CN104923258A - Catalyst regeneration method - Google Patents
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- CN104923258A CN104923258A CN201510241371.3A CN201510241371A CN104923258A CN 104923258 A CN104923258 A CN 104923258A CN 201510241371 A CN201510241371 A CN 201510241371A CN 104923258 A CN104923258 A CN 104923258A
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Abstract
The invention discloses a low-carbon alkane dehydrogenation catalyst regeneration method. The method comprises the following steps: (1) a deactivated catalyst is treated with CO gas; (2) the deactivated catalyst treated in the step (1) is treated in a mixed atmosphere comprising low-carbon oxygen-containing hydrocarbon and HCl; (3) the deactivated catalyst treated in the step (2) is treated in a mixed atmosphere comprising low-carbon oxygen-containing hydrocarbon; and (4) the deactivated catalyst treated in the step (3) is subjected to a charcoaling treatment in mixed gas comprising low-concentration oxygen, such that a regenerated catalyst is obtained. With the low-carbon alkane dehydrogenation catalyst regeneration method provided by the invention, problems in existing low-carbon alkane dehydrogenation catalyst regeneration processes are well solved. The performances of the regenerated catalyst can be restored to the level of fresh agent.
Description
Technical field
The present invention relates to a kind of renovation process 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 a large amount of low-carbon alkanes resources, and cause the raw material lighting of ethylene cracker, the output 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 becomes a kind of trend gradually.It is the effective way addressed this problem that the propane of middle for natural gas (conventional gas, shale gas, coal bed gas, combustible ice etc.) by-product is carried out dehydrogenation reaction preparing propone.In recent years, the technology that dehydrogenating propane produces propylene achieved large development, had become the third-largest propylene production.
Low-carbon alkanes (propane, iso-butane) dehydrogenation is strong endothermic reaction, limits, severe reaction conditions by thermodynamical equilibrium, and it is the reason affecting catalyst activity and stability that carbon deposit and active metal sinter always.Propane dehydrogenation catalyst generally needs to regenerate frequently, could maintain long-time continuous application.Especially precious metal-based dehydrogenation, be subject to cost factor restriction, regeneration just seems even more important.Renovation process directly affects the activity of regenerated catalyst, selective 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 directly making charcoal, and under higher regeneration temperature, the carbon deposit of burn off catalyst surface, in this process, Pt component can be assembled further, has a strong impact on the performance of regenerated catalyst.In order to address this problem, many researchers much attempt.
USP4473656 discloses a kind of renovation process of Pt-Ir catalyst, adopt two sections of circular regeneration methods, main feature is contacting reduction-state with HCl under oxygen-free atmosphere containing Pt, Ir catalyst, under high temperature and higher oxygen content, carry out oxi-chlorination again, obtain the Pt-Ir catalyst that chlorinity is suitable.USP4444897 discloses a kind of renovation process of Pt-Ir catalyst, and the method first by Pt-Ir catalyst reduction, then uses the helium process containing HCl and water under oxygen-free atmosphere, and then carries out dispersion treatment again with the gas containing HCl and elemental oxygen.In the method that US Patent No. 5087792 discloses, the regeneration of catalyst is the purge by inert gas, make oxygenous admixture of gas by wherein, the purge of inert gas and make HCl/ oxygen mixture by wherein so that active metal is redispersed on carrier.In these methods, all introduce halogen Cl to carry out disperseing again of Pt, and follow-uply do not carry out dechlorination process, these halogens stay in the catalyst, for dehydrogenating low-carbon alkane reaction, increase lytic activity, reduce selective, add more carbon deposit.
CN1541140A discloses a kind of renovation process of dehydrogenation, and the method, by 300 ~ 800 DEG C of temperature, changes the regeneration that oxygen concentration, regeneration pressure and air speed reach dehydrogenation.This method only adopts oxygen to make charcoal, and easily makes regenerated catalyst active metal assemble.
CN1589970A discloses the renovation process that a kind of alkyl aromatics dehydrogenation produces alkyl alkenyl arene catalyst, the method employing synchronously passes into water vapour and air regenerates catalyst, the method needs higher regeneration temperature, the carbon deposit on catalyst could be burnt completely, and regeneration temperature is when being below 500 DEG C, the carbon deposit on catalyst can not be burnt completely.CN101940959A discloses a kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin, the method regenerates first at a lower temperature in air atmosphere, the carbon deposit of burn off catalyst surface and most of carbon deposit of inside, duct, more further regeneration process is carried out to catalyst in the mixed atmosphere of water vapour and air.These two kinds of methods, when carrying out catalyst regeneration, are all introduced water vapour, not only can be caused 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.
As can be seen from the renovation process of above-mentioned precious metal-based dehydrogenation, in existing renovation process, good performance is obtained in order to make regenerated catalyst, usually be all have employed these three kinds of materials of oxygen, halogen or water vapour, although to a certain degree solve carbon deposit, accumulation of metal and alkali metal losing issue, also inevitably have impact on performance and the life-span of dehydrogenating low-carbon alkane regenerated catalyst.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin, particularly the renovation process of a kind of propane, dehydrogenation of isobutane noble metal catalyst.The inventive method utilizes CO methanation reaction and disproportionated reaction, reduce the hydrogen-carbon ratio of catalyst carbon deposit, adopt low-carbon oxygen-containing hydro carbons to coordinate HCl to carry out dispersion again and the dechlorination in activated centre simultaneously, finally adopt the mist containing low concentration oxygen to remove carbon deposit at lower temperature, obtain good regeneration effect.
The renovation process of catalyst for dehydrogenation of low-carbon paraffin of the present invention, comprises following process:
(1) CO gas treatment decaying catalyst is used;
(2) decaying catalyst after step (1) being processed processes in the mixed atmosphere of low-carbon oxygen-containing hydro carbons and HCl;
(3) decaying catalyst after step (2) being processed processes in containing the mixed atmosphere of low-carbon oxygen-containing hydro carbons;
(4) decaying catalyst after step (3) being processed carries out process of making charcoal in containing the mist of low concentration oxygen, obtains the catalyst after regenerating.
In the inventive method, the detailed process of step (1) described use CO process decaying catalyst is as follows: under inert atmosphere, by decaying catalyst temperature control to 300 DEG C-600 DEG C, be preferably 400 DEG C-500 DEG C, Stress control is at 1MPa-5MPa, be preferably 2MPa-4MPa, then switch to CO gas, CO intake presses catalyst volume air speed 500h
-1-5000h
-1, be preferably 1000h
-1-3000h
-1, the processing time is 1h-12h, is preferably 2h-4h.After process terminates, switch to inert gas, step-down.
In the inventive method, step processes described in (2) in the mixed atmosphere of low-carbon oxygen-containing hydro carbons, HCl and inert gas, detailed process is as follows: under inert atmosphere, and the decaying catalyst after step (1) being processed is cooled to 150 DEG C-400 DEG C, is preferably 200 DEG C-300 DEG C.Then switch to the mist containing low-carbon oxygen-containing hydro carbons, HCl and inert gas, in gaseous mixture, low-carbon oxygen-containing hydro carbons volume content is 5%-30%, preferred 10%-20%; In gaseous mixture, HCl volume content is 0.1%-3%, preferred 0.5%-1.5%.Gaseous mixture volume space velocity is 100h
-1-1000h
-1, be preferably 200h
-1-400h
-1; Time is 0.5h-8h, is preferably 1h-3h.
In the inventive method, process in containing the mixed atmosphere of low-carbon oxygen-containing hydro carbons described in step (3), detailed process is as follows: after step (2) process terminates, switch to the mist containing low-carbon oxygen-containing hydro carbons and inert gas again, in gaseous mixture, low-carbon oxygen-containing hydro carbons volume content is 5%-30%, preferred 10%-20%, gaseous mixture volume space velocity is 100h
-1-1000h
-1, be preferably 200h
-1-400h
-1; Time is 0.5h-4h, is preferably 1h-2h.
Above-mentioned low-carbon oxygen-containing hydro carbons refers to that carbon number is alcohols, the ethers of 1-2, as methyl alcohol, ethanol, ethylene glycol, dimethyl ether etc., is preferably methyl alcohol or dimethyl ether.
In the inventive method, to make charcoal process in containing the mixed atmosphere of low concentration oxygen described in step (4), detailed process is: under inert atmosphere, decaying catalyst temperature control to 200 DEG C-450 DEG C after step (3) is processed, be preferably 300 DEG C-400 DEG C, then pass into mist that is oxygenous and inert gas, in gaseous mixture, oxygen volume content is 0.1%-1%, preferred 0.4%-0.8%; Volume space velocity is 200h
-1-5000h
-1, be preferably 500h
-1-1500h
-1, the time is 1h-8h, is preferably 2h-4h; Then keep temperature, mist air speed constant, oxygen volume content in gaseous mixture is increased to 1%-3%, be preferably 1.5%-2.5%, continue process 1h-8h, be preferably 2h-4h; In a manner described, oxygen volume content in gaseous mixture is increased to 3%-6%, is preferably 4%-5% and continues to make charcoal.Make charcoal after terminating, switch to inert gas, cooling, obtains regenerated catalyst.
In the inventive method, in the mist of step (4) containing low concentration oxygen, can also containing appropriate N
2o gas, N
2the volumetric concentration of O is 0.001%-0.1%, is preferably 0.01%-0.05%.
The renovation process of catalyst for dehydrogenation of low-carbon paraffin of the present invention, is applicable to the regeneration of the catalyst for dehydrogenation of low-carbon paraffin such as propane, iso-butane.
In the inventive method, described dehydrogenation is platinum family loaded catalyst, take high-temperature inorganic oxide as carrier, and one or more in the platinum in platinum family, palladium, iridium, rhodium or osmium are active component, is preferably platinum.0.01% ~ 2% of vehicle weight is counted with simple substance in the catalyst in platinum group metal.Described high-temperature inorganic oxide comprises: aluminium oxide, magnesia, chromium oxide, boron oxide, titanium oxide, zinc oxide, zirconia, or the mixture of above two oxides, and various pottery, various alumina, silica, synthesis or naturally occurring various silicate or clay.Preferred high-temperature inorganic oxide carrier is Al
2o
3, its crystal habit can be γ-Al
2o
3, θ-Al
2o
3or η-Al
2o
3, preferred γ-Al
2o
3.
Simultaneously containing suitable auxiliaries in dehydrogenation of the present invention, as IVA race element and alkali metal.Wherein IVA race element is preferably tin, germanium, is more preferably tin, IVA race element in element in the catalyst weight percentage for 0.1%-1%; Alkali metal is preferably sodium, potassium, is more preferably potassium, alkali metal in element in the catalyst weight percentage for 0.1%-1%.
The present invention relates to dehydrogenation, its preparation method comprises the steps: (1) introduces IVA race element in the carrier; (2) platinum group metal is introduced; (3) steam treatment; (4) alkali metal is introduced.Wherein (1) step is introduced IVA race element and (2) step and is introduced platinum group metal and also can carry out simultaneously.
Introduce IVA race element method described in above-mentioned dehydrogenation preparation method to introduce in aluminium oxide plastic process, also can be introduced by the mode of load, kneading can also introduce in aluminium oxide forming process.The predecessor of IVA race element is its oxide, chloride, nitrate, sulfate or containing IVA race element acid group salt, as stannous chloride, butter of tin, butter of 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, be 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 impregnated carriers in water-soluble platinum group metal compounds or complex.Water-soluble platinum group metal compounds or complex are chloroplatinic acid, chloro-iridic acid, the acid of chlorine palladium, ammonium chloroplatinate, bromoplatinic acid, tri-chlorination platinum, palladium 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, is more preferably the chlorine-containing compound of platinum, 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 comprise steam treatment, treatment conditions are: under the moisture vapor mixed atmosphere of continuous-flow, and 400 DEG C-800 DEG C process 1h-10h, process 2h-4h at being preferably 500 DEG C-700 DEG C; In described moisture vapor mixed atmosphere, water vapour volume content is 5%-50%, and be preferably 10%-30%, all the other are inert gas; Gaseous mixture air speed is 100h
-1-10000h
-1, be preferably 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 for containing K solubility salt, and can be inorganic salts, also can be organic salt, is preferably potassium nitrate.Maceration extract can be the aqueous solution, also can be organic solution.
Adopt a dehydrogenation prepared by said method, with Al
2o
3for carrier, preferred γ-Al
2o
3; In catalyst, Pt is in element weight percentage for 0.01%-2%, is preferably 0.1%-1%, more preferably 0.4%-0.8%; Sn in element weight percentage for 0.1%-1%, preferred 0.2%-0.6%; K in element wt percentage composition for 0.1%-1%, preferred 0.2%-0.6%.
Inert gas described in the present invention is the gas that chemical reaction does not occur under condition involved in the present invention for nitrogen, argon gas, helium etc., is preferably nitrogen.
The inventive method, utilize CO methanation reaction and disproportionated reaction, reduce the hydrogen-carbon ratio of catalyst carbon deposit, adopt low-carbon oxygen-containing hydro carbons to coordinate HCl to carry out dispersion again and the dechlorination in activated centre simultaneously, the mist containing low concentration oxygen is finally adopted to remove carbon deposit at lower temperature, overcome the problem that in coke combustion, activated centre is assembled, reach the object of catalyst regeneration.The dehydrogenation activity of the renovation process regenerated catalyst that the present invention relates to can reach the level of fresh catalyst, and in regenerative process, variations in temperature is little simultaneously, is easy to operation, extends the service life of catalyst.
Detailed description of the invention
Further illustrate technology contents of the present invention and effect below in conjunction with embodiment, but therefore do not limit the present invention.
The present invention is in specific implementation process, and the dehydrogenation evaluation of fresh catalyst and regenerated catalyst is carried out on continuous-flow fixed-bed micro-devices.Fresh catalyst carries out reduction treatment before the reaction, and reducing condition is: pure hydrogen atmosphere, normal pressure, 530 DEG C, volume space velocity 2000 h
-1.Fresh catalyst and regenerative agent performance evaluation condition are: 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 process is carried out after fresh catalyst and regenerated catalyst reaction 72h.Product detects it through gas chromatograph and forms and calculate conversion ratio and selective.
Embodiment 1
Take commercial alumina carrier (γ phase, spherical, diameter 0.5mm, pore volume 0.71cm
3/ g, specific area 224m
2/ g) 30g, drip deionized water to just moistening, the volume consuming water is 27mL.By Sn element wt content 0.4% in final catalyst, the stannous chloride taken containing 0.12g Sn is dissolved in ethanol, uses ethanol to be settled to 27mL.By being added in 30g alumina support containing Sn ethanolic solution of configuring, mix, 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, the chloroplatinic acid taken containing Pt 0.18g is dissolved in deionized water, is settled to 27mL, be added to containing in Sn alumina support, mix, 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% water vapour, and air speed is 2000h
-1.By K element weight content 0.4% in final catalyst, the potassium nitrate taken containing K 0.12g is dissolved in deionized water, is settled to 27mL, be added in the catalyst precarsor after steam treatment, mix, ageing 2h at 70 DEG C, 100 DEG C of dry 6h, roasting 4h in 600 DEG C.In obtained catalyst, the weight content of each component is: Pt 0.5%, Sn 0.4%, K 0.4 %.Gained catalyst is designated as C-1.
C-1 fresh dose of reactivity worth is in table 1.
Embodiment 2
Unstripped gas is switched nitrogen after reacting 72h by fresh dose of C-1, and purge 1h, then temperature is down to 450 DEG C, and pressure rises to 3MPa, then passes into CO gas simultaneously, and volume space velocity is 2000h
-1, the processing time is 3h.After process terminates, switch to nitrogen, be down to normal pressure, and be down to 250 DEG C, then pass into the mist that volume content is 15% methyl alcohol, 1%HCl and nitrogen, gaseous mixture air speed is 300h
-1, process 2h.Then stop passing into HCl, continue the gaseous mixture process 1.5h with 15% methyl alcohol and nitrogen.After process terminates, switch to nitrogen, be warming up to 350 DEG C, pass into the mist that volume content is 0.6% oxygen and nitrogen, air speed is 1000h
-1, the processing time is 3h; Then improving oxygen volume content in gaseous mixture is 2%, by above-mentioned the same manner process; Be finally 4.5% by oxygen volume content in gaseous mixture, by above-mentioned the same manner process, obtain the agent of C-1 primary recycling.
C-1 primary recycling agent reactivity worth is in table 1.
Embodiment 3
After C-1 primary recycling agent reaction 72h, unstripped gas is switched nitrogen, and purge 1h, then temperature is down to 400 DEG C, and pressure rises to 4MPa, then passes into CO gas simultaneously, and volume space velocity is 1000h
-1, the processing time is 4h.After process terminates, switch to nitrogen, be down to normal pressure, and be down to 300 DEG C, then pass into the mist that volume content is 10% methyl alcohol, 1.5%HCl and nitrogen, gaseous mixture air speed is 200h
-1, process 1h.Then stop passing into HCl, continue the gaseous mixture process 2h with 10% methyl alcohol and nitrogen.After process terminates, switch to nitrogen, be warming up to 300 DEG C, pass into the mist that volume content is 0.8% oxygen and nitrogen, air speed is 500h
-1, the processing time is 4h; Then improving oxygen volume content in gaseous mixture is 2.5%, by above-mentioned the same manner process; Be finally 5% by oxygen volume content in gaseous mixture, by above-mentioned the same manner process, obtain the agent of C-1 secondary recycling.
C-1 secondary recycling agent reactivity worth is in table 1.
Embodiment 4
After C-1 secondary recycling agent reaction 72h, unstripped gas is switched nitrogen, and purge 1h, then temperature is down to 500 DEG C, and pressure rises to 2MPa, then passes into CO gas simultaneously, and volume space velocity is 3000h
-1, the processing time is 2h.After process terminates, switch to nitrogen, be down to normal pressure, and be down to 200 DEG C, then pass into the mist that volume content is 20% methyl alcohol, 0.5%HCl and nitrogen, gaseous mixture air speed is 400h
-1, process 3h.Then stop passing into HCl, continue the gaseous mixture process 1h with 20% methyl alcohol and nitrogen.After process terminates, switch to nitrogen, be warming up to-400 DEG C, pass into the mist that volume content is 0.4% oxygen and nitrogen, air speed is 1500h
-1, the processing time is 2h; Then improving oxygen volume content in gaseous mixture is 1.5%, by above-mentioned the same manner process; Be finally 4% by oxygen volume content in gaseous mixture, by above-mentioned the same manner process, obtain the agent of C-1 tertiary recycling.
C-1 tertiary recycling agent reactivity worth is in table 1.
Embodiment 5
After C-1 tertiary recycling agent reaction 72h, unstripped gas is switched nitrogen, and purge 1h, then temperature is down to 450 DEG C, and pressure rises to 3MPa, then passes into CO gas simultaneously, and volume space velocity is 2000h
-1, the processing time is 3h.After process terminates, switch to nitrogen, be down to normal pressure, and be down to 250 DEG C, then pass into the mist that volume content is 15% methyl alcohol, 1%HCl and nitrogen, gaseous mixture air speed is 300h
-1, process 2h.Then stop passing into HCl, continue the gaseous mixture process 1.5h with 15% methyl alcohol and nitrogen.After process terminates, switch to nitrogen, be warming up to 350 DEG C, passing into volume content is 0.6% oxygen, 0.03%N
2the mist of O and nitrogen, air speed is 1000h
-1, the processing time is 3h; Then improving oxygen volume content in gaseous mixture is 2%, by above-mentioned the same manner process; Be finally 4.5% by oxygen volume content in gaseous mixture, by above-mentioned the same manner process, obtain C-1 tetra-regenerative agents.
C-1 tetra-regenerative agent reactivity worth are in table 1.
Embodiment 6
After C-1 tetra-regenerative agent reaction 72h, regenerate by embodiment 2 mode, obtain C-1 five regenerative agents.In this way, then five times repeatedly, obtain C-1 ten regenerative agents.
C-1 five regenerative agent reactivity worth are in table 1.
Comparative example 1
Adopt conventional method coke-burning regeneration.
After fresh dose of C-1 reacts 72h, when being cooled to 350 DEG C after purging 1h with nitrogen, then switch to the mist of oxygen and nitrogen, in gaseous mixture, carrier of oxygen volume concentrations is 0.5%, and volume space velocity is 2000h
-1, process 6h; Again with the ramp to 450 DEG C of 1 DEG C/min, carry to 5% by carrier of oxygen volume concentrations in gaseous mixture, volume space velocity is 1000h
-1, process 4h; Again with the ramp to 500 DEG C of 1 DEG C/min, carry to 10% by carrier of oxygen volume concentrations in gaseous mixture, volume space velocity is 500h
-1, process 2h.Obtain C-1 regenerative agent, carry out performance evaluation, five times repeatedly.
Regenerated catalyst reactivity worth is in table 1.
Table 1
As can be seen from Table 1, after adopting the renovation process that the present invention relates to regenerate, compared with fresh catalyst, after reaction 1h, regenerated catalyst catalytic performance remains unchanged substantially, and after first time regenerated catalyst reaction 72h, slightly declining appears in conversion of propane, but after secondary recycling, 72h catalytic performance, with regard to kept stable, no longer changes.And in a comparative example, adopting conventional oxygen progressively coke-burning regeneration method, conversion ratio and selective appearance downward trend gradually after regenerated catalyst reaction 1h, regeneration effect is poor.
Claims (10)
1. a renovation process for catalyst for dehydrogenation of low-carbon paraffin, comprises following process: (1) uses CO gas treatment decaying catalyst; (2) decaying catalyst after step (1) being processed processes in the mixed atmosphere containing low-carbon oxygen-containing hydro carbons and HCl; (3) decaying catalyst after step (2) being processed processes in containing the mixed atmosphere of low-carbon oxygen-containing hydro carbons; (4) decaying catalyst after step (3) being processed carries out process of making charcoal in containing the mist of low concentration oxygen, obtains the catalyst after regenerating.
2. renovation process as claimed in claim 1, is characterized in that: step (1) described use CO gas treatment decaying catalyst, its condition is, temperature 300 DEG C-600 DEG C, Stress control presses catalyst volume air speed 500h in 1MPa-5MPa, CO intake
-1-5000h
-1, the processing time is 1h-12h.
3. renovation process as claimed in claim 1, it is characterized in that: decaying catalyst processes by step (2) in the mixed atmosphere containing low-carbon oxygen-containing hydro carbons and HCl, its condition is, temperature 150 DEG C-400 DEG C, pass into the mist containing low-carbon oxygen-containing hydro carbons, HCl and inert gas, in gaseous mixture, low-carbon oxygen-containing hydro carbons volume content is 5%-30%, and in gaseous mixture, HCl volume content is 0.1%-3%, and gaseous mixture volume space velocity is 100h
-1-1000h
-1processing time is 0.5h-8h, decaying catalyst is processing containing in low-carbon oxygen-containing hydro carbons mixed atmosphere by step (3), its condition is, temperature 150 DEG C-400 DEG C, pass into the mist containing low-carbon oxygen-containing hydro carbons and inert gas, 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, the processing time is 0.5h-4h
.
4. as claim 1 and renovation process according to claim 3, it is characterized in that: described low-carbon oxygen-containing hydro carbons carbon number is alcohols, the ethers of 1-2, as methyl alcohol, ethanol, ethylene glycol, dimethyl ether etc., be preferably methyl alcohol or dimethyl ether
.
5. renovation process as claimed in claim 1, it is characterized in that: step (4) described decaying catalyst carries out process of making charcoal in containing the mist of low concentration oxygen, its condition is, temperature 200 DEG C-450 DEG C, then mist that is oxygenous and inert gas is passed into, in gaseous mixture, oxygen volume content is 0.1%-1%, volume space velocity is 200h
-1-5000h
-1, the time is 1h-8h; Then keep temperature, mist air speed constant, oxygen volume content in gaseous mixture is increased to 1%-3%, continue process 1h-8h; In a manner described still, oxygen volume content in gaseous mixture is increased to 3%-6% and continues process of making charcoal finally.
6. renovation process as claimed in claim 5, is characterized in that: in the mixed atmosphere containing low concentration oxygen, can also containing appropriate N
2o gas, N
2the volumetric concentration of O is 0.001%-0.1%.
7. the renovation process as described in claim 3,5,6, is characterized in that: inert gas is nitrogen, argon gas or helium.
8. the renovation process as described in claim 1-7, it is characterized in that: described catalyst for dehydrogenation of low-carbon paraffin is platinum family loaded catalyst, be carrier with high-temperature inorganic oxide, one or more in the platinum in platinum family, palladium, iridium, rhodium or osmium are active component.
9. renovation process as claimed in claim 8, is characterized in that: described catalyst for dehydrogenation of low-carbon paraffin, with Al
2o
3for carrier, in catalyst Pt in element weight percentage for 0.01%-2%, Sn in element weight percentage for 0.1%-1%, K in element wt percentage composition for 0.1%-1%.
10. renovation process as described in claim 1-9, is characterized in that: the regeneration being applicable to the catalyst for dehydrogenation of low-carbon paraffin such as propane, iso-butane.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105689014A (en) * | 2016-03-14 | 2016-06-22 | 辽宁石油化工大学 | Regeneration method of precious metal dehydrogenation catalyst |
| CN105749990A (en) * | 2016-03-14 | 2016-07-13 | 辽宁石油化工大学 | Dehydrogenation catalyst regeneration method |
| CN108607619A (en) * | 2018-06-15 | 2018-10-02 | 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 |
| CN109382122A (en) * | 2017-08-11 | 2019-02-26 | 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 |
| CN112536064A (en) * | 2019-09-20 | 2021-03-23 | 中国石油化工股份有限公司 | Regeneration method of deactivated propane dehydrogenation catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56168838A (en) * | 1980-05-29 | 1981-12-25 | Mitsubishi Chem Ind Ltd | Regenerating method for dehydrogenation catalyst |
| 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 | Regeneration method of C10-C13 long-chain n-alkanes 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 |
-
2015
- 2015-05-13 CN CN201510241371.3A patent/CN104923258B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56168838A (en) * | 1980-05-29 | 1981-12-25 | Mitsubishi Chem Ind Ltd | Regenerating method for dehydrogenation catalyst |
| 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 | Regeneration method of C10-C13 long-chain n-alkanes 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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