CN1660499A - Method of preparing catalyst camied by composite oxides and application - Google Patents

Method of preparing catalyst camied by composite oxides and application Download PDF

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CN1660499A
CN1660499A CN 200410061375 CN200410061375A CN1660499A CN 1660499 A CN1660499 A CN 1660499A CN 200410061375 CN200410061375 CN 200410061375 CN 200410061375 A CN200410061375 A CN 200410061375A CN 1660499 A CN1660499 A CN 1660499A
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catalyst
composite oxide
carrier
tert
oxide supported
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CN100335174C (en
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马玉龙
冯俊
刘琳
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Wuhan University WHU
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Wuhan University WHU
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Abstract

A carried composite oxide catalyst is prepared through dissolving the Co, Ni and cocatalyst in water or organic solvent, immersing the calcined carrier in it, baking, and activating. The used catalyst can be re-activated for cyclic used. Its application is also disclosed.

Description

Composite oxide supported Preparation of catalysts methods and applications
Technical field
The present invention relates to a kind of composite oxide supported Preparation of catalysts method, also relate to the application in the tert-butyl benzene nitrile is prepared simultaneously.
Technical background
The virtue nitrile is synthetic dyestuffs, agricultural chemicals, medicine, reaches the important intermediate of various materials that purposes is very extensive.At present, synthetic simple, the most economic method of fragrant nitrile compound is to be raw material with toluene and derivative thereof, in the presence of catalyst, adopts one step of process for gas phase ammonoxidation to synthesize.But, the reaction temperature of gas phase ammonoxidation is generally all between 400～500 ℃, can stand the toluene derivative and the methylic Hete rocyclic derivatives and few of such high temperature, common have toluene class, chlorotoluene class and a picoline class etc., and most toluene derivatives (replacing toluene and hydroxyl replaces toluene etc. as the tert-butyl group) are under this temperature during ammoxidation, because of structural instability, the selectivity of target nitrile compounds is lower, has to adopt traditional multistep reaction method to be synthesized.So the application of process for gas phase ammonoxidation is limited.With p-tert-butyltoluene (PTT) is example, when application gas phase ammonoxidation method is synthetic, easily generates para-Phthalonitrile, to low (the Chmyr I.M. of tert-butyl benzene nitrile (PTBN) productive rate; BukeikhanovN.R.; Suvorov B.V, Izv.Akad.Nauk Kaz.SSR, Ser Khim., 1982, (3): 61-64).About synthesizing of structural unstable fragrant carbonitrile derivatives, existing a large amount of bibliographical information, for example, with corresponding aldehyde, oxime or hydrazone (Talukdar S., Hsu J.L., Chou T.C., Fang J.H., Tetrahedron Lett.2001,42 (6): 1103-1105; Sabitha G., Syamala M., Synth Commun.1998,28 (24): 4577-4580; Ramalingam T., Subba Reddy B.V., Srimivas R.et al., Synth.Commun.2000,30 (24): 4507-4512), acid amides (Bose D.S., Sunder K.S.A., Synth Commun.1999,29 (23): 4235-4239) and carboxylic acid and ester (Erben H.G, Graefe J., Moser W.et al.EP 745,585,1996) etc. synthetic for raw material.Wherein, bibliographical information is maximum is to be that raw material is synthetic with aldehyde and oxime, but aromatic aldehyde generally all is to be that the raw material method that adopts chlorination and hydrolysis to combine is synthetic with the toluene derivative, so reactions steps is many, environmental pollution is big, and post processing is loaded down with trivial details, the production cost height.Also there is similar shortcoming in the method for other synthetic fragrant nitrile.
As everyone knows, liquid phase oxidation is carried out about 423K usually, many under the gas phase ammonoxidation reaction temperature unstable compounds, but be stable under the liquid phase oxidation temperature, as (VerbruggeP.A., Kramer P.A., Van H.R.GB1 such as p-tert-butyltoluenes, 561,464,1977).Liu Lin and Ma Yulong once adopted liquid phase oxidation cobalt salt and manganese salt commonly used to make catalyst, carried out the research (Liu Lin of the synthetic PTBN of liquid phase ammonia oxidation PTT, horse Yulong. Wuhan University's journal (version of science) 2002,48 (2): 167-170), the result shows, catalyst also is difficult to reclaim usefulness again, and the selectivity of ammoxidation reaction speed and PTBN is also still on the low side.Therefore, it is good to develop a kind of selectivity, the yield height, and supported catalyst that can be repeatedly used and suitable process conditions thereof reduce environmental pollution, are major technique keys of the present invention.
Summary of the invention
The object of the present invention is to provide a kind of composite oxide supported Preparation of catalysts method, easy to operate, technology is simple, feed stock conversion height, good product selectivity, catalyst can be repeatedly used, and the consumption of ammonia is little, and equipment is not had corrosion, and environmental pollution is little.
Another object of the present invention is that composite oxide supported catalyst is preparing the application in the tert-butyl benzene nitrile.
Technical scheme provided by the invention is: a kind of composite oxide supported catalyst that is used to prepare to the tert-butyl benzene nitrile, comprise major catalyst and co-catalyst, and the active material of major catalyst is Co 3O 4And NiO, its amount of substance is than being Co 3O 4: NiO=1: 0.5～5.0; The active material of co-catalyst is an oxide also, is selected from least a oxide among Mo, Fe, Ti, Mn, Bi, Li, Na, K, Rb and the Cs, and its amount of substance ratio to Co is 0.015～3.0: 1.The amount of substance ratio of major catalyst and co-catalyst is all by oxide.
At least a oxide among the preferred Mo of the active material of above-mentioned co-catalyst, Fe, Ti, Bi, Li, Na, K, Rb and the Cs.
The carrier of catalyst of the present invention is spherical α-Al 2O 3Or SiO 2Particle, the active component mass content is 1～35%, is preferably 5～30%.
Synthetic used major catalyst and the co-catalyst raw material of catalyst of the present invention is inorganic acid salt, acylate and oxide etc., and inorganic acid salt commonly used has nitrate, carbonate, phosphate, ammonium salt and chloride etc.; Acylate has oxalates, acetate and citrate etc.
The present invention also provides above-mentioned Preparation of catalysts method.After the oxide and the salt of each active component dissolved respectively, mixes, burnt carrier is poured in the above-mentioned solution, made it to be submerged just, between 373～433K, dry then, activate 3～8 hours between 733～823K and promptly get needed catalyst.
The used carrier of catalyst of the present invention is α-Al 2O 3And SiO 2In a kind of, in order to improve selection of catalysts, before using, carrier must be calcined 8 hours at 1073K.
Preparation of catalysts method of the present invention is:
A, employing equi-volume impregnating are dissolved in cobalt, nickel and co-catalyst raw material in water or the organic solvent;
B, burnt carrier is poured in the A step solution into submergence;
C, will be impregnated with the carrier oven dry of active component, bake out temperature is 373-433k;
D, there is the catalyst activity component between 733-823k, to activate 3-8 hour load at carrier;
E, in the repeated use process of catalyst, when carbon distribution causes active the reduction, adopt same condition reactivation, the burning-off carbon distribution.
It is synthetic to the tert-butyl benzene nitrile to be used for the liquid phase ammonia oxidation reaction by the prepared catalyst of the present invention, and its reaction principle is as follows:
Figure A20041006137500051
P-tert-butyltoluene liquid phase ammonia oxidation reaction is carried out in having the stainless steel autoclave of agitator, and reactor volume is 300ml, and reaction temperature is controlled by PID, and the process conditions of reaction are:
Reaction temperature: 423～493K;
Mixing speed: 500～1000 rev/mins;
Reaction pressure: 0.5～1.0MPa;
Air: the amount of substance ratio of ammonia is 10～20: 1.0.
This reaction is gas-liquid-solid three phase catalytic reaction, the size of mixing speed is bigger to the mass transfer rate influence of reactant, mixing speed is low excessively, reaction is subjected to the influence of diffusion process control, reaction rate is less, and mixing speed is when surpassing 1000 rev/mins, and the influence of mixing speed can be ignored, so the mixing speed that suits is 500～1000 rev/mins; Reaction pressure also can not be ignored the influence of gas-liquid-solid phase reaction, and pressure increases, and the concentration of dissolved oxygen and ammonia is bigger in the reactant liquor, also can control higher reaction temperature, so reaction rate is very fast.But reaction temperature is too high, and the selectivity of reaction reduces, and preferred reaction pressure is 0.8～1.0MPa, and preferred reaction temperature is 423～453K.The size of reaction rate can be judged by remaining oxygen content in the online detection tail gas of oxygen amount meter.Usually, remaining oxygen content is lower, and reaction rate is bigger.
The method of purified product is a lot of from reactant mixture, as adopting vacuum distillation method, product and raw material is separated, and these all are known methods.
With existing preparation the method for tert-butyl benzene nitrile is compared, adopt catalyst of the present invention and corresponding liquid phase ammonia method for oxidation, can synthesize in a step the tert-butyl benzene nitrile, and catalyst also can be repeatedly used as process for gas phase ammonoxidation, and selectivity is then much higher than process for gas phase ammonoxidation.Compare with other conventional method, reactions steps few (single step reaction) not only, technology is simple, the utilization rate height of atom, catalyst recovery is convenient, and more much smaller than conventional method to the influence of environment.
The specific embodiment
Embodiment 1
Preparation of Catalyst
1. with 4g CoCl 26H 2O, 4.5g NiCl 26H 2O adds in the deionized water, is mixed with solution; 2. in this solution, add 2.8g (NH 4) 6Mo 7O 244H 2O and 1g Na 2O, water-bath heating (about 333K) makes it to become clear solution; 3. with burnt 40g fine grained SiO 2(Qingdao Marine Chemical Co., Ltd.'s product) joins in the above-mentioned clear solution, stirs; 4. after the 373K oven dry, promptly got needed catalyst in 8 hours in the 823K activation again, its atomic ratio is Co 3O 4: NiO: MoO 2: Na 2O=1: 3.38: 2.83: 2.89.
The oxidation of p-tert-butyltoluene liquid phase ammonia
With 172.2g (1.164mol) p-tert-butyltoluene, the 5g catalyst adds in the autoclave, symmetry screws kettle cover, control temperature 453K, with air: the amount of substance ratio of ammonia is 13: 1.0 bubbling airs and ammonia, and with the size of oxygen content in the oxygen detection instrument on-line tracing detection tail gas.React after 10 hours, take out reactant mixture, filtering catalyst with the mother liquor decompression distillation, promptly gets the tert-butyl benzene nitrile.The conversion ratio of p-tert-butyltoluene is 58%, is 98.56% to the selectivity of tert-butyl benzene nitrile.
Embodiment 2
Preparation of Catalyst
With 4g CoCl 26H 2O, 4.5g NiCl 26H 2O adds in the deionized water, is mixed with solution, adds 2.8g (NH again in this solution 4) 6Mo 7O 244H 2O and 1.6g LiCl, careful heating makes it to become the active component clear solution, again with burnt 40g fine grained SiO 2(Qingdao Marine Chemical Co., Ltd.'s product) joins in the above-mentioned solution and stirs, activation then, and its activation condition is identical with embodiment 1, and atomic ratio is Co 3O 4: NiO: MoO 2: Li 2O=1: 3.38: 2.83: 3.36.
The oxidation of p-tert-butyltoluene liquid phase ammonia
In example 1 described autoclave, add catalyst 5g by this routine described method preparation, p-tert-butyltoluene 172.2g (1.164mol), the control reaction condition identical with embodiment 1 reacted 10 hours, adopt the method separated product identical with example 1, the conversion ratio of p-tert-butyltoluene is 54%, is 91.56% to the selectivity of tert-butyl benzene nitrile.
Embodiment 3
Preparation of Catalyst
With 4g CoCl 26H 2O, 4.5g NiCl 26H 2O adds in the deionized water, is mixed with solution, adds 4g FeCl again in this solution 3With 1g Na 2O, careful heating makes it to become the active component clear solution, again with burnt 40g fine grained SiO 2(Qingdao Marine Chemical Co., Ltd.'s product) joins in the above-mentioned solution and stirs, activation then, and its activation condition is identical with embodiment 1, and atomic ratio is Co 3O 4: NiO: Fe 2O 3: Na 2O=1: 3.38: 1.32: 3.36.
The oxidation of p-tert-butyltoluene liquid phase ammonia
Add the catalyst 5g by this routine described method preparation, all the other are identical with embodiment 1, and the conversion ratio of p-tert-butyltoluene is 50.5%, are 93.56% to the selectivity of tert-butyl benzene nitrile.
Comparing embodiment 1
Preparation of Catalyst
Catalyst carrier is used α-Al instead 2O 3, all the other are identical with embodiment 1.
The oxidation of p-tert-butyltoluene liquid phase ammonia
The oxidation of p-tert-butyltoluene liquid phase ammonia is identical with embodiment 1, and the conversion ratio of p-tert-butyltoluene is 51%, is 95.56% to the selectivity of tert-butyl benzene nitrile.

Claims (5)

1, a kind of composite oxide supported Preparation of catalysts method, it comprises the following steps:
A, employing equi-volume impregnating are dissolved in cobalt, nickel and co-catalyst raw material in water or the organic solvent;
B, burnt carrier is poured in the A step solution into submergence;
C, will be impregnated with the carrier oven dry of active component, bake out temperature is 373-433k;
D, there is the catalyst activity component between 733-823k, to activate 3-8 hour load at carrier;
E, in the repeated use process of catalyst, when carbon distribution causes active the reduction, adopt same condition reactivation, the burning-off carbon distribution.
2, a kind of composite oxide supported Preparation of catalysts method according to claim 1 is characterized in that catalyst comprises major catalyst and co-catalyst, and the active material of major catalyst is Co 3O 4And NiO, its amount of substance is than being Co 3O 4: NiO=1: 0.5～5.0; The active material of co-catalyst is an oxide.
3, a kind of composite oxide supported Preparation of catalysts method according to claim 2, it is characterized in that oxide is at least a oxide among Mo, Fe, Ti, Mn, Bi, Li, Na, K, Rb and the Cs, is 0.015～3.0: 1 to the amount of substance ratio of Co.
4, a kind of composite oxide supported Preparation of catalysts method according to claim 1 is characterized in that the carrier of catalyst is α-Al 2O 3Or SiO 2, the active component mass content is 5-30%.
5, the described a kind of composite oxide supported catalyst of claim 1 is preparing the application in the tert-butyl benzene nitrile.
CNB2004100613755A 2004-12-17 2004-12-17 Method of preparing catalyst camied by composite oxides and application Expired - Fee Related CN100335174C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100379493C (en) * 2006-04-10 2008-04-09 武汉大学 Catalyst for synthesizing para-hydroxy-benzonitrile and its preparing method and use
CN100439352C (en) * 2006-07-05 2008-12-03 浙江工业大学 Process for catalytic synthesis of phthalide from phthalic anhydride
CN104525203A (en) * 2014-12-17 2015-04-22 华东师范大学 Preparation method and application of Co3O4/NiO composite mesoporous nanoparticles

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0623158B2 (en) * 1988-04-26 1994-03-30 三菱瓦斯化学株式会社 Process for producing aromatic nitrile
CN1015902B (en) * 1988-08-20 1992-03-18 北京大学 Catalyst for hydrodesulfurization of hydrocarbons
EP1113001B1 (en) * 1999-12-27 2008-11-05 Mitsubishi Gas Chemical Company, Inc. Process for producing nitrile compounds
CN1124331C (en) * 2000-11-03 2003-10-15 中国石油天然气股份有限公司 Hydrofining catalyst and preparation method thereof
CN1097482C (en) * 2000-12-25 2003-01-01 化学工业部天津化工研究设计院 Process for preparing O(P)-methylbenzonitrile catalyst

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100379493C (en) * 2006-04-10 2008-04-09 武汉大学 Catalyst for synthesizing para-hydroxy-benzonitrile and its preparing method and use
CN100439352C (en) * 2006-07-05 2008-12-03 浙江工业大学 Process for catalytic synthesis of phthalide from phthalic anhydride
CN104525203A (en) * 2014-12-17 2015-04-22 华东师范大学 Preparation method and application of Co3O4/NiO composite mesoporous nanoparticles
CN104525203B (en) * 2014-12-17 2016-06-29 华东师范大学 A kind of Co3O4The preparation method of/NiO composite mesopore nanoparticle and application

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