CN107118124B - A method of inhibiting ammoxidation of cyclohexanone catalyst loss - Google Patents
A method of inhibiting ammoxidation of cyclohexanone catalyst loss Download PDFInfo
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- CN107118124B CN107118124B CN201710464752.7A CN201710464752A CN107118124B CN 107118124 B CN107118124 B CN 107118124B CN 201710464752 A CN201710464752 A CN 201710464752A CN 107118124 B CN107118124 B CN 107118124B
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- 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
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Abstract
The invention discloses a kind of methods for inhibiting ammoxidation of cyclohexanone catalyst loss, under the conditions of existing for the ammoxidation catalyst Titanium Sieve Molecular Sieve and solvent tertiary butanol, cyclohexanone, ammonia and hydrogen peroxide introduce sacrifice agent while reacting, it is set to substitute Ti-Si catalyst by alkali soluble solution, the sacrifice agent is pure silicon molecular sieve S-1.The additional amount of the S-1 of the sacrifice agent pure silicon is the 0.5-10% of catalyst weight.The sacrifice agent pure silicon S-1 and ammoxidation catalyst Titanium Sieve Molecular Sieve topological structure having the same.The present invention is using the pure silicon molecular sieve S-1 of not titaniferous as sacrifice agent; 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, to play the role of guard catalyst；And the sacrifice agent can be mixed with catalyst, when addition need not other design technology route, investment reduction cost.
Description
Technical field
The present invention relates to a kind of methods for inhibiting ammoxidation of cyclohexanone catalyst loss.
Background technique
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, Titanium Sieve Molecular Sieve 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 alkalinity is stronger, lead to titanium-silicon molecular sieve catalyst
It is comparatively fast inactivated since silicon is seriously lost.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 Titanium Sieve Molecular Sieve structural stability in ammonia solution alkaline reaction environment method, honest and clean
During valence method synthesizes TS-1, by the addition standby TS-1 (Al-TS-1) containing aluminium of aluminum, to improve the steady of silicon on molecular sieve
It is qualitative.
The industrial applications catalyst product of ammoxidation of cyclohexanone is the Nano grade of 100-200, since particle is smaller, in alkali
Property condition stability inferior is poor, and the silicon on catalyst is easier to be dissolved away；The TS-1 product that cheap system obtains in document 1 is micro-
Meter level product, grain size is larger, itself has stronger alkali resistant dissolubility, but since granularity is larger, diffusion admittance is longer, causes
Catalytic activity is much lower compared with the nanoscale product industrially applied at present.And the property due to the presence of aluminium to catalyst is brought
Large change, also has an impact to later period catalytic activity.
Using the method for addition silica solution or silicic acid come the silicon concentration in equilibrium system in document US6828459, thus
Achieve the purpose that extend catalyst service life, the case where 6 hours occur as soon as inactivation originally can be made, postpones to 15 hours also not
Occur.But addition silica solution or silicic acid need to design new feeding line in the industrial production, addition ancillary equipment just may be used
It is not only complicated for operation to complete charging, but also increase cost.
Summary of the invention
The present invention provides a kind of method that inhibition ammoxidation of cyclohexanone Ti-Si catalyst is lost, using addition and cyclohexanone ammonia
Oxidation catalyst has 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, to play the role of guard catalyst；And the sacrifice agent can be mixed with catalyst, and it need not when addition
In addition design technology route, investment reduction cost.
The invention is realized by the following technical scheme:
A method of inhibiting ammoxidation of cyclohexanone catalyst loss, in ammoxidation catalyst Titanium Sieve Molecular Sieve and solvent uncle
Under the conditions of butanol is existing, cyclohexanone, ammonia and hydrogen peroxide introduce sacrifice agent while reacting, it is made to substitute the catalysis of titanium silicon
By alkali soluble solution, the sacrifice agent is pure silicon molecular sieve S-1 for 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, concentration 1- with monocrystalline partial size
Time of contact is 60-100min in the reactor by 10 weight %, the preferably Titanium Sieve Molecular Sieve of 2-5% weight %, in reaction mass
The molar ratio of hydrogen peroxide and cyclohexanone is that the molar ratio of 0.8-1.3 0:1, preferably 1.0-1.15:1 ammonia and cyclohexanone is 1.1-
The molar ratio of 2.6:1, preferably 1.4-2.2:1, the tert-butyl alcohol and cyclohexanone is 1.0-5.0, preferably 2.0-4.0.
The additional amount of the S-1 of the sacrifice agent pure silicon is the 0.5-10% of catalyst quality.
The granular size of the S-1 of the sacrifice agent pure silicon is 50-400nm.
The sacrifice agent pure silicon S-1 and ammoxidation catalyst Titanium Sieve Molecular Sieve topological structure having the same.
Specific 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, particle after molding
Diameter is at 10-60 μm, and preferably 20-30 μm；Sacrifice agent nanometer S-1 monocrystalline average grain diameter used is 150nm, grain diameter after molding
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
Grade；Solvent tertiary butanol is SILVER REAGENT, and tert-butyl alcohol mass fraction is 85%, remaining is water and a small amount of impurity.
In embodiment, the active solvent of reaction is 1L, has a mechanical stirring and collet heating function, reaction raw materials and anti-
It answers material to be back to back, there is backwashing function, the reactor cycles that are delivered to of catalyst in filter can be used.
In embodiment, cyclohexanone, cyclohexanone oxime and the tert-butyl alcohol have gas chromatographic analysis；Between the concentration of hydrogen peroxide uses
It connects iodine method and carries out titrimetry；The concentration of ammonia uses the method for acid base titration.
In embodiment, the separating effect of Titanium Sieve Molecular Sieve is determined by the solid content of clear liquid in measurement filter.
The measuring method of solid content are as follows: take 100ml liquid 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, be transferred to 500-550 DEG C of roasting 6h in Muffle furnace later, be slowly dropped to room temperature, finally will as point
It analyses on balance (being accurate to 0.00002g) and weighs, to obtain the Titanium Sieve Molecular Sieve content in clear liquid.
In embodiment, the silicone content in reaction solution is obtained by extracting outlet reaction solution progress icp analysis, extraction side
Method are as follows: take 10ml reaction solution in centrifuge tube, be centrifuged 10min under the speed of 15000 turns/min of supercentrifuge, take upper layer clear
Liquid carries out icp analysis.The additional amount of sacrifice agent is determined by result.
In embodiment, each index meaning is as follows:
Yclohexanone 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
Selectivity (in terms of cyclohexanone)=remaining oximate cyclohexanone/cyclohexanone inversion quantity
Hydrogen peroxide effective rate of utilization=remnants oximate dioxygen water/participation reaction dioxygen water inventory
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 that sacrifice agent is not added.
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 Titanium Sieve Molecular Sieve mass concentration is 4.0%, object
The mean residence time of material in the reactor is 80min, and reaction temperature is 80 DEG C, reaction pressure 0.3MPa, every in filter
25s backwash is primary, and after reacting 150h, 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 Titanium Sieve Molecular Sieve is 5ppm in agent filter, and the silicone content in reactor outlet material is 4wt%.
Embodiment 1
Comparative example 1 is repeated, but sacrifice agent S-1, additional amount 4wt% are added during the investment of catalyst, 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 92.6%, titanium silicon point in catalyst filter
The content of son sieve is 5ppm, and the silicone content in reactor outlet material is 4wt%.Continue after extending the reaction time to 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 90.7%, the content of Titanium Sieve Molecular Sieve in 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 investment of catalyst, additional amount becomes
5wt%, after reacting 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 Titanium Sieve Molecular Sieve is 5ppm in filter, and the silicone content in reactor outlet material is 4wt%.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 88.2%, titanium silicon point in catalyst filter
The content of son sieve is 5ppm, and the silicone content in reactor outlet material is 4wt%.
Embodiment 3
Comparative example 1 is repeated, but sacrifice agent S-1 is added during the investment of catalyst, additional amount becomes
6wt%, after reacting 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 Titanium Sieve Molecular Sieve is 5ppm in device, and the silicone content in reactor outlet material is 4wt%.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 90.2%, titanium silicon point in catalyst filter
The content of son sieve is 5ppm, and the silicone content in reactor outlet material is 4wt%.
Embodiment 4
Embodiment 3 is repeated, but the sacrifice agent S-1 being added during the investment of catalyst, the sacrifice agent of addition become
Micron S-1-1#, after reacting 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 Titanium Sieve Molecular Sieve is 5ppm in agent filter, and the silicone content in reactor outlet material is 4wt%.
Embodiment 5
Embodiment 4 is repeated, but the sacrifice agent being added during the investment of catalyst becomes 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)
It is 92.3%, the effective rate of utilization of hydrogen peroxide is 50.8%, and the yield of cyclohexanone oxime is 85.4%, titanium silicon in catalyst filter
The content of molecular sieve is 5ppm, and the silicone content in reactor outlet material is 4wt%.
Embodiment 6
Embodiment 4 is repeated, but the sacrifice agent being added during the investment of catalyst becomes 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)
It is 93.9%, the effective rate of utilization of hydrogen peroxide is 52.7%, and the yield of cyclohexanone oxime is 87.8%, titanium silicon in catalyst filter
The content of molecular sieve is 5ppm, and the silicone content in reactor outlet material is 4wt%.
Claims (2)
1. a kind of method for inhibiting ammoxidation of cyclohexanone catalyst loss, it is characterised in that: in ammoxidation catalyst titanium silicon molecule
Under the conditions of sieve and solvent tertiary butanol are existing, cyclohexanone, ammonia and hydrogen peroxide introduce sacrifice agent while reacting, and replace it
For Ti-Si catalyst by alkali soluble solution, the sacrifice agent is pure silicon molecular sieve S-1；
The additional amount of the S-1 of the sacrifice agent pure silicon is the 0.5-10% of catalyst weight；
The granular size of the S-1 of the sacrifice agent pure silicon is 50-400nm；
The sacrifice agent pure silicon S-1 and ammoxidation catalyst Titanium Sieve Molecular Sieve topological structure having the same.
2. according to the method described in claim 1, it is characterized by: reaction mass at 60-90 DEG C, normal pressure to 0.6Mpa condition
Under, with monocrystalline partial size be 50-400nm, concentration be 1-10 weight %, Titanium Sieve Molecular Sieve in the reactor time of contact be 60-
100min, the molar ratio of hydrogen peroxide and cyclohexanone is 0.8-1.30:1 in reaction mass, and the molar ratio of ammonia and cyclohexanone is 1.1-
The molar ratio of 2.6:1, the tert-butyl alcohol and cyclohexanone is 1.0-5.0.
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