CN1191125C - Separation process of molecular sieve catalyst in ketone oxamidinating reaction system - Google Patents
Separation process of molecular sieve catalyst in ketone oxamidinating reaction system Download PDFInfo
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- CN1191125C CN1191125C CNB021002274A CN02100227A CN1191125C CN 1191125 C CN1191125 C CN 1191125C CN B021002274 A CNB021002274 A CN B021002274A CN 02100227 A CN02100227 A CN 02100227A CN 1191125 C CN1191125 C CN 1191125C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention discloses a separating method of titanium silicalite molecular sieves in a ketone ammoximation system. In a ketone ammoximation system of water mutually soluble low-carbon alcohol with a concentration of 30 to 50 wt% and excessive ammonia water, materials including the titanium silicalite molecular sieves are deposited in a depositing device for at least 10 minutes at a temperature of 60 to 85 DEG C and a linear speed rate of 0.5 to 3 cm/min. The method is capable of realizing the continuous separation of the titanium silicalite molecular sieves from reaction liquid with a good separation effect, and is suitable for cyclohexanone ammoximation systems directly using the titanium silicalite molecular sieves whose granularity is from 0.1 to 0.3 mum as catalysts.
Description
Technical field
The invention relates to the separation method of a kind of reaction product and molecular sieve catalyst, further say so about a kind of in ketone oxamidinating reaction system the separation method of reaction product ketoxime and molecular sieve catalyst.
Background technology
Cyclohexanone-oxime is the key intermediate of synthesis of caprolactam, is a kind of important chemical material, mainly as the raw material nylon 6 monomeric raw materials of preparation fiber and nylon 6 and engineering plastics.
About the preparation of cyclohexanone-oxime, in documents such as EP0384390, EP0311983 and EP0496385, disclosure is arranged all.EniChem company at first discloses the method that cyclohexanone oxamidinating generates cyclohexanone-oxime, is to exist next step to generate the process of cyclohexanone-oxime at the trimethyl carbinol or toluene solvant and titanium-silicon molecular sieve catalyst pimelinketone, ammonia, hydrogen peroxide.Characteristics such as this method has the reaction conditions gentleness, technology is simple, plant investment is few, the three wastes are few, environmentally friendly.But the titanium-silicon molecular sieve catalyst that this method adopted is not the former powder of HTS, but with molecular screen primary powder add behind the caking agent through spray shaping be granularity between 5～100 μ m, mean particle size is to use behind the 20 μ m; Also having disclosed in EP0496385 and at inside reactor the aperture being set is the technology of the porous plate of 5 μ m with separating catalyst.
In the above-mentioned existing technology, there are the following problems to use the molecular sieve of moulding and the setting of porous plate:
(1) use of caking agent in the moulding of molecular sieve and moulding process has not only caused the loss of molecular sieve, and influential to the pore volume and the specific surface area of catalyzer;
(2) porous plate that 5 μ m directly are installed in reactor is tackled molecular sieve catalyst, although separate fairly simplely, so little hole is not having under the situation of blowback, is very easy to stop up, this situation has also proposed very high requirement to stirring simultaneously, stirs and freely is not easy to cause the parking accident; And the built-in separative element of reactor, all very inconvenience of its maintenance and replacing operation;
(3) molecular sieve catalyst after the moulding causes wearing and tearing because of stirring, through the porous plate of 5 μ m and run off.
Summary of the invention
The object of the present invention is to provide a kind of the deficiencies in the prior art that overcome, can be at directly being the product ketoxime of ketone oxamidinating reaction system of catalyzer and the separation method of molecular sieve catalyst with the HTS.
The separation method of molecular sieve catalyst is to comprise that the heavy % of reaction product ketoxime and 0.5-10, granularity are that the reaction mass of HTS of 0.1-0.3 μ m is in settling vessel in the ketone oxamidinating reaction system provided by the present invention, under temperature 60-85 ℃, with the 0.5-3 cm per minute, the linear rate of preferred 1-2 cm per minute, settling time is not less than 10 minutes, preferred 10-20 minute.
In method provided by the invention, said ketone oxamidinating reaction system is made up of reaction raw materials low-carbon alcohol, ammoniacal liquor, pimelinketone and hydrogen peroxide, and this reaction raw materials is formation reaction product ketoxime in the presence of HTS.Said low-carbon alcohol is selected from a kind of in methyl alcohol, ethanol, Virahol or the trimethyl carbinol or two or more mixture in them, and in system, low-carbon alcohol concentration is the heavy % of 30-50; Said ammoniacal liquor is excessive to the mole number of pimelinketone, and its concentration is the heavy % of 0.2-6.0.
Separation method provided by the invention is reaction product and HTS to be drawn out to reactor separate outward, fully rely on the settlement action of molecular sieve in the reaction feed liquid, realize that HTS and the continuous of reaction product separate, method good separating effect provided by the invention, solid content is few in the clear liquid, all be no more than 10ppm, mostly below 5ppm, it is that the HTS of 0.1-0.3 μ m is the cyclohexanone oxamidinating reaction system of catalyzer that this separation method is adapted to directly to adopt granularity.
Description of drawings
Accompanying drawing is the synoptic diagram that the invention provides the ketone oxamidinating reaction system at method place.In the accompanying drawings, 1 is constant temperature oil bath, and 2 is thermometer, and 3 are the tank level control pipe, and 4 is there-necked flask, and 5 is magnetic stirring apparatus, and 6 is recycle pump, and 7 is sedimentation pipe, and 8 is the feed liquid receiving flask.
Embodiment
The following examples will the present invention is described further.
In each of the embodiments described below, used HTS, granularity are 0.1-0.3 μ m, and the Chang Ling catalyst plant is produced; Pimelinketone is a hawk mountain petroleum chemical plant product, and the hydrogen peroxide of 27.5 heavy % is a Dongting Lake nitrogen fertilizer plant product; Liquefied ammonia is Beijing Chemical Testing Factory's product; The trimethyl carbinol is Beijing smooth-going chemical industry company limited Industrial products.
In an embodiment, the separating effect of HTS is determined by solid content in the analysis clear liquid.The analytical procedure of solid content is in the outlet clear liquid: get 100 milliliters of liquid from purified liquor outlet, be placed in the beaker, complete the trimethyl carbinol and water evaporation as far as possible in oil bath, then liquid is moved to crucible, 120 ℃ of dryings 4 hours, then in muffle furnace in 400～500 ℃ of roastings 2～3 hours, at last crucible is accurate to 0.0002g on analytical balance and weighs, thereby obtain solid content in the clear liquid.
As shown in drawings, the there-necked flask of placing in constant temperature oil bath 14 is the ketone oxamidinating reactor, reaction feed liquid hybrid reaction under the stirring of magnetic stirring apparatus 5, slurry in the reactor relies on high-order differential pressure to enter settling vessel 7, by thermometer 2 thermometrics, guarantee the temperature of feed liquid in settling vessel, material in settling vessel the residence time greater than 10 minutes.The denseer slurries in sedimentation pipe bottom return in the there-necked flask 4 so that catalyzer is reused by 6 dozens of circulations of recycle pump, and the top clear liquid enters feed liquid receiving flask 8 as the discharging of qualified product.
Keeping in the there-necked flask 4 ammonia concentration is 1.8 heavy %, and t-butanol solvent concentration is 40.2 heavy %, 80 ℃ of reaction mass temperature, and temperature of charge is 65 ℃ in the settling vessel 7, and the material linear rate is 1.8 cm per minute, and material residence time in settling vessel 7 is 12 minutes.The concentration of the HTS that records from feed liquid receiving flask 8 is 2ppm.
Keeping in the there-necked flask 4 ammonia concentration is 3.0 heavy %, and alcohol solvent concentration is 40.2 heavy %, 80 ℃ of reaction mass temperature, and temperature of charge is 75 ℃ in the settling vessel 7, and the material linear rate is 3.0 cm per minute, and material residence time in settling vessel 7 is 12 minutes.The concentration of the HTS that records from feed liquid receiving flask 8 is 9ppm.
Keeping in the there-necked flask 4 ammonia concentration is 5.0 heavy %, and isopropanol solvent concentration is 35.2 heavy %, 80 ℃ of reaction mass temperature, and temperature of charge is 80 ℃ in the settling vessel 7, and the material linear rate is 1.0 cm per minute, and material residence time in settling vessel 7 is 12 minutes.The concentration of the HTS that records from feed liquid receiving flask 8 is 6ppm.
Keeping in the there-necked flask 4 ammonia concentration is 0.5 heavy %, and methanol solvate concentration is 45.5 heavy %, 80 ℃ of temperature of charge, and temperature of charge is 70 ℃ in the settling vessel 7, material is that 2.0 cm per minute stopped 11 minutes with linear rate.The concentration of the HTS that records from feed liquid receiving flask 8 is 5ppm.
Keeping in the there-necked flask 4 ammonia concentration is 1.8 heavy %, and t-butanol solvent concentration is 40.2 heavy %, 80 ℃ of reaction mass temperature, and temperature of charge is 65 ℃ in the settling vessel 7, and the material linear rate is 2.4 cm per minute, and material residence time in settling vessel 7 is 12 minutes.The concentration of the HTS that records from feed liquid receiving flask 8 is 6ppm.
Keeping in the there-necked flask 4 ammonia concentration is 1.8 heavy %, and t-butanol solvent concentration is 40.2 heavy %, 80 ℃ of reaction mass temperature, and temperature of charge is 80 ℃ in the settling vessel 7, and the material linear rate is 1.8 cm per minute, and material residence time in settling vessel 7 is 12 minutes.The concentration of the HTS that records from feed liquid receiving flask 8 is 4ppm.
Claims (5)
1, the separation method of molecular sieve catalyst in a kind of ketone oxamidinating reaction system, it is characterized in that to comprise that the heavy % of reaction product ketoxime and 0.5-10, granularity are that the reaction mass of HTS of 0.1-0.3 μ m is in settling vessel, under temperature 60-85 ℃, with the linear rate of 0.5-3 cm per minute, the settling time is not less than 10 minutes.
2, in accordance with the method for claim 1, it is characterized in that said ketone oxamidinating reaction system is made of formation reaction product ketoxime in the presence of HTS the low-carbon alcohol, ammoniacal liquor, pimelinketone and the hydrogen peroxide that dissolve each other with water.
3, in accordance with the method for claim 1, it is characterized in that the linear rate of said reaction mass, sedimentation 10-20 minute with the 1-2 cm per minute.
4, according to claim 1 or 2 described methods, it is characterized in that in the said reaction system that low-carbon alcohol concentration is the heavy % of 30-50, low-carbon alcohol is selected from a kind of in methyl alcohol, ethanol, Virahol or the trimethyl carbinol or two or more mixture in them.
5, in accordance with the method for claim 1, it is characterized in that said ammonia concentration is the heavy % of 0.2-6.0.
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| CNB021002274A CN1191125C (en) | 2002-01-10 | 2002-01-10 | Separation process of molecular sieve catalyst in ketone oxamidinating reaction system |
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| CNB021002274A CN1191125C (en) | 2002-01-10 | 2002-01-10 | Separation process of molecular sieve catalyst in ketone oxamidinating reaction system |
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| CN1191125C true CN1191125C (en) | 2005-03-02 |
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