CN105797788A - Regeneration method of paraffin dehydrogenation catalyst - Google Patents
Regeneration method of paraffin dehydrogenation catalyst Download PDFInfo
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- CN105797788A CN105797788A CN201610160952.9A CN201610160952A CN105797788A CN 105797788 A CN105797788 A CN 105797788A CN 201610160952 A CN201610160952 A CN 201610160952A CN 105797788 A CN105797788 A CN 105797788A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/42—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material
- B01J38/44—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material and adding simultaneously or subsequently free oxygen; using oxyhalogen compound
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/485—Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a regeneration method of a paraffin dehydrogenation catalyst. The method includes the following steps of firstly, carbon-burning an inactivated dehydrogenation catalyst in an oxygen-containing atmosphere; secondly, conducting oxychlorination treatment on the catalyst carbon-burned in the first step; thirdly, conducting vapor dechlorination treatment on the catalyst subjected to oxychlorination treatment in the second step; fourthly, conducting alkaline metal promoter compensation treatment on the catalyst subjected to vapor treatment in the third step; fifthly, conducting high-temperature air treatment on the catalyst obtained in the fourth step to obtain the regenerated catalyst. By means of the method, alkali metal lost in the reaction process and the regeneration process can be effectively compensated for, the dehydrogenation activity of the regenerated catalyst can reach the level of a fresh catalyst, operation is easy, and the service life of the catalyst is prolonged.
Description
Technical field
The present invention relates to the renovation process of a kind of catalyst for dehydrogenation of low-carbon paraffin, relate in particular to the renovation process of a kind of propane, dehydrogenation of isobutane noble metal-based catalysts.
Background technology
North America shale revolution brings substantial amounts of low-carbon alkanes resource, causes the raw material lighting of ethylene cracker, and the yield of propylene declines to a great extent.Simultaneously under the overall background that petroleum resources are day by day deficient, the production of propylene has been that raw material changes to the diversified technology path of raw material sources from the simple oil that relies on, and is increasingly becoming a kind of trend.The propane of by-product in natural gas (conventional gas, shale gas, coal bed gas, combustible ice etc.) is carried out dehydrogenation reaction and produces the effective way that propylene is this problem of solution.In recent years, dehydrogenating propane produced the technology of propylene and achieved large development, had become as the third-largest propylene production.
Low-carbon alkanes (propane, iso-butane) dehydrogenation is strong endothermic reaction, is limited by thermodynamical equilibrium, severe reaction conditions, and carbon deposit is always up affecting the reason of catalyst activity and stability with active metal sintering.Propane dehydrogenation catalyst, it is generally required to regenerate frequently, could maintain long-time continuous application.Especially precious metal-based dehydrogenation, is subject to cost factor restriction, and regeneration just seems even more important.Renovation process directly affects the activity of regeneration catalyzing agent, selectivity and life-span, and therefore, the regeneration of research catalyst for dehydrogenation of low-carbon paraffin is very important.
Current Pt based dehydrogenation catalyst renovation process mostly is process of first making charcoal, and under higher regeneration temperature, the carbon deposit of burn off catalyst surface, in this process, Pt component can be assembled further.In order to recover the catalyst based activity of Pt, generally re-use halogen and process the redispersion carrying out Pt.Introducing again Cl in this process, cause regeneration catalyzing agent acid and the change of acid amount, for low-carbon alkanes catalytic dehydrogenation catalyst, when can cause reaction, selectivity reduces, and coke content increases.Therefore, the mode of hydro-thermal must be adopted again to carry out dechlorination, but this can make again alkali metal in catalyst run off.In order to solve these problems, many researcheres are much attempted.
USP4473656 discloses the renovation process of a kind of Pt-Ir catalyst, adopt two sections of circular regeneration methods, it is mainly characterized by contacting reduction-state under oxygen-free atmosphere containing Pt, Ir catalyst with HCl, under high temperature and higher oxygen content, carry out oxi-chlorination again, obtain the Pt-Ir catalyst that chlorinity is suitable.USP4444897 discloses the renovation process of a kind of Pt-Ir catalyst, and the method is first by Pt-Ir catalyst reduction, then processes with the helium containing HCl and water under oxygen-free atmosphere, then carries out redispersion process with the gas containing HCl and elemental oxygen again.In the method that US Patent No. 5087792 is disclosed, the regeneration of catalyst is the purging by noble gas, make oxygenous admixture of gas by wherein, the purging of noble gas and make HCl/ oxygen mixture by wherein so that active metal is redispersed on carrier.In these methods, all introducing halogen Cl to carry out the redispersion of Pt, and follow-up do not carry out dechlorination process, these halogens stay in the catalyst, react for dehydrogenating low-carbon alkane, increase lytic activity, reduce selectivity, add more carbon deposit.
CN1541140A discloses the renovation process of a kind of dehydrogenation, and the method is by, at 300～800 DEG C of temperature, changing oxygen concentration, regeneration pressure and air speed and reach the regeneration of dehydrogenation.This method is made charcoal only with oxygen, it is easy to make regeneration catalyzing agent active metal assemble.
CN1589970A discloses a kind of alkyl aromatics dehydrogenation and produces the renovation process of alkyl alkenyl arene catalyst, the method adopts synchronization to pass into steam and catalyst is regenerated by air, the method needs higher regeneration temperature, carbon deposit on the completely burned off catalyst of ability, and regeneration temperature is when being below 500 DEG C, can not carbon deposit on completely burned off catalyst.CN101940959A discloses the renovation process of a kind of catalyst for dehydrogenation of low-carbon paraffin, the method regenerates first at a lower temperature in air atmosphere, most of carbon deposit within the carbon deposit of burn off catalyst surface and duct, more further catalyst is carried out Regeneration Treatment in the mixed atmosphere of steam and air.Both approaches, when carrying out catalyst regeneration, all introduces steam, not only results in the transformation of alumina support crystalline phase, alkali metal in low-carbon alkanes catalyst also can be made to run off, also can cause accumulation of metal to a certain extent simultaneously.
Can be seen that from the renovation process of above-mentioned precious metal-based dehydrogenation, its regenerative process is all generally purposive introduce oxygen, halogen or steam, although having certain effect, but often also bring other side effect, the steam particularly introduced, the loss of base agent on precious metal-based dehydrogenation can be caused, inevitably have impact on the performance of dehydrogenating low-carbon alkane regeneration catalyzing agent and life-span.
Summary of the invention
For the deficiencies in the prior art, the invention provides the renovation process of a kind of alkane dehydrogenating catalyst.Renovation process provided by the invention is made charcoal and chlorination redispersion first under proper condition, is supplemented with alkali metal promoter after dechlorinated, makes the catalysis activity of regenerated catalyst reach the level of fresh catalyst.
The renovation process of alkane dehydrogenating catalyst of the present invention, including following process:
Step (1), the dehydrogenation of inactivation is made charcoal in oxygen-containing atmosphere: temperature is 440 DEG C-500 DEG C, pass into the oxygen-containing atmosphere that oxygen content is 12v%-15v% tentatively to make charcoal, time is 2h-3h, increase the temperature to 500 DEG C-550 DEG C to make charcoal further, increasing oxygen content to 16v%-21v%, the time is 2h-3h；Finally being warmed up to 550 DEG C-600 DEG C to make charcoal, oxygen content is 21v%-35v%, and the time is 3h-5h, possibly together with noble gas in described oxygen-containing atmosphere；
Step (2), step (1) is made charcoal after catalyst carry out oxychlorination process: at 300 DEG C of-500 DEG C of temperature, in oxygen and noble gas mixed atmosphere, in 5h-10h, the steam of chloride agent is uniformly injected in system；
Step (3), by step (2) oxychlorination process after catalyst carry out steam dechlorination process: in the mixed atmosphere of steam and air, process 2h-8h, treatment temperature is 450 DEG C-600 DEG C, and processing pressure is lower than 30kPa；Mixing gas space velocity is 500h-1-3000h-1, in mixed atmosphere, steam volume content is 30v%-70v%；
Step (4), the catalyst after step (3) steam treatment is carried out supplement alkali metal promoter process: under inert gas atmosphere, under 50 DEG C of-70 DEG C of conditions, in system, pass into the alcoholic solution of alkali metal containing auxiliary agent, make the alkali metal promoter of estimate be uniformly injected into beds in 0.5h-4h；
Step (5), by step (4) gained catalyst high temperature air process: under air atmosphere, treatment temperature is 300 DEG C-600 DEG C, and air gas air speed is 500h-1-3000h-1, the process time is 2h-6h, obtains regeneration catalyzing agent.
In described step (2), described injection steam vapour amount is by every gram of catalyst 3000 μ g-5000 μ g, in the steam of described chloride agent, and H2The mol ratio of O/Cl is 40:1-90:1, and described chlorinating agent is one or more in the chlorine-containing compound of chloromethanes, HCl or carbon dichloride；Described oxygen is with noble gas mixed atmosphere, and oxygen volume content is 2v%-20v%.
In described step (2), described injection steam vapour amount is preferably by every gram of catalyst 3500 μ g-4500 μ g；In the steam of chloride agent, H2The mol ratio of O/Cl is preferably 50:1-80:1；Described oxygen is with noble gas mixed atmosphere, and oxygen volume content is preferably 5v%-15v%.
In described step (3), in the mixed atmosphere of steam and air, the process time is preferably 4h-6h；Treatment temperature is preferably 500 DEG C-580 DEG C；Processing pressure is preferably 10kPa-20kPa；Mixing gas space velocity is preferably 800h-1-2500h-1。
In described step (4), injecting alkali metal promoter and be calculated as the 500ppm-1500ppm of catalyst weight with element wt, described alkali metal promoter predecessor is KOH and NaOH, and the alcoholic solution volume space velocity passing into alkali metal containing auxiliary agent is 1h-1-10h-1, the alcoholic solution of described alkali metal containing auxiliary agent is methanol, ethanol or ethylene glycol, and described noble gas air speed is 500h-1-1500h-1。
In described step (4), inject alkali metal promoter and be calculated as the 800ppm-1200ppm of catalyst weight with element wt；Described alkali metal promoter predecessor is preferably KOH；The alcoholic solution volume space velocity passing into alkali metal containing auxiliary agent is preferably 3h-1-5h-1；The alcoholic solution of described alkali metal containing auxiliary agent is preferably ethanol；Described noble gas air speed is preferably 800h-1-1200h-1。
In described step (5), carry out high-temperature process to mending alkali metal rear catalyst, it is preferable that condition is: under air atmosphere, and treatment temperature is 450 DEG C-550 DEG C, and air gas air speed is 1000h-1-2000h-1。
The dehydrogenation of described inactivation is platinum family loaded catalyst, and with high-temperature inorganic oxide for carrier, one or more in platinum in platinum family, palladium, iridium, rhodium or osmium are active component.
Described platinum family loaded catalyst catalyst for dehydrogenation of low-carbon paraffin, with Al2O3For carrier, in catalyst, Pt counts weight percentage with element and counts weight percentage for 0.1%-1%, K with element wt meter percentage composition for 0.1%-1% for 0.01%-2%, Sn with element.
Renovation process of the present invention is applicable to the regeneration of the catalyst for dehydrogenation of low-carbon paraffin such as propane, iso-butane.
Advantages of the present invention effect is as follows:
In the present invention, use after oxygen atmosphere roasting, carry out oxychlorination process, it is to avoid the gathering of active component.By steam dechlorination, introduce the Cl acid amount caused after reducing regeneration and change.Finally carrying out supplementing the process of alkali metal promoter, the alkali metal promoter that when compensate for regeneration, steam dechlorination process causes runs off, and makes the dehydrogenation activity of regenerated catalyst reach the level of fresh catalyst.Regenerative process has carried out the dispersion of active metal, alkali metal promoter supplement, improve catalyst regeneration stability, process is simple, it is easy to operation, extend life cycle and the life-span of catalyst.
Detailed description of the invention
Further illustrate technology contents and the effect of the present invention below in conjunction with embodiment, but be not so limited the present invention.
The present invention is in specific implementation process, and the dehydrogenation evaluation of fresh catalyst and regenerated catalyst carries out on flowing fixed-bed micro-devices continuously.Fresh catalyst and regeneration catalyzing agent carry out reduction treatment before the reaction, and reducing condition is: pure hydrogen atmosphere, normal pressure, 530 DEG C, volume space velocity 2000h-1；Performance evaluation condition is: unstripped gas is the gaseous mixture (volume ratio 1:1) of hydrogen and propane, volume space velocity 3000h-1, reaction temperature 600 DEG C, normal pressure；Regeneration Treatment is carried out after fresh catalyst and regeneration catalyzing agent reaction 72h.Product detects it through gas chromatograph and forms and calculate conversion ratio and selectivity.
Embodiment 1
Weigh commercial alumina carrier (γ phase, spherical, diameter 0.5mm, pore volume 0.71cm3/ g, specific surface area 224m2/ g) 30g, dropping deionized water is to just profit, and the volume consuming water is 27mL.By Sn element wt content 0.4% in final catalyst, weigh the stannous chloride containing 0.12gSn and be dissolved in ethanol, use ethanol to be settled to 27mL.Add what configured to 30g alumina support containing Sn alcoholic solution, mix homogeneously, aged at room temperature 2h.80 DEG C of dry 8h, then at 600 DEG C of roasting 4h.
By Pt element wt content 0.5% in final catalyst, weigh the chloroplatinic acid containing Pt0.18g and be dissolved in deionized water, be settled to 27mL, add to containing in Sn alumina support, mix homogeneously, aged at room temperature 4h, 100 DEG C of dry 6h, roasting 4h in 600 DEG C.Above-mentioned steps gained sample, at 600 DEG C, processes 3h under the nitrogen atmosphere containing 20% steam, air speed is 2000h-1.By K element weight content 0.4% in final catalyst, weigh the potassium nitrate containing K0.12g and be dissolved in deionized water, be settled to 27mL, add in the catalyst precarsor to steam treatment, mix homogeneously, ageing 2h at 70 DEG C, 100 DEG C of dry 6h, roasting 4h in 600 DEG C.Preparing the weight content of each component in catalyst is: Pt0.5%, Sn0.4%, K0.4%.Gained catalyst is designated as C-1.
Fresh dose of reactivity worth of C-1 is in Table 1.
Embodiment 2
Weigh commercial alumina carrier (γ phase, spherical, diameter 0.5mm, pore volume 0.71cm3/ g, specific surface area 224m2/ g) 30g, dropping deionized water is to just profit, and the volume consuming water is 27mL.By Sn element wt content 0.6% in final catalyst, weigh the stannous chloride containing 0.18gSn and be dissolved in ethanol, be settled to 27mL.Add what configured to 30g alumina support containing Sn alcoholic solution, mix homogeneously, aged at room temperature 4h.100 DEG C of dry 6h, then at 500 DEG C of roasting 6h.
By Pt element wt content 0.7% in final catalyst, weigh the chloroplatinic acid containing Pt0.12g and be dissolved in deionized water, be settled to 27mL, add to containing in Sn alumina support, mix homogeneously, aged at room temperature 2h, 120 DEG C of dry 4h, roasting 6h in 500 DEG C.Above-mentioned steps gained sample, at 700 DEG C, processes 2h under the nitrogen atmosphere containing 10% steam, air speed is 3000h-1.By K element weight content 0.2% in final catalyst, weigh the potassium nitrate containing K0.06g and be dissolved in deionized water, be settled to 27mL, add in the catalyst precarsor to steam treatment, mix homogeneously, ageing 1h at 80 DEG C, 120 DEG C of dry 4h, roasting 4h in 600 DEG C.Preparing the weight content of each component in catalyst is: Pt0.7%, Sn0.6%, K0.2%.Gained catalyst is designated as C-2.
Fresh dose of reactivity worth of C-2 catalyst is in Table 1.
Embodiment 3
After fresh dose of C-1 reacts 72h, unstripped gas is switched to pure hydrogen gas, purge 1h；Then temperature is down to 470 DEG C, the nitrogen, oxygen mixing gas switching to oxygen content to be 15v%, processes 2h；It is warming up to 530 DEG C again, the nitrogen, oxygen mixing gas switching to oxygen content to be 21v%, process 2h；Then proceed to be warming up to 580 DEG C, the nitrogen, oxygen mixing gas switching to oxygen content to be 35v%, process 3h.
Make charcoal after end, switch to nitrogen, be cooled to 400 DEG C, pass into the nitrogen, oxygen mixing gas that oxygen content is 10v% and H2The mol ratio of O/Cl be 60:1 containing carbon dichloride steam, pass into by the 10h time containing carbon dichloride steam, the total intake of steam is by every gram of catalyst 4000 μ g.
Decaying catalyst oxychlorination switches to nitrogen, is warming up to 540 DEG C after updating, and system pressure controls in 15kPa (gauge pressure), then switches to the mixing gas of air and steam, and wherein steam volume content is 50v%, and gaseous mixture volume space velocity is 1600h-1, process 5h.
After decaying catalyst dechlorination, switch to nitrogen, be then cooled to 60 DEG C, nitrogen volume space velocity is controlled as 1000h-1, and the alcoholic solution simultaneously passing into potassium hydroxide processes, and the process time is 2h, and the potassium element passed into is by weight for the 1000ppm of catalyst weight amount, and potassium hydroxide-ethanol solution liquid volume air speed is 4.
Decaying catalyst, after potassium hydroxide-ethanol solution processes, passes into air, and is warming up to 500 DEG C, processes 4h, and volume of air air speed is 1500h-1.After process terminates, obtain C-1 primary recycling agent.
C-1 primary recycling agent reactivity worth is in Table 1.
Embodiment 4
After C-1 primary recycling agent reaction 72h, unstripped gas is switched to pure hydrogen gas, purges 1h；Then temperature is down to 500 DEG C, the nitrogen, oxygen mixing gas switching to oxygen content to be 12v%, processes 3h；It is warming up to 550 DEG C again, the nitrogen, oxygen mixing gas switching to oxygen content to be 16v%, process 3h；Then proceed to be warming up to 600 DEG C, the nitrogen, oxygen mixing gas switching to oxygen content to be 21v%, process 5h.
Make charcoal after end, switch to nitrogen, be cooled to 300 DEG C, pass into the nitrogen, oxygen mixing gas that oxygen content is 15v% and H2The mol ratio of O/Cl be 50:1 containing carbon dichloride steam, pass into by the 5h time containing carbon dichloride steam, the total intake of steam is by every gram of catalyst 3500 μ g.
Decaying catalyst oxychlorination switches to nitrogen, is warming up to 580 DEG C after updating, and system pressure controls in 10kPa (gauge pressure), then switches to the mixing gas of air and steam, and wherein steam volume content is 70v%, and gaseous mixture volume space velocity is 800h-1, process 6h.
After decaying catalyst dechlorination, switch to nitrogen, be then cooled to 50 DEG C, nitrogen volume space velocity is controlled as 1200h-1, and the alcoholic solution simultaneously passing into potassium hydroxide processes, and the process time is 4h, and the potassium element passed into is by weight for the 800ppm of catalyst weight amount, and potassium hydroxide-ethanol solution liquid volume air speed is 3h-1。
Decaying catalyst, after potassium hydroxide-ethanol solution processes, passes into air, and is warming up to 450 DEG C, processes 6h, and volume of air air speed is 2000h-1.After process terminates, obtain C-1 secondary recycling agent.
C-1 secondary recycling agent reactivity worth is in Table 1.
Embodiment 5
After C-1 secondary recycling agent reaction 72h, unstripped gas is switched to pure hydrogen gas, purges 1h；Then temperature is down to 440 DEG C, the nitrogen, oxygen mixing gas switching to oxygen content to be 15v%, processes 3h；It is warming up to 500 DEG C again, the nitrogen, oxygen mixing gas switching to oxygen content to be 21v%, process 3h；Then proceed to be warming up to 600 DEG C, the nitrogen, oxygen mixing gas switching to oxygen content to be 35v%, process 5h.
Make charcoal after end, switch to nitrogen, be cooled to 500 DEG C, pass into the nitrogen, oxygen mixing gas that oxygen content is 5v% and H2The mol ratio of O/Cl be 80:1 containing carbon dichloride steam, pass into by the 10h time containing carbon dichloride steam, the total intake of steam is by every gram of catalyst 4500 μ g.
Decaying catalyst oxychlorination switches to nitrogen, is warming up to 500 DEG C after updating, and system pressure controls in 20kPa (gauge pressure), then switches to the mixing gas of air and steam, and wherein steam volume content is 30v%, and gaseous mixture volume space velocity is 800h-1, process 4h.
After decaying catalyst dechlorination, switch to nitrogen, be then cooled to 70 DEG C, nitrogen volume space velocity is controlled as 1200h-1, and the alcoholic solution simultaneously passing into potassium hydroxide processes, and the process time is 0.5h, and the potassium element passed into is by weight for the 1200ppm of catalyst weight amount, and potassium hydroxide-ethanol solution liquid volume air speed is 5h-1。
Decaying catalyst, after potassium hydroxide-ethanol solution processes, passes into air, and is warming up to 550 DEG C, processes 2h, and volume of air air speed is 1000h-1.After process terminates, obtain C-1 tertiary recycling agent.
C-1 tertiary recycling agent reactivity worth is in Table 1.
Embodiment 6
After C-1 tertiary recycling agent reaction 72h, unstripped gas is switched to pure hydrogen gas, purges 1h；Then temperature is down to 470 DEG C, the nitrogen, oxygen mixing gas switching to oxygen content to be 15v%, processes 2h；It is warming up to 530 DEG C again, the nitrogen, oxygen mixing gas switching to oxygen content to be 21v%, process 2h；Then proceed to be warming up to 580 DEG C, the nitrogen, oxygen mixing gas switching to oxygen content to be 35v%, process 3h.
Make charcoal after end, switch to nitrogen, be cooled to 400 DEG C, pass into the nitrogen, oxygen mixing gas that oxygen content is 10v% and H2The mol ratio of O/Cl be 60:1 containing carbon dichloride steam, pass into by the 10h time containing carbon dichloride steam, the total intake of steam is by every gram of catalyst 4000 μ g.
Decaying catalyst oxychlorination switches to nitrogen, is warming up to 540 DEG C after updating, and system pressure controls in 15kPa (gauge pressure), then switches to the mixing gas of air and steam, and wherein steam volume content is 50v%, and gaseous mixture volume space velocity is 1600h-1, process 5h.
After decaying catalyst dechlorination, switch to nitrogen, be then cooled to 60 DEG C, nitrogen volume space velocity is controlled as 800h-1, and the alcoholic solution simultaneously passing into potassium hydroxide processes, and the process time is 4h, and the potassium element passed into is by weight for the 1200ppm of catalyst weight amount, and potassium hydroxide-ethanol solution liquid volume air speed is 3h-1。
Decaying catalyst, after potassium hydroxide-ethanol solution processes, passes into air, and is warming up to 500 DEG C, processes 4h, and volume of air air speed is 1500h-1.After process terminates, obtain tetra-regenerative agents of C-1.
Tetra-regenerative agent reactivity worth of C-1 are in Table 1.
Embodiment 7
After tetra-regenerative agent reaction 72h of C-1, regenerate by embodiment 3 mode, obtain five regenerative agents of C-1.
Five regenerative agent reactivity worth of C-1 are in Table 1.
Embodiment 8
Fresh dose of C-2 regenerates by embodiment 3 mode, and carries out performance evaluation after reacting 72h, five times repeatedly.
C-2 regenerative agent reactivity worth is in Table 1.
Comparative example 1
Regenerative process does not adopt kalium replenishment measure.
Regenerate by embodiment 3 mode, the difference is that process does not adopt kalium replenishment operating procedure.Repeated regeneration five times.
Regeneration catalyzing agent reactivity worth is in Table 1.
From table 1 it follows that after adopting the renovation process that the present invention relates to regenerate, regeneration catalyzing agent catalytic performance is basic identical with fresh catalyst.And in a comparative example, not adopting kalium replenishment to operate, declining to a great extent occurs in regeneration catalyzing agent performance, and particularly olefine selective declines clearly.
In the inventive method, described dehydrogenation is platinum family loaded catalyst, and with high-temperature inorganic oxide for carrier, one or more in platinum in platinum family, palladium, iridium, rhodium or osmium are active component, it is preferred to platinum.Platinum group metal is calculated as the 0.01%-2% of catalyst weight in the catalyst with element.Described high-temperature inorganic oxide includes: aluminium oxide, magnesium oxide, chromium oxide, boron oxide, titanium oxide, zinc oxide, zirconium oxide, or both the above hopcalite, and various Alumina ceramic, various, silicon dioxide, synthesis or naturally occurring various silicate or clay.Preferred high-temperature inorganic oxide carrier is Al2O3, its crystal habit can be γ-Al2O3、θ-Al2O3Or η-Al2O3, it is preferable that γ-Al2O3。
Dehydrogenation of the present invention contains suitable auxiliaries simultaneously, such as IVA race element and alkali metal.Wherein IVA race element is preferably stannum, germanium, more preferably stannum, IVA race element with element count in the catalyst weight percentage for 0.1%-1%；Alkali metal is preferably sodium, potassium, more preferably potassium, alkali metal with element count in the catalyst weight percentage for 0.1%-1%.
The present invention relates to dehydrogenation, its preparation method comprises the steps: that (1) introduces IVA race element in the carrier；(2) platinum group metal is introduced；(3) steam treatment；(4) alkali metal is introduced.Wherein (1st) step introducing IVA race element and (2nd) step introducing platinum group metal can also carry out simultaneously.
Introduce IVA race element method described in above-mentioned dehydrogenation preparation method to introduce in aluminium oxide plastic process, it is also possible to introduced by the mode of load, it is also possible in aluminium oxide forming process, kneading introduces.The predecessor of IVA race element is its oxide, chloride, nitrate, sulfate or containing IVA race element acid group salt, such as stannous chloride, butter of tin, butter of tin pentahydrate, Tin dibromide., germanium dioxide, germanium tetrachloride, nitric acid stannum, tin acetate, sodium stannate, potassium stannate etc., it is preferably butter of tin, stannous chloride, more preferably stannous chloride.
In above-mentioned dehydrogenation preparation method, platinum family element can adopt co-precipitation, ion exchange or impregnating mode to introduce.Preferred method is infusion process, namely adopts one or more the dipping carriers in water solublity platinum group metal compounds or coordination compound.Water solublity platinum group metal compounds or coordination compound are chloroplatinic acid, chloro-iridic acid, the acid of chlorine palladium, ammonium chloroplatinate, bromoplatinic acid, tri-chlorination platinum, Palladous nitrate., diaminourea palladium hydroxide, chlorine four ammonia palladium, chlorine six ammonia palladium, rhodium chloride hydrate, rhodium nitrate, tribromide iridium, iridochloride, iridic chloride, potassium hexachloroiridate or iridium sodium chloride etc..The chlorine-containing compound of preferred platinum, palladium, iridium, rhodium or osmium, more preferably the chlorine-containing compound of platinum, such as chloroplatinic acid.Introducing platinum family element by mode of loading is method well known to those skilled in the art.
In the preparation method of above-mentioned dehydrogenation, also including steam treatment, treatment conditions are: under the containing water vapor mixed atmosphere of flowing continuously, and 400 DEG C-800 DEG C process 1h-10h, it is preferred to process 2h-4h at 500 DEG C-700 DEG C；In described containing water vapor mixed atmosphere, steam volume content is 5%-50%, it is preferred to 10%-30%, and all the other are noble gas；Gaseous mixture air speed is 100h-1-10000h-1, it is preferred to 1000h-1-3000h-1；In process rear catalyst, chlorine element wt content is less than 0.15%.
In the preparation method of above-mentioned dehydrogenation, the introducing method of alkali metal promoter is dipping method well known to those skilled in the art.The predecessor of K is containing K solubility salt, it is possible to be inorganic salt, it is also possible to be organic salt, it is preferred to potassium nitrate.Impregnation liquid can be aqueous solution, it is also possible to for organic solution.
A kind of dehydrogenation adopting said method to prepare, with Al2O3For carrier, it is preferable that γ-Al2O3；In catalyst, Pt counts weight percentage for 0.01%-2% with element, it is preferred to 0.1%-1%, more preferably 0.4%-0.8%；Sn counts weight percentage for 0.1%-1% with element, it is preferable that 0.2%-0.6%；K is with element wt meter percentage composition for 0.1%-1%, it is preferable that 0.2%-0.6%.
Heretofore described noble gas is the gas that chemical reaction does not occur under condition involved in the present invention for nitrogen, argon, helium etc., it is preferred to nitrogen.
Table 1
Claims (10)
1. the renovation process of an alkane dehydrogenating catalyst, it is characterised in that comprise the steps:
Step (1), the dehydrogenation of inactivation is made charcoal in oxygen-containing atmosphere: temperature is 440 DEG C-500 DEG C,
Passing into the oxygen-containing atmosphere that oxygen content is 12v%-15v% tentatively to make charcoal, the time is 2h-3h, increases the temperature to 500 DEG C-550 DEG C and makes charcoal further, increases oxygen content to 16v%-21v%, and the time is 2h-3h；Finally being warmed up to 550 DEG C-600 DEG C to make charcoal, oxygen content is 21v%-35v%, and the time is 3h-5h, possibly together with noble gas in described oxygen-containing atmosphere；
Step (2), step (1) is made charcoal after catalyst carry out oxychlorination process: at 300 DEG C-500 DEG C
At temperature, in oxygen with noble gas mixed atmosphere, in 5h-10h, the steam of chloride agent is uniformly injected in system；
Step (3), by step (2) oxychlorination process after catalyst carry out steam dechlorination process: at water
In the mixed atmosphere of steam and air, processing 2h-8h, treatment temperature is 450 DEG C-600 DEG C, and processing pressure is lower than 30kPa；Mixing gas space velocity is 500h-1-3000h-1, in mixed atmosphere, steam volume content is 30v%-70v%；
Step (4), the catalyst after step (3) steam treatment is carried out supplement alkali metal promoter process:
Under inert gas atmosphere, under 50 DEG C of-70 DEG C of conditions, in system, pass into the alcoholic solution of alkali metal containing auxiliary agent, make the alkali metal promoter of estimate be uniformly injected into beds in 0.5h-4h；
Step (5), by step (4) gained catalyst high temperature air process: under air atmosphere, treatment temperature is 300 DEG C-600 DEG C, and air gas air speed is 500h-1-3000h-1, the process time is 2h-6h, obtains regeneration catalyzing agent.
2. the renovation process of a kind of alkane dehydrogenating catalyst according to claim 1, it is characterised in that in described step (2), described injection steam vapour amount is by every gram of catalyst 3000 μ g-5000 μ g, in the steam of described chloride agent, H2The mol ratio of O/Cl is 40:1-90:1, and described chlorinating agent is one or more in the chlorine-containing compound of chloromethanes, HCl or carbon dichloride；Described oxygen is with noble gas mixed atmosphere, and oxygen volume content is 2v%-20v%.
3. the renovation process of a kind of alkane dehydrogenating catalyst according to claim 2, it is characterised in that in described step (2), described injection steam vapour amount is preferably by every gram of catalyst 3500 μ g-4500 μ g；In the steam of chloride agent, H2The mol ratio of O/Cl is preferably 50:1-80:1；Described oxygen is with noble gas mixed atmosphere, and oxygen volume content is preferably 5v%-15v%.
4. the renovation process of a kind of alkane dehydrogenating catalyst according to claim 1, it is characterised in that in described step (3), in the mixed atmosphere of steam and air, the process time is preferably 4h-6h；Treatment temperature is preferably 500 DEG C-580 DEG C；Processing pressure is preferably 10kPa-20kPa；Mixing gas space velocity is preferably 800h-1-2500h-1。
5. the renovation process of a kind of alkane dehydrogenating catalyst according to claim 1, it is characterized in that in described step (4), inject alkali metal promoter and be calculated as the 500ppm-1500ppm of catalyst weight with element wt, described alkali metal promoter predecessor is KOH and NaOH, and the alcoholic solution volume space velocity passing into alkali metal containing auxiliary agent is 1h-1-10h-1, the alcoholic solution of described alkali metal containing auxiliary agent is methanol, ethanol or ethylene glycol, and described noble gas air speed is 500h-1-1500h-1。
6. the renovation process of a kind of alkane dehydrogenating catalyst according to claim 5, it is characterised in that in described step (4), injects alkali metal promoter and is calculated as the 800ppm-1200ppm of catalyst weight with element wt；Described alkali metal promoter predecessor is preferably KOH；The alcoholic solution volume space velocity passing into alkali metal containing auxiliary agent is preferably 3h-1-5h-1；The alcoholic solution of described alkali metal containing auxiliary agent is preferably ethanol；Described noble gas air speed is preferably 800h-1-1200h-1。
7. the renovation process of a kind of alkane dehydrogenating catalyst according to claim 1, it is characterized in that in described step (5), carry out high-temperature process to mending alkali metal rear catalyst, it is preferable that condition is: under air atmosphere, treatment temperature is 450 DEG C-550 DEG C, and air gas air speed is 1000h-1-2000h-1。
8. the renovation process of a kind of alkane dehydrogenating catalyst according to claim 1, it is characterised in that institute
The dehydrogenation stating inactivation is platinum family loaded catalyst, and with high-temperature inorganic oxide for carrier, one or more in platinum in platinum family, palladium, iridium, rhodium or osmium are active component.
9. the renovation process of a kind of alkane dehydrogenating catalyst according to claim 8, it is characterised in that described platinum family loaded catalyst catalyst for dehydrogenation of low-carbon paraffin, with Al2O3For carrier, in catalyst, Pt counts weight percentage with element and counts weight percentage for 0.1%-1%, K with element wt meter percentage composition for 0.1%-1% for 0.01%-2%, Sn with element.
10. the renovation process of a kind of alkane dehydrogenating catalyst according to claim 1, it is characterised in that suitable in the regeneration of the catalyst for dehydrogenation of low-carbon paraffin such as propane, iso-butane.
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| CN107866237A (en) * | 2016-09-28 | 2018-04-03 | 中国石油化工股份有限公司 | A kind of method for activating and reducing of catalyst for dehydrogenation of low-carbon paraffin |
| CN112746170A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Treatment process of deactivated hydrogenation catalyst containing molecular sieve carrier |
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| CN1015513B (en) * | 1988-10-22 | 1992-02-19 | 金陵石油化工公司烷基苯厂 | Regeneration of non-acid loading type platinum catalyst |
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| CN102909013B (en) * | 2011-08-01 | 2014-08-20 | 中国石油化工股份有限公司 | Preparation method for dehydrogenation catalyst with steam dechlorination and reduction performed simultaneously |
| CN103801330B (en) * | 2012-11-07 | 2015-12-16 | 中国石油化工股份有限公司 | A kind of renovation process of dehydrogenation |
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| CN107866237A (en) * | 2016-09-28 | 2018-04-03 | 中国石油化工股份有限公司 | A kind of method for activating and reducing of catalyst for dehydrogenation of low-carbon paraffin |
| CN107866237B (en) * | 2016-09-28 | 2021-01-08 | 中国石油化工股份有限公司 | Activation reduction method of low-carbon alkane dehydrogenation catalyst |
| CN112746170A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Treatment process of deactivated hydrogenation catalyst containing molecular sieve carrier |
| CN112746172A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Treatment method of deactivated hydrogenation catalyst |
| CN112746172B (en) * | 2019-10-29 | 2023-01-10 | 中国石油化工股份有限公司 | Treatment method of deactivated hydrogenation catalyst |
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| CN114425458A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Activation method of sulfur-poisoned light paraffin isomerization catalyst |
| CN114425394A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Regeneration method of inactivated light alkane isomerization catalyst |
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