CN107376985A - The preparation method and applications of the fluorinated modified Ni-based dehydrogenation of ammonium fluosilicate - Google Patents
The preparation method and applications of the fluorinated modified Ni-based dehydrogenation of ammonium fluosilicate Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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Abstract
The preparation method and applications of the fluorinated modified Ni-based dehydrogenation of ammonium fluosilicate, it is related to diphenylamines dehydrocyclization synthesis carbazole technical field, using Y molecular sieve nickel-loaded, lanthanum, and carries out fluorine, diphenylamines dehydrogenation prepared by boron modification；Continuously face hydrogen dehydrocyclization using fixed bed and prepare carbazole technique compared with batch production process, carbazole product quality is stable, and production operation is convenient.Main active component on nickel-base catalyst after reduction treatment, is reduced to metallic nickel, lanthanum in hydrogen atmosphere by the fluorinated modified Ni-based dehydrogenation of the ammonium fluosilicate, then mixed with diphenylamines, dehydrogenation reaction is carried out in hydrogen atmosphere.The shortcomings of noble metal can be avoided using as the defects of production cost is high caused by catalyst, while also avoid and use a large amount of organic solvents, intermittently reacted, the service life of catalyst of the present invention are up to more than 180 days, it is not necessary to are frequently changed.
Description
Technical field
The present invention relates to the production technology of diphenylamines dehydrocyclization synthesis carbazole technical field, especially cyclisation catalyst
Field.
Background technology
Diphenylamines is a kind of widely used chemical intermediate, compared among tetrahydro carbazole, 2,2- benzidines etc.
Body, cheap and easy to get, so diphenylamines method synthesis carbazole is also the focus that people study always, but there is reaction efficiency always
Low, severe reaction conditions, expensive catalyst, and the shortcomings of easy in inactivation.
Albert Schnatterrer etc.（Process for the preparation of carbazole [P].
US5760247, 1998-06-02）A kind of technique of diphenylamines dehydrogenation in liquid phase Cyclization carbazole is proposed, by diphenylamines, 5%
Platinum/C catalyst is added in the flask with thermometer and distilling apparatus, and 5 were reacted at 290 DEG C as a child, is distilled off low
Boilers, mainly water, benzene and aniline etc., bottoms acetone solution and filtration catalytic agent, after redistillation removes acetone
Carbazole product can be obtained, its reaction selectivity is 60%, and the conversion ratio of diphenylamines is 65.9%, and its once through yield is about 40%, and this is one
Kind batch process, is unfavorable for industrialized production.
Islam A. etc.（Thermal cyclisation of diphenylamine to carbazole:
synthesis of the natural product glycozolidine [J]. Journal of the Chemical
Society, Chemical Communications, 1972 (9): 537a-537a）It has studied another catalytic cyclization
The technique of diphenylamines carbazole, diphenylamines is heated to be placed in again in closed pipeline after 350 DEG C, using iodine as catalyst reaction 2
Hour, its reaction efficiency then is calculated by analysis means again, total recovery is up to 45%.But it is iodine to start distillation under iodine low temperature
Steam, it is toxic, while product color is influenceed, solid-state iodine is easily sublimated into the cold, easily blocks pipeline, is unfavorable for industrial metaplasia
Production.
Beno t Li é gault etc.（Intramolecular Pd (II)-catalyzed oxidative biaryl
synthesis under air: reaction development and scope[J]. The Journal of
organic chemistry, 2008, 73(13): 5022-5028）Research report, in depositing for palladium and a small amount of potassium carbonate
Under, diphenylamines can obtain the carbazole that yield is 8%-82% in 110 DEG C of reactions.
Chinese patent literature 201210410069.2（A kind of method that diphenylamines prepares carbazole）Then disclose a kind of diphenylamines liquid
The method that phase method synthesizes carbazole, electromagnetic agitation compressive reaction kettle is added to by diphenylamines, solvent butyric acid, catalyst trifluoracetic acid palladium
In, oxygen pressing to 0.5MPa, 5h is reacted in 120 DEG C, while hot sampling analysis, the conversion ratio of diphenylamines is 98.2%, carbazole selection
Property is 99.9%.The technical literature contents such as this method and Beno t Li é gault are similar, used a large amount of solvents and noble metal
Catalyst, using batch tank liquid phase reactor, bulk industrial production is not suitable for equally.
The content of the invention
Noble metal catalyst is expensive used by being studied for existing diphenylamines, course of reaction use it is a large amount of organic molten
The shortcomings of agent, reaction process use batch process, the present invention propose that one kind continuously faces hydrogen dehydrocyclization beneficial to diphenylamines and prepares click
The preparation method of the fluorinated modified Ni-based dehydrogenation of the ammonium fluosilicate of azoles.
Preparation method of the present invention is：Nickel nitrate, lanthanum nitrate aqueous solution are mixed, after Y type molecular sieve impregnates, carried out successively
Drying for the first time and for the first time roasting；Product after first time is calcined is mixed with the ammonium fluosilicate aqueous solution and be fluorinated instead
Should, second of drying is carried out successively again after suction filtration and second is calcined；Product after second is calcined is water-soluble through boric acid
After liquid dipping, third time drying is carried out；Product after third time is dried mixes with shaping assistant, after shaping, then successively through the
Four drying and third time are calcined, and obtain the fluorinated modified Ni-based dehydrogenation of ammonium fluosilicate.
The present invention carries out fluorine, diphenylamines dehydrogenation prepared by boron modification using Y molecular sieve nickel-loaded, lanthanum, reaction
Activity is high, selectivity is good；Continuously face hydrogen dehydrocyclization using fixed bed and prepare carbazole technique compared with batch production process, carbazole
Product quality is stable, and production operation is convenient.
Further, in nickel nitrate of the present invention in nickel, lanthanum nitrate the mass ratio that feeds intake of lanthanum and Y type molecular sieve for 10~
15: 0.5~2: 100.Experiment shows, for this catalyst, in this above-mentioned process parameters range, and the conversion ratio of carbazole
And selectivity ratios are higher, outside this process parameters range, also there are the conversion ratio and selectivity of certain carbazole, but than relatively low, or
Say no industrial value.
The temperature conditionss of the first time drying are 105 DEG C, and the temperature conditionss of roasting are 350~650 DEG C for the first time, roasting
0.5~5h of time.Experiment shows, for this catalyst, in this above-mentioned process parameters range, the conversion ratio of carbazole and
Selectivity ratios are higher, outside this process parameters range, also there is the conversion ratio and selectivity of certain carbazole, but than relatively low, in other words
There is no industrial value.
The mass percent of ammonium fluosilicate is 2~5% in the ammonium fluosilicate aqueous solution, the system after the first time roasting
The mixing ratio of product and the ammonium fluosilicate aqueous solution is 1g: 5~10 mL.Experiment shows, for this catalyst, it is above-mentioned this
In process parameters range, the conversion ratio and selectivity ratios of carbazole are higher.
The temperature conditionss of second of drying are 105 DEG C, and the temperature conditionss of second of roasting are 450~650 DEG C, roasting
1~5h of time.In this above-mentioned process parameters range, the conversion ratio and selectivity ratios of carbazole are higher.
The third time and the temperature conditionss of the 4th drying are 105 DEG C, the temperature conditionss of third time roasting for 450~
550 DEG C, 0.5~4h of roasting time.
The present invention particularly prepares carbazole another object is that purposes prepared by proposition above method in diphenylamines catalytic dehydrogenation
In application.
The nickel-base catalyst obtained using this preparation method has been that nickel oxide, lanthana etc. have been loaded on Y molecular sieve, and
Fluorine, the acidity of boron modification regulation catalyst have been carried out, but has been lived because the nickel oxide on Y molecular sieve, lanthana etc. do not have dehydrogenation
Property, therefore before use, first by the fluorinated modified Ni-based dehydrogenation of the ammonium fluosilicate in hydrogen atmosphere after reduction treatment,
Main active component on nickel-base catalyst is reduced to metallic nickel, lanthanum, then mixed with diphenylamines, is taken off in hydrogen atmosphere
Hydrogen reacts.
After above dehydrogenation reaction, diphenylamines conversion ratio is at least 60.35%, carbazole selectivity more than 95.11%.Will be anti-
Material is answered to be absorbed with water, you can to obtain the crude product of certain moisture content, obtain fine work after refined, this technique processing method is simple, does not have
There is the diphenylamines reuse of reaction.
Present invention process, which avoids, uses noble metal as the defects of production cost is high caused by catalyst, while also avoids
Using a large amount of organic solvents, intermittently reacted the shortcomings of, the service life of catalyst of the present invention is up to more than 180 days, no
Must frequently it change.
The operation of specific reduction treatment is：The fluorinated modified Ni-based dehydrogenation of the ammonium fluosilicate is placed in described de-
In hydrogen reaction fixed bed, in a hydrogen atmosphere, with 5 DEG C/min heating rate by fluorinated modified Ni-based of the ammonium fluosilicate
Dehydrogenation is warming up to 450 DEG C, recovery time 4h.The purpose reduced that sequentially heats up is：Gentle steady lifting reduction
Temperature, prevent from burning out catalyst because reduction reaction heat release causes reduction process temperature runaway during hydrogenating reduction, influence to be catalyzed
The activity of agent and selectivity；Experiment shows, recovery time 4h at 450 DEG C, you can to ensure that the metal oxides such as nickel oxide are complete
Elemental metals are reduced to, the active of catalyst, selectivity are optimal.
After the catalyst temperature after processing to be restored is down to reaction temperature, then it is passed through diphenylamines to fixed bed and is taken off
Hydrogen reacts.
The condition of the dehydrogenation reaction is：Pressure is -0.02~-0.01atm, temperature is 350~450 DEG C, air speed 0.5
~ 4/h, hydrogen and diphenylamines mixing mol ratio are 1~10: 1.The process conditions such as the temperature of dehydrogenation reaction are the property with catalyst
Can be closely related, therefore, not the problems such as the Common Parameters of conventional dehydrogenation.Experiment shows, for this catalyst,
In this above-mentioned process parameters range, the conversion ratio and selectivity ratios of carbazole are higher.
Embodiment
Embodiment 1：
Weigh six water nickel nitrate 49.54g（Ni：10g）, lanthanum nitrate hexahydrate 3.12g（La：1g）Soluble in water and Y molecular sieve 100g
Incipient impregnation 1 day at room temperature, 105 DEG C of drying 4h, 450 DEG C of roasting 4h；Add the ammonium fluosilicate aqueous solution that concentration is 2 %
1000mL, stirring fluorination 1h at 85 DEG C, filtering, 105 DEG C of drying 4h, 550 DEG C of roasting 4h；Take 8.88g boric acid to mix with water to be made into
Boric acid aqueous solution impregnates to above-mentioned material room temperature volumetric, then 105 DEG C of drying, adds shaping assistant aftershaping, 105 DEG C of bakings
Dry, 450 DEG C of roasting 3h obtain catalyst.
Take a certain amount of above-mentioned catalyst to be added in fixed bed, in a hydrogen atmosphere, heated up with 5 DEG C/min heating rate
To 450 DEG C of hydrogenating reduction 4h；Treat that reaction bed temperature is down to reaction temperature, adjustment reaction pressure is -0.02atm, and control is anti-
360 DEG C of temperature is answered, diphenylamines, air speed 0.5h are imported with pump-1, the mixing mol ratio of hydrogen and diphenylamines is 2: 1.
Reaction mass is directly absorbed with water, analysis product, and diphenylamines conversion ratio is 60.35%, carbazole selectivity 99.03%.
Embodiment 2：
Weigh six water nickel nitrate 74.31g（Ni：15g）, lanthanum nitrate hexahydrate 6.23g（La：2g）Soluble in water and Y molecular sieve 100g
Incipient impregnation 1 day at room temperature, 105 DEG C of drying 4h, 500 DEG C of roasting 4h；Add the ammonium fluosilicate aqueous solution that concentration is 5 %
500mL, stirring fluorination 2h at 80 DEG C, filtering, 105 DEG C of drying 4h, 500 DEG C of roasting 4h；8.88g boric acid and water is taken to be made into boric acid water
Solution impregnates to above-mentioned material room temperature volumetric, then 105 DEG C of drying, adds shaping assistant aftershaping, 105 DEG C of drying, 450
DEG C roasting 3h obtain catalyst.
Take a certain amount of above-mentioned catalyst to be added in fixed bed, in a hydrogen atmosphere, heated up with 5 DEG C/min heating rate
To 450 DEG C of hydrogenating reduction 4h；Treat that reaction bed temperature is down to reaction temperature, adjustment reaction pressure is -0.01atm, and control is anti-
350 DEG C of temperature is answered, diphenylamines, air speed 1h are imported with pump-1, the mixing mol ratio of hydrogen and diphenylamines is 5: 1.
Reaction mass is directly absorbed with water, analysis product, and diphenylamines conversion ratio is 76.21%, carbazole selectivity 99.36%.
Embodiment 3：
Weigh six water nickel nitrate 61.93g（Ni：12.5g）, lanthanum nitrate hexahydrate 1.56g（La：0.5g）Soluble in water and Y molecular sieve
100g incipient impregnation 1 day at room temperature, 105 DEG C of drying 4h, 500 DEG C of roasting 4h；It is water-soluble to add the ammonium fluosilicate that concentration is 4 %
Liquid 600mL, stirring fluorination 1.5h at 85 DEG C, filtering, 105 DEG C of drying 4h, 450 DEG C of roasting 4h；14.21g boric acid and water is taken to be made into
Boric acid aqueous solution impregnates to above-mentioned material room temperature volumetric, then 105 DEG C of drying, adds shaping assistant aftershaping, 105 DEG C of bakings
Dry, 500 DEG C of roasting 4h obtain catalyst.
Take a certain amount of above-mentioned catalyst to be added in fixed bed, in a hydrogen atmosphere, heated up with 5 DEG C/min heating rate
To 450 DEG C of hydrogenating reduction 4h；Treat that reaction bed temperature is down to reaction temperature, adjustment reaction pressure is -0.02atm, and control is anti-
440 DEG C of temperature is answered, diphenylamines, air speed 2h are imported with pump-1, the mixing mol ratio of hydrogen and diphenylamines is 10: 1.
Reaction mass is directly absorbed with water, analysis product, and diphenylamines conversion ratio is 79.37%, carbazole selectivity 95.11%.
Embodiment 4：
Weigh six water nickel nitrate 74.31g（Ni：15g）, lanthanum nitrate hexahydrate 6.23g（La：2g）Soluble in water and Y molecular sieve 100g
Incipient impregnation 1 day at room temperature, 105 DEG C of drying 4h, 550 DEG C of roasting 3h；Add the ammonium fluosilicate aqueous solution that concentration is 3 %
700mL, stirring fluorination 1h at 75 DEG C, filtering, 105 DEG C of drying 4h, 500 DEG C of roasting 3h；3.55g boric acid and water is taken to be made into boric acid water
Solution impregnates to above-mentioned material room temperature volumetric, then 105 DEG C of drying, adds shaping assistant aftershaping, 105 DEG C of drying, 550
DEG C roasting 4h obtain catalyst.
Take a certain amount of above-mentioned catalyst to be added in fixed bed, in a hydrogen atmosphere, heated up with 5 DEG C/min heating rate
To 450 DEG C of hydrogenating reduction 4h；Treat that reaction bed temperature is down to reaction temperature, adjustment reaction pressure is -0.01atm, and control is anti-
450 DEG C of temperature is answered, diphenylamines, air speed 4h are imported with pump-1, the mixing mol ratio of hydrogen and diphenylamines is 1: 1.
Reaction mass is directly absorbed with water, analysis product, and diphenylamines conversion ratio is 71.65%, carbazole selectivity 97.21%.
Comparative example 1（Without fluorination treatment）：
Weigh six water nickel nitrate 74.31g（Ni：15g）, lanthanum nitrate hexahydrate 6.23g（La：2g）Soluble in water and Y molecular sieve 100g
Incipient impregnation 1 day at room temperature, 105 DEG C of drying 4h, 500 DEG C of roasting 4h；8.88g boric acid and water is taken to be made into boric acid aqueous solution to upper
The material room temperature volumetric dipping stated, then 105 DEG C of drying, add shaping assistant aftershaping, 105 DEG C of drying, 450 DEG C of roasting 3h
Obtain catalyst.
Take a certain amount of above-mentioned catalyst to be added in fixed bed, in a hydrogen atmosphere, heated up with 5 DEG C/min heating rate
To 450 DEG C of hydrogenating reduction 4h；Treat that reaction bed temperature is down to reaction temperature, adjustment reaction pressure is -0.02atm, and control is anti-
380 DEG C of temperature is answered, diphenylamines, air speed 1h are imported with pump-1, the mixing mol ratio of hydrogen and diphenylamines is 5: 1.
Reaction mass is directly absorbed with water, analysis product, and diphenylamines conversion ratio is 37.56%, carbazole selectivity 91.94%.
Comparative example 2（Handled without boron modification）：
Weigh six water nickel nitrate 74.31g（Ni：15g）, lanthanum nitrate hexahydrate 6.23g（La：2g）Soluble in water and Y molecular sieve 100g
Incipient impregnation 1 day at room temperature, 105 DEG C of drying 4h, 500 DEG C of roasting 4h；Add the ammonium fluosilicate aqueous solution that concentration is 5 %
500mL, stirring fluorination 2h at 80 DEG C, filtering, 105 DEG C of drying 4h, 500 DEG C of roasting 4h；Handle, be directly added into without boron modification
Shaping assistant aftershaping, 105 DEG C of drying, 450 DEG C of roasting 3h obtain catalyst.
Take a certain amount of above-mentioned catalyst to be added in fixed bed, in a hydrogen atmosphere, heated up with 5 DEG C/min heating rate
To 450 DEG C of hydrogenating reduction 4h；Treat that reaction bed temperature is down to reaction temperature, adjustment reaction pressure is -0.02atm, and control is anti-
380 DEG C of temperature is answered, diphenylamines, air speed 1h are imported with pump-1, the mixing mol ratio of hydrogen and diphenylamines is 5: 1.
Reaction mass is directly absorbed with water, analysis product, and diphenylamines conversion ratio is 59.34%, carbazole selectivity 36.36%.
Comparative example 3（Not adding assistant La）：
Weigh six water nickel nitrate 74.31g（Ni：15g）Incipient impregnation 1 day soluble in water at room temperature with Y molecular sieve 100g, 105
DEG C drying 4h, 500 DEG C roasting 4h；Add the % ammonium fluosilicate solutions 500mL that concentration is 5, stirring fluorination 2h at 80 DEG C, filtering,
105 DEG C of drying 4h, 500 DEG C of roasting 4h；8.88g boric acid and water is taken to be made into boric acid aqueous solution and above-mentioned material room temperature volumetric
Dipping, then 105 DEG C of drying, addition shaping assistant aftershaping, 105 DEG C of drying, 450 DEG C of roasting 3h obtain catalyst.
Take a certain amount of above-mentioned catalyst to be added in fixed bed, in a hydrogen atmosphere, heated up with 5 DEG C/min heating rate
To 450 DEG C of hydrogenating reduction 4h；Treat that reaction bed temperature is down to reaction temperature, adjustment reaction pressure is -0.02atm, and control is anti-
380 DEG C of temperature is answered, diphenylamines, air speed 1h are imported with pump-1, the mixing mol ratio of hydrogen and diphenylamines is 5: 1.
Reaction mass is directly absorbed with water, analysis product, and diphenylamines conversion ratio is 46.21%, carbazole selectivity 51.36%.
By the way that above comparative example 1,2,3 and embodiment 1,2,3,4 are contrasted, it is seen then that urged using made from present invention process
Agent is prepared in carbazole applied to diphenylamines catalytic dehydrogenation, is greatly improved the conversion ratio of diphenylamines, improves the selectivity of carbazole.
Embodiment 5, life experiment：
The catalyst prepared with embodiment 2 is added in fixed bed, in a hydrogen atmosphere, is heated up with 5 DEG C/min heating rate
To 450 DEG C of hydrogenating reduction 4h；Treat that reaction bed temperature is down to reaction temperature, adjustment reaction pressure is -0.01atm, and control is anti-
380 DEG C of temperature is answered, diphenylamines, air speed 0.5h are imported with pump-1, the mixing mol ratio of hydrogen and diphenylamines is 5: 1.It is continuous anti-
Answer 6 months, reaction mass is directly absorbed with water, and periodic analysis product, diphenylamines conversion ratio and carbazole selectively see the table below.
Catalyst reaction life-span record sheet
As seen from the above table：Catalyst was slightly decreased in first three day activity, and later stage catalytic activity is almost unchanged, illustrated that the catalyst has
There is preferable service life.
Claims (10)
1. the preparation method of the fluorinated modified Ni-based dehydrogenation of ammonium fluosilicate, it is characterised in that：
Nickel nitrate, lanthanum nitrate aqueous solution are mixed, after Y type molecular sieve impregnates, drying for the first time is carried out successively and roasts for the first time
Burn；
Product after first time is calcined is mixed with the ammonium fluosilicate aqueous solution and carries out fluorination reaction, is carried out successively again after suction filtration
Second of drying and second of roasting；
By the product after second is calcined after boric acid aqueous solution impregnates, third time drying is carried out；
Product after third time is dried mixes with shaping assistant, after shaping, then is calcined successively through the 4th drying and third time,
Obtain the fluorinated modified Ni-based dehydrogenation of ammonium fluosilicate.
2. the preparation method of catalyst according to claim 1, it is characterised in that：Lanthanum in nickel, lanthanum nitrate in the nickel nitrate
The mass ratio that feeds intake with Y type molecular sieve is 10~15: 0.5~2: 100.
3. the preparation method of catalyst according to claim 1 or claim 2, it is characterised in that：The temperature strip of the first time drying
Part is 105 DEG C, and the temperature conditionss of roasting are 350~650 DEG C for the first time, 0.5~5h of roasting time.
4. the preparation method of catalyst according to claim 1, it is characterised in that：Fluosilicic acid in the ammonium fluosilicate aqueous solution
The mass percent of ammonium is 2~5%, the mixing ratio of the product after first time roasting and the ammonium fluosilicate aqueous solution for 1g: 5~
10 mL。
5. according to the preparation method of the catalyst of claim 1 or 4, it is characterised in that：The temperature strip of second of drying
Part is 105 DEG C, and the temperature conditionss of second of roasting are 450~650 DEG C, 1~5h of roasting time.
6. the preparation method of catalyst according to claim 1, it is characterised in that：The third time and the temperature of the 4th drying
Degree condition is 105 DEG C, and the temperature conditionss of third time roasting are 450~550 DEG C, 0.5~4h of roasting time.
7. the fluorinated modified Ni-based dehydrogenation of the ammonium fluosilicate of method preparation as claimed in claim 1 is de- in diphenylamines catalysis
Hydrogen prepares the application of carbazole, it is characterised in that：First by the fluorinated modified Ni-based dehydrogenation of the ammonium fluosilicate in hydrogen gas
In atmosphere after reduction treatment, then mix with diphenylamines, dehydrogenation reaction is carried out in hydrogen atmosphere.
8. application according to claim 7, it is characterised in that：By the fluorinated modified Ni-based catalysis dehydrogenation of the ammonium fluosilicate
Agent is placed in the dehydrogenation reaction fixed bed, in a hydrogen atmosphere, with 5 DEG C/min heating rate by the ammonium fluosilicate fluorine
Change modified Ni-based dehydrogenation and be warming up to 450 DEG C, recovery time 4h.
9. application according to claim 8, it is characterised in that：The catalyst temperature after processing to be restored is down to reaction
After temperature, then it is passed through diphenylamines to fixed bed and carries out dehydrogenation reaction.
10. application according to claim 9, it is characterised in that：The condition of the dehydrogenation reaction is：Pressure be -0.02~-
0.01atm, temperature are 350~450 DEG C, air speed is 0.5 ~ 4 h-1, hydrogen and diphenylamines mixing mol ratio be 1~10: 1.
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| US3954670A (en) * | 1974-03-27 | 1976-05-04 | Exxon Research & Engineering Co. | Boria-alumina catalyst base |
| CN1056473A (en) * | 1990-05-16 | 1991-11-27 | 中国石油化工总公司抚顺石油化工研究院 | A kind of preparation method of low-Na and high-Si Y-type molecular sieve |
-
2017
- 2017-08-09 CN CN201710673321.1A patent/CN107376985B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3954670A (en) * | 1974-03-27 | 1976-05-04 | Exxon Research & Engineering Co. | Boria-alumina catalyst base |
| CN1056473A (en) * | 1990-05-16 | 1991-11-27 | 中国石油化工总公司抚顺石油化工研究院 | A kind of preparation method of low-Na and high-Si Y-type molecular sieve |
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