CN105435782A - Performance adjustable Pt-based dehydrogenation catalyst and method for improving stability of same - Google Patents
Performance adjustable Pt-based dehydrogenation catalyst and method for improving stability of same Download PDFInfo
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Abstract
The present invention discloses a performance adjustable Pt-based dehydrogenation catalyst. The catalyst comprises the following components and contents: 0.1-1.0 wt% of Pt oxide serving as a main active component; one or more of Na, K, Ca, Zr, Sn, La and Ce as an aid agent, wherein the content of an oxide of an element of the aid agent is 0.01-10 wt%; and the balance of a carrier. The present invention also provides a method for improving activity and stability of the catalyst in a reaction process of light alkane dehydrogenation. According to the change for catalytic activity, in the method, an adjustment gas for stabilizing the catalytic activity is added into a reaction system; the adjustment gas consists of adjustment components and dilution components, wherein the adjustment components are gases of one or more elements in the VIIA element, and the content of the adjustment components is 0.001-1 v%; the dilution components are one or more gases of water vapor, air, nitrogen, methane or ethane gas. According to the method provided by the present invention, in the reaction process, the active component Pt can be dispersed, the catalyst deactivation is slowed down, and the service life of the catalyst is prolonged.
Description
Technical field
The present invention relates to dehydrogenation field, specifically relate to the platinum-based dehydrogenation catalyst that a kind of performance is adjustable, and improve the method for this catalyst activity and stability.
Background technology
Propylene is important Organic Chemicals, and the byproduct of the conventional refinery process such as steam cracking and catalytic cracking is its main source, therefore propone output is limited by the production of major product ethene and product oil.The propone output of current traditional handicraft can not meet the demand of market to propylene, the alternative production new technique of propylene is paid close attention in market gradually, comprises five kinds of techniques such as dehydrogenating propane (PDH), methanol-to-olefins (MTO, MTP), DCC (DCC), olefin cracking and olefin(e) disproportionation.Comparatively speaking, the advantages such as dehydrogenating propane technical advantage is more obvious, and it possesses technology maturation, good product quality, conversion ratio is high, accessory substance is few.The industrialized preparing propylene by dehydrogenating propane production technology of current major part uses precious metals pt catalyst.
Some reaction, although the dehydrogenation reaction as alkane not exclusively relies on acidity of catalyst to carry out catalytic reaction, the acidity of catalyst still has certain facilitation to catalytic reaction.Propane catalytic dehydrogenating reaction, by the restriction of thermodynamical equilibrium, must carry out under the harsh conditions of high temperature, low pressure.The Cl content of precious metals pt catalyst under this reaction condition in catalyst there will be loss, and surface there will be the loss of acid amount, and there will be reunion sintering and cause catalysqt deactivation.Traditional renovation process be all to inactivation after catalyst carry out the process of benefit chlorine, and then disperseing again active component Pt in catalyst.
Patent CN103801330A and CN103801331A is after the Burning Coke on Catalyst by inactivation, carries out the process of benefit chlorine, then carries out oxidation processes, and it is loaded down with trivial details that this mends chlorine process, and does not solve the fast problem of catalysqt deactivation, and catalyst needs to mend chlorine in constantly regeneration.Patent CN104107704A is after the Burning Coke on Catalyst by inactivation, and pass into chloride elemental gas to catalyst and contain oxygen element gas, chlorine process is mended in realization and oxidation processes is carried out simultaneously.Benefit chlorine process is improved.Decaying catalyst is transferred to outside reactor by patent CN104084218A, the inorganic salts that backward catalyst soakage of making charcoal is chloride, reaches the effect of mending chlorine.Which solve the problem of chlorine-containing gas body etching apparatus, but above-mentioned two patents still do not solve the fast difficult problem of catalysqt deactivation.
Summary of the invention
For the current Pt-Sn/Al for dehydrogenating low-carbon alkane
2o
3catalyst, it is in use along with the carrying out of dehydrogenating propane reaction, catalyst activity reduces, the shortcoming that inactivation is fast, the invention discloses the adjustable Pt based dehydrogenation catalyst of a kind of performance, preparation method and the method for its stability is provided, make this catalyst catalyst activity in dehydrogenating low-carbon alkane process keep stable while, there is the advantages such as inactivation is slow, carbon accumulation resisting ability is strong.
The invention provides the Pt based dehydrogenation catalyst that a kind of performance is adjustable, this catalyst is with aluminium oxide and aktivton for carrier, and Pt is the main active component of catalyst, and one or more in Na, K, Ca, Zr, Sn, La and Ce are auxiliary agent; The mass percentage of catalyst components is: the content of main active component Pt is 0.1 ~ 1.0wt%, is preferably 0.1 ~ 0.5wt%; The oxide content of auxiliary element is 0.01 ~ 10wt%, is preferably 0.1 ~ 2wt%; All the other are carrier, and carrier is that the mixture of aluminium oxide and silica is made, wherein aluminium oxide: silica=1 ~ 99:1.
Present invention also offers the preparation method of above-mentioned catalyst, comprise the steps:
1) by a certain amount of aluminium hydroxide powder, silica powder and account for alumina powder jointed mass fraction be 0.5 ~ 5% sesbania powder mix, adding mass concentration is again that 1 ~ 30% dust technology carries out kneading, the kneading time is 10min ~ 2h, finally carry out shaping again on forming machine, carrier after shaping is after room temperature dries in the air 1 ~ 12h, dry 1 ~ 8h in 80 ~ 150 DEG C again, the carrier of oven dry finally obtains carrier after 500 ~ 1000 DEG C of roasting 1 ~ 12h in Muffle furnace;
2) adopt co-impregnation to come the main active component of load and auxiliary agent, preparation contains the soluble salt solutions of main active component and auxiliary agent as dipping solution, soaks or sprays saturated impregnated carrier, and then dry, roasting obtains catalyst for dehydrogenation of low-carbon paraffin.
Step 1 in the preparation method of catalyst of the present invention) in, prepare the shaping machine of carrier and comprise tablet press machine, rolling granulators, pellet processing machine, moulding machine, banded extruder etc.Shape after carrier is shaping comprises spherical, sheet, cylinder, star, trilobal, quatrefoil.
Step 2 in the preparation method of catalyst of the present invention) in, dipping rear catalyst is dry at 120 ~ 220 DEG C, in the mist of 500 ~ 850 DEG C, carry out roasting, mist is that the steam of 0 ~ 20% and the air of percent by volume 80 ~ 100% form by comprising percent by volume.
In the present invention, hydrothermal treatment consists under high temperature not only has certain regulating action to the pore structure of catalyst and carrier, also there is regulating action for the interaction between active component Pt and carrier, improve active component crystal grain decentralization on a catalyst, and then the stability of promoting catalyst.
When catalyst of the present invention is used for dehydrogenating low-carbon alkane, generally under higher than the reaction temperature of 500 DEG C, carry out dehydrogenation reaction, in paraffinic feedstock gas, the content of low-carbon alkanes is generally not less than 80%, the general condition of reaction is reaction pressure :-0.1 ~ 1MPa, reaction temperature 500 ~ 680 DEG C, low-carbon alkanes gas space velocity is 150 ~ 1000h
-1.
Current regulating catalyst is acid and mend chlorine process respectively mainly at catalyst preparation stages and regeneration stage.But for the dehydrogenation reaction that low-carbon alkanes carries out on Pt is catalyst based, along with the carrying out of reaction, due to the impact of catalyst carbon deposition and hot environment, the Cl content in catalyst can decline, and acidity can reduce.Catalyst dehydrogenation activity needs the synergy of the acid of some strength and distribution on catalyst, and therefore, catalyst Cl content reduction in use can affect the activity of catalyst, and catalyst activity and selectivity is reduced.Provide in the present invention and be a kind ofly applicable in the use procedure of catalyst for dehydrogenation of low-carbon paraffin, the catalyst that carries out according to reaction can forfeiture Cl element gradually and acidity, thus add adjustments of gas to reaction system, regulate catalyst surface character, make catalyst surface acid a rational scope, catalyst activity is made to keep stable or reduction catalyst deactivation rate preferably, the service life of extending catalyst.
Provided by the inventionly a kind ofly improve the activity of the adjustable Pt based dehydrogenation catalyst of above-mentioned performance in dehydrogenating low-carbon alkane reaction and the method for stability, the method comprises: adopt fixed bed to carry out dehydrogenating low-carbon alkane reaction, course of reaction comprises dehydrogenation reaction process and coke combustion hockets; Wherein certain embodiments is the unstrpped gas containing low-carbon alkanes 80 ~ 100% passing into certain flow to reaction system, and dehydrogenation reaction carries out 1 ~ 15h, and Burning Coke on Catalyst process is for pass into oxygen containing gas to reaction system, and coke combustion carries out 0 ~ 8h; Dehydrogenation reaction temperature controls at 500 ~ 700 DEG C, and reaction pressure is normal pressure or negative pressure; In dehydrogenation reaction process or coke combustion, or in dehydrogenation reaction process and coke combustion, the adjustments of gas that the catalyst activity passed into unstripped gas to reaction system is stable, described adjustments of gas forms by regulating component and dilution component, component is wherein regulated to be containing one or more the gas in the VIIth A race element, its constituent content is 0.001 ~ 0.5v%, be preferably 0.01 ~ 0.5v%, all the other are dilution component, and dilution component is one or more in steam, air, nitrogen, methane or ethane gas.
Along with the carrying out of the dehydrogenating propane reaction under the catalyst based existence of Pt, under a reaction condition, in catalyst a period of time, as in the times of 2 days to 60 days, the mean value (representing with X) of alkane conversion or olefine selective mean value (representing with S) can reach a more stable stage, namely substantially keep becoming or slightly raising in the alkane conversion of catalyst during this period of time or olefine selective, the alkane conversion of this section or the mean value of olefine selective are labeled as initial value, are designated as original alkane conversion ratio X0 and the selective S0 of olefin streams.Along with proceeding of reaction, when the alkane conversion of catalyst or olefine selective are within the time of next 2 days to 60 days, its alkane conversion mean value general X's or olefine selective mean value S comparatively X0 or S0 reduces ratio T when being 0.01 ~ 2%, just need beginning to pass into the adjustments of gas possessing catalyst activity stabilization containing Cl elemental substance to reaction system, regulate the volume flow that adds of gas to calculate with following formula:
Reduce ratio T=(variable-variable 0)/variable 0;
Adjustments of gas amasss flow=paraffinic feedstock volume flow × T;
Wherein, variable be catalyst at 2 days to the alkane conversion in 60 days or olefine selective mean value.
Catalyst of the present invention the low-carbon alkanes raw material that is suitable for be the liquefied petroleum gas of low-carbon alkanes content more than 80%, raw material low-carbon alkanes refers to the alkane gaseous mixture, particularly propane of below the C4 of arbitrary proportion and the mist of butane.When taking propane as raw material, at reaction pressure 0.01 ~ 0.5MPa, reaction temperature 570 ~ 650 DEG C, propane feed gas gas space velocity 200 ~ 2000h
-1condition under, conversion of propane is greater than 40%; When the mixed alkanes pressing 1:1 with propane and butane is for raw material, at reaction pressure 0.03 ~ 0.5MPa, reaction temperature 550 ~ 620 DEG C, mist air speed 200 ~ 2000h
-1condition under, the conversion ratio of mixed alkanes is more than 40%.Meanwhile, by carrying out situation according to what react, adopting pass into Active Regulation gas in reaction system after, catalyst life more than 10%, achieving gratifying result.
The remarkable advantage of technology of the present invention is: (1) adopts the distinguishing feature of catalyst of the present invention to be carry out modification with alkalies and alkaline earth auxiliary agent to carrier, make carrier have suitable surface acidic-basic property, improve the dehydrating alkanes conversion ratio of catalyst and the selective of alkene; (2) distinguishing feature of another aspect is by course of reaction, according to the change of catalyst activity, the adjustments of gas of stabilizing catalyst activity is passed into reaction system, namely stabilizing catalyst activity is contributed to, well can promote again the elimination to carbon distribution, catalyst surface character can also be regulated, extend catalyst service life; (3) carry out surface nature adjustment by catalyst preparation stages to catalyst, the change simultaneously according to catalyst in catalyst use procedure is adjusted, and two processes cooperatively interact, and makes the performance that catalyst reaches optimum.By the synergy of these aspects, ensure that the technology that the present invention proposes is different from the feature having invention and technology: 1) simple catalyst preparation technology; 2) stable dehydrogenating low-carbon alkane activity and olefine selective; 3) longer catalyst service life.
Specific embodiment
Below will the invention will be further described by specific embodiment, but the present invention is not limited to these embodiments.
Embodiment 1
Prepared by carrier.By a certain amount of aluminium oxide: silica be 1:1 mixed powder with account for mixed powder mass fraction be 8% sesbania powder mix, add again mass concentration be 5% citric acid and mass concentration be that 22% dust technology carries out kneading, the kneading time is 30min, finally carry out shaping again on forming machine, carrier after shaping after room temperature dries in the air 8h, then dries 4h, carrier finally 900 DEG C of roasting 6h in Muffle furnace of oven dry in 120 DEG C, obtain final carrier A, its water absorption rate is 62.3%.
The hydrochloric acid solution being 0.18M stannous chloride by 2ml concentration 0.2M chloroplatinic acid aqueous solution and 7.4ml concentration mixes, according to the saturated water adsorptive value of used carrier, in above-mentioned Pt-Sn maceration extract, add hydrochloric acid and water makes the concentration of the hydrochloric acid of the maceration extract be finally mixed be 1.5M.The potassium nitrate of 0.58g is dissolved in above-mentioned maceration extract, and with the 26.66g carrier incipient impregnation 12h in (1), 120 DEG C dry 12 hours, at 550 DEG C, roasting 4 hours, obtains finished catalyst A.
Consisting of of catalyst A: Pt-Sn-K/Al
2o
3, wherein the mass percentage of each component is: Pt:0.3%, Sn:0.6%, K:0.9%, and all the other are aluminium oxide and silica.
The catalytic activity of catalyst A is tested at twice: adopt 20ml fixed bed minisize reaction evaluation system, and getting 20 milliliters of loading internal diameters is carry out the test of dehydrogenating propane reactivity worth in the stainless steel reactor of 8 millimeters.
Catalyst A catalytic performance test condition: reaction temperature 620 DEG C, pressure is normal pressure, and the volume space velocity of propane is 2000h
-1, the charge proportion of raw material is: n (propane): n (H2): n (H20)=1:0.2:1.Catalyst needs to carry out hydrogen reducing process before the reaction, and treatment conditions are 500 DEG C, reduction 4h.
Comparative evaluation's condition: the comparative evaluation's test carrying out catalyst according to above-mentioned appreciation condition, difference is, react the time period in the time interval at 5 days, when conversion of propane reduction ratio reaches 0.05%, the dehydrogenation reaction stage with unstripped gas to reaction system add chloride be 0.05% Active Regulation gas, Active Regulation gas is the gas containing monochlorethane with nitrogen dilution, the results are shown in Table 1.
When conversion of propane lower than 25% time, think catalyst inactivation terminate evaluation response, result table 1.
Embodiment 2
Prepared by carrier.By a certain amount of aluminium oxide: silica be 5:1 mixed powder with account for mixed powder mass fraction be 5% sesbania powder mix, add again mass concentration be 5% citric acid and mass concentration be that 20% dust technology carries out kneading, the kneading time is 30min, finally carry out shaping again on forming machine, carrier after shaping after room temperature dries in the air 8h, then dries 4h, carrier finally 850 DEG C of roasting 12h in Muffle furnace of oven dry in 120 DEG C, obtain final carrier B, its water absorption rate is 55.1%.
The hydrochloric acid solution being 0.18M stannous chloride by 2ml concentration 0.2M chloroplatinic acid aqueous solution and 7.4ml concentration mixes, according to the saturated water adsorptive value of used carrier, in above-mentioned Pt-Sn maceration extract, add hydrochloric acid and water makes the concentration of the hydrochloric acid of the maceration extract be finally mixed be 1.5M.The eight water basic zirconium chlorides of 0.94g are dissolved in above-mentioned maceration extract, and with the 26.66g carrier incipient impregnation 12h in (1), 120 DEG C dry 12 hours, at 550 DEG C, roasting 4 hours, obtains finished catalyst B, consisting of of catalyst B: Pt-Sn-Zr/Al
2o
3, wherein the mass percentage of each component is: Pt:0.3%, Sn:0.6%, Zr:1.0%, and all the other are aluminium oxide and silica.
The performance evaluation condition of catalyst B is with embodiment 1.
Comparative evaluation's condition of catalyst B is with the performance evaluation condition of catalyst B, and difference is to add chloride Active Regulation gas for 0.01v% with unstripped gas to reaction system in the dehydrogenation reaction stage, and Active Regulation gas is the gas containing dichloroethanes with methane gas dilution.
When conversion of propane lower than 25% time, think catalyst inactivation terminate evaluation response.Evaluation result is in table 1.
Embodiment 3
Prepared by carrier.By a certain amount of aluminium oxide: silica be 50:1 mixed powder with account for mixed powder mass fraction be 6% sesbania powder mix, add again mass concentration be 5% citric acid and mass concentration be that 20% dust technology carries out kneading, the kneading time is 30min, finally carry out shaping again on forming machine, carrier after shaping after room temperature dries in the air 8h, then dries 4h, carrier finally 800 DEG C of roasting 6h in Muffle furnace of oven dry in 120 DEG C, obtain final support C, its water absorption rate is 58.6%.
The hydrochloric acid solution being 0.18M stannous chloride by 2ml concentration 0.2M chloroplatinic acid aqueous solution and 7.4ml concentration mixes, according to the saturated water adsorptive value of used carrier, in above-mentioned Pt-Sn maceration extract, add hydrochloric acid and water makes the concentration of the hydrochloric acid of the maceration extract be finally mixed be 1.5M.The lanthanum nitrate of 0.83g is dissolved in above-mentioned maceration extract, and with the 26.66g carrier incipient impregnation 12h in (1), 120 DEG C dry 12 hours, at 550 DEG C, roasting 4 hours, obtains finished catalyst B, consisting of of catalyst B: Pt-Sn-La/Al
2o
3, wherein the mass percentage of each component is: Pt:0.3%, Sn:0.6%, La:1.0%, and all the other are aluminium oxide and silica.
The performance evaluation condition of catalyst C is with embodiment 1.
Comparative evaluation's condition of catalyst C and the performance evaluation condition of catalyst C are distinguished and are to add chloride Active Regulation gas for 0.01v% with unstripped gas to reaction system in the dehydrogenation reaction stage, and Active Regulation gas is the gas containing monochlorethane with the dilution of steam gas.
When conversion of propane lower than 25% time, think catalyst inactivation terminate evaluation response.Evaluation result is in table 1.
Embodiment 4
Prepared by carrier.By a certain amount of aluminium oxide: silica be 99:1 mixed powder with account for mixed powder mass fraction be 9% sesbania powder mix, add again mass concentration be 6% citric acid and mass concentration be that 15% dust technology carries out kneading, the kneading time is 30min, finally carry out shaping again on forming machine, carrier after shaping after room temperature dries in the air 8h, then dries 4h, carrier finally 600 DEG C of roasting 8h in Muffle furnace of oven dry in 120 DEG C, obtain final carrier D, its water absorption rate is 51.3%.The hydrochloric acid solution being 0.18M stannous chloride by 2ml concentration 0.2M chloroplatinic acid aqueous solution and 7.4ml concentration mixes, according to the saturated water adsorptive value of used carrier, in above-mentioned Pt-Sn maceration extract, add hydrochloric acid and water makes the concentration of the hydrochloric acid of the maceration extract be finally mixed be 1.5M.The eight water basic zirconium chlorides of the potassium nitrate of 0.58g, 0.94g and the lanthanum nitrate of 0.83g are dissolved in above-mentioned maceration extract, and with the 26.66g carrier incipient impregnation 12h in (1), dry 12 hours at 120 DEG C, roasting 4 hours at 550 DEG C, obtain finished catalyst B, consisting of of catalyst B: Pt-Sn-K-Zr-La/Al
2o
3, wherein the mass percentage of each component is: Pt:0.3%, Sn:0.6%, K:0.9%, Zr:1.0%, La:1.0%, and all the other are aluminium oxide and silica.
The performance evaluation condition of catalyst D, with embodiment 1, the results are shown in Table 1.
Comparative evaluation's condition of catalyst D and the performance evaluation condition of catalyst D are distinguished and are to add chloride Active Regulation gas for 0.1v% with unstripped gas to reaction system in the stage of reaction of making charcoal, and Active Regulation gas is the gas containing dichloroethanes with methane gas dilution.
When conversion of propane lower than 25% time, think catalyst inactivation terminate evaluation response.Evaluation result is in table 1.
The dehydrating alkanes performance of table 1 different catalysts
As can be seen from Table 1, in use, the service life of catalyst all improves more than 10% to catalyst.
Claims (6)
1. the Pt based dehydrogenation catalyst that performance is adjustable, is characterized in that,
Catalyst by main active component, auxiliary agent and carrier three part form, active component and auxiliary agent adopt the mode of dipping to load on carrier: wherein, main active component is Pt, and content is 0.1 ~ 1.0wt%; Auxiliary agent is one or more in Na, K, Ca, Zr, Sn, La and Ce, and the content of auxiliary element is 0.01 ~ 10wt%; All the other are carrier, and carrier is that the mixture of aluminium oxide and silica is made, wherein aluminium oxide: silica weight ratio is 1 ~ 99:1.
2. the Pt based dehydrogenation catalyst that performance according to claim 1 is adjustable, is characterized in that, the content of described main active component Pt is 0.1 ~ 0.5wt%, and the oxide content of auxiliary element is 0.1 ~ 2wt%.
3. a preparation method for the Pt based dehydrogenation catalyst that performance according to claim 1 is adjustable, is characterized in that, comprise step:
1) by a certain amount of aluminium hydroxide powder, silica powder and account for alumina powder jointed mass fraction be 0.5 ~ 5% sesbania powder mix, adding mass concentration is again after 1 ~ 30% dust technology carries out kneading, carry out shaping again on forming machine, carrier after shaping is after room temperature dries in the air 1 ~ 12h, 1 ~ 8h is dried again in 80 ~ 150 DEG C, carrier finally 500 ~ 1000 DEG C of roasting 1 ~ 12h in Muffle furnace of drying, obtain carrier;
2) adopt co-impregnation to come supported active metals and auxiliary agent, preparation contains the soluble salt solutions of main active component and auxiliary agent as aqueous impregnation solution, soaks or sprays saturated impregnated carrier, and then dry, roasting obtains catalyst for dehydrogenation of low-carbon paraffin.
4. improve a method for the adjustable Pt based dehydrogenation catalyst of performance according to claim 1 stability in dehydrogenating low-carbon alkane reaction, it is characterized in that:
Adopt fixed bed to carry out dehydrogenating low-carbon alkane reaction, course of reaction comprises dehydrogenation reaction process and coke combustion hockets; Wherein certain embodiments is the unstrpped gas containing low-carbon alkanes 80 ~ 100% passing into certain flow to reaction system, and dehydrogenation reaction carries out 1 ~ 15h, and Burning Coke on Catalyst process is for pass into oxygen containing gas to reaction system, and coke combustion carries out 0 ~ 8h; Dehydrogenation reaction temperature controls at 500 ~ 700 DEG C, and reaction pressure is normal pressure or negative pressure; In dehydrogenation reaction process or coke combustion, pass into a kind of adjustments of gas of stabilizing catalyst activity to reaction system with reaction raw materials; Adjustments of gas forms by regulating component and dilution component, wherein regulates component to be the gas containing one or more elements in the VIIth A race element of 0.001 ~ 1v%, and dilution component is one or more in steam, air, nitrogen, methane or ethane gas.
5. in accordance with the method for claim 4, it is characterized in that, described adjustment component is the gas of chloride element, and content accounts for 0.001 ~ 0.5% of reacting gas cumulative volume, and dilution component is one or more in steam, air, methane gas.
6. in accordance with the method for claim 4, it is characterized in that, described adjustments of gas adds in dehydrogenation reaction process, or adds in coke combustion, or all adds in dehydrogenation reaction process and coke combustion.
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