CN103980155A - Method for directly synthesizing cyclohexanone-oxime through hydrogenation of nitrobenzene - Google Patents
Method for directly synthesizing cyclohexanone-oxime through hydrogenation of nitrobenzene Download PDFInfo
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- CN103980155A CN103980155A CN201410243095.XA CN201410243095A CN103980155A CN 103980155 A CN103980155 A CN 103980155A CN 201410243095 A CN201410243095 A CN 201410243095A CN 103980155 A CN103980155 A CN 103980155A
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- hydrogenation
- ketoxime
- reaction
- chloronitrobenzene
- oxime
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Abstract
The invention discloses a method for directly synthesizing cyclohexanone-oxime through hydrogenation of nitrobenzene. The method comprises the following steps: adding nitrobenzene, a catalyst, an additive, a surfactant and a solvent to a high-pressure kettle, filling N2 for replacement; heating up to 30-150 DEG C; filling hydrogen to 0.1-5MPa and maintaining the pressure; adding 0.1-10mol/L of a hydroxylamine or hydroxylamine salt water solution constantly at a uniform speed in a reaction process; reacting for 0.1-4 hours, stopping filling the hydrogen, cooling to room temperature, decompressing, filtering and separating the catalyst and a reaction solution, and extracting and separating the reaction solution to obtain an organic phase containing the cyclohexanone-oxime. The method disclosed by the invention has such characteristics as cheap and easily available nitrobenzene as a raw material, more convenient and simpler synthesis process, mild reaction condition and high yield. Yield of the cyclohexanone-oxime prepared by the method disclosed by the invention is close to 70%.
Description
Technical field
The present invention relates to a kind of method by the direct synthesizing cyclohexane 1 ketoxime of hydrogenation of chloronitrobenzene, belong to chemical process technology field.
Background technology
Cyclohexanone-oxime is to produce hexanolactam (CPL), and then manufactures the intermediate raw material of the staple products such as daiamid-6 fiber (nylon 6), engineering plastics and film.
At present, the production of cyclohexanone-oxime mainly contains traditional pimelinketone and azanol carries out pimelinketone, NH on oximation reaction route and TS-1 molecular sieve catalyst
3and H
2o
2reaction generates the new technology route of cyclohexanone-oxime.And wherein the production process route of pimelinketone divides and mainly contains three kinds by raw material: cyclohexane liquid-phase oxidation method (U.Schuchardt, D.Cardoso, R.Sercheli, et al. " Cyclohexane oxidation continues to be a challenge ", Applied Catalysis A:General, 2001, 211 (1): 1-17), phenol hydrogenation method (L.M.Sikhwivhilu, N.J.Coville, D.Naresh, et al. " Nanotubular titanate supported palladium catalysts:The influence of structure and morphology on phenol hydrogenation activity ", Applied Catalysis A:General, 2007, 324:52-61) with cyclohexene hydration method (H.Zhang, S.M.Mahajani, M.M.Sharma, et al. " Hydration of cyclohexene with solid acid catalysts ", Chemical Engineering Science, 2002, 57:315-322).In these three kinds of routes, cyclohexane oxidation process accounts for more than 90%.
(1) cyclohexane liquid-phase oxidation method.Industrial cyclohexane liquid-phase oxidation comprises route (Guo Zhiwu, Jin Haibo, the Tong Zemin of catalyzed oxidation and non-catalyst oxidation.Pimelinketone, hexalin progress of Preparation Technology, chemical industry progress, 2006,25 (8): 852-859).Non-catalyst oxidation method, taking pimelinketone, hexalin as initiator, directly becomes cyclohexyl hydroperoxide with air or oxygen by cyclohexane oxidation in the situation that not adding catalyzer.Cyclohexyl hydroperoxide, through the concentrated metal oxide oxidation catalysts such as molybdenum, vanadium, cobalt that adopt, makes it to resolve into the mixture of hexalin and pimelinketone under low temperature, alkalescence, oxygen free condition.Non-catalyst oxidation method oxidizing reaction temperature and pressure are all high compared with catalysis method, and general reaction pressure is 1.4～2.0MPa, and temperature of reaction is 170～200 DEG C, and per pass conversion is 4%～5%, and hexalin and pimelinketone selectivity are 80%.Because reactivity ratio's hexanaphthene of hexalin and pimelinketone is high, easy deep oxidation under reaction conditions, so (comprise without catalysis and cobalt salt catalysis) in traditional cyclohexane liquid-phase oxidation method, in order to obtain higher selectivity (80%), not high (<5%) of transformation efficiency of general hexanaphthene, a large amount of unreacted hexanaphthenes need to be separated oxidation again by the method for distillation again, whole process circulating consumption is very high, and three-waste pollution is serious, in addition, hexanaphthene is with forming explosive mixture after air mixed, and process safety is poor.Therefore this technique is all considered to nonideal technique all the time.
(2) phenol hydrogenation method.Phenol synthesis pimelinketone technique is the technique that is applied to the earliest suitability for industrialized production pimelinketone, and this technique is divided into two steps in early days: the first step phenol hydrogenation is hexalin, and second step cyclohexanol dehydrogenation generates pimelinketone.20 century 70s have been succeeded in developing the novel process of a step hydrogenation method synthesizing cyclohexanone.Taking Pd/C as catalyzer, when 180 DEG C of temperature of reaction, the transformation efficiency of phenol is 50%, pimelinketone selectivity approaches 100% (K.V.R.Chary, D.Naresh, V.Vishwanathan, er al. " Vapour phase hydrogenation of phenol over Pd/C catalysts:A relationship between dispersion; metal area and hydrogenation activity ", Catalysis Communication, 2007,8 (3): 471-477).The pimelinketone quality that phenol hydrogenation method is produced is better, safe, but because the production of industrial phenol generates isopropyl benzene through benzene alkylation, and then cumene oxidation is to isopropyl benzene hydroperoxide, more multiple steps such as coproduction phenol and acetone.So consider the relatively complicated and price difference larger with benzene of the technique of producing phenol, and the utilization of by-product acetone has difficulties, the application of phenol hydrogenation synthesizing cyclohexanone technique is also very limited.
(3) cyclohexene hydration method.Cyclohexene hydration method is mainly taking benzene as raw material, first synthesizing cyclohexene, and the further synthesizing cyclohexanol of tetrahydrobenzene, last cyclohexanol dehydrogenation generates pimelinketone.The eighties in 20th century Japan (O.Mitsui of Asahi Chemical Industry, Y.Fukuoka.Cycloalkanols:JP, 83209150.1983-11-09) develop cyclohexene hydration hexalin technique processed, this technique is taking benzene as raw material, at 100～180 DEG C, 3～10MPa, under the condition of ruthenium catalyst, carry out Partial hydrogenation reaction and prepare tetrahydrobenzene, the transformation efficiency 50%～60% of benzene, the selectivity of tetrahydrobenzene is 80%, 20% by product is hexanaphthene, under supersiliceous zeolite ZSM-5 catalyst action, cyclohexene hydration generates hexalin, the per pass conversion 10%～15% of tetrahydrobenzene, the selectivity of hexalin can reach 99.13%.Hexalin is under the effect of the catalyzer such as zinc calcium, copper magnesium, copper zinc and copper silicon, and catalytic dehydrogenation, can obtain pimelinketone.This processes expend is low, and has effectively avoided the waste lye producing in cyclohexane oxidation technological process, has reduced environmental protection pressure.But this operational path complexity.Especially the efficiency of partial hydrogenation of benzene synthesizing cyclohexene is not high, thereby causes production cost higher.
As can be seen here, existing cyclohexanone-oxime product all will just can obtain through complicated polystep reaction, complex manufacturing, and production efficiency is lower.
Based on this, the present invention proposes a kind of novel method by the direct synthesizing cyclohexane 1 ketoxime of hydrogenation of chloronitrobenzene, taking oil of mirbane as raw material, and the technological process of the direct synthesizing cyclohexane 1 ketoxime of load type metal catalyst catalysis hydrogenation of chloronitrobenzene oximate.
Summary of the invention
The present invention is directed to current cyclohexanone-oxime complex manufacturing, the present situation that cost is increased, provides the novel method of a kind of low temperature, efficient, inexpensive synthesizing cyclohexane 1 ketoxime.The present invention constructs the cyclohexanone-oxime synthetic method as shown in reaction process (1), this method taking oil of mirbane as raw material, load type metal is catalyzer, in azanol or the hydroxylammonium salt aqueous solution, the technological process of the direct synthesizing cyclohexane 1 ketoxime of hydrogenation.
Technical scheme of the present invention is:
By a method for the direct synthesizing cyclohexane 1 ketoxime of hydrogenation of chloronitrobenzene, the method comprises the following steps:
Oil of mirbane, catalyzer, auxiliary agent, tensio-active agent and solvent, as in autoclave, are led to N
2replace, be then warming up to 30～150 DEG C, then pass into hydrogen to 0.1～5MPa and keep, in reaction process, at the uniform velocity adding all the time concentration is the azanol of 0.1～10mol/L or the aqueous solution of hydroxylammonium salt; After reaction 0.1～4h, stop logical hydrogen, be cooled to room temperature, filtration under diminished pressure separating catalyst and reaction solution, reaction solution obtains the organic phase that contains cyclohexanone-oxime after extracting and separating;
Wherein, material mole proportioning is oil of mirbane: catalyzer: auxiliary agent: tensio-active agent: solvent=1:0.001～1:0.01～100:0.0001～0.1:1～10000; The azanol altogether adding in reaction process or the amount of hydroxylammonium salt are: mole proportioning is oil of mirbane: azanol or hydroxylammonium salt=1:1～10;
Described catalyzer is load type metal catalyst, and the composition of this catalyzer comprises active metal and carrier, and wherein active metal charge capacity is mass percent 0.1～10%; The molar weight of catalyzer is in the molar weight of active metal;
The active metal of described load type metal catalyst is Pd, Pt, Ru, Rh or Au;
Described support of the catalyst is activated carbon, carbon fiber, carbon pipe, Al
2o
3, SiO
2, TiO
2, MgO, ZrO
2, zeolite, molecular sieve, clay, diatomite, hydrotalcite or hydroxyapatite;
Described auxiliary agent is Lewis acid or Bronsted acid;
Described tensio-active agent is cetyl trimethylammonium bromide.
Described Lewis acid is AlCl
3, ZnCl
2, FeCl
3, SnCl
2, InCl
3, CeCl
3or ZnSO
4.
Described Bronsted acid is HCl, H
2sO
4or CH
3cOOH.
Described solvent is water, alcohol, hexanaphthene or methylene dichloride.
Described hydroxylammonium salt can be oxammonium hydrochloride, oxammonium sulfate or phosphatic hydroxylamine.
Described material proportion is preferably: oil of mirbane: catalyzer: auxiliary agent: tensio-active agent: solvent=1:0.005～0.1:0.05～10:0.001～0.01:10～1000.
Described temperature of reaction is preferably 50～120 DEG C.
Described reaction pressure is preferably 0.5～3MPa.
The described reaction times is preferably 0.1～2h.
Mole proportion optimization of described azanol or hydroxylammonium salt and oil of mirbane is 1～5; The concentration of described azanol or the hydroxylammonium salt aqueous solution is preferably 0.5～5mol/L.
The present invention compared with prior art has following beneficial effect:
The novel method of the direct synthesizing cyclohexane 1 ketoxime of a kind of hydrogenation of chloronitrobenzene provided by the present invention, has not yet to see the relevant report taking oil of mirbane as the operational path of the direct one-step synthesis cyclohexanone-oxime of raw material.And compare traditional complicated pimelinketone building-up process of first passing through, and then carry out pimelinketone oximate reaction synthesizing cyclohexane 1 ketoxime, method of the present invention has that raw material oil of mirbane is cheaply easy to get, building-up process is more simple and direct, reaction conditions is gentle, yield high.Experiment showed, that method of the present invention prepares cyclohexanone-oxime, the yield of cyclohexanone-oxime approaches 70%.And other cyclohexanone-oxime synthetic method step is various, efficiency is lower.The method that hydrogenation of chloronitrobenzene one step of the present invention is prepared cyclohexanone-oxime is a kind of low temperature, efficient, inexpensive novel method, has opened up the synthetic technological line of cyclohexanone-oxime.
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 can content according to the present invention make some nonessential improvement and adjustment.In following embodiment, method therefor is ordinary method if no special instructions, and agents useful for same all can obtain from commercial channels.Below by embodiment, the present invention is further illustrated.
The load type metal catalyst adopting in following embodiment is well known materials, can directly be purchased or adopt preparation with the following method:
(be PdCl by the active metal muriate of required charge capacity
2, RhCl
3, RuCl
3, H
2ptCl
6or HAuCl
4) solution is dissolved in the hydrochloric acid soln of 10mol/L or the aqueous solution and is made into steeping fluid, incipient impregnation is to carrier (activated carbon, carbon fiber, carbon pipe, Al
2o
3, SiO
2, TiO
2, MgO, ZrO
2, zeolite, molecular sieve, clay, diatomite, hydrotalcite or hydroxyapatite) upper, after dipping 24h, at 100 DEG C of dry 5h, then at 300 DEG C with H
2reductase 12 h.
Embodiment 1
In autoclave, add successively oil of mirbane 0.49g, Pd/MCM-41 (molecular sieve) the catalyzer 0.78g that mass percent is 2%, AlCl
30.54g, cetyl trimethylammonium bromide 0.006g, and water 10ml (its mol ratio is 1:0.037:1:0.004:139).Logical N
2replace.Then be warming up to 80 DEG C, pass into again hydrogen to reaction pressure 1.3MPa and keep, then add the aqueous hydroxylamine of concentration as 1mol/L with piston pump taking the speed of 0.072ml/min, after reaction 1h, stop logical hydrogen, stop adding aqueous hydroxylamine simultaneously, be cooled to room temperature, filtration under diminished pressure separating catalyst and reaction solution, reaction solution can obtain organic phase after toluene extracting and separating, and organic phase is carried out gas chromatographic analysis.The yield of quantitative Analysis product cyclohexanone-oxime is 65.1%.
Embodiment 2～5
Identical with operation steps and the reaction conditions of synthesizing cyclohexane 1 ketoxime process in embodiment 1, the active metal of catalyzer is changed into respectively Ru, Rh, Pt, Au.Adopt gas chromatographic analysis organic phase, the yield of quantitative Analysis product cyclohexanone-oxime.Experimental result is as shown in table 1.
The impact of table 1 catalyst activity metal pair synthesizing cyclohexane 1 ketoxime reaction
| Embodiment | Active metal | The yield (%) of cyclohexanone-oxime |
| 2 | Ru | 10.8 |
| 3 | Rh | 27.5 |
| 4 | Pt | 8.6 |
| 5 | Au | 39.7 |
Embodiment 6～10
Identical with operation steps and the reaction conditions of synthesizing cyclohexane 1 ketoxime process in embodiment 1, the carrier of catalyzer is changed into respectively AC, γ-Al
2o
3, TS-1, HZSM-5, SBA-15 etc.Adopt gas chromatographic analysis organic phase, the yield of quantitative Analysis product cyclohexanone-oxime.Experimental result is as shown in table 2.
The impact of table 2 support of the catalyst on synthetic cyclohexanone-oxime reaction
| Embodiment | Support of the catalyst | The yield (%) of cyclohexanone-oxime |
| 6 | AC | 10.2 |
| 7 | γ-Al 2O 3 | 15.6 |
| 8 | TS-1 | 9.7 |
| 9 | HZSM-5 | 48.9 |
| 10 | SBA-15 | 59.6 |
Embodiment 11～13
Identical with operation steps and the reaction conditions of synthesizing cyclohexane 1 ketoxime process in embodiment 1, just catalyzer adopts 2%Pd/HZSM-5, and the reaction times is changed into respectively 0.25h, 0.5h, 2h.Adopt gas chromatographic analysis organic phase, the yield of quantitative Analysis product cyclohexanone-oxime.Experimental result is as shown in table 3.
The impact of table 3 reaction times on synthetic cyclohexanone-oxime reaction
| Embodiment | Reaction times (h) | The yield (%) of cyclohexanone-oxime |
| 11 | 0.25 | 15.9 |
| 12 | 0.5 | 49.6 |
| 13 | 2 | 65.4 |
Embodiment 14～15
Identical with operation steps and the reaction conditions of synthesizing cyclohexane 1 ketoxime process in embodiment 1, just catalyzer adopts 2%Pd/HZSM-5, and hydrogen pressure is changed into respectively 0.5MPa, 2.0MPa.Adopt gas chromatographic analysis organic phase, the yield of quantitative Analysis product cyclohexanone-oxime.Experimental result is as shown in table 4.
The impact of table 4 reaction pressure on synthetic cyclohexanone-oxime reaction
| Embodiment | Reaction pressure (MPa) | The yield (%) of cyclohexanone-oxime |
| 14 | 0.5 | 39.7 |
| 15 | 2.0 | 45.8 |
Embodiment 16～19
Identical with operation steps and the reaction conditions of synthesizing cyclohexane 1 ketoxime process in embodiment 1, just the charge capacity of catalyst activity component Pd changes into respectively 0.5%, 1%, 3%, 5%.Adopt gas chromatographic analysis organic phase, the yield of quantitative Analysis product cyclohexanone-oxime.Experimental result is as shown in table 5.
The impact of the charge capacity of table 5Pd on synthetic cyclohexanone-oxime reaction
| Embodiment | The charge capacity (wt%) of Pd | The yield (%) of cyclohexanone-oxime |
| 16 | 0.5 | 48.7 |
| 17 | 1.0 | 65.8 |
| 18 | 3.0 | 62.7 |
| 19 | 5.0 | 56.8 |
Embodiment 20～24
Identical with operation steps and the reaction conditions of synthesizing cyclohexane 1 ketoxime process in embodiment 1, just auxiliary agent is changed into respectively FeCl
3, SnCl
2, ZnSO
4, HCl, CH
3cOOH.Adopt gas chromatographic analysis organic phase, the yield of quantitative Analysis cyclohexanone-oxime.Experimental result is as shown in table 6.
The impact of table 6 auxiliary agent on synthetic cyclohexanone-oxime reaction
| Embodiment | Auxiliary agent | The yield (%) of cyclohexanone-oxime |
| 20 | FeCl 3 | 35.8 |
| 21 | SnCl 2 | 20.7 |
| 22 | ZnSO 4 | 6.4 |
| 23 | HCl | 26.1 |
| 24 | CH 3COOH | 67.8 |
Embodiment 25～27
Identical with operation steps and the reaction conditions of synthesizing cyclohexane 1 ketoxime process in embodiment 1, just aqueous hydroxylamine add that speed changes into respectively 0.144,0.217ml/min.Adopt gas chromatographic analysis organic phase, the yield of quantitative Analysis cyclohexanone-oxime.Experimental result is as shown in table 7.
Table 7 azanol adds the impact of speed on synthetic cyclohexanone-oxime reaction
Embodiment 28～30
Identical with operation steps and the reaction conditions of synthesizing cyclohexane 1 ketoxime process in embodiment 1, just azanol raw material is changed into respectively oxammonium hydrochloride, phosphatic hydroxylamine, hydroxylamine sulfate solution.Adopt gas chromatographic analysis organic phase, the yield of quantitative Analysis cyclohexanone-oxime.Experimental result is as shown in table 8.
The impact of the different azanol raw materials of table 8 on synthetic cyclohexanone-oxime reaction
| Embodiment | Hydroxylammonium salt | The yield (%) of cyclohexanone-oxime |
| 28 | Oxammonium hydrochloride | 66.5 |
| 29 | Oxammonium sulfate | 64.1 |
| 30 | Phosphatic hydroxylamine | 60.7 |
Embodiment 31～32
Identical with operation steps and the reaction conditions of synthesizing cyclohexanone process in embodiment 1, just auxiliary agent A lCl
3consumption respectively solvent change into respectively 0.054g and 0.27g.Adopt gas chromatographic analysis organic phase, the yield of quantitative Analysis cyclohexanone-oxime.Experimental result is as shown in table 9.
The impact of table 9 auxiliary dosage on synthetic cyclohexanone-oxime reaction
| Embodiment | Auxiliary agent (AlCl 3) consumption/g | The yield (%) of cyclohexanone-oxime |
| 25 | 0.054 | 15.8 |
| 26 | 0.27 | 48.5 |
Unaccomplished matter of the present invention is known technology.
Claims (10)
1. by a method for the direct synthesizing cyclohexane 1 ketoxime of hydrogenation of chloronitrobenzene, it is characterized by the method and comprise the following steps:
Oil of mirbane, catalyzer, auxiliary agent, tensio-active agent and solvent, as in autoclave, are led to N
2replace, be then warming up to 30 ~ 150 DEG C, then pass into hydrogen to 0.1 ~ 5MPa and keep, in reaction process, at the uniform velocity adding all the time concentration is the azanol of 0.1 ~ 10mol/L or the aqueous solution of hydroxylammonium salt; After reaction 0.1 ~ 4h, stop logical hydrogen, be cooled to room temperature, filtration under diminished pressure separating catalyst and reaction solution, reaction solution obtains the organic phase that contains cyclohexanone-oxime after extracting and separating;
Wherein, material mole proportioning is oil of mirbane: catalyzer: auxiliary agent: tensio-active agent: solvent=1:0.001 ~ 1:0.01 ~ 100:0.0001 ~ 0.1:1 ~ 10000; The azanol altogether adding in reaction process or the amount of hydroxylammonium salt are: mole proportioning is oil of mirbane: azanol or hydroxylammonium salt=1:1 ~ 10;
Described catalyzer is load type metal catalyst, and the composition of this catalyzer comprises active metal and carrier, and wherein active metal charge capacity is mass percent 0.1 ~ 10%; The molar weight of catalyzer is in the molar weight of active metal;
The active metal of described load type metal catalyst is Pd, Pt, Ru, Rh or Au;
Described support of the catalyst is activated carbon, carbon fiber, carbon pipe, Al
2o
3, SiO
2, TiO
2, MgO, ZrO
2, zeolite, molecular sieve, clay, diatomite, hydrotalcite or hydroxyapatite;
Described auxiliary agent is Lewis acid or Bronsted acid;
Described tensio-active agent is cetyl trimethylammonium bromide.
2. the method by the direct synthesizing cyclohexane 1 ketoxime of hydrogenation of chloronitrobenzene as claimed in claim 1, it is characterized by described Lewis acid is AlCl
3, ZnCl
2, FeCl
3, SnCl
2, InCl
3, CeCl
3or ZnSO
4.
3. the method by the direct synthesizing cyclohexane 1 ketoxime of hydrogenation of chloronitrobenzene as claimed in claim 1, it is characterized by described Bronsted acid is HCl, H
2sO
4or CH
3cOOH.
4. the method by the direct synthesizing cyclohexane 1 ketoxime of hydrogenation of chloronitrobenzene as claimed in claim 1, it is characterized by described solvent is water, alcohol, hexanaphthene or methylene dichloride.
5. the method by the direct synthesizing cyclohexane 1 ketoxime of hydrogenation of chloronitrobenzene as claimed in claim 1, is characterized by described hydroxylammonium salt and can be oxammonium hydrochloride, oxammonium sulfate or phosphatic hydroxylamine.
6. the method by the direct synthesizing cyclohexane 1 ketoxime of hydrogenation of chloronitrobenzene as claimed in claim 1, is characterized by described material proportion and is preferably: oil of mirbane: catalyzer: auxiliary agent: tensio-active agent: solvent=1:0.005 ~ 0.1:0.05 ~ 10:0.001 ~ 0.01:10 ~ 1000.
7. the method by the direct synthesizing cyclohexane 1 ketoxime of hydrogenation of chloronitrobenzene as claimed in claim 1, is characterized by described temperature of reaction and is preferably 50 ~ 120 DEG C.
8. the method by the direct synthesizing cyclohexane 1 ketoxime of hydrogenation of chloronitrobenzene as claimed in claim 1, is characterized by described reaction pressure and is preferably 0.5 ~ 3MPa.
9. the method by the direct synthesizing cyclohexane 1 ketoxime of hydrogenation of chloronitrobenzene as claimed in claim 1, the reaction times described in it is characterized by is preferably 0.1 ~ 2h.
10. the method by the direct synthesizing cyclohexane 1 ketoxime of hydrogenation of chloronitrobenzene as claimed in claim 1, it is characterized by described azanol or mole proportion optimization of hydroxylammonium salt and oil of mirbane is 1 ~ 5; The concentration of described azanol or the hydroxylammonium salt aqueous solution is preferably 0.5 ~ 5mol/L.
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|---|---|---|---|---|
| CN111153831A (en) * | 2020-02-19 | 2020-05-15 | 湘潭大学 | Preparation method of cyclohexanone oxime |
| CN111253281A (en) * | 2020-02-19 | 2020-06-09 | 湘潭大学 | Preparation method of cyclohexanone oxime |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111153831A (en) * | 2020-02-19 | 2020-05-15 | 湘潭大学 | Preparation method of cyclohexanone oxime |
| CN111253281A (en) * | 2020-02-19 | 2020-06-09 | 湘潭大学 | Preparation method of cyclohexanone oxime |
| CN111153831B (en) * | 2020-02-19 | 2022-11-01 | 湘潭大学 | Preparation method of cyclohexanone oxime |
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Application publication date: 20140813 |