CN107376985B - 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 PDF

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CN107376985B
CN107376985B CN201710673321.1A CN201710673321A CN107376985B CN 107376985 B CN107376985 B CN 107376985B CN 201710673321 A CN201710673321 A CN 201710673321A CN 107376985 B CN107376985 B CN 107376985B
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diphenylamines
dehydrogenation
ammonium fluosilicate
drying
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CN107376985A (en
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李为民
马雪荣
邱玉华
郭登峰
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Haian Changzhou University High-Tech R & D Center
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • 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
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • 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 are related to diphenylamines dehydrocyclization synthesis carbazole technical field, using Y molecular sieve nickel-loaded, lanthanum, and carry out the diphenylamines dehydrogenation of fluorine, boron modification preparation；Continuously face hydrogen dehydrocyclization using fixed bed and prepare carbazole technique compared with batch production process, carbazole stable product quality, production operation is conveniently.Main active component on nickel-base catalyst after reduction treatment, is reduced to metallic nickel, lanthanum, then mix with diphenylamines, dehydrogenation reaction is carried out in hydrogen atmosphere by the fluorinated modified Ni-based dehydrogenation of the ammonium fluosilicate in hydrogen atmosphere.The service life of the disadvantages of can avoid using noble metal for the defect of high production cost brought by catalyst, while also avoiding and using a large amount of organic solvents, intermittently being reacted, catalyst of the present invention is up to 180 days or more, it is not necessary to frequently replacement.

Description

The preparation method and applications of the fluorinated modified Ni-based dehydrogenation of ammonium fluosilicate
Technical field
The present invention relates to diphenylamines dehydrocyclizations to synthesize the production technology that catalyst is used in carbazole technical field, especially cyclisation Field.
Background technique
Diphenylamines is a kind of widely used chemical intermediate, intermediate compared to tetrahydro carbazole, 2,2- benzidine etc. Body, it is cheap and easy to get, so diphenylamines method synthesis carbazole is also the hot spot that people study always, but always exist reaction efficiency Low, severe reaction conditions, expensive catalyst, and the disadvantages of easy in inactivation.
(Process for the preparation of carbazole [P] such as Albert Schnatterrer 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, reaction selectivity 60% can be obtained, the conversion ratio of diphenylamines is 65.9%, and one-way yield is about 40%, 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) have studied another catalytic cyclization Diphenylamines is heated to be placed in again in closed pipeline after 350 DEG C, using iodine as catalyst reaction 2 by the technique of diphenylamines carbazole Hour, its reaction efficiency then is calculated by analysis means again, total recovery is up to 45%.But starting distillation under iodine low temperature is iodine Steam, it is toxic, while product color is influenced, solid-state iodine is easily sublimated into the cold, is easy blocking pipeline, is unfavorable for industrial metaplasia It produces.
(Intramolecular Pd (the II)-catalyzed oxidative biaryl such as Beno t Li é gault synthesis under air: reaction development and scope[J]. The Journal of Organic chemistry, 2008,73 (13): 5022-5028) research report, in depositing for palladium acetate and a small amount of potassium carbonate Under, diphenylamines is reacted in 110 DEG C, and the carbazole that yield is 8%-82% can be obtained.
The method that a kind of diphenylamines of Chinese patent literature 201210410069.2(prepares carbazole) then disclose a kind of hexichol It is anti-to be added to electromagnetic agitation pressurization by the method that amine liquid phase method synthesizes carbazole for diphenylamines, solvent butyric acid, catalyst trifluoracetic acid palladium It answers in kettle, oxygen pressing to 0.5MPa, in 120 DEG C of reaction 5h, sampling analysis, the conversion ratio of diphenylamines are 98.2% while hot, carbazole Selectivity is 99.9%.The technical literatures contents such as this method and Beno t Li é gault are similar, used a large amount of solvents and expensive Metallic catalyst is not suitable for bulk industrial production equally using batch tank liquid phase reactor.
Summary of the invention
For noble metal catalyst used by the research of existing diphenylamines, expensive, reaction process is used a large amount of organic molten The disadvantages of agent, reaction process use batch process, the present invention propose that one kind continuously faces hydrogen dehydrocyclization conducive 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 being mixed, after Y type molecular sieve impregnates, successively carried out Drying for the first time and for the first time roasting；Product after roasting for the first time is mixed with ammonium fluosilicate aqueous solution and be fluorinated instead It answers, successively carries out second of drying again after filtering and second roasts；Product after roasting for the second time is water-soluble through boric acid After liquid dipping, third time drying is carried out；Product after third time is dried is mixed with shaping assistant, after molding, then successively through the Four drying and third time roast, and obtain the fluorinated modified Ni-based dehydrogenation of ammonium fluosilicate.
The present invention uses Y molecular sieve nickel-loaded, lanthanum, and carries out the diphenylamines dehydrogenation of fluorine, boron modification preparation, reaction Activity is high, selectivity is good；Continuously face hydrogen dehydrocyclization using fixed bed and prepares carbazole technique compared with batch production process, carbazole Stable product quality, production operation are convenient.
Further, nickel in nickel nitrate of the present invention, in lanthanum nitrate the mass ratio that feeds intake of lanthanum and Y type molecular sieve be 10~ 15: 0.5~2: 100.Experiment shows for this catalyst, in this above-mentioned process parameters range, the conversion ratio of carbazole And selectivity is relatively high, outside this process parameters range, also has the conversion ratio and selectivity of certain carbazole, but relatively low, or Say no industrial value.
The temperature condition of the first time drying is 105 DEG C, and the temperature condition of roasting is 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 is relatively high, outside this process parameters range, also has the conversion ratio and selectivity of certain carbazole, but 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 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 of carbazole are relatively high.
The temperature condition of second of drying is 105 DEG C, and the temperature condition of second of roasting is 450~650 DEG C, roasting 1~5h of time.In this above-mentioned process parameters range, the conversion ratio and selectivity of carbazole are relatively high.
The third time and the 4th time drying temperature condition be 105 DEG C, third time roasting temperature condition be 450~ 550 DEG C, 0.5~4h of calcining time.
The present invention especially prepares carbazole in diphenylamines catalytic dehydrogenation another object is that purposes prepared by proposition above method In application.
Be using the nickel-base catalyst that this preparation method obtains nickel oxide, lanthana etc. have been loaded on Y molecular sieve, and Carried out fluorine, boron modification adjusts the acidity of catalyst, but since that there is no dehydrogenations is living for nickel oxide, lanthana on Y molecular sieve etc. 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 is mixed with diphenylamines, is taken off in hydrogen atmosphere Hydrogen reaction.
After the above dehydrogenation reaction, diphenylamines conversion ratio is at least 60.35%, 95.11% or more carbazole selectivity.It will be anti- It answers material to be absorbed with water, the crude product of certain moisture content can be obtained, fine work is obtained after purification, this technique processing method is simple, does not have There is the diphenylamines reuse of reaction.
Present invention process avoids the defect for using noble metal for high production cost brought by catalyst, while also avoiding Using a large amount of organic solvents, intermittently reacted the disadvantages of, the service life of catalyst of the present invention is up to 180 days or more, no It must frequently replace.
The operation of specific reduction treatment is: the fluorinated modified Ni-based dehydrogenation of the ammonium fluosilicate being placed in described de- Hydrogen reaction is in fixed bed, in a hydrogen atmosphere, with the heating rate of 5 DEG C/min by fluorinated modified Ni-based of the ammonium fluosilicate Dehydrogenation is warming up to 450 DEG C, recovery time 4h.The purpose restored that sequentially heats up is: mild steady promoted restores Temperature prevents hydrogenating reduction from burning out catalyst since reduction reaction heat release leads to reduction process temperature runaway in the process, influences to be catalyzed The activity of agent and selectivity；Experiment shows recovery time 4h at 450 DEG C, it can guarantees that the metal oxides such as nickel oxide are complete Elemental metals are reduced to, the active of catalyst, selectivity are best.
To be restored treated after the catalyst temperature is down to reaction temperature, then is passed through diphenylamines to fixed bed and is taken off Hydrogen reaction.
The condition of the dehydrogenation reaction are as follows: pressure is -0.02~-0.01atm, temperature is 350~450 DEG C, air speed 0.5 The mixing molar ratio of ~ 4/h, hydrogen and diphenylamines are 1~10: 1.The process conditions such as the temperature of dehydrogenation reaction are the property with catalyst Can be closely related, therefore, the problems such as there is no the Common Parameters of conventional dehydrogenation.Experiment shows for this catalyst, In this above-mentioned process parameters range, the conversion ratio and selectivity of carbazole are relatively high.
Specific 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 Incipient impregnation 1 day at room temperature 100g, 105 DEG C of drying 4h, 450 DEG C of roasting 4h；It is water-soluble to add the ammonium fluosilicate that concentration is 2 % Liquid 1000mL, stirring fluorination 1h at 85 DEG C, filtering, 105 DEG C of drying 4h, 550 DEG C of roasting 4h；It takes 8.88g boric acid to mix with water to match Above-mentioned material room temperature volumetric is impregnated at boric acid aqueous solution, then 105 DEG C of drying, molding, 105 DEG C after shaping assistant is added Drying, 450 DEG C of roasting 3h obtain catalyst.
It takes a certain amount of above-mentioned catalyst to be added in fixed bed, in a hydrogen atmosphere, is heated up with the heating rate of 5 DEG C/min To 450 DEG C of hydrogenating reduction 4h；It is down to reaction temperature to reaction bed temperature, adjustment reaction pressure is -0.02atm, and control is anti- 360 DEG C of temperature are answered, imports diphenylamines, air speed 0.5h with pump-1, the mixing molar ratio of hydrogen and diphenylamines is 2: 1.
Reaction mass is directly absorbed with water, analyzes 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 Incipient impregnation 1 day at room temperature 100g, 105 DEG C of drying 4h, 500 DEG C of roasting 4h；It is water-soluble to add the ammonium fluosilicate that concentration is 5 % Liquid 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 Aqueous solution impregnates above-mentioned material room temperature volumetric, then 105 DEG C of drying, be added molding after shaping assistant, 105 DEG C of drying, 450 DEG C of roasting 3h obtain catalyst.
It takes a certain amount of above-mentioned catalyst to be added in fixed bed, in a hydrogen atmosphere, is heated up with the heating rate of 5 DEG C/min To 450 DEG C of hydrogenating reduction 4h；It is down to reaction temperature to reaction bed temperature, adjustment reaction pressure is -0.01atm, and control is anti- 350 DEG C of temperature are answered, imports diphenylamines, air speed 1h with pump-1, the mixing molar ratio of hydrogen and diphenylamines is 5: 1.
Reaction mass is directly absorbed with water, analyzes 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) it is soluble in water with Y point Son sieves incipient impregnation 1 day at room temperature 100g, 105 DEG C of drying 4h, 500 DEG C of roasting 4h；Add the ammonium fluosilicate that concentration is 4 % Aqueous solution 600mL, stirring fluorination 1.5h at 85 DEG C, filtering, 105 DEG C of drying 4h, 450 DEG C of roasting 4h；Take 14.21g boric acid and water It is made into boric acid aqueous solution to impregnate above-mentioned material room temperature volumetric, then 105 DEG C of drying, molding, 105 after shaping assistant is added DEG C drying, 500 DEG C of roasting 4h obtain catalyst.
It takes a certain amount of above-mentioned catalyst to be added in fixed bed, in a hydrogen atmosphere, is heated up with the heating rate of 5 DEG C/min To 450 DEG C of hydrogenating reduction 4h；It is down to reaction temperature to reaction bed temperature, adjustment reaction pressure is -0.02atm, and control is anti- 440 DEG C of temperature are answered, imports diphenylamines, air speed 2h with pump-1, the mixing molar ratio of hydrogen and diphenylamines is 10: 1.
Reaction mass is directly absorbed with water, analyzes 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 Incipient impregnation 1 day at room temperature 100g, 105 DEG C of drying 4h, 550 DEG C of roasting 3h；It is water-soluble to add the ammonium fluosilicate that concentration is 3 % Liquid 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 Aqueous solution impregnates above-mentioned material room temperature volumetric, then 105 DEG C of drying, be added molding after shaping assistant, 105 DEG C of drying, 550 DEG C of roasting 4h obtain catalyst.
It takes a certain amount of above-mentioned catalyst to be added in fixed bed, in a hydrogen atmosphere, is heated up with the heating rate of 5 DEG C/min To 450 DEG C of hydrogenating reduction 4h；It is down to reaction temperature to reaction bed temperature, adjustment reaction pressure is -0.01atm, and control is anti- 450 DEG C of temperature are answered, imports diphenylamines, air speed 4h with pump-1, the mixing molar ratio of hydrogen and diphenylamines is 1: 1.
Reaction mass is directly absorbed with water, analyzes product, and diphenylamines conversion ratio is 71.65%, carbazole selectivity 97.21%.
Comparative example 1(is 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 Incipient impregnation 1 day at room temperature 100g, 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 Above-mentioned material room temperature volumetric is impregnated, then 105 DEG C of drying, molding, 105 DEG C of drying, 450 DEG C of roastings after shaping assistant are added It burns 3h and obtains catalyst.
It takes a certain amount of above-mentioned catalyst to be added in fixed bed, in a hydrogen atmosphere, is heated up with the heating rate of 5 DEG C/min To 450 DEG C of hydrogenating reduction 4h；It is down to reaction temperature to reaction bed temperature, adjustment reaction pressure is -0.02atm, and control is anti- 380 DEG C of temperature are answered, imports diphenylamines, air speed 1h with pump-1, the mixing molar ratio of hydrogen and diphenylamines is 5: 1.
Reaction mass is directly absorbed with water, analyzes product, and diphenylamines conversion ratio is 37.56%, carbazole selectivity 91.94%.
Comparative example 2(is without boron modification processing):
Weigh six water nickel nitrate 74.31g(Ni:15g), lanthanum nitrate hexahydrate 6.23g(La:2g) soluble in water and Y molecular sieve Incipient impregnation 1 day at room temperature 100g, 105 DEG C of drying 4h, 500 DEG C of roasting 4h；It is water-soluble to add the ammonium fluosilicate that concentration is 5 % Liquid 500mL, stirring fluorination 2h at 80 DEG C, filtering, 105 DEG C of drying 4h, 500 DEG C of roasting 4h；Without boron modification processing, directly add Enter molding after shaping assistant, 105 DEG C of drying, 450 DEG C of roasting 3h obtain catalyst.
It takes a certain amount of above-mentioned catalyst to be added in fixed bed, in a hydrogen atmosphere, is heated up with the heating rate of 5 DEG C/min To 450 DEG C of hydrogenating reduction 4h；It is down to reaction temperature to reaction bed temperature, adjustment reaction pressure is -0.02atm, and control is anti- 380 DEG C of temperature are answered, imports diphenylamines, air speed 1h with pump-1, the mixing molar ratio of hydrogen and diphenylamines is 5: 1.
Reaction mass is directly absorbed with water, analyzes 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 of drying 4h, 500 DEG C of roasting 4h；The % ammonium fluosilicate solution 500mL that concentration is 5 is added, stirring fluorination 2h, mistake at 80 DEG C Filter, 105 DEG C of drying 4h, 500 DEG C of roasting 4h；Take that 8.88g boric acid and water are made into boric acid aqueous solution and above-mentioned material room temperature is inferior Volume impregnation, then 105 DEG C drying, be added shaping assistant after molding, 105 DEG C drying, 450 DEG C of roasting 3h obtain catalyst.
It takes a certain amount of above-mentioned catalyst to be added in fixed bed, in a hydrogen atmosphere, is heated up with the heating rate of 5 DEG C/min To 450 DEG C of hydrogenating reduction 4h；It is down to reaction temperature to reaction bed temperature, adjustment reaction pressure is -0.02atm, and control is anti- 380 DEG C of temperature are answered, imports diphenylamines, air speed 1h with pump-1, the mixing molar ratio of hydrogen and diphenylamines is 5: 1.
Reaction mass is directly absorbed with water, analyzes product, and diphenylamines conversion ratio is 46.21%, carbazole selectivity 51.36%.
By the way that the above comparative example 1,2,3 and embodiment 1,2,3,4 are compared, it is seen then that urged using made from present invention process Agent is applied to diphenylamines catalytic dehydrogenation and prepares in carbazole, is greatly improved the conversion ratio of diphenylamines, improves the selectivity of carbazole.
Embodiment 5, life experiment:
It is added in fixed bed with catalyst prepared by embodiment 2, in a hydrogen atmosphere, with the heating rate of 5 DEG C/min It is warming up to 450 DEG C of hydrogenating reduction 4h；It is down to reaction temperature to reaction bed temperature, adjustment reaction pressure is -0.01atm, control 380 DEG C of reaction temperature processed, diphenylamines, air speed 0.5h are imported with pump-1, the mixing molar ratio of hydrogen and diphenylamines is 5: 1.Even Continuous reaction 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 service life record sheet
As seen from the above table: catalyst is slightly decreased in first three days activity, and later period catalytic activity is almost unchanged, illustrates the catalysis Agent has preferable service life.

Claims (9)

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 successively carried out and roasts for the first time It burns；
Product after roasting for the first time is mixed with ammonium fluosilicate aqueous solution and carries out fluorination reaction, is successively carried out again after filtering Second of drying and second of roasting；The mass percent of ammonium fluosilicate is 2~5%, described the in the ammonium fluosilicate aqueous solution The mixing ratio of product and ammonium fluosilicate aqueous solution after primary roasting is 1g: 5~10 mL；
By the product after roasting for the second time after boric acid aqueous solution impregnates, third time drying is carried out；
Product after third time is dried is mixed with shaping assistant, after molding, then is successively roasted 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: nickel in the nickel nitrate, lanthanum in lanthanum 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 condition of roasting is 350~650 DEG C for the first time, 0.5~5h of calcining time.
4. the preparation method of catalyst according to claim 1, it is characterised in that: the temperature condition of second drying is 105 DEG C, the temperature condition of second of roasting is 450~650 DEG C, 1~5h of calcining time.
5. the preparation method of catalyst according to claim 1, it is characterised in that: the temperature of the third time and the 4th drying Degree condition is 105 DEG C, and the temperature condition of third time roasting is 450~550 DEG C, 0.5~4h of calcining time.
6. the fluorinated modified Ni-based dehydrogenation of the ammonium fluosilicate of method preparation as described 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 It in atmosphere after reduction treatment, then mixes with diphenylamines, dehydrogenation reaction is carried out in hydrogen atmosphere.
7. application according to claim 6, 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 the heating rate of 5 DEG C/min by the ammonium fluosilicate fluorine Change modified Ni-based dehydrogenation and is warming up to 450 DEG C, recovery time 4h.
8. application according to claim 7, it is characterised in that: to be restored treated that the catalyst temperature is down to reaction After temperature, then diphenylamines is passed through to fixed bed and carries out dehydrogenation reaction.
9. application according to claim 8, it is characterised in that: the condition of the dehydrogenation reaction are as follows: pressure be -0.02~- 0.01atm, temperature are 350~450 DEG C, air speed is 0.5 ~ 4 h-1, hydrogen and diphenylamines mixing molar ratio be 1~10: 1.
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Patent Citations (2)

* Cited by examiner, † Cited by third party
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