CN103012263B - A kind of preparation method of hexanolactam - Google Patents
A kind of preparation method of hexanolactam Download PDFInfo
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- CN103012263B CN103012263B CN201110290117.4A CN201110290117A CN103012263B CN 103012263 B CN103012263 B CN 103012263B CN 201110290117 A CN201110290117 A CN 201110290117A CN 103012263 B CN103012263 B CN 103012263B
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Abstract
The invention discloses a kind of preparation method of hexanolactam, the method comprises: under rearrangement reaction condition, by cyclohexanone-oxime and catalyst exposure, it is characterized in that, said catalyzer contains HTS and multiple-metal oxygen-containing is sour and/or Polyoxometalate.The method environmental friendliness, production process is simple, requires low, be beneficial to suitability for industrialized production and application to material purity.
Description
Technical field
The invention relates to a kind of method that catalysis of pimelinketone oxime rearrangement prepares hexanolactam.
Background technology
Hexanolactam is from look thin slice or molten mass, water-soluble, chlorinated solvent, petroleum hydrocarbon, tetrahydrobenzene, benzene, methyl alcohol, ethanol, ether etc.The hexanolactam overwhelming majority for the production of polycaprolactam, and then produces synthon, and small part is used as plastics, for the manufacture of gear, bearing, tubing, medicine equipment and electrically, insulating material etc.Also for coating, plastic agent and marginally for the synthesis of Methionin etc.Hexanolactam is the main raw material producing tynex and resin, and tynex claims nylon in the U.S., and in China on polyamide fibre, namely polyamide fibre 6 is hexanolactam ring-opening polymerization.
Last century the forties, German method our company by pimelinketone-azanol synthesis of caprolactam (now referred to as oxime method), first achieves Caprolactam Industry and produces.Along with the development of synthetic fiber industry, the preparation methods such as toluene method, process for caprolactam, caprolactone method, hexanaphthene nitrofication process and pimelinketone nitrofication process are successively there is.In each production method of industrialized hexanolactam, oxime method is still the widest method of current industrial application, and its output accounts for the overwhelming majority in hexanolactam output.The pimelinketone ammoxidation method developed in recent years, owing to not needing to adopt azanol to carry out pimelinketone oximate in production process, and flow process is simple, has caused the concern of people.The rearrangement of cyclohexanone-oxime method of current main flow is catalyzer by the cyclohexanone-oxime separated with oleum, be crude caprolactam at 80 ~ 110 DEG C through Beckmann rearrangement transposition, crude caprolactam, by operations such as extraction, distillation, crystallizations, obtains high purity caprolactam.Developing cyclohexanone-oxime vapor phase rearrangement technology at present.
Therefore, explore and be a kind ofly initial feed with cyclohexanone-oxime and transformation efficiency is high, hexanolactam selectivity is good, the method for particularly environmental friendliness and simply new rearrangement cyclohexanone-oxime, be of great practical significance.In today that environmental problem comes into one's own day by day, more seem very necessary.
Titanium-silicon molecular sieve TS-1 is the novel hetero-atom molecular-sieve of the eighties exploitation in last century, is the Typical Representative in environmental friendly catalysis field.It is research report [as ThangarajA etc., J.Catal., 1992,137:252-256] that catalyzer carries out rearrangement of cyclohexanone-oxime aspect that document also has with HTS, but the leeway that cyclohexanone-oxime transformation efficiency and hexanolactam selectivity still improve.
Summary of the invention
The object of this invention is to provide a kind of method preparing hexanolactam compared with prior art cyclohexanone-oxime transformation efficiency and the higher catalysis of pimelinketone oxime rearrangement of hexanolactam selectivity.
The present inventor finds in long-term research practice, in rearrangement of cyclohexanone-oxime process, introduce multiple-metal oxygen-containing acid and/or Polyoxometalate bonding titanium si molecular sieves can improve cyclohexanone-oxime transformation efficiency in rearrangement process and hexanolactam selectivity greatly as catalyzer, and complete the present invention based on this.
The method preparing hexanolactam provided by the invention, the method comprises: under rearrangement reaction condition, by cyclohexanone-oxime and catalyst exposure, it is characterized in that, said catalyzer contains HTS and multiple-metal oxygen-containing is sour and/or Polyoxometalate.
Rearrangement of cyclohexanone-oxime provided by the invention prepares the method for hexanolactam, has following advantage:
1, reaction conditions is relatively gentle, environmental friendliness.
2, production process is simple, easily controls, is beneficial to suitability for industrialized production.
3, particularly under the condition of relative low temperature and format high throughput, compared with the single titanium-silicon molecular sieve catalyst of routine, under the prerequisite that selectivity improves, transformation efficiency also increases.
As can be seen from the comparative result of embodiment and comparative example, in the inventive method, the transformation efficiency of cyclohexanone-oxime can reach 94%, hexanolactam selectivity 96% (embodiment 1), and under the same reaction conditions, only use that TS-1 is only 91% as the comparative example 2 cyclohexanone oxime transformation efficiency of catalyzer, hexanolactam selectivity 90%, then transformation efficiency only has 14%, hexanolactam selectivity only has 17% not use the cyclohexanone-oxime in the comparative example 1 of catalyzer; In addition, as can be seen from the result of embodiment 1-13, method catalytic activity of the present invention is high, and hexanolactam selectivity is good.
Embodiment
The method preparing hexanolactam provided by the invention, the method comprises: under rearrangement reaction condition, by cyclohexanone-oxime and catalyst exposure, it is characterized in that, said catalyzer contains HTS and multiple-metal oxygen-containing is sour and/or Polyoxometalate.Namely described catalyzer can containing HTS and at least one be selected from multiple-metal oxygen-containing acid and Polyoxometalate.
According to method of the present invention, in catalyzer, the range of choices of the weight ratio of HTS and multiple-metal oxygen-containing acid and/or Polyoxometalate is wider, in order to obtain higher cyclohexanone-oxime transformation efficiency and hexanolactam selectivity, under preferable case, the weight ratio of described multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS can be 1: 0.05-200, more preferably, in situation, the weight ratio of described multiple-metal oxygen-containing acid and/or Polyoxometalate and HTS is 1: 0.1-100.It should be explicitly made clear at this point, the multiple-metal oxygen-containing acid in the present invention and/or the weight of Polyoxometalate refer to: the weight sum of the multiple-metal oxygen-containing acid that may exist and the Polyoxometalate that may exist.
According to method of the present invention, the acid of multiple-metal oxygen-containing described in the present invention can for conventional various multiple-metal oxygen-containing acid (comprising the acid of reduction-state multiple-metal oxygen-containing), described Polyoxometalate can for conventional various Polyoxometalates (comprising reduction-state Polyoxometalate), such as described multiple-metal oxygen-containing acid can be heteropolyacid and/or isopoly-acid, and described Polyoxometalate can be heteropolyacid salt and/or isopoly-acid salt.
The concept of described isopoly-acid is well known to those skilled in the art, and refers to the class acid be made up of identical acid anhydrides, also can think the acid of two or more simple oxygen acid molecule of the same race condensations.What in transition metal, easily form isopoly-acid has the elements such as Mo, W, V, Cr.Hydrogen ion in isopoly-acid is replaced by metal ion can generate corresponding isopoly-acid salt.
The concept of described heteropolyacid is also well known to those skilled in the art, and generally refers to that the class consisted of oxygen atom ligand bridging by certain structure heteroatoms (as P, Si, Fe, Co etc.) and polyatom (as Mo, W, V, Nb, Ta etc.) contains oxygen polyacid.Hydrogen ion in heteropolyacid is replaced by metal ion can generate corresponding heteropolyacid salt.
In the present invention, described isopoly-acid (salt) comprises the isopoly-acid (salt) of reduced form, namely with how blue.Described heteropolyacid (salt) comprises the heteropolyacid (salt) of reduced form, i.e. heteropoly blue, and heteropoly blue is the general name of the transition metal heteropolyacid (salt) of a large class lower valency.Heteropoly blue is usually reduced by heteropolyacid or heteropolyacid salt and obtains, and such as phosphato-molybdic heteropolyacid Reduction with Stannous Chloride obtains blue P-Mo blue, again such as [SiW
11o
39]
8-reducible is [SiW
12o
40]
6-blue compound, tungsten is wherein the mixed valence of+5 and+6 valencys, P
3+, Fe
3+and Cr
3+also can replace the position of a tungsten atom.Other heteropoly blue also can be obtained by its corresponding acid of reduction or salt, and this is no longer going to repeat them.
In research process, the present inventor finds, when the metallic element in described multiple-metal oxygen-containing acid and/or metal oxyacid salts is selected from one or more in IVB race, VB race, group vib and VIIB race metallic element, the transformation efficiency of reactant can improve further; Under further preferable case, the metallic element in the acid of described multiple-metal oxygen-containing and/or metal oxyacid salts be selected from VB race, group vib metallic element one or more; Particularly, the metallic element in the acid of described multiple-metal oxygen-containing and/or metal oxyacid salts is one or more in titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, is preferably one or more in molybdenum, tungsten, vanadium, chromium, tantalum and niobium; Particularly preferably, described multiple-metal oxygen-containing acid be phosphorus heteropoly tungstic acid, phosphato-molybdic heteropolyacid, phosphorus vanadium heteropolyacid, molybdenum vanadium heteropolyacid, molybdenum heteropoly tungstic acid, substituted complexes, metallic element molybdenum formed isopoly-acid, metallic element tungsten formed isopoly-acid and metallic element vanadium formed isopoly-acid in one or more, described isopoly-acid is specifically as follows H
4v
2o
7, H
6v
4o
13, H
7v
5o
16, H
6v
10o
28, H
6mo
7o
24, H
4mo
8o
26and H
10mo
12o
41in one or more.Described Polyoxometalate can be corresponding with the acid of above-mentioned multiple-metal oxygen-containing, the salt that hydrogen ion is replaced by metal ion and reduzate thereof, such as, described Polyoxometalate can be one or more in ammonium corresponding to above-mentioned multiple-metal oxygen-containing acid, basic metal, alkaline earth salt, as ammonium salt, sodium salt, sylvite, calcium salt, magnesium salts etc., this is no longer going to repeat them.In addition, also comprise reduced form, heteropoly blue corresponding with described multiple-metal oxygen-containing acid (salt), as one or more in phosphorus tungsten heteropoly blue, phosphorus molybdenum heteropoly blue, phosphorus vanadium heteropoly blue, molybdenum vanadium heteropoly blue, molybdenum tungsten heteropoly blue and tungsten silicon heteropoly blue.The present invention without particular requirement, can be various structure, as being the structures such as Keggin, Dawson, Silverton, Waugh, Anderson to the structure of the acid of described multiple-metal oxygen-containing and/or Polyoxometalate.
According to method of the present invention, HTS described in the present invention can be the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS of two dimension hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, at least one in the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structures.
Under preferable case, described HTS is one or more in the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure, be more preferably the HTS of MFI structure, more preferably, described HTS is the MFI structure HTS of hollow structure crystal grain, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.
In the present invention, described HTS can be commercially available, and also can prepare, prepare the method for described HTS for conventionally known to one of skill in the art, as the method described in document (Zeolites, 1992, Vol.12 943-950 page).
According to method of the present invention, and in order to make the homogeneous and reaction conditions milder of reaction system, described contact is generally carried out in a solvent, and the consumption of described solvent can change in very wide in range scope, preferably, the weight ratio of described solvent and cyclohexanone-oxime is 0.1-2000: 1, is preferably 0.2-500: 1, more preferably 0.5-100: 1.
In titanium molecular sieve catalysis system, the effect of solvent is mainly in order to make reaction solution be homogeneous phase and make reaction conditions milder.Under this basic premise, the sterically hindered of solvent self can not be too large, can ensure that reaction is carried out efficiently like this, and in the chosen process of solvent, those skilled in the art generally can select according to mentioned above principle.But can not be confined to above-mentioned requirements, concrete selection also needs to carry out according to concrete oxidizing reaction system.The present inventor finds, in the reaction system of rearrangement of cyclohexanone-oxime, in the solvent meeting aforementioned claim, all can realize the present invention, but the transformation efficiency of cyclohexanone-oxime is still limited.The present inventor finds further, using one or more in alcohol, ketone, nitrile and alkane or aromatic hydrocarbons as reaction effect during solvent better, one or more in the aromatic hydrocarbons of the more preferably alkane of the nitrile of the ketone of the alcohol of C1-C6, C3-C8, C2-C8, C1-C12, C6-C9; Wherein, the alcohol of described C1-C6 can be one or more in the organic alcohol solvent such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol and isopropylcarbinol; The ketone of described C3-C8 can be one or more in the organic ketone solvent such as acetone and butanone, the nitrile of described C2-C8 can be one or more in the nitrile solvents such as acetonitrile, propionitrile, vinyl cyanide and benzyl cyanide, the alkane of described C1-C12 can be one or more in methane, ethane, propane, butane, Trimethylmethane, pentane, pentamethylene, normal hexane, hexanaphthene, octane, octane-iso etc., and the aromatic hydrocarbons of described C6-C9 can be one or more in benzene, toluene, ethylbenzene, dimethylbenzene, the first and second benzene, trimethylbenzene, isopropyl benzene etc.More preferably, described solvent is one or more in acetonitrile, acetone, benzene, toluene, the trimethyl carbinol and hexanaphthene.Most preferred solvent is hexanaphthene, and such as, react 2 hours when embodiment 13, its cyclohexanone-oxime transformation efficiency and hexanolactam selectivity all can reach 99%.
Method provided by the invention, be 100-350 DEG C and pressure in temperature be 0.1-3.0MPa, preferable temperature carries out under be 150-300 DEG C and pressure being the condition of 0.1-2.5MPa, the mass ratio of cyclohexanone-oxime and catalyzer is react under the ratio of 1-100: 1, preferably 5-80: 1, wherein in catalyzer HTS and multiple-metal oxygen-containing acid or its salt ratio 0.05-200: 1, be preferably 0.1-100: 1.
In method provided by the invention, reinforced order, without special requirement, first can add cyclohexanone-oxime, first can add solvent, also can add after cyclohexanone-oxime and solvent.
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.In embodiment and comparative example, if no special instructions, reaction is carried out in the universal autoclave of 250mL, and used reagent is commercially available analytical reagent.
The method preparation described in document (Zeolites, 1992, Vol.12 943-950 page) pressed by HTS (TS-1) catalyzer used, and titanium oxide content is 2.5 % by weight.
The Industrial products of HTS described in hollow HTS HTS system Chinese patent CN1301599A used in embodiment (build feldspathization stock company and manufacture by Hunan, be the HTS of MFI structure through X-ray diffraction analysis, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, crystal grain is hollow crystal grain and the radical length of chamber portion is 15-180 nanometer; This sieve sample at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is 78 milligrams/gram), titanium oxide content is 2.5 % by weight.
The multiple-metal oxygen-containing acid that the present invention is used and Polyoxometalate are all purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
In the present invention, adopt gas-chromatography to carry out the analysis of each composition in system, being undertaken quantitatively, all can refer to prior art and carrying out by correcting normalization method, calculating the evaluation index such as the transformation efficiency of reactant and the selectivity of product on this basis.
In comparative example and embodiment:
Comparative example 1
Be 1: 10 by cyclohexanone-oxime and solvent toluene according to the mol ratio of cyclohexanone-oxime and solvent toluene, react under be 300 DEG C of pressure being 1.5MPa in temperature.React after 2 hours, the transformation efficiency of cyclohexanone-oxime is 14%; Hexanolactam selectivity is 17%.
Comparative example 2
Be 40: 1 by cyclohexanone-oxime, solvent toluene and catalyzer (TS-1) according to solvent toluene and cyclohexanone-oxime mass ratio, the mass ratio of cyclohexanone-oxime and catalyzer is 30: 1, reacts under 200 DEG C and 1.5MPa.The result of reacting 2 hours is as follows: cyclohexanone-oxime transformation efficiency is 91%; Hexanolactam selectivity is 90%.
Comparative example 3
By cyclohexanone-oxime, solvent toluene and catalyzer (phosphorus heteropoly tungstic acid H
3pW
12o
40) be 40: 1 according to solvent toluene and cyclohexanone-oxime mass ratio, the mass ratio of cyclohexanone-oxime and catalyzer is 30: 1, reacts under be 200 DEG C of pressure being 1.5MPa in temperature.The result of reacting 2 hours is as follows: cyclohexanone-oxime transformation efficiency is 19%; Hexanolactam selectivity is 72%.
Embodiment 1
By cyclohexanone-oxime, solvent toluene and catalyzer (TS-1 and phosphorus heteropoly tungstic acid H
3pW
12o
40mass ratio be 100: 1) be 40: 1 according to solvent toluene and cyclohexanone-oxime mass ratio, the mass ratio of cyclohexanone-oxime and catalyzer is 30: 1, reacts under be 200 DEG C of pressure being 1.5MPa in temperature.The result of reacting 2 hours is as follows: cyclohexanone-oxime transformation efficiency is 94%; Hexanolactam selectivity is 96%.
Embodiment 2
By cyclohexanone-oxime, solvent benzol and catalyzer (TS-1 and molybdenum tungsten heteropoly blue H
5moW
12o
40mass ratio be 0.1: 1) be 100: 1 according to the mass ratio of solvent benzol and cyclohexanone-oxime, the mass ratio of cyclohexanone-oxime and catalyzer is 40: 1, reacts under be 250 DEG C of pressure being 1.0MPa in temperature.The result of reacting 2 hours is as follows: cyclohexanone-oxime transformation efficiency is 95%; Hexanolactam selectivity is 94%.
Embodiment 3
By cyclohexanone-oxime, solvent acetone and catalyzer (TS-1 with vanadium polyacid H
4v
2o
7mass ratio be 50: 1) be 50: 1 according to the mass ratio of solvent acetone and cyclohexanone-oxime, the mass ratio of cyclohexanone-oxime and catalyzer is 80: 1, reacts under be 160 DEG C of pressure being 1.0MPa in temperature.The result of reacting 2 hours is as follows: cyclohexanone-oxime transformation efficiency is 96%; Hexanolactam selectivity is 99%.
Embodiment 4
By cyclohexanone-oxime, solvent tertiary butanol and catalyzer (TS-1 and phosphato-molybdic heteropolyacid H
3pMo
12o
40mass ratio be 10: 1) be 80: 1 according to the mass ratio of solvent tertiary butanol and cyclohexanone-oxime, the mass ratio of cyclohexanone-oxime and catalyzer is 2: 1, reacts under be 180 DEG C of pressure being 0.5MPa in temperature.The result of reacting 2 hours is as follows: cyclohexanone-oxime transformation efficiency is 97%; Hexanolactam selectivity is 96%.
Embodiment 5
By cyclohexanone-oxime, solvent hexane and catalyzer (TS-1 and phosphorus tungsten heteropoly blue H
5pW
12o
40mass ratio be 20: 1) be 10: 1 according to the mass ratio of solvent hexane and cyclohexanone-oxime, the mass ratio of cyclohexanone-oxime and catalyzer is 5: 1, reacts under be 190 DEG C of pressure being 1.0MPa in temperature.The result of reacting 2 hours is as follows: benzo ring hexanone oxime transformation efficiency is 93%; Hexanolactam selectivity is 95%.
Embodiment 6
By cyclohexanone-oxime, solvent toluene and catalyzer (TS-1 and ammonium phosphomolybdate (NH
4)
3pMo
12o
40mass ratio be 2: 1) be 5: 1 according to the mass ratio of solvent toluene and cyclohexanone-oxime, the mass ratio of cyclohexanone-oxime and catalyzer is 10: 1, reacts under be 240 DEG C of pressure being 0.5MPa in temperature.The result of reacting 2 hours is as follows: cyclohexanone-oxime transformation efficiency is 94%; Hexanolactam selectivity is 93%.
Embodiment 7
By cyclohexanone-oxime, solvent acetone and catalyzer (TS-1 with molybdenum polyacid H
4mo
8o
26mass ratio be 5: 1) be 15: 1 according to the mass ratio of solvent acetone and cyclohexanone-oxime, the mass ratio of cyclohexanone-oxime and catalyzer is 100: 1, reacts under be 250 DEG C of pressure being 0.5MPa in temperature.The result of reacting 2 hours is as follows: cyclohexanone-oxime transformation efficiency is 92%; Hexanolactam selectivity is 98%.
Embodiment 8
By cyclohexanone-oxime, solvent acetonitrile and catalyzer (TS-1 with tungsten polyacid ammonium (NH
4)
4w
8o
26mass ratio be 50: 1) be 1: 1 according to the mass ratio of solvent acetonitrile and cyclohexanone-oxime, the mass ratio of cyclohexanone-oxime and catalyzer is 60: 1, reacts under be 280 DEG C of pressure being 1.5MPa in temperature.The result of reacting 2 hours is as follows: cyclohexanone-oxime transformation efficiency is 94%; Hexanolactam selectivity is 99%.
Embodiment 9
Identical with the method for embodiment 1, unlike, TS-1 by etc. the HTS of weight replace.
The result of reacting 2 hours is as follows: cyclohexanone-oxime transformation efficiency is 96%; Hexanolactam selectivity is 99%.
Embodiment 10
Identical with the method for embodiment 1, unlike, TS-1 by etc. the Ti-MCM-41 (for by prior art: Corma etc., Chem.Commun., the method preparation described in 1994,147-148, titanium oxide content is 3%) of weight replace.
The result of reacting 2 hours is as follows: cyclohexanone-oxime transformation efficiency is 91%; Hexanolactam selectivity is 98%.
Embodiment 11
Identical with the method for embodiment 1, unlike, TS-1 by etc. the Ti-Beta of weight (for by prior art: TakashiTatsumi etc., J.Chem.Soc., method preparation described in Chem.Commun.1997,677-678, titanium oxide content is 2.6%) replace.
The result of reacting 2 hours is as follows: cyclohexanone-oxime transformation efficiency is 93%; Hexanolactam selectivity is 95%.
Embodiment 12
Identical with the method for embodiment 1, unlike, phosphorus heteropoly tungstic acid H
3pW
12o
40add-on constant, the weight ratio of TS-1 and phosphorus heteropoly tungstic acid is 1000: 1.
The result of reacting 2 hours is as follows: cyclohexanone-oxime transformation efficiency is 92%; Hexanolactam selectivity is 90%.
Embodiment 13
Identical with the method for embodiment 1, unlike, the hexanaphthene of the weight such as use replaces toluene as solvent.
The result of reacting 2 hours is as follows: cyclohexanone-oxime transformation efficiency is 99%; Hexanolactam selectivity is 99%.
As can be seen from embodiment and comparative example: the inventive method catalytic activity is high, selectivity is good.
Claims (9)
1. the preparation method of a hexanolactam, the method comprises: under rearrangement reaction condition, by cyclohexanone-oxime and catalyst exposure, it is characterized in that, said contact carries out under temperature is 100-350 DEG C and pressure is the condition of 0.1-3.0MPa, the mass ratio of cyclohexanone-oxime and catalyzer is 1-100: 1, said catalyzer contains HTS and multiple-metal oxygen-containing is sour and/or Polyoxometalate, ratio 0.1-100: 1 of HTS and multiple-metal oxygen-containing acid or its salt in catalyzer, described contact is carried out in a solvent, the weight ratio of described cyclohexanone-oxime and solvent is 1: 0.1-100, described solvent is hexanaphthene.
2., according to the process of claim 1 wherein, described multiple-metal oxygen-containing acid is heteropolyacid and/or isopoly-acid.
3. the metallic element according to the method for claim 2, wherein, in described multiple-metal oxygen-containing acid be selected from IVB race, VB race, group vib and VIIB race metallic element one or more.
4. the metallic element according to the method for claim 2, wherein, in described multiple-metal oxygen-containing acid be selected from VB race, group vib metallic element one or more.
5. the metallic element according to the method for claim 4, wherein, in described multiple-metal oxygen-containing acid is one or more in molybdenum, tungsten, vanadium, chromium, tantalum and niobium.
6. according to the method for claim 5, wherein, described multiple-metal oxygen-containing acid be phosphorus heteropoly tungstic acid, phosphato-molybdic heteropolyacid, phosphorus vanadium heteropolyacid, molybdenum vanadium heteropolyacid, molybdenum heteropoly tungstic acid, substituted complexes, metallic element molybdenum formed isopoly-acid, metallic element tungsten formed isopoly-acid and metallic element vanadium formed isopoly-acid in one or more.
7. according to the method for claim 1, wherein, described HTS is at least one in the HTS of the HTS of MFI structure, the HTS of MEL structure, the HTS of BEA structure, the HTS of MWW structure, the HTS of MOR structure, the HTS of TUN structure and two-dimentional hexagonal structure.
8. according to the method for claim 7, wherein, described HTS is the HTS of MFI structure, and described HTS crystal grain is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.
9., according to the method for claim 1, it is characterized in that temperature is 150-300 DEG C, pressure is 0.1-2.5MPa.
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| CN1314348A (en) * | 2001-03-30 | 2001-09-26 | 清华大学 | Method for synthesizing hexanolactam by using titanium silicon molecular sieve to catalyze gas phase rearrangement of cyclohexanone-oxime |
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