CN105218398B - Method for preparing cyclohexanone-oxime from cyclohexanone through liquid-phase ammoximation - Google Patents
Method for preparing cyclohexanone-oxime from cyclohexanone through liquid-phase ammoximation Download PDFInfo
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Abstract
The invention relates to a method for preparing cyclohexanone-oxime from cyclohexanone through liquid-phase ammoximation. The method includes the following steps that cyclohexanone, ammonia water, hydrogen peroxide, a catalyst, a surfactant, solvent and cosurfactant are added into a reactor and react for 2.5-4.5 h on the stirring condition at the temperature of 55 DEG C-80 DEG C; after the reaction is finished, cyclohexanone-oxime is obtained when the temperature falls to the room temperature; the catalyst is zirconium hydrogen phosphate or titanium hydrogen phosphate. The problems of equipment corrosion and generation of a great number of useless ammonium salt side products are solved by using the catalyst, the conversion rate of cyclohexanone can reach 95.3%, and the yield and selectivity of cyclohexanone are 69.1% and 72.5% respectively.
Description
Technical field
The present invention relates to Green Chemical Technology field, adopt the phosphoric acid hydrogen zirconium with the resistance to highly basic of resistance to strong acid or phosphoric acid hydrogen titanium for
Catalyst Ketohexamethylene liquid phase ammonia oximate synthesizing cyclohexane 1 ketoxime, environmental protection, low cost are adapted to commercial production.
Background technology
Cyclohexanone-oxime is important chemical intermediate and fine chemicals, is the key intermediate of synthesis of caprolactam.Oneself
Lactams are the monomers of synthetic nylon -6, engineering plastics etc..With the increase of caprolactam market demand, the need of cyclohexanone-oxime
The amount of asking also accordingly increases.The method of production cyclohexanone-oxime mainly has：Ketohexamethylene-hydroxylamine assay, nitrocyclohexane catalytic hydrogenation method, first
Benzene method, photo-nitrosation of cyclohexane process.Ketohexamethylene-hydroxylamine assay, TS-1 catalyst cyclohexanone oxamidinatings are used industrially
Method.Although after the former does not need catalyst, reaction to terminate, needing to be neutralized with ammonia, producing substantial amounts of ammonium salt, economic benefit
Difference.The latter employs the TS-1 of costliness as catalyst.TS-1 catalyst synthesis processes are loaded down with trivial details, will use 4 third costly
Base ammonium hydroxide (TPAOH) is used as template, and TPAOH consumptions are big.TPAOH tonne of batch import price be about according to statistics
1000000 yuan/t, often synthesize 1tTS-1, TPAOH consumptions are about 1.33t.TS-1 is easily inactivated under alkaline environment in addition, particle diameter
It is little, reclaim difficult.Therefore, while to TS-1 study on the modification, exploitation new catalyst is used for cyclohexanone oxamidinating reaction to be had
Industrial significance.
The content of the invention
The technical problem to be solved in the present invention is numerous for there is preparation process in the reaction of TS-1 catalysis of pimelinketone oxamidine
It is trivial, time-consuming, template costliness, little particle diameter, difficult separation and recycling, alkali resistance is weak, the problems such as easily inactivate, find one kind and newly urge
Agent phosphoric acid hydrogen zirconium/phosphoric acid hydrogen titanium, substitutes the reaction of TS-1 catalysis of pimelinketone oxamidine, and invents a kind of suitable phosphoric acid hydrogen zirconium catalysis
The microemulsion system of cyclohexanone oxamidinating reaction：Water-Ketohexamethylene-polyethylene glycol 6000-tert-butyl alcohol, wherein by surfactant
Choose and hydrogen peroxide is added, hydrogen peroxide and Ketohexamethylene, solvent can share a transfer passage, allow this technique to save dioxygen
The conveyer device of water, saves cost of equipment.
The concrete technical scheme of the present invention is as follows：
A kind of method of preparing cyclohexanone oxime through cyclohexanone liquid phase ammonia oximate, the method are comprised the following steps：
Ketohexamethylene, ammonia, hydrogen peroxide, catalyst, surfactant, solvent is added in reactor and helps surface activity
Agent, 2.5～4.5h of stirring reaction at 55～80 DEG C；Reaction treats that temperature is down to room temperature after terminating, and obtains cyclohexanone-oxime；
Wherein material proportion is：The quality of catalyst for Ketohexamethylene quality 30～70%, mol ratio Ketohexamethylene：NH3：
H2O2=1：4～6：1.7～2.5；Described surfactant is solid surfactant or liquid surfactant, per 0.01
Mole of cyclohexanone adds 0.01～1ml of 0.01～1.5g of solid surfactant or liquid surfactant；Solvent and help surface
The volume ratio of activating agent is 2:1；It is 4～6ml that every 0.01 mole of cyclohexanone adds the volume of solvent；
Described catalyst is phosphoric acid hydrogen zirconium or phosphoric acid hydrogen titanium.
Described hydrogen peroxide adopts Deca (time for adding is 5～40min), disposably adds or be intermittently added.
Described solvent is water or the tert-butyl alcohol.
Described surfactant is acetamide, SDS, AEO-9 or PEG-M (M is 400-20000).
Described cosurfactant is the tert-butyl alcohol.
Beneficial effects of the present invention：(1) present invention is to prepare cyclohexanone-oxime with phosphoric acid hydrogen zirconium catalysis of pimelinketone oxamidine, is replaced
For Ketohexamethylene-hydroxylamine assay, TS-1 catalysis of pimelinketone oxamidine methods.The former is substituted, equipment corrosion is solved and by-product is useless in a large number
Ammonium salt side-product the problems such as.The latter is substituted, soluble, the active component that TS-1 silicon skeletons in alkaline environment solved from side
Loss becomes unformed TiO2, generate the problem of a large amount of by-products.From in preparation, the material for preparing TS-1 needs has metatitanic acid fourth
Ester, tetraethyl orthosilicate, TPAOH (TPAOH) etc., need several days of crystallization at high temperature, and crystal formation are wayward,
Reaction effect is different.Phosphoric acid hydrogen zirconium only aerobic zirconium chloride and phosphoric acid solution is prepared, is flowed back one day at 100 DEG C, and consumption is few.Remove
Difference in tetraethyl orthosilicate and butyl titanate and phosphoric acid, zirconium oxychloride price, also eliminates the use of TPAOH.TPAOH enters
Mouth 1,000,000/t of valency, synthesizes 1tTS-1, needs 1.33t.According to 100,000 tTS-1 are produced per year, 13,300,000 can be saved.From in separation,
TS-1 particle diameters are little, difficult separation and recycling, industrially adopt membrance separation, and phosphoric acid hydrogen zirconium particle diameter is big, and typically directly filtering just can be with,
Separation expense can be reduced.
(2) present invention phosphoric acid hydrogen zirconium catalysis of pimelinketone oxamidine prepares cyclohexanone-oxime, and finds the micro- of suitable catalytic reaction
Newborn system：Ketohexamethylene-water-PEG 6000- the tert-butyl alcohols.Surfactant PEG -6000 can be effectively improved the hydrophilic, close of system
The interaction of oil, surfactant and cosurfactant, can cause microemulsion most stable.Microemulsion is conducive to mass transfer,
Effectively improve the yield and selectivity of cyclohexanone-oxime.When being not added with surfactant, the conversion ratio of Ketohexamethylene is 54.6%, hexamethylene
Ketoxime yield and selectivity are respectively 25.0%, 45.8%, and after adding surfactant, Ketohexamethylene conversion ratio is 70.1%, ring
Hexanone oxime yield and selectivity are 41.3%, 58.9%.The present invention is disposably added using hydrogen peroxide in addition, is effectively improved
Reaction effect, can industrially simplify conveyer device, and Ketohexamethylene conversion ratio is 95.3%, and cyclohexanone-oxime yield and selectivity are distinguished
For 69.1%, 72.5%.
Specific embodiment
Phosphoric acid hydrogen titanium catalyst according to the present invention is known products, and its preparation method can be using in embodiment 1 or 2
Method.Embodiment 1
By butyl titanate and phosphoric acid according to different mol ratio stirring mixing, the mixed liquor is proceeded to into polytetrafluoroethyllining lining
Stainless steel cauldron in, be put into 180 DEG C of thermostatic drying chamber and be dried 6h, be cooled to room temperature, centrifugation is fully washed into
Property, 80 DEG C of dried in vacuum overnight.It is 1 by Ti/P mol ratios:28.4、1:38、1:50、1:The phosphoric acid hydrogen titanium catalyst of 65.4 synthesis
TP-1, TP-2, TP-3, TP-4 is designated as respectively.
Embodiment 2
In phosphoric acid solution, tetraethyl orthosilicate (dehydrated alcohol containing equal-volume), CTAB and butyl titanate is added, different
At a temperature of, 8h is stirred vigorously, room temperature is cooled to, centrifugation is fully washed to neutrality, 80 DEG C of dried in vacuum overnight.Wherein titanium
Acid butyl ester, phosphoric acid, tetraethyl orthosilicate, CTAB mol ratios are 1:4:3.93:0.018.By what is synthesized at 110 DEG C, 140 DEG C, 180 DEG C
Phosphoric acid hydrogen titanium catalyst is designated as TP-5, TP-6, TP-7 respectively.
Embodiment 3
In equipped with condensing tube, the 100ml flask with three necks,round bottom of thermometer, (phosphoric acid hydrogen zirconium is urged to add phosphoric acid hydrogen zirconium 0.5g
Agent is commercially available, is being dried overnight using front), 1ml surfactant As EO-9, cosurfactant tert-butyl alcohol 2ml, water 4ml,
Ketohexamethylene 0.01mol (0.9814g, molal weight 98.14g/mol of Ketohexamethylene), is put in 70 DEG C of thermostat water bath, in
Under the rotating speed stirring of 495r/min, 0.05molNH is disposably added3(mass fraction is 25% ammonia spirit), then Deca
The H of 0.02mol2O2(mass fraction is 30% hydrogen peroxide solution), time for adding 25min, 70 DEG C of isothermal reactions after completion of dropping
4h.Reaction terminates rear question response liquid temp and is down to room temperature, by reactant liquor toluene extracted several times, combining extraction liquid, uses n-heptanol
Do internal standard, chromatogram ration analysis product assay, the conversion ratio of Ketohexamethylene is 51.8%, cyclohexanone-oxime yield and selectivity point
Wei 21.3%, 41.1%.
Embodiment 4
With embodiment 3, difference is that surfactant is acetamide 0.5g to step, and reaction result is：Ketohexamethylene
Conversion ratio is 41.2%, and cyclohexanone-oxime yield and selectivity are respectively 10.1%, 24.5%.
Embodiment 5
With embodiment 3, difference is that surfactant is SDS0.5g to step, and reaction result is：The conversion of Ketohexamethylene
Rate is 63.7%, and cyclohexanone-oxime yield and selectivity are respectively 23.0%, 36.1%.
Embodiment 6
With embodiment 3, difference is that surfactant is PEG-400 to step, and reaction result is：The conversion of Ketohexamethylene
Rate is 61.6%, and cyclohexanone-oxime yield and selectivity are respectively 30.6%, 49.7%.
Embodiment 7
With embodiment 3, difference is that surfactant is PEG-2000 1g to step, and reaction result is：Ketohexamethylene
Conversion ratio is 61.3%, and cyclohexanone-oxime yield and selectivity are respectively 32.5%, 53.0%.
Embodiment 8
With embodiment 3, difference is that surfactant is PEG-6000 1g to step, and reaction result is：Ketohexamethylene
Conversion ratio is 67.0%, and cyclohexanone-oxime yield and selectivity are respectively 36.6%, 54.6%.
Embodiment 9
With embodiment 3, difference is that surfactant is PEG-10000 1g to step, and reaction result is：Ketohexamethylene
Conversion ratio be 57.1%, cyclohexanone-oxime yield and selectivity are respectively 24.1%, 42.2%.
Embodiment 10
With embodiment 3, difference is that surfactant is PEG-20000 1g to step, and reaction result is：Ketohexamethylene
Conversion ratio be 51.3%, cyclohexanone-oxime yield and selectivity are respectively 19.1%, 37.2%.
Embodiment 11
In equipped with condensing tube, the 100ml flask with three necks,round bottom of thermometer, phosphoric acid hydrogen zirconium (commercial goods) 0.5g is added,
1g surfactant polyethylene -6000, cosurfactant tert-butyl alcohol 2ml, water 4ml, Ketohexamethylene 0.01mol, are put into 65 DEG C
Thermostat water bath in, in 495r/min rotating speed stirring under, disposably add 0.04molNH3(mass fraction is 25% ammonia
Aqueous solution), then Deca hydrogen peroxide 0.018mol (mass fraction is 30% hydrogen peroxide solution), time for adding 5min, Deca
65 DEG C of isothermal reaction 4h after finishing.Reaction terminates rear question response liquid temp and is down to room temperature, and reactant liquor toluene extracted several times are closed
And extract, internal standard is done with n-heptanol, chromatogram ration analysis product assay, the conversion ratio of Ketohexamethylene is 50.4%, hexamethylene
Ketoxime yield and selectivity are respectively 20.5%, 44.7%.
Embodiment 12
With embodiment 11, it is 25min that difference is the time for adding of hydrogen peroxide to step, and reaction result is:Ketohexamethylene
Conversion ratio be 77.1%, cyclohexanone-oxime yield and selectivity are respectively 47.2%, 61.2%.
Embodiment 13
With embodiment 11, it is 40min that difference is the time for adding of hydrogen peroxide to step, and reaction result is:Ketohexamethylene
Conversion ratio be 56.0%, cyclohexanone-oxime yield and selectivity are respectively 21.9%, 41.3%.
Embodiment 14
With embodiment 11, difference is that hydrogen peroxide is added using uniform intervals equivalent in three times to step, reaction result
It is:The conversion ratio of Ketohexamethylene is 63.5%, and cyclohexanone-oxime yield and selectivity are respectively 23.5%, 37.0%.
Embodiment 15
With embodiment 11, difference is that hydrogen peroxide is added using disposable to step, and the response time is 2.5h, reaction knot
It is really:The conversion ratio of Ketohexamethylene is 95.1%, and cyclohexanone-oxime yield and selectivity are respectively 65.1%, 68.5%.
Embodiment 16
With embodiment 11, difference is hydrogen peroxide using disposable addition to step, and the response time is 3h, reaction result
It is:The conversion ratio of Ketohexamethylene is 94.9%, and cyclohexanone-oxime yield and selectivity are respectively 65.4%, 68.9%.
Embodiment 17
With embodiment 11, difference is that hydrogen peroxide is added using disposable to step, and the response time is 3.5h, reaction knot
It is really:The conversion ratio of Ketohexamethylene is 95.3%, and cyclohexanone-oxime yield and selectivity are respectively 69.1%, 72.5%.
Embodiment 18
With embodiment 11, difference is hydrogen peroxide using disposable addition to step, and the response time is 4h, reaction result
It is:The conversion ratio of Ketohexamethylene is 95.7%, and cyclohexanone-oxime yield and selectivity are respectively 67.0%, 70.0%.
Embodiment 19
With embodiment 11, difference is that hydrogen peroxide is added using disposable to step, and the response time is 4.5h, reaction knot
It is really:The conversion ratio of Ketohexamethylene is 96.1%, and cyclohexanone-oxime yield and selectivity are respectively 66.8%, 69.5%.
Embodiment 20
In equipped with condensing tube, the 100ml flask with three necks,round bottom of thermometer, phosphorus obtained in 0.5g preceding embodiments 1 is added
TP-1 in sour hydrogen titanium catalyst, tert-butyl alcohol 6ml, Ketohexamethylene 0.01mol, are put in 65 DEG C of thermostat water bath, in 495r/
Min rotating speed stirring under, be separately added into 0.023mol hydrogen peroxide (mass fraction is 30% hydrogen peroxide solution) and
0.05molNH3(mass fraction is 25% ammonia spirit), in 65 DEG C of isothermal reaction 3.5h.Reaction terminates rear question response liquid temperature
Degree is down to room temperature, by reactant liquor toluene extracted several times, combining extraction liquid, does internal standard, chromatogram ration analysis with n-heptanol
Product assay, the conversion ratio of Ketohexamethylene is 48.8%, and cyclohexanone-oxime yield and selectivity are respectively 25.0%, 51.2%.
Embodiment 21
With embodiment 20, it is TP-2 that difference is catalyst to step.The conversion ratio of Ketohexamethylene is 55.7%, Ketohexamethylene
Oxime yield and selectivity are respectively 29.6%, 53.1%.
Embodiment 22
With embodiment 20, it is TP-3 that difference is catalyst to step.The conversion ratio of Ketohexamethylene is 58.1%, Ketohexamethylene
Oxime yield and selectivity are respectively 28.6%, 49.1%.
Embodiment 23
With embodiment 20, it is TP-4 that difference is catalyst to step.The conversion ratio of Ketohexamethylene is 61.3%, Ketohexamethylene
Oxime yield and selectivity are respectively 28.2%, 46.0%.
Embodiment 24
With embodiment 20, it is TP-5 that difference is catalyst to step.The conversion ratio of Ketohexamethylene is 56.1%, Ketohexamethylene
Oxime yield and selectivity are respectively 30.4%, 54.2%.
Embodiment 25
With embodiment 20, it is TP-6 that difference is catalyst to step.The conversion ratio of Ketohexamethylene is 54.4%, Ketohexamethylene
Oxime yield and selectivity are respectively 31.4%, 57.7%.
Embodiment 26
With embodiment 20, it is TP-7 that difference is catalyst to step.The conversion ratio of Ketohexamethylene is 57.3%, Ketohexamethylene
Oxime yield and selectivity are respectively 28.4%, 49.6%.
From the present invention as can be seen that phosphoric acid hydrogen zirconium or the reaction of phosphoric acid hydrogen titanium catalysis of pimelinketone oxamidine obtain preferably reaction
Effect.Catalyst strong alkali-acid resistance, is suitable for the alkaline system of cyclohexanone oxamidinating reaction.And catalyst is easily from reactant
Separate in system, industrial separation cost can be reduced.Polyethylene Glycol environmental protection, free from environmental pollution in addition, meets the requirement of Green Chemistry.
Particularly in Polyethylene Glycol, the tert-butyl alcohol, aqueous systems, the reaction of phosphoric acid hydrogen zirconium catalysis of pimelinketone oxamidine, the conversion ratio of Ketohexamethylene
Up to 95.3%, the yield and selectivity of cyclohexanone-oxime are up to 69.1%, 72.5%.
24 embodiment summary sheets
The impact that 1 surfactant of table is reacted to cyclohexanone oxamidinating
Table 1 Influence of surfactant on ammoximation of cyclohexanone
The impact that 2 hydrogen peroxide time for adding of table is reacted to cyclohexanone oxamidinating
Table2 Influence of the adding time hydrogen peroxide on ammoximation
of cyclohexanone
The impact that 3 hydrogen peroxide addition manner of table is reacted to cyclohexanone oxamidinating
Table3 Influence of the adding manner of hydrogen peroxide on
ammoximation of cyclohexanone
The impact that 4 response time of table is reacted to cyclohexanone oxamidinating
Table 4 Influence of the reaction time on ammoximation of
cyclohexanone
The impact that the phosphoric acid hydrogen titanium synthesized under 5 different condition of table is reacted to cyclohexanone oxamidinating
Table 5 Influence of titanium hydrogen phosphate prepared under
different conditions on ammoximation of cyclohexanone
Unaccomplished matter of the present invention is known technology.
Claims (2)
1. a kind of method of preparing cyclohexanone oxime through cyclohexanone liquid phase ammonia oximate, it is characterized by the method is comprised the following steps：
Ketohexamethylene, ammonia, hydrogen peroxide, catalyst, surfactant, solvent and cosurfactant is added in reactor,
2.5～4.5h of stirring reaction at 55～80 DEG C；Reaction treats that temperature is down to room temperature after terminating, and obtains cyclohexanone-oxime；
Wherein material proportion is：The quality of catalyst for Ketohexamethylene quality 30～70%, mol ratio Ketohexamethylene：NH3：H2O2=1：
4～6：1.7～2.5；Described surfactant is solid surfactant or liquid surfactant, per 0.01 mole of hexamethylene
Ketone adds 0.01～1ml of 0.01～1.5g of solid surfactant or liquid surfactant；Solvent and cosurfactant
Volume ratio is 2:1；It is 4～6ml that every 0.01 mole of cyclohexanone adds the volume of solvent；
Described solvent is water or the tert-butyl alcohol；
Described surfactant is acetamide, SDS, AEO-9 or PEG-M, and M is 400-20000；
Described cosurfactant is the tert-butyl alcohol；
Described catalyst is prepared from by following methods：
Method one：Comprise the following steps：
By butyl titanate and phosphoric acid according to mol ratio 1:28.4、1:38、1:50 or 1:65.4 ratio stirring mixing, this is mixed
Liquid is proceeded in teflon-lined stainless steel cauldron, is put into 180 DEG C of thermostatic drying chamber and is dried 6h, is cooled to room temperature, from
The heart is separated, and is fully washed to neutrality, 80 DEG C of dried in vacuum overnight；
Or method two, comprise the following steps：
In phosphoric acid solution, add the tetraethyl orthosilicate containing equal-volume dehydrated alcohol, CTAB and butyl titanate, 110 DEG C, 140
DEG C or 180 DEG C at, be stirred vigorously 8h, be cooled to room temperature, centrifugation is fully washed to neutrality, 80 DEG C of dried in vacuum overnight；Its
Middle butyl titanate, the mol ratio between phosphoric acid, tetraethyl orthosilicate, CTAB are 1:4:3.93:0.018.
2. the method for preparing cyclohexanone oxime through cyclohexanone liquid phase ammonia oximate as claimed in claim 1, it is characterized by described dioxygen
Water is added or is intermittently added using Deca, disposably；When for Deca when, time for adding be 5～40min.
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| CN107556213B (en) * | 2016-08-16 | 2019-11-22 | 沧州旭阳化工有限公司 | A kind of technique of cyclohexanone oxamidinating and the technique for manufacturing caprolactam |
| CN110372536B (en) * | 2019-08-15 | 2022-08-12 | 中触媒新材料股份有限公司 | Method for preparing cyclohexanone oxime by cyclohexanone ammoximation |
| CN114471699B (en) * | 2020-10-28 | 2023-09-19 | 万华化学集团股份有限公司 | Catalyst composition for cyclododecanone ammoximation reaction and application thereof |
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