CN104591943B - Saturated alkane dehydrogenation method - Google Patents
Saturated alkane dehydrogenation method Download PDFInfo
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- CN104591943B CN104591943B CN201310532081.5A CN201310532081A CN104591943B CN 104591943 B CN104591943 B CN 104591943B CN 201310532081 A CN201310532081 A CN 201310532081A CN 104591943 B CN104591943 B CN 104591943B
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a saturated alkane dehydrogenation method. According to the method, a reduced dehydrogenation catalyst Zn-Sn-Pt/SBA-15 is loaded on the upper part of a reactor, a presulphided dehydrogenation catalyst is loaded in the middle part of the reactor, and a reduced Pt-K-Sn/Al2O3 dehydrogenation catalyst is loaded on the lower part of the reactor. The conditions are regulated to those needed by a dehydrogenation reaction, and the dehydrogenation reaction is carried out. According to the method, a reduction process can be eliminated before the reaction. Therefore, an operation process is simplified; an operation cost is reduced; monolithic catalyst initial activity and monolithic catalyst activity stable performance can be improved; catalyst deactivation rate can be reduced; one-way reaction time is increased; and the monolithic catalyst can maintain a relatively high selectivity during the reaction process.
Description
Technical field
The present invention relates to a kind of method of dehydrogenating of saturated alkane, the particularly method of c3 ~ c7 dehydrating alkanes alkene.
Background technology
Since entering new century, the mankind to the demand of worldwide petrochemical raw material and petroleum chemicals will sustainable growth, as stone
The demand changing basic material propylene will continue to increase, and traditional conventional method can not meet the demand of rapid growth so as to city
Field occurs in that global in short supply.And increasingly deficient with petroleum resources, the production of propylene from the simple oil that relies on is
Raw material changes to the technology path of diversification of feedstock, particularly with low-carbon alkanes for the technology path of waste propylene.In recent years
Come, very fast in the regional development having resources advantage for the technology of waste propylene with low-carbon alkanes, become the third-largest propylene life
Product method.
Propane catalytic dehydrogenating reaction is limited by thermodynamical equilibrium, must carry out under high temperature, the harsh conditions of low pressure.Too high
Reaction temperature, makes Deposition During Propane Pyrolysis react and deep dehydrogenation aggravation, and selectivity declines；Accelerate catalyst surface carbon deposit simultaneously, make to urge
Agent fast deactivation.Due to the shortening of catalyst life under relatively low conversion of propane and harsh reaction condition, make pdh method
It is restricted in commercial Application.Therefore, exploitation has the catalyst for preparing propylene with propane dehydrogenation of high selectivity and high stability
And supporting technique becomes the key of this technology.Dehydrogenating propane technology is with the oleflex technique of uop company and U.S. air
The catafin technique of product company is representative.Oleflex technique mainly based on pt base catalyst, catafin technique master
Will be with cr2o3/al2o3Based on.
Platinum family loaded catalyst is an important class in alkane dehydrogenating catalyst, and the production method of such catalyst also exists
Disclosed in this area.Usp4914075, usp4353815, usp4420649, usp4506032, usp4595673, ep562906,
Ep98622 etc. reports for propane and other dehydrogenating low-carbon alkane pt base catalyst, has high alkane conversion and alkene
Hydrocarbon-selective.Although alkane conversion under some reaction conditions for these catalyst and olefine selective are high, due to
The easy coking deactivation of catalyst under hot conditionss, leads to the stability of catalytic reaction poor, the service life of catalyst is shorter.
Usp3897368 and cn87108352 discloses a kind of method producing core-shell catalyst, and pt optionally concentrates and is deposited on
On the outer surface of catalyst carrier, the internal pt content of catalyst carrier is relatively low, can improve the utilization rate of active metal.Above-mentioned negative
Load type platino alkane dehydrogenating catalyst passes through the activity adding metal can improve catalyst further, and such as cn1201715a is public
Open the pt-sn-k/al for low-carbon alkanes (c1 ~ c5) dehydrogenation2o3The preparation method of catalyst, but metal promoter sn plus
Enter to be easy to the effect of active component pt and generate snpt alloy, the impact utilization rate of noble metal pt and the stability of catalyst.And, on
When stating this kind of activation of catalyst, need first the reduction under hydrogen could be active, but in catalyst generation snpt alloy, meeting
The reduction of impact catalyst and the performance of activity.
Except the selection of carrier and the molding of catalyst very crucial in addition to, to presulfiding of catalyst be also good measure it
One.The effect of presulfurization is closely related with catalyst stability.In prior art, dehydrogenation method for pre-sulphuration is mainly taken
In-situ presulfurization, Catalyst packing is entered reactor, then introduces vulcanizing agent and is vulcanized, cn87101513a discloses one kind
Before reduction, sulfuration introduces sulphur component in a wet process, promotes the activity of catalyst and the method for stability, sulphur component in the method
For inorganic sulphides such as ammonium sulfide, Potassium monosulfide., sodium sulfide, experiment shows, vulcanizes selectivity and the stability deficiency of rear catalyst.
Introduce vulcanizing agent before catalyst reduction, on-stream time can be saved, make to go into operation easier, the scene of going into operation avoids using poisonous
Sulfide, nor need special vulcanizing deice is installed.Therefore, if introducing sulphur component before catalyst reduction to catalysis
The impact of the serviceability of agent can further improve, then significant to commercial Application.
Cn201010535868.3 discloses a kind of start-up method of dehydrogenation, wherein by the catalysis dehydrogenation of presulfurization
The dehydrogenation layering of agent and non-presulfurization or mixed packing in the reactor, then carry out heating reduction, adjust to dehydrogenation
The required condition of reaction carries out dehydrogenation reaction.The platinum family support type that the dehydrogenation that the method is adopted is prepared for conventional method
, presented in oxidation state, needing could be active through heating reduction for catalyst, wherein platinum group metal, but reduction process
The overall activity of catalyst, and the usage cycles of catalyst can be affected.
Content of the invention
For the deficiencies in the prior art, the invention provides a kind of method of dehydrogenating of saturated alkane.The method can be anti-
Save reduction process before answering, not only simplify operating process, reduce running cost, and the initial activity of integer catalyzer is high,
Selectivity is high, and deactivation rate is slow, and usage cycles are long.
The method of dehydrogenating of saturated alkane of the present invention, comprising:
(1) prepare presulfurization dehydrogenation, the vulcanizing agent consumption containing in presulfurization dehydrogenation is required pre- sulfur
Fluidized dehydrogenation catalyst theory needs the 80% ~ 120% of sulfur content；
(2) the dehydrogenation pt-k-sn/al of preparation reduction2o3；
(3) the dehydrogenation zn-sn-pt/ sba-15 of preparation reduction；
(4) catalysis dehydrogenation of reduction prepared by presulfurization dehydrogenation, step (2) and the step (3) that prepared by step (1)
Agent loads in reactor, adjusts the condition needed for dehydrogenation reaction, then carries out dehydrogenation reaction；What wherein prepared by step (3) goes back
Former dehydrogenation is seated in top, and presulfurization dehydrogenation is seated in middle part, and the dehydrogenation of reduction prepared by step (2) is urged
Agent is seated in bottom, the dehydrogenation of reduction prepared by step (3), presulfurization dehydrogenation, step (2) prepare also
The admission space of former dehydrogenation is than for 0.1 ~ 0.5:1:0.5 ~ 2.
In the present invention, the dehydrogenation of the reduction of step (2) is pt-k-sn/al2o3Catalyst, using following method systems
Standby:
(i) chloroplatinic acid ethylene glycol solution is mixed with alumina support containing sn, and the 1h that flows back under 60 DEG C ~ 120 DEG C stirring conditions ~
6h；
(ii) koh ethylene glycol solution is added to the system of step (1), be warming up to 150 DEG C ~ 200 DEG C and continue backflow
5min ~ 120min, is cooled to room temperature after terminating；
(iii) the solidliquid mixture of separating step (2) gained, scrubbed after be vacuum dried and inert gas atmosphere under
Roasting；
(iv) using kno3Aqueous impregnation step (3) gained solid is vacuum dried, after roasting under inert gas atmosphere
The dehydrogenation of reduction is obtained.
In the preparation method of the dehydrogenation of the reduction used by the present invention, (i) middle chloroplatinic acid ethylene glycol solution is dense for step
Spend for 0.001mol/l ~ 0.01 mol/l, preferably 0.002 mol/l ~ 0.006 mol/l.(i) reflux temperature is step
80 DEG C ~ 100 DEG C, return time is 2h ~ 4h.Described alumina support containing sn can be using existing goods it is also possible to by routine side
Prepared by method, the content of sn is calculated as the 0.1% ~ 10% of vehicle weight with element.Alumina support containing sn can be spherical, bar shaped, micro-
Ball or abnormity, particle size 0.1mm ~ 5mm, preferred particle size is 0.5mm ~ 3mm.Alumina support containing sn preferably exists
Introduce sn during aluminium oxide plastic, then prepare the alumina support containing sn.Described containing sn alumina support with cogelled
Prepared by mode, introduce the material containing sn in aluminium oxide plastic, and the material containing sn is generally soluble-salt, such as nitrate, chlorination
Thing etc., then presses this area existing method molding, such as drips ball forming, extrusion molding etc., and aluminium oxide plastic is ripe for technical staff
Know.The preparation method of above-mentioned carrier is the method known to technical staff.
In the preparation method of the dehydrogenation of the reduction used by the present invention, step (ii) middle koh ethylene glycol solution concentration
For 0.1 mol/l ~ 1 mol/l, preferably 0.2 mol/l ~ 0.5 mol/l.Step (ii) reflux temperature is 170 DEG C ~ 190
DEG C, return time 10min ~ 60min.Koh ethylene glycol solution addition is counted than for 15 ~ 25 with potassium with pt atom.
In the preparation method of the dehydrogenation of the reduction used by the present invention, step (iii) described in separation method be institute
Known to solid-liquid separating method, including centrifugation, membrane filtration etc..Step (iii) described in chloride test method be ripe
The method known.(iii) middle baking temperature is 60 DEG C ~ 200 DEG C to step, preferably 80 DEG C ~ 120 DEG C；Sintering temperature is 200 DEG C ~ 800
DEG C, preferably 400 DEG C ~ 600 DEG C, described noble gases include nitrogen, helium, argon etc..
In the preparation method of the dehydrogenation of the reduction used by the present invention, step (iv) described in kno3Concentration of aqueous solution
For 0.1 ~ 2.0mol/l, preferably 0.5 ~ 1.0mol/l.Described dipping method is known method, including equal-volume vacuum
Impregnate, spray, first moistening method impregnating.Dipping temperature is 60-80 DEG C, and dip time is 1h ~ 6h, optimizes 2h ~ 4h.Baking temperature is
60 DEG C ~ 200 DEG C, preferably 80 DEG C ~ 120 DEG C, sintering temperature is 200 DEG C ~ 800 DEG C, preferably 400 DEG C ~ 600 DEG C.Described inertia
Gas includes nitrogen, helium, argon etc..
Dehydrogenation (the pt-k-sn/al of the reduction used by step (2) of the present invention2o3Catalyst), adopt the above
Prepared by method, in prepared final catalyst, the content of each component is as follows: sn 0.2 wt% ~ 1.5wt%, pt 0.2wt% ~
0.8wt%, k 0.1wt% ~ 2.0wt%, preferably sn 0.3 wt% ~ 1.0wt%, pt 0.4wt% ~ 0.6wt%, k 0.5wt% ~
1.5wt%.
In the present invention, the dehydrogenation of the reduction of step (3) is zn-sn-pt/ sba-15 catalyst, using following sides
Prepared by method:
A () is first immersed in sn on sba-15 carrier, sba-15 carrier containing sn is obtained after drying, roasting；
B () chloroplatinic acid ethylene glycol solution is mixed with the sba-15 carrier containing sn, flow back under 60 DEG C ~ 120 DEG C stirring conditions
1h~6h；
C () adds koh ethylene glycol solution to the system of step (a), be warming up to 150 DEG C ~ 200 DEG C and continue backflow 5min
~ 120min, is cooled to room temperature after terminating；
The solidliquid mixture of (d) separating step (c) gained, scrubbed after be vacuum dried and inert gas atmosphere under roast
Burn；
E () uses zn(no3)2Aqueous impregnation step (d) gained solid is vacuum dried, roasting under inert gas atmosphere
The dehydrogenation of reduction is obtained afterwards.
In the preparation method of the dehydrogenation of the reduction used by the present invention, the sba-15 carrier containing sn can be spherical,
Bar shaped, microsphere or abnormity, particle size 0.1mm ~ 5mm, preferred particle size is 0.5mm ~ 3mm.Sba-15 carrier containing sn
Preparation method can using infusion process preparation, first prepare sba-15 carrier, then adopt dip loading sn.Detailed process is such as
Under: add appropriate binding agent in sba-15 molecular sieve, through kneading and compacting, then after drying and roasting, obtain sba-15 and carry
Body.Then by sba-15 carrier impregnation in butter of tin solution, then drying and roasting, obtain the sba-15 carrier containing sn.
Wherein binding agent can be using conventional little porous aluminum oxide etc..It is also possible to add conventional molding to help in carrier forming process
Agent, such as extrusion aid etc..Sba-15 molecular sieve adopts conventional method to synthesize, and typically adopts hydro-thermal method synthesis.Chlorine platinum in step (b)
Sour ethylene glycol solution concentration is 0.001mol/l ~ 0.01 mol/l, preferably 0.002 mol/l ~ 0.006 mol/l.Step
B () reflux temperature is 80 DEG C ~ 100 DEG C, return time is 2h ~ 4h.
In the preparation method of the dehydrogenation of the reduction used by the present invention, in step (c), koh ethylene glycol solution concentration is
0.1 mol/l ~ 1 mol/l, preferably 0.2 mol/l ~ 0.5 mol/l.Step (c) reflux temperature is 170 DEG C ~ 190 DEG C, returns
Stream time 10min ~ 60min.Koh ethylene glycol solution addition is counted than for 15 ~ 25 with potassium with pt atom.
In the preparation method of the dehydrogenation of the reduction used by the present invention, separation method described in step (d) is ripe
The solid-liquid separating method known, including centrifugation, membrane filtration etc..Chloride test method described in step (d) is known
Method.In step (d), baking temperature is 60 DEG C ~ 200 DEG C, preferably 80 DEG C ~ 120 DEG C；Sintering temperature is 200 DEG C ~ 800 DEG C, excellent
Elect 400 DEG C ~ 600 DEG C as, described noble gases include nitrogen, helium, argon etc..
In the preparation method of the dehydrogenation of the reduction used by the present invention, zn(no described in step (e)3)2Aqueous solution is dense
Spend for 0.2 ~ 3.0mol/l, preferably 0.5 ~ 2.5mol/l.Described dipping method is known method, including equal-volume vacuum
Dipping, sprays, just moistening method impregnating.Dipping temperature is 60-80 DEG C, and dip time is 1h ~ 6h, optimizes 2h ~ 4h.Baking temperature is
60 DEG C ~ 200 DEG C, preferably 80 DEG C ~ 120 DEG C, sintering temperature is 200 DEG C ~ 800 DEG C, preferably 400 DEG C ~ 600 DEG C.Described inertia
Gas includes nitrogen, helium, argon etc..
The dehydrogenation (zn-sn-pt/ sba-15 catalyst) of the reduction used by step (3) of the present invention, more than employing
Prepared by methods described, in prepared final catalyst, the content of each component is as follows: sn 0.2wt% ~ 1.5wt%, pt 0.2wt% ~
0.8wt%, zn 0.2wt% ~ 3.0wt%, preferably sn 0.3wt% ~ 1.0wt%, pt 0.4wt% ~ 0.6wt%, zn 0.5wt% ~
2.5wt%.
In the present invention, presulfurization dehydrogenation typically with aluminium oxide as carrier, with the platinum in platinum family, palladium, iridium, rhodium or osmium
One or more of be active component, active component weight content in the catalyst is counted for 0.01% ~ 2% with element.Described
Catalyst in can contain suitable auxiliaries, such as sn, k, rare earth metal etc., the content of sn weight in the catalyst in terms of element
Content is that the content of 0.1% ~ 10%, k counts weight content in the catalyst for 0.1% ~ 10% with element.Catalyst can be using this
The conventional method preparation in field, such as loads dehydrogenation active component using infusion process, auxiliary agent can in carrier preparation process and/or
Introduced using infusion process.The presulfurization of dehydrogenation processes and includes following process: with the solution impregnation dehydrogenation containing vulcanizing agent
Catalyst, is finally dried to obtain final dehydrogenation.From vulcanizing agent be inorganic sulfur agent, i.e. ammonium sulfide, sodium sulfide, sulfur
Change the inorganic sulfur agents such as potassium.After the solution impregnation dehydrogenation containing vulcanizing agent, generally 80 ~ 200 DEG C of baking temperature, do
Generally 1 ~ 10 hour dry time.The vulcanizing agent consumption containing in pre-sulfide catalyst is that required presulfurization dehydrogenation is theoretical
Need the 80% ~ 120% of sulfur content.
The Catalyst packing method being provided using the present invention and dehydrogenating technology start-up method, its process is simple, simple operation,
And there is higher catalysis activity.
Inventive process avoids the equipment corrosion being brought in conventional method and problem of environmental pollution, being suitable to industry should
With.
In the preparation process of the dehydrogenation of the reduction used by the present invention, active component pt can be direct in the liquid phase
It is reduced to metal simple-substance phase, simple substance pt crystal grain is dispersed in catalyst surface with nanoscale heights, restrained effectively snpt and close
The generation of gold, not only saves before the reaction or shortens reducing program, simplify preparation process, and improve the utilization of noble metal pt
Rate and the stability of catalyst.
The inventive method adopts presulfurization and reduction catalyst grading loading, can save reduction process before the reaction,
Not only simplify operating process, reduce running cost, and be conducive to improving initial activity and the selectivity of integer catalyzer, fall
The deactivation rate of low catalyst, extends usage cycles, additionally, carry out level using two kinds of different reduced form dehydrogenations joining,
Wherein zn-sn-pt/ sba-15 is seated in topmost, makes full use of the of a relatively high feature of its selectivity, improve overall urging
The selectivity of agent.With the carrying out of reaction, pre-sulfide catalyst constantly discharges hydrogen sulfide, and pre-sulfide catalyst constantly recovers
Activity, the ability of zn-sn-pt/sba-15 adsorption of hydrogen sulfide is stronger simultaneously, so in its degree of passivation of initial reaction stage than k-
sn-pt/al2o3Height, so that the activity of integer catalyzer reaches a kind of dynamic balance, is conducive to integer catalyzer activity
Stable performance, slows down deactivation rate, increased the one way response time, and integer catalyzer course of reaction keeps higher selection simultaneously
Property.
Specific embodiment
Preferably with aluminium oxide containing sn as carrier, sn introduces containing sn's the pre-sulfide catalyst of the present invention in aluminium oxide plastic
Material, then makes carrier.In the presulfurization dehydrogenation with aluminium oxide containing sn as carrier for the present invention, dehydrogenation activity metal group
Divide and can be evenly distributed on catalyst surface, preferably dehydrogenation activity metal component integrated distribution in catalyst outer layer, form core
Core/shell-type catalyst.
Be described below a kind of typical case presulfurization dehydrogenation preparation detailed process and condition:
(a) prepare the alumina globule containing sn, wherein content can by using it needs to be determined that, preferably oxygen is calculated as with element
Change the 0.1% ~ 5% of aluminum weight；
B () contains 800 DEG C of roastings of alumina globule of sn after, dehydrogenation active component is introduced using supersaturation infusion process；Permissible
By controlling the conditions such as ph value and the dip time of dipping solution, make dehydrogenation active component basic load in the outer layer of carrier,
Keep certain thickness；
C the catalyst intermediate after heat treatment in () step (b) carries out vapor dechlorination；
Add a certain amount of alkali metal promoter needed for catalyst in d catalyst that () step (c) obtains；
E dehydrogenation that () step (d) obtains vulcanizes in a wet process, and vulcanizing agent is the nothing such as ammonium sulfide, sodium sulfide, Potassium monosulfide.
Machine vulcanizing agent, impregnates dehydrogenation using above-mentioned inorganic sulfur agent, is then dried.The aluminium oxide of sn is contained in step (a)
Carrier introduces sn in aluminium oxide plastic, then prepares the alumina support containing sn.Described containing sn alumina support with altogether
Prepared by the mode of gel, introduce the material containing sn in aluminium oxide plastic, and the material containing sn is generally soluble-salt, such as nitric acid
Salt, chloride etc., then press this area existing method molding, such as drips ball forming, extrusion molding etc., and aluminium oxide plastic is technology people
Member is known.The preparation method of above-mentioned carrier is the method known to technical staff.
Dehydrogenation activity metal wherein described in step (b) is selected generally from one of platinum in platinum family, palladium, iridium, rhodium or osmium
Or several element, content can by using it needs to be determined that, be typically calculated as the 0.1% ~ 2% of vehicle weight with element.
Vapor dechlorination described in step (c) is to process 1 ~ 20 hour at 300 ~ 700 DEG C, and the atmosphere of dechlorination is containing 10v%
The air of ~ 30v% water vapour, chlorinity is less than 0.15wt%.
Vulcanizing agent consumption described in step (e) for dehydrogenation total dehydrogenation activity theoretical metal need sulfur content 80% ~
120%, it is that on catalyst, contained dehydrogenation activity metal component is converted into sulfide (as curing that dehydrogenation theory needs sulfur content
Platinum) when need the amount of sulfur.
Content using each component in the presulfurization dehydrogenation of approach described above preparation is as follows: sn 0.1 wt % ~
5%wt%, pt 0.1 wt % ~ 2%wt%, k 0.1wt% ~ 2.0wt%.
In the inventive method, dehydrogenation reaction is carried out under appropriate conditions, using hydrogen as diluent, dehydrogenation reaction bar
Part is: 450 ~ 650 DEG C of reaction temperature, volume space velocity 1000 ~ 3000h-1, absolute pressure 0.1 ~ 0.3mpa, hydrogen: the ratio of alkane
For 1:1 ~ 6:1(mol ratio).Alkane can be the alkane of c3 ~ c7.
Embodiment below by dehydrogenating propane is described further to the technology of the present invention.In the present invention, catalyst
In each constituent content all in terms of element.
Comparative example 1
The alumina support containing sn for the preparation.By the aluminum trichloride solution of a certain amount of 0.98 mol/l and 0.01 mol/l tetra-
After tin chloride solution mixing, add a certain amount of 8% ammonia (weight), mix homogeneously, control in neutralizing tank at 60 ~ 80 DEG C
Ph value 7.0 ~ 9.0, filter, washing, after acidifying, balling-up of pressurizeing in oil ammonia column, through drying, aging, in 650 DEG C of roastings 4 hours,
Obtain final product the alumina support containing sn 0.3wt%.
By the alumina support containing 0.3wt% sn in 800 DEG C of roasting 3h, by the carrier after roasting and containing chloroplatinic acid
Aqueous solution impregnates 6h at 70 DEG C, dries 2h, roasting 4h at 500 DEG C at 120 DEG C.In 450 DEG C of air containing water vapour 20v%
Middle dechlorination 4h.Then at 70 DEG C with contain kno3Aqueous impregnation 2h, same under conditions of be dried, roasting, make catalysis
Agent da, in catalyst, the content of each component is: pt 0.5wt%, sn 0.3wt%, k0.5wt%.
Carry out restoring operation, volume space velocity is 900h-1, reduce 1 hour at 480 DEG C, hydrogen is High Purity Hydrogen.Activation condition:
The volume space velocity of the mixing gas of hydrogen sulfide, hydrogen and nitrogen is 900h-1, molar ratio is 1:9:5, and 480 DEG C of temperature, during activation
Between 1h.Reaction condition is: volume space velocity 2000 h-1, reaction pressure 0.2mpa, reaction temperature is 630 DEG C, hydrogen: the rubbing of propane
That ratio is 1:1.The evaluation result of catalyst is shown in Table 1, table 2.
Embodiment 1
Make catalyst Precursors according to comparative example 1 identical method.Then catalyst, with vulcanizing agent consumption for all taking off
Hydrogen catalyst active metal theory needs the impregnated catalyst of the 120% of sulfur content, and vulcanizing agent is ammonium sulfide, in 120 DEG C of drying (air
Atmosphere) 4 hours, obtain the dehydrogenation a of presulfurization process.
0.005 mol/l chloroplatinic acid ethylene glycol solution is contained and adds to alumina support containing sn (butt), stirring, heating
Backflow 2h, 80 DEG C of reflux temperature.Then by 0.4 mol/l koh ethylene glycol solution, it is slowly added to above-mentioned system, improves back
Stream temperature, to 180 DEG C, after being heated to reflux 30min, is cooled to room temperature.Solution is filtered off, using deionized water wash, until filtrate
Till middle no chloride ion.120 DEG C of vacuum drying 4h, then roasting 4h under 500 DEG C of nitrogen atmospheres.Gained solid, makes at 70 DEG C
With containing kno3Aqueous impregnation 2h, 120 DEG C of vacuum drying 4h, then roasting 4h under 500 DEG C of nitrogen atmospheres, prepared catalyst b,
In catalyst, the content of each component is: pt 0.5wt%, sn 0.3wt%, k0.5wt%.
Sba-15 molecular sieve adds binding agent, the weight of sba-15 molecular sieve and binding agent ratio for 8:2, through kneading, molding
Afterwards, in 110 DEG C of dryings 4 hours, then constant temperature calcining 4 hours at 650 DEG C, then soaked with 0.01 mol/l butter of tin solution
Stain, in 100 DEG C of dryings 2 hours, then roasting 4 hours at 750 DEG C, is obtained the sba-15 carrier containing sn.By 0.005 mol/l
Chloroplatinic acid ethylene glycol solution contains and adds to the sba-15 carrier (butt) containing sn, and stirring is heated to reflux 2h, reflux temperature 80
℃.Then by 0.4 mol/l koh ethylene glycol solution, it is slowly added to above-mentioned system, improve reflux temperature to 180 DEG C, plus
After hot reflux 30min, it is cooled to room temperature.Solution is filtered off, using deionized water wash, until filtrate in no chloride ion, potassium from
Till son.120 DEG C of vacuum drying 4h, then roasting 4h under 500 DEG C of nitrogen atmospheres.Gained solid, uses zn(no3)2Water-soluble immersion
Stain, 120 DEG C of vacuum drying 4h, then roasting 4h under 500 DEG C of nitrogen atmospheres.Prepared catalyst c, the content of each component in catalyst
For: pt 0.5wt%, sn 0.3wt%, zn1.0wt%.
In the upper end loading catalyst c of dehydrogenation reactor, stage casing loading catalyst a, lower end loading catalyst b.
The loadings volume ratio of catalyst is 0.5:1:1.
Reaction condition is: volume space velocity 2000 h-1, reaction pressure 0.2mpa, reaction temperature is 630 DEG C, hydrogen: propane
Mol ratio is 1:1.The evaluation result of catalyst is shown in Table 1, table 2.
Embodiment 2
Make pre-sulfide catalyst a according to embodiment 1 identical method.Make catalysis according to embodiment 1 identical method
Agent d and catalyst e, in catalyst d, the content of each component is: pt 0.5wt%, sn 0.5wt%, zn 0.8wt%, in catalyst e
The content of each component is: pt 0.5wt%, sn 0.5wt%, k0.8wt%.
In the upper end loading catalyst d of dehydrogenation reactor, lower end loading catalyst e, middle part loading catalyst a, catalyst
Loadings volume ratio be 0.5:1:1.5.
Reaction condition is: volume space velocity 2000 h-1, reaction pressure 0.2mpa, reaction temperature is 630 DEG C, hydrogen: propane
Mol ratio is 1:1.The evaluation result of catalyst is shown in Table 1, table 2.
Embodiment 3
Make pre-sulfide catalyst a according to embodiment 1 identical method.Make catalysis according to embodiment 1 identical method
Agent f and catalyst g, in catalyst f, the content of each component is: pt 0.6wt%, sn 0.3wt%, zn 1.5wt%, in catalyst g
The content of each component is: pt 0.6wt%, sn 0.3wt%, k0.5wt%.
In the upper end loading catalyst f of dehydrogenation reactor, lower end loading catalyst g, middle part loading catalyst a, catalyst
Loadings volume ratio be 0.5:1:0.5.
Reaction condition is: volume space velocity 2000 h-1, reaction pressure 0.2mpa, reaction temperature is 630 DEG C, hydrogen: propane
Mol ratio is 1:1.The evaluation result of catalyst is shown in Table 1, table 2.
Embodiment 4
Make pre-sulfide catalyst a according to embodiment 1 identical method.Make catalysis according to embodiment 1 identical method
Agent h and catalyst l, in catalyst h, the content of each component is: pt 0.5wt%, sn 0.4wt%, zn 2.0wt%, catalyst l
In the content of each component be: the catalyst l of pt 0.5wt%, sn 0.4wt%, k1.0wt%.
In the upper end loading catalyst h of dehydrogenation reactor, lower end loading catalyst l, middle part loading catalyst a, catalyst
Loadings volume ratio be 0.3:1:0.8.
Reaction condition is: volume space velocity 2000 h-1, reaction pressure 0.2mpa, reaction temperature is 630 DEG C, hydrogen: propane
Mol ratio is 1:1.The evaluation result of catalyst is shown in Table 1, table 2.
Comparative example 2
Using the catalyst da of comparative example 1 preparation, make catalyst a by embodiment 1 identical method.
Upper end loading catalyst a in dehydrogenation reactor, lower end loading catalyst da.Wherein, catalyst a and catalyst da
Admission space than for 1:1.
Carry out restoring operation, volume space velocity is 900h-1, reduce 1 hour at 480 DEG C, hydrogen for high-purity hydroformylation reaction condition is:
Volume space velocity 2000 h-1, reaction pressure 0.2mpa, reaction temperature is 630 DEG C, hydrogen: the mol ratio of propane is 1:1.Catalyst
Evaluation result be shown in Table 1, table 2.
Comparative example 3
Using the catalyst da of comparative example 1 preparation, make catalyst a by embodiment 1 identical method.By embodiment 1 phase
Same method is obtained the sba-15 carrier containing sn, and the carrier after roasting and the aqueous solution containing chloroplatinic acid are impregnated at 70 DEG C
6h, dries 2h, roasting 4h at 500 DEG C at 120 DEG C.In 450 DEG C of in the air dechlorination 4h containing water vapour 20v%.Then 70
At DEG C with contain zn(no3)2Aqueous impregnation 2h, same under conditions of be dried, roasting, make catalyst db, each in catalyst
The content of component is: pt 0.5wt%, sn 0.3wt%, zn1.0wt%.
Upper end loading catalyst db in dehydrogenation reactor, middle part loading catalyst a, lower end loading catalyst da.Wherein,
The admission space of catalyst db, catalyst a and catalyst da is than for 0.5:1:1.
Carry out restoring operation, volume space velocity is 900h-1, reduce 1 hour at 480 DEG C, hydrogen for high-purity hydroformylation reaction condition is:
Volume space velocity 2000 h-1, reaction pressure 0.2mpa, reaction temperature is 630 DEG C, hydrogen: the mol ratio of propane is 1:1.Catalyst
Evaluation result be shown in Table 1, table 2.
Table 1 dehydrogenation evaluation result
| 20 minutes propane of reaction Conversion ratio % | 20 minutes propylene of reaction Selectivity % | 70 minutes propane of reaction Conversion ratio % | 70 minutes propylene of reaction Selectivity % | 40 hours propane of reaction Conversion ratio % | 40 hours propylene of reaction Selectivity % | 75 hours propane of reaction Conversion ratio % | Reaction 75 hours third Alkene selectivity % | |
| Relatively Example 1 | 28.17 | 97.0 | 27.43 | 97.1 | 26.50 | 97.4 | 25.42 | 97.6 |
| Implement Example 1 | 32.30 | 97.9 | 31.64 | 97.9 | 30.97 | 97.9 | 30.25 | 97.9 |
| Implement Example 2 | 32.07 | 97.9 | 31.41 | 97.9 | 30.69 | 97.9 | 29.91 | 98.1 |
| Implement Example 3 | 32.63 | 97.9 | 31.99 | 97.9 | 31.30 | 97.9 | 30.53 | 98.0 |
| Implement Example 4 | 31.87 | 97.7 | 31.22 | 97.7 | 30.52 | 97.8 | 29.76 | 98.0 |
| Relatively Example 2 | 29.81 | 97.3 | 29.05 | 97.4 | 28.23 | 97.6 | 27.21 | 97.8 |
| Relatively Example 3 | 30.43 | 97.5 | 29.71 | 97.6 | 28.89 | 97.7 | 27.85 | 97.9 |
Table 1: reaction condition is: volume space velocity 2000 h-1, reaction pressure 0.2mpa, reaction temperature is 630 DEG C, hydrogen: third
The mol ratio of alkane is 1:1.
Table 2 dehydrogenation evaluation result
| 20 minutes propene yields of reaction, % | 70 minutes propene yields of reaction, % | 40 hours propene yields of reaction, % | 75 hours propene yields of reaction, % | |
| Comparative example 1 | 27.32 | 26.63 | 25.81 | 24.81 |
| Embodiment 1 | 31.62 | 30.98 | 30.32 | 29.61 |
| Embodiment 2 | 31.40 | 30.75 | 30.04 | 29.34 |
| Embodiment 3 | 31.95 | 31.32 | 30.64 | 29.92 |
| Embodiment 4 | 31.14 | 30.50 | 29.85 | 29.17 |
| Comparative example 2 | 29.01 | 28.29 | 27.55 | 26.61 |
| Comparative example 3 | 29.67 | 29.00 | 28.22 | 27.26 |
Claims (16)
1. a kind of method of dehydrogenating of saturated alkane, comprising:
(1) prepare presulfurization dehydrogenation, it is that required presulfurization takes off that presulfurization processes the vulcanizing agent consumption containing in catalyst
Hydrogen catalyst theory needs the 80% ~ 120% of sulfur content；
(2) the dehydrogenation pt-k-sn/al of preparation reduction2o3；
(3) the dehydrogenation zn-sn-pt/ sba-15 of preparation reduction；
(4) the dehydrogenation dress of reduction prepared by presulfurization dehydrogenation, step (2) and the step (3) that prepared by step (1)
Enter in reactor, adjust the condition needed for dehydrogenation reaction, then carry out dehydrogenation reaction；The reduction that wherein prepared by step (3)
Dehydrogenation is seated in top, and presulfurization dehydrogenation is seated in middle part, the dehydrogenation of reduction prepared by step (2)
It is seated in bottom, reduction prepared by the dehydrogenation of reduction prepared by step (3), presulfurization dehydrogenation, step (2)
The admission space of dehydrogenation is than for 0.1 ~ 0.5:1:0.5 ~ 2.
2. in accordance with the method for claim 1 it is characterised in that the dehydrogenation of the reduction of step (2) adopts following methods
Preparation:
(i) chloroplatinic acid ethylene glycol solution is mixed with alumina support containing sn, and flow back under 60 DEG C ~ 120 DEG C stirring conditions 1h ~ 6h；
(ii) koh ethylene glycol solution is added to step system (i), be warming up to 150 DEG C ~ 200 DEG C continue backflow 5min ~
120min, is cooled to room temperature after terminating；
(iii) the solidliquid mixture of separating step (ii) gained, scrubbed after be vacuum dried and inert gas atmosphere under roast
Burn；
(iv) using kno3(iii) gained solid is vacuum dried for aqueous impregnation step, be obtained after roasting under inert gas atmosphere
The dehydrogenation of reduction.
3. method according to claim 1 it is characterised in that: the dehydrogenation of the reduction of step (3) be zn-sn-pt/
Sba-15 catalyst, using the preparation of following methods:
A () is first immersed in sn on sba-15 carrier, sba-15 carrier containing sn is obtained after drying, roasting；
B () chloroplatinic acid ethylene glycol solution is mixed with the sba-15 carrier containing sn, and the 1h that flows back under 60 DEG C ~ 120 DEG C stirring conditions ~
6h；
C () adds koh ethylene glycol solution to the system of step (a), be warming up to 150 DEG C ~ 200 DEG C continue backflow 5min ~
120min, is cooled to room temperature after terminating；
The solidliquid mixture of (d) separating step (c) gained, scrubbed after be vacuum dried and inert gas atmosphere under roasting；
E () uses zn(no3)2Aqueous impregnation step (d) gained solid is vacuum dried, make after roasting under inert gas atmosphere
The dehydrogenation that must reduce.
4. according to the method in claim 2 or 3 it is characterised in that: chloroplatinic acid ethylene glycol solution concentration be 0.001 ~ 0.01
mol/l；Koh ethylene glycol solution concentration is 0.1 ~ 1 mol/l.
5. according to the method in claim 2 or 3 it is characterised in that: step (i) or step (b) reflux temperature be 80 DEG C ~
100 DEG C, return time is 2h ~ 4h；Step is (ii) or step (c) reflux temperature is 170 DEG C ~ 190 DEG C, and return time 10min ~
60min.
6. method according to claim 2 it is characterised in that: step (i) in, in alumina support containing sn the content of sn with
Element is calculated as the 0.1% ~ 10% of vehicle weight.
7. according to the method in claim 2 or 3 it is characterised in that: step (i) in, alumina support containing sn be spherical, bar
Shape, microsphere or abnormity, particle size 0.1mm ~ 5mm；In step (a), sba-15 carrier containing sn is spherical, bar shaped, microsphere or
Abnormity, particle size 0.1mm ~ 5mm.
8. according to the method in claim 2 or 3 it is characterised in that: step is (ii) or in step (c), koh ethylene glycol solution
Addition is counted than for 15 ~ 25 with potassium with pt atom.
9. according to the method in claim 2 or 3 it is characterised in that: step (iii) or in step (d) baking temperature be 60
℃~200℃；Sintering temperature is 200 DEG C ~ 800 DEG C, and noble gases include one or more of nitrogen, helium, argon.
10. according to the method in claim 2 or 3 it is characterised in that: step (iv) described in kno3Concentration of aqueous solution is 0.1
~2 mol/l；(iv) middle dipping temperature is 60 ~ 80 DEG C to step, and dip time is 1h ~ 6h；Baking temperature is 60 DEG C ~ 200 DEG C, roasting
Burn temperature and be 200 DEG C ~ 800 DEG C.
11. according to the method in claim 2 or 3 it is characterised in that: zn(no described in step (e)3)2Concentration of aqueous solution is
0.1~2 mol/l；In step (e), dipping temperature is 60 ~ 80 DEG C, and dip time is 1h ~ 6h；Baking temperature is 60 DEG C ~ 200 DEG C,
Sintering temperature is 200 DEG C ~ 800 DEG C.
12. methods according to claim 1 and 2 it is characterised in that: each group in the dehydrogenation of reduction of step (2)
The content divided is as follows: sn 0.2 wt% ~ 1.5wt%, pt 0.2wt% ~ 0.8wt%, k 0.1wt% ~ 2.0wt%.
13. methods according to claim 1 or 3 it is characterised in that: in the dehydrogenation of reduction used by step (3)
The content of each component is: sn 0.2wt% ~ 1.5wt%, pt 0.2wt% ~ 0.8wt%, zn 0.2wt% ~ 3.0wt%.
14. methods according to claim 1 it is characterised in that: the dehydrogenation of presulfurization adopt platinum family support type take off
Hydrogen catalyst, catalyst with aluminium oxide as carrier, with one or more of the platinum in platinum family, palladium, iridium, rhodium or osmium as activearm
Point, active component weight content in the catalyst is counted for 0.01% ~ 2% with element.
15. method according to claim 14 it is characterised in that: the dehydrogenation of presulfurization contains in auxiliary agent sn, k
One or more, the content of sn is counted the weight content in the catalyst content for 0.1% ~ 10%, k with element and is being urged in terms of element
Weight content in agent is 0.1% ~ 10%.
16. methods according to claim 1 it is characterised in that: dehydrogenation reaction conditions are: 450 ~ 650 DEG C of reaction temperature, body
Long-pending air speed 1000 ~ 3000h-1, absolute pressure 0.1 ~ 0.3mpa, hydrogen: the mol ratio of alkane is 1:1 ~ 6:1, and alkane is c3 ~ c7
Alkane.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030191351A1 (en) * | 2002-04-08 | 2003-10-09 | Voskoboynikov Timur V. | Dehydrogenation catalyst composition |
| CN101898138A (en) * | 2009-05-25 | 2010-12-01 | 中国石油化工股份有限公司 | Method for preparing vulcanized dehydrogenation catalyst |
| CN102464542A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Startup method of dehydrogenation catalyst |
| CN103058814A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing aromatic hydrocarbon and olefin from liquefied gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030191351A1 (en) * | 2002-04-08 | 2003-10-09 | Voskoboynikov Timur V. | Dehydrogenation catalyst composition |
| US20050033101A1 (en) * | 2002-04-08 | 2005-02-10 | Voskoboynikov Timur V. | Process for the dehydrogenation of hydrocarbons |
| CN101898138A (en) * | 2009-05-25 | 2010-12-01 | 中国石油化工股份有限公司 | Method for preparing vulcanized dehydrogenation catalyst |
| CN102464542A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Startup method of dehydrogenation catalyst |
| CN103058814A (en) * | 2011-10-20 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing aromatic hydrocarbon and olefin from liquefied gas |
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