CN106278940B - Method that is a kind of while producing cyclohexanone oxime and acetone - Google Patents
Method that is a kind of while producing cyclohexanone oxime and acetone Download PDFInfo
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Abstract
The invention provides method that is a kind of while producing cyclohexanone oxime and acetone, this method includes in the presence of oxygen, cyclohexanone, ammonia and isopropanol being contacted with HTS, obtain the mixture containing cyclohexanone oxime and acetone., while can also by-product acetone using method of the invention, it is possible to obtain higher cyclohexanone conversion ratio and higher cyclohexanone oxime selectivity.The method according to the invention can produce cyclohexanone oxime and acetone simultaneously, and used raw material environmental protection, caused environmental contaminants are few, are more beneficial for environmental protection.Meanwhile the method according to the invention can be without using solvent, various raw materials directly use, and without being first configured to solution, do not interfere with the effective treating capacity of device.
Description
Technical field
The present invention relates to method that is a kind of while producing cyclohexanone oxime and acetone.
Background technology
Cyclohexanone oxime is the key intermediate of synthesis of caprolactam, is a kind of important industrial chemicals, mainly as preparation
The raw material of the monomer of feedstock nylon 6 of fiber and nylon 6 and engineering plastics.
Because titanium-silicon molecular sieve catalyst has very important effect in terms of organic compound selective oxidation, because
This, the preparation method as cyclohexanone oxime, it has been proposed that in the presence of titanium-silicon molecular sieve catalyst, using hydrogen peroxide and
Ammonia carries out oximes method to cyclohexanone.The advantages of the method is method that need not be as carrying out oximate with HAS in the past
Like that, ammonia neutralisation of sulphuric acid is utilized.
But generally carried as oxidant the most frequently used in peroxide oxidation method, hydrogen peroxide in the form of hydrogen peroxide
For its concentration typically between 20-50 weight %, inevitably introduces a large amount of water so in reaction system, reduces dress
The effective treating capacity put.In actual mechanical process, hydrogen peroxide (hydrogen peroxide) is generally current existing system, thus with hydrogen peroxide
(hydrogen peroxide) is typically equipped with hydrogen peroxide (hydrogen peroxide) production unit as the process units of oxidant, adds building for device
It is set as this and operating cost.In addition, hydrogen peroxide may decompose during the course of the reaction, thus reduce hydrogen peroxide
Effective rate of utilization, further increase the operating cost of device.In general, reacted in titanium molecular sieve catalysis oxidizing cyclohexanone
During, acetone can be used as solvent.It is but rarely seen directly to be made with isopropanol mixed liquor using cyclohexanone in the presence of oxygen
To produce the report of acetone and cyclohexanone oxime simultaneously for raw material.
The content of the invention
The invention provides a kind of new method for preparing cyclohexanone oxime, this method not only safety and environmental protection, and can obtaining
Higher cyclohexanone conversion ratio and cyclohexanone oxime selectivity, while can also by-product acetone, this method is a large amount of without introducing in addition
Solvent, higher device effective treating capacity can be obtained.
The invention provides method that is a kind of while producing cyclohexanone oxime and acetone, this method is included in the presence of oxygen,
Cyclohexanone, ammonia and isopropanol are contacted with HTS, obtain the mixture containing cyclohexanone oxime and acetone.
Using method of the invention, it is possible to obtain higher cyclohexanone conversion ratio and higher cyclohexanone oxime selectivity, together
When can also by-product acetone.
The method according to the invention can produce cyclohexanone oxime and acetone, used raw material environmental protection, caused ring simultaneously
Border pollutant is few, is more beneficial for environmental protection.Meanwhile the method according to the invention can be direct without using solvent, various raw materials
Use, without being first configured to solution, do not interfere with the effective treating capacity of device.
The method technological process of the present invention is easy, easily operated, implements suitable for extensive.
Embodiment
The invention provides method that is a kind of while producing cyclohexanone oxime and acetone, this method is included in the presence of oxygen,
Cyclohexanone, ammonia and isopropanol are contacted with HTS, obtain the mixture containing cyclohexanone oxime and acetone.
The HTS is the general name of a kind of zeolite of a part of silicon atom in titanium atom substitution lattice framework, can be with
With chemical formula xTiO2·SiO2Represent.The present invention is not particularly limited for the content of titanium atom in HTS, Ke Yiwei
The conventional selection of this area.Specifically, x can be 0.0001-0.05, preferably 0.01-0.03, more preferably 0.015-
0.025。
The HTS can be the common HTS with various topological structures, such as：The titanium silicon
Molecular sieve can be the HTS (such as TS-1) selected from MFI structure, the HTS (such as TS-2) of MEL structures, BEA knots
The HTS (such as Ti-Beta) of structure, the HTS (such as Ti-MCM-22) of MWW structures, the titanium silicon molecule of hexagonal structure
Sieve (such as Ti-MCM-41, Ti-SBA-15), HTS (such as Ti-MOR), the HTS of TUN structures of MOR structures
One or more in (such as Ti-TUN) and the HTS of other structures (such as Ti-ZSM-48).
Preferably, the HTS be the HTS selected from MFI structure, MEL structures HTS and
One or more in the HTS of BEA structures.It is highly preferred that the HTS is the titanium silicon molecule of MFI structure
Sieve, such as TS-1 molecular sieves.
From the further angle for improving cyclohexanone conversion ratio and selectivity of product, at least partly described HTS
For the HTS of MFI structure, and the crystal grain of the HTS is hollow-core construction, the footpath of the chamber portion of the hollow-core construction
It is 5-300 nanometers to length, and the HTS is in 25 DEG C, P/P0=0.10, adsorption time is to be surveyed under conditions of 1 hour
Benzene adsorbance be at least 70 milligrams per grams, the adsorption isotherm and desorption isotherm of the nitrogen absorption under low temperature of the HTS
Between hysteresis loop be present.Herein, the HTS with the structure is referred to as hollow HTS.The hollow titanium silicon point
Son sieve be commercially available (such as commercially available from Hunan Jianchang Petrochemical Co., Ltd the trade mark be HTS molecular sieve), also may be used
To be prepared according to the method disclosed in CN1132699C.
The method according to the invention, in the contact of cyclohexanone, ammonia and isopropanol with HTS in fixed bed reactors
During middle progress, in the preferred embodiment of the present invention, hollow HTS is filled with the fixed bed reactors
And titanium-silicon molecular sieve TS-1, hollow HTS and titanium-silicon molecular sieve TS-1 filling order cause containing cyclohexanone, ammonia and
The liquid mixture of isopropanol successively contacts with the hollow HTS and the titanium-silicon molecular sieve TS-1.That is, with containing
On the basis of flow direction of the liquid mixture of cyclohexanone, ammonia and isopropanol in fixed bed reactors, the hollow titanium silicon point
Son sieve is positioned at the upstream of the titanium-silicon molecular sieve TS-1.Can be by the way that hollow HTS and titanium-silicon molecular sieve TS-1 be layered
It is seated in fixed bed reactors, the liquid mixture containing cyclohexanone, ammonia and isopropanol is successively somebody's turn to do with hollow so as to realize
Si molecular sieves and titanium-silicon molecular sieve TS-1 contact.According to the preferred embodiment, higher selectivity of product can be obtained, together
When can also further extend catalyst service life.
In the preferred embodiment, the mass ratio of the hollow HTS and the titanium-silicon molecular sieve TS-1 can
Think 1-10：1, preferably 1-5：1.
In the preferred embodiment, the liquid mixture flows through hollow HTS and titanium-silicon molecular sieve TS-1
Superficial velocity can be identical, or it is different.Preferably, the liquid mixture flows through the table of hollow HTS
Sight speed is v1, the superficial velocity for flowing through titanium-silicon molecular sieve TS-1 is v2, wherein, v1＜ v2, so can further extend titanium silicon
The single trip use life-span of molecular sieve.It is highly preferred that v2/v1=1.5-10.It is further preferred that v2/v1=2-5.
In the present invention, the superficial velocity refers in the unit interval by the matter of the whole liquid mixture of beds
Flow (in terms of kg/s) is measured with the area of a certain cross section of beds (with m2Meter) ratio.Usually, can be by list
The quality of the liquid mixture of fixed bed reactors is sent into the time of position as " unit interval is interior to pass through whole beds
The mass flow of liquid mixture ".In the present invention, the superficial velocity for flowing through hollow HTS for liquid mixture does not have
Particular/special requirement, typically can be in 0.001-200kg/ (m2S) in the range of.
The liquid mixture can be adjusted using various methods and flows through hollow HTS and HTS TS-
1 superficial velocity.For example, the superficial velocity of raw mixture can be adjusted by the cross-sectional area of selecting catalyst bed.
Specifically, the cross-sectional area of the beds containing hollow HTS can be made to be more than containing titanium-silicon molecular sieve TS-1
The cross-sectional area of beds, so that v1＜ v2, it is preferable that v2/v1For 1.5-10, more preferably cause v2/v1For 2-5.
Determine that the method for the cross-sectional area of beds is known in those skilled in the art, sheet according to expected superficial velocity
Text is no longer described in detail.
Method according to the invention it is possible to introduced between the hollow HTS and titanium-silicon molecular sieve TS-1 fresh
Material, but the liquid mixture flows through the whole process of hollow HTS and the whole process of titanium-silicon molecular sieve TS-1, the liquid
Body mixture is not included in the fresh material introduced between hollow HTS and titanium-silicon molecular sieve TS-1, previously described
Whether superficial velocity determines by the liquid mixture, not by introducing fresh material and influenceed.
The HTS can be HTS original powder, or shaping HTS.
For the HTS as catalyst, its dosage, can be according to titanium silicon point can realize that catalysis is defined
Son sieve carries out catalytic concrete mode with cyclohexanone, ammonia and isopropanol and selected.Such as：By HTS and ring
Hexanone, ammonia and isopropanol are mixed to form slurry, and during so as to carry out haptoreaction, the weight ratio of cyclohexanone and HTS can be with
For 0.01-100：1, preferably 0.02-50：1；It is anti-in fixed bed in HTS contact with cyclohexanone, ammonia and isopropanol
Answer when being carried out in device, the weight space velocity of cyclohexanone can be 0.1-100h-1, preferably 1-50h-1.In the present invention, weight (hourly) space velocity (WHSV)
On the basis of whole HTSs in beds.
The method according to the invention, the contact of cyclohexanone, ammonia and isopropanol with HTS are carried out in the presence of oxygen.
Can be by being passed through oxygen into reactor so that be containing oxygen condition, so as to realize that the contact exists in oxygen in reactor
Lower progress.The oxygen can use the oxygen of pure state, oxygen-containing gas can also be used, as long as in oxygen-containing gas in addition to oxygen
Gas be non-active gas.The non-active gas refer to not with reactant (such as cyclohexanone, ammonia and isopropanol) and
Chemically interactive gas occurs for reaction product (such as cyclohexanone oxime and acetone), such as：Nitrogen and/or group 0 element gas
(such as argon gas).The dosage of oxygen typically can be 0.1-99 volume %, preferably 0.5-50 volumes % in oxygen-containing gas.It is described to contain
Carrier of oxygen can be air, or pass through the gaseous mixture for being obtained by mixing pure oxygen and pure non-active gas.Make
During by the use of air as oxygen-containing gas, air can be directly used, can also be by purification of air, to remove after particulate matter therein again
Use.The function of oxygen is to interact with isopropanol, and realize turns into cyclohexanone oxime, the dosage of oxygen by ammoxidation of cyclohexanone
Can realize that above-mentioned function is defined.Usually, the dosage of oxygen make it that the partial pressure of oxygen in reaction system is 0.01-5MPa, excellent
Elect 0.05-3MPa, more preferably 0.1-2MPa as.
The method according to the invention, under the collective effect of isopropanol and oxygen, ammoxidation of cyclohexanone is turned into cyclohexanone
Oxime, the dosage of isopropanol is can realize that above-mentioned function is defined.Usually, the mol ratio of cyclohexanone and isopropanol is 1：0.01-
20.Preferably, the mol ratio of cyclohexanone and isopropanol is 1：0.1-10, more preferably 1：0.2-5.
The method according to the invention, from the further angle for improving cyclohexanone conversion ratio and selectivity of product, hexamethylene
The contact of ketone, ammonia and isopropanol with HTS is preferably carried out in the presence of at least one peroxide of catalytic amount.
That is, at least one peroxide of cyclohexanone, ammonia, isopropanol and catalytic amount is contacted with HTS.Specifically,
The mol ratio of the peroxide and cyclohexanone can be 0.0001-0.1：1, preferably 0.0005-0.05：1.
The peroxide refers to the compound for containing-O-O- keys in molecular structure, can be hydrogen peroxide and/or organic
Peroxide, the organic peroxide refer to that one or both of hydrogen peroxide molecule structure hydrogen atom is substituted by organic group
And the material formed.The instantiation of the peroxide can include but is not limited to：Hydrogen peroxide, TBHP,
Dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic acid, Perpropionic Acid, cumyl peroxide, di-t-butyl peroxide,
Dibenzoyl peroxide and dilauroyl peroxide.In the present invention, the organic peroxide is preferably R1-O-O-R2, R1And R2Phase
It is same or different, can be each H, C4-C12Straight or branched alkyl orR3For C4-C12Straight or branched alkane
Base, R1And R2It is asynchronously H.
The method according to the invention, in the presence of oxygen, guaranteeing ammoxidation of cyclohexanone turning into cyclohexanone oxime
Under the premise of, from the further angle for improving selectivity of product, particularly acetone selectivity, cyclohexanone and isopropanol and appoint
The auxiliary agent (such as peroxide) of choosing is with the contact conditions of HTS preferably so that the conversion ratio of isopropanol is 10-20 weights
Measure %, more preferably 12-18 weight %.The condition that control can be selected to contact, such as catalytic temperature and pressure
To adjust the conversion ratio of isopropanol.
The method according to the invention, in the presence of oxygen, cyclohexanone, ammonia, isopropanol and optional other auxiliary agent (such as mistakes
Oxide) with the contact conditions of HTS, so that ammoxidation of cyclohexanone can be defined as cyclohexanone oxime.Usually, institute
Stating contact can be carried out at a temperature of 40-160 DEG C, preferably 60-140 DEG C, more preferably 60-120 DEG C.In terms of gauge pressure, connect
Pressure in tactile reactor can be 0-5MPa, preferably 0.1-3MPa, more preferably 0.5-3MPa.
The method according to the invention can also be carried out intermittently using continuous operation.In the presence of oxygen, HTS with
Cyclohexanone, ammonia, isopropanol and contacting for optional auxiliary agent (such as peroxide) can be carried out in conventional various reactors,
Such as fixed bed reactors, slurry bed reactor.
The method according to the invention, in the presence of oxygen, cyclohexanone, ammonia and isopropanol and HTS are connect
Touch, obtain the mixture containing cyclohexanone oxime and acetone.The method according to the invention can also include dividing from the mixture
The step of separating out cyclohexanone oxime and acetone.Conventional various methods can be used to isolate cyclohexanone oxime and third from the mixture
Ketone, such as the mixture is fractionated.The leftover materials for having isolated cyclohexanone oxime and acetone are purified or without pure
Change can recycle.
Describe the present invention in detail with reference to embodiments, but and be not so limited the scope of the present invention.
In following examples and comparative example, agents useful for same is commercially available AR.
In following examples and comparative example, titanium-silicon molecular sieve TS-1 used is volume according to Zeolites 1992,12,
Prepared by the method described in the 943-950 pages, its titanium oxide content is 2.5 weight %.
In following examples, hollow HTS used is prepared according to the method disclosed in CN1132699C, its oxygen
Change Ti content is 2.5 weight %.
In following examples and comparative example, the content of each composition in obtained reaction solution is analyzed using gas chromatography,
Below equation is respectively adopted on this basis to calculate cyclohexanone conversion ratio, iso-propanol conversion rate, cyclohexanone oxime selectivity and third
Ketone selectivity：
Cyclohexanone conversion ratio=[(mole of the mole of the cyclohexanone of addition-unreacted cyclohexanone)/add
The mole of cyclohexanone] × 100%；
Iso-propanol conversion rate=[(mole of the mole of the isopropanol of addition-unreacted isopropanol)/add
The mole of isopropanol] × 100%；
Cyclohexanone oxime selectivity=[mole of the cyclohexanone oxime of reaction generation/(mole of the cyclohexanone of addition-not
The mole of the cyclohexanone of reaction)] × 100%；
Acetone selectivity=[mole/(mole of the isopropanol of addition-unreacted different of the acetone of reaction generation
The mole of propyl alcohol)] × 100%.
Embodiment 1-18 is used for the method for illustrating the present invention.
Embodiment 1
In tank reactor, under oxygen atmosphere (atmosphere formed by the oxygen that purity is 99%), by cyclohexanone, liquid
Ammonia and isopropanol and the titanium-silicon molecular sieve TS-1 original powder haptoreaction as catalyst, wherein, mole of cyclohexanone and isopropanol
Than for 1：5, the mol ratio of cyclohexanone and ammonia is 1：1.5, the weight ratio of cyclohexanone and catalyst is 20：1, temperature is 90 DEG C, pressure
Power is 1.5MPa (gauge pressure), partial pressure of oxygen 1.5MPa.After reaction 2 hours, obtained mixture is filtered, collects what is obtained
Liquid mixture is simultaneously analyzed with gas-chromatography, so as to obtain cyclohexanone conversion ratio, iso-propanol conversion rate, cyclohexanone oxime selection
Property and acetone selectivity, as a result listed in table 1.
Embodiment 2
Using method same as Example 1 by oxidizing cyclohexanone, unlike, the hollow titanium silicon molecule of quality such as use
Sieve replaces titanium-silicon molecular sieve TS-1, and temperature is 60 DEG C.Experimental result is listed in table 1.
Embodiment 3
Using method same as Example 1 by oxidizing cyclohexanone, the difference is that, reaction temperature is 120 DEG C.Experimental result
Listed in table 1.
Embodiment 4
Using method same as Example 1 by oxidizing cyclohexanone, the difference is that, a small amount of peroxide is also added into reactor
Hydrogen (being provided in the form of 30 weight % hydrogen peroxide) is provided, wherein, the mol ratio of hydrogen peroxide and cyclohexanone is 0.0005：1.It is real
Result is tested to list in table 1.
Embodiment 5
Using method same as Example 1 by oxidizing cyclohexanone, the difference is that, a small amount of peroxide is also added into reactor
Hydrogen (being provided in the form of 30 weight % hydrogen peroxide) is provided, wherein, the mol ratio of hydrogen peroxide and cyclohexanone is 0.05：1.Experiment
As a result listed in table 1.
Embodiment 6
Using method same as Example 5 by oxidizing cyclohexanone, unlike, with etc. material amount peroxidating isopropyl
Benzene replaces hydrogen peroxide.Experimental result is listed in table 1.
Comparative example 1
Using method same as Example 1 by oxidizing cyclohexanone, the difference is that, without using titanium-silicon molecular sieve TS-1.It is real
Result is tested to list in table 1.
Comparative example 2
Using method same as Example 1 by oxidizing cyclohexanone, the difference is that, without using isopropanol.Experimental result exists
Listed in table 1.
Comparative example 3
Using method same as Example 1 by oxidizing cyclohexanone, the difference is that, without using oxygen, but use nitrogen
Substitute.Experimental result is listed in table 1.
Comparative example 4
Using method same as Example 1 by oxidizing cyclohexanone, the difference is that, without using isopropanol and oxygen, but
Using hydrogen peroxide (offer in the form of 30 weight % hydrogen peroxide), the mol ratio of cyclohexanone and hydrogen peroxide is 2：1.Experiment
As a result listed in table 1.
Table 1
Embodiment 1 can be seen that in the presence of oxygen compared with comparative example 1, in the presence of HTS,
By cyclohexanone, ammonia and isopropanol haptoreaction, high cyclohexanone conversion ratio can be obtained, while higher cyclohexanone can also be obtained
Oxime selectivity and acetone selectivity.
Embodiment 1 and comparative example 2 and 3 as a result, it was confirmed that only oxygen and isopropanol are applied in combination, could be with higher
Oxidizing cyclohexanone is turned into cyclohexanone oxime, while by-product acetone by conversion ratio.
Embodiment 1 is with comparative example 4 as a result, it was confirmed that the method for the present invention can not only can obtain oxidizing cyclohexanone
Higher cyclohexanone oxime selectivity, while can also by-product acetone；And present method avoids using hydrogen peroxide as
During oxidant, because hydrogen peroxide is provided in the form of hydrogen peroxide, cause the apparent treating capacity for adding device, but reduce dress
The deficiency for the effective treating capacity put, while reduce cost.
Embodiment 7
In tank reactor, in air atmosphere, using cyclohexanone, ammonia and isopropanol and the titanium silicon point as catalyst
Son sieve TS-1 original powder haptoreactions, wherein, the mol ratio of cyclohexanone and isopropanol is 1：3, the mol ratio of cyclohexanone and ammonia is 1:
3, the weight ratio of cyclohexanone and catalyst is 40：1, temperature is 50 DEG C, and pressure is 1.5MPa (gauge pressure), partial pressure of oxygen 0.3MPa.
After reaction 2 hours, obtained mixture is filtered, obtained liquid mixture is collected and is entered with gas-chromatography
Row analysis, so as to obtain cyclohexanone conversion ratio, iso-propanol conversion rate, cyclohexanone oxime selectivity and acetone selectivity, as a result in table 2
In list.
Embodiment 8
In tank reactor, in the oxygen-containing atmosphere (mixing for the nitrogen that the oxygen and purity for being 99% by purity are 99%
The atmosphere that thing is formed, wherein, the volume ratio of oxygen and nitrogen is 1：1) under, using cyclohexanone, liquefied ammonia and isopropanol and as catalysis
The titanium-silicon molecular sieve TS-1 original powder haptoreaction of agent, wherein, the mol ratio of cyclohexanone and isopropanol is 1：8, cyclohexanone and ammonia
Mol ratio is 1:1, the weight ratio of cyclohexanone and catalyst is 80：1, temperature is 60 DEG C, and pressure is 1.2MPa (gauge pressure), partial pressure of oxygen
For 0.5MPa.
After reaction 2 hours, obtained mixture is filtered, obtained liquid mixture is collected and is entered with gas-chromatography
Row analysis, so as to obtain cyclohexanone conversion ratio, iso-propanol conversion rate, cyclohexanone oxime selectivity and acetone selectivity, as a result in table 2
In list.
Embodiment 9
In tank reactor, under oxygen atmosphere (atmosphere formed by the oxygen that purity is 99%), by cyclohexanone, ammonia
Titanium-silicon molecular sieve TS-1 original powder haptoreaction with isopropanol and as catalyst, wherein, the mol ratio of cyclohexanone and isopropanol
For 1：6, the mol ratio of cyclohexanone and ammonia is 1:2, the weight ratio of cyclohexanone and catalyst is 2：1, temperature is 40 DEG C, and pressure is
1.0MPa (gauge pressure), partial pressure of oxygen 0.5MPa.
After reaction 4 hours, obtained mixture is filtered, obtained liquid mixture is collected and is entered with gas-chromatography
Row analysis, so as to obtain cyclohexanone conversion ratio, iso-propanol conversion rate, cyclohexanone oxime selectivity and acetone selectivity, as a result in table 2
In list.
Embodiment 10
In tank reactor, under oxygen atmosphere (atmosphere formed by the oxygen that purity is 99%), by cyclohexanone, ammonia
Titanium-silicon molecular sieve TS-1 original powder haptoreaction with isopropanol and as catalyst, wherein, the mol ratio of cyclohexanone and isopropanol
For 1：5, the mol ratio of cyclohexanone and ammonia is 1:4, the weight ratio of cyclohexanone and catalyst is 5：1, temperature is 90 DEG C, and pressure is
2.5MPa (gauge pressure), partial pressure of oxygen 1.0MPa.
After reaction 1 hour, obtained mixture is filtered, obtained liquid mixture is collected and is entered with gas-chromatography
Row analysis, so as to obtain cyclohexanone conversion ratio, iso-propanol conversion rate, cyclohexanone oxime selectivity and acetone selectivity, as a result in table 2
In list.
Table 2
Embodiment 11
Will shaping titanium-silicon molecular sieve TS-1 (volume average particle size is 150 μm, using be molded the total amount of titanium-silicon molecular sieve TS-1 as
Benchmark, the content of titanium-silicon molecular sieve TS-1 is 75 weight %, and the content of silica is 25 weight %) it is seated in miniature isometrical fixation
In bed reactor, beds are formed.By cyclohexanone, isopropanol and ammoniacal liquor (concentration is 30 weight %) from positioned at reactor bottom
The charging aperture in portion be sent into reactor with titanium-silicon molecular sieve TS-1 haptoreaction, in course of reaction, continue to be passed through into reactor
Oxygen-containing gas (gaseous mixture for the nitrogen for being 99% with purity for the oxygen that purity is 99%, wherein, the volume ratio of oxygen and nitrogen
For 0.25：1).Wherein, the mol ratio of cyclohexanone and isopropanol is 1：5, the mol ratio of cyclohexanone and ammonia is 1:2, the weight of cyclohexanone
Amount air speed is 2h-1.Temperature in beds is 70 DEG C, and the pressure in reactor is 0.8MPa (gauge pressure), and partial pressure of oxygen is
0.1MPa。
Gas chromatographic analysis is carried out to the liquid mixture of reactor output in the process of running and calculates cyclohexanone conversion
Rate, iso-propanol conversion rate, cyclohexanone oxime selectivity and acetone selectivity, are as a result listed in table 3.
Embodiment 12
Using with the identical method of embodiment 11 by oxidizing cyclohexanone, unlike, with etc. quality shaping hollow titanium silicon
Molecular sieve (volume average particle size is 150 μm, on the basis of being molded the total amount of hollow HTS, hollow HTS
Content is 75 weight %, and the content of silica is 25 weight %) replace shaping titanium-silicon molecular sieve TS-1.
Gas chromatographic analysis is carried out to the liquid mixture of reactor output in the process of running and calculates cyclohexanone conversion
Rate, iso-propanol conversion rate, cyclohexanone oxime selectivity and acetone selectivity, are as a result listed in table 3.
Embodiment 13
Using with the identical method of embodiment 11 by oxidizing cyclohexanone, unlike, the general assembly of catalyst in the reactor
Under conditions of the amount of filling out is constant, first filling is molded hollow titanium si molecular sieves (identical with embodiment 12) in the reactor, refills and fills into
Type titanium-silicon molecular sieve TS-1 (identical with embodiment 11) so that cyclohexanone, ammoniacal liquor and isopropanol are first passed through by shaping hollow titanium silicon
The bed that molecular sieve is formed, then the bed by being formed by shaping titanium-silicon molecular sieve TS-1.Wherein, it is molded hollow HTS
Weight ratio with being molded titanium-silicon molecular sieve TS-1 is 1：1.
Gas chromatographic analysis is carried out to the liquid mixture of reactor output in the process of running and calculates cyclohexanone conversion
Rate, iso-propanol conversion rate, cyclohexanone oxime selectivity and acetone selectivity, are as a result listed in table 3.
Embodiment 14
Using with the identical method of embodiment 13 by oxidizing cyclohexanone, unlike, the general assembly of catalyst in the reactor
Under conditions of the amount of filling out is constant, it is 5 to be molded hollow HTS with the weight ratio for being molded titanium-silicon molecular sieve TS-1：1.
Gas chromatographic analysis is carried out to the liquid mixture of reactor output in the process of running and calculates cyclohexanone conversion
Rate, iso-propanol conversion rate, cyclohexanone oxime selectivity and acetone selectivity, are as a result listed in table 3.
Embodiment 15
Using with the identical method of embodiment 14 by oxidizing cyclohexanone, unlike, also by positioned at reactor bottom
Charging aperture is sent into TBHP into reactor, wherein, the mol ratio of TBHP and cyclohexanone is 0.02：
1。
Gas chromatographic analysis is carried out to the liquid mixture of reactor output in the process of running and calculates cyclohexanone conversion
Rate, iso-propanol conversion rate, cyclohexanone oxime selectivity and acetone selectivity, are as a result listed in table 3.
Embodiment 16
Using with the identical method peroxyester of embodiment 14, unlike, using miniature reducing fixed bed reactors,
Wherein, the catalyst of the internal diameter of the beds of filling shaping hollow titanium si molecular sieves and filling shaping titanium-silicon molecular sieve TS-1
The ratio of the internal diameter of bed is 2：1, the internal diameter of the beds of filling shaping titanium-silicon molecular sieve TS-1 is identical with embodiment 14.
Gas chromatographic analysis is carried out to the liquid mixture of reactor output in the process of running and calculates cyclohexanone conversion
Rate, iso-propanol conversion rate, cyclohexanone oxime selectivity and acetone selectivity, are as a result listed in table 3.
Embodiment 17
Using with the identical method peroxyester of embodiment 14, unlike, using miniature reducing fixed bed reactors,
Wherein, the catalyst of the internal diameter of the beds of filling shaping hollow titanium si molecular sieves and filling shaping titanium-silicon molecular sieve TS-1
The ratio of the internal diameter of bed is 1：2, the internal diameter of the beds of filling shaping titanium-silicon molecular sieve TS-1 is identical with embodiment 14.
Gas chromatographic analysis is carried out to the liquid mixture of reactor output in the process of running and calculates cyclohexanone conversion
Rate, iso-propanol conversion rate, cyclohexanone oxime selectivity and acetone selectivity, are as a result listed in table 3.
Embodiment 18
Using with the identical method peroxyester of embodiment 14, unlike, using miniature reducing fixed bed reactors,
Wherein, the catalyst of the internal diameter of the beds of filling shaping hollow titanium si molecular sieves and filling shaping titanium-silicon molecular sieve TS-1
The ratio of the internal diameter of bed is 5：1, the internal diameter of the beds of filling shaping titanium-silicon molecular sieve TS-1 is identical with embodiment 14.
Gas chromatographic analysis is carried out to the liquid mixture of reactor output in the process of running and calculates cyclohexanone conversion
Rate, iso-propanol conversion rate, cyclohexanone oxime selectivity and acetone selectivity, are as a result listed in table 3.
Table 3
By embodiment 13 and 14 as can be seen that by by hollow HTS and titanium compared with embodiment 11 and 12
Silicalite TS-1 layering filling in the reactor, makes cyclohexanone and isopropanol priority and hollow HTS and hollow titanium silicon
Molecular sieve TS-1 haptoreaction, higher selectivity of product can be obtained, simultaneously effective extend the service life of catalyst.
By embodiment 14 as can be seen that by hollow HTS and titanium silicon molecule compared with embodiment 15-18
Sieve TS-1 layerings are seated in reactor, and when hollow HTS is located at the upstream of titanium-silicon molecular sieve TS-1, make reaction solution
The superficial velocity for flowing through hollow HTS is less than the superficial velocity for flowing through titanium-silicon molecular sieve TS-1, can further extend and urge
The service life of agent.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
Claims (9)
1. method that is a kind of while producing cyclohexanone oxime and acetone, this method is included in the presence of oxygen, by cyclohexanone, ammonia and different
Propyl alcohol contacts with HTS, obtains the mixture containing cyclohexanone oxime and acetone, the contact is in fixed bed reactors
Carry out, be filled with hollow HTS and titanium-silicon molecular sieve TS-1 in the fixed bed reactors, hollow HTS and
The filling order of titanium-silicon molecular sieve TS-1 causes the liquid mixture priority containing cyclohexanone, ammonia and isopropanol and the hollow titanium
Si molecular sieves and titanium-silicon molecular sieve TS-1 contact, the crystal grain of the hollow HTS are hollow-core construction, the hollow knot
The radical length of the chamber portion of structure is 5-300nm, and the HTS is in 25 DEG C, P/P0=0.10, adsorption time is
The benzene adsorbance measured under conditions of 1h is at least 70mg/g, the adsorption isotherm of the nitrogen absorption under low temperature of the HTS and de-
Hysteresis loop be present between attached thermoisopleth.
2. according to the method for claim 1, wherein, the mol ratio of cyclohexanone and isopropanol is 1：0.01-20.
3. method according to claim 1 or 2, wherein, the contact is carried out in the presence of at least one peroxide,
The mol ratio of the peroxide and cyclohexanone is 0.0001-0.1：1.
4. the method according to claim 11, wherein, the matter of the hollow HTS and the titanium-silicon molecular sieve TS-1
It is 1-10 to measure ratio：1.
5. the method according to claim 1 or 4, wherein, the liquid mixture flows through the hollow HTS
Superficial velocity is v1, the superficial velocity for flowing through the titanium-silicon molecular sieve TS-1 is v2, v1＜ v2。
6. the method according to claim 11, wherein, v2/v1=1.5-10.
7. according to the method for claim 1, wherein, the weight ratio of cyclohexanone and HTS is 0.01-100：1；Or
Person, the weight space velocity of cyclohexanone is 0.1-100h-1。
8. according to the method for claim 1, wherein, the condition of the contact make it that the conversion ratio of isopropanol is 10-20 weights
Measure %.
9. according to the method for claim 1, wherein, the condition of the contact includes：Temperature is 40-160 DEG C, with gauge pressure
Meter, pressure 0-5MPa, partial pressure of oxygen 0.01-5MPa.
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| CN1556098A (en) * | 2004-01-12 | 2004-12-22 | 天津大学 | Integrated technology of isopropanol oxidation preparing hydrogen peroxide and ammonia oxidation perparing cyclohexanone axime |
| CN101314577A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Method for catalysis of pimelinketone oxamidine |
| CN103172535A (en) * | 2013-03-15 | 2013-06-26 | 华东师范大学 | Liquid-phase fixed bed preparation method of cyclohexanone oxime |
| CN104556111A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Ti-Si molecular sieve and synthesis method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556098A (en) * | 2004-01-12 | 2004-12-22 | 天津大学 | Integrated technology of isopropanol oxidation preparing hydrogen peroxide and ammonia oxidation perparing cyclohexanone axime |
| CN101314577A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Method for catalysis of pimelinketone oxamidine |
| CN103172535A (en) * | 2013-03-15 | 2013-06-26 | 华东师范大学 | Liquid-phase fixed bed preparation method of cyclohexanone oxime |
| CN104556111A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Ti-Si molecular sieve and synthesis method thereof |
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