CN104941638B - A kind of dehydrogenation and its preparation and application - Google Patents
A kind of dehydrogenation and its preparation and application Download PDFInfo
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- CN104941638B CN104941638B CN201410118263.2A CN201410118263A CN104941638B CN 104941638 B CN104941638 B CN 104941638B CN 201410118263 A CN201410118263 A CN 201410118263A CN 104941638 B CN104941638 B CN 104941638B
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Abstract
The present invention relates to a kind of dehydrogenation, including (a), using aluminum oxide as carrier, the heap density of the carrier is 0.4~0.6g/ml, and specific surface area is 100~300m2/g；(b) using metal platinum as active component, the metal platinum is the 0.3 0.5% of the catalyst gross mass；(c) using tin, alkali metal, alkaline-earth metal, zirconium and at least one rare earth metal as accelerator, tin accounts for the 0.6 1.0% of the catalyst gross mass in the accelerator；Zirconium accounts for the 0.1 1.0% of the catalyst gross mass；Alkali metal accounts for the 0 2% of the catalyst gross mass；Alkaline-earth metal accounts for the 0 2% of the catalyst gross mass；Rare earth metal accounts for the 0.1 1.0% of the catalyst gross mass；(d) using halogen as modifying agent, the halogen accounts for the 0.05 0.5% of the catalyst gross mass.The invention further relates to the preparation method of the catalyst and application method.
Description
Technical field
The present invention relates to a kind of catalyst for producing isobutylene by catalytic dehydrogenation of isobutane and its preparation method and catalytic dehydrogenation work
Skill.
Background technology
Isobutene is a kind of very important Organic Chemicals, and its demand remains that what is increased becomes in the world
Gesture, it may not only be applied to produce the elastomers such as isoprene rubber, butyl rubber, polyisobutene, available for making gasoline and lubricating oil
Additive, and also act as the raw material of other fine chemical products.Isobutene has become the most popular essence in the whole world at present
One of chemical product is refined, but very big breach but occurs in the supply of isobutene.Growth and potentiality in isobutene production line
Maximum is dehydrogenation of isobutane technique.Dehydrogenation of isobutane reaction is controlled by thermodynamical equilibrium, and high temperature, the harsh conditions of low pressure are favourable
In the progress of reaction.But too high reaction temperature, not only aggravate iso-butane cracking reaction and deep dehydrogenation, selective isobutene
Decline；The carbon deposit of catalyst surface is also accelerated simultaneously, makes rapid catalyst deactivation.Therefore, the exploitation of dehydrogenation of isobutane technique,
Emphasis is to develop the dehydrogenation with high stability, high activity and high selectivity.
Chinese patent 201010207838.X discloses a kind of catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof,
The catalyst is support modification agent with alkalinous metal auxiliary agent using the stanniferous mesoporous aluminum oxide molecular sieve of skeleton as carrier, total immersion
H2PtCl6And SnCl4Mixed aqueous solution, and after drying, activating and reducing be made.Alkalinous metal is group ia, group iia, dilute
The combination of one or several kinds of metals in earth metal.Based on mesoporous aluminum oxide molecular sieve quality meter, carrier middle skeleton tin metal
Weight/mass percentage composition be 0.01~20%；Based on the mesoporous aluminum oxide molecular sieve carrier quality meter that skeleton is stanniferous, active metal platinum
Weight/mass percentage composition be 0.01~10%, promoter metal tin is 0.01~10wt.%, and auxiliary agent alkalinous metal is 0.01~5wt.%.
Although the catalyst has higher selectivity and conversion ratio under conditions of high temperature, low pressure, selected after evaluation time is 180h
Selecting property and conversion ratio are respectively 94.7% and 36.2%, but still are had much room for improvement.
Chinese patent CN102000593 discloses a kind of dehydrogenation of isobutane and produces the catalyst of isobutene, its preparation method
And dehydrogenating technology.Using refractory oxides as carrier, its active component includes catalyst described in the invention：As major catalyst
Platinum group, as the first auxiliary agent with IVA races metal element, as the alkali metal of the second auxiliary agent, and conduct
Modifying agent is with halogen.Then catalyst is made using equi-volume impregnating dipping active component solution by being calcined.At this
The iso-butane of patent is prepared in the dehydrogenating technology of isobutene, is reduced coking amount as diluent using hydrogen and steam mixture, is prolonged
The service cycle of catalyst has been grown, has obtained higher iso-butane conversion ratio, selective isobutene.Such as the patent Example 3
Shown in table 4, selectivity and conversion ratio are respectively 99.3% and 40.4% after evaluation time 45h；After evaluation time 96h, choosing
Selecting property and conversion ratio are respectively 98.7% and 41.6%；After evaluation time 168h, selectivity and conversion ratio are respectively 98.6% He
43.6%；After evaluation time 220h, selectivity and conversion ratio are respectively 97.4% and 41.0%, but be can be seen that from as above data,
Its conversion ratio and stability still have much room for improvement.
The content of the invention
It is an object of the invention to provide the dehydrogenation of isobutane catalyst of high stability, while a kind of iso-butane is also provided and taken off
The technique of hydrogen.
The invention discloses the dehydrogenation that a kind of iso-butane for adding vapor faces hydrogen dehydrogenation preparing isobutene.The catalysis
Agent is using aluminum oxide as carrier, and the heap density of carrier is 0.4~0.6g/ml, and specific surface area is 100~300m2/g.Load platinum family gold
Belong to active component, with alkaline-earth metal, alkali metal, zirconium metal and rare earth metal contain halogen family member as auxiliary agent in catalyst
Element is used as modifying agent.
The present invention provides a kind of dehydrogenation, including：
(a) using aluminum oxide as carrier, the heap density of the carrier is 0.4~0.6g/ml, specific surface area is 100~
300m2/g；
(b) using metal platinum as active component, the metal platinum is the 0.3-0.5% of the catalyst gross mass；
(c) using tin, alkali metal, alkaline-earth metal, zirconium and at least one rare earth metal as accelerator, tin in the accelerator
Account for the 0.6-1.0% of the catalyst gross mass；Zirconium accounts for the 0.1-1.0% of the catalyst gross mass；Alkali metal accounts for the catalysis
The 0-2% of agent gross mass；Alkaline-earth metal accounts for the 0-2% of the catalyst gross mass；Rare earth metal accounts for the catalyst gross mass
0.1-1.0%；
(d) using halogen as modifying agent, the halogen accounts for the 0.05-0.5% of the catalyst gross mass.
In a preferred embodiment of the present invention, the alumina support is γ-Al2O3。
In a preferred embodiment of the present invention, described halogen modified dose in fluorine, chlorine, bromine and iodine at least one
Kind.
The present invention provides a kind of method for preparing above-mentioned catalyst, comprises the following steps：
I) alumina support is impregnated into the solution containing rare earth metal, carrier is loaded with rare earth ion；
Ii the alumina support that rare earth metal is loaded with step i) Suo Shu) is impregnated into the molten of alkali metal containing and alkaline-earth metal again
Liquid, make carrier loaded upper alkali and alkaline earth metal ions ion；
Iii) with step ii) it is obtained be loaded with rare earth ion, alkali and alkaline earth metal ions alumina support again
The ethanol solution hydrochloride containing platinum salt, pink salt and zirconates is impregnated, is then dried and is calcined, finally reduce and obtain in hydrogen
The catalyst.
In a preferred embodiment of the present invention, in the preparation method of above-mentioned catalyst, step iii) described in
Dry to dry 1-10 hours at being 50-200 DEG C in temperature, it is described to be roasted in 400-600 DEG C of roasting temperature 1-10 hour.
Step i) and ii) in, after carrier loaded rare earth ion and after carrier loaded alkali and alkaline earth metal ions ion, it can also enter
The row drying and roasting.
In a preferred embodiment of the present invention, step iii) described in be reduced in hydrogen at 400-600 DEG C
At a temperature of reduce 1-10 hours.
In a preferred embodiment of the present invention, the platinum salt is chloroplatinic acid, the pink salt be stannous chloride and/or
Stannic chloride, the zirconates are zirconium nitrate or zirconyl nitrate, the solution of the alkali metal containing and/or alkaline-earth metal and containing rare earth metal
Solution be nitrate corresponding with the metal and/or chlorination salting liquid.
In a preferred embodiment of the present invention, hydrochloric acid is 36-38 mass % concentration in the ethanol solution hydrochloride
Hydrochloric acid after concentrated hydrochloric acid or dilution, ethanol are the hydrous ethanol after absolute ethyl alcohol or dilution, and the body of concentrated hydrochloric acid and absolute ethyl alcohol
Product proportioning is 1:2-1:3.
Catalyst of the present invention can also use the method for total immersion to prepare：
A kind of method for preparing above-mentioned catalyst, it is with γ-Al2O3For carrier, with containing platinum, tin, zirconium, alkali metal, alkaline earth
The ethanol solution hydrochloride dipping of at least one of metal and rare earth metal, at 50-200 DEG C, preferably 80-150 DEG C, dry
1-10 hours, preferably 5-8 hours；At 400-600 DEG C, preferably 450-550 DEG C, 1-10 hours are calcined, preferably 5-8 hours, are obtained
To catalyst precarsor；Then in hydrogen, at 400-600 DEG C, preferably 500-550 DEG C, 1-10 hours are reduced, preferably 5-10 is small
When, i.e., the catalyst of the dehydrogenation of isobutane of the obtained present invention.
The catalyst of preparation presses the Mass Calculation of catalyst, and the weight/mass percentage composition of platinum element is：0.3-0.5%；Tin element
Weight/mass percentage composition be：0.6-1.0%；Alkali metal is 0-2%, alkaline-earth metal 0-2%, and zirconium is：0.1-1.0%；Rare earth metal
For：0.1-1.0%；Chlorine is：0.05-0.5%.
The present invention also provides a kind of method of the progress preparing isobutene through dehydrogenation of iso-butane using the catalyst, including as follows
Step：
I the catalyst) is filled in the reactor, and is passed through vapor；
II the gaseous mixture of iso-butane, hydrogen and/or vapor composition) is then passed to, carries out dehydrogenation of isobutane reaction.
In a preferred embodiment of the present invention, step II) described in the mol ratio of the iso-butane that is passed through and hydrogen
For 0.1-4.0, the mol ratio of vapor and iso-butane is 0-5, and reaction pressure 0-0.5MPa, reaction temperature is 500-700 DEG C,
The air speed of the iso-butane of charging is 1-1000h-1。
For reaction product after isolating hydrogen gas and water, pyrolysis product and alkene, unreacted raw material iso-butane is recycled back to reaction
Device import uses as other industrial chemicals and fuel.
The technique of preparing isobutene through dehydrogenation of iso-butane of the present invention is first to add vapor in dehydrogenation reaction process, so
The gaseous mixture for being passed through iso-butane, hydrogen and/or vapor composition afterwards is principal character.During the course of the reaction, water is first added to steam
Gas, thus it is possible to vary the state of catalyst surface, the carbon deposit of catalyst surface can be suppressed.Vapor is added during the course of the reaction,
Carbon deposit except suppressing catalyst surface, the partial pressure of system can also be reduced, improve the conversion ratio of reaction.Meanwhile iso-butane takes off
Hydrogen reaction is a highly endothermic reaction, and the addition of vapor can provide heat for reaction, reach the purpose for improving conversion ratio.
The mode that vapor adds can be directly added into vapor, can also add water and raw material gasifies together.
The method of above-mentioned preparing isobutene through dehydrogenation of iso-butane is a kind of to face hydrogen dehydrogenation work on above-mentioned dehydrogenation
Skill.The dehydrogenating technology containing hydrogen namely in alkane is fed.Although the addition of hydrogen is advantageous to the side reaction of dehydrogenation reaction
Progress, but its addition can suppress the carbon deposit of catalyst surface, be advantageous to extend the life-span of catalyst, while also be reaction
Heat is provided.
Beneficial effects of the present invention：
The technique of preparing isobutene through dehydrogenation of iso-butane of the present invention is applicable preparing isobutene through dehydrogenation of iso-butane.Taken off with iso-butane
It is excellent using the catalyst of the present invention and the preparing isobutene through dehydrogenation of iso-butane reactivity worth of technique exemplified by hydrogen preparing isobutene, one way
Conversion ratio is more than 46.9%, and selectivity more than 99.1%, catalyst can maintain more than 150 days.Compared with prior art, it is of the invention
The catalyst and its preparation method and dehydrogenating technology of the catalytic dehydrogenation of isobutane of offer have conversion ratio, selectivity and high excellent of stability
Point.To solve the catalyst that the industrialized unit of preparing propylene by dehydrogenating propane or preparing isobutene through dehydrogenation of iso-butane uses in the world at present
Inactivated because of easy carbon deposit under high temperature, need this topic of cyclic regeneration, there is provided new method.Propylene and isobutene, which can be alleviated, to be needed
The situation of aggravation, Optimum utilization refinery gas and associated gas are asked, there is significant Social benefit and economic benefit.
Embodiment
The present invention is further detailed with reference to embodiments, but the scope of the present invention is not limited to following reality
Apply example.
Catalyst Preparation Example
Embodiment 1：
The present invention uses γ-Al2O3Carrier is prepared with known method, and it is any to can use known method to be processed into
Form.The embodiment uses average length 4mm, average diameter 2mm strip γ-Al2O3。
Take above-mentioned strip γ-Al2O3Cerous nitrate solution is impregnated using incipient impregnation method, carrier is loaded with cerium, through 120
DEG C, dry 10 hours；Through 600 DEG C, it is calcined 6 hours.
Cerium strip γ-Al are loaded with by above-mentioned2O3The carrier solution of incipient impregnation potassium nitrate and magnesium nitrate again, bears carrier
Potassium and magnesium in load, dried 10 hours through 120 DEG C；It is calcined 6 hours through 600 DEG C.
By the above-mentioned strip γ-Al for being loaded with metallic cerium, potassium and magnesium2O3Carrier impregnates the salt containing platinum salt, pink salt and zirconates again
Sour ethanol solution, concentrated hydrochloric acid in the ethanol solution hydrochloride（36-38 mass %）Volume proportion with absolute ethyl alcohol is 2:4, so
The carrier is contained platinum, tin and zirconium, dried 10 hours through 120 DEG C, and be calcined 6 hours at 600 DEG C, before obtaining catalyst
Body；Then in hydrogen atmosphere, and reduce at 500 DEG C the catalyst precarsor 10 hours, that is, obtain catalyst A.
By the Mass Calculation of catalyst, catalyst A contains：Platinum 0.5%, tin 1.5%, potassium 1.0%, magnesium 1.0%, cerium 1.0%, zirconium
1.0% and chlorine 0.4%.
Embodiment 2
Take a diameter of 2mm spherical shape γ-Al2O3Lanthanum nitrate hexahydrate is impregnated using incipient impregnation method, is loaded with carrier
Lanthanum, through 120 DEG C, dry 10 hours；Through 600 DEG C, it is calcined 6 hours.
By the above-mentioned spherical shape γ-Al for being loaded with lanthanum2O3The carrier solution of incipient impregnation potassium nitrate and magnesium nitrate again, makes load
The upper potassium of body load and magnesium, are dried 10 hours through 120 DEG C；It is calcined 6 hours through 600 DEG C.
By the above-mentioned spherical shape γ-Al for being loaded with lanthanum, potassium and magnesium2O3Carrier, then incipient impregnation contain platinum salt, pink salt and zirconium
The ethanol solution hydrochloride of salt, wherein the concentrated hydrochloric acid in the ethanol solution hydrochloride（36-38 mass %）Match somebody with somebody with the volume of absolute ethyl alcohol
Than for 1:3, the carrier is loaded with platinum, tin and zirconium, dried 10 hours through 120 DEG C, and be calcined 6 hours at 600 DEG C, urged
Agent precursor；Then in hydrogen atmosphere, and reduce at 500 DEG C the catalyst precarsor 10 hours, that is, obtain catalyst B.
By the Mass Calculation of catalyst, catalyst B contains：Platinum 0.5%, tin 1.5%, potassium 1.0%, magnesium 1.0%, lanthanum 1.0%, zirconium
1.0% and chlorine 0.3%.
Embodiment 3
It is 4mm, a diameter of 2mm trilobes γ-Al to take length2O3It is molten using incipient impregnation method dipping cerous nitrate
Liquid, carrier is loaded with cerium, through 120 DEG C, dry 10 hours；Through 600 DEG C, it is calcined 6 hours.
Metal cerium ion trilobes γ-Al are loaded with by above-mentioned2O3Carrier incipient impregnation potassium nitrate and magnesium nitrate again it is molten
Liquid, make carrier loaded upper potassium and magnesium, dried 10 hours through 120 DEG C；It is calcined 6 hours through 600 DEG C.
By the above-mentioned strip γ-Al for being loaded with cerium, potassium and magnesium2O3Carrier, then incipient impregnation contain platinum salt, pink salt and zirconates
Ethanol solution hydrochloride, wherein the concentrated hydrochloric acid in the ethanol solution hydrochloride（36-38 mass %）With the volume proportion of absolute ethyl alcohol
For 2:4, the carrier is loaded with platinum, tin and zirconium, dried 10 hours through 120 DEG C, and be calcined 6 hours at 600 DEG C, obtain catalyst
Precursor；Then in hydrogen atmosphere, and reduce at 500 DEG C the catalyst precarsor 10 hours, that is, obtain catalyst C.
By the Mass Calculation of catalyst, catalyst C contains：Platinum 0.5%, tin 1.5%, potassium 1%, magnesium 1.0%, cerium 1.0%, zirconium
1.5% and chlorine 0.4%.
Comparative example 1
It is 4mm, a diameter of 2mm trilobes γ-Al to take length2O3It is molten using incipient impregnation method dipping cerous nitrate
Liquid, carrier is loaded with cerium, through 120 DEG C, dry 10 hours；Through 600 DEG C, it is calcined 6 hours.
Cerium trilobes γ-Al are loaded with by above-mentioned2O3The carrier solution of incipient impregnation potassium nitrate and magnesium nitrate again, makes load
The upper potassium of body load and magnesium, are dried 10 hours through 120 DEG C；It is calcined 6 hours through 600 DEG C.
By the above-mentioned trilobes γ-Al for being loaded with cerium, potassium and magnesium2O3Carrier, then incipient impregnation contain platinum salt, pink salt and
Concentrated hydrochloric acid in the aqueous hydrochloric acid solution of zirconates, wherein aqueous hydrochloric acid solution（36-38 mass %）Volume proportion with water is 2:4, make institute
State carrier and be loaded with platinum, tin and zirconium, dried 10 hours through 120 DEG C, and be calcined 6 hours at 600 DEG C, obtain catalyst precarsor；So
Afterwards in hydrogen atmosphere, and reduce at 500 DEG C the catalyst precarsor 10 hours, that is, obtain comparative catalyst D.
By the Mass Calculation of catalyst, the weight/mass percentage composition of comparative catalyst's D platiniferous is：0.5%, stanniferous quality hundred
Point content is：1.5%（The content range of the present invention is exceeded）；The weight/mass percentage composition of alkali metal containing potassium and alkaline-earth metal magnesium is all
For：1.0%；Weight/mass percentage composition containing rare-earth element cerium is：1.0%；Weight/mass percentage composition containing zirconium is 1.5%（This hair is exceeded
Bright content range）, chloride weight/mass percentage composition is：0.4%.
Catalyst Application Example
Embodiment 5
Dehydrogenation of isobutane reaction is carried out in a stainless steel tubular reactor, is separately added into catalyst A, B, C and contrast is urged
Agent D10ml, pre-reduction temperature are 500 DEG C, 10 hours time.Catalyst after reduction can be used to dehydrogenation reaction.Reaction is opened
Before beginning, it is 1000h first to lead to air speed-1Vapor, the gaseous mixture that iso-butane and hydrogen are added after 5min carries out dehydrogenation reaction, described
The volume ratio of iso-butane, hydrogen and vapor is 1 in gaseous mixture:1:1, the initial temperature of dehydrogenation reaction is 560 DEG C, reaction pressure
For 0.1MPa, the air speed of iso-butane is 1000h-1, reaction product uses gas chromatographic analysis after cooling, according to the result meter of analysis
Calculate the conversion ratio of iso-butane and the selectivity of isobutene.Catalyst A, B, C and D reaction result are shown in Table 2.
Embodiment 6
Dehydrogenation of isobutane reaction is carried out in a stainless steel tubular reactor, catalyst A loading amount 10ml, and pre-reduction temperature is
500 DEG C, 10 hours time.Catalyst after reduction can be used to dehydrogenation reaction.Before reaction starts, it is 1000h first to lead to air speed-1's
Vapor, the gaseous mixture that iso-butane and hydrogen are added after 5min carry out dehydrogenation reaction, iso-butane, hydrogen and water in the gaseous mixture
The volume ratio of steam is 2:2:1, the initial temperature of dehydrogenation reaction is 560 DEG C, reaction pressure 0.1MPa, and the air speed of iso-butane is
1000h-1, reaction product uses gas chromatographic analysis after cooling, according to the conversion ratio and isobutyl of the result of analysis calculating iso-butane
The selectivity of alkene, the present embodiment the results are shown in Table 3.
Comparative example 2
Dehydrogenation of isobutane reaction is carried out in a stainless steel tubular reactor, catalyst A loading amount 10ml, and pre-reduction temperature is
500 DEG C, 10 hours time.Catalyst after reduction can be used to dehydrogenation reaction.Reaction is passed through iso-butane, hydrogen and water when starting
The gaseous mixture of steam carries out dehydrogenation reaction, and the volume ratio of iso-butane, hydrogen and vapor is 2 in the gaseous mixture:2:1, dehydrogenation
The initial temperature of reaction is 560 DEG C, reaction pressure 0.1MPa, and the air speed for feeding alkane is 1000h-1, reaction product is through cooling
Gas chromatographic analysis is used afterwards, and the conversion ratio of iso-butane and the selectivity of isobutene are calculated according to the result of analysis.This comparative example
Reaction result is shown in Table 3.
Comparative example 3
Dehydrogenation of isobutane reaction is carried out in a stainless steel tubular reactor, catalyst A loading amount 10ml, and pre-reduction temperature is
500 DEG C, 10 hours time.Catalyst after reduction can be used to dehydrogenation reaction.Reaction is passed through iso-butane and hydrogen when starting
Gaseous mixture carries out dehydrogenation reaction, and the volume ratio of iso-butane and hydrogen is 1 in the gaseous mixture:1, the initial temperature of dehydrogenation reaction is
560 DEG C, reaction pressure 0.1MPa, the air speed for feeding alkane is 1000h-1, reaction product uses gas chromatographic analysis after cooling,
The conversion ratio of iso-butane and the selectivity of isobutene are calculated according to the result of analysis.The reaction result of this comparative example is shown in Table 3.
The catalyst with being prepared without using the preparation method of ethanol solution hydrochloride is compared it can be seen from table 1 and 2
（Comparative example 1）, the iso-butane conversion of the catalyst prepared in the present invention using the method for preparing catalyst of ethanol solution hydrochloride
Rate, selectivity and stability will be more excellent, and the ethanol solution hydrochloride for illustrating to use in the present invention is improving iso-butane conversion
Rate, selectivity and stability and aspect serve key effect.
As can be seen from Table 3, for identical catalyst A, after identical evaluation time, in this patent embodiment 6
Iso-butane conversion ratio and selectivity are than high in comparative example 2 and comparative example 3, this explanation embodiment
The preparing isobutene through dehydrogenation of iso-butane technique of vapor is first passed through described in 6 can improve conversion ratio and the choosing of iso-butane
Selecting property.
Table 1
Table 2
* conversion ratio herein is iso-butane conversion ratio, and selectivity is selective isobutene.
Table 3
* conversion ratio herein is iso-butane conversion ratio, and selectivity is selective isobutene.
Claims (10)
1. a kind of method that preparing isobutene through dehydrogenation of iso-butane is carried out using dehydrogenation, the dehydrogenation are included：
(a) using aluminum oxide as carrier, the heap density of the carrier is 0.4~0.6g/mL, and specific surface area is 100~300m2/g；
(b) using metal platinum as active component, the metal platinum is the 0.3-0.5% of the catalyst gross mass；
(c) using tin, alkali metal, alkaline-earth metal, zirconium and at least one rare earth metal as accelerator, tin accounts for institute in the accelerator
State the 0.6-1.0% of catalyst gross mass；Zirconium accounts for the 0.1-1.0% of the catalyst gross mass；Alkali metal accounts for the catalyst
The 0-2% of gross mass；Alkaline-earth metal accounts for the 0-2% of the catalyst gross mass；Rare earth metal accounts for the catalyst gross mass
0.1-1.0%；
(d) using halogen as modifying agent, the halogen accounts for the 0.05-0.5% of the catalyst gross mass；
Methods described comprises the following steps：
I the dehydrogenation) is filled in the reactor, and is passed through vapor；
II the gaseous mixture of iso-butane, hydrogen and/or vapor composition) is then passed to, carries out dehydrogenation of isobutane reaction.
2. according to the method for claim 1, it is characterised in that the aluminum oxide is γ-Al2O3。
3. method according to claim 1 or 2, it is characterised in that described halogen modified dose in fluorine, chlorine, bromine and iodine
At least one.
4. method according to claim 1 or 2, it is characterised in that the preparation method of the dehydrogenation includes as follows
Step：
I) alumina support is impregnated into the solution containing rare earth metal, carrier is loaded with rare earth ion；
Ii) alumina support that rare earth metal is loaded with step i) Suo Shu is impregnated to the solution of alkali metal containing and alkaline-earth metal again, made
Carrier loaded upper alkali and alkaline earth metal ions ion；
Iii) with step ii) it is obtained be loaded with rare earth ion, the alumina support of alkali and alkaline earth metal ions impregnates again
Ethanol solution hydrochloride containing platinum salt, pink salt and zirconates, is then dried and is calcined, and is finally reduced in hydrogen described in obtaining
Catalyst.
Dried described in 5. according to the method for claim 4, it is characterised in that step iii) to be 50-200 DEG C in temperature
It is lower dry 1-10 hours, described to be roasted in 400-600 DEG C of roasting temperature 1-10 hour.
6. it is reduced to described according to the method for claim 4, it is characterised in that step iii) in hydrogen in 400-
1-10 hours are reduced at a temperature of 600 DEG C.
7. according to the method for claim 4, it is characterised in that the platinum salt is chloroplatinic acid, and the pink salt is stannous chloride
And/or stannic chloride, the zirconates are zirconium nitrate or zirconyl nitrate, the solution of the alkali metal containing and alkaline-earth metal and containing rare earth gold
The solution of category is nitrate corresponding with the metal and/or chlorination salting liquid.
8. according to the method for claim 4, it is characterised in that hydrochloric acid is 36-38 mass % in the ethanol solution hydrochloride
Hydrochloric acid after the hydrochloric acid of concentration or dilution, ethanol are absolute ethyl alcohol or the hydrous ethanol after water dilutes, and concentrated hydrochloric acid and anhydrous
The volume proportion of ethanol is 1:2-1:3.
9. method according to claim 1 or 2, it is characterised in that step II) described in the iso-butane that is passed through and hydrogen
Mol ratio is 0.1-4.0, and the mol ratio of vapor and iso-butane is 0-5, reaction pressure 0-0.5MPa, reaction temperature 500-
700 DEG C, the air speed of the iso-butane of charging is 1-1000h-1。
10. the iso-butane that is passed through described according to the method for claim 9, it is characterised in that step II) and hydrogen rub
Your ratio is 0.1-2.0；The mol ratio of vapor and iso-butane is 0.1-0.5；Reaction pressure is 0.1-0.2MPa.
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| CN112237929B (en) * | 2019-07-19 | 2023-04-07 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenating light alkane and method for preparing olefin |
| CN115364876A (en) * | 2021-05-19 | 2022-11-22 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof, and hydrogenation reaction method of polystyrene |
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| CN1088482A (en) * | 1992-12-21 | 1994-06-29 | 中国石油化工总公司 | Catalyst for dehydrogen of saturated hydrocarbon |
| CN1201715A (en) * | 1997-06-09 | 1998-12-16 | 中国科学院大连化学物理研究所 | Catalyst for dehydrogenation of saturated hydrocarbon and preparation thereof |
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| CN102698750B (en) * | 2012-05-22 | 2014-10-01 | 南京沃来德能源科技有限公司 | Catalyst for catalytic dehydrogenation of alkane and preparation method and application thereof |
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| CN1088482A (en) * | 1992-12-21 | 1994-06-29 | 中国石油化工总公司 | Catalyst for dehydrogen of saturated hydrocarbon |
| CN1201715A (en) * | 1997-06-09 | 1998-12-16 | 中国科学院大连化学物理研究所 | Catalyst for dehydrogenation of saturated hydrocarbon and preparation thereof |
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| Title |
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| 铂系丙烷脱氢催化剂助剂研究进展;马占华等;《现代化工》;20111031;第31卷(第10期);第20-23页 * |
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