CN105503648B - A kind of method that decomposing ammonium chloride prepares organic basis of hydrochloride and cyclohexanone oxime simultaneously - Google Patents
A kind of method that decomposing ammonium chloride prepares organic basis of hydrochloride and cyclohexanone oxime simultaneously Download PDFInfo
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- CN105503648B CN105503648B CN201510995088.XA CN201510995088A CN105503648B CN 105503648 B CN105503648 B CN 105503648B CN 201510995088 A CN201510995088 A CN 201510995088A CN 105503648 B CN105503648 B CN 105503648B
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- hydrochloride
- ammonium chloride
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
Abstract
A kind of method that the present invention prepares organic basis of hydrochloride and cyclohexanone oxime simultaneously for decomposing ammonium chloride, this method comprises the following steps：Titanium-silicon molecular sieve catalyst, chloride solid are placed in reactor, organic base, cyclohexanone is added, stirring is warming up to 40 ~ 90 DEG C, dripping hydrogen peroxide solution, the h of synthesis under normal pressure 1 ~ 6；Catalyst and reaction solution, the reaction solution obtained by centrifugation are centrifuged, organic phase can be obtained after extract and separate, organic phase is again through vacuum distillation, you can obtain white solid cyclohexanone oxime product；After raffinate phase vacuum distillation, washing can obtain organic basis of hydrochloride after drying.Described organic base is specially cyclohexylamine, dimethylamine, trimethylamine, diethylamine, triethylamine, ethylenediamine or monoethanolamine.The present invention is utilized by direct synthesizing cyclohexane 1 ketoxime and the catalytic reaction process of organic basis of hydrochloride while realizing in ammonium chloride molecule N element with Cl elements.
Description
Technical field
The present invention relates to a kind of while using the chlorine element and nitrogen in ammonium chloride, preparing organic basis of hydrochloride and hexamethylene
The new method of ketoxime, belongs to chemical process technology field.
Background technology
Ammonium chloride (chemical formula：NH4Cl), abbreviation " oronain ", also known as salmiak, clear crystal or white crystalline powder.Chlorine
Neutralization reaction can be occurred with hydrochloric acid and be obtained by ammonia and hydrogen chloride, or ammoniacal liquor by changing ammonium.Industrial soda and sociation center production soda ash
(Na2CO3) during, the substantial amounts of ammonium chloride (NH of by-product4Cl).Wherein, a part of ammonium chloride is used for agricultural production as nitrogenous fertilizer,
And remaining most of ammonium chloride there is no suitable outlet, so that " overflowing ", as restriction soda industry sustainable development
Bottleneck.
Ammonium chloride can be decomposed directly under 350 DEG C of high temperature, obtain two kinds of gases of ammonia and hydrogen chloride, but during temperature reduction again
Generation chloride solid can be recombined.Therefore, researcher, which does not turn off, sends decomposition indirectly, utilizes the method for ammonium chloride.At present,
The decomposition of ammonium chloride is using there is a variety of methods, and being summed up mainly has following four：One is sulfuric acid process, ammonium chloride and finite concentration
Sulfuric acid under initiator effect generation ammonium sulfate and hydrogen chloride gas, further decomposing ammonia sulfate obtains ammonium hydrogen sulfate and ammonia
Gas.The law technology comparative maturity, technique is simple；But sulfuric acid corrosion equipment, ammonia utilization rate is relatively low, laboratory scale is only limitted to, it is difficult
In industrially using (Shao Yuchang, soda industry, 2008,4,3-13)；Two be disulfate method, poor with some heat endurances
Disulfate be carrier, reacted at 240~270 DEG C of temperature with ammonium chloride, discharge hydrogen chloride gas, and generate ammonium sulfate
Salt, ammonium sulfate is decomposed at 290~380 DEG C higher of temperature, and discharges ammonia, while obtained disulfate returns to system
System is recycled.The method reaction temperature is higher, causes raw material ammonium chloride to vaporize, and is difficult to solve ammonium chloride in engineering and hydrogen chloride is mixed
Close the separation problem (Cao Ziying, Chongqing Industry ＆ Trade Polytechinc's journal, 2014,4,17-21) of gas；Three be metal oxide
Method, using some metal oxides as oxidant, reacts, generation metal chloride and ammonia, gold with ammonium chloride under certain condition
Category chloride is decomposed at high temperature obtains metal oxide, discharges hydrogen chloride gas, metal oxide return system circulation profit
With.The method reaction condition is gentle, and hydrogen chloride and ammonia yield are higher, but reaction scheme length, technical process are cumbersome, equipment investment
Larger (Sun Mingshuai etc., chemical industry progress, 2014,33 (4)：999-1005)；Four be catalytic decomposition, and ammonium chloride is having catalyst bar
Reacted under part with displacer, displace ammonia, residue leads to hydrogen and discharges hydrogen chloride again, or logical oxygen discharges chlorine
Gas.Conventional catalyst is Fe2O3, KCl, LiCl etc., conventional displacer is Cu, Mn, rare earth compound etc..The method displacer
Costliness, severe reaction conditions are unfavorable for industrializing (Zeng Fengchun, inorganic chemicals industry, 2009,41 (9)：1-3).
The content of the invention
The present invention is utilized in ammonium chloride simultaneously for the decomposition of current ammonium chloride using present situation there is provided a kind of decomposing ammonium chloride
Chlorine element and nitrogen, pass through appropriate organic base：Ammonium chloride：The material proportion of cyclohexanone, prepare organic basis of hydrochloride and
The new method of cyclohexanone oxime.The present invention prepares organic basis of hydrochloride and ammonia, such as reaction equation by ammonium chloride and organic base reaction first
(1) shown in；Then the ammonia in reaction system generates cyclohexanone oxime with cyclohexanone, hydrogen peroxide reaction, shown in such as reaction equation (2).Should
The net reaction of process is such as shown in (3).The process route is not only by the nitrogen trans-utilization in ammonium chloride, i.e., by low value chlorination
Nitrogen in ammonium waste material, is converted into the cyclohexanone oxime product of high added value；But also be converted into the chlorine element in ammonium chloride organic
Alkali salt hydrochlorate.It is not only that low value ammonium chloride opens up a kind of method of the utilization of resources, is organic basis of hydrochloride and cyclohexanone oxime yet
Synthesis expanded technology path.
The technical scheme is that：
A kind of method that decomposing ammonium chloride prepares organic basis of hydrochloride and cyclohexanone oxime simultaneously, comprises the following steps：
Titanium-silicon molecular sieve catalyst, chloride solid are placed in reactor, water, organic base, cyclohexanone is added, stirred
40~90 DEG C are warming up to, hydrogen peroxide solution is added dropwise, while 1~6h of synthesis under normal pressure；Centrifuge catalyst and reaction solution, centrifugation point
From the reaction solution of gained, organic phase can be obtained after extract and separate, organic phase is again through vacuum distillation, you can obtain white solid hexamethylene
Ketoxime product；After raffinate phase vacuum distillation, washing can obtain organic basis of hydrochloride after drying.
Wherein, material proportion is mol ratio ammonium chloride：Organic base：Water：Hydrogen peroxide：Cyclohexanone is 1.5~4.5：1.0~
2.5：9.0~31.4：1.3~3.8：1, the quality of solid catalyst is the 0.7~6.2% of participation reaction mass gross mass；It is double
Oxygen aqueous solution time for adding is 0.5~1.5h.
It is described participate in reaction mass gross mass for add the ammonium chloride in reactor, solid catalyst, water, organic base,
The quality sum of cyclohexanone, hydrogen peroxide.
Described titanium-silicon molecular sieve catalyst is specially TS-1 molecular sieves.
Described organic base is specially cyclohexylamine, dimethylamine, trimethylamine, diethylamine, triethylamine, ethylenediamine or monoethanolamine.
Extractant in described extract and separate is toluene.
Described reaction temperature is preferably 60~80 DEG C.
The described reaction time is preferably 1.5~5h.
Described ammonium chloride：Organic base：Water：Hydrogen peroxide：The mol ratio of cyclohexanone is preferably 2.0~3.5:1.5~2.5:
19.0~31.0:1.5~3.5：1.
Described solid catalyst quality is preferably participate in reaction mass gross mass 1.0~5.5%.
Described hydrogen peroxide solution time for adding is preferably 0.8~1.2h.
It is further comprising the steps of after described centrifugation：The catalyst of gained washes through alcohol, wash after, 80 DEG C of vacuum drying
12h, 500 DEG C of Muffle furnaces are calcined 4h, are used as the catalyst in subsequent cycle；
The present invention substantive distinguishing features be：
(1) realize using ammonium chloride as nitrogen source and chlorine source, while the safety for preparing cyclohexanone oxime and organic basis of hydrochloride is clear
Clean process route.Traditional nitrogen source is ammonia or ammoniacal liquor, and chlorine source is hydrogen chloride, and there is safety in its transport, storage, use asks
Topic；And chloride solid, it is readily transported, stores, and above-mentioned safety problem can be overcome as nitrogen source and chlorine source.
(2) importantly, ammonium chloride as combined soda method industry byproduct, it is cheap be easy to get, production cost it is low.
(3) in the presence of organic base, using ammonium chloride as raw material, direct synthesizing cyclohexane 1 ketoxime and organic basis of hydrochloride are urged
Change course of reaction, utilized while realizing in ammonium chloride molecule N element with Cl elements.
(4) present invention is highlighted while using the N element and Cl elements in ammonium chloride, the same of cyclohexanone oxime is obtained in synthesis
When, organic basis of hydrochloride product can also be obtained.And when participating in reaction using different organic bases, can obtain different having
Machine alkali salt hydrochlorate.Every kind of organic basis of hydrochloride has respective application value, can be used separately as a kind of product.
Beneficial effects of the present invention are：One aspect of the present invention provides a kind of decomposing ammonium chloride and utilizes the chlorine in ammonium chloride simultaneously
Element and nitrogen, prepare the new method of organic basis of hydrochloride and cyclohexanone oxime；Meanwhile, it is organic basis of hydrochloride and cyclohexanone again
Technology path has been expanded in the synthesis of oxime.With the conversion of existing ammonium chloride compared with Resource Utilization, the present invention can be by ammonium chloride
Converting waste material is organic basis of hydrochloride and cyclohexanone oxime product.Wherein, product organic basis of hydrochloride has important in the industry
Using such as cyclohexylamine hydrochloride has good application on cleaning environment protection soldering fluid, hot air leveling-up scaling powder；Dimethylamine hydrochloric acid
Salt is used as catalyst when acetylation is analyzed, and is also used for organic synthesis and the preparation of dimethylamine agueous solution；Trimethylamine hydrochloride master
Be used for synthesizing cationic etherifying agent, emulsified in pharmacy, solubilising, disperse, wetting action, make flotation agent in synthesis；
Triethylamine hydrochloride can be as phase transfer catalyst, and is used as medicine, agricultural chemicals, dyestuff and the base stock of other organic syntheses.
In addition, another product cyclohexanone oxime is even more to have important commercial Application, it is the intermediate product for producing caprolactam, and in oneself
Acid amides is synthesis nylon fibre, engineering plastics, the important source material of plastic sheeting.It is reported that the consumption figure of world's caprolactam will
Speed with average annual 3.4% increases, and 5,000,000 tons of (http are up to aggregate consumption in 2017://www.china-
consulting.cn/news/20131218/s93520.html).Therefore, cyclohexanone oxime will also keep considerable demand
Prospect.In addition, traditional nitrogen source is ammonia or ammoniacal liquor, chlorine source is hydrogen chloride, there is safety problem in transport, storage, use；And
Chloride solid, is readily transported, stores, and can overcome above-mentioned safety problem as nitrogen source and chlorine source.In addition, more important
, ammonium chloride is the byproduct of combined soda method, cheap to be easy to get, and ammonium chloride there is no suitable outlet.The present invention is just
Low value ammonium chloride has opened up a kind of method of the utilization of resources, and technology has been expanded in the also synthesis for organic basis of hydrochloride and cyclohexanone oxime
Route.Moreover, the catalyst of the technical process may be reused for several times, experimental implementation is simple, and chlorination is utilized compared to tradition
The corrosion resistant harsh reaction condition of the HTHP of ammonium, equipment, the process reaction mild condition, normal pressure, 60~80 DEG C, reaction
1.5~5h, it is not harsh to equipment requirement, and cyclohexanone oxime and organic basis of hydrochloride yield up to 89.1% and 94.9%.
Brief description of the drawings
Fig. 1 is the self-control in embodiment 1 and the infrared spectrum of commercially available cyclohexylamine hydrochloride, wherein 1 is cyclohexylamine hydrochloride
Make sample by oneself, 2 be cyclohexylamine hydrochloride commercial samples；
Fig. 2 is the self-control in embodiment 2 and the infrared spectrum of commercially available dimethylamine hydrochloride, wherein 1 is dimethylamine hydrochloride
Commercial samples, 2 be that dimethylamine hydrochloride makes sample by oneself；
Fig. 3 is the self-control in embodiment 3 and the infrared spectrum of commercially available trimethylamine hydrochloride, wherein 1 is trimethylamine hydrochloride
Make sample by oneself, 2 be trimethylamine hydrochloride commercial samples；
Fig. 4 is the self-control in embodiment 4 and the infrared spectrum of commercially available diethylamine hydrochloride, wherein 1 is diethylamine hydrochloride
Commercial samples, 2 be that diethylamine hydrochloride makes sample by oneself；
Fig. 5 is the self-control in embodiment 5 and the infrared spectrum of commercially available triethylamine hydrochloride, wherein 1 is triethylamine hydrochloride
Make sample by oneself, 2 be triethylamine hydrochloride commercial samples；
Fig. 6 is the self-control in embodiment 6 and the infrared spectrum of commercially available ethylenediamine-hydrochloride, wherein 1 is ethylenediamine-hydrochloride
Make sample by oneself, 2 be ethylenediamine-hydrochloride commercial samples；
Fig. 7 is the self-control in embodiment 7 and the infrared spectrum of commercially available ethanolamine hydrochloric salt, wherein 1 is ethanolamine hydrochloric salt
Make sample by oneself, 2 be ethanolamine hydrochloric salt commercial samples.
Embodiment
The substantive features and remarkable result of the present invention can be emerged from from following embodiments, but they are not to this hair
Bright to impose any restrictions, person skilled in art can make some nonessential modifications and adaptations according to present disclosure.
Below by embodiment, the present invention is further illustrated.
Described titanium-silicon molecular sieve catalyst of the present invention is commercially available prod.
Embodiment 1
TS-1 Ti-Si catalysts 3.0g, chloride solid 8.0g (150mmol) are placed in reactor, water 20mL is added
(1111.1mmol), cyclohexylamine 17.2mL (150mmol), cyclohexanone 6.4mL (62mmol), stirring are warming up to 70 DEG C, add
Hydrogen peroxide 20mL (the H of mass percent concentration 30%2O2For 196mmol), hydrogen peroxide is added dropwise using micro-injection pump injection,
20mL/h (1 hour completion of dropping), starts simultaneously at synthesis under normal pressure 1.5h；Centrifuge catalyst and reaction solution, the catalysis of gained
Agent washes through alcohol, wash after, 80 DEG C of vacuum drying 10h, 500 DEG C of Muffle furnaces are calcined 4h, standby；Reaction obtained by centrifuging
Liquid, organic phase is obtained through toluene extract and separate, using gas chromatographic analysis organic phase, quantitatively calculates the yield of product cyclohexanone oxime
For 86.1%；Above-mentioned organic phase can obtain white solid product cyclohexanone oxime 5.5g again through vacuum distillation.Raffinate aqueous phase vacuum distillation
Afterwards, wash and can obtain white solid cyclohexylamine hydrochloride product 18.5g after drying.Product cyclohexylamine hydrochloride is carried out infrared
Analysis, as a result as shown in annex Fig. 1, self-control sample is consistent with the infrared spectrum of commercially available cyclohexylamine hydrochloride sample.
Embodiment 2~7
It is identical with the operating procedure and reaction condition of embodiment 1, cyclohexylamine is simply replaced by other organic bases, respectively
For dimethylamine, trimethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, addition is 150mmol.Using gas-chromatography point
Organic phase is analysed, the yield of product cyclohexanone oxime and the quality of organic basis of hydrochloride is quantitatively calculated, and to various organic basis of hydrochloride
Product carries out IR Characterization.Experimental result is as shown in table 1, characterization result such as accompanying drawing 2~7.
The influence that the different organic base pairings of table 1 are reacted into cyclohexanone oxime
Embodiment 8
Identical with the operating procedure and reaction condition of embodiment 1, simply in oximation reaction, the addition of cyclohexylamine is changed into
7.6mL, the amount of the material of cyclohexylamine is 66mmol, after reaction terminates, centrifuges catalyst and reaction solution, through toluene extraction point
From organic phase is obtained, using the organic phase composition of gas chromatographic analysis；After raffinate aqueous phase vacuum distillation, washing is i.e. available after drying
White solid cyclohexylamine hydrochloride crude product 12.2g (wherein containing 4.1g ammonium chlorides).Experimental result is as shown in table 2.
Example 9
TS-1 Ti-Si catalysts 3.0g, chloride solid 8.0g (150mmol) are placed in reactor, water 20mL is added
(1111.1mmol), cyclohexylamine 14.5mL (125mmol), cyclohexanone 6.4mL (62mmol), stirring are warming up to 70 DEG C, add
Hydrogen peroxide 20mL (the H of mass percent concentration 30%2O2For 196mmol), hydrogen peroxide is added dropwise using micro-injection pump injection,
20mL/h (1 hour completion of dropping), starts simultaneously at synthesis under normal pressure 1.5h；Catalyst and reaction solution are centrifuged, is extracted through toluene
Isolated organic phase, using gas chromatographic analysis organic phase, the yield for quantitatively calculating product cyclohexanone oxime is 87.1%；Raffinate
After aqueous phase vacuum distillation, i.e. can obtain white solid cyclohexylamine hydrochloride crude product 16.5g (wherein there are about 1.3g chlorine after washing is dried
Change ammonium), as a result such as table 2.
The influence that the addition pairing of the cyclohexylamine of table 2 is reacted into cyclohexanone oxime
Example 10
Identical with the operating procedure and reaction condition of embodiment 1, simply in oximation reaction, the addition of cyclohexylamine is changed into
The amount of the material of 18mL cyclohexylamine is 157mmol.Experimental result is as shown in table 3.
The influence that the addition pairing of the cyclohexylamine of table 3 is reacted into cyclohexanone oxime
Embodiment 11
It is identical with the operating procedure and reaction condition of synthesizing cyclohexane 1 ketoxime process in embodiment 9, simply in oximation reaction, chlorine
The addition for changing ammonium changes into 5.35g respectively, and the amount of the material of ammonium chloride is 100mmol.Experimental result is as shown in table 4.
The influence that the addition pairing of the ammonium chloride of table 4 is reacted into cyclohexanone oxime
Embodiment 12
TS-1 Ti-Si catalysts 3.0g, chloride solid 6.96g (130mmol) are placed in reactor, water is added
20mL (1111.1mmol), cyclohexylamine 14.5mL (125mmol), cyclohexanone 6.4mL (62mmol), stirring are warming up to 70 DEG C, then
Add the hydrogen peroxide 20mL (H of mass percent concentration 30%2O2For 196mmol), hydrogen peroxide, which is added dropwise, uses micro-injection infusion
Enter, 20mL/h (1 hour completion of dropping) starts simultaneously at synthesis under normal pressure 1.5h；Catalyst and reaction solution are centrifuged, is extracted through toluene
Isolated organic phase is taken, using gas chromatographic analysis organic phase, the yield for quantitatively calculating product cyclohexanone oxime is 89.1%；Extraction
After remaining aqueous phase vacuum distillation, washing can obtain white solid cyclohexylamine hydrochloride crude product 15.7g after drying and (wherein there are about
0.26g ammonium chlorides), as a result such as table 5.
Embodiment 13
It is identical with the operating procedure and reaction condition of synthesizing cyclohexane 1 ketoxime process in embodiment 9, simply in oximation reaction, chlorine
The addition for changing ammonium changes into 13.4g, and the amount of the material of ammonium chloride is respectively 250mmol.Experimental result is as shown in table 5.
The influence that the addition pairing of the ammonium chloride of table 5 is reacted into cyclohexanone oxime
Embodiment 14~16
Identical with the operating procedure and reaction condition of embodiment 12, simply in oximation reaction, the addition of water changes respectively
For 10mL, 25mL, 35mL (amount of the material of water is respectively 555.6mmol, 1388.9mmol, 1944.4mmol).Oximation reaction
Experimental result it is as shown in table 6.
The influence that the addition pairing of the water of table 6 is reacted into cyclohexanone oxime
Embodiment 17~19
Identical with the operating procedure and reaction condition of embodiment 12, simply the reaction temperature of oximate changes into 40 DEG C respectively,
60 DEG C, 90 DEG C.The experimental result of oximation reaction is as shown in table 7.
The influence that the reaction temperature pairing of table 7 is reacted into cyclohexanone oxime
| Embodiment | Reaction temperature (DEG C) | The yield (%) of cyclohexanone oxime |
| 17 | 40 | 34.8 |
| 18 | 60 | 87.2 |
| 19 | 90 | 54.8 |
Embodiment 20~22
It is identical with the operating procedure and reaction condition of embodiment 12, simply the reaction time of oximate change into 1.0h respectively,
3.0h, 6.0h.The experimental result of oximation reaction is as shown in table 8.
The influence that 8 reaction time of table pairing is reacted into cyclohexanone oxime
| Embodiment | Reaction time (h) | The yield (%) of cyclohexanone oxime |
| 20 | 1.0 | 85.4 |
| 21 | 3.0 | 83.8 |
| 22 | 6.0 | 81.4 |
Embodiment 23~25
Identical with the operating procedure and reaction condition of embodiment 12, simply in oximation reaction, the addition of hydrogen peroxide changes
For 8.0mL, 15.0mL, 24.0mL (H2O2Mole is respectively 78.4mmol, 147mmol, 235mmol).The experiment of oximation reaction
As a result it is as shown in table 9.
The influence that the addition pairing of the hydrogen peroxide of table 9 is reacted into cyclohexanone oxime
| Embodiment | The volume (mL) of hydrogen peroxide | Hydrogen peroxide/cyclohexanone mol ratio | The yield (%) of cyclohexanone oxime |
| 23 | 8.0 | 1.3 | 32.5 |
| 24 | 15.0 | 2.4 | 77.2 |
| 25 | 24.0 | 3.8 | 85.7 |
Embodiment 26~28
Identical with the operating procedure and reaction condition of embodiment 12, simply in oximation reaction, the drop rate of hydrogen peroxide changes
It is changed into 14.0mL/h, 17.0mL/h, 23.0mL/h.The experimental result of oximation reaction is as shown in table 10.
The influence that the drop rate pairing of the hydrogen peroxide of table 10 is reacted into cyclohexanone oxime
Embodiment 29~31
It is identical with the operating procedure and reaction condition in embodiment 12, simply in oximation reaction, the addition of TS-1 molecular sieves
Measure and change into 0.5g respectively, 2.0g, 4.0g (weight percentages of the TS-1 in reaction system is respectively 0.77%, 3.1%,
6.2%).The experimental result of oximation reaction is as shown in table 11.
The influence that the addition pairing of the titanium-silicon molecular sieve TS-1 of table 11 is reacted into cyclohexanone oxime
| Embodiment | TS-1(g) | The yield (%) of cyclohexanone oxime |
| 29 | 0.5 | 12.8 |
| 30 | 2.0 | 56.9 |
| 31 | 4.0 | 88.7 |
Embodiment 32
TS-1 catalyst identical with the operating procedure and reaction condition in embodiment 12, simply adding, is embodiment 12
It is middle wash, wash through alcohol after, dry, the regeneration TS-1 catalyst 2.955g after roasting, to investigate the reusability of catalyst.Extraction
After remaining aqueous phase vacuum distillation, washing can obtain white solid cyclohexylamine hydrochloride 17.1g after drying.Using gas chromatographic analysis
Organic phase, the yield for quantitatively calculating cyclohexanone oxime is 87.7%.
From table 1~11, a kind of decomposing ammonium chloride of the present invention prepares organic basis of hydrochloride and cyclohexanone oxime
New method, be substantially by aminating agent of ammonium chloride, hydrogen peroxide be oxidant, HTS is catalyst, builds ammonium chloride, double
The technical process of " one pot " synthesis organic basis of hydrochloride of oxygen water and cyclohexanone and cyclohexanone oxime.Wherein, cyclohexanone oxime building-up process
Suitable reaction condition be：Material proportion ammonium chloride：Organic base：Water：Hydrogen peroxide：The mol ratio of cyclohexanone is preferably 2.0~
3.5:1.5~2.5:19.0~31.0:1.5~3.5：1, the quality of solid catalyst is the 0.7 of participation reaction mass gross mass
~6.2%；Hydrogen peroxide solution time for adding is 0.8~1.2h, and reaction temperature is 60~80 DEG C, and the reaction time is 1.5~5h.
Under above-mentioned suitable reaction condition, the yield of cyclohexanone oxime is close to 90%, and solid catalyst TS-1 molecular sieves can reclaim circulation
Use.
Unaccomplished matter of the present invention is known technology.
Claims (7)
1. a kind of method that decomposing ammonium chloride prepares organic basis of hydrochloride and cyclohexanone oxime simultaneously, it is characterized in that including following step
Suddenly：
Titanium-silicon molecular sieve catalyst, chloride solid are placed in reactor, water, organic base, cyclohexanone, stirring heating is added
To 40 ~ 90 DEG C, hydrogen peroxide solution is added dropwise, while the h of synthesis under normal pressure 1 ~ 6；Catalyst and reaction solution are centrifuged, institute is centrifuged
The reaction solution obtained, can obtain organic phase, organic phase is again through vacuum distillation, you can obtain white solid cyclohexanone oxime after extract and separate
Product；After raffinate phase vacuum distillation, washing can obtain organic basis of hydrochloride after drying；
Wherein, material proportion is mol ratio ammonium chloride：Organic base：Water：Hydrogen peroxide：Cyclohexanone is 1.5 ~ 4.5：1.0~2.5：9.0~
31.4：1.3~3.8：1, the quality of solid catalyst is the 0.7 ~ 6.2% of participation reaction mass gross mass；Hydrogen peroxide solution is added dropwise
Time is 0.5~1.5 h；
Described titanium-silicon molecular sieve catalyst is specially TS-1 molecular sieves；
Described organic base is specially cyclohexylamine, dimethylamine, trimethylamine, diethylamine, triethylamine, ethylenediamine or monoethanolamine；
Extractant in described extract and separate is toluene.
2. the method that decomposing ammonium chloride as claimed in claim 1 prepares organic basis of hydrochloride and cyclohexanone oxime simultaneously, its feature
It it is 60 ~ 80 DEG C for described reaction temperature.
3. the method that decomposing ammonium chloride as claimed in claim 1 prepares organic basis of hydrochloride and cyclohexanone oxime simultaneously, its feature
It is 1.5 ~ 5 h for the described reaction time.
4. the method that decomposing ammonium chloride as claimed in claim 1 prepares organic basis of hydrochloride and cyclohexanone oxime simultaneously, its feature
For described ammonium chloride：Organic base：Water：Hydrogen peroxide：The mol ratio of cyclohexanone is preferably 2.0 ~ 3.5: 1.5~2.5 : 19.0~
31.0 : 1.5~3.5：1.
5. the method that decomposing ammonium chloride as claimed in claim 1 prepares organic basis of hydrochloride and cyclohexanone oxime simultaneously, its feature
For described solid catalyst quality be participate in reaction mass gross mass 1.0 ~ 5.5%.
6. the method that decomposing ammonium chloride as claimed in claim 1 prepares organic basis of hydrochloride and cyclohexanone oxime simultaneously, its feature
It is 0.8~1.2 h for described hydrogen peroxide solution time for adding.
7. the method that decomposing ammonium chloride as claimed in claim 1 prepares organic basis of hydrochloride and cyclohexanone oxime simultaneously, its feature
To be further comprising the steps of after described centrifugation：The catalyst of gained washes through alcohol, wash after, 80 DEG C of 12 h of vacuum drying,
500 DEG C of Muffle furnaces are calcined 4 h, are used as the catalyst in subsequent cycle.
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