CN105503648A - Method for decomposing ammonium chloride to prepare organic base hydrochloride and cyclohexanone-oxime synchronously - Google Patents
Method for decomposing ammonium chloride to prepare organic base hydrochloride and cyclohexanone-oxime synchronously Download PDFInfo
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- 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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- 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
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Abstract
The invention discloses a method for decomposing ammonium chloride to prepare organic base hydrochloride and cyclohexanone-oxime synchronously. The method comprises the steps of placing a titanium silicalite molecular sieve based catalyst and ammonium chloride solid in a reactor, adding organic base and cyclohexanone, conducting stirring, increasing temperature to 40-90 DEG C, and adding hydrogen peroxide solution dropwise for normal-pressure reaction lasting 1-6 h; conducting centrifugal separation on the catalyst and reaction solution, conducting extraction separation on reaction solution obtained after centrifugal separation so that an organic phase can be obtained, and conducting reduced pressure distillation on the organic phase so that the white solid cyclohexanone-oxime product can be obtained; conducting reduced pressure distillation on raffinate, and then conducting washing and drying so that organic base hydrochloride can be obtained, wherein organic base is cyclohexylamine, dimethylamine, trimethylamine, diethylamine, triethylamine, ethylenediamine or ethanol amine. Through the catalytic reaction process for direct synthesis of cyclohexanone-oxime and organic base hydrochloride, N and Cl in ammonium chloride molecules are utilized at the same time.
Description
Technical field
The present invention relates to and a kind ofly utilize chlorine element in ammonium chloride and nitrogen element simultaneously, prepare the novel method of organic basis of hydrochloride and cyclohexanone-oxime, belong to chemical process technology field.
Background technology
Ammonium chloride (chemical formula: NH
4cl), be called for short " oronain ", also known as salmiak, clear crystal or white crystalline powder.Ammonium chloride can by ammonia and hydrogenchloride, or ammoniacal liquor and hydrochloric acid generation neutralization reaction obtain.Industrial soda and sociation center produces soda ash (Na
2cO
3) in process, the ammonium chloride (NH that by-product is a large amount of
4cl).Wherein, a part of ammonium chloride is used for agriculture production as nitrogenous fertilizer, and all the other most of ammonium chlorides there is no applicable outlet, so that " overflowing ", becomes the bottleneck of restriction soda industry Sustainable development.
Ammonium chloride is meeting Direct Resolution under 350 DEG C of high temperature, obtains ammonia and hydrogenchloride two kinds of gases, but recombine can generate chloride solid again when temperature reduces.Therefore, investigator continually develops out indirect decomposition, utilizes the method for ammonium chloride.At present, the decomposition of ammonium chloride utilizes multiple method, being summed up and mainly containing following four kinds: one is sulfuric acid process, and ammonium chloride and certain density sulfuric acid generate ammonium sulfate and hydrogen chloride gas under initiator effect, and further decomposing ammonia sulfate obtains monoammonium sulfate and ammonia.This law technology comparative maturity, technique is simple; But sulfuric acid corrosion equipment, ammonia utilization ratio is lower, is only limitted to laboratory scale, is difficult to industrially apply (Shao Yuchang, soda industry, 2008,4,3-13); Two is hydrosulfate methods, with the poor hydrosulfate of some thermostability for carrier, react with ammonium chloride at temperature 240 ~ 270 DEG C, discharge hydrogen chloride gas, and generate ammonium sulfate, ammonium sulfate decomposes at higher temperature 290 ~ 380 DEG C, and discharges ammonia, and the hydrosulfate retrieval system simultaneously obtained recycles.This method temperature of reaction is higher, causes raw material ammonium chloride to be vaporized, and engineering is difficult to the separation problem (Cao Ziying, Chongqing Industry & Trade Polytechinc's journal, 2014,4,17-21) solving ammonium chloride and chlorine hydride mixed gas; Three is metal oxide methods, with some metal oxide for oxygenant, reacts under certain condition with ammonium chloride, generate metal chloride and ammonia, metal chloride at high temperature decomposes and obtains metal oxide, discharges hydrogen chloride gas, the recycle of metal oxide retrieval system.This method reaction conditions is gentle, hydrogenchloride and ammonia yield higher, but reaction scheme is long, technological process is loaded down with trivial details, facility investment comparatively large (Sun Mingshuai etc., chemical industry is in progress, 2014,33 (4): 999-1005); Four is catalytic decompositions, and ammonium chloride reacts with displacer having under catalysts conditions, displaces ammonia, and resistates more logical hydrogen discharges hydrogenchloride, or logical oxygen discharges chlorine.Conventional catalyzer is Fe
2o
3, KCl, LiCl etc., conventional displacer is Cu, Mn, rare earth compound etc.This method displacer is expensive, and severe reaction conditions, is unfavorable for industrialization (Zeng Fengchun, inorganic chemicals industry, 2009,41 (9): 1-3).
Summary of the invention
The decomposition that the present invention is directed to current ammonium chloride utilizes present situation, there is provided a kind of decomposing ammonium chloride to utilize chlorine element in ammonium chloride and nitrogen element simultaneously, organic bases by appropriate: ammonium chloride: the material proportion of pimelinketone, prepares the novel method of organic basis of hydrochloride and cyclohexanone-oxime.First the present invention is reacted by ammonium chloride and organic bases and prepares organic basis of hydrochloride and ammonia, as shown in reaction formula (1); Then the ammonia in reaction system and pimelinketone, hydrogen peroxide react and generate cyclohexanone-oxime, as shown in reaction formula (2).The net reaction of this process is as shown in (3).Nitrogen cycling of elements in ammonium chloride not only utilizes by this operational path, by the nitrogen in low value ammonium chloride waste material, is converted into the cyclohexanone-oxime product of high added value; But also be organic basis of hydrochloride by the chlorine cycling of elements in ammonium chloride.It is not only a kind of method that low value ammonium chloride opens up utilization of resources, for technological line has been expanded in the synthesis of organic basis of hydrochloride and cyclohexanone-oxime yet.
Technical scheme of the present invention is:
Decomposing ammonium chloride prepares a method for organic basis of hydrochloride and cyclohexanone-oxime simultaneously, comprises the following steps:
Titanium-silicon molecular sieve catalyst, chloride solid are placed in reactor, then add water, organic bases, pimelinketone, stir and be warming up to 40 ~ 90 DEG C, drip hydrogen peroxide solution, simultaneously synthesis under normal pressure 1 ~ 6h; Centrifugation catalyzer and reaction solution, the reaction solution of centrifugation gained, can obtain organic phase after extracting and separating, and organic phase, again through underpressure distillation, can obtain white solid cyclohexanone-oxime product; After extracting phase underpressure distillation, after washing drying, organic basis of hydrochloride can be obtained.
Wherein, material proportion is mol ratio ammonium chloride: organic bases: water: hydrogen peroxide: pimelinketone is 1.5 ~ 4.5:1.0 ~ 2.5:9.0 ~ 31.4:1.3 ~ 3.8:1, and the quality of solid catalyst is participate in reaction mass total mass 0.7 ~ 6.2%; Hydrogen peroxide solution time for adding is 0.5 ~ 1.5h.
Described participation reaction mass total mass is the quality sum of the ammonium chloride added in reactor, solid catalyst, water, organic bases, pimelinketone, hydrogen peroxide.
Described titanium-silicon molecular sieve catalyst is specially TS-1 molecular sieve.
Described organic bases is specially hexahydroaniline, dimethylamine, Trimethylamine 99, diethylamine, triethylamine, quadrol or thanomin.
Extraction agent in described extracting and separating is toluene.
Described temperature of reaction is preferably 60 ~ 80 DEG C.
The described reaction times is preferably 1.5 ~ 5h.
Described ammonium chloride: organic bases: water: hydrogen peroxide: the mol ratio of pimelinketone is preferably 2.0 ~ 3.5:1.5 ~ 2.5:19.0 ~ 31.0:1.5 ~ 3.5:1.
Described solid catalyst quality optimization is participate in reaction mass total mass 1.0 ~ 5.5%.
Described hydrogen peroxide solution time for adding is preferably 0.8 ~ 1.2h.
Further comprising the steps of after described centrifugation: the catalyzer of gained is after alcohol wash, washing, and 80 DEG C of vacuum-drying 12h, 500 DEG C of retort furnace roasting 4h, use as the catalyzer in next circulation;
Substantive distinguishing features of the present invention is:
(1) achieving with ammonium chloride is nitrogenous source and chlorine source, prepares the safely cleaning operational path of cyclohexanone-oxime and organic basis of hydrochloride simultaneously.Tradition nitrogenous source is ammonia or ammoniacal liquor, and chlorine source is hydrogenchloride, there is safety problem in its transport, storage, use; And chloride solid, be convenient to transport, store, and as nitrogenous source and chlorine source, above-mentioned safety problem can be overcome.
(2) the more important thing is, ammonium chloride, as the byproduct of combined soda method industry, to be cheaply easy to get, production cost is low.
(3) be raw material under existing for organic bases, with ammonium chloride, the catalytic reaction process of direct synthesizing cyclohexane 1 ketoxime and organic basis of hydrochloride, achieves in ammonium chloride molecule and utilizes while N element and Cl element.
(4) the present invention highlights and utilizes N element in ammonium chloride and Cl element simultaneously, while synthesis obtains cyclohexanone-oxime, can also obtain organic basis of hydrochloride product.And when adopting different organic basess to participate in reaction, different organic basis of hydrochloride can be obtained.Often kind of organic basis of hydrochloride has respective using value, can use as a kind of product separately.
Beneficial effect of the present invention is: one aspect of the present invention provides a kind of decomposing ammonium chloride to utilize chlorine element in ammonium chloride and nitrogen element simultaneously, prepares the novel method of organic basis of hydrochloride and cyclohexanone-oxime; Meanwhile, again for technological line has been expanded in the synthesis of organic basis of hydrochloride and cyclohexanone-oxime.Transform compared with Resource Utilization with existing ammonium chloride, ammonium chloride converting waste material can be organic basis of hydrochloride and cyclohexanone-oxime product by the present invention.Wherein, product organic basis of hydrochloride has important application in the industry, as cyclohexylamine hydrochloride has good application on cleaning environment protection soldering fluid, hot air leveling-up scaling powder; Dimethylamine hydrochloride is used as catalyzer when acetylize is analyzed, also for the preparation of organic synthesis and dimethylamine agueous solution; Trimethylamine hydrochloride is mainly used in synthesizing cationic etherifying agent, makes emulsification, solubilising in pharmaceutics, and dispersion, wetting action, make flotation agent in synthesis; Triethylamine hydrochloride can be used as phase-transfer catalyst, and is used as the basic raw material of medicine, agricultural chemicals, other organic syntheses of dye well.In addition, another product cyclohexanone-oxime has important industrial application especially, and it is the intermediate product producing hexanolactam, and hexanolactam is the important source material of synthesis nylon fibre, engineering plastics, plastics film.It is reported, the consumption of world's hexanolactam by with average annual 3.4% speed increment, will reach 5,000,000 tons (http://www.china-consulting.cn/news/20131218/s93520.html) to aggregate consumption in 2017.Therefore, cyclohexanone-oxime also will keep appreciable demand prospect.In addition, traditional nitrogenous source is ammonia or ammoniacal liquor, and chlorine source is hydrogenchloride, there is safety problem in transport, storage, use; And chloride solid, be convenient to transport, store, and as nitrogenous source and chlorine source, above-mentioned safety problem can be overcome.In addition, the more important thing is, ammonium chloride is the byproduct of combined soda method, is cheaply easy to get, and ammonium chloride there is no applicable outlet.The present invention has just opened up a kind of method of the utilization of resources for low value ammonium chloride, also for technological line has been expanded in the synthesis of organic basis of hydrochloride and cyclohexanone-oxime.And, the catalyzer of this technological process can be reused for several times, experimental implementation is simple, the corrosion resistant harsh reaction conditions of the High Temperature High Pressure of ammonium chloride, equipment is utilized compared to tradition, this process reaction mild condition, normal pressure, 60 ~ 80 DEG C, reaction 1.5 ~ 5h, not harsh to equipment requirements, and the yield of cyclohexanone-oxime and organic basis of hydrochloride can reach 89.1% and 94.9%.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of self-control in embodiment 1 and commercially available cyclohexylamine hydrochloride, and wherein 1 is cyclohexylamine hydrochloride self-control sample, and 2 is cyclohexylamine hydrochloride commercial samples;
Fig. 2 is the infrared spectrum of self-control in embodiment 2 and commercially available dimethylamine hydrochloride, and wherein 1 is dimethylamine hydrochloride commercial samples, and 2 is dimethylamine hydrochloride self-control sample;
Fig. 3 is the infrared spectrum of self-control in embodiment 3 and commercially available trimethylamine hydrochloride, and wherein 1 is trimethylamine hydrochloride self-control sample, and 2 is trimethylamine hydrochloride commercial samples;
Fig. 4 is the infrared spectrum of self-control in embodiment 4 and commercially available diethylamine hydrochloride, and wherein 1 is diethylamine hydrochloride commercial samples, and 2 is diethylamine hydrochloride self-control sample;
Fig. 5 is the infrared spectrum of self-control in embodiment 5 and commercially available triethylamine hydrochloride, and wherein 1 is triethylamine hydrochloride self-control sample, and 2 is triethylamine hydrochloride commercial samples;
Fig. 6 is the infrared spectrum of self-control in embodiment 6 and commercially available ethylenediamine-hydrochloride, and wherein 1 is ethylenediamine-hydrochloride self-control sample, and 2 is ethylenediamine-hydrochloride commercial samples;
Fig. 7 is the infrared spectrum of self-control in embodiment 7 and commercially available ethanolamine hydrochloric salt, and wherein 1 is ethanolamine hydrochloric salt self-control sample, and 2 is ethanolamine hydrochloric salt commercial samples.
Embodiment
Substantive features of the present invention and unusual effect can be embodied from following embodiment, but they do not impose any restrictions the present invention, and person skilled in art content according to the present invention can make some nonessential improvement and adjustment.Below by embodiment, the present invention is further illustrated.
The described titanium-silicon molecular sieve catalyst that the present invention relates to is commercially available prod.
Embodiment 1
TS-1 Ti-Si catalyst 3.0g, chloride solid 8.0g (150mmol) are placed in reactor, add water 20mL (1111.1mmol), hexahydroaniline 17.2mL (150mmol), pimelinketone 6.4mL (62mmol) again, stirring is warming up to 70 DEG C, then adds the hydrogen peroxide 20mL (H of mass percent concentration 30%
2o
2for 196mmol), hydrogen peroxide drips and adopts micro-injection pump to inject, and 20mL/h (dropwising for 1 hour), starts synthesis under normal pressure 1.5h simultaneously; Centrifugation catalyzer and reaction solution, the catalyzer of gained after alcohol wash, washing, 80 DEG C of vacuum-drying 10h, 500 DEG C of retort furnace roasting 4h, for subsequent use; The reaction solution that centrifugation obtains, obtains organic phase through toluene extracting and separating, and adopt gas chromatographic analysis organic phase, the yield of quantitative Analysis product cyclohexanone-oxime is 86.1%; Above-mentioned organic phase, again through underpressure distillation, can obtain white solid product cyclohexanone-oxime 5.5g.After the underpressure distillation of raffinate aqueous phase, after washing drying, white solid cyclohexylamine hydrochloride product 18.5g can be obtained.Carry out infrared analysis to product cyclohexylamine hydrochloride, result is as shown in annex Fig. 1, and self-control sample is consistent with the infrared spectrum of commercially available cyclohexylamine hydrochloride sample.
Embodiment 2 ~ 7
Identical with the operation steps of embodiment 1 and reaction conditions, just hexahydroaniline is replaced by other organic bases, be respectively dimethylamine, Trimethylamine 99, diethylamine, triethylamine, quadrol, thanomin, add-on is 150mmol.Adopt gas chromatographic analysis organic phase, the yield of quantitative Analysis product cyclohexanone-oxime and the quality of organic basis of hydrochloride, and Infrared Characterization is carried out to various organic basis of hydrochloride product.Experimental result is as shown in table 1, and characterization result is as accompanying drawing 2 ~ 7.
The different organic bases of table 1 is on the impact of synthesis cyclohexanone-oxime reaction
Embodiment 8
Identical with the operation steps of embodiment 1 and reaction conditions, just in oximation reaction, the add-on of hexahydroaniline changes into 7.6mL, the amount of substance of hexahydroaniline is 66mmol, after reaction terminates, centrifugation catalyzer and reaction solution, obtain organic phase through toluene extracting and separating, adopts gas chromatographic analysis organic phase composition; After the underpressure distillation of raffinate aqueous phase, white solid cyclohexylamine hydrochloride crude product 12.2g (wherein containing 4.1g ammonium chloride) after washing drying, can be obtained.Experimental result is as shown in table 2.
Example 9
TS-1 Ti-Si catalyst 3.0g, chloride solid 8.0g (150mmol) are placed in reactor, add water 20mL (1111.1mmol), hexahydroaniline 14.5mL (125mmol), pimelinketone 6.4mL (62mmol) again, stirring is warming up to 70 DEG C, then adds the hydrogen peroxide 20mL (H of mass percent concentration 30%
2o
2for 196mmol), hydrogen peroxide drips and adopts micro-injection pump to inject, and 20mL/h (dropwising for 1 hour), starts synthesis under normal pressure 1.5h simultaneously; Centrifugation catalyzer and reaction solution, obtain organic phase through toluene extracting and separating, and adopt gas chromatographic analysis organic phase, the yield of quantitative Analysis product cyclohexanone-oxime is 87.1%; After the underpressure distillation of raffinate aqueous phase, can obtain white solid cyclohexylamine hydrochloride crude product 16.5g (wherein about having 1.3g ammonium chloride) after washing drying, result is as table 2.
The add-on of table 2 hexahydroaniline is on the impact of synthesis cyclohexanone-oxime reaction
Example 10
Identical with the operation steps of embodiment 1 and reaction conditions, just in oximation reaction, the amount of substance that the add-on of hexahydroaniline changes into 18mL hexahydroaniline is 157mmol.Experimental result is as shown in table 3.
The add-on of table 3 hexahydroaniline is on the impact of synthesis cyclohexanone-oxime reaction
Embodiment 11
Identical with the operation steps of synthesizing cyclohexane 1 ketoxime process in embodiment 9 and reaction conditions, just in oximation reaction, the add-on of ammonium chloride changes into 5.35g respectively, and the amount of substance of ammonium chloride is 100mmol.Experimental result is as shown in table 4.
The add-on of table 4 ammonium chloride is on the impact of synthesis cyclohexanone-oxime reaction
Embodiment 12
TS-1 Ti-Si catalyst 3.0g, chloride solid 6.96g (130mmol) are placed in reactor, add water 20mL (1111.1mmol), hexahydroaniline 14.5mL (125mmol), pimelinketone 6.4mL (62mmol) again, stirring is warming up to 70 DEG C, then adds the hydrogen peroxide 20mL (H of mass percent concentration 30%
2o
2for 196mmol), hydrogen peroxide drips and adopts micro-injection pump to inject, and 20mL/h (dropwising for 1 hour), starts synthesis under normal pressure 1.5h simultaneously; Centrifugation catalyzer and reaction solution, obtain organic phase through toluene extracting and separating, and adopt gas chromatographic analysis organic phase, the yield of quantitative Analysis product cyclohexanone-oxime is 89.1%; After the underpressure distillation of raffinate aqueous phase, can obtain white solid cyclohexylamine hydrochloride crude product 15.7g (wherein about having 0.26g ammonium chloride) after washing drying, result is as table 5.
Embodiment 13
Identical with the operation steps of synthesizing cyclohexane 1 ketoxime process in embodiment 9 and reaction conditions, just in oximation reaction, the add-on of ammonium chloride changes into 13.4g, and the amount of substance of ammonium chloride is respectively 250mmol.Experimental result is as shown in table 5.
The add-on of table 5 ammonium chloride is on the impact of synthesis cyclohexanone-oxime reaction
Embodiment 14 ~ 16
Identical with the operation steps of embodiment 12 and reaction conditions, just in oximation reaction, the add-on of water changes into 10mL respectively, 25mL, 35mL (amount of substance of water is respectively 555.6mmol, 1388.9mmol, 1944.4mmol).The experimental result of oximation reaction is as shown in table 6.
The add-on of table 6 water is on the impact of synthesis cyclohexanone-oxime reaction
Embodiment 17 ~ 19
Identical with the operation steps of embodiment 12 and reaction conditions, just the temperature of reaction of oximate changes into 40 DEG C, 60 DEG C, 90 DEG C respectively.The experimental result of oximation reaction is as shown in table 7.
Table 7 temperature of reaction is on the impact of synthesis cyclohexanone-oxime reaction
| Embodiment | Temperature of reaction (DEG C) | The yield (%) of cyclohexanone-oxime |
| 17 | 40 | 34.8 |
| 18 | 60 | 87.2 |
| 19 | 90 | 54.8 |
Embodiment 20 ~ 22
Identical with the operation steps of embodiment 12 and reaction conditions, just the reaction times of oximate changes into 1.0h, 3.0h, 6.0h respectively.The experimental result of oximation reaction is as shown in table 8.
Table 8 reaction times is on the impact of synthesis cyclohexanone-oxime reaction
| Embodiment | Reaction times (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 operation steps of embodiment 12 and reaction conditions, just in oximation reaction, the add-on of hydrogen peroxide changes into 8.0mL, 15.0mL, 24.0mL (H
2o
2molar weight is respectively 78.4mmol, 147mmol, 235mmol).The experimental result of oximation reaction is as shown in table 9.
The add-on of table 9 hydrogen peroxide is on the impact of synthesis cyclohexanone-oxime reaction
| Embodiment | The volume (mL) of hydrogen peroxide | Hydrogen peroxide/pimelinketone 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 operation steps of embodiment 12 and reaction conditions, just in oximation reaction, the drop rate of hydrogen peroxide changes into 14.0mL/h, 17.0mL/h, 23.0mL/h.The experimental result of oximation reaction is as shown in table 10.
The drop rate of table 10 hydrogen peroxide is on the impact of synthesis cyclohexanone-oxime reaction
Embodiment 29 ~ 31
Identical with the operation steps in embodiment 12 and reaction conditions, just in oximation reaction, the add-on of TS-1 molecular sieve changes into 0.5g respectively, 2.0g, 4.0g (weight percentage of 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 add-on of table 11 titanium-silicon molecular sieve TS-1 is on the impact of synthesis cyclohexanone-oxime reaction
| 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
Identical with the operation steps in embodiment 12 and reaction conditions, the TS-1 catalyzer just added is that the regeneration TS-1 catalyzer 2.955g after drying, roasting, to investigate the reusability of catalyzer in embodiment 12 after alcohol wash, washing.After the underpressure distillation of raffinate aqueous phase, after washing drying, white solid cyclohexylamine hydrochloride 17.1g can be obtained.Adopt gas chromatographic analysis organic phase, the yield of quantitative Analysis cyclohexanone-oxime is 87.7%.
From table 1 ~ 11, a kind of decomposing ammonium chloride of the present invention prepares the novel method of organic basis of hydrochloride and cyclohexanone-oxime, essence is take ammonium chloride as ammoniation agent, hydrogen peroxide is oxygenant, HTS is catalyzer, builds the technological process that ammonium chloride, hydrogen peroxide and pimelinketone " a pot " synthesize organic basis of hydrochloride and cyclohexanone-oxime.Wherein, the suitable reaction condition of cyclohexanone-oxime building-up process is: material proportion ammonium chloride: organic bases: water: hydrogen peroxide: the mol ratio of pimelinketone is preferably 2.0 ~ 3.5:1.5 ~ 2.5:19.0 ~ 31.0:1.5 ~ 3.5:1, and the quality of solid catalyst is participate in reaction mass total mass 0.7 ~ 6.2%; Hydrogen peroxide solution time for adding is 0.8 ~ 1.2h, and temperature of reaction is 60 ~ 80 DEG C, and the reaction times 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 sieve can recycling use.
Unaccomplished matter of the present invention is known technology.
Claims (10)
1. decomposing ammonium chloride prepares a method for organic basis of hydrochloride and cyclohexanone-oxime simultaneously, it is characterized by and comprises the following steps:
Titanium-silicon molecular sieve catalyst, chloride solid are placed in reactor, then add water, organic bases, pimelinketone, stir and be warming up to 40 ~ 90 DEG C, drip hydrogen peroxide solution, simultaneously synthesis under normal pressure 1 ~ 6h; Centrifugation catalyzer and reaction solution, the reaction solution of centrifugation gained, can obtain organic phase after extracting and separating, and organic phase, again through underpressure distillation, can obtain white solid cyclohexanone-oxime product; After extracting phase underpressure distillation, after washing drying, organic basis of hydrochloride can be obtained;
Wherein, material proportion is mol ratio ammonium chloride: organic bases: water: hydrogen peroxide: pimelinketone is 1.5 ~ 4.5:1.0 ~ 2.5:9.0 ~ 31.4:1.3 ~ 3.8:1, and the quality of solid catalyst is participate in reaction mass total mass 0.7 ~ 6.2%; Hydrogen peroxide solution time for adding is 0.5 ~ 1.5h.
2. decomposing ammonium chloride as claimed in claim 1 prepares the method for organic basis of hydrochloride and cyclohexanone-oxime simultaneously, it is characterized by described titanium-silicon molecular sieve catalyst and is specially TS-1 molecular sieve.
3. decomposing ammonium chloride as claimed in claim 1 prepares the method for organic basis of hydrochloride and cyclohexanone-oxime simultaneously, it is characterized by described organic bases and is specially hexahydroaniline, dimethylamine, Trimethylamine 99, diethylamine, triethylamine, quadrol or thanomin.
4. decomposing ammonium chloride as claimed in claim 1 prepares the method for organic basis of hydrochloride and cyclohexanone-oxime simultaneously, and the extraction agent that it is characterized by described extracting and separating is toluene.
5. decomposing ammonium chloride as claimed in claim 1 prepares the method for organic basis of hydrochloride and cyclohexanone-oxime simultaneously, it is characterized by described temperature of reaction and is preferably 60 ~ 80 DEG C.
6. decomposing ammonium chloride as claimed in claim 1 prepares the method for organic basis of hydrochloride and cyclohexanone-oxime simultaneously, it is characterized by the described reaction times to be preferably 1.5 ~ 5h.
7. decomposing ammonium chloride as claimed in claim 1 prepares the method for organic basis of hydrochloride and cyclohexanone-oxime simultaneously, it is characterized by described ammonium chloride: organic bases: water: hydrogen peroxide: the mol ratio of pimelinketone is preferably 2.0 ~ 3.5
:1.5 ~ 2.5
:19.0 ~ 31.0:1.5 ~ 3.5:1.
8. decomposing ammonium chloride as claimed in claim 1 prepares the method for organic basis of hydrochloride and cyclohexanone-oxime simultaneously, and it is characterized by described solid catalyst quality optimization is participate in reaction mass total mass 1.0 ~ 5.5%.
9. decomposing ammonium chloride as claimed in claim 1 prepares the method for organic basis of hydrochloride and cyclohexanone-oxime simultaneously, it is characterized by described hydrogen peroxide solution time for adding and is preferably 0.8 ~ 1.2h.
10. decomposing ammonium chloride as claimed in claim 1 prepares the method for organic basis of hydrochloride and cyclohexanone-oxime simultaneously, further comprising the steps of after it is characterized by described centrifugation: the catalyzer of gained is after alcohol wash, washing, 80 DEG C of vacuum-drying 12h, 500 DEG C of retort furnace roasting 4h, use as the catalyzer in next circulation.
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