CN1432432A - 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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- CN1432432A CN1432432A CN02100227A CN02100227A CN1432432A CN 1432432 A CN1432432 A CN 1432432A CN 02100227 A CN02100227 A CN 02100227A CN 02100227 A CN02100227 A CN 02100227A CN 1432432 A CN1432432 A CN 1432432A
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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
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Abstract
In the ketone oxamidinating reaction system with water mutually soluble low-carbon alcohol of 30-50 wt% concentration and excessive ammonia water content, the material including titania-silica molecular sieve is deposited at 60-85 deg.c in deposition rate of 0.5-3 cm/min for at least 10 min. The present invention can realize the continuous separation of titania-silica molecular sieve from reaction liquid and is suitable for cyclohexanone oxamidinating reaction system with titania-silica molecular sieve catalyst of 0.1-0.3 micron size.
Description
Technical field
The invention relates to a kind of separation method of molecular sieve catalyst, further say so about a kind of separation method of the molecular sieve catalyst in ketone oxamidinating reaction system.
Background technology
Cyclohexanone oxime is the key intermediate of synthesis of caprolactam, is a kind of important chemical material, mainly as the raw material of raw material nylon 6 monomers that prepare 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 tert-butyl alcohol or toluene solvant and titanium-silicon molecular sieve catalyst cyclohexanone, ammonia, hydrogen peroxide.Characteristics such as this method has the reaction condition 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 bonding agent through spray shaping be granularity between 5～100 μ m, particle mean 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 bonding agent in the moulding of molecular sieve and forming process has not only caused the loss of molecular sieve, and influential to the pore volume and the specific area of catalyst;
(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 resolution 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 the separation method of molecular sieve catalyst that directly is the ketone oxamidinating reaction system of catalyst with the HTS.
The separation method of molecular sieve catalyst is to comprise that the heavy % of 0.5-10, granularity are that the reaction mass of HTS of 0.1-0.3 μ m is in settler in the ketone oxamidinating reaction system provided by the present invention, under temperature 60-85 ℃, with the 0.5-3 cm per minute, the wire rate of preferred 1-2 cm per minute, sedimentation time is not less than 10 minutes, preferred 10-20 minute.
In method provided by the invention, form by low-carbon alcohols, ammoniacal liquor, cyclohexanone and hydrogen peroxide in the said ketone oxamidinating reaction system.Said low-carbon alcohols is selected from a kind of in methyl alcohol, ethanol, isopropyl alcohol or the tert-butyl alcohol or two or more mixture in them, and in system, low-carbon alcohols concentration is the heavy % of 30-50; Said ammoniacal liquor is excessive to the molal quantity of cyclohexanone, and its concentration is the heavy % of 0.2-6.0.
Separation method provided by the invention is 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 reactant liquor 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 catalyst that this separation method is adapted to directly to adopt granularity.
Description of drawings
Accompanying drawing is the schematic 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 level control pipe, and 4 is there-necked flask, and 5 is magnetic stirring apparatus, and 6 is circulating pump, and 7 is sedimentation pipe, and 8 is the feed liquid receiving flask.
The specific embodiment
The following examples will the present invention is described further.
In each of the embodiments described below, used HTS, granularity is 0.1-0.3 μ m, the Chang Ling catalyst plant is produced; Cyclohexanone is a hawk mountain petrochemical 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 tert-butyl alcohol is Beijing smooth-going chemical industry Co., Ltd industrial products.
In an embodiment, the separating effect of HTS is determined by solid content in the analysis clear liquid.The analytical method 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 tert-butyl alcohol 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 assay 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 settler 7, by thermometer 2 thermometrics, guarantee the temperature of feed liquid in settler, material in settler the time of staying greater than 10 minutes.The denseer slurries in sedimentation pipe bottom return in the there-necked flask 4 so that catalyst is reused by 6 dozens of circulations of circulating pump, and the top clear liquid enters feed liquid receiving flask 8 as the discharging of qualified products.
Embodiment 1
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 settler 7, and the material wire rate is 1.8 cm per minute, and material time of staying in settler 7 is 12 minutes.The concentration of the HTS that records from feed liquid receiving flask 8 is 2ppm.
Embodiment 2
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 settler 7, and the material wire rate is 3.0 cm per minute, and material time of staying in settler 7 is 12 minutes.The concentration of the HTS that records from feed liquid receiving flask 8 is 9ppm.
Embodiment 3
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 settler 7, and the material wire rate is 1.0 cm per minute, and material time of staying in settler 7 is 12 minutes.The concentration of the HTS that records from feed liquid receiving flask 8 is 6ppm.
Embodiment 4
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 settler 7, material is that 2.0 cm per minute stopped 11 minutes with wire rate.The concentration of the HTS that records from feed liquid receiving flask 8 is 5ppm.
Embodiment 5
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 settler 7, and the material wire rate is 2.4 cm per minute, and material time of staying in settler 7 is 12 minutes.The concentration of the HTS that records from feed liquid receiving flask 8 is 6ppm.
Embodiment 6
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 settler 7, and the material wire rate is 1.8 cm per minute, and material time of staying in settler 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 0.5-10, granularity are that the reaction mass of HTS of 0.1-0.3 μ m is in settler, under temperature 60-85 ℃, with the wire rate of 0.5-3 cm per minute, the sedimentation time is not less than 10 minutes.
2, in accordance with the method for claim 1, it is characterized in that what said ketone oxamidinating reaction system was made up of the low-carbon alcohols, ammoniacal liquor, cyclohexanone 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 wire 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 alcohols concentration is the heavy % of 30-50, low-carbon alcohols is selected from a kind of in methyl alcohol, ethanol, isopropyl alcohol or the tert-butyl alcohol 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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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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| Application Number | Priority Date | Filing Date | Title |
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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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| CN1432432A true CN1432432A (en) | 2003-07-30 |
| CN1191125C CN1191125C (en) | 2005-03-02 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10654795B2 (en) | 2017-03-03 | 2020-05-19 | Chemical Technology Academy Of Shandong Province | Method for synthesizing ketoxime |
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2002
- 2002-01-10 CN CNB021002274A patent/CN1191125C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10654795B2 (en) | 2017-03-03 | 2020-05-19 | Chemical Technology Academy Of Shandong Province | Method for synthesizing ketoxime |
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