CN102698750B - Catalyst for catalytic dehydrogenation of alkane and preparation method and application thereof - Google Patents
Catalyst for catalytic dehydrogenation of alkane and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for catalytic dehydrogenation of low-carbon alkane. The gamma-Al2O3 is used as the carrier, wherein the carrier has the bulk density of 0.4-0.6g/ml and the specific surface area of 100-300m<2>/g; the active component which is Pt is supported on the carrier; the Sn, the Na and the La are used as assistants, and the Cl is used as a modifier; the content of the Pt accounts for 0.3-0.5% of the mass of the catalyst, the content of the Sn accounts for 0.6-1.0%, the content of the Na accounts for 0.75-1.0%, the content of the La accounts for 0.8-1.0%, and the content of the Cl accounts for 0.1-0.2%. The process for preparing the corresponding olefin by using the catalyst for dehydrogenation of low-carbon alkane comprises the following steps: adding the precursor of the catalyst into a reactor, introducing hydrogen, reducing the precursor of the catalyst for 1-10 hours at 400-600 DEG C, introducing preheated mixture of low-carbon alkane, hydrogen and steam, and carrying out the dehydrogenation reaction of low-carbon alkane at 500-700 DEG C. The isobutene prepared by adopting the process and the catalyst through dehydrogenation of isobutene has the average conversion rate of more than 30% and the selectivity of more than 95% and can retain for more than 40 days.
Description
Technical field
The present invention relates to a kind of catalyst for the corresponding alkene of low-carbon alkanes catalytic dehydrogenation system and method for making and catalytic dehydrogenation process, especially dehydrogenation of isobutane is produced the production technology of isobutene.
background technology
The corresponding alkene of low-carbon alkanes catalytic dehydrogenation system is an important petrochemical process, and wherein propane and dehydrogenation of isobutane propylene processed and isobutene are even more important.Propylene is the Organic Chemicals of producing polypropylene, acrylonitrile and expoxy propane.In recent years, along with increasing rapidly of the derivative demands such as polypropylene, to the requirement of propylene also expanding day.Isobutene is also a kind of important industrial chemicals, is widely used in multiple Organic Chemicals and the fine chemicals such as synthetic rubber, butyl rubber and polyisobutene.There are a large amount of carbon three carbon four resources in China, is mainly derived from the by-product C of ethylene unit
3c
4after cut, refinery catalytic cracking unit's liquefied gas and MTBE device etherification reaction, residue is mixed carbon four, combination gas etc.And C in these resources
3c
4cut is contained iso-butane composition especially wherein, mostly underuses, and is mostly to burn as fuel, has caused the huge waste of resource.
Various countries, the whole world increase day by day to the demand of propylene, isobutene at present, and various propylene, isobutene production technology and technique are arisen at the historic moment, and utilizing propane and dehydrogenation of isobutane production propylene and isobutene is a main technique wherein.Object of the present invention is developed high conversion exactly, catalyst and technique that the propane of high selectivity and high stability, dehydrogenation of isobutane are produced propylene, isobutene.
For catalyst for dehydrogenation of low-carbon paraffin, a lot of patents are disclosed.Chinese patent 200710023431 discloses a kind of catalyst of take the preparing propylene by dehydrogenating propane that skeleton is carrier containing the ZSM-5 molecular sieve of Sn, Sn in molecular sieve carrier skeleton is the part of catalyst promoter, Sn can also load on ZSM-5 molecular sieve, common promoter effect, the silica alumina ratio (SiO of ZSM-5 molecular sieve of rising
2/ Al
2o
3) be: 5-320; Active component is one or more elements in platinum, palladium, iridium, rhodium, osmium or rhenium, one or more elements in alkalinous metal auxiliary agent Wei IA Zu HeⅡ A family; The mass percentage content of active metal component is: 0.01-2.0%; The gross mass degree of Sn element is 0.1-10%; The mass percentage content of alkalinous metal component is 0.01-5.0%; Catalyst is for dehydrogenating propane reaction, and activity is higher and anti-carbon deposition ability is stronger.
Chinese patent 200710020064 discloses a kind of catalyst for preparing propylene by dehydrogenating propane, take refractory oxides as carrier, take platinum family element metal as major catalyst, YiⅣ A family metal element, rare earth elemental metals are auxiliary agent, halogen is modifier, take resistant to elevated temperatures inorganic oxide as binding agent moulding.This catalyst has higher conversion of propane, Propylene Selectivity and reaction stability under the condition of high temperature, low pressure.Its preparation method is: at 60～100 ℃, refractory oxides is flooded to the rare earth elemental metals aqueous solution 2～10h; Then at 60～180 ℃, dry 2～10h, 400～600 ℃ of roasting 3～10h; By above-mentioned carrier and aqueous solution total immersion 2～10h at 60～100 ℃ of containing platinum family element metal, Ⅳ A family metal element, dry 2～10h at 60～180 ℃; Then add binding agent, extrusion aid and Aci-Jel solvent, extruded moulding.Above-mentioned preformed catalyst is dried to 2～10h at 60～180 ℃, in the air of 400～600 ℃, activate 3～10h, reductase 12～10h in the hydrogen stream of 400～600 ℃.
Chinese patent 200610086006 discloses a kind of catalyst for low-carbon alkanes catalytic dehydrogenation and take the method for its catalytic dehydrogenation of paraffin for preparing propylene that is catalyst.It is characterized in that this catalyst take molecular sieve as carrier, in carrier loaded platinum group metal, it is active component, YiⅣ A family's metallic element and alkaline element are as auxiliary agent, take resistant to elevated temperatures inorganic oxide as binding agent, reaction temperature when above-mentioned catalyst is used for catalytic dehydrogenation of paraffin for preparing propylene is 500～700 ℃, pressure is 0～0.2MPa, and mass space velocity is 2～5h
-1, catalyst regeneration temperature is 500～700 ℃, air air speed is 100～1000h
-1, pressure is 0～1.0Mpa.Adopt preparing propylene by dehydrogenating propane reactivity worth of the present invention excellent, average conversion is 30%, selectively more than 95% can maintain 50 days.
Chinese patent 200810155908 discloses a kind of catalyst for preparing propylene with propane dehydrogenation and preparation method thereof, the Catalysts and its preparation method of the preparing propylene by dehydrogenating propane that the skeleton of take is carrier containing the molecular sieve of rare earth elemental metals, be applicable to gas solid catalytic reaction, it is carrier that this catalyst be take the molecular sieve that skeleton contains rare earth elemental metals, take platinum family element metal as major catalyst, Ⅳ A family metal element, Ⅰ A Zu HuoⅡ A family metal element are auxiliary agent, halogen is modifier, take resistant to elevated temperatures inorganic oxide as binding agent moulding.This catalyst has higher conversion of propane, Propylene Selectivity and reaction stability under the condition of high temperature, low pressure, and anti-Coking Behavior is excellent.
Chinese patent 200710133324 discloses a kind of method that improves the catalyst reaction activity of preparing propylene by dehydrogenating propane:
Step 1 adds inorganic oxide binder, extrusion aid and Aci-Jel solvent in refractory oxides, after mediating evenly, and spin or extruded moulding;
Step 2 is dried 2～10h by the catalyst carrier of above-mentioned preparation at 60 ℃～180 ℃, at 400～800 ℃ of roasting 3～10h;
Step 3 is flooded the carrier after roasting the rare earth metal aqueous solution 2～10h at 60～100 ℃, suction filtration, and distilled water washing, dries 2～10h, 400～600 ℃ of roasting 3～10h for 60 ℃～180 ℃;
Step 4 is rare earth modified catalyst carrier and aqueous solution total immersion 2～10h at 60～100 ℃ of containing platinum group, Ⅳ A family metallic element, suction filtration, and distilled water washing, dries 2～10h at 60 ℃～180 ℃;
Step 5 activates 3～10h by the catalyst making in the air of 400～600 ℃, reductase 12～10h in the hydrogen stream of 400～600 ℃, and the catalyst after reduction is for the catalytic reaction of preparing propylene by dehydrogenating propane.
Chinese patent 201010207838.X discloses a kind of catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof, and it is carrier that this catalyst be take the stanniferous mesoporous aluminum oxide molecular sieve of skeleton, with alkalinous metal auxiliary agent, is support modification agent, total immersion H
2ptCl
6and SnCl
4mixed aqueous solution, and make after drying, activating and reducing.The combination of one or several metals in alkalinous metal Wei IA family, IIA family, rare earth metal.Based on mesoporous aluminum oxide molecular sieve quality meter, in carrier, the quality percentage composition of skeleton tin metal is 0.01～20%; Based on the stanniferous mesoporous aluminum oxide molecular sieve carrier quality meter of skeleton, the quality percentage composition of active metal platinum is 0.01～10%, and promoter metal tin is 0.01～10wt.%, and auxiliary agent alkalinous metal is 0.01～5wt.%.This catalyst has higher iso-butane conversion ratio, selective isobutene and reaction stability under the condition of high temperature, low pressure.
Above-mentioned patent is disclosed is all the composition of catalyst, and the carrier of use and preparation method also have the condition of evaluating catalyst and the result of catalyst performance evaluation.The technical process that does not relate to dehydrogenating low-carbon alkane.Dehydrogenating low-carbon alkane reaction is controlled by thermodynamical equilibrium, and the harsh conditions of high temperature, low pressure are conducive to the carrying out of reaction.But too high reaction temperature, not only makes alkane cracking reaction and degree of depth dehydrogenation aggravation, selectively declines; Also the carbon deposit of having accelerated catalyst surface, makes rapid catalyst deactivation simultaneously.Therefore, not only the dehydrogenation with high stability, high activity and high selectivity to be developed, also the dehydrogenating technology adapting with it will be developed.Could realize the breakthrough of dehydrogenating low-carbon alkane technology.
Summary of the invention
Object of the present invention is just to provide a kind of catalyst and corresponding technique of dehydrogenating low-carbon alkane.
The invention discloses a kind of low-carbon alkanes of water vapour that adds and face the technique of the corresponding alkene of hydrogen Oxidative Dehydrogenation and the dehydrogenation that uses.This catalyst is with γ-Al
2o
3for carrier, the bulk density of carrier is 0.4～0.6g/ml; Specific area is 100～300m
2/ g.Load platinum family metal active constituent, YiⅣ A family metallic element, alkaline element and rare earth element are as auxiliary agent.In catalyst, also can contain halogen as modifier simultaneously.
Technical scheme of the present invention is as follows:
A catalyst for dehydrogenating low-carbon alkane, it is γ-Al
2o
3for carrier, the bulk density of carrier is 0.4～0.6g/ml; Specific area is 100～300m
2/ g, on carrier, load has platinum active component, usings Sn, Na and La as auxiliary agent, in catalyst, also can contain Cl as modifier simultaneously, their content is: by the Mass Calculation of catalyst, the quality percentage composition of platiniferous is: 0.3-0.5%, and stanniferous quality percentage composition is: 0.6-1.0%; Quality percentage composition containing sodium is: 0.75-1.0%, and the quality percentage composition that contains lanthanum is 0.8-1.0%, chloride quality percentage composition is: 0.1-0.2%, above-mentioned low-carbon alkanes is C
2-C
5alkane.
A method of preparing above-mentioned catalyst, it comprises the steps:
That step 1. is prepared with known ball forming method and through the γ-Al of 120 ℃ of oven dry
2o
3bead, the concentration of first flooding same volume is 4--5mgLa/ml lanthanum nitrate hexahydrate, makes carrier be loaded with metal La ion, through 50-200 ℃, preferably 80-150 ℃, is dried 1-10 hour, preferably 4-8 hour; Through 400-600 ℃, preferred 450-550 ℃, roasting 1-10 hour, preferably 5-8 hour;
γ-the Al that is loaded with metal La ion described in step 1 for step 2.
2o
3the concentration that bead carrier floods same volume is again 3.75--5mgNa/ml sodium chloride solution, makes carrier loaded upper sodium metal ion, and through 50-200 ℃, preferably 80-150 ℃, is dried 1-10 hour, preferably 5-8 hour; Through 400-600 ℃, preferred 450-550 ℃, roasting 1-10 hour, preferably 5-8 hour;
γ-the Al that is loaded with metal La ion and sodium metal ion that step 3. makes by step 2
2o
3contain 1.5-2.5mgPt/ml chloroplatinic acid and 3-5mgSn/ml stannic chloride and 0.15-0.25% hydrochloric acid solution that bead carrier floods same volume again flood, and through 50-200 ℃, preferably 80-150 ℃, is dried 1-10 hour, preferably 5-8 hour; Through 400-600 ℃, preferred 450-550 ℃, roasting 1-10 hour, preferably 5-8 hour, obtain catalyst precarsor, then in hydrogen, 400-600 ℃, preferably 500-550 ℃, reduction 1-10 hour, 5-10 hour preferably, makes the catalyst of dehydrogenating low-carbon alkane of the present invention.
The catalyst of preparing with said method, by the Mass Calculation of catalyst, the quality percentage composition of platinum element is: 0.3-0.5%; The quality percentage composition of tin element is: 0.6-1.0%; The quality percentage composition of sodium element is: 0.75-1.0%; The quality percentage composition of rare-earth elements of lanthanum is 0.8-1.0%; The quality percentage composition of halogen chlorine is: 0.1-0.2%.
Catalyst of the present invention also can be prepared by the method for total immersion:
A method of preparing above-mentioned catalyst, it by preparing with known ball forming method, the γ-Al of 120 ℃ of oven dry
2o
3bead contains 2.5mgPt/ml chloroplatinic acid and 5mgSn/ml stannic chloride and 5mgNa/ml sodium chloride and 5mgLa/ml lanthanum nitrate and 0.25% hydrochloric acid solution dipping with same volume, through 50-200 ℃, and preferred 80-150 ℃, dry 1-10 hour, preferably 5-8 hour; Through 400-600 ℃, preferred 450-550 ℃, roasting 1-10 hour, preferably 5-8 hour.Then in hydrogen, 400-600 ℃, preferred 500-550 ℃ of reduction 1-10 hour, preferred 5-10 hour, the catalyst of preparation is pressed the Mass Calculation of catalyst, and the quality percentage composition of platinum element is: 0.3-0.5%; The quality percentage composition of tin metal element is: 06-1.0%; The quality percentage composition of sodium element is: 0.75-1.0%; The quality percentage composition of lanthanum element is 0.8-1.0%; The quality percentage composition of chlorine element is: 0.1-0.2%.
The technique that a kind of low-carbon alkanes that adds water vapour of the present invention faces the corresponding alkene of hydrogen Oxidative Dehydrogenation is that the alkane of take containing 2-5 carbon is raw material, the technique of the corresponding monoolefine of Oxidative Dehydrogenation under certain process conditions.This technique is particularly useful for propane and dehydrogenation of isobutane propylene processed and isobutene.
A kind of dehydrogenating low-carbon alkane that adopts above-mentioned catalyst is prepared the technique of corresponding alkene: in reactor, fill above-mentioned catalyst for dehydrogenation of low-carbon paraffin precursor, pass into hydrogen, at 400-600 ℃ of reduction 1-10 hour, make catalyst precarsor be reduced into catalyst for dehydrogenation of low-carbon paraffin, then pass into the low-carbon alkanes of preheating, the gaseous mixture that hydrogen and steam form, at 500-700 ℃, 550-650 ℃ preferably, carry out dehydrogenating low-carbon alkane reaction, wherein: the mol ratio of low-carbon alkanes and hydrogen is for being 0.33-4.0, 0.1-2.0 preferably, the mol ratio of steam and low-carbon alkanes is 0.1-5, 0.1-0.5 preferably, reaction pressure is 0.05-0.3MPa, 0.1-0.2 MPa preferably, the mass space velocity of the low-carbon alkanes of charging is 2-10h
-1, 3-8h preferably
-1, product is after isolating hydrogen, water, pyrolysis product and alkene, and unreacted raw material low-carbon alkanes loops back Reactor inlet.
Above-mentioned dehydrogenating low-carbon alkane is prepared the technique of corresponding alkene, and dehydrogenation reaction is carried out in fixed bed reactors, and this reactor both can adopt isothermal reactor, also can adopt adiabatic reactor.Both A reactor can be adopted, also multistage reactor can be adopted.Preferably multistage radial adiabatic reactor, passes through the required heat of heater postreaction between each stage reactor.
The technique that a kind of dehydrogenating low-carbon alkane of the present invention is prepared corresponding alkene be take in dehydrogenation reaction process and is added water vapour as principal character.Dehydrogenating low-carbon alkane reaction is carried out under the harsh conditions of high temperature, low pressure and low hydrogen-hydrocarbon ratio.Alkane cracking reaction and the aggravation of degree of depth dehydrogenation reaction under hot conditions, the easy carbon deposit in surface of catalyst, makes rapid catalyst deactivation.Adding the carbon deposit that can suppress catalyst surface, the life-span of extending catalyst of water vapour.Water vapour add the dividing potential drop that can reduce system, improve the conversion ratio of reaction.Meanwhile, dehydrogenating low-carbon alkane reaction is also the reaction of a strong heat absorption, and adding of water vapour can, for reaction provides heat, reach the object that improves conversion ratio.The mode that water vapour adds can directly add water vapour, also can add water to gasify together with raw material.
The technique that dehydrogenating low-carbon alkane of the present invention is prepared corresponding alkene is a kind ofly on above-mentioned dehydrogenation, to face hydrogen dehydrogenating technology.The dehydrogenating technology that namely contains hydrogen in charging alkane.Although the carrying out that adds the back reaction that is conducive to dehydrogenation reaction of hydrogen, it add the carbon deposit that can suppress catalyst surface, be conducive to the life-span of extending catalyst.Simultaneously also for reaction provides heat.
The technique of the corresponding alkene of dehydrogenating low-carbon alkane system of the present invention is applicable to low-carbon alkanes catalytic dehydrogenation and produces alkene.Be specially adapted to preparing propylene by dehydrogenating propane or preparing isobutene through dehydrogenation of iso-butane.Take preparing isobutene through dehydrogenation of iso-butane as example, adopt the preparing isobutene through dehydrogenation of iso-butane reactivity worth of technique of the present invention and catalyst excellent, average conversion is more than 30%, selective more than 95%, and catalyst can maintain more than 40 days.Solve under the catalyst Yin Gaowen that the industrialized unit of preparing propylene by dehydrogenating propane or preparing isobutene through dehydrogenation of iso-butane is used in the world at present easy carbon deposit and inactivation, needed the problem of cyclic regeneration, opened up the variation route of dehydrogenating technology.Can alleviate the situation of propylene and the aggravation of isobutene demand, optimize and utilize refinery gas and associated gas, there is significant Social benefit and economic benefit.
The specific embodiment
Following examples are to further illustrate of the present invention, but not limitation of the present invention.
Embodiment 1:
Spherical gamma-Al that the present invention uses
2o
3carrier is prepared with known ball forming method, and through 120 ℃ of oven dry, 600 ℃ of γ-Al that roasting forms
2o
3bead, the average diameter 2mm of bead.
Above-mentioned γ-Al
2o
3bead 10g is first the liquid infiltration that 40mgLa/ml lanthanum nitrate hexahydrate is made into by 17.5ml distilled water and 2.5ml concentration, makes carrier be loaded with metal La ion.Through 150 ℃, dry 4 hours, 550 ℃, roasting 5 hours.
With the above-mentioned metal La ion γ-Al that is loaded with
2o
3bead carrier is the liquid infiltration that 25mgNa/ml sodium chloride solution is made into by 16ml distilled water and 4ml concentration again, makes carrier loaded upper alkali metal receive ion.150 ℃, dry 5 hours, 550 ℃, roasting 5 hours.
With the above-mentioned γ-Al that is loaded with metal La ion and alkali metallic sodium ion
2o
3bead carrier is that 12.5mgPt/ml platinum acid chloride solution and 2.5ml concentration are the liquid infiltration that hydrochloric acid solution that 40mgSn/ml tin chloride solution and 1ml concentration are 5% is made into by 12.5ml distilled water and 4ml concentration again.Through 150 ℃, dry 5 hours, through 550 ℃, roasting 5 hours,, reduced 10 hours by then in hydrogen 500 ℃.Obtain catalyst A, by the Mass Calculation of catalyst, the quality percentage composition of catalyst A platiniferous is: 0.5%, and stanniferous quality percentage composition is: 1.0%; The quality percentage composition of alkali metal containing sodium is: 1.0%, and the quality percentage composition that contains rare-earth elements of lanthanum is 1.0%, chloride quality percentage composition is: 0.2%.
Embodiment 2:
Above-mentioned γ-Al
2o
3bead 10g is 12.5mgPt/ml platinum acid chloride solution 4ml by 6.0ml distilled water and concentration, concentration is 25mgNa/ml sodium chloride solution 4ml, concentration is that 40mgLa/ml lanthanum nitrate hexahydrate 2.5ml and concentration are the liquid infiltration that hydrochloric acid solution that 40mgSn/ml tin chloride solution 2.5ml and 1ml concentration are 5% is made into, through 150 ℃, dry 5 hours, 550 ℃, roasting 5 hours, then in hydrogen, 500 ℃, reduce 10 hours.Obtain catalyst B, by the Mass Calculation of catalyst, the quality percentage composition of this catalyst platiniferous is: 0.5%, and stanniferous quality percentage composition is: 1.0%; The quality percentage composition of alkali metal containing sodium is: 1.0%, and the quality percentage composition that contains rare-earth elements of lanthanum is 1.0, chloride quality percentage composition is: 0.1%.
Embodiment 3
Above-mentioned γ-Al
2o
3bead 10g is 10mgPt/ml platinum acid chloride solution 3ml by 9.5ml distilled water and concentration, concentration is 25mgNa/ml sodium chloride solution 3ml, concentration is that 40mgLa/ml lanthanum nitrate hexahydrate 2ml and concentration are the liquid infiltration that hydrochloric acid solution that 40mgSn/ml tin chloride solution 1.5ml and 1ml concentration are 5% is made into, through 80 ℃, dry 8 hours, 450 ℃, roasting 8 hours, then in hydrogen, 550 ℃, reduce 5 hours.Obtain catalyst C, by the Mass Calculation of catalyst, the quality percentage composition of this catalyst platiniferous is: 0.3%, and stanniferous quality percentage composition is: 0.6%; The quality percentage composition of alkali metal containing sodium is: 0.75%, and the quality percentage composition that contains rare-earth elements of lanthanum is 0.8%, chloride quality percentage composition is: 0.2%.
Embodiment 4
Dehydrogenation of isobutane reaction is to carry out in a stainless steel tubular type reactor, catalyst A loading amount 100ml, and prereduction temperature is 500 ℃, 10 hours time.Catalyst after reduction can be used for dehydrogenation reaction.Raw material alkane mixes with hydrogen and water vapour and by heater, is heated to predetermined temperature and enters beds and carry out catalytic dehydrogenating reaction.The initial temperature of dehydrogenation reaction is 550 ℃; Heat up gradually to control reaction conversion ratio and be not less than 30%, be selectively not less than 95%, reaction terminating temperature is 620 ℃, and reaction pressure is 0.1MPa; Hydrocarbon hydrogen mol ratio is 2.0; The mass space velocity of charging alkane is 5 h
-1, water hydrocarbon mol ratio is 0.1, product with gas chromatographic analysis, is calculated the selective of the conversion ratio of iso-butane and isobutene according to the result of analyzing after cooling.Keep reaction conversion ratio to be not less than 30%, be selectively not less than 95%.Catalyst A continuous operation single pass life reaches 40 days.Under same reaction condition, catalyst B continuous operation single pass life reaches 40 days.Catalyst C continuous operation single pass life reaches 35 days.
Embodiment 5
Dehydrogenating propane reaction is to carry out in a stainless steel tubular type reactor, catalyst B loading amount 100ml, and prereduction temperature is 600 ℃, 10 hours time.Catalyst after reduction is for dehydrogenation reaction.Raw material alkane mixes with hydrogen and water vapour and by heater, is heated to predetermined temperature and enters beds and carry out catalytic dehydrogenating reaction.The initial temperature of dehydrogenation reaction is 550 ℃; Heat up gradually to control reaction conversion ratio and be not less than 30%, be selectively not less than 95%, reaction terminating temperature is 650 ℃, and reaction pressure is 0.3MPa; Hydrocarbon hydrogen mol ratio is 0.33; The mass space velocity of charging alkane is 8 h
-1, water hydrocarbon mol ratio is 0.3, product with gas chromatographic analysis, is calculated the selective of the conversion ratio of propane and propylene according to the result of analyzing after cooling.Keep reaction conversion ratio to be not less than 30%, be selectively not less than 95%.Catalyst B continuous operation single pass life reaches 30 days.Under same reaction condition, catalyst A continuous operation single pass life reaches 30 days.Catalyst C continuous operation single pass life reaches 25 days.
Embodiment 6
Ethane dehydrogenation reaction is to carry out in a stainless steel tubular type reactor, catalyst A loading amount 100ml, and prereduction temperature is 650 ℃, 6 hours time.Catalyst after reduction can be used for dehydrogenation reaction.Raw material alkane mixes with hydrogen and water vapour and by heater, is heated to predetermined temperature and enters beds and carry out catalytic dehydrogenating reaction.The initial temperature of dehydrogenation reaction is 580 ℃; Heat up gradually to control reaction conversion ratio and be not less than 30%, be selectively not less than 90%, reaction terminating temperature is 650 ℃, and reaction pressure is 0.2MPa; Hydrogen hydrocarbon mol ratio is 0.5; The mass space velocity of charging alkane is 3 h
-1, water hydrocarbon mol ratio is 0.5, product with gas chromatographic analysis, is calculated the selective of the conversion ratio of ethane and ethene according to the result of analyzing after cooling.Keep reaction conversion ratio to be not less than 30%, be selectively not less than 90%.Catalyst A continuous operation single pass life reaches 25 days.Under same reaction condition, catalyst B continuous operation single pass life reaches 25 days.Catalyst C continuous operation single pass life reaches 20 days.
Claims (2)
1. a dehydrogenating low-carbon alkane is prepared the technique of corresponding alkene, it is characterized in that: in reactor, fill catalyst for dehydrogenation of low-carbon paraffin precursor, pass into hydrogen, at 400-600 ℃ of reduction 1-10 hour, make catalyst precarsor be reduced into catalyst for dehydrogenation of low-carbon paraffin, then pass into the low-carbon alkanes of preheating, the gaseous mixture that hydrogen and steam form, at 500-700 ℃, carry out dehydrogenating low-carbon alkane reaction, wherein: the mol ratio of low-carbon alkanes and hydrogen is 0.33-4.0, the mol ratio of steam and low-carbon alkanes is 0.1-5, reaction pressure is 0.05-0.3MPa, the mass space velocity of the low-carbon alkanes of charging is 2-10h
-1, product is after isolating hydrogen, water, pyrolysis product and alkene, and unreacted raw material low-carbon alkanes loops back Reactor inlet,
Described catalyst for dehydrogenation of low-carbon paraffin, it is with γ-Al
2o
3for carrier, the bulk density of carrier is 0.4～0.6g/ml; Specific area is 100～300m
2/ g, on carrier, load has platinum active component, usings Sn, Na and La as auxiliary agent, in catalyst, also contain Cl as modifier simultaneously, their content is: by the Mass Calculation of catalyst, the quality percentage composition of platiniferous is: 0.3-0.5%, and stanniferous quality percentage composition is: 0.6-1.0%; Quality percentage composition containing sodium is: 0.75-1.0%, and the quality percentage composition that contains lanthanum is 0.8-1.0%, chloride quality percentage composition is 0.1-0.2%; Described low-carbon alkanes is C
2-C
5alkane.
2. dehydrogenating low-carbon alkane according to claim 1 is prepared the technique of corresponding alkene, it is characterized in that: in reactor, fill catalyst for dehydrogenation of low-carbon paraffin precursor, pass into hydrogen, at 400-600 ℃ of reduction 1-10 hour, make catalyst precarsor be reduced into catalyst for dehydrogenation of low-carbon paraffin, then pass into the low-carbon alkanes of preheating, the gaseous mixture that hydrogen and steam form, at 550-650 ℃, carry out dehydrogenating low-carbon alkane reaction, wherein: the mol ratio of low-carbon alkanes and hydrogen is 0.33-2.0, the mol ratio of steam and low-carbon alkanes is 0.1-0.5, reaction pressure is 0.1-0.2 MPa, the mass space velocity of the low-carbon alkanes of charging is 3-8h
-1, product is after isolating hydrogen, water, pyrolysis product and alkene, and unreacted raw material low-carbon alkanes loops back Reactor inlet.
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| CN104275179B (en) * | 2013-07-09 | 2018-01-09 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof |
| CN104437485B (en) * | 2013-09-24 | 2017-02-15 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by low-carbon alkane dehydrogenation and preparation method of catalyst for preparing olefin by low-carbon alkane dehydrogenation |
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