
Light phase component is separated with heavy phase component, and wherein, light phase component is the oil phase containing diacetylmonoxime, heavy phase component
For the aqueous phase containing oximate catalyst (TS-1).Light phase component sends rearrangement or refined, heavy phase component warp
Again after cyclonic separation, oximate catalyst (TS-1) and major part water are recycled back to Ammoximation reaction device
In, a small amount of water is sent to waste water treatment and reclamation operation.By analysis and calculate understand, the conversion ratio of butanone is
99.92%, the selectivity of diacetylmonoxime is 99.89%.
Embodiment 3
The present embodiment is used for ketoxime and/or the preparation method of aldoxime that the present invention provides is described.
Prepare diacetylmonoxime in the present inventive method.First by 100.00 tons of water, 3.00 tons of oximate catalyst
(TS-1) adding in Ammoximation reaction device, then by butanone, ammonia, hydrogen peroxide, (concentration is 27.5 weight
%) being continuously introduced in Ammoximation reaction device by pump, wherein, the flow of above-mentioned several materials is followed successively by
20000kg/h、5431kg/h、40662kg/h.The temperature of reaction system is controlled at 50-55 DEG C, pressure
Controlling at 0.30-0.40MPa, the material time of staying in Ammoximation reaction device is 60 minutes, obtains
Containing diacetylmonoxime and the product of oximate catalyst (TS-1).By obtain containing diacetylmonoxime and oximate
The product of catalyst (TS-1) is continuously introduced in cyclone separator and decanter and separates, to incite somebody to action
Light phase component is separated with heavy phase component, and wherein, light phase component is the oil phase containing diacetylmonoxime, heavy phase component
For the aqueous phase containing oximate catalyst (TS-1).Light phase component sends rearrangement or refined, heavy phase component warp
Again after cyclonic separation, oximate catalyst (TS-1) and major part water are recycled back to Ammoximation reaction device
In, a small amount of water is sent to waste water treatment and reclamation operation.By analysis and calculate understand, the conversion ratio of butanone is
99.92%, the selectivity of diacetylmonoxime is 99.75%.
Embodiment 4
The present embodiment is used for ketoxime and/or the preparation method of aldoxime that the present invention provides is described.
Prepare diacetylmonoxime in the present inventive method.First by 100.00 tons of water, 3.00 tons of oximate catalyst
(TS-1) adding in Ammoximation reaction device, then by butanone, ammonia, hydrogen peroxide, (concentration is 27.5 weight
%) being continuously introduced in Ammoximation reaction device by pump, wherein, the flow of above-mentioned several materials is followed successively by
25000kg/h、6788kg/h、50656kg/h.The temperature of reaction system is controlled at 80-85 DEG C, pressure
Control at 0.25-0.35MPa.The material time of staying in Ammoximation reaction device is 50 minutes, obtains
Containing diacetylmonoxime and the product of oximate catalyst (TS-1).By obtain containing diacetylmonoxime and oximate
The product of catalyst (TS-1) is continuously introduced in cyclone separator and decanter and separates, to incite somebody to action
Light phase component is separated with heavy phase component, and wherein, light phase component is the oil phase containing diacetylmonoxime, heavy phase component
For the aqueous phase containing oximate catalyst (TS-1).Light phase component sends rearrangement or refined, heavy phase component warp
Again after cyclonic separation, oximate catalyst (TS-1) and major part water are looped back in Ammoximation reaction device,
A small amount of water is sent to waste water treatment and reclamation operation.By analysis and calculate understand, the conversion ratio of butanone is
99.85%, the selectivity of diacetylmonoxime is 99.78%.
Embodiment 5
The present embodiment is used for ketoxime and/or the preparation method of aldoxime that the present invention provides is described.
Prepare octanal oxime in the present inventive method.First by 100.00 tons of water, 3.00 tons of oximate catalyst
(TS-1) adding in Ammoximation reaction device, then by octanal, ammonia, hydrogen peroxide, (concentration is 27.5 weight
%) being continuously introduced in Ammoximation reaction device by pump, wherein, the flow of above-mentioned several materials is followed successively by
10500kg/h、1604kg/h、11968kg/h.The temperature of reaction system is controlled at 60-70 DEG C, pressure
Controlling at 0.3-0.4MPa, the material time of staying in Ammoximation reaction device is 70 minutes, is contained
There are octanal oxime and the product of oximate catalyst (TS-1).Urge obtain containing octanal oxime and oximate
The product of agent (TS-1) is continuously introduced in cyclone separator and decanter and separates, with by light
Phase component separates with heavy phase component, and wherein, light phase component is the oil phase containing octanal oxime, and heavy phase component is
Aqueous phase containing oximate catalyst (TS-1).Light phase component sends rearrangement or refined, and heavy phase component is through again
After secondary cyclonic separation, oximate catalyst (TS-1) and major part water are recycled back in Ammoximation reaction device,
A small amount of water is sent to waste water treatment and reclamation operation.By analysis and calculate understand, the conversion ratio of octanal is
99.88%, the selectivity of octanal oxime is 99.81%.
Embodiment 6
The present embodiment is used for ketoxime and/or the preparation method of aldoxime that the present invention provides is described.
Prepare cyclohexanone-oxime in the present inventive method.Ketoxime is prepared according to the method for embodiment 1, different
It is that the butanone Ketohexamethylene of identical total consumption and flow is substituted, and by the temperature control of oximation reaction system
System is at 90-99 DEG C.By analysis and calculate understand, the conversion ratio of Ketohexamethylene is 99.94%, cyclohexanone-oxime
Selectivity be 99.89%.
Comparative example 1
This comparative example is for illustrating the ketoxime of reference and/or the preparation method of aldoxime.
Prepare diacetylmonoxime according to the method for embodiment 1, except for the difference that, will add in Ammoximation reaction device
The water of 100.00 tons substitute with the tert-butyl alcohol of 100.00 tons.By analysis and calculate understand, butanone
Conversion ratio is 98.87%, and the selectivity of diacetylmonoxime is 99.69%.
Comparative example 2
This comparative example is for illustrating the ketoxime of reference and/or the preparation method of aldoxime.
Diacetylmonoxime is prepared, except for the difference that, by the temperature control of oximation reaction system according to the method for embodiment 1
System is at 20-25 DEG C.By analysis and calculate understand, the conversion ratio of butanone is 96.92%, the choosing of diacetylmonoxime
Selecting property is 98.48%.
From the result of above example it can be seen that use the present invention provide method prepare ketoxime and/or
Aldoxime, is possible not only to obtain higher ketone and/or the conversion ratio of aldehyde and ketoxime and/or the selectivity of aldoxime,
And follow-up eliminate traditional organic solvent recovery process, directly have employed cyclonic separation and decantation separates
Just ketoxime and/or aldoxime can be separated from product and send, oximate catalyst then can circulate and return
It is back in response system continue on for Ammoximation reaction, has prospects for commercial application.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. ketoxime and/or a preparation method for aldoxime, the method is included in the presence of oximate catalyst
And under conditions of without any organic solvent, ketone and/or aldehyde, ammonia and hydrogen peroxide are carried out in aqueous
Ammoximation reaction, and the temperature of described Ammoximation reaction is 50-200 DEG C.
Method the most according to claim 1, wherein, with described ketone and total consumption of aldehyde of 1kg
Meter, in oxamidinating reaction system, the consumption of water is 5-25kg.
Method the most according to claim 1, wherein, the temperature of described Ammoximation reaction is described
The fusing point of ketone and/or ketoxime corresponding to aldehyde and/or aldehyde is to higher than described ketoxime and/or the 5-100 of aldoxime fusing point
℃。
Method the most according to claim 1, wherein, the pressure of described Ammoximation reaction is
0.1-0.5MPa, the time is 10-300 minute；Preferably, the pressure of described Ammoximation reaction is
0.3-0.45MPa, the time is 30-120 minute.
Method the most according to claim 1, wherein, described hydrogen peroxide is with the form of hydrogen peroxide
Add.
6. according to the method described in any one in claim 1-5, wherein, with the described ketone of 1mol
With total gauge of aldehyde, the consumption of described hydrogen peroxide is 1-1.5mol.
7. according to the method described in any one in claim 1-5, wherein, with the described ketone of 1mol
With total gauge of aldehyde, the consumption of described ammonia is 1-1.5mol.
8. according to the method described in any one in claim 1-5, wherein, described ketone is carbon atom
Aliphatic ketone and/or carbon number that number is 3-20 are the aromatic ketone of 8-25, and preferably carbon number is
The aliphatic ketone of 4-10 and/or carbon number are the aromatic ketone of 8-13.
9. according to the method described in any one in claim 1-5, wherein, described aldehyde is carbon atom
Aliphatic aldehyde and/or carbon number that number is 3-20 are the aromatic aldehyde of 7-24, and preferably carbon number is
The aliphatic aldehyde of 4-10 and/or carbon number are the aromatic aldehyde of 7-15.
10. according to the method described in any one in claim 1-5, wherein, described oximate catalyst
For titanium-silicon molecular sieve catalyst.
11. according to the method described in any one in claim 1-5, wherein, the method also include by
The product of described Ammoximation reaction is separated into containing ketoxime and/or the oil phase of aldoxime and is catalyzed containing oximate
Agent and the aqueous phase of water, then isolate oximate catalyst from aqueous phase, and circulated by described oximate catalyst
For described Ammoximation reaction.
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| CN112479925A (en) * | 2020-11-30 | 2021-03-12 | 中国天辰工程有限公司 | Large naphthenone ammoximation method |
| CN113230986A (en) * | 2021-06-07 | 2021-08-10 | 北京诚化科技有限公司 | Device and method for industrially preparing butanone oxime by heterogeneous reaction system |
| WO2022073525A1 (en) * | 2020-11-02 | 2022-04-14 | 湖北金湘宁化工科技有限公司 | Method for integrating ammoximation reaction and separation and device thereof |
| CN114669325A (en) * | 2022-04-19 | 2022-06-28 | 清华大学 | Preparation method and application of supported TS-1 catalyst |
| CN115974720A (en) * | 2023-01-09 | 2023-04-18 | 衢州巨化锦纶有限责任公司 | Method for preparing ketoxime by two-stage ammoximation reaction |
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| CN1687018A (en) * | 2005-04-04 | 2005-10-26 | 浙江新宇化工有限公司 | Method for preparing aldoxime or ketoxime |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022073525A1 (en) * | 2020-11-02 | 2022-04-14 | 湖北金湘宁化工科技有限公司 | Method for integrating ammoximation reaction and separation and device thereof |
| CN114436889A (en) * | 2020-11-02 | 2022-05-06 | 湖北金湘宁化工科技有限公司 | Ammoximation reaction and separation integrated method and device thereof |
| CN114436889B (en) * | 2020-11-02 | 2024-06-14 | 湖北金湘宁化工科技有限公司 | Ammonia oximation reaction and separation integration method and device thereof |
| CN112479925A (en) * | 2020-11-30 | 2021-03-12 | 中国天辰工程有限公司 | Large naphthenone ammoximation method |
| WO2022110930A1 (en) * | 2020-11-30 | 2022-06-02 | 中国天辰工程有限公司 | Method for ammoximation of macrocycloalkanone |
| CN113230986A (en) * | 2021-06-07 | 2021-08-10 | 北京诚化科技有限公司 | Device and method for industrially preparing butanone oxime by heterogeneous reaction system |
| CN113230986B (en) * | 2021-06-07 | 2022-05-10 | 北京诚化科技有限公司 | Device and method for industrially preparing butanone oxime by heterogeneous reaction system |
| CN114669325A (en) * | 2022-04-19 | 2022-06-28 | 清华大学 | Preparation method and application of supported TS-1 catalyst |
| CN115974720A (en) * | 2023-01-09 | 2023-04-18 | 衢州巨化锦纶有限责任公司 | Method for preparing ketoxime by two-stage ammoximation reaction |
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