CN105435782B - A kind of method performance adjustable Pt based dehydrogenation catalyst and improve its stability - Google Patents
A kind of method performance adjustable Pt based dehydrogenation catalyst and improve its stability Download PDFInfo
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Abstract
The invention discloses a kind of adjustable Pt based dehydrogenation catalysts of performance, the catalytic component and content are as follows: 0.1~1.0wt% of oxide of main active component Pt, auxiliary agent is one of Na, K, Ca, Zr, Sn, La and Ce or a variety of, the oxide content of auxiliary element is 0.01~10wt%, remaining is carrier.The present invention also provides a kind of catalyst that improves in the method for dehydrogenating low-carbon alkane reaction process activity and stability, according to the variation of catalyst activity in this method, a kind of regulating gas of stabilizing catalyst activity is added into reaction system, the regulating gas is grouped as by adjusting component and dilution group, wherein adjusting group is divided into the gas of one of the VIIth A race element or multiple element, content is 0.001~1v%, and dilution group is divided into one of vapor, air, nitrogen, methane or ethane gas or a variety of.The method of the present invention can divided active component Pt during the reaction, slow down catalyst inactivation, extend catalyst life.
Description
Technical field
The present invention relates to dehydrogenation fields, are specifically related to a kind of adjustable platinum-based dehydrogenation catalyst of performance, and
The method for improving the catalyst activity and stability.
Background technique
Propylene is important Organic Chemicals, and the byproduct of the conventional refinery process such as steam cracking and catalytic cracking is it
Main source, therefore propylene yield is limited by the production of major product ethylene and product oil.The propylene yield of current traditional handicraft cannot
Meets the needs of market is to propylene, the substitution production new technique of propylene, including dehydrogenating propane (PDH), methanol are gradually paid close attention in market
Five kinds of techniques such as alkene (MTO, MTP), deep catalytic cracking (DCC), olefin cracking and olefin(e) disproportionation processed.In comparison, third
Alkane De-hydrogen Technology advantage becomes apparent, and has the advantages that technology maturation, good product quality, high conversion rate, by-product are few.At present
It is precious metals pt catalyst used in most of industrialized preparing propylene by dehydrogenating propane production technology.
Some reactions, although being urged as the dehydrogenation reaction of alkane not exclusively carries out catalysis reaction by acidity of catalyst
The acid of agent still has certain facilitation to catalysis reaction.Limit of the propane catalytic dehydrogenating reaction by thermodynamical equilibrium
System, must high temperature, low pressure harsh conditions under carry out.Cl of the precious metals pt catalyst under this reaction condition in catalyst contains
Amount will appear loss, and surface will appear the loss of acid amount, and will appear reunion sintering and cause catalyst inactivation.Traditional regeneration
Method is to carry out mending chlorine processing to the catalyst after inactivation, and then to the redisperse of active component Pt in catalyst.
After patent CN103801330A and CN103801331A are the Burning Coke on Catalyst that will be inactivated, carry out mending chlorine processing, then
Oxidation processes are carried out, it is cumbersome that this mends chlorine process, and does not solve the problems, such as that catalyst inactivation is fast, and catalyst needs continuous regeneration
Middle benefit chlorine.After patent CN104107704A is the Burning Coke on Catalyst that will be inactivated, gas containing chlorine element and oxygen-containing is passed through to catalyst
Elemental gas realizes that mend chlorine processing and oxidation processes carries out simultaneously.Chlorine process is mended to be improved.Patent CN104084218A be by
Decaying catalyst is transferred to outside reactor, impregnates the inorganic salts containing chlorine to catalyst after making charcoal, and achievees the effect that mend chlorine.It is solved
The problem of chlorine-containing gas body corrosion equipment, but above-mentioned two patent does not still solve the problems, such as that catalyst inactivation is fast.
Summary of the invention
For the Pt-Sn/Al currently used for dehydrogenating low-carbon alkane2O3Catalyst, in use with dehydrogenating propane
The progress of reaction, catalyst activity reduce, and inactivate fast disadvantage, the invention discloses a kind of adjustable Pt base catalysis dehydrogenations of performance
Agent, preparation method and its method of its stability is provided, so that catalyst catalyst activity during dehydrogenating low-carbon alkane
While keeping stablizing, has many advantages, such as that inactivation is slow, has strong anti-carbon capacity.
The present invention provides a kind of adjustable Pt based dehydrogenation catalyst of performance, which is mixed with aluminium oxide and silica
Object is carrier, and Pt is the main active component of catalyst, and one of Na, K, Ca, Zr, Sn, La and Ce or a variety of are auxiliary agent；Catalyst
The mass percentage of each component are as follows: the content of main active component Pt is 0.1~1.0wt%, preferably 0.1~0.5wt%；It helps
The oxide content of agent element is 0.01~10wt%, preferably 0.1~2wt%；Remaining is carrier, and carrier is aluminium oxide and oxygen
The mixture of SiClx is made, wherein aluminium oxide: silica=1~99:1.
The present invention also provides the preparation methods of above-mentioned catalyst, include the following steps:
It 1) is 0.5~5% with alumina powder mass fraction is accounted for by a certain amount of aluminium hydroxide powder, silica powder
Sesbania powder is uniformly mixed, and adding mass concentration is that 1~30% dust technology carries out kneading, and the kneading time is 10min~2h, finally
It is formed on forming machine again, carrier after molding, then at 80~150 DEG C of 1~8h of drying, dries after room temperature dries in the air 1~12h
Dry carrier finally obtains carrier after 500~1000 DEG C of 1~12h of roasting in Muffle furnace；
2) main active component and auxiliary agent are loaded using co-impregnation, prepare the solubility for containing main active component and auxiliary agent
Salting liquid impregnates as dipping solution or dehydrogenating low-carbon alkane catalysis is made in spray saturation impregnated carrier, then dry, roasting
Agent.
In the step 1) of the preparation method of catalyst of the present invention, preparing the molding machine of carrier includes tablet press machine, roll-type
Granulator, pellet processing machine, moulding machine, banded extruder etc..Carrier shape after molding includes spherical shape, sheet, cylindrical body, star, three leaves
Shape, quatrefoil.
In the step 2) of the preparation method of catalyst of the present invention, rear catalyst drying at 120~220 DEG C is impregnated,
Roasted in 500~850 DEG C of mixed gas, mixed gas by include percent by volume be 0~20% vapor and body
The air composition of product percentage 80~100%.
In the present invention, the hydro-thermal process under high temperature not only has certain adjustment effect to the pore structure of catalyst and carrier,
For the interaction between active component Pt and carrier also there is adjustment effect, improves active component crystal grain on a catalyst
Dispersion degree, and then promote the stability of catalyst.
When catalyst of the present invention is used for dehydrogenating low-carbon alkane, it is anti-that dehydrogenation is generally carried out under the reaction temperature higher than 500 DEG C
It answers, the content of low-carbon alkanes is typically no less than 80% in paraffinic feedstock gas, and the general condition of reaction is reaction pressure: -0.1~
1MPa, 500~680 DEG C of reaction temperature, low-carbon alkanes gas space velocity is 150~1000h-1。
Regulating catalyst acidity and benefit chlorine process are respectively mainly in catalyst preparation stages and regeneration stage at present.However
For the dehydrogenation reaction that low-carbon alkanes carry out on Pt base catalyst, with the progress of reaction, due to catalyst carbon deposition and height
The influence of warm environment, the Cl content in catalyst can decline, and acidity can reduce.Catalyst dehydrogenation activity needs certain on catalyst
The synergistic effect of intensity and the acid of distribution, therefore, the Cl content of catalyst in use reduce the work that will affect catalyst
Property, so that catalyst activity and selectivity reduces.Provide in the present invention a kind of makes suitable for catalyst for dehydrogenation of low-carbon paraffin
With in the process, Cl element and acidity can gradually be lost according to the carry out catalyst of reaction, adjusted to be added to reaction system
Gas adjusts catalyst surface property so that catalyst surface acidity in a reasonable range, make catalyst activity keep compared with
Good stabilization reduces catalyst deactivation rate, extends the service life of catalyst.
A kind of above-mentioned adjustable Pt based dehydrogenation catalyst of performance of raising provided by the invention is in dehydrogenating low-carbon alkane reaction
Activity and stability method, this method comprises: carrying out dehydrogenating low-carbon alkane reaction using fixed bed, reaction process includes de-
Hydrogen reaction process and coke combustion are alternately；Wherein certain embodiments be passed through to reaction system certain flow containing low-carbon alkanes
80~100% unstrpped gas, dehydrogenation reaction carry out 1~15h, and Burning Coke on Catalyst process is to be passed through oxygen containing gas to reaction system
Body, coke combustion carry out 0~8h；For the control of dehydrogenation reaction temperature at 500~700 DEG C, reaction pressure is normal pressure or negative pressure；In dehydrogenation
In reaction process or coke combustion, or in dehydrogenation reaction process and coke combustion, urged to reaction system with what unstripped gas was passed through
The activity stabilized regulating gas of agent, the regulating gas are grouped as by adjusting component and dilution group, and wherein adjusting group is divided into
Containing one of the VIIth A race element or a variety of gas, constituent content is 0.001~0.5v%, preferably 0.01~
0.5v%, remaining is dilution component, and dilution group is divided into one of vapor, air, nitrogen, methane or ethane gas or more
Kind.
With the progress of dehydrogenating propane reaction in the presence of Pt base catalyst, under a reaction condition, catalyst one
In the section time, as in 2 days to 60 days times, the average value (being indicated with X) or olefine selective average value of alkane conversion (with
S is indicated) can reach a more stable stage, i.e., this period catalyst alkane conversion or olefine selective protect substantially
It holds change or slightly increases, the average value of the alkane conversion of this section or olefine selective is labeled as initial value, is denoted as initial alkane
Hydrocarbon conversion rate X0 and olefin streams selectivity S0.With continuing for reaction, when the alkane conversion or alkene of catalyst are selected
Selecting property within next 2 days to 60 days time, its general alkane conversion average value X's or olefine selective average value S compared with
When X0 or S0 reduction ratio T is 0.01~2%, just need to start to be passed through has catalysis containing Cl elemental substance to reaction system
The regulating gas of the activity stabilized effect of agent, the addition volume flow for adjusting gas are calculated as follows:
Reduce ratio T=(variable-variable 0)/variable 0；
Regulating gas accumulates flow=paraffinic feedstock volume flow × T；
Wherein, variable is alkane conversion or olefine selective average value of the catalyst in 2 days to 60 days.
The low-carbon alkanes raw material that catalyst of the present invention is applicable in is liquefied petroleum gas of the low-carbon alkanes content 80% or more,
Raw material low-carbon alkanes refer to the C4 of arbitrary proportion alkane gaseous mixture below, the especially mixed gas of propane and butane.With third
When alkane is raw material, in 0.01~0.5MPa of reaction pressure, 570~650 DEG C of reaction temperature, propane feed gas gas space velocity 200~
2000h-1Under conditions of, conversion of propane is greater than 40%；When pressing the mixed alkanes of 1:1 as raw material using propane and butane, reacting
0.03~0.5MPa of pressure, 550~620 DEG C of reaction temperature, 200~2000h of mixed gas air speed-1Under conditions of, mixed alkanes
Conversion ratio 40% or more.Meanwhile by the carry out situation according to reaction, using being passed through Active Regulation gas into reaction system
After body, 10% or more catalyst life achieves satisfactory result.
The remarkable advantage of technology of the invention is: (1) being with alkali metal and alkali using the distinguishing feature of catalyst of the present invention
Earth metal auxiliary agent is modified carrier, so that carrier has suitable surface acidic-basic property, the dehydrating alkanes for improving catalyst turn
The selectivity of rate and alkene；(2) distinguishing feature of another aspect is by during the reaction, according to the change of catalyst activity
Change, the regulating gas of stabilizing catalyst activity is passed through to reaction system, that is, facilitates stabilizing catalyst activity, and can promote well
Into the elimination to carbon distribution, moreover it is possible to adjust catalyst surface property, extend catalyst service life；(3) pass through catalyst preparation
Stage carries out surface nature adjusting to catalyst, while being adjusted according to the variation of catalyst to it in catalyst use process
Section, two processes cooperate, so that the performance that catalyst is optimal.By the synergistic effect in terms of these, this ensure that
The technology that invention proposes is different from having the characteristics of invention and technology: 1) simple and easy catalyst preparation technology；2) stable
Dehydrogenating low-carbon alkane activity and olefine selective；3) longer catalyst service life.
Specific embodiment
Below will by specific embodiment, the invention will be further described, but the invention is not limited to these implement
Example.
Embodiment 1
Carrier preparation.By a certain amount of aluminium oxide: the mixed powder that silica is 1:1 is with mixed powder mass fraction is accounted for
8% sesbania powder is uniformly mixed, and adding citric acid that mass concentration is 5% and mass concentration is that 22% dust technology is mixed
Pinch, the kneading time be 30min, finally formed on forming machine again, carrier after molding after room temperature dries in the air 8h, then at
120 DEG C of drying 4h, the last 900 DEG C of roasting 6h in Muffle furnace of the carrier of drying, obtain final carrier A, water absorption rate is
62.3%.
The hydrochloric acid solution that 2ml concentration 0.2M chloroplatinic acid aqueous solution and 7.4ml concentration are 0.18M stannous chloride is mixed equal
Even, according to the saturated water adsorptive value of used carrier, hydrochloric acid and water are added in Xiang Shangshu Pt-Sn maceration extract makes the dipping being finally configured to
The concentration of the hydrochloric acid of liquid is 1.5M.The potassium nitrate of 0.58g is dissolved in above-mentioned maceration extract, and with the 26.66g carrier etc. in (1)
Volume impregnation 12h roasts 4 hours at drying 12 hours, 550 DEG C at 120 DEG C, obtains finished catalyst A.
The composition of catalyst A are as follows: Pt-Sn-K/Al2O3, the wherein mass percentage of each component are as follows: Pt:0.3%, Sn:
0.6%, K:0.9%, remaining is aluminium oxide and silica.
The catalytic activity of catalyst A is tested in two times: being used 20ml fixed bed minisize reaction evaluation system, is taken 20 milliliters of dresses
Enter and carries out the test of dehydrogenating propane reactivity worth in the stainless steel reactor that internal diameter is 8 millimeters.
Catalyst A catalytic performance test condition: 620 DEG C of reaction temperature, pressure is normal pressure, and the volume space velocity of propane is
2000h-1, the charge proportion of raw material are as follows: n (propane): n (H2): n (H20)=1:0.2:1.Catalyst needs to carry out hydrogen before the reaction
Gas reduction treatment, treatment conditions are 500 DEG C, restore 4h.
Comparative evaluation's condition: testing according to the comparative evaluation that above-mentioned evaluation condition carries out catalyst, the difference is that, instead
It should be in 5 days time interval periods, when conversion of propane reduction ratio reaches 0.05%, in the dehydrogenation reaction stage with unstripped gas
The Active Regulation gas for being 0.05% containing chlorine is added to reaction system, Active Regulation gas is with the diluted gas containing monochlorethane of nitrogen
Body the results are shown in Table 1.
When conversion of propane is lower than 25%, it is believed that catalyst has inactivated end evaluation response, as a result table 1.
Embodiment 2
Carrier preparation.By a certain amount of aluminium oxide: the mixed powder that silica is 5:1 is with mixed powder mass fraction is accounted for
5% sesbania powder is uniformly mixed, and adding citric acid that mass concentration is 5% and mass concentration is that 20% dust technology is mixed
Pinch, the kneading time be 30min, finally formed on forming machine again, carrier after molding after room temperature dries in the air 8h, then at
120 DEG C of drying 4h, the last 850 DEG C of roasting 12h in Muffle furnace of the carrier of drying, obtain final carrier B, water absorption rate is
55.1%.
The hydrochloric acid solution that 2ml concentration 0.2M chloroplatinic acid aqueous solution and 7.4ml concentration are 0.18M stannous chloride is mixed equal
Even, according to the saturated water adsorptive value of used carrier, hydrochloric acid and water are added in Xiang Shangshu Pt-Sn maceration extract makes the dipping being finally configured to
The concentration of the hydrochloric acid of liquid is 1.5M.The zirconium oxychloride octahydrate of 0.94g is dissolved in above-mentioned maceration extract, and with the 26.66g in (1)
Carrier incipient impregnation 12h roasts 4 hours at drying 12 hours, 550 DEG C at 120 DEG C, obtains finished catalyst B, catalyst B's
Composition are as follows: Pt-Sn-Zr/Al2O3, the wherein mass percentage of each component are as follows: and Pt:0.3%, Sn:0.6%, Zr:1.0%,
Remaining is aluminium oxide and silica.
The performance evaluation condition of catalyst B is the same as embodiment 1.
Comparative evaluation's condition of catalyst B with catalyst B performance evaluation condition, difference be the dehydrogenation reaction stage with
The Active Regulation gas that it is 0.01v% containing chlorine that unstripped gas is added to reaction system, Active Regulation gas are to contain two with methane gas is diluted
The gas of chloroethanes.
When conversion of propane is lower than 25%, it is believed that catalyst has inactivated end evaluation response.Evaluation results are shown in Table 1.
Embodiment 3
Carrier preparation.By a certain amount of aluminium oxide: silica is the mixed powder of 50:1 and accounts for mixed powder mass fraction
It is uniformly mixed for 6% sesbania powder, adding citric acid that mass concentration is 5% and mass concentration is that 20% dust technology is mixed
Pinch, the kneading time be 30min, finally formed on forming machine again, carrier after molding after room temperature dries in the air 8h, then at
120 DEG C of drying 4h, the last 800 DEG C of roasting 6h in Muffle furnace of the carrier of drying, obtain final support C, water absorption rate is
58.6%.
The hydrochloric acid solution that 2ml concentration 0.2M chloroplatinic acid aqueous solution and 7.4ml concentration are 0.18M stannous chloride is mixed equal
Even, according to the saturated water adsorptive value of used carrier, hydrochloric acid and water are added in Xiang Shangshu Pt-Sn maceration extract makes the dipping being finally configured to
The concentration of the hydrochloric acid of liquid is 1.5M.The lanthanum nitrate of 0.83g is dissolved in above-mentioned maceration extract, and with the 26.66g carrier etc. in (1)
Volume impregnation 12h roasts 4 hours at drying 12 hours, 550 DEG C at 120 DEG C, obtains finished catalyst B, the composition of catalyst B are as follows:
Pt-Sn-La/Al2O3, the wherein mass percentage of each component are as follows: Pt:0.3%, Sn:0.6%, La:1.0%, remaining is oxygen
Change aluminium and silica.
The performance evaluation condition of catalyst C is the same as embodiment 1.
Comparative evaluation's condition of catalyst C and the difference of the performance evaluation condition of catalyst C be the dehydrogenation reaction stage with
The Active Regulation gas that it is 0.01v% containing chlorine that unstripped gas is added to reaction system, Active Regulation gas are to be contained with vapor gas is diluted
The gas of monochlorethane.
When conversion of propane is lower than 25%, it is believed that catalyst has inactivated end evaluation response.Evaluation results are shown in Table 1.
Embodiment 4
Carrier preparation.By a certain amount of aluminium oxide: silica is the mixed powder of 99:1 and accounts for mixed powder mass fraction
It is uniformly mixed for 9% sesbania powder, adding citric acid that mass concentration is 6% and mass concentration is that 15% dust technology is mixed
Pinch, the kneading time be 30min, finally formed on forming machine again, carrier after molding after room temperature dries in the air 8h, then at
120 DEG C of drying 4h, the last 600 DEG C of roasting 8h in Muffle furnace of the carrier of drying, obtain final carrier D, water absorption rate is
51.3%.The hydrochloric acid solution that 2ml concentration 0.2M chloroplatinic acid aqueous solution and 7.4ml concentration are 0.18M stannous chloride is uniformly mixed,
According to the saturated water adsorptive value of used carrier, hydrochloric acid and water are added in Xiang Shangshu Pt-Sn maceration extract makes the maceration extract being finally configured to
Hydrochloric acid concentration be 1.5M.The lanthanum nitrate of the potassium nitrate of 0.58g, the zirconium oxychloride octahydrate of 0.94g and 0.83g is dissolved in
State maceration extract, and with the 26.66g carrier incipient impregnation 12h in (1), roasting 4 is small at drying 12 hours, 550 DEG C at 120 DEG C
When, obtain finished catalyst B, the composition of catalyst B are as follows: Pt-Sn-K-Zr-La/Al2O3, the wherein mass percentage of each component
Are as follows: Pt:0.3%, Sn:0.6%, K:0.9%, Zr:1.0%, La:1.0%, remaining is aluminium oxide and silica.
The performance evaluation condition of catalyst D the results are shown in Table 1 with embodiment 1.
Comparative evaluation's condition of catalyst D and the difference of the performance evaluation condition of catalyst D be make charcoal the stage of reaction with
The Active Regulation gas that it is 0.1v% containing chlorine that unstripped gas is added to reaction system, Active Regulation gas are to contain dichloro with methane gas is diluted
The gas of ethane.
When conversion of propane is lower than 25%, it is believed that catalyst has inactivated end evaluation response.Evaluation results are shown in Table 1.
The dehydrating alkanes performance of 1 different catalysts of table
As it can be seen from table 1 catalyst is in use, the service life of catalyst improves 10% or more.
Claims (2)
1. a kind of method for improving the adjustable Pt based dehydrogenation catalyst stability of performance, which is characterized in that
Catalyst is made of main active component, auxiliary agent and carrier three parts, and active component and auxiliary agent are loaded by the way of dipping
Onto carrier: where main active component is Pt, and content is 0.1~1.0wt%；Auxiliary agent is in Na, K, Ca, Zr, Sn, La and Ce
It is one or more, the content of auxiliary element is 0.01~10wt%；Remaining is carrier, and carrier is the mixed of aluminium oxide and silica
Close object to be made, wherein aluminium oxide: silica weight ratio is 1~99:1；
Dehydrogenating low-carbon alkane reaction is carried out using fixed bed, reaction process include dehydrogenation reaction process and coke combustion alternately into
Row；Wherein certain embodiments are that the unstrpped gas containing low-carbon alkanes 80~100% of certain flow is passed through to reaction system, and dehydrogenation is anti-
1~15h should be carried out, Burning Coke on Catalyst process is that oxygen containing gas is passed through to reaction system, and coke combustion carries out 0~8h, and not
Include 0h；For the control of dehydrogenation reaction temperature at 500~700 DEG C, reaction pressure is normal pressure or negative pressure；In dehydrogenation reaction process and/or
In coke combustion, a kind of regulating gas of stabilizing catalyst activity is passed through to reaction system with reaction raw materials；Regulating gas is by adjusting
Section component and dilution group are grouped as, wherein adjusting group be divided into 0.001~1v% containing one of the VIIth A race element or a variety of members
The gas of element, dilution group are divided into one of vapor, air, nitrogen, methane or ethane gas or a variety of.
2. according to the method for claim 1, which is characterized in that the adjusting group is divided into the gas containing chlorine element, content
The 0.001~0.5% of reaction gas total volume is accounted for, dilution group is divided into one of vapor, air, methane gas or a variety of.
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| CN108080002A (en) * | 2017-12-01 | 2018-05-29 | 中海油天津化工研究设计院有限公司 | The catalyst for dehydrogenation of low-carbon paraffin and preparation method of multicomponent reactive component high degree of dispersion |
| CN108786801B (en) * | 2018-04-28 | 2021-01-05 | 钦州学院 | Pt-based dehydrogenation catalyst and preparation method thereof |
| EA202191028A1 (en) * | 2018-10-30 | 2021-07-01 | Клариант Интернэшнл Лтд | DEHYDRATION CATALYSTS AND METHODS FOR THEIR PREPARATION AND USE |
| CN111589445A (en) * | 2019-02-21 | 2020-08-28 | 中国石油天然气股份有限公司 | Catalyst for preparing long-chain mono-olefin by dehydrogenation of long-chain alkane and preparation method thereof |
| CN113968767A (en) * | 2020-07-23 | 2022-01-25 | 中国石油天然气股份有限公司 | Method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane |
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| CN101015802A (en) * | 2007-02-09 | 2007-08-15 | 东南大学 | Catalyst for preparing propylene by propane dehydrogenation and its prepn. |
| CN103801330A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Regeneration method for dehydrogenation catalyst |
| CN104107704A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for regenerating platinum-containing low carbon alkane dehydrogenation catalyst |
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| CN1082018A (en) * | 1992-06-23 | 1994-02-16 | 埃尼里塞奇公司 | Process for dehydrogenating light paraffins in the fluidized-bed reactor |
| CN101015802A (en) * | 2007-02-09 | 2007-08-15 | 东南大学 | Catalyst for preparing propylene by propane dehydrogenation and its prepn. |
| CN103801330A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Regeneration method for dehydrogenation catalyst |
| CN104107704A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for regenerating platinum-containing low carbon alkane dehydrogenation catalyst |
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