CN106380424A - Ammoximation system and method for aldehyde or ketone - Google Patents
Ammoximation system and method for aldehyde or ketone Download PDFInfo
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- CN106380424A CN106380424A CN201610201286.9A CN201610201286A CN106380424A CN 106380424 A CN106380424 A CN 106380424A CN 201610201286 A CN201610201286 A CN 201610201286A CN 106380424 A CN106380424 A CN 106380424A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00011—Laboratory-scale plants
- B01J2219/00013—Miniplants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00783—Laminate assemblies, i.e. the reactor comprising a stack of plates
- B01J2219/00786—Geometry of the plates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00851—Additional features
- B01J2219/00867—Microreactors placed in series, on the same or on different supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00889—Mixing
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Abstract
The invention discloses an ammoximation system and method for aldehyde or ketone. The system comprises a micro-reactor unit, a buffer container (3), a solid-liquid separation device (4) and a storage container (5), wherein the outlet of the micro-reactor unit is connected with the inlet of the buffer container (3); the outlet of the buffer container (3) is connected with the inlet of the solid-liquid separation device (4); and the outlet of the solid-liquid separation device (4) is separately connected with the inlet of the micro-reactor unit and the inlet of the storage container (5). The ammoximation system for aldehyde or ketone has the advantages of capacity of realizing uniform mixing and dispersion of reactants, high mass transfer and heat transfer efficiency, fast reaction rate, high conversion rate of aldehyde or ketone, and the like.
Description
Technical field
A kind of the present invention relates to Chemical Reaction Engineering field, in particular it relates to Ammoximation reaction of aldehydes or ketones
System and method.
Background technology
Ketoxime or aldoxime are important industrial chemicals intermediate., cyclohexanone-oxime is system taking cyclohexanone-oxime as a example
The intermediate of standby caprolactam, and caprolactam is to produce the monomer of nylon 6 and important industrial chemicals.
The prior synthesizing method of cyclohexanone-oxime is using azanol and hexamethylene reactive ketone, and the method exists middle
Step is many, complex process, and three wastes discharge amount is big, and course of reaction needs to use and corrodes and seriously polluted
The deficiency such as raw material.The Ammoximation reaction of Ketohexamethylene is the effective ways solving the above problems, the method with
HTS is as catalyst Ketohexamethylene, H2O2Generate cyclohexanone-oxime, hexamethylene with ammonia reaction one step
The selectivity of the conversion ratio of ketone and cyclohexanone-oxime is all very high.This technique and traditional cyclohexanone-oxime production technology
Compare, have that reaction condition is gentle, technological process is simple, plant investment is few and the features such as environmental friendliness,
But still come with some shortcomings：As slurry-bed reaction kettle amasss larger, mechanical agitation effect is poor, easily
Lead to reactant mixing dispersion uneven；Mass transfer and heat transfer efficiency difference lead to reaction conversion ratio low, reaction system
Need in system to arrange multiple stage heat exchanger；Simultaneous reactions kettle hydrogen peroxide storage capacity is big, easily decomposes and causes peace
Full accident.
Content of the invention
It is an object of the invention to provide a kind of Ammoximation reaction system and method for aldehydes or ketones, this response system
Can solve in existing Ammoximation reaction system with method that reactant mixing is uneven and heat exchange efficiency is low leads
The reaction conversion ratio causing and the low technical problem of selectivity of product.
To achieve these goals, the present invention provides a kind of Ammoximation reaction system of aldehydes or ketones, this system
Including microreactor unit, buffer container, solid-liquid separating equipment and storage container；Described microreactor list
The outlet of unit is connected with the entrance of described buffer container, the outlet of described buffer container and described solid-liquid separation
The entrance of equipment connects, the outlet entrance with described microreactor unit respectively of described solid-liquid separating equipment
Connect with the entrance of described storage container；
Wherein, described microreactor unit includes a microreactor or the multiple micro- reaction being sequentially connected in series
Device, the number of the plurality of microreactor is 2-5；
The entrance of described microreactor unit is the reactant entrance of one microreactor or described many
The reactant entrance of the first microreactor in individual microreactor, the outlet of described microreactor unit is institute
State a microreactor reaction mixture outlet or the plurality of microreactor in last position microreactor
Reaction mixture outlet.
Alternatively, the number of multiple microreactors be two, include the first microreactor being sequentially connected in series with
Second microreactor, the reaction mixture outlet of described second microreactor and the entrance of described buffer container
Connect.
Alternatively, microreactor is each independently selected from cardioid micro passage reaction, T-shaped microchannel plate
Answer one of device, Y type micro passage reaction and cross micro passage reaction.
Alternatively, microreactor is cardioid micro passage reaction.
Alternatively, it is provided with cooling circulating water passage in microreactor, and the microchannel equivalent of microreactor is straight
Footpath is 0.5-5mm.
Alternatively, solid-liquid separating equipment is inorganic membrane filter and/or metal film filter.
The present invention also provides the side carrying out Ammoximation reaction using the Ammoximation reaction system of above-mentioned aldehydes or ketones
Method, the method comprises the following steps：
(1) aldehydes or ketones, Ammoximation reaction catalyst, ammonia, solvent and hydrogen peroxide are made one
In microreactor, mix homogeneously concurrent ammonifying oximation reaction, obtains reaction mixture；
Or, make aldehydes or ketones, Ammoximation reaction catalyst, ammonia, solvent and hydrogen peroxide the plurality of
Mix homogeneously concurrent ammonifying oximation reaction in the first microreactor in microreactor, obtains the first reaction and mixes
Close liquid, so that described first reaction mixture is sequentially entered in the plurality of microreactor and remove the first microreactor
Other microreactors in addition, and supplement with other microreactors in addition to the first microreactor respectively
Hydrogen peroxide mix homogeneously carry out Ammoximation reaction, obtain last position reaction mixture；
(2) described reaction mixture or described end position reaction mixture is made to enter buffer container；
(3) reaction mixture in described buffer container or last position reaction mixture is made to enter solid-liquid separation
Equipment carries out solid-liquid separation, makes the supernatant separately obtaining enter storage container, makes separately obtain to contain
After the filter of Ammoximation reaction catalyst, dope returns one microreactor or described first place microreactor
Proceed Ammoximation reaction；
Wherein, described aldehyde is benzaldehyde and/or butyraldehyde, and described ketone is selected from Ketohexamethylene, Ketocyclopentane, ring
One or more of octanone, butanone and acetone, described solvent is the tert-butyl alcohol.
Alternatively, carry out the reaction condition of Ammoximation reaction in a microreactor or multiple microreactor
For：Reaction temperature 65-90 DEG C, reaction pressure 0.01-0.45MPa, time of staying 0.5-20min.
Alternatively, in step (1), in multiple microreactors, other in addition to the first microreactor are micro-
The consumption of the hydrogen peroxide supplementing in reactor is identical or different, and the hydrogen peroxide each independently supplementing
In consumption and the first reaction mixture, the mol ratio of unconverted aldehydes or ketones is (1.1-2)：1.
Alternatively, Ammoximation reaction catalyst is titanium-silicon molecular sieve catalyst, and granularity is 5nm-100 μm,
In first microreactor and the second microreactor, Ammoximation reaction catalyst concn is 0.3-10 weight %.
By technique scheme, Ammoximation reaction is carried out using the response system containing microreactor, profit
There are with microreactor the construction featuress of large specific surface area, mass transfer and the heat transfer effect of reactant can be improved
Rate.The Ammoximation reaction system of the aldehydes or ketones of the present invention have reactant mixing be uniformly dispersed and mass transfer and
The advantages of heat transfer efficiency is high.Ammoximation reaction is carried out using the response system of the present invention and can improve aldehydes or ketones
Conversion ratio, accelerate reaction rate, simplification of flowsheet, reduce production cost.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not construed as limiting the invention.?
In accompanying drawing：
Fig. 1 is a kind of signal of the Ammoximation reaction system of the aldehydes or ketones of currently preferred embodiment
Figure.
Fig. 2 is the MCA schematic diagram of the cardioid micro passage reaction that the present invention provides.
Fig. 3 is cooling circulating water channel design schematic diagram in the micro passage reaction that the present invention provides.
Description of reference numerals
1 first microreactor 2 second microreactor
3 buffer container 4 solid-liquid separating equipment
5 storage containers
Specific embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.It should be appreciated that
Specific embodiment described herein is merely to illustrate and explains the present invention, is not limited to this
Bright.
As shown in figure 1, according to an aspect of the present invention, providing a kind of Ammoximation reaction system of aldehydes or ketones
System, this system includes microreactor unit, buffer container 3, solid-liquid separating equipment 4 and storage container 5；
The outlet of described microreactor unit is connected with the entrance of described buffer container 3, described buffer container 3
Outlet is connected with the entrance of described solid-liquid separating equipment 4, the outlet of described solid-liquid separating equipment 4 respectively with
The entrance of the entrance of described microreactor unit and described storage container 5 connects；
Wherein, described microreactor unit includes a microreactor or the multiple micro- reaction being sequentially connected in series
Device, the number of the plurality of microreactor is 2-5；
The entrance of described microreactor unit is the reactant entrance of one microreactor or described many
The reactant entrance of the first microreactor in individual microreactor, the outlet of described microreactor unit is institute
State a microreactor reaction mixture outlet or the plurality of microreactor in last position microreactor
Reaction mixture outlet.
The present invention carries out Ammoximation reaction using the response system containing microreactor, using microreactor tool
There are the construction featuress of large specific surface area, improve mass transfer and the heat transfer efficiency of reactant.The aldehyde of the present invention or
The Ammoximation reaction system of ketone has reactant mixing and is uniformly dispersed and mass transfer and heat transfer efficiency height etc. are excellent
Point.The conversion ratio that Ammoximation reaction can improve aldehydes or ketones is carried out using the response system of the present invention, accelerates
Reaction rate, simplification of flowsheet, reduces production cost.
In the response system according to the present invention, the microreactor in microreactor unit is sent out as aldehydes or ketones
The reacting environment of ammonifying oximation reaction, is used for making aldehydes or ketones Ammoximation reaction occur and improve reaction further
Conversion ratio and selectivity of product.One of the present invention preferred embodiment in, aldehydes or ketones are oximes anti-
System is answered to include the multiple microreactors being sequentially connected in series, reactant feed flows through the many of above-mentioned series connection successively
Individual reactor, the first microreactor in plurality of microreactor refers to along reactant feed flow direction
First microreactor；Last position microreactor in multiple microreactors refers to flow to along reactant feed
Last microreactor.For example, it is being followed in series to form microreactor unit by 3 microreactors
Ammoximation reaction system in, the first microreactor be along reactant feed flow direction first micro- reaction
Device, last position microreactor is the 3rd microreactor along reactant feed flow direction.
One according to the present invention preferred embodiment, carries out ammonia to improve aldehydes or ketones in response system
The reaction conversion ratio of oximation reaction, can contain multiple microreactors, multiple micro- reactions in this response system
The number of device is preferably two, including the first microreactor 1 being sequentially connected in series and the second microreactor 2,
The reaction mixture outlet of described second microreactor 2 is connected with the entrance of described buffer container 3.
Carry out reaction conversion ratio and the selectivity of product of Ammoximation reaction in order to improve aldehydes or ketones further, excellent
Selection of land, above-mentioned microreactor can be each independently selected from cardioid micro passage reaction, T-shaped microchannel
One or more of reactor, Y type micro passage reaction and cross micro passage reaction.Above-mentioned kind
There is inside the micro passage reaction of class a plurality of microchannel, specific surface area is greatly improved, and can make aldehydes or ketones
Mixing with other reactants and be uniformly dispersed, improving reactor inner transmission matter heat transfer efficiency, thus improving aldehydes or ketones
Conversion ratio and product selectivity.
In a currently preferred embodiment, above-mentioned microreactor can react for cardioid microchannel
Device.As shown in Fig. 2 being provided with a plurality of microchannel with heart-shaped structure in cardioid micro passage reaction,
And it is provided with the rapids to strengthen fluid in microchannel for multiple first baffles as shown in Figure 2 in this microchannel
Traverse degree, improves the efficiency of material mixing and heat exchange in microreactor, thus improving aldehydes or ketones further
Conversion ratio.
In a currently preferred embodiment, cooling circulating water in micro passage reaction, can be provided with
Passage, the shape of cooling circulating water passage and set-up mode particularly do not require, and can be this area skill
Known to art personnel, for example, as shown in figure 3, can be that the cooling being provided with multiple second baffles follows
Ring aquaporin.Setting cooling circulating water passage can strengthen the exchange capability of heat of microreactor, improves aldehydes or ketones
Conversion ratio and product selectivity.
In the response system according to the present invention, the microchannel equivalent diameter of microreactor can be in very big model
Enclose interior change, the present invention does not do special requirement, in order to improve mass transfer and the heat transfer of microreactor further
Efficiency, the microchannel equivalent diameter of microreactor is preferably 0.5-5mm independently of one another.Wherein, micro- logical
The implication of road equivalent diameter is well known to those skilled in the art, and is the equal pipe diameter of hydraulic radius
It is defined as the equivalent diameter of non-round.In the range of the equivalent diameter of above-mentioned preferred microchannel, microreactor can
More effectively to improve the reaction rate that aldehydes or ketones occur Ammoximation reaction, strengthening mass transfer and heat transfer efficiency,
Thus improving the conversion ratio of aldehydes or ketones.
In order to adjust the flow of the reaction mixture entering solid-liquid separating equipment 4, according to the reaction of the present invention
Buffer container 3 can also be included in system, for example, can be surge tank.The entrance of buffer container 3 is permissible
The outlet of the last position microreactor with said one microreactor or in multiple microreactors of being sequentially connected in series
Connect, to accept the reaction mixture flowing out in microreactor, the outlet of buffer container 3 can be with solid-liquid
The entrance of separation equipment 4 connects.One of the present invention preferred embodiment in, in order to adjust entrance
The pressure of the reaction mixture of solid-liquid separating equipment 4, the outlet of buffer container 3 can be divided with solid-liquid through pump
Entrance from equipment 4 connects, so that entering back into solid-liquid separating equipment, thus carrying after reaction mixture boosting
Catalyst and the separation efficiency reacting clear liquid in high reaction mixture.
For the Ammoximation reaction catalyst being separated and recovered from reaction mixture, the response system of the present invention
In can also include solid-liquid separating equipment 4, reaction mixture carries out solid-liquid separation through solid-liquid separating equipment 4,
The reaction clear liquid containing product isolated can enter in storage container 5, and that isolates contains ammonia
After the filter of oximation reaction catalyst underflow can be back in the first microreactor 1 continue to participate in oximes anti-
Should.Wherein, the species of solid-liquid separating equipment 4 does not have special requirement, as long as meet to make aldehydes or ketones
Ammoximation reaction catalyst in the mixed serum of Ammoximation reaction separates with product clear liquid, example
As being membrane filter system, centrifugal separation equipment or settlement separate equipment, in order to improve Ammoximation reaction
Catalyst and the separation efficiency reacting clear liquid, under preferable case, solid-liquid separating equipment 4 can be inoranic membrane
Filter and/or metal film filter.Above-mentioned preferred solid-liquid separating equipment 4 can improve Ammoximation reaction
Catalyst and the separation efficiency of reaction clear liquid, improve the organic efficiency of catalyst and the quality of product.
According to another aspect of the present invention, the Ammoximation reaction system using above-mentioned aldehydes or ketones is also provided to enter
The method of row Ammoximation reaction, the method comprises the following steps：
(1) make aldehydes or ketones, Ammoximation reaction catalyst, ammonia, solvent and hydrogen peroxide micro- anti-at one
Answer the concurrent ammonifying oximation reaction of mix homogeneously in device, obtain reaction mixture；
Or, make aldehydes or ketones, Ammoximation reaction catalyst, ammonia, solvent and hydrogen peroxide multiple micro- anti-
Answer mix homogeneously concurrent ammonifying oximation reaction in the first microreactor in device, obtain the first reaction mixing
Liquid, makes described first reaction mixture sequentially enter in multiple microreactors in addition to the first microreactor
Other microreactors, and the peroxide with supplement in other microreactors in addition to the first microreactor respectively
Change hydrogen mix homogeneously and carry out Ammoximation reaction, obtain last position reaction mixture；
(2) reaction mixture or last position reaction mixture is made to enter buffer container 3；
(3) reaction mixture in buffer container 3 or last position reaction mixture is made to enter solid-liquid separation and set
Standby 4 carry out solid-liquid separation, make the supernatant separately obtaining enter storage container 5, make separately obtain to contain
After having the filter of Ammoximation reaction catalyst, dope returns one microreactor or described the first micro- reaction
Device proceeds Ammoximation reaction.
One of the present invention preferred embodiment in, as shown in figure 1, the oximes reaction of aldehydes or ketones
The first microreactor 1 and the second microreactor 2 being sequentially connected in series can be included, using this system in system
The method carrying out Ammoximation reaction can be for comprising the steps：
(1) make aldehydes or ketones, Ammoximation reaction catalyst, ammonia, solvent and hydrogen peroxide micro- anti-first
Answer mix homogeneously concurrent ammonifying oximation reaction in device 1, obtain the first reaction mixture；
(2) make the first reaction mixture enter the second microreactor 2 to mix all with the hydrogen peroxide supplementing
Even and carry out Ammoximation reaction, obtain last position reaction mixture and enter buffer container 3；
(3) make the last position reaction mixture in buffer container 3 enter solid-liquid separating equipment 4 and carry out solid-liquid
Separately, make to separate the supernatant entrance storage container 5 obtaining, make separately obtain to contain Ammoximation reaction
After the filter of catalyst, dope return the first microreactor 1 proceeds Ammoximation reaction.
In the method according to the invention, the aldehyde as raw material can be butyraldehyde or benzaldehyde, as raw material
Ketone can be aliphatic ketone, alicyclic ketone or aromatic ketone, and the arbitrary composition in them.Tool
The compound of body can be enumerated, the dialkyl ketone such as acetone, butanone；Ketohexamethylene, Ketocyclopentane, cyclooctanone etc.
Cyclanone.Under preferable case, the aldehydes or ketones as raw material are cyclanone, more preferably Ketohexamethylene.
In the method according to the invention, the ammonia as raw material can be used with gaseous state or liquid, or permissible
Used with its solution form in organic solvent.Under preferable case, raw material ammonia is with liquid or solution state
Use.The usage amount of ammonia does not particularly require, and can be well known to those skilled in the art, aldehyde or
The conventional amount used of ammonia in ketone oxamidinating reaction, such as ammonia can be (1-3) with the mol ratio of aldehydes or ketones：1,
It is preferably (1.5-2.5)：1.Raw material ammonia can improve further in above-mentioned preferred amount ranges aldehyde or
The conversion ratio of ketone and the selectivity of product oxime, thus improve the reaction yield of product oxime.
In the method according to the invention, in reaction raw materials, the consumption of hydrogen peroxide does not particularly require,
Can be the conventional amount used of hydrogen peroxide in Ammoximation reaction, for example, hydrogen peroxide and Ketohexamethylene mole
Ratio can be (0.8-1.5)：1.Hydrogen peroxide is added preferably in the form of hydrogen peroxide, and hydrogen peroxide can be by
Add according to concentration conventional use of in industry.
In the method for the aldehydes or ketones Ammoximation reaction of the present invention, also contain molten in reacting material mixture
Agent, the selection of solvent does not particularly require, and can be the common solvent of Ammoximation reaction, for example permissible
For alcohols solvent, can be specifically selected from toluene, dimethylbenzene, methanol, ethanol, normal propyl alcohol, isopropyl
One or more of alcohol, n-butyl alcohol and tert-butyl alcohol.Under preferable case, solvent can be the tert-butyl alcohol.Uncle
Butanol can more effectively promote reactant mixing to disperse and improve Ammoximation reaction efficiency as solvent.
In the method for the aldehydes or ketones Ammoximation reaction of the present invention, reaction is in Ammoximation reaction catalyst
Carry out under catalysis.What wherein Ammoximation reaction catalyst can be well known to those skilled in the art is permissible
For the catalyst of Ammoximation reaction, for example, titanium-silicon molecular sieve catalyst.For example, HTS is urged
Agent can be TS-1 type titanium-silicon molecular sieve catalyst, TS-2 type titanium-silicon molecular sieve catalyst and TWW
One or more of type titanium-silicon molecular sieve catalyst.The titanium-silicon molecular sieve catalyst of mentioned kind to aldehyde or
The selectivity of ketone oxamidinating reaction is good, high conversion rate, is conducive to improving the yield of product.
Wherein, the particle diameter of titanium-silicon molecular sieve catalyst can change in very large range, for example, can be
5nm-200 μm, under preferable case, the particle diameter of titanium-silicon molecular sieve catalyst can be 5nm-100 μm, on
The titanium-silicon molecular sieve catalyst stated in particle size range is higher to the catalytic efficiency of aldehydes or ketones Ammoximation reaction, and
It is easy to separate from reaction mixture by solid-liquid separating equipment 4, be conducive to the recycling of catalyst.
In the method according to the invention, carry out in a microreactor or multiple microreactor oximes anti-
The reaction condition answered particularly does not require, can be according to well-known to those skilled in the art oximes anti-
Condition is answered to limit.In order to improve the reaction conversion ratio of aldehydes or ketones further, under preferable case, reaction temperature
Degree can be 65-90 DEG C, and reaction pressure can be 0.01-0.45MPa, and the time of staying can be
0.5-20min.
According to the present invention, the use of the Ammoximation reaction catalyst in a microreactor or multiple microreactor
Amount does not particularly require, such as Ammoximation reaction catalyst in one microreactor or multiple microreactor
Concentration can be 0.1-20 weight %, under preferable case, in a microreactor or multiple microreactor
Ammoximation reaction catalyst concn can be 0.3-10 weight %.In the range of above-mentioned preferred catalyst amount,
Ammoximation reaction catalyst can be catalyzed aldehydes or ketones and be reacted under suitable reaction rate, and improves
The reaction conversion ratio of aldehydes or ketones.
According to the present invention, mend in other microreactors in addition to the first microreactor in multiple microreactors
The hydrogen peroxide use filling can change in very large range, and the present invention is not special requirement, Duo Gewei
The consumption of the hydrogen peroxide supplementing in other microreactors in addition to the first microreactor in reactor can
Think identical or different, under preferable case, each independent consumption of hydrogen peroxide supplementing and the first reaction
In mixed liquor, the mol ratio of unconverted aldehydes or ketones is (1.1-2)：1.Supplement in above-mentioned amount ranges
Hydrogen peroxide can with the first microreactor in not reaction completely aldehydes or ketones continue occur Ammoximation reaction,
To improve the conversion ratio of aldehydes or ketones further, thus improving reaction yield.
In the method according to the invention, the reaction mixture obtaining in a microreactor or last position are micro- anti-
After answering the last position reaction mixture obtaining in device to enter buffer-stored in buffer container 3, solid-liquid can be entered
Separation equipment 4 carries out solid-liquid separation.For example, according to a kind of currently preferred embodiment, such as Fig. 1
Shown, the last position reaction mixture obtaining in the second microreactor 2 enters buffer-stored in buffer container 3
Afterwards, solid-liquid separating equipment 4 can be entered and carry out solid-liquid separation.
One of the present invention preferred embodiment in, reaction mixture in buffer container 3 can be through
Enter back into solid-liquid separating equipment 4 after pump boosting, in this embodiment, after boosting, enter solid-liquid separation
The reaction mixture of equipment 4 carries out the in hgher efficiency of solid-liquid separation, is conducive to the amidoxime in reaction mixture
Change catalyst and efficiently separate with reacting clear liquid, thus improving the whole efficiency of reaction unit and product
Quality.
In the method according to the invention, that isolates from solid-liquid separating equipment 4 contains Ammoximation reaction
The serosity of catalyst can be back to the first microreactor in a microreactor or multiple microreactor
In continue to participate in Ammoximation reaction, complete recycling of catalyst, obtain from solid-liquid separating equipment 4
The reaction clear liquid containing aldoxime or ketoxime product can enter in storage container 5 as crude product store up
Deposit.Crude product in storage container 5 can also obtain aldoxime or ketoxime through further process for separating and purifying
Product.
Further illustrate the present invention below by embodiment, but the present invention is not therefore subject to any limit
System.
In the examples below, conversion ratio and oxime selectivity can be calculated according to following calculating formula (with
As a example Ketohexamethylene).
Ketohexamethylene conversion ratio=(mole of Ketohexamethylene in the mole-product of the Ketohexamethylene of charging)/enter
Mole × 100% of the Ketohexamethylene of material
The mole of cyclohexanone-oxime in cyclohexanone-oxime selectivity=product/(mole of the Ketohexamethylene of charging-
The mole of Ketohexamethylene in product) × 100%
Wherein, the data of Ketohexamethylene and cyclohexanone-oxime adopts gas chromatogram (Shimadzu GC14B, DB-1 hair
Capillary column 30m × 0.25mm × 0.25 μm) analysis obtain.
Titanium-silicon molecular sieve catalyst is the TS-1 titanium-silicon molecular sieve catalyst purchased from middle catalyst company, remaining
Reagent is commercial products.
Embodiment 1
The present embodiment is used for the Ammoximation reaction system and method for the present invention are described.
In the present embodiment, Ammoximation reaction system includes a T-shaped micro passage reaction, and microchannel is worked as
Measure a diameter of 0.5mm.
Ketohexamethylene, ammonia, hydrogen peroxide and titanium-silicon molecular sieve catalyst and solvent tertiary butanol is made to initially enter T
Mix homogeneously in type micro passage reaction, the mol ratio of Ketohexamethylene, ammonia and hydrogen peroxide is 1：1.8：1.5,
In material liquid, the concentration of titanium-silicon molecular sieve catalyst (5nm-50 μm of particle diameter) is 0.3 weight %, reaction
Temperature is 65 DEG C, and reaction pressure is 0.45MPa, and the time of staying is 0.5min；The reaction mixture obtaining
Enter inorganic membrane filter 4 after buffered tank 3 buffering and carry out solid-liquid separation, the supernatant being filtrated to get
Enter crude product storage tank 5 to store, after the filter containing catalyst, underflow is back to T-shaped micro passage reaction and continues
Continuous participation Ammoximation reaction.
In product, the conversion ratio of Ketohexamethylene is 99.3%, and the selectivity of cyclohexanone-oxime is 99.1%.
Embodiment 2
The present embodiment is used for the Ammoximation reaction system and method for the present invention are described.
In the present embodiment, Ammoximation reaction system includes the micro passage reaction of two series connection, and first is micro-
Reactor 1 is T-shaped micro passage reaction, and the second microreactor 2 is cross micro passage reaction, the
The microchannel equivalent diameter of one microreactor 1 and the second microreactor 2 is 5mm.
As shown in figure 1, making butyraldehyde, ammonia, hydrogen peroxide and titanium-silicon molecular sieve catalyst and solvent toluene first
It is introduced into mix homogeneously in the first microreactor 1, the mol ratio of Ketohexamethylene, ammonia and hydrogen peroxide is 1：2：
2, in material liquid, the concentration of titanium-silicon molecular sieve catalyst (20 μm -100 μm of particle diameter) is 10 weight %,
Reaction temperature is 90 DEG C, and reaction pressure is 0.1MPa, and the time of staying is 20min；First obtaining is anti-
Answer mixed liquor to enter the second microreactor 2 and proceed Ammoximation reaction with the hydrogen peroxide supplementing, reaction
Condition is identical with the first microreactor 1, and the hydrogen peroxide supplementing is unconverted with the first reaction mixture
The mol ratio of aldehydes or ketones is 2：1；Metal is entered after last position reaction mixture buffered tank 3 buffering obtaining
Film filter 4 carries out solid-liquid separation, and the supernatant being filtrated to get enters crude product storage tank 5 and stores, and contains
After having the filter of catalyst, underflow is back to the first microreactor 1 and continues to participate in Ammoximation reaction.
In product, the conversion ratio of Ketohexamethylene is 99.1%, and the selectivity of cyclohexanone-oxime is 99%.
Embodiment 3
The present embodiment is used for the Ammoximation reaction system and method for the present invention are described.
In the present embodiment, Ammoximation reaction system includes the T-shaped micro passage reaction of 5 series connection, and
Microchannel equivalent diameter is 0.5mm.
Butanone, ammonia, hydrogen peroxide and titanium-silicon molecular sieve catalyst and solvent tertiary butanol is made to initially enter first place
Mix homogeneously in microreactor, the mol ratio of Ketohexamethylene, ammonia and hydrogen peroxide is 1：2.5：2.5, raw material
In liquid, the concentration of titanium-silicon molecular sieve catalyst (0.15-0.5 μm of particle diameter) is 2 weight %, and reaction temperature is
75 DEG C, reaction pressure is 0.3MPa, and the time of staying is 5min；The first reaction mixture obtaining is successively
Enter remaining 4 microreactor and proceed with the hydrogen peroxide of the supplement of equimolar amountss oximes respectively
Reaction, reaction condition is identical with the first microreactor, in the hydrogen peroxide and the first reaction mixture that supplement
The mol ratio of unconverted aldehydes or ketones is 1.1：1；The buffered tank 3 of last position reaction mixture obtaining buffers
Enter inorganic membrane filter 4 afterwards and carry out solid-liquid separation, the supernatant being filtrated to get enters crude product storage tank
5 storages, after the filter containing catalyst, underflow is back to the first microreactor and continues to participate in Ammoximation reaction.
In product, the conversion ratio of Ketohexamethylene is 99.7%, and the selectivity of cyclohexanone-oxime is 99.2%.
Embodiment 4
The present embodiment is used for the Ammoximation reaction system and method for the present invention are described.
In the present embodiment, the first microreactor 1 and second that Ammoximation reaction system includes connecting is micro- anti-
Device 2, the first microreactor 1 and the second microreactor 2 is answered to be cardioid micro passage reaction, and micro- logical
Road equivalent diameter is 0.5mm.
As shown in figure 1, making Ketohexamethylene, ammonia, hydrogen peroxide and titanium-silicon molecular sieve catalyst and the tertiary fourth of solvent
Alcohol initially enters mix homogeneously in the first microreactor 1, and the mol ratio of Ketohexamethylene, ammonia and hydrogen peroxide is
1：1.8：1.5, in material liquid, the concentration of titanium-silicon molecular sieve catalyst (0.15-0.5 μm of particle diameter) is 3.5
Weight %, reaction temperature is 80 DEG C, and reaction pressure is 0.35MPa, and the time of staying is 15min；Obtain
The first reaction mixture enter the second microreactor 2 with the hydrogen peroxide supplementing proceed oximes anti-
Should, reaction condition is identical with the first microreactor 1, in the hydrogen peroxide and the first reaction mixture that supplement
The mol ratio of unconverted aldehydes or ketones is 1.5：1；The buffered tank 3 of last position reaction mixture obtaining buffers
Enter inorganic membrane filter 4 afterwards and carry out solid-liquid separation, the supernatant being filtrated to get enters crude product storage tank
5 storages, after the filter containing catalyst, underflow is back to the first microreactor 1 and continues to participate in Ammoximation reaction.
In product, the conversion ratio of Ketohexamethylene is 99.9%, and the selectivity of cyclohexanone-oxime is 99.99%.
Embodiment 5
The present embodiment is used for the Ammoximation reaction system and method for the present invention are described.
Using Ammoximation reaction system and method same as Example 4, except that, by solvent uncle
Butanol such as replaces with the isopropanol of weight.
In product, the conversion ratio of Ketohexamethylene is 99.5%, and the selectivity of cyclohexanone-oxime is 99%.
Embodiment 6
The present embodiment is used for the Ammoximation reaction system and method for the present invention are described.
Using Ammoximation reaction system and method same as Example 4, except that, reaction temperature
For 40 DEG C, reaction pressure is 0.05MPa, and the time of staying is 30min.
In product, the conversion ratio of Ketohexamethylene is 99.4%, and the selectivity of cyclohexanone-oxime is 99.2%.
Embodiment 7
The present embodiment is used for the Ammoximation reaction system and method for the present invention are described.
Using Ammoximation reaction system and method same as Example 4, except that, the mistake supplemented
Hydrogen oxide is 0.5 with the mol ratio of unconverted aldehydes or ketones in described first reaction mixture：1.
In product, the conversion ratio of Ketohexamethylene is 99.4%, and the selectivity of cyclohexanone-oxime is 99.2%.
Embodiment 8
The present embodiment is used for the Ammoximation reaction system and method for the present invention are described.
Using Ammoximation reaction system and method same as Example 4, except that, first is micro- anti-
Device 1 and the second microreactor 2 is answered to be T-shaped micro passage reaction.
In product, the conversion ratio of Ketohexamethylene is 99.5%, and the selectivity of cyclohexanone-oxime is 99.3%.
Comparative example 1
This comparative example is used for the explanation Ammoximation reaction system and method different from the present invention.
Titanium-silicon molecular sieve catalyst is filled in a diameter of 20 millimeters, length is 1200 millimeters of fixed bed
In reactor, total filling volume is 50 milliliters.Material rate is：Hydrogen peroxide is rubbed with Ketohexamethylene
Your ratio is 1.5: 1, and ammonia is 1.8: 1 with the mol ratio of Ketohexamethylene, and Ketohexamethylene is 8: 1 with the volume ratio of water；
Reaction condition is：95 DEG C of temperature, absolute pressure 0.5MPa, the volume space velocity 1h of Ketohexamethylene-1..Continuously
Reaction obtains product cyclohexanone-oxime in 100 hours afterwards.
In product, Ketohexamethylene conversion ratio is 94.5%, and cyclohexanone-oxime selectivity is 95.1%.
Comparative example 2
This comparative example is used for the explanation Ammoximation reaction system and method different from the present invention.
Using Ammoximation reaction method same as Example 4, except that, Ammoximation reaction system
In do not comprise the second microreactor 2, the first reaction mixture obtaining in the first microreactor 1 directly enters
Enter inorganic membrane filter after entering surge tank 3 to be filtered.
In product, Ketohexamethylene conversion ratio is 95.9%, and cyclohexanone-oxime selectivity is 95.4%.
Comparative example 3
This comparative example is used for the explanation Ammoximation reaction system and method different from the present invention.
Using Ammoximation reaction system and method same as Example 4, except that, second is micro- anti-
Answer the hydrogen peroxide being added without supplement in device 2.
In product, Ketohexamethylene conversion ratio is 96.5%, and cyclohexanone-oxime selectivity is 96.2%.
According to above-described embodiment data, phase be can be seen that by the Data Comparison of embodiment 4 and comparative example 1
For using common fixed bed reactors, the present invention is entered using the response system containing microreactor and method
During the Ammoximation reaction of row aldehydes or ketones, the conversion ratio of aldehydes or ketones is higher, the choosing of product aldoxime or ketoxime
Selecting property is higher；Currently preferred adopting be can be seen that by the Data Comparison of embodiment 4 and comparative example 2-3
Carry out the Ammoximation reaction of aldehydes or ketones with the response system of two microreactors containing series connection, and to second
The method supplementing hydrogen peroxide in microreactor 2, can improve turning of aldehydes or ketones Ammoximation reaction further
Rate and the selectivity of product.
Be can be seen that in currently preferred solvent by the Data Comparison of embodiment 4 and embodiment 5 is uncle
In the case of butanol, the response system of the present invention and method carry out the conversion ratio of the Ammoximation reaction of aldehydes or ketones
Higher, selectivity of product is high；Be can be seen that at this by the Data Comparison of embodiment 4 and embodiment 6
Bright preferred reaction temperature 65-90 DEG C, reaction pressure 0.01-0.45MPa, time of staying 0.5-20min
In the case of, the response system of the present invention and method carry out the conversion ratio of Ammoximation reaction and the product of aldehydes or ketones
Thing selectivity is high；Be can be seen that currently preferred by the Data Comparison of embodiment 4 and embodiment 7
In the hydrogen peroxide supplementing and the first reaction mixture, the mol ratio of unconverted aldehydes or ketones is (1.1-2)：1
In the case of, the response system of the present invention and method carry out Ammoximation reaction, the conversion ratio of aldehydes or ketones and product
Thing selectivity is higher；Be can be seen that preferred in the present invention by the Data Comparison of embodiment 4 and embodiment 8
Microreactor be cardioid micro passage reaction in the case of, the Ammoximation reaction system and method for the present invention
More effectively improve aldehydes or ketones and carry out the conversion ratio of Ammoximation reaction and the selectivity of product.
Describe the preferred embodiment of the present invention above in association with accompanying drawing in detail, but, the present invention does not limit
Detail in above-mentioned embodiment, in the range of the technology design of the present invention, can be to the present invention
Technical scheme carry out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention no longer separately illustrates to various possible compound modes.
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 equally should be considered as content disclosed in this invention.
Claims (10)
1. a kind of Ammoximation reaction system of aldehydes or ketones is it is characterised in that this system includes microreactor
Unit, buffer container (3), solid-liquid separating equipment (4) and storage container (5)；Described microreactor
The outlet of unit is connected with the entrance of described buffer container (3), the outlet of described buffer container (3) with
The entrance of described solid-liquid separating equipment (4) connects, the outlet of described solid-liquid separating equipment (4) respectively with
The entrance of the entrance of described microreactor unit and described storage container (5) connects；
Wherein, described microreactor unit includes a microreactor or the multiple micro- reaction being sequentially connected in series
Device, the number of the plurality of microreactor is 2-5；
The entrance of described microreactor unit is the reactant entrance of one microreactor or described many
The reactant entrance of the first microreactor in individual microreactor, the outlet of described microreactor unit is institute
State a microreactor reaction mixture outlet or the plurality of microreactor in last position microreactor
Reaction mixture outlet.
2. system according to claim 1 it is characterised in that the plurality of microreactor
Number is two, including the first microreactor (1) being sequentially connected in series and the second microreactor (2), described
The reaction mixture outlet of the second microreactor (2) is connected with the entrance of described buffer container (3).
3. system according to claim 1 and 2 it is characterised in that described microreactor each
Independently be selected from cardioid micro passage reaction, T-shaped micro passage reaction, Y type micro passage reaction and
One of cross micro passage reaction.
4. system according to claim 3 is it is characterised in that described microreactor is that cardioid is micro-
Channel reactor.
5. system according to claim 1 and 2 is it is characterised in that set in described microreactor
There is cooling circulating water passage, and the microchannel equivalent diameter of microreactor is 0.5-5mm.
6. system according to claim 1 and 2 is it is characterised in that described solid-liquid separating equipment
(4) it is inorganic membrane filter and/or metal film filter.
7. aldehydes or ketones Ammoximation reaction is carried out using the system described in any one in claim 1-6
Method is it is characterised in that the method comprises the following steps：
(1) aldehydes or ketones, Ammoximation reaction catalyst, ammonia, solvent and hydrogen peroxide are made one
In microreactor, mix homogeneously concurrent ammonifying oximation reaction, obtains reaction mixture；
Or, make aldehydes or ketones, Ammoximation reaction catalyst, ammonia, solvent and hydrogen peroxide the plurality of
Mix homogeneously concurrent ammonifying oximation reaction in the first microreactor in microreactor, obtains the first reaction and mixes
Close liquid, so that described first reaction mixture is sequentially entered in the plurality of microreactor and remove the first microreactor
Other microreactors in addition, and supplement with other microreactors in addition to the first microreactor respectively
Hydrogen peroxide mix homogeneously carry out Ammoximation reaction, obtain last position reaction mixture；
(2) described reaction mixture or described end position reaction mixture is made to enter buffer container (3)；
(3) reaction mixture in described buffer container (3) or last position reaction mixture is made to enter solid-liquid
Separation equipment (4) carries out solid-liquid separation, makes to separate supernatant entrance storage container (5) obtaining, makes
After separating the filter containing Ammoximation reaction catalyst obtaining, dope returns one microreactor or institute
State the first microreactor and proceed Ammoximation reaction；
Wherein, described aldehyde is benzaldehyde and/or butyraldehyde, and described ketone is selected from Ketohexamethylene, Ketocyclopentane, ring
One or more of octanone, butanone and acetone, described solvent is the tert-butyl alcohol.
8. method according to claim 7 is it is characterised in that one microreactor or many
The reaction condition carrying out Ammoximation reaction in individual microreactor is：Reaction temperature 65-90 DEG C, reaction pressure
0.01-0.45MPa, time of staying 0.5-20min.
9. method according to claim 7 is it is characterised in that in step (1), the plurality of
The consumption of the hydrogen peroxide supplementing in other microreactors in addition to the first microreactor in microreactor
Identical or different, and in each independently supplementary consumption of hydrogen peroxide and described first reaction mixture not
The mol ratio of the aldehydes or ketones of conversion is (1.1-2)：1.
10. method according to claim 7 is it is characterised in that described Ammoximation reaction catalyst
For titanium-silicon molecular sieve catalyst, particle diameter is 5nm-100 μm, one microreactor or multiple micro- reaction
In device, Ammoximation reaction catalyst concn is 0.3-10 weight %.
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| CN108530316A (en) * | 2018-05-10 | 2018-09-14 | 中国平煤神马集团尼龙科技有限公司 | A kind of fixed bed heat reclamation type Ammoximation reaction system |
| CN109092225A (en) * | 2018-11-02 | 2018-12-28 | 南京正源搪瓷设备制造有限公司 | Red heart K-type microreactor |
| CN114031521A (en) * | 2021-12-08 | 2022-02-11 | 中国天辰工程有限公司 | Method for quickly and efficiently preparing azino butanone |
| CN116926692A (en) * | 2023-09-18 | 2023-10-24 | 江苏青昀新材料有限公司 | Flash spinning heart-shaped microreactor |
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| CN108530316A (en) * | 2018-05-10 | 2018-09-14 | 中国平煤神马集团尼龙科技有限公司 | A kind of fixed bed heat reclamation type Ammoximation reaction system |
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| CN109092225B (en) * | 2018-11-02 | 2024-06-07 | 南京正源搪瓷设备制造有限公司 | Red heart K-type microreactor |
| CN114031521A (en) * | 2021-12-08 | 2022-02-11 | 中国天辰工程有限公司 | Method for quickly and efficiently preparing azino butanone |
| CN114031521B (en) * | 2021-12-08 | 2023-09-29 | 中国天辰工程有限公司 | Method for preparing butanone azine |
| CN116926692A (en) * | 2023-09-18 | 2023-10-24 | 江苏青昀新材料有限公司 | Flash spinning heart-shaped microreactor |
| CN116926692B (en) * | 2023-09-18 | 2024-01-02 | 江苏青昀新材料有限公司 | Flash spinning heart-shaped microreactor |
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