CN107118124A - A kind of method for suppressing ammoxidation of cyclohexanone catalyst loss - Google Patents
A kind of method for suppressing ammoxidation of cyclohexanone catalyst loss Download PDFInfo
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- CN107118124A CN107118124A CN201710464752.7A CN201710464752A CN107118124A CN 107118124 A CN107118124 A CN 107118124A CN 201710464752 A CN201710464752 A CN 201710464752A CN 107118124 A CN107118124 A CN 107118124A
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- catalyst
- cyclohexanone
- sacrifice agent
- ammoxidation
- pure silicon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
Abstract
The invention discloses a kind of method for suppressing ammoxidation of cyclohexanone catalyst loss, under conditions of ammoxidation catalyst HTS and solvent tertiary butanol are present, cyclohexanone, ammonia and hydrogen peroxide introduce sacrifice agent while reacting, it is set to substitute Ti-Si catalyst by alkali soluble solution, described sacrifice agent is pure silicon molecular sieve S 1.The S 1 of described sacrifice agent pure silicon addition is the 0.5 10% of catalyst weight.Described sacrifice agent pure silicon S 1 has identical topological structure with ammoxidation catalyst HTS.The present invention is used as sacrifice agent using the pure silicon molecular sieve S 1 of not titaniferous; due to being pure silicon structure; granular size is very nearly the same with catalyst, so being easier to be dissolved compared with this province of catalyst in the reaction system of ammoxidation of cyclohexanone, so as to play a part of guard catalyst；, need not design technology route, investment reduction cost in addition when addition and the sacrifice agent can be mixed with catalyst.
Description
Technical field
The present invention relates to a kind of method for suppressing ammoxidation of cyclohexanone catalyst loss.
Background technology
Cyclohexanone oxime is the intermediate product in caprolactam production process, and the caprolactam product of synthesis is important chemical industry
Raw material, mainly passes through the monomer of polymerization daiamid-6 fiber.
In the reaction system of ammoxidation of cyclohexanone, HTS carries out ring as catalyst hydrogen peroxide and ammonia
Hexanone Ammoximation reaction.Due to there is the presence of ammonia in reaction system so that system alkalescence is stronger, causes titanium-silicon molecular sieve catalyst
Because silicon is seriously lost in and comparatively fast inactivates.The Ti-Si zeolite molecular sieve structure stability and catalytic performance of document cheap system synthesis
Research Liu Na disclose it is a kind of improve HTS structural stability in ammonia solution alkaline reaction environment method, honest and clean
During valency method synthesis TS-1, by adding the standby TS-1 (Al-TS-1) containing aluminium of aluminum, so as to improve the steady of silicon on molecular sieve
It is qualitative.
The industrial applications catalyst product of ammoxidation of cyclohexanone is 100-200 Nano grade, because particle is smaller, in alkali
Silicon on less stable under the conditions of property, catalyst is easier to be dissolved away；The TS-1 products that cheap system is obtained in document 1 are micro-
Meter level product, grain size is larger, inherently there is stronger alkali resistant dissolubility, but because granularity is larger, diffusion admittance is longer, causes
Catalytic activity is much lower compared with the nanoscale product industrially applied at present.And because the presence of aluminium is brought to the property of catalyst
Large change, also has an impact to later stage catalytic activity.
Using the method for addition Ludox or silicic acid come the silicon concentration in equilibrium system in document US6828459, so that
The purpose of extension catalyst service life is reached, 6 hours of script can be made to occur as soon as the situation of inactivation, is postponed to 15 hours also not
Occur.But addition Ludox or silicic acid need to design new feeding line in the industrial production, addition auxiliary equipment just may be used
To complete charging, not only complex operation, and add cost.
The content of the invention
The present invention provides a kind of method for suppressing the loss of ammoxidation of cyclohexanone Ti-Si catalyst, using addition and cyclohexanone ammonia
Oxidation catalyst has a same crystal structure, but is free from the pure silicon molecular sieve S-1 of titanium as sacrifice agent, due to being pure silicon knot
Structure, granular size is very nearly the same with catalyst, so compared with catalyst, this province is easier in the reaction system of ammoxidation of cyclohexanone
It is dissolved, so as to play a part of guard catalyst；, need not when addition and the sacrifice agent can be mixed with catalyst
Other design technology route, investment reduction cost.
The present invention is achieved through the following technical solutions：
A kind of method for suppressing ammoxidation of cyclohexanone catalyst loss, in ammoxidation catalyst HTS and solvent uncle
Under conditions of butanol is present, cyclohexanone, ammonia and hydrogen peroxide introduce sacrifice agent while reacting, and it is substituted the catalysis of titanium silicon
Agent is pure silicon molecular sieve S-1 by alkali soluble solution, described sacrifice agent.Wherein, reaction mass is at 60-90 DEG C, preferably 70-85 DEG C, often
It is depressed under the conditions of 0.6Mpa, preferably 0.2-0.45Mpa, is 50-400nm, preferably 100-300nm with monocrystalline particle diameter, concentration is 1-
Time of contact is 60-100min in the reactor by 10 weight %, preferably 2-5% weight % HTS, in reaction mass
The mol ratio of hydrogen peroxide and cyclohexanone is 0.8-1.3 0：1st, preferably 1.0-1.15:The mol ratio of 1 ammonia and cyclohexanone is 1.1-
2.6:1st, preferably 1.4-2.2:1, the mol ratio of the tert-butyl alcohol and cyclohexanone is 1.0-5.0, preferably 2.0-4.0.
The S-1 of described sacrifice agent pure silicon addition is the 0.5-10% of catalyst quality.
The S-1 of described sacrifice agent pure silicon granular size is 50-400nm.
Described sacrifice agent pure silicon S-1 has identical topological structure with ammoxidation catalyst HTS.
Embodiment
The following examples are to the further invention of the present invention, but the present invention is not limited to these examples.
In embodiment, titanium-silicon molecular sieve catalyst TS-1 monocrystalline average grain diameter used is 200nm, the particle after shaping
Footpath is at 10-60 μm, preferably 20-30 μm；Sacrifice agent nanometer S-1 monocrystalline average grain diameter used is 150nm, the grain diameter after shaping
At 10-60 μm, preferably 20-30 μm；Sacrifice agent micron S-1-1# monocrystalline average grain diameter used is 1 μm；Sacrifice agent micron S- used
1-2# monocrystalline average grain diameter is 10 μm；Cyclohexanone is grade product；The hydrogen peroxide that ammonia and mass fraction are 30% is reagent
Level；Solvent tertiary butanol is SILVER REAGENT, and tert-butyl alcohol mass fraction is 85%, and remaining is water and a small amount of impurity.
In embodiment, the active solvent of reaction is 1L, possesses mechanical agitation and chuck heating function, reaction raw materials and anti-
Answer material to be back to back, with backwashing function, the reactor cycles that are delivered to of catalyst in filter can be used.
In embodiment, cyclohexanone, cyclohexanone oxime has gas chromatographic analysis with the tert-butyl alcohol；Between the concentration of hydrogen peroxide is used
Connect iodine method and carry out titrimetry；The concentration of ammonia uses the method for acid base titration.
In embodiment, the separating effect of HTS is determined by determining the solid content of clear liquid in filter.
The assay method of solid content is：100ml liquid is taken in crucible, 12h removes solvent and moisture in 60 DEG C of low temperature baking oven, so
After rise to 120 DEG C of baking 6h, 500-550 DEG C of roasting 6h is transferred in Muffle furnace afterwards, room temperature is slowly dropped to, finally will as point
Analyse (being accurate to 0.00002g) on balance to weigh, so as to obtain the HTS content in clear liquid.
In embodiment, the silicone content in reaction solution is obtained, extraction side by extracting outlet reaction solution progress icp analysis
Method is：Take 10ml reaction solutions in centrifuge tube, centrifuge 10min under 15000 turns/min of supercentrifuge speed, take upper strata clear
Liquid carries out icp analysis.The addition of sacrifice agent is determined by result.
In embodiment, each index implication is as follows：
Cyclohexanone conversion ratio=(Reactor inlet cyclohexanone content-reactor outlet cyclohexanone content)/Reactor inlet
Cyclohexanone content
Hydrogen peroxide conversion ratio=(Reactor inlet hydrogen peroxide content-reactor outlet hydrogen peroxide content)/reactor inlet
Hydrogen peroxide content
The inversion quantity of cyclohexanone/cyclohexanone of selectivity (in terms of cyclohexanone)=remaining oximate
The dioxygen water inventory of the dioxygen water of hydrogen peroxide effective rate of utilization=remnants oximates/participation reaction
The content of the silicon of reaction solution outlet is in terms of silica
What comparative example 1 illustrated is the catalyst using effect and reaction condition for being not added with sacrifice agent.
Comparative example 1
The charging rate of cyclohexanone is 130g/h, and the feed rate of solvent tertiary butanol is 450g/h, hydrogen peroxide 30wt%'s
Charging rate is 150g/h, and the charging rate of ammonia (99.99%) is 45g/h, and HTS mass concentration is 4.0%, thing
Material mean residence time in the reactor is 80min, and reaction temperature is 80 DEG C, and reaction pressure is every in 0.3MPa, filter
25s is backwashed once, after reaction 150h, and the conversion ratio of cyclohexanone is 92.5%, and the conversion ratio of hydrogen peroxide is 95%, the choosing of reaction
Selecting property (in terms of cyclohexanone) is 93.6%, and the effective rate of utilization of hydrogen peroxide is 45.7%, and the yield of cyclohexanone oxime is 86.6%, is urged
The content of HTS is that the silicone content in 5ppm, reactor outlet material is 4wt% in agent filter.
Embodiment 1
Comparative example 1 is repeated, but sacrifice agent S-1 is added during the input of catalyst, addition is 4wt%, reaction
After 100h, the conversion ratio of cyclohexanone is 96%, and the conversion ratio of hydrogen peroxide is 98%, and the selectivity (in terms of cyclohexanone) of reaction is
96.5%, the effective rate of utilization of hydrogen peroxide is 52.4%, and the yield of cyclohexanone oxime is titanium silicon point in 92.6%, catalyst filter
The content of son sieve is that the silicone content in 5ppm, reactor outlet material is 4wt%.Continue to extend the reaction time to after 200h, ring
The conversion ratio of hexanone is 95%, and the conversion ratio of hydrogen peroxide is 97%, and the selectivity (in terms of cyclohexanone) of reaction is 95.5%, dioxygen
The effective rate of utilization of water is 51.8%, and the yield of cyclohexanone oxime is the content of HTS in 90.7%, catalyst filter
For 5ppm, the silicone content in reactor outlet material is 4wt%.
Embodiment 2
Comparative example 1 is repeated, but sacrifice agent S-1 is added during the input of catalyst, addition is changed into
After 5wt%, reaction 200h, the conversion ratio of cyclohexanone is 96.5%, and the conversion ratio of hydrogen peroxide is 98%, the selectivity of reaction (with
Cyclohexanone meter) it is 96.5%, the effective rate of utilization of hydrogen peroxide is 52.4%, and the yield of cyclohexanone oxime is 92.6%, catalyst mistake
The content of HTS is that the silicone content in 5ppm, reactor outlet material is 4wt% in filter.Continue to extend the reaction time
To 300h, the conversion ratio of cyclohexanone is 94%, and the conversion ratio of hydrogen peroxide is 96%, and the selectivity (in terms of cyclohexanone) of reaction is
93.8%, the effective rate of utilization of hydrogen peroxide is 50.9%, and the yield of cyclohexanone oxime is titanium silicon point in 88.2%, catalyst filter
The content of son sieve is that the silicone content in 5ppm, reactor outlet material is 4wt%.
Embodiment 3
Comparative example 1 is repeated, but sacrifice agent S-1 is added during the input of catalyst, addition is changed into
After 6wt%, reaction 300h, the conversion ratio of cyclohexanone is 96%, and the conversion ratio of hydrogen peroxide is 98%, and the selectivity of reaction is (with ring
Hexanone meter) it is 96.5%, the effective rate of utilization of hydrogen peroxide is 52.4%, and the yield of cyclohexanone oxime is 92.6%, catalyst filtration
The content of HTS is that the silicone content in 5ppm, reactor outlet material is 4wt% in device.Continue to extend the reaction time extremely
After 400h, the conversion ratio of cyclohexanone is 95.4%, and the conversion ratio of hydrogen peroxide is 97%, and the selectivity (in terms of cyclohexanone) of reaction is
94.6%, the effective rate of utilization of hydrogen peroxide is 51.9%, and the yield of cyclohexanone oxime is titanium silicon point in 90.2%, catalyst filter
The content of son sieve is that the silicone content in 5ppm, reactor outlet material is 4wt%.
Embodiment 4
Repetition embodiment 3, but the sacrifice agent S-1 added during the input of catalyst, the sacrifice agent of addition are changed into
After micron S-1-1#, reaction 300h, the conversion ratio of cyclohexanone is 92%, and the conversion ratio of hydrogen peroxide is 93.5%, the selection of reaction
Property (in terms of cyclohexanone) be 92.1%, the effective rate of utilization of hydrogen peroxide is 50.6%, and the yield of cyclohexanone oxime is 84.7%, catalysis
The content of HTS is that the silicone content in 5ppm, reactor outlet material is 4wt% in agent filter.
Embodiment 5
Embodiment 4 is repeated, but the sacrifice agent added during the input of catalyst is changed into a micron S-1-2#, reaction
After 250h, the conversion ratio of cyclohexanone is 92.5%, and the conversion ratio of hydrogen peroxide is 93.9%, the selectivity of reaction (in terms of cyclohexanone)
For 92.3%, the effective rate of utilization of hydrogen peroxide is 50.8%, and the yield of cyclohexanone oxime is titanium silicon in 85.4%, catalyst filter
The content of molecular sieve is that the silicone content in 5ppm, reactor outlet material is 4wt%.
Embodiment 6
Embodiment 4 is repeated, but the sacrifice agent added during the input of catalyst is changed into nano pure silicone beta, reaction
After 250h, the conversion ratio of cyclohexanone is 93.5%, and the conversion ratio of hydrogen peroxide is 94.9%, the selectivity of reaction (in terms of cyclohexanone)
For 93.9%, the effective rate of utilization of hydrogen peroxide is 52.7%, and the yield of cyclohexanone oxime is titanium silicon in 87.8%, catalyst filter
The content of molecular sieve is that the silicone content in 5ppm, reactor outlet material is 4wt%.
Claims (5)
1. a kind of method for suppressing ammoxidation of cyclohexanone catalyst loss, it is characterised in that：In ammoxidation catalyst titanium silicon molecule
Under conditions of sieve and solvent tertiary butanol are present, cyclohexanone, ammonia and hydrogen peroxide introduce sacrifice agent while reacting, and replace it
For Ti-Si catalyst by alkali soluble solution, described sacrifice agent is pure silicon molecular sieve S-1.
2. according to the method described in claim 1, it is characterised in that：The S-1 of described sacrifice agent pure silicon addition is catalysis
The 0.5-10% of agent weight.
3. according to the method described in claim 1, it is characterised in that：The S-1 of described sacrifice agent pure silicon granular size is 50-
400nm。
4. according to the method described in claim 1, it is characterised in that：Described sacrifice agent pure silicon S-1 and ammoxidation catalyst titanium
Si molecular sieves have identical topological structure.
5. according to the method described in claim 1, it is characterised in that：Reaction mass is in 60-90 DEG C, normal pressure to 0.6Mpa conditions
Under, with monocrystalline particle diameter be 50-400nm, concentration be 1-10 weight %, HTS in the reactor time of contact be 60-
The mol ratio of hydrogen peroxide and cyclohexanone is 0.8-1.30 in 100min, reaction mass：1, the mol ratio of ammonia and cyclohexanone is 1.1-
2.6:1, the mol ratio of the tert-butyl alcohol and cyclohexanone is 1.0-5.0.
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