CN103288679B - Method for preparing cyclohexanone oxime - Google Patents
Method for preparing cyclohexanone oxime Download PDFInfo
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- CN103288679B CN103288679B CN201210049932.6A CN201210049932A CN103288679B CN 103288679 B CN103288679 B CN 103288679B CN 201210049932 A CN201210049932 A CN 201210049932A CN 103288679 B CN103288679 B CN 103288679B
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Abstract
The invention provides a method for preparing cyclohexanone oxime. The method comprises the following steps of: enabling cyclohexanone, ammonia, oxygen gas and hydrogen gas to be subjected to continuous reaction in a reactor in the presence of water and 100 parts by weight of fresh catalyst and/or regenerated catalyst, so as to obtain a reaction mixture, and adding 5-50 parts by weight of the fresh catalyst and/or the regenerated catalyst to the reactor when the concentration of the cyclohexanone in the reaction mixture exceeds 2wt% at first time; and when the concentration of the cyclohexanone in the reaction mixture exceeds 2wt% again, taking out 5-50 parts by weight of spent catalyst from the reactor, and adding 5-50 parts by weight of the fresh catalyst and/or the regenerated catalyst to the reactor, wherein the fresh catalyst and the regenerated catalyst contain titanium-silicon materials with MWW structures. According to the method for preparing cyclohexanone oxime, provided by the invention, a higher cyclohexanone conversion ratio and cyclohexanone oxime selectivity can be obtained in the case that water is used as a solvent.
Description
Technical field
The present invention relates to a kind of preparation method of cyclohexanone-oxime.
Background technology
Cyclohexanone-oxime is the key intermediate of synthesis of caprolactam, is a kind of important industrial chemicals, mainly as the raw material of feedstock nylon 6 monomer preparing fiber and nylon 6 and engineering plastics.
Because titanium-silicon molecular sieve catalyst has very important effect in organic compound selective oxidation, therefore, as one of the preparation method of cyclohexanone-oxime, propose under the existence of titanium-silicon molecular sieve catalyst, utilized hydrogen peroxide and ammonia to carry out oximes method to pimelinketone.In the past the advantage of this method does not need, as carried out the method for oximate with oxammonium sulfate, to utilize ammonia neutralisation of sulphuric acid.
Prepare in the process of cyclohexanone-oxime traditional cyclohexanone-oxime is oximes, need to use a large amount of hydrogen peroxide.But due to the chemical property extremely unstable of hydrogen peroxide, heat, light, heavy metal and other impurity can decompose, thus cause the utilization ratio of hydrogen peroxide lower; And hydrogen peroxide needs to take safety measures, as this in turn increases production cost in transport, storage and production process.
For attempting solving the problem, CN101314577A and CN101274765 discloses and introduces in titanium-silicon molecular sieve TS-1, TS-2 etc. by precious metals such as such as Pt, Pd, utilize hydrogen and cheap oxygen source (oxygen or air) fabricated in situ hydrogen peroxide, carry out catalysis of pimelinketone oximate simultaneously.But, the pimelinketone transformation efficiency of usual this method is lower, and need with an organic solvent as methyl alcohol, ethanol, propyl alcohol, Virahol etc., and with an organic solvent usually easily cause environmental pollution, and make the separation of product and other postprocessing working procedures comparatively complicated.
Summary of the invention
The object of the invention is, in order to overcome in existing cyclohexanone oxamidinating process the above-mentioned defect existed, to provide a kind of preparation method of new cyclohexanone-oxime.
The invention provides a kind of preparation method of cyclohexanone-oxime, the method comprises: under the existence of water and 100 weight part live catalysts and/or regenerated catalyst, pimelinketone, ammonia, oxygen and hydrogen is made to carry out successive reaction in the reactor, obtain reaction mixture, when the concentration control of described reaction mixture cyclohexanone is once more than 2 % by weight, in described reactor, add live catalyst and/or the regenerated catalyst of 5-50 weight part; When the concentration of described reaction mixture cyclohexanone is again more than 2 % by weight, from described reactor, take out the reclaimable catalyst of 5-50 weight part, and add live catalyst and/or the regenerated catalyst of 5-50 weight part in described reactor; Described live catalyst and regenerated catalyst contain the titanium silicalite material with MWW structure, described in there is MWW structure titanium silicalite material contain SiO
2, TiO
2, M
2o
3, E
mo
n, E and F, and SiO
2, TiO
2, M
2o
3, E
mo
n, E and F mol ratio be 1: x: y: a: b: c, wherein, M is selected from least one in Al, B, Cr, Ga and Fe; E is selected from least one in Ru, Rh, Pd, Re, Os, Ir, Pt and Au, and F is fluorine, m and n is for meeting the numerical value needed for E oxidation state, and to be 0.0005-0.2, y be x that 0.0001-0.1, a+b are 0.0001-0.2 and a/b < 1, c is 0-0.04.
Method according to the present invention has the following advantages:
(1) method according to the present invention can obtain higher pimelinketone transformation efficiency and cyclohexanone-oxime selectivity;
(2) in described method of the present invention, by making hydrogen and oxygen in situ synthesize hydrogen peroxide, avoiding hydrogen peroxide and decomposing, thus the problem causing utilization ratio low;
(3) method according to the present invention can use water as solvent, and without the need to an organic solvent, makes the environmental protection more of whole reaction process.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The preparation method of cyclohexanone-oxime according to the present invention comprises: under the existence of water and 100 weight part live catalysts and/or regenerated catalyst, pimelinketone, ammonia, oxygen and hydrogen is made to carry out successive reaction in the reactor, obtain reaction mixture, when the concentration control of described reaction mixture cyclohexanone is once more than 2 % by weight, in described reactor, add live catalyst and/or the regenerated catalyst of 5-50 weight part; When the concentration of described reaction mixture cyclohexanone is again more than 2 % by weight, from described reactor, take out the reclaimable catalyst of 5-50 weight part, and add live catalyst and/or the regenerated catalyst of 5-50 weight part in described reactor; Described live catalyst and regenerated catalyst contain the titanium silicalite material with MWW structure, described in there is MWW structure titanium silicalite material contain SiO
2, TiO
2, M
2o
3, E
mo
n, E and F, and SiO
2, TiO
2, M
2o
3, E
mo
n, E and F mol ratio be 1: x: y: a: b: c, wherein, M is selected from least one in Al, B, Cr, Ga and Fe; E is selected from least one in Ru, Rh, Pd, Re, Os, Ir, Pt and Au, and F is fluorine, m and n is for meeting the numerical value needed for E oxidation state, and to be 0.0005-0.2, y be x that 0.0001-0.1, a+b are 0.0001-0.2 and a/b < 1, c is 0-0.04.
In the preferred case, when the concentration control of described reaction mixture cyclohexanone is once more than 2 % by weight, in described reactor, live catalyst and/or the regenerated catalyst of 10-40 weight part is added; When the concentration of described reaction mixture cyclohexanone is again more than 2 % by weight, from described reactor, take out the reclaimable catalyst of 10-40 weight part, and add live catalyst and/or the regenerated catalyst of 10-40 weight part in described reactor.
The amount of the catalyzer (live catalyst and/or regenerated catalyst) added in described reactor when the concentration control of described reaction mixture cyclohexanone oxime is once more than 2 % by weight, and the amount of the amount of the catalyzer (reclaimable catalyst) taken out from described reactor when the concentration of described reaction mixture cyclohexanone is again more than 2 % by weight and the catalyzer (live catalyst and/or regenerated catalyst) of interpolation, three can be identical or different, preferably identical.
In the present invention, live catalyst, regenerated catalyst and reclaimable catalyst are only for the catalyzer of different steps in distinguishing reaction process, the catalyzer added in reactor is called live catalyst or regenerated catalyst, the catalyzer taken out from reactor is called reclaimable catalyst, but now reclaimable catalyst not represents this catalyzer complete deactivation.
In the present invention, term " again more than 2 % by weight " refers to all batches after first time is more than 2 % by weight, also the concentration control secondary namely not only comprising described reaction mixture cyclohexanone oxime more than 2 % by weight, also comprise described reaction mixture cyclohexanone oxime concentration third time, the 4th time, the 5th inferior all more than 2 % by weight batch.
In one embodiment, the composition described in the titanium silicalite material of MWW structure is expressed as SiO
2: xTiO
2: yM
2o
3: aE
mo
n: bE, wherein, x is 0.0005-0.2, y is that 0.0001-0.1, a+b are 0.0001-0.2 and a/b < 1.
In another kind of preferred implementation, described in there is the titanium silicalite material of MWW structure composition be expressed as SiO
2: xTiO
2: yM
2o
3: aE
mo
n: bE:cF, wherein, to be 0.0005-0.2, y be x that 0.0001-0.1, a+b are 0.0001-0.2 and a/b < 1, c is 0.001-0.04.
Further preferred, have in the titanium silicalite material of MWW structure described, x is 0.005-0.2, y be 0.0001-0.05, a+b is 0.0001-0.05.
For the selection of M element, the above-mentioned element enumerated all can play the effect of the structure of auxiliary carrying titanium silicalite material, the angle that can not have an impact to the catalytic activity of titanium silicalite material (reaction as catalysis of pimelinketone oximate of the present invention) from a small amount of existence of this element is considered, preferred M is boron (B) and/or aluminium (Al), and more preferably M is B.
For the selection of E element, the above-mentioned element enumerated all has hydrogen catalyzed and ability that is oxygen Hydrogen Peroxide, and because Pt, Pd and Au have higher catalytic activity, especially Pt and Pd, therefore preferably E is Pt and/or Pd.
In the present invention, described titanium silicalite material can be prepared according to the method for routine.Concrete, the preparation method of described composite catalyst prepares preferably by the method comprised the following steps:
(i) by silicon-containing compound, titanium-containing compound, containing element M compound, template and water mixing, element M is selected from least one in Al, B, Cr, Ga and Fe, and silicon-containing compound is with SiO
2meter, titanium-containing compound are with TiO
2meter, containing the compound of element M with M
2o
3meter, with molar ratio computing, silicon-containing compound: titanium-containing compound: the compound containing M element: template: water=1: 0.001-0.5: 0.0005-5: 0.1-5: 5-150, described template is piperidines and/or hexamethylene imine; Said mixture is crystallization under crystallization condition, and described crystallization condition comprises: temperature is 130-200 DEG C, the time is 5-200 hour, after crystallization more successively through filtering, washing and dry;
(ii) step (i) products therefrom contacts with containing mineral acid or organic acid acidic solution, the weight ratio of step (i) products therefrom and acidic solution is 1: 5-100, in described acidic solution, mineral acid or organic acid concentration are 0.1-18mol/L, contact conditions comprises: temperature is 50-200 DEG C, the time is 10 minutes-72 hours, after contact again through filtering, washing and dry;
(iii) at 400-700 DEG C by step (ii) products therefrom roasting 3-20 hour;
(iv) step (iii) products therefrom, noble metal source are contacted in water with reductive agent, noble metal source is in precious metal element, precious metal element is selected from least one in Ru, Rh, Pd, Re, Os, Ir, Pt and Au, in mole, the silicon-containing compound of step (i): noble metal source: water=1: 0.0005-0.5: 5-150, noble metal source: reductive agent=1: 0.1-10, the condition of described contact comprises: temperature is 80-200 DEG C, the time is 2-30 hour, then through filtering and drying.
In step (i), in mole, preferred silicon-containing compound: titanium-containing compound: the compound containing M element: template: water=1: 0.001-0.25: 0.05-0.5: 0.5-3: 15-50.For using silicon-containing compound, titanium-containing compound, containing the kind of the compound of M element, there is no particular limitation, such as, described silicon-containing compound is selected from least one in silicic acid, silicate, silicon oxide, silica gel and silicic acid tetraalkyl ester, preferred silicic acid tetraalkyl ester, more preferably the carbonatoms of alkyl is the silicic acid tetraalkyl ester (as tetraethyl orthosilicate etc.) of 1-4; Described titanium compound is selected from least one in halogenated titanium, titanium oxide and tetralkyl titanate, and halogenated titanium and tetralkyl titanate can enumerate titanium tetrafluoride, titanium tetrachloride, tetraethyl titanate, titanium isopropylate and tetrabutyl titanate; The described compound containing M element is preferably boron-containing compound, and boron-containing compound is selected from least one in boric acid, borate, boron oxide, halogenation boron and trialkylboron, and preferred boron-containing compound adds with the form of borate (as Sodium Tetraborate etc.).To silicon-containing compound, titanium-containing compound, containing the order of addition of the compound of M element and template, there is no particular limitation, as long as make above-mentioned substance mix in water, in addition, do not have particular requirement for the time mixed and temperature, preferred mixing time is no more than 5 hours, temperature is no more than 100 DEG C.Described crystallization condition preferably includes: temperature is 150-190 DEG C, the time is 15-80 hour.Filtration after crystallization, washing and drying all adopt ordinary method.
In step (ii), can contain mineral acid or organic acid in acidic solution, mineral acid can be selected from least one in hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and described organic acid is selected from least one in formic acid, acetic acid, propionic acid and tartrate.The weight ratio of step (i) products therefrom and acidic solution is preferably 1: 10-50.In described acidic solution, mineral acid or organic acid concentration are preferably 0.6-5mol/L, and contact conditions preferably includes: temperature is 80-120 DEG C, the time is 2-30 hour, contact the filtration of after product, washing and drying and all adopt ordinary method.
In step (iii), in order to prevent calcining temperature too high cause may to MWW structure produce destroy, therefore preferred at 400-600 DEG C by step (ii) products therefrom roasting 3-10 hour.
In step (iv), preferred noble metal source is for containing palladium and/or containing platinic compound, compound containing palladium and/or platiniferous can for containing organism and/or the inorganics of palladium and/or platiniferous, inorganics such as containing palladium and/or platiniferous can be selected from oxide compound, halogenide, carbonate, at least one in nitrate and complex compound etc., particularly, palladous oxide can be enumerated containing palladium compound, carbonate palladium, Palladous chloride, palladium hydroxide, dichloro diamino palladium, two ammino palladium nitrate, palladium and palladium acetylacetonate etc., platinum oxide can be enumerated containing platinic compound, platinic hydroxide, Platinic chloride, platinum chloride (II), platinum chloride (IV), cyaniding platinum (II) and dichloro four ammino platinum etc.In mole, the silicon-containing compound of preferred steps (i): noble metal source: water=1: 0.0005-0.3: 10-50, noble metal source: reductive agent=1: 0.5-5, described reductive agent can be hydrazine, hydroborate or Citrate trianion, described hydrazine can be selected from least one in hydrazine hydrate, hydrazine hydrochloride and hydrazonium sulfate, described hydroborate can be sodium borohydride and/or POTASSIUM BOROHYDRIDE, and described Citrate trianion can be Trisodium Citrate and/or Tripotassium Citrate.The condition optimization of described contact comprises: temperature is 100-130 DEG C, the time is 2-10 hour.Filtration and dry (as the 1-5 hour dry at 100-200 DEG C) of contact after product can adopt ordinary method.
When the titanium silicalite material of aforesaid method for the preparation of fluorine-containing MWW structure, fluorochemicals (in fluorine element) can be added in the mixing of step (i).The consumption of described fluorochemicals suitably can be chosen in a big way, such as, in mole, silicon-containing compound: fluorochemicals=1: 0.01-0.3.In addition, the kind for fluorochemicals has no particular limits, described fluorochemicals can be selected from Sodium Fluoride, Potassium monofluoride, Neutral ammonium fluoride, hydrofluoric acid, silicofluoric acid, Sodium Silicofluoride and potassium silicofluoride one or more.
The method that above-mentioned preparation has the titanium silicalite material of MWW structure is only a kind of preferred implementation of the present invention, is directed to the selection that noble metal source adds opportunity, can with reference to the method described in CN101274765A.Particularly, in step (i), adding noble metal source, (consumption of noble metal source is identical with step (iv), omit step (iv)), after crystallization, roasting, then in following step, make product of roasting contact with reductive agent.
In described live catalyst and regenerated catalyst, described in there is the titanium silicalite material of MWW structure content be preferably more than 50 % by weight, be more preferably more than 70 % by weight.
In the present invention, as long as there is MWW structure described in using and containing the titanium silicalite material of precious metal element as catalyzer, just with pimelinketone, ammonia, hydrogen and oxygen for raw material, cyclohexanone-oxime can be prepared.In addition, also described titanium silicalite material and other HTS can be combined and use as catalyzer, other HTS can be selected from HTS that is known and commercially available, that pimelinketone oximation reaction is had to catalytic activity, such as, be selected from one or more in TS-1 HTS, TS-2 HTS and the hollow HTS of HTS.When using described titanium silicalite material and other HTS to combine as catalyzer, the consumption for other HTS has no particular limits.In described live catalyst and regenerated catalyst, the content of other HTS described can be 0-50 % by weight, is preferably 0-30 % by weight, is more preferably 1-20 % by weight.
In the preparation method of cyclohexanone-oxime of the present invention, the condition of pimelinketone, ammonia, oxygen and hydrogen successive reaction can be comprised: temperature is 50-180 DEG C, pressure is 0.1-3MPa, and during the liquid of pimelinketone, volume space velocity is 0.1-20h
-1.In the present invention, described pressure refers to absolute pressure.
In the preparation method of cyclohexanone-oxime of the present invention, the mol ratio of pimelinketone, ammonia, oxygen and hydrogen can be 1: 1-10: 1-5: 1-5, and the weight ratio of pimelinketone and water is 1: 2-50.In the preferred case, the mol ratio of pimelinketone and ammonia, oxygen, hydrogen is 1: 1-2: 1-3: 1-2, and the weight ratio of catalyzer and water is 1: 20-200, and the weight ratio of pimelinketone and water is 1: 1-10.
The preparation method of described cyclohexanone-oxime of the present invention can adopt fixed-bed reactor or slurry bed reactor operation.Concrete operating process can comprise: first live catalyst and/or regenerated catalyst and stirring solvent are formed slurries, then in reactor, add slurries, pimelinketone, ammonia, oxygen and hydrogen continuously, continuous separated product.Ammonia can add with the form of ammonia or ammoniacal liquor, and preferred ammonia adds with the form of ammonia; When adding with the form of ammoniacal liquor, the water in ammoniacal liquor also needs to count in above-mentioned each material proportion.In order to improve production safety coefficient, also can add rare gas element for reducing the ratio of hydrogen in gaseous mixture, described rare gas element can be selected from nitrogen, helium or argon gas etc.
The invention will be further described by the following examples.
TS-1 HTS used be in the following Examples and Comparative Examples capable by the 296th page of 9-24 in document [Cyclohexane Oxidation Catalyzed by Titanium Silicalite (T S-1) With HydrogenPeroxide Journal of Natural Gas Chemistry 2001,10 (4): 295-307] described by (TS-1) sieve sample of preparing of method.
(Hunan Jian Chang company manufactures the Industrial products of HTS described in hollow HTS HTS system CN1301599A used in the following Examples and Comparative Examples, 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), content of titanium dioxide is 2.5 % by weight.
In the following Examples and Comparative Examples, pimelinketone transformation efficiency and cyclohexanone-oxime selectivity can calculate according to following calculating formula.
Mole number × 100% of the pimelinketone of pimelinketone transformation efficiency=(molar weight of the molar weight-product cyclohexanone of the pimelinketone of charging)/charging
Molar weight/(molar weight of the molar weight-product cyclohexanone of the pimelinketone of charging) × 100% of cyclohexanone-oxime selectivity=product cyclohexanone oxime
Wherein, the data acquisition of pimelinketone and cyclohexanone-oxime obtains with gas-chromatography (Shimadzu GC14B, DB-1 capillary column 30m × 0.25mm × 0.25 μm) analysis.
Embodiment 1
The present embodiment is for illustration of the preparation method of described cyclohexanone-oxime of the present invention.
(1) Kaolinite Preparation of Catalyst
A water glass, tetrabutyl titanate, potassium borate, hexamethylene imine, Sodium Fluoride and water are uniformly mixed 40 minutes with mol ratio 1: 0.1: 0.05: 1: 0.3: 20 by () at 80 DEG C, then mixture be warming up to 190 DEG C and maintain 15 hours, then filtering, washing with water and drying.
B (), at 110 DEG C, by the product obtained in (b), according to weight ratio 1: 30 and 1mol/L sulfuric acid contact 3 hours, is then filtered, to be washed with water and dry.
C () is by the roasting 8 hours at 500 DEG C of the product that obtains in (b).
D () is at 120 DEG C, the product making to obtain in (c), platinum chloride (II) contact 6 hours with sodium borohydride in water, in mole, the water glass used in (a): platinum chloride (II): water=1: 0.15: 50, platinum chloride (II): sodium borohydride=1: 0.5, then filter, wash with water and at 180 DEG C dry 3 hours, obtain titanium silicalite material Al.
Use method of X-ray diffraction, X-ray fluorescence spectra analysis assay method and 19F MAS-NMR nuclear magnetic resonance spectroscopy method to analyze to the titanium silicalite material obtained, result determines that this titanium silicalite material has MWW structure, and composition can be expressed as SiO
2: 0.089TiO
2: 0.0048B
2o
3: 0.0007PtO:0.0034Pt:0.0027F.
(2) cyclohexanone-oxime is prepared
Be add the middle described titanium silicalite material A1 prepared of 6 grams of above-mentioned steps (1) in the slurry bed reactor of 1 liter as catalyzer to capacity, maintenance temperature is 100 DEG C, pressure is 2.0MPa.Then, pimelinketone, water, ammonia, oxygen, hydrogen and nitrogen is added in reactor, wherein, the speed that adds of pimelinketone is 60 Grams Per Hours, and the mol ratio of pimelinketone, ammonia, oxygen, hydrogen, nitrogen G&W is 1: 2: 5: 3: 20: 2, start successive reaction, and collect reaction mixture, and catalyzer is turned back in reactor.
Learning by carrying out analysis to reaction mixture, starting about after 5 hours in reaction, find that the content of reaction mixture cyclohexanone is more than 2 % by weight, in reactor, therefore additionally add 2 grams of catalyzer (also i.e. described titanium silicalite material A1).Start about after 60 hours in reaction, find that the content of reaction mixture cyclohexanone is more than 2 % by weight, therefore from reactor, 2 grams of catalyzer (being converted into dry weight) are taken out, and by remaining catalyzer Returning reactor, extra interpolation 2 grams of described titanium silicalite material A1 in reactor simultaneously.Start about after 90 hours in reaction, find that the content of reaction mixture cyclohexanone is more than 2 % by weight, therefore from reactor, 2 grams of catalyzer (being converted into dry weight) are taken out, and by remaining catalyzer Returning reactor, extra interpolation 2 grams of described titanium silicalite material A1 in reactor simultaneously.
The reaction mixture that takes out after 100 hours of reaction beginning is analyzed, result, by analysis with calculate, pimelinketone rate of rotation is 31.5%, and cyclohexanone-oxime selectivity is 99.5%.
Comparative example 1
(1) Kaolinite Preparation of Catalyst
Relative to 100 grams of hollow HTS HTS, 3 grams of platinum chlorides (II) (in platinum element) and 0.58 gram of sodium borohydride is added in 2 premium on currency, contact reacts 2 hours at 130 DEG C, then filter, wash with water and at 180 DEG C dry 3 hours, obtain titanium silicalite material D1.
Use method of X-ray diffraction and X-ray fluorescence spectra analysis to measure to the titanium silicalite material obtained, result determines that the composition of this titanium silicalite material can be expressed as SiO
2: 0.08TiO
2: 0.0004PtO:0.0047Pt.
(2) cyclohexanone-oxime is prepared
Method according to embodiment 1 prepares cyclohexanone-oxime, and difference is, in preparation process, replaces described titanium silicalite material A1 with the described titanium silicalite material D1 of identical weight.
The reaction mixture that takes out after 100 hours of reaction beginning is analyzed, result, by analysis with calculate, pimelinketone transformation efficiency is 7.8%, and cyclohexanone-oxime selectivity is 85.4%.
Comparative example 2
According to method Kaolinite Preparation of Catalyst and the cyclohexanone-oxime of embodiment 1, difference is, directly to adding 10 grams of described titanium silicalite material A1 in reactor, and carries out reaction continuously and prepares cyclohexanone-oxime.
The reaction mixture that takes out after 100 hours of reaction beginning is analyzed, result, by analysis with calculate, pimelinketone transformation efficiency is 11.5%, and cyclohexanone-oxime selectivity is 89.2%.
Embodiment 2
The present embodiment is for illustration of the preparation method of described cyclohexanone-oxime of the present invention.
(1) Kaolinite Preparation of Catalyst
According to the method Kaolinite Preparation of Catalyst of embodiment 1, difference is, in preparation process, do not add Sodium Fluoride, thus obtained titanium silicalite material A2.
Use method of X-ray diffraction and X-ray fluorescence spectra analysis to measure to the titanium silicalite material obtained, result determines that this titanium silicalite material has MWW structure, composition can be expressed as SiO
2: 0.087TiO
2: 0.0047B
2o
3: 0.0006PtO:0.0035Pt.
(2) cyclohexanone-oxime is prepared
Method according to embodiment 1 prepares cyclohexanone-oxime, and difference is, replaces described titanium silicalite material A1 with the described titanium silicalite material A2 of identical weight.
The reaction mixture that takes out after 100 hours of reaction beginning is analyzed, result, by analysis with calculate, pimelinketone transformation efficiency is 28.9%, and cyclohexanone-oxime selectivity is 99.1%.
Embodiment 3
The present embodiment is for illustration of the preparation method of described cyclohexanone-oxime of the present invention.
(1) Kaolinite Preparation of Catalyst
A tetraethyl orthosilicate, tetraethyl titanate, Sodium Tetraborate, piperidines, hydrofluoric acid and water are uniformly mixed 2 minutes with mol ratio 1: 0.05: 0.2: 1.5: 0.11: 50 by () at 50 DEG C, then mixture be warming up to 150 DEG C and maintain 40 hours, then filtering, washing with water and drying.
B (), at 80 DEG C, by the product obtained in (b), contacts 10 hours according to weight ratio 1: 10 with 3mol/L hydrochloric acid, then filters, washes with water and drying.
C () is by the roasting 5 hours at 600 DEG C of the product that obtains in (b).
D () is at 100 DEG C, the product making to obtain in (c), two ammino palladium nitrate, dichloro four ammino platinum contact 3 hours with hydrazine hydrochloride in water, in mole, the tetraethyl orthosilicate used in (a): two ammino palladium nitrate: dichloro four ammino platinum: water=1: 0.01: 0.01: 40, two ammino palladium nitrate: dichloro four ammino platinum: hydrazine hydrochloride=1: 1: 3, then filter, wash with water and at 150 DEG C dry 4 hours, obtain titanium silicalite material A3.
Use method of X-ray diffraction and X-ray fluorescence spectra analysis to measure to the titanium silicalite material obtained, result determines that this titanium silicalite material has MWW structure, composition can be expressed as SiO
2: 0.04TiO
2: 0.0005B
2o
3: 0.0005PtO:0.0004PdO:0.003Pt:0.002Pd:0.001F.
(2) cyclohexanone-oxime is prepared
Be add the middle described titanium silicalite material A3 prepared of 6 grams of above-mentioned steps (1) in the slurry bed reactor of 1 liter as catalyzer to capacity, maintenance temperature is 85 DEG C, pressure is 0.25MPa.Then, pimelinketone, water, ammonia, oxygen, hydrogen and nitrogen is added in reactor, wherein, the speed that adds of pimelinketone is 6 Grams Per Hours, and the mol ratio of pimelinketone, ammonia, oxygen, hydrogen, nitrogen G&W is 1: 10: 3: 1: 20: 5, start successive reaction, and collect reaction mixture, and catalyzer is turned back in reactor.
Learning by carrying out analysis to reaction mixture, starting about after 6 hours in reaction, find that the content of reaction mixture cyclohexanone is more than 2 % by weight, therefore extra 1 gram of catalyzer (also i.e. described titanium silicalite material A3) in reactor.Start about after 65 hours in reaction, find that the content of reaction mixture cyclohexanone is more than 2 % by weight, therefore from reactor, 1 gram of catalyzer (being converted into dry weight) is taken out, and by remaining catalyzer Returning reactor, extra interpolation 1 gram of described titanium silicalite material A3 in reactor simultaneously.Start about after 93 hours in reaction, find that the content of reaction mixture cyclohexanone is more than 2 % by weight, therefore from reactor, 1 gram of catalyzer (being converted into dry weight) is taken out, and by remaining catalyzer Returning reactor, extra interpolation 1 gram of described titanium silicalite material A3 in reactor simultaneously.
The reaction mixture that takes out after 100 hours of reaction beginning is analyzed, result, by analysis with calculate, pimelinketone rate of rotation is 30.2%, and cyclohexanone-oxime selectivity is 99.4%.
Embodiment 4
The present embodiment is for illustration of the preparation method of described cyclohexanone-oxime of the present invention.
(1) Kaolinite Preparation of Catalyst
A tetraethyl orthosilicate, titanium tetrachloride, Sodium Tetraborate, piperidines, Sodium Silicofluoride and water are uniformly mixed 1 minute with mol ratio 1: 0.03: 0.3: 3: 1.2: 30 by () at 70 DEG C, then mixture be warming up to 160 DEG C and maintain 20 hours, then filtering, washing with water and drying.
B (), at 90 DEG C, by the product obtained in (b), contacts 24 hours according to weight ratio 1: 40 with 5mol/L hydrochloric acid, then filters, washes with water and drying.
C () is by the roasting 6 hours at 600 DEG C of the product that obtains in (b).
D () is at 130 DEG C, the product making to obtain in (c), Palladous nitrate contact 2 hours with hydrazonium sulfate in water, in mole, the tetraethyl orthosilicate used in (a): Palladous nitrate: water=1: 0.05: 30, Palladous nitrate: hydrazine hydrochloride=1: 1, then filter, wash with water and at 180 DEG C dry 3 hours, obtain titanium silicalite material A4.
Use method of X-ray diffraction and X-ray fluorescence spectra analysis to measure to the titanium silicalite material obtained, result determines that this titanium silicalite material has MWW structure, composition can be expressed as SiO
2: 0.027TiO
2: 0.0055B
2o
3: 0.0005PdO:0.0055Pd:0.04F.
(2) cyclohexanone-oxime is prepared
Be add the middle described titanium silicalite material A4 prepared of 6 grams of above-mentioned steps (1) in the slurry bed reactor of 1 liter as catalyzer to capacity, maintenance temperature is 150 DEG C, pressure is 3MPa.Then, pimelinketone, water, ammonia, oxygen, hydrogen and nitrogen is added in reactor, wherein, the speed that adds of pimelinketone is 100 Grams Per Hours, and the mol ratio of pimelinketone, ammonia, oxygen, hydrogen, nitrogen G&W is 1: 1: 1: 5: 20: 8, start successive reaction, and collect reaction mixture, and catalyzer is turned back in reactor.
Learning by carrying out analysis to reaction mixture, starting about after 4 hours in reaction, find that the content of reaction mixture cyclohexanone is more than 2 % by weight, in reactor, therefore additionally add 3 grams of catalyzer (also i.e. described titanium silicalite material A4).Start about after 58 hours in reaction, find that the content of reaction mixture cyclohexanone is more than 2 % by weight, therefore from reactor, 3 grams of catalyzer (being converted into dry weight) are taken out, and by remaining catalyzer Returning reactor, extra interpolation 3 grams of described titanium silicalite material A4 in reactor simultaneously.Start about after 89 hours in reaction, find that the content of reaction mixture cyclohexanone is more than 2 % by weight, therefore from reactor, 3 grams of catalyzer (being converted into dry weight) are taken out, and by remaining catalyzer Returning reactor, extra interpolation 3 grams of described titanium silicalite material A4 in reactor simultaneously.
The reaction mixture that takes out after 100 hours of reaction beginning is analyzed, result, by analysis with calculate, pimelinketone rate of rotation is 33.6%, and cyclohexanone-oxime selectivity is 99.8%.
Embodiment 5
The present embodiment is for illustration of the preparation method of described cyclohexanone-oxime of the present invention.
(1) Kaolinite Preparation of Catalyst
Prepare titanium silicalite material A4 according to the method for embodiment 4, and titanium silicalite material A4 is mixed with weight ratio 7: 3 with hollow HTS HTS, obtain catalyst A 5.
(2) cyclohexanone-oxime is prepared
Method according to embodiment 4 prepares cyclohexanone-oxime, and difference is, replaces described titanium silicalite material A4 by the described catalyst A 5 of identical weight.
The reaction mixture that takes out after 100 hours of reaction beginning is analyzed, result, by analysis with calculate, pimelinketone transformation efficiency is 26.9%, and cyclohexanone-oxime selectivity is 99.2%.
Embodiment 6
The present embodiment is for illustration of the preparation method of described cyclohexanone-oxime of the present invention.
(1) Kaolinite Preparation of Catalyst
Prepare titanium silicalite material A4 according to the method for embodiment 4, and titanium silicalite material A4 is mixed with weight ratio 5: 5 with titanium-silicon molecular sieve TS-1, obtain catalyst A 6.
(2) cyclohexanone-oxime is prepared
Method according to embodiment 4 prepares cyclohexanone-oxime, and difference is, replaces described titanium silicalite material A4 by the described catalyst A 6 of identical weight.
The reaction mixture that takes out after 100 hours of reaction beginning is analyzed, result, by analysis with calculate, pimelinketone transformation efficiency is 22.7%, and cyclohexanone-oxime selectivity is 99.1%.
As can be seen here, in the preparation method of described cyclohexanone-oxime of the present invention, when using water as solvent, higher pimelinketone transformation efficiency and cyclohexanone-oxime selectivity can be obtained.
Claims (8)
1. the preparation method of a cyclohexanone-oxime, the method comprises: under the existence of water and 100 weight part live catalysts and/or regenerated catalyst, pimelinketone, ammonia, oxygen and hydrogen is made to carry out successive reaction in the reactor, obtain reaction mixture, when the concentration control of described reaction mixture cyclohexanone is once more than 2 % by weight, in described reactor, add live catalyst and/or the regenerated catalyst of 5-50 weight part; When the concentration of described reaction mixture cyclohexanone is again more than 2 % by weight, from described reactor, take out the reclaimable catalyst of 5-50 weight part, and add live catalyst and/or the regenerated catalyst of 5-50 weight part in described reactor; Described live catalyst and regenerated catalyst contain the titanium silicalite material with MWW structure, described in there is MWW structure titanium silicalite material contain SiO
2, TiO
2, M
2o
3, E
mo
n, E and F, and SiO
2, TiO
2, M
2o
3, E
mo
n, E and F mol ratio be 1:x:y:a:b:c, wherein, F is fluorine, m and n is for meeting the numerical value needed for E oxidation state, and to be 0.0005-0.2, y be x that 0.0001-0.1, a+b are 0.0001-0.2 and a/b < 1, c is 0-0.04; Have in the titanium silicalite material of MWW structure described, M is B; E is Pt and/or Pd; The mol ratio of pimelinketone and ammonia, oxygen, hydrogen is 1:1-10:1-5:1-5, and the weight ratio of pimelinketone and water is 1:1-10.
2. method according to claim 1, wherein, when the concentration control of described reaction mixture cyclohexanone is once more than 2 % by weight, adds live catalyst and/or the regenerated catalyst of 10-40 weight part in described reactor; When the concentration of described reaction mixture cyclohexanone is again more than 2 % by weight, from described reactor, take out the reclaimable catalyst of 10-40 weight part, and add live catalyst and/or the regenerated catalyst of 10-40 weight part in described reactor.
3. method according to claim 1, wherein, described in there is the titanium silicalite material of MWW structure composition be expressed as SiO
2: xTiO
2: yM
2o
3: aE
mo
n: bE, wherein, x is 0.0005-0.2, y is that 0.0001-0.1, a+b are 0.0001-0.2 and a/b < 1.
4. method according to claim 1, wherein, described in there is the titanium silicalite material of MWW structure composition be expressed as SiO
2: xTiO
2: yM
2o
3: aE
mo
n: bE:cF, wherein, to be 0.0005-0.2, y be x that 0.0001-0.1, a+b are 0.0001-0.2 and a/b < 1, c is 0.001-0.04.
5. according to the method in claim 1,3 and 4 described in any one, wherein, have in the titanium silicalite material of MWW structure described, x is 0.005-0.2, y be 0.0001-0.05, a+b is 0.0001-0.05.
6. according to the method in claim 1,2,3 and 4 described in any one, wherein, in described live catalyst and regenerated catalyst, described in there is the titanium silicalite material of MWW structure content be more than 50 % by weight.
7. method according to claim 6, wherein, in described live catalyst and regenerated catalyst, described in there is the titanium silicalite material of MWW structure content be more than 70 % by weight.
8. method according to claim 1, wherein, the condition of described successive reaction comprises: temperature is 50-180 DEG C, pressure is 0.1-3MPa, and during the liquid of pimelinketone, volume space velocity is 0.1-20h
-1.
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|---|---|---|---|---|
| CN1709574A (en) * | 2005-04-18 | 2005-12-21 | 华东师范大学 | Titanium-silicon molecular sieve catalyst with MWW structure, and its preparing method and use |
| CN101274765A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Noble metal-contained micropore titanium-silicon material and preparation thereof |
| CN101314577A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Method for catalysis of pimelinketone oxamidine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709574A (en) * | 2005-04-18 | 2005-12-21 | 华东师范大学 | Titanium-silicon molecular sieve catalyst with MWW structure, and its preparing method and use |
| CN101274765A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Noble metal-contained micropore titanium-silicon material and preparation thereof |
| CN101314577A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Method for catalysis of pimelinketone oxamidine |
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