CN105289679B - A kind of ruthenium cobalt copper three-way catalyst preparation process and its application - Google Patents
A kind of ruthenium cobalt copper three-way catalyst preparation process and its application Download PDFInfo
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- CN105289679B CN105289679B CN201510826417.8A CN201510826417A CN105289679B CN 105289679 B CN105289679 B CN 105289679B CN 201510826417 A CN201510826417 A CN 201510826417A CN 105289679 B CN105289679 B CN 105289679B
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- cobalt copper
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Abstract
The invention discloses a kind of ruthenium cobalt copper catalyst and preparation method thereof, the hydrotalcite stratified material that the ruthenium cobalt copper three-way catalyst forms for three kinds of metals of ruthenium cobalt copper, it can make isoborneol dehydrogenation under conditions of more gently when it is applied in isoborneol dehydrogenating technology, and dehydrogenation facilities are simple, energy consumption is low, and reaction selectivity is high, and no coupling product produces in reaction process, ruthenium cobalt copper catalyst can repeatedly use, and environment will not be polluted.
Description
Technical field
The present invention relates to the preparation method of catalyst, particularly a kind of ruthenium cobalt copper three-way catalyst preparation process and its answer
With.
Background technology
Camphor has effects that qi stagnation removing, desinsection be antipruritic, swelling and pain relieving, it has widely applied to medicine and chemical work
In industry.Industrial most common technique is exactly using australene as raw material, by isomerization, esterification, saponification and isoborneol at present
Camphor is made in four steps such as dehydrogenation.
Wherein, traditional isoborneol dehydrogenation step uses basic copper carbonate as catalyst, and adds dimethylbenzene as anti-
Solvent is answered, vigorous reflux stoichiometric number ten hours at 180 DEG C.There are severe reaction conditions, high energy consumption, catalyst use for this method
Short life, it is high to equipment requirement the shortcomings of.
Japanese document（Rattan original meaning people et al., Japanization Hui Chi,（2）, 366（1975））Report copper-zinc binary catalyst
System, the catalyst need make isoborneol dehydrogenation at 250-270 DEG C, and the technique is to the more demanding of equipment；Deutsche Bundespatent
（Ger.（East）65,566）A kind of copper-zinc-chromium three-element catalytic system has been synthesized, high temperature gas-phase dehydrogenation, the company of realizing can be carried out
Continuous reaction, but the catalyst easily produces threat containing toxic very big chromium to product safety, and it is unfriendly to environment；China
Patent（Patent publication No. CN 1059710A）A kind of calcium-zinc binary catalyst system is developed, it can make isoborneol in 240-320
DEG C gas-phase dehydrogenation prepares camphor, but to equipment requirement height.Therefore, developing a kind of environmental-friendly and low energy consumption dehydrogenation is
One research with positive effect.
The content of the invention
It is an object of the present invention to provide a kind of ruthenium cobalt copper three-way catalyst available for isoborneol dehydrogenation.
Realize that the technical solution of one of the object of the invention is to provide a kind of ruthenium cobalt copper three-way catalyst, the ruthenium cobalt copper ternary
The hydrotalcite stratified material that catalyst forms for three kinds of metals of ruthenium cobalt copper, its chemical formula are abbreviated as Ru-Co-Cu-OH-CO3。
The second object of the present invention is to provide a kind of ruthenium cobalt copper three-way catalyst preparation process, it comprises the following steps：
1）The ratio between amount by material is（1.5~3.5）: 1 NaOH and Na2CO3It is added to the water to obtain alkaline mixed solution,
Wherein water and Na2CO3The ratio between the amount of material（100~150）:1, the addition of water is too low will to make reaction solution excessively sticky, it is difficult to
Stirring；
Preferably, the NaOH and Na2CO3The ratio between the amount of material be（1.55~2.1）∶1.
2）By RuCl3·3H2O、Co(NO3)2·6H2O and Cu (NO3)2·3H2O is added to the water, and stirring is so that solid is whole
Dissolving, the RuCl3·3H2O、Co(NO3)2·6H2O、Cu(NO3)2·3H2The ratio between amount of material of O is 1:（4~10）∶（6~
15）, wherein water and RuCl3·3H2The ratio between amount of material of O（500~650）:1.
Preferably, the RuCl3·3H2O、Co(NO3)2·6H2O、Cu(NO3)2·3H2The ratio between amount of material of O is 1:（5
~6.7）∶（6.7~7.3）.
3）Will be through step 2）Obtained mixed solution is slowly dropped to through step 1）It is in obtained alkaline mixed solution and acute
Strong stirring, then be warming up to 60~70 DEG C, the reaction was continued 18-25 h are filtered after having reacted and are washed with deionized to obtain ruthenium cobalt
Copper three-way catalyst solid primary product, then ruthenium cobalt copper three-way catalyst solid primary product are dried 8 at a temperature of 105~125 DEG C
~12 it is small when, obtain finished product；Wherein, NaOH and Na2CO3The amount summation and RuCl of both materials3·3H2O、Co(NO3)2·
6H2O、Cu(NO3)2·3H2The ratio between amount summation of the material of O three is（3~4): 1.If NaOH and Na2CO3Amount deficiency will
Make precipitation by metallic ion incomplete；The excessive form that will change catalyst of drying temperature, so that the activity reduction of catalyst.
Preferably, the NaOH and Na2CO3The amount summation and RuCl of both materials3·3H2O、Co(NO3)2·6H2O、
Cu(NO3)2·3H2The ratio between amount summation of the material of O three is（3.15~3.63): 1.
The third object of the present invention in provide it is a kind of using ruthenium cobalt copper three-way catalyst in isoborneol dehydrogenating technology
Using, ruthenium cobalt copper three-way catalyst, isoborneol and organic solvent be mixed in air atmosphere and be warming up to 100 by it~
110 DEG C of 7~20 h of reaction, then stop heating, and ruthenium cobalt copper three-way catalyst is recovered by filtration, then filtrate distillation is molten to recycle
Agent, by remaining solid heating sublimation, obtains camphor；Wherein, the organic solvent is toluene or dimethylbenzene；Isoborneol, catalysis
The mass ratio of agent and solvent is 100:（1~5）∶（25~50）.Reaction temperature is excessive to cause energy consumption to increase, and temperature will be too low to be made
It will spin out the reaction time with the conversion ratio of isoborneol to decline；The dosage of catalyst is too low to be caused under the conversion ratio of isoborneol
Drop.
Preferably, the reaction time is 10~15 h, and isoborneol, the mass ratio of catalysts and solvents are 100:（1~2）∶
（34.6~43.3）.
Further, the ruthenium cobalt copper three-way catalyst inactivation realizes reusing for catalyst after being activated in hydrogen.
The ruthenium cobalt copper catalyst that the present invention develops, it can make isoborneol dehydrogenation under conditions of more gently, ruthenium cobalt copper
Catalyst can repeatedly use, and reaction condition is gentle, and equipment is simple, and energy consumption is low, and reaction selectivity is high, without pair in reaction process
Product produces, and environment will not be polluted.
Embodiment
The present invention is described in detail with reference to embodiments
Embodiment 1：
The preparation process of ruthenium cobalt copper three-way catalyst, it comprises the following steps：
1）By NaOH（3.72 g, 93 mmol）And Na2CO3(4.77 g, 45 mmol) are added in 10 mL water and are obtained alkalescence
Mixed solution；
2）By RuCl3·3H2O（0.78 g, 3 mmol）、Co(NO3)2·6H2O（4.37 g, 15 mmol）And Cu
(NO3)2·3H2O（4.83 g, 20 mmol）Add in 27 mL water, stirring is so that solid all dissolves;
3）Will be through step 2）Obtained mixed solution is slowly dropped to through step 1）It is in obtained alkaline mixed solution and acute
Strong stirring, is warming up to 60 DEG C again after being added dropwise to complete, the reaction was continued 20 h, is filtered after having reacted and is washed with deionized to obtain ruthenium
Cobalt copper three-way catalyst solid primary product, then that ruthenium cobalt copper three-way catalyst solid primary product are dried 10 at a temperature of 110 DEG C is small
When, obtain finished product (4.10 g).
Embodiment 2：
1）By NaOH（3.20 g, 80 mmol）And Na2CO3(4.24 g, 40 mmol) are added in 10 mL water and are obtained alkalescence
Mixed solution；
2）By RuCl3·3H2O（0.78 g, 3 mmol）、Co(NO3)2·6H2O（4.37 g, 15 mmol）And Cu
(NO3)2·3H2O（4.83 g, 20 mmol）Add in 27 mL water, stirring is so that solid all dissolves；
3）Will be through step 2）Obtained mixed solution is slowly dropped to through step 1）It is in obtained alkaline mixed solution and acute
Strong stirring, is warming up to 60 DEG C again after being added dropwise to complete, the reaction was continued 20 h, is filtered after having reacted and is washed with deionized to obtain ruthenium
Cobalt copper three-way catalyst solid primary product, then that ruthenium cobalt copper three-way catalyst solid primary product are dried 10 at a temperature of 110 DEG C is small
When, obtain finished product (4.02 g).
Embodiment 3：
1）By NaOH（3.72 g, 93 mmol）And Na2CO3(6.36 g, 60 mmol) are added in 12 mL water and are obtained alkalescence
Mixed solution；
2）By RuCl3·3H2O（0.78 g, 3 mmol）、Co(NO3)2·6H2O（5.82 g, 20 mmol）And Cu
(NO3)2·3H2O（5.32g, 22 mmol）Add in 30 mL water, stirring is so that solid all dissolves;
3）Will be through step 2）Obtained mixed solution is slowly dropped to through step 1）It is in obtained alkaline mixed solution and acute
Strong stirring, is warming up to 60 DEG C again after being added dropwise to complete, the reaction was continued 20 h, is filtered after having reacted and is washed with deionized to obtain ruthenium
Cobalt copper three-way catalyst solid primary product, then that ruthenium cobalt copper three-way catalyst solid primary product are dried 10 at a temperature of 110 DEG C is small
When, obtain finished product (4.28 g).
Embodiment 4：
1）By NaOH（3.72 g, 93 mmol）And Na2CO3(4.77 g, 45 mmol) are added in 10 mL water and are obtained alkalescence
Mixed solution；
2）By RuCl3·3H2O（0.78 g, 3 mmol）、Co(NO3)2·6H2O（4.37 g, 15 mmol）And Cu
(NO3)2·3H2O（4.83 g, 20 mmol）Add in 27 mL water, stirring is so that solid all dissolves;
3）Will be through step 2）Obtained mixed solution is slowly dropped to through step 1）It is in obtained alkaline mixed solution and acute
Strong stirring, is warming up to 65 DEG C again after being added dropwise to complete, the reaction was continued 20 h, is filtered after having reacted and is washed with deionized to obtain ruthenium
Cobalt copper three-way catalyst solid primary product, then that ruthenium cobalt copper three-way catalyst solid primary product are dried 10 at a temperature of 115 DEG C is small
When, obtain finished product (4.12 g).
Embodiment 5：
The preparation process of ruthenium cobalt copper three-way catalyst, it comprises the following steps：
1）By NaOH（3.72 g, 93 mmol）And Na2CO3(4.77 g, 45 mmol) are added in 12 mL water and are obtained alkalescence
Mixed solution；
2）By RuCl3·3H2O（0.78 g, 3 mmol）、Co(NO3)2·6H2O（4.37g, 15 mmol）And Cu
(NO3)2·3H2O（4.83 g, 20 mmol）Add in 32 mL water, stirring is so that solid all dissolves；
3）Will be through step 2）Obtained mixed solution is slowly dropped to through step 1）It is in obtained alkaline mixed solution and acute
Strong stirring, is warming up to 65 DEG C again after being added dropwise to complete, the reaction was continued 20 h, is filtered after having reacted and is washed with deionized to obtain ruthenium
Cobalt copper three-way catalyst solid primary product, then that ruthenium cobalt copper three-way catalyst solid primary product are dried 10 at a temperature of 110 DEG C is small
When, obtain finished product (4.02 g).
Embodiment 6：
Application of the ruthenium cobalt copper three-way catalyst in isoborneol dehydrogenating technology, it comprises the following steps：
4 ml of ruthenium cobalt copper catalyst 0.2 g, 10.0 g of isoborneol and toluene is sequentially added into reaction bulb（Toluene density
0.866 gram per centimeter3, remaining embodiment all same）, it is mixed in air atmosphere and is warming up to 105 DEG C, react 10 h, is led to
The disappearance for crossing isoborneol raw material peak in gas-chromatography judges that reaction terminates, and then stops heating, catalyst, redistillation is recovered by filtration
Recycling design, remaining solid heating sublimation obtain 9.6 g of camphor, and yield is 97 %.
Catalyst after recycling reacts under the same conditions again, repeats above operation 3 times, obtains the yield of camphor successively
For 97%, 96%, 94%.
Embodiment 7：
Application of the ruthenium cobalt copper three-way catalyst in isoborneol dehydrogenating technology, it comprises the following steps：
Ruthenium cobalt copper catalyst 4 ml of 0.1 g, 10.0 g of isoborneol and toluene is sequentially added into reaction bulb, is stirred, heating
To 110 DEG C, 19h is reacted, then stops heating, catalyst, redistillation recycling design is recovered by filtration, remaining solid heating rises
China, obtains 9.5 g of camphor, yield 96%.
Embodiment 8：
Application of the ruthenium cobalt copper three-way catalyst in isoborneol dehydrogenating technology, it comprises the following steps：
Ruthenium cobalt copper catalyst 4 ml of 0.15 g, 10.0 g of isoborneol and toluene is sequentially added into reaction bulb, is stirred, heating
To 110 DEG C, 12h is reacted, then stops heating, catalyst, redistillation recycling design is recovered by filtration, remaining solid heating rises
China, obtains 9.7 g of camphor, yield 98%.
Catalyst after recycling reacts under the same conditions again, repeats above operation 3 times, obtains the yield of camphor successively
For 99%, 97%, 95%.
Embodiment 9：
Application of the ruthenium cobalt copper three-way catalyst in isoborneol dehydrogenating technology, it comprises the following steps：
Ruthenium cobalt copper catalyst 5 ml of 0.2 g, 10.0 g of isoborneol and toluene is sequentially added into reaction bulb, is stirred, heating
To 100 DEG C, 15h is reacted, then stops heating, catalyst, redistillation recycling design is recovered by filtration, remaining solid heating rises
China, obtains 9.7 g of camphor, yield 98%.
Claims (4)
1. a kind of preparation process of ruthenium cobalt copper three-way catalyst, it is characterised in that it comprises the following steps：
1) it is (1.5~3.5): 1 NaOH and Na by the ratio between amount of material2CO3It is added to the water to obtain alkaline mixed solution, wherein
Water and Na2CO3The ratio between the amount of material (100~150): 1；
2) by RuCl3·3H2O、Co(NO3)2·6H2O and Cu (NO3)2·3H2O is added to the water, and stirring causes solid all to dissolve,
The RuCl3·3H2O、Co(NO3)2·6H2O、Cu(NO3)2·3H2The ratio between amount of material of O is 1: (4~10): (6~15),
Wherein water and RuCl3·3H2The ratio between amount of material of O (500~650): 1；
3) mixed solution obtained through step 2) is slowly dropped in the alkaline mixed solution obtained through step 1) and acutely stirred
Mix, be warming up to 60~70 DEG C after being added dropwise to complete again, the reaction was continued 18-25h is filtered after having reacted and is washed with deionized to obtain
Ruthenium cobalt copper three-way catalyst solid primary product, then ruthenium cobalt copper three-way catalyst solid primary product are dried at a temperature of 105~125 DEG C
Dry 8~12h obtains finished product；Wherein, NaOH and Na2CO3The amount summation and RuCl of both materials3·3H2O、Co(NO3)2·
6H2O、Cu(NO3)2·3H2The ratio between amount summation of the material of O three is (3~4): 1；The finished product ruthenium cobalt copper three-way catalyst is
The hydrotalcite stratified material of three kinds of metal compositions of ruthenium cobalt copper, its chemical formula are abbreviated as Ru-Co-Cu-OH-CO3。
2. a kind of ruthenium cobalt copper three-way catalyst, it is made as the preparation process of the ruthenium cobalt copper three-way catalyst described in claim 1,
It is characterized in that, hydrotalcite stratified material of the ruthenium cobalt copper three-way catalyst for three kinds of metal compositions of ruthenium cobalt copper, its chemical formula
It is abbreviated as Ru-Co-Cu-OH-CO3。
3. ruthenium cobalt copper three-way catalyst prepared by a kind of method of the ruthenium cobalt copper three-way catalyst described in claim 1 is in isoborneol
The application process of dehydrogenating technology, it is characterised in that it is by ruthenium cobalt copper three-way catalyst, isoborneol and organic solvent in air gas
It is mixed in atmosphere and is warming up to 100~110 DEG C of 7~20h of reaction, is judged by the disappearance at isoborneol raw material peak in gas-chromatography
Reaction terminates, and then stops heating, catalyst is recovered by filtration, redistillation recycling design, remaining solid heating sublimation obtains
Camphor；Wherein, the organic solvent is toluene or dimethylbenzene；Isoborneol, the mass ratio of catalysts and solvents are 100: (1~5):
(25~50).
4. application process of the ruthenium cobalt copper three-way catalyst according to claim 3 in isoborneol dehydrogenating technology, its feature
It is, ruthenium cobalt copper three-way catalyst inactivation in hydrogen after activating.
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| CN1065451A (en) * | 1991-03-22 | 1992-10-21 | 中国科学院广州化学研究所 | The method of preparation of high purity camphor from dehydrogenated and impuritier removal iso-borneo camphor |
| CN103084178B (en) * | 2013-01-17 | 2015-06-03 | 中国科学院上海高等研究院 | Copper-contained hydrotalcite-based catalyst for preparing mixed alcohol by using synthesis gas as well as preparation method and application thereof |
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