CN104923258B - A kind of renovation process of catalyst - Google Patents
A kind of renovation process of catalyst Download PDFInfo
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- CN104923258B CN104923258B CN201510241371.3A CN201510241371A CN104923258B CN 104923258 B CN104923258 B CN 104923258B CN 201510241371 A CN201510241371 A CN 201510241371A CN 104923258 B CN104923258 B CN 104923258B
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Abstract
The invention discloses a kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin.This method includes following process：（1）Use CO gas treatment decaying catalysts；（2）By step（1）Decaying catalyst after processing is handled in hydro carbons containing low-carbon oxygen-containing and HCl mixed atmosphere；（3）By step（2）Decaying catalyst after processing is handled in the mixed atmosphere of the hydro carbons containing low-carbon oxygen-containing；（4）By step（3）Decaying catalyst after processing carries out processing of making charcoal in the mixed gas of the oxygen containing low concentration, the catalyst after being regenerated.Catalyst for dehydrogenation of low-carbon paraffin renovation process provided by the invention, the problem of preferably resolving in existing catalyst for dehydrogenation of low-carbon paraffin regenerative process, the catalyst catalytic performance after regeneration can return to fresh dose of level.
Description
Technical field
The present invention relates to a kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin, a kind of propane, isobutyl are related in particular to
The renovation process of alkane dehydrogenation noble metal base catalyst.
Background technology
North America shale revolution brings substantial amounts of low-carbon alkanes resource, causes the raw material lighting of ethylene cracker, propylene
Yield decline to a great extent.Simultaneously under the increasingly deficient overall background of petroleum resources, the production of propylene is from the simple oil that relies on
Raw material changes to the diversified technology path of raw material sources, and is increasingly becoming a kind of trend.By natural gas（Conventional gas, page
Rock gas, coal bed gas, combustible ice etc.）It is the effective way for solving this problem that the propane of middle by-product, which carries out dehydrogenation reaction and produces propylene,
Footpath.In recent years, the technology of dehydrogenating propane production propylene achieved large development, had become the third-largest propylene production.
Low-carbon alkanes（Propane, iso-butane）Dehydrogenation is strong endothermic reaction, is limited by thermodynamical equilibrium, severe reaction conditions,
Carbon deposit is always the reason for influenceing catalyst activity and stability with active metal sintering.Propane dehydrogenation catalyst generally requires frequency
Numerous regeneration, long-time continuous application could be maintained.Especially noble metal based dehydrogenation catalyst, is limited by cost factor, then
It is born with and seems even more important.Renovation process directly affects the activity, selectivity and life-span of regenerated catalyst, therefore, studies low-carbon
The regeneration of alkane dehydrogenating catalyst is very important.
Pt based dehydrogenation catalysts renovation process is mostly directly made charcoal processing at present, and under higher regeneration temperature, burn off is urged
The carbon deposit on agent surface, in this process, Pt components can further be assembled, and have a strong impact on the performance of regenerated catalyst.In order to
Solves this problem, many researchers are much attempted.
USP4473656 discloses a kind of renovation process of Pt-Ir catalyst, using two sections of circular regeneration methods, main feature
It is being contacted reduction-state containing Pt, Ir catalyst under oxygen-free atmosphere with HCl, then oxygen chlorine is carried out under high temperature and higher oxygen content
Change reaction, obtain the suitable Pt-Ir catalyst of chlorinity.USP4444897 discloses a kind of renovation process of Pt-Ir catalyst,
This method is handled first by Pt-Ir catalyst reductions, then under oxygen-free atmosphere with the helium containing HCl and water, then again with containing HCl and
The gas of elemental oxygen carries out redisperse processing.In method disclosed in United States Patent (USP) US5087792, the regeneration of catalyst is to pass through
The purging of inert gas, make oxygenous admixture of gas by wherein, the purging of inert gas and make HCl/ oxygen mixtures
By wherein so that active metal is redispersed on carrier.In these methods, halogen Cl is introduced to carry out Pt redisperse,
And it is follow-up without dechlorination processing is carried out, these halogens stay in the catalyst, for dehydrogenating low-carbon alkane reaction, increase cracking
Activity, selectivity is reduced, adds more carbon deposits.
CN1541140A discloses a kind of renovation process of dehydrogenation, this method by a temperature of 300 ~ 800 DEG C,
Change the regeneration that oxygen concentration, regeneration pressure and air speed reach dehydrogenation.This method is made charcoal only with oxygen, is held
Easily assemble regenerated catalyst active metal.
CN1589970A discloses a kind of renovation process of alkyl aromatics dehydrogenation production alkyl alkenyl arene catalyst, this method
Using water vapour is synchronously passed through and air regenerates to catalyst, this method needs higher regeneration temperature, could burn completely
Fall the carbon deposit on catalyst, and when regeneration temperature is less than 500 DEG C, carbon deposit that can not be on completely burned off catalyst.
CN101940959A discloses a kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin, and this method is first at a lower temperature in sky
Regenerated in gas atmosphere, most of carbon deposit inside the carbon deposit of burn off catalyst surface and duct, then in the mixed of water vapour and air
Close in atmosphere and regeneration treatment further is carried out to catalyst.Both approaches introduce water vapour when carrying out catalyst regeneration,
The transformation of alumina support crystalline phase is not only resulted in, alkali metal in low-carbon alkanes catalyst can also be lost in, while also can be certain
Cause accumulation of metal in degree.
From the renovation process of above-mentioned noble metal based dehydrogenation catalyst as can be seen that in existing renovation process, in order to
Regenerated catalyst is obtained preferable performance, be generally all to employ oxygen, halogen or water vapour these three materials, although necessarily
Degree solves carbon deposit, accumulation of metal and alkali metal losing issue, but also inevitably have impact on dehydrogenating low-carbon alkane again
The performance of raw catalyst and life-span.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin, particularly
A kind of renovation process of propane, dehydrogenation of isobutane noble metal catalyst.The inventive method is anti-using CO methanation reactions and disproportionation
Should, the hydrogen-carbon ratio of catalyst carbon deposit is reduced, while coordinate HCl to carry out the redisperse in activated centre and take off using low-carbon oxygen-containing hydro carbons
Chlorine, carbon deposit is finally removed in lower temperature using the mixed gas of the oxygen containing low concentration, obtains good regeneration effect.
The renovation process of catalyst for dehydrogenation of low-carbon paraffin of the present invention, including following process：
（1）Use CO gas treatment decaying catalysts；
（2）By step（1）Decaying catalyst after processing is located in low-carbon oxygen-containing hydro carbons and HCl mixed atmosphere
Reason；
（3）By step（2）Decaying catalyst after processing is handled in the mixed atmosphere of the hydro carbons containing low-carbon oxygen-containing；
（4）By step（3）Decaying catalyst after processing carries out processing of making charcoal in the mixed gas of the oxygen containing low concentration,
Catalyst after being regenerated.
In the inventive method, step（1）The detailed process using CO processing decaying catalysts is as follows：Inert atmosphere
Under, by decaying catalyst temperature control to 300 DEG C -600 DEG C, preferably 400 DEG C -500 DEG C, Stress control is preferably in 1MPa-5MPa
2MPa-4MPa, then switches to CO gases, and CO intakes press catalyst volume air speed 500h-1-5000h-1, preferably 1000h-1-3000h-1, processing time 1h-12h, preferably 2h-4h.After processing terminates, inert gas is switched to, is depressured.
In the inventive method, step（2）Described in enter in the mixed atmosphere of low-carbon oxygen-containing hydro carbons, HCl and inert gas
Row processing, detailed process are as follows：Under inert atmosphere, by step（1）Decaying catalyst after processing is cooled to 150 DEG C -400 DEG C,
Preferably 200 DEG C -300 DEG C.Then switch to the mixed gas of hydro carbons containing low-carbon oxygen-containing, HCl and inert gas, it is low in gaseous mixture
The oxygen-containing hydro carbons volume content of carbon is 5%-30%, preferably 10%-20%；HCl volume contents are 0.1%-3%, preferably 0.5%- in gaseous mixture
1.5%.Gaseous mixture volume space velocity is 100h-1-1000h-1, preferably 200h-1-400h-1；Time is 0.5h-8h, preferably 1h-
3h。
In the inventive method, step（3）Described in handled in the mixed atmosphere of the hydro carbons containing low-carbon oxygen-containing, specific mistake
Journey is as follows：Step（2）After processing terminates, then the mixed gas of hydro carbons containing low-carbon oxygen-containing and inert gas is switched to, in gaseous mixture
Low-carbon oxygen-containing hydro carbons volume content is 5%-30%, preferably 10%-20%, and gaseous mixture volume space velocity is 100h-1-1000h-1, it is preferably
200h-1-400h-1；Time is 0.5h-4h, preferably 1h-2h.
Above-mentioned low-carbon oxygen-containing hydro carbons refer to carbon number be 1-2 alcohols, ethers, such as methanol, ethanol, ethylene glycol, dimethyl ether,
Preferably methanol or dimethyl ether.
In the inventive method, step（4）Described in made charcoal in the mixed atmosphere of the oxygen containing low concentration processing, detailed process
For：Under inert atmosphere, by step（3）Decaying catalyst temperature control after processing is to 200 DEG C -450 DEG C, preferably 300 DEG C -400 DEG C,
Oxygenous and inert gas mixed gas is then passed to, oxygen volume content is 0.1%-1%, preferably 0.4%- in gaseous mixture
0.8%；Volume space velocity is 200h-1-5000h-1, preferably 500h-1-1500h-1, time 1h-8h, preferably 2h-4h；Then
Keeping temperature, mixed gas air speed are constant, and oxygen volume content in gaseous mixture is increased into 1%-3%, preferably 1.5%-2.5%,
Continue with 1h-8h, preferably 2h-4h；In a manner described, oxygen volume content in gaseous mixture is increased into 3%-6%, is preferably
4%-5% continues to make charcoal.Make charcoal after end, switch to inert gas, cool, obtain regenerated catalyst.
In the inventive method, step（4）In the mixed gas of the oxygen containing low concentration, appropriate N can also be contained2O gases,
N2O volumetric concentration is 0.001%-0.1%, preferably 0.01%-0.05%.
The renovation process of catalyst for dehydrogenation of low-carbon paraffin of the present invention, urged suitable for dehydrogenating low-carbon alkanes such as propane, iso-butanes
The regeneration of agent.
In the inventive method, the dehydrogenation is platinum family loaded catalyst, using high-temperature inorganic oxide as load
Body, the one or more in platinum, palladium, iridium, rhodium or osmium in platinum family are active component, preferably platinum.Platinum group metal is in catalyst
In vehicle weight is calculated as with simple substance 0.01% ~ 2%.The high-temperature inorganic oxide includes：Aluminum oxide, magnesia, chromium oxide,
Boron oxide, titanium oxide, zinc oxide, zirconium oxide, or both the above hopcalite, and various ceramic, various alumina,
Silica, synthesis or naturally occurring various silicate or clay.Preferable high-temperature inorganic oxide carrier is Al2O3, its
Crystal habit can be γ-Al2O3、θ-Al2O3Or η-Al2O3, preferably γ-Al2O3。
Contain suitable auxiliaries simultaneously in dehydrogenation of the present invention, such as IVA races element and alkali metal.Wherein IVA races
Element is preferably tin, germanium, more preferably tin, IVA races element using element count in the catalyst weight percentage as 0.1%-1%；
Alkali metal is preferably sodium, potassium, more preferably potassium, and weight percentage is alkali metal in the catalyst in terms of element
0.1%-1%。
The present invention relates to dehydrogenation, its preparation method comprises the following steps：（1）IVA races element is introduced in the carrier；
（2）Introduce platinum group metal；（3）Steam treatment；（4）Introduce alkali metal.Wherein（1）Step introduces IVA race's elements and the（2）Step
Introducing platinum group metal can also be carried out simultaneously.
IVA races element method is introduced described in above-mentioned dehydrogenation preparation method to be drawn during aluminum oxide plastic
Enter, can also be introduced by way of load, kneading can also be introduced in aluminum oxide forming process.The forerunner of IVA races element
Thing is its oxide, chloride, nitrate, sulfate or the element acid group salt of race containing IVA, such as stannous chloride, butter of tin, tetrachloro
Change tin pentahydrate, stannous bromide, germanium dioxide, germanium tetrachloride, nitric acid tin, tin acetate, sodium stannate, potassium stannate etc., be preferably
Butter of tin, stannous chloride, more preferably stannous chloride.
Platinum family element can use co-precipitation, ion exchange or impregnating mode to draw in above-mentioned dehydrogenation preparation method
Enter.Preferable method is infusion process, i.e., is carried using one or more of dippings in water-soluble platinum group metal compounds or complex
Body.Water-soluble platinum group metal compounds or complex are chloroplatinic acid, chloro-iridic acid, chlorine palladium acid, ammonium chloroplatinate, bromoplatinic acid, tri-chlorination
Platinum, palladium nitrate, diaminourea palladium hydroxide, the ammonia palladium of chlorine four, the ammonia palladium of chlorine six, rhodium chloride hydrate, rhodium nitrate, tribromide iridium,
Iridochloride, iridic chloride, potassium hexachloroiridate or iridium sodium chloride etc..It is preferred that platinum, palladium, iridium, the chlorine-containing compound of rhodium or osmium, more preferably
For the chlorine-containing compound of platinum, such as chloroplatinic acid.It is method well known to those skilled in the art to introduce platinum family element by mode of loading.
In the preparation method of above-mentioned dehydrogenation, in addition to steam treatment, treatment conditions are：Contain what is continuously flowed
Under water vapor mixture atmosphere, 400 DEG C -800 DEG C handle 1h-10h, and 2h-4h is handled at preferably 500 DEG C -700 DEG C；It is described aqueous
Mixture of steam atmosphere reclaimed water vapour volume content is 5%-50%, preferably 10%-30%, and remaining is inert gas；Gaseous mixture air speed
For 100h-1-10000h-1, preferably 1000h-1-3000h-1；Handle chlorine element weight content in rear catalyst and be less than 0.15%.
In the preparation method of above-mentioned dehydrogenation, the introducing method of alkali metal promoter is well known to those skilled in the art
Dipping method.K predecessor is solubility salt containing K, can be inorganic salts or organic salt, preferably potassium nitrate.Leaching
Stain liquid can be the aqueous solution, or organic solution.
A kind of dehydrogenation prepared using the above method, with Al2O3For carrier, preferably γ-Al2O3；Pt in catalyst
Weight percentage is counted as 0.01%-2% using element, preferably 0.1%-1%, more preferably 0.4%-0.8%；Sn is with element
Meter weight percentage is 0.1%-1%, preferably 0.2%-0.6%；K counts percentage composition as 0.1%-1% using element wt, preferably
0.2%-0.6%。
Heretofore described inert gas is that chemistry does not occur under the conditions of involved in the present invention for nitrogen, argon gas, helium etc.
The gas of reaction, preferably nitrogen.
The inventive method, using CO methanation reactions and disproportionated reaction, the hydrogen-carbon ratio of catalyst carbon deposit is reduced, is adopted simultaneously
Redisperse and the dechlorination in activated centre are carried out with low-carbon oxygen-containing hydro carbons cooperation HCl, finally uses the gaseous mixture of the oxygen containing low concentration
Body removes carbon deposit in lower temperature, overcomes the problem of activated centre is assembled in coke combustion, reaches the purpose of catalyst regeneration.
The dehydrogenation activity of renovation process regenerated catalyst of the present invention can reach the level of fresh catalyst, while regenerate
Temperature change is small in journey, easily operated, extends the service life of catalyst.
Embodiment
The technology contents and effect of the present invention are further illustrated with reference to embodiment, but are not so limited the present invention.
The present invention in specific implementation process, evaluate in continuous stream by the dehydrogenation of fresh catalyst and regenerated catalyst
Carried out on dynamic fixed-bed micro-devices.Fresh catalyst carries out reduction treatment before the reaction, and reducing condition is：Pure hydrogen atmosphere, often
Pressure, 530 DEG C, the h of volume space velocity 2000-1.Fresh catalyst is with regenerative agent performance evaluation condition：Unstripped gas is hydrogen and propane
Gaseous mixture（Volume ratio 1:1）, volume space velocity 3000h-1, 600 DEG C of reaction temperature, normal pressure；Fresh catalyst and regenerated catalyst
Regeneration treatment is carried out after reaction 72h.Reaction product detects it through gas chromatograph and forms and calculate conversion ratio and selectivity.
Embodiment 1
Weigh commercial alumina carrier（γ phases, spherical, diameter 0.5mm, pore volume 0.71cm3/ g, specific surface area 224m2/g）
30g, deionized water is added dropwise to first profit, the volume for consuming water is 27mL.Based on Sn element wts content 0.4% in final catalyst,
The stannous chloride for weighing the Sn containing 0.12g is dissolved in ethanol, and 27mL is settled to using ethanol.The ethanol containing Sn configured is molten
Liquid is added into 30g alumina supports, is well mixed, at room temperature aging 2h.80 DEG C of dry 8h, then it is calcined 4h at 600 DEG C.
Based on the % of Pt element wts content 0.5 in final catalyst, weigh the 0.18g containing Pt chloroplatinic acid be dissolved in from
In sub- water, 27mL is settled to, is added into alumina support containing Sn, is well mixed, at room temperature aging 4h, 100 DEG C of dry 6h,
4h is calcined in 600 DEG C.Sample obtained by above-mentioned steps handles 3h under 600 DEG C, the nitrogen atmosphere containing 20% water vapour, and air speed is
2000h-1.Based on K element weight content 0.4% in final catalyst, the potassium nitrate for weighing the 0.12g containing K is dissolved in deionized water,
27mL is settled to, is added in the catalyst precarsor to steam treatment, is well mixed, 2h, 100 DEG C of dryings is aged at 70 DEG C
6h, 4h is calcined in 600 DEG C.The weight content of each component is in obtained catalyst：The % of Pt 0.5%, Sn 0.4%, K 0.4.Institute
Obtain catalyst and be designated as C-1.
Fresh dose of reactivity worth of C-1 is shown in Table 1.
Embodiment 2
After fresh dose of reaction 72h of C-1, unstripped gas is switched into nitrogen, purges 1h, then temperature is down to 450 DEG C, and pressure rises to
3MPa, then it is passed through CO gases, volume space velocity 2000h simultaneously-1, processing time 3h.After processing terminates, nitrogen is switched to,
Normal pressure is down to, and is down to 250 DEG C, then passes to the mixed gas that volume content is 15% methanol, 1%HCl and nitrogen, gaseous mixture is empty
Speed is 300h-1, handle 2h.Then stop being passed through HCl, continue the mixing gas disposal 1.5h with 15% methanol and nitrogen.Processing terminates
Afterwards, nitrogen is switched to, is warming up to 350 DEG C, is passed through mixed gas of the volume content for 0.6% oxygen and nitrogen, air speed 1000h-1, processing time 3h；Then it is 2% to improve oxygen volume content in gaseous mixture, is handled by above-mentioned the same manner；Finally will mixing
Oxygen volume content is 4.5% in gas, is handled by above-mentioned the same manner, obtains C-1 primary recycling agent.
C-1 primary recycling agent reactivity worth is shown in Table 1.
Embodiment 3
After C-1 primary recyclings agent reaction 72h, unstripped gas is switched into nitrogen, purges 1h, then temperature is down to 400 DEG C, pressure
4MPa is risen to, is then passed through CO gases, volume space velocity 1000h simultaneously-1, processing time 4h.After processing terminates, nitrogen is switched to
Gas, normal pressure is down to, and is down to 300 DEG C, then passed to the mixed gas that volume content is 10% methanol, 1.5%HCl and nitrogen, mix
It is 200h to close gas air speed-1, handle 1h.Then stop being passed through HCl, continue the mixing gas disposal 2h with 10% methanol and nitrogen.Processing
After end, nitrogen is switched to, is warming up to 300 DEG C, is passed through mixed gas of the volume content for 0.8% oxygen and nitrogen, air speed is
500h-1, processing time 4h；Then it is 2.5% to improve oxygen volume content in gaseous mixture, is handled by above-mentioned the same manner；Finally
It is 5% by oxygen volume content in gaseous mixture, is handled by above-mentioned the same manner, obtain C-1 secondary recycling agent.
C-1 secondary recycling agent reactivity worth is shown in Table 1.
Embodiment 4
After C-1 secondary recyclings agent reaction 72h, unstripped gas is switched into nitrogen, purges 1h, then temperature is down to 500 DEG C, pressure
2MPa is risen to, is then passed through CO gases, volume space velocity 3000h simultaneously-1, processing time 2h.After processing terminates, nitrogen is switched to
Gas, normal pressure is down to, and is down to 200 DEG C, then passed to the mixed gas that volume content is 20% methanol, 0.5%HCl and nitrogen, mix
It is 400h to close gas air speed-1, handle 3h.Then stop being passed through HCl, continue the mixing gas disposal 1h with 20% methanol and nitrogen.Processing
After end, nitrogen is switched to, is warming up to -400 DEG C, is passed through mixed gas of the volume content for 0.4% oxygen and nitrogen, air speed is
1500h-1, processing time 2h；Then it is 1.5% to improve oxygen volume content in gaseous mixture, is handled by above-mentioned the same manner；Most
It is afterwards 4% by oxygen volume content in gaseous mixture, is handled by above-mentioned the same manner, obtain C-1 tertiary recycling agent.
C-1 tertiary recycling agent reactivity worth is shown in Table 1.
Embodiment 5
After C-1 tertiary recyclings agent reaction 72h, unstripped gas is switched into nitrogen, purges 1h, then temperature is down to 450 DEG C, pressure
3MPa is risen to, is then passed through CO gases, volume space velocity 2000h simultaneously-1, processing time 3h.After processing terminates, nitrogen is switched to
Gas, normal pressure is down to, and is down to 250 DEG C, then pass to the mixed gas that volume content is 15% methanol, 1%HCl and nitrogen, mixing
Gas air speed is 300h-1, handle 2h.Then stop being passed through HCl, continue the mixing gas disposal 1.5h with 15% methanol and nitrogen.Processing
After end, nitrogen is switched to, is warming up to 350 DEG C, is passed through volume content as 0.6% oxygen, 0.03%N2O and nitrogen gaseous mixture
Body, air speed 1000h-1, processing time 3h；Then it is 2% to improve oxygen volume content in gaseous mixture, by above-mentioned the same manner
Processing；It is finally 4.5% by oxygen volume content in gaseous mixture, is handled by above-mentioned the same manner, obtain tetra- regenerative agents of C-1.
Tetra- regenerative agent reactivity worth of C-1 are shown in Table 1.
Embodiment 6
After tetra- regenerative agent reaction 72h of C-1, regenerated by the mode of embodiment 2, obtain five regenerative agents of C-1.In this way,
Repeatedly five times again, obtain ten regenerative agents of C-1.
Five regenerative agent reactivity worth of C-1 are shown in Table 1.
Comparative example 1
Using conventional method coke-burning regeneration.
After fresh dose of C-1 reactions 72h, when being cooled to 350 DEG C after purging 1h with nitrogen, oxygen and nitrogen are then switched to
Mixed gas, oxygen volumetric concentration is 0.5% in gaseous mixture, volume space velocity 2000h-1, handle 6h；Again with 1 DEG C/min speed
450 DEG C are warming up to, oxygen volumetric concentration in gaseous mixture is carried to 5%, volume space velocity 1000h-1, handle 4h；Again with 1 DEG C/min
Speed be warming up to 500 DEG C, oxygen volumetric concentration in gaseous mixture is carried to 10%, volume space velocity 500h-1, handle 2h.Obtain C-
1 regenerative agent, progress performance evaluation, five times repeatedly.
Regenerated catalyst reactivity worth is shown in Table 1.
Table 1
From table 1 it follows that after being regenerated using renovation process of the present invention, compared with fresh catalyst,
After reacting 1h, regenerated catalyst catalytic performance is held essentially constant, and conversion of propane goes out after first time regenerated catalyst reaction 72h
Now slightly decline, but after secondary recycling, 72h catalytic performances no longer change with regard to kept stable.And comparing
In example, using the oxygen progressively coke-burning regeneration method of routine, conversion ratio occurs gradual with selectivity after regenerated catalyst reaction 1h
Downward trend, regeneration effect are poor.
Claims (10)
1. a kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin, it is characterised in that comprise the following steps：
Step（1）, using CO gas treatment decaying catalysts, actual conditions be：Under inert atmosphere, decaying catalyst temperature control is extremely
300 DEG C -600 DEG C, Stress control switches to CO gases, CO intakes press catalyst volume air speed 500h in 1MPa-5MPa-1-
5000h-1, processing time 1h-12h, after terminating, inert gas is switched to, is depressured；
Step（2）, by step（1）Decaying catalyst after processing is carried out in hydro carbons containing low-carbon oxygen-containing and HCl mixed atmosphere
Processing, actual conditions are：Temperature control is passed through the mixed gas of hydro carbons containing low-carbon oxygen-containing, HCl and inert gas to 150 DEG C -400 DEG C,
Low-carbon oxygen-containing hydro carbons volume content is 5%-30% in gaseous mixture, and HCl volume contents are 0.1%-3% in gaseous mixture, gaseous mixture volume
Air speed is 100h-1-1000h-1, processing time 0.5h-8h；
Step（3）, by step（2）Decaying catalyst after processing is handled in the mixed atmosphere of the hydro carbons containing low-carbon oxygen-containing,
Actual conditions is：Temperature control is passed through the mixed gas of hydro carbons containing low-carbon oxygen-containing and inert gas to 150 DEG C -400 DEG C, in gaseous mixture
Low-carbon oxygen-containing hydro carbons volume content is 5%-30%, and gaseous mixture volume space velocity is 100h-1-1000h-1, processing time 0.5h-4h；
Step（4）, by step（3）Decaying catalyst after processing carries out the place that makes charcoal in the mixed gas of the oxygen containing low concentration
Reason, actual conditions are：200 DEG C -450 DEG C of temperature, then pass to oxygenous with inert gas mixed gas, oxygen in gaseous mixture
Volume content is 0.1%-1%, volume space velocity 200h-1-5000h-1, time 1h-8h；Then keeping temperature, mixed gas are empty
Speed is constant, and oxygen volume content in gaseous mixture is increased into 1%-3%, continues with 1h-8h；In a manner described still, will be mixed finally
Close oxygen volume content in gas to increase to 3%-6% and continue processing of making charcoal, finally obtain the catalyst after regenerating.
2. renovation process according to claim 1, it is characterised in that：Step（1）It is described to be urged using CO gas treatments inactivation
Agent, temperature are preferably 400 DEG C -500 DEG C；Pressure is preferably 2MPa-4MPa；It is preferably 1000h to be passed through CO volume space velocities-1-
3000h-1；Processing time is preferably 2h-4h.
3. renovation process according to claim 1, it is characterised in that：Step（2）By decaying catalyst containing low-carbon oxygen-containing
Handled in hydro carbons and HCl mixed atmosphere, control temperature is preferably 200 DEG C -300 DEG C；Be passed through hydro carbons containing low-carbon oxygen-containing,
HCl and inert gas mixed gas, low-carbon oxygen-containing hydro carbons volume content is preferably 10%-20% in gaseous mixture；HCl in gaseous mixture
Volume content is preferably 0.5%-1.5%；Gaseous mixture volume space velocity is preferably 200h-1-400h-1, processing time is preferably 1h-3h；
Step（3）Decaying catalyst is handled in the mixed atmosphere of hydro carbons containing low-carbon oxygen-containing, 150 DEG C -400 DEG C of temperature, is passed through and contains
The mixed gas of low-carbon oxygen-containing hydro carbons and inert gas, low-carbon oxygen-containing hydro carbons volume content is preferably 10%-20% in gaseous mixture, is mixed
It is preferably 200h to close air volume air speed-1-400h-1, processing time is preferably 1h-2h.
4. according to the renovation process described in claim 1 or claim 3, it is characterised in that：The low-carbon oxygen-containing hydro carbons carbon number
For 1-2 alcohols, ethers.
5. renovation process according to claim 4, it is characterised in that：The low-carbon oxygen-containing hydrocarbon is preferably methanol or diformazan
Ether.
6. renovation process according to claim 1, it is characterised in that：Step（4）The decaying catalyst is containing low concentration
Processing of making charcoal is carried out in the mixed gas of oxygen, temperature is preferably 300 DEG C -400 DEG C, is then passed to oxygenous and inert gas
Mixed gas, oxygen volume content is preferably 0.4%-0.8% in gaseous mixture, and volume space velocity is preferably 500h-1-1500h-1, the time
Preferably 2h-4h；Then keeping temperature, mixed gas air speed are constant, and oxygen volume content is preferably 1.5%- in gaseous mixture
2.5%, it is preferably 2h-4h to continue with the time；In a manner described still, it is preferably 4%- by oxygen volume content in gaseous mixture finally
5% continues processing of making charcoal.
7. the renovation process according to claim 1 or 6, it is characterised in that：In the mixed atmosphere of the oxygen containing low concentration, may be used also
To contain appropriate N2O gases, N2O volumetric concentration is 0.001%-0.1%.
8. according to the renovation process described in claim 1 or 2 or 3 or 6, it is characterised in that：The catalyst for dehydrogenation of low-carbon paraffin
For platinum family loaded catalyst, using high-temperature inorganic oxide as carrier, the platinum, palladium, iridium, rhodium in platinum family or one kind in osmium or
Several is active component.
9. renovation process according to claim 8, it is characterised in that：The catalyst for dehydrogenation of low-carbon paraffin, with Al2O3To carry
Body, Pt counts weight percentage as 0.01%-2% using element in catalyst, and Sn counts weight percentage as 0.1%-1% using element, K
Percentage composition is counted as 0.1%-1% using element wt.
10. renovation process according to claim 1, it is characterised in that：Suitable for propane, dehydrogenation of isobutane alkene catalyst
Regeneration.
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| CN105749990A (en) * | 2016-03-14 | 2016-07-13 | 辽宁石油化工大学 | Dehydrogenation catalyst regeneration method |
| CN105689014A (en) * | 2016-03-14 | 2016-06-22 | 辽宁石油化工大学 | Regeneration method of precious metal dehydrogenation catalyst |
| CN109382122B (en) * | 2017-08-11 | 2021-04-06 | 中国石油化工股份有限公司 | Activation reduction method of low-carbon alkane dehydrogenation catalyst |
| CN108607619B (en) * | 2018-06-15 | 2019-11-19 | 西南化工研究设计院有限公司 | A kind of regeneration method of Dimethyl ether carbonylation methyl acetate catalysis agent |
| CN112536064B (en) * | 2019-09-20 | 2022-07-12 | 中国石油化工股份有限公司 | Regeneration method of deactivated propane dehydrogenation catalyst |
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| CN101940959A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Regeneration method of catalyst for dehydrogenation of low-carbon alkanes |
| CN102806094A (en) * | 2011-06-03 | 2012-12-05 | 中国石油天然气股份有限公司 | C10-C13Regeneration method of long-chain normal alkane dehydrogenation deactivated catalyst |
| 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 |
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| CN101940959A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Regeneration method of catalyst for dehydrogenation of low-carbon alkanes |
| CN102806094A (en) * | 2011-06-03 | 2012-12-05 | 中国石油天然气股份有限公司 | C10-C13Regeneration method of long-chain normal alkane dehydrogenation deactivated catalyst |
| 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 |
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