CN104084218A - Method for regenerating light alkane dehydrogenation catalyst - Google Patents

Method for regenerating light alkane dehydrogenation catalyst Download PDF

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CN104084218A
CN104084218A CN201410326939.7A CN201410326939A CN104084218A CN 104084218 A CN104084218 A CN 104084218A CN 201410326939 A CN201410326939 A CN 201410326939A CN 104084218 A CN104084218 A CN 104084218A
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catalyst
low
dehydrogenation
temperature
aqueous solution
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CN104084218B (en
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黄力
王向华
吴沛成
刘宽
周钰明
张建国
孙勇
徐隽
白静玄
王丽
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Nanjing Wo Laide Energy Science Co Ltd
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Nanjing Wo Laide Energy Science Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a method for regenerating a light alkane dehydrogenation catalyst. The method comprises the following steps: by adopting charcoal burning outside a device, in an air atmosphere, burning coke deposited on the catalyst in three stages of maintaining for 0.5-2 hours at the temperature of 100-300 DEG C, maintaining for 1-5 hours at the temperature of 300-450 DEG C and maintaining for 2-10 hours at the temperature of 450-550 DEG C; impregnating the catalyst subjected to coke burning in an aqueous solution of chloride, drying, transferring the catalyst into a stainless steel reactor, roasting for 1-10 hours at the temperature of 400-600 DEG C in air atmosphere, injecting water vapor into the reactor, and maintaining for 1-6 hours at the temperature of 400-600 DEG C; and finally, reducing the catalyst for 1-10 hours in a hydrogen atmosphere at the temperature of 400-600 DEG C so as to obtain the regenerated light alkane dehydrogenation catalyst.

Description

A kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin
Technical field
The present invention relates to a kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin, be applicable to propane, catalytic dehydrogenation of isobutane reaction, belong to Industrial Catalysis technical field.
Background technology
Along with the demand of propylene and isobutene constantly increases, propylene enhancing and isobutene become the study hotspot in petrochemical industry gradually.The C of China 3, C 4aboundresources, burns but the overwhelming majority is but used as domestic fuel, has caused the huge waste of resource.By low-carbon alkanes catalytic dehydrogenating reaction, the large inexpensive low-carbon alkanes of amount is changed into the corresponding alkene of market high added value in short supply, there is important Research Significance and economic worth.Low-carbon alkanes catalytic dehydrogenating reaction is a strong endothermic process, need under the condition of high temperature, low pressure, carry out.Catalyst is easy to be covered by the carbon distribution being produced in course of reaction, and then inactivation.Because dehydrogenation is mainly precious metals pt series catalysts, production cost and the processing charges of catalyst are higher, and therefore, it is particularly important that the regeneration techniques of catalyst seems.
The Pt of report is the regeneration techniques of catalyst for dehydrogenation of low-carbon paraffin at present, as patent USP4133743, USP4210519, USP5087792, USP6916756, USP7585803, CN1541140A, CN101765576A, CN101940959A etc., its regenerative process generally comprises following several step: first, to the gaseous mixture that passes into air and inert gas in the reactor of catalyst is housed, make charcoal; The second, make charcoal after end, continue blowing air, with pump, in reactor, inject as the chlorine-containing compounds such as liquid chlorine, carbon tetrachloride and a certain amount of steam simultaneously, 500 ° of C left and right, carry out oxychloride reaction, the Pt metal on catalyst is disperseed again; The 3rd, by catalyst roasting under air atmosphere of mending after chlorine, rear steam dechlorination is finally reduced catalyst in hydrogen atmosphere, obtains the catalyst after regeneration.
In first step coke combustion, catalyst is easy to produce the situation of hot-spot, i.e. so-called " temperature runaway " phenomenon causes the permanent deactivation of catalyst.For fear of this phenomenon, in coke combustion, need to pass into a large amount of inert gases and as diluent, reduce the oxygen content in mist as nitrogen, steam etc. in reactor.Thereby the time of making charcoal is long, energy consumption is high, and gas consumption is large.The benefit chlorine process of second step requires high, and energy consumption is high, operates more complicatedly, and equipment investment is large.Therefore, the regeneration techniques of catalyst has necessity of further exploitation.CN103801330A discloses the renovation process of catalyst for dehydrogenation of low-carbon paraffin, and the catalyst after oxidation processes is carried out to synchronous dechlorination and reduction processing, has shortened the recovery time, has reduced energy consumption.CN101940959A discloses and a kind of catalyst for dehydrogenation of low-carbon paraffin has first been regenerated in air, and then the two step in-situ regeneration methods of regenerating in the mixed atmosphere of steam and air, has shortened the time of regeneration.Yet still there is the problems such as energy consumption is high, gas consumption is large in said method.
Summary of the invention
technical problem:the renovation process that the object of the present invention is to provide a kind of catalyst for dehydrogenation of low-carbon paraffin, the method is simple to operate, and energy consumption is low, and gas consumption is little, and the activity of the catalyst after regeneration and stability restoring are to the level of fresh catalyst .
technical scheme:a renovation process for catalyst for dehydrogenation of low-carbon paraffin, is characterized in that comprising the following steps:
The catalyst for dehydrogenation of low-carbon paraffin of step 1. carbon distribution inactivation adopts the device mode of making charcoal outward, in air atmosphere, carry out, charcoal temperature is divided into three steps, the 100-300 ° of C that is respectively low-temperature prewarming section maintains 0.5-2h, preferably 200-280 ° of C maintains 1-2h, and the 300-450 of a middle temperature charcoal burning step ° C maintains 1-5h, and preferably 320-400 ° of C maintains 2-4h, and the 450-550 of a high temperature charcoal burning step ° C maintains 2-10h, preferably 480-520 ° of C maintains 4-6h.
Step 2. is the muriatic aqueous solution of catalyst soakage of burning-off coke in step 1, makes on catalyst chlorine element in load, and dipping temperature is 30-150 ° of C, preferred 50-120 ° of C, and dip time is 0.5-8h, preferably 1-8h.Then through 50-200 ° of C, preferably 80-150 ° of C, is dried 1-10h, preferably 2-8h.The load capacity of chlorine is counted the 0.05-5wt% of catalyst gross mass with element, preferably 0.2-3wt%.
Step 3. moves into dried catalyst in step 2 in stainless steel reactor, 400-600 ° of C roasting 1-10h in air atmosphere, preferably 500-550 ° of C roasting 5-8h.Subsequently, continue blowing air, simultaneously to injected water steam in reactor, and maintain 1-6h at 400-600 ° of C, preferably 450-550 ° of C maintains 2-5h, and the mass percent of steam and air is 1:10-8:10, preferred 3:10-7:10.Finally by catalyst in hydrogen atmosphere, 400-600 ° of C reduction 1-10h, preferably 500-550 ° of C roasting 5-10h.Both the catalyst for dehydrogenation of low-carbon paraffin after must having regenerated.
In the regeneration step 1 of above-mentioned catalyst for dehydrogenation of low-carbon paraffin, to make charcoal be under air atmosphere, in swinging roaster or carry out in tunnel cave.
In the regeneration step 2 of above-mentioned catalyst for dehydrogenation of low-carbon paraffin, the aqueous chloride solution that impregnation steps is used can be one or more the combination in aqueous hydrochloric acid solution, aqueous ammonium chloride solution, the alchlor aqueous solution, the chloroacetic acid aqueous solution, the dichloroacetic acid aqueous solution, trichloroacetic acid solution, the sodium chloroacetate aqueous solution, water lithium chloride solution, sodium-chloride water solution, potassium chloride solution, magnesium chloride brine, calcium chloride water, the strontium chloride aqueous solution.
Above-mentioned catalyst for dehydrogenation of low-carbon paraffin is PtSn loaded catalyst, adopts infusion process preparation, and carrier is γ-Al 2o 3bead, also contains a kind of in rare-earth metals La, Ce in catalyst, and one or more the combination in alkali metal or alkali earth metal Li, Na, K, Mg, Ca, Sr is as auxiliary agent; The metal element weight of the load capacity of each component based in catalyst gross mass is just calculated as: the content of Pt element is 0.3-0.5wt%, the content of Sn element is 0.6-1.0wt%, the content of thulium is 0.8-1.0wt%, and the content of alkali metal or alkali earth metal is 0.2-1.0wt%.
Above-mentioned low-carbon alkanes is C 2-C 5alkane, be mainly propane and iso-butane.
beneficial effect:the invention provides a kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin.The method is simple to operate, and energy consumption is low, and gas consumption is little, and the catalyst performance after regeneration can return to the level of fresh catalyst, is the regeneration technology that is applicable to dehydrogenating low-carbon alkane commercial plant.
Feature of the present invention is:
(1) in the present invention, the coke combustion of decaying catalyst carries out in swinging roaster or in tunnel cave.In coke combustion, temperature is controlled evenly, can avoid " temperature runaway " phenomenon, has guaranteed that the pore structure of catalyst is stable, active metal Pt is not sintered on catalyst.In addition, in coke combustion, without diluent gas such as nitrogen, steam, reduced gas consumption.
(2) in renovation process of the present invention, the benefit chlorine step of catalyst is by the catalyst soakage chloride solution to making charcoal later, what in air atmosphere, roasting realized again after drying.Contrast tradition mend chlorine process to the method for injecting chloride solution and air in high-temperature reactor, technological requirement of the present invention is lower, and can avoid equipment corrosion, has merged oxychloride reactions steps and calcination activation step simultaneously, has reduced energy consumption.
(3) renovation process of the present invention, is applicable to the regeneration of catalyst for dehydrogenation of low-carbon paraffin, is specially adapted to the regeneration of dehydrogenating propane and dehydrogenation of isobutane catalyst.The activity of the catalyst after regeneration and stability can return to the level of fresh catalyst.
The specific embodiment
In the present invention, catalyst for dehydrogenation of low-carbon paraffin adopts infusion process preparation.Introduce the detailed preparation method of catalyst for dehydrogenation of low-carbon paraffin in the present invention below.
First, under 80 ° of C, with the nitrate aqueous solution dipping γ-Al of rare earth metal 2o 3bead 4h, after the dry 8h of 120 ° of C, then under air atmosphere 550 ° of C roasting 5h.With the nitrate aqueous solution dipping of alkali metal or alkaline-earth metal, 80 ° of C maintain 4h again, after the dry 8h of 120 ° of C, then under air atmosphere 550 ° of C roasting 5h.Then the liquid infiltration being made into the hydrochloric acid solution of chloroplatinic acid aqueous solution, the butter of tin aqueous solution and 2.5wt%, 80 ° of C maintain 4h.After the dry 8h of 120 ° of C, then under air atmosphere 500 ° of C roasting 5h, last 550 ° of C reduction 8h in hydrogen atmosphere, both catalyst for dehydrogenation of low-carbon paraffin.
In the present invention, catalyst for dehydrogenation of low-carbon paraffin can also adopt total immersion legal system standby.By γ-Al 2o 3bead is placed in the liquid infiltration that the hydrochloric acid solution of nitrate aqueous solution, chloroplatinic acid aqueous solution, the butter of tin aqueous solution and the 5wt% of nitrate aqueous solution, alkali metal or the alkaline-earth metal of rare earth metal is made into, and 80 ° of C maintain 6h.After the dry 8h of 120 ° of C, then under air atmosphere 550 ° of C roasting 10h, last 550 ° of C reduction 8h in hydrogen atmosphere, both catalyst for dehydrogenation of low-carbon paraffin.
Following examples are the further illustrating that the present invention is given of the renovation process by catalyst for dehydrogenation of low-carbon paraffin, but not limitation of the present invention.
embodiment 1:
First, under 80 ° of C, with lanthanum nitrate aqueous solution, flood γ-Al 2o 3bead 4h, after the dry 8h of 120 ° of C, then under air atmosphere 550 ° of C roasting 5h.With sodium nitrate aqueous solution dipping, 80 ° of C maintain 4h again.After the dry 8h of 120 ° of C, then under air atmosphere 550 ° of C roasting 5h.Then the liquid infiltration being made into the hydrochloric acid solution of chloroplatinic acid aqueous solution, the butter of tin aqueous solution and 2.5wt%, 80 ° of C maintain 4h.After the dry 8h of 120 ° of C, then under air atmosphere 500 ° of C roasting 5h, finally 550 ° of C reduction 8h in hydrogen atmosphere, make catalyst for dehydrogenation of low-carbon paraffin.The metal element weight of the load capacity of each component based in catalyst gross mass is just calculated as: Pt content is 0.5wt%; Sn content is 1.0wt%; Na content is 1.0wt%; La content is 1.0wt%.
Decaying catalyst is made charcoal in swinging roaster, and charcoal temperature is divided into three steps, and 280 ° of C that are respectively low-temperature prewarming section maintain 1h, and 350 ° of C of middle temperature charcoal burning step maintain 3h, and 500 ° of C of high temperature charcoal burning step maintain 5h.The catalyst soakage aqueous hydrochloric acid solution of burning-off coke, 50 ° of C maintain 8h, then in the dry 8h of 120 ° of C.The load capacity of chlorine is counted the 0.8wt% of catalyst gross mass with element
Subsequently, catalyst is moved in stainless steel reactor to 500 ° of C roasting 8h in air atmosphere.Then, continue blowing air, simultaneously to injected water steam in reactor, and maintain 4h at 500 ° of C.Wherein, the mass percent of steam and air is 3:10.Finally, by the catalyst after calcination activation, steam dechlorination in hydrogen atmosphere, 500 ° of C reduction 10h, the catalyst for dehydrogenation of low-carbon paraffin after both must having regenerated.
Appreciation condition: stainless steel reactor reacts, catalyst loading amount 1kg.Propane mixes with hydrogen and steam and by heater, is heated to predetermined temperature and enters beds and carry out catalytic dehydrogenating reaction.The initial temperature of dehydrogenation reaction is 550 ° of C, and reaction terminating temperature is 650 ° of C, and reaction pressure is 0.3Mpa, and hydrogen hydrocarbon mol ratio is 0.33, and propane mass space velocity is 8h -1, water hydrocarbon mol ratio is 0.3.Product with gas chromatographic analysis, is calculated the selective of the conversion ratio of propane and propylene according to the result of analyzing after cooling.
Evaluation result: fresh catalyst is evaluated 7d continuously, conversion of propane is 31.8%, Propylene Selectivity is 97.7%.Catalyst after regeneration is evaluated 7d continuously, and conversion of propane is 31.1%, and Propylene Selectivity is 97.9%.
embodiment 2:
First under 80 ° of C, with cerous nitrate aqueous solution dipping γ-Al 2o 3bead 4h, after the dry 8h of 120 ° of C, then under air atmosphere 550 ° of C roasting 5h.With Alkitrate dipping, 80 ° of C maintain 4h again.After the dry 8h of 120 ° of C, then under air atmosphere 550 ° of C roasting 5h.Then the liquid infiltration being made into the hydrochloric acid solution of chloroplatinic acid aqueous solution, the butter of tin aqueous solution and 2.5wt%, 80 ° of C maintain 4h.After the dry 8h of 120 ° of C, then under air atmosphere 500 ° of C roasting 5h, finally 550 ° of C reduction 8h in hydrogen atmosphere, make catalyst for dehydrogenation of low-carbon paraffin.The metal element weight of the load capacity of each component based in catalyst gross mass is just calculated as: Pt content is 0.5wt%; Sn content is 0.9wt%; K content is 0.8wt%; Ce content is 0.7wt%.
Decaying catalyst is made charcoal in swinging roaster, and charcoal temperature is divided into three steps, and 250 ° of C that are respectively low-temperature prewarming section maintain 1.5h, and 400 ° of C of middle temperature charcoal burning step maintain 2h, and 520 ° of C of high temperature charcoal burning step maintain 4h.The catalyst soakage alchlor aqueous solution of burning-off coke, 120 ° of C maintain 1h, then in the dry 8h of 120 ° of C.The load capacity of chlorine is counted the 1.5wt% of catalyst gross mass with element
Subsequently, catalyst is moved in stainless steel reactor to 500 ° of C roasting 8h in air atmosphere.Then, continue blowing air, simultaneously to injected water steam in reactor, and maintain 5h at 550 ° of C.Wherein, the mass percent of steam and air is 7:10.Finally, by the catalyst after calcination activation, steam dechlorination in hydrogen atmosphere, 500 ° of C reduction 10h, the catalyst for dehydrogenation of low-carbon paraffin after both must having regenerated.
Appreciation condition: stainless steel reactor reacts, catalyst loading amount 1kg.Propane mixes with hydrogen and steam and by heater, is heated to predetermined temperature and enters beds and carry out catalytic dehydrogenating reaction.The initial temperature of dehydrogenation reaction is 550 ° of C, and reaction terminating temperature is 650 ° of C, and reaction pressure is 0.3Mpa, and hydrogen hydrocarbon mol ratio is 0.33, and propane mass space velocity is 8h -1, water hydrocarbon mol ratio is 0.3.Product with gas chromatographic analysis, is calculated the selective of the conversion ratio of propane and propylene according to the result of analyzing after cooling.
Evaluation result: fresh catalyst is evaluated 6d continuously, conversion of propane is 32.3%, Propylene Selectivity is 98.4%.Catalyst after regeneration is evaluated 6d continuously, and conversion of propane is 31.9%, and Propylene Selectivity is 98.1%.
embodiment 3:
First, under 80 ° of C, with lanthanum nitrate aqueous solution, flood γ-Al 2o 3bead 4h, after the dry 8h of 120 ° of C, then under air atmosphere 550 ° of C roasting 5h.With magnesium nitrate aqueous solution dipping, 80 ° of C maintain 4h again.After the dry 8h of 120 ° of C, then under air atmosphere 550 ° of C roasting 5h.Then the liquid infiltration being made into the hydrochloric acid solution of chloroplatinic acid aqueous solution, the butter of tin aqueous solution and 2.5wt%, 80 ° of C maintain 4h.After the dry 8h of 120 ° of C, then under air atmosphere 500 ° of C roasting 5h, finally 550 ° of C reduction 8h in hydrogen atmosphere, make catalyst for dehydrogenation of low-carbon paraffin.The metal element weight of the load capacity of each component based in catalyst gross mass is just calculated as: Pt content is 0.5wt%; Sn content is 0.6wt%; Mg content is 0.8wt%; La content is 0.9wt%.
Decaying catalyst is made charcoal in tunnel cave, and charcoal temperature is divided into three steps, and 230 ° of C that are respectively low-temperature prewarming section maintain 2h, and 320 ° of C of middle temperature charcoal burning step maintain 4h, and 480 ° of C of high temperature charcoal burning step maintain 6h.The catalyst soakage aqueous ammonium chloride solution of burning-off coke, 100 ° of C maintain 4h, then in the dry 8h of 120 ° of C.The load capacity of chlorine is counted the 0.2wt% of catalyst gross mass with element
Subsequently, catalyst is moved in stainless steel reactor to 550 ° of C roasting 5h in air atmosphere.Then, continue blowing air, simultaneously to injected water steam in reactor, and maintain 2h at 500 ° of C.Wherein, the mass percent of steam and air is 5:10.Finally, by the catalyst after calcination activation, steam dechlorination in hydrogen atmosphere, 550 ° of C reduction 5h, the catalyst for dehydrogenation of low-carbon paraffin after both must having regenerated.
Appreciation condition: stainless steel reactor reacts, catalyst loading amount 1kg.Iso-butane mixes with hydrogen and steam and by heater, is heated to predetermined temperature and enters beds and carry out catalytic dehydrogenating reaction.The initial temperature of dehydrogenation reaction is 550 ° of C, and reaction terminating temperature is 620 ° of C, and reaction pressure is 0.1Mpa, hydrogen hydrocarbon mol ratio 2.0, and propane mass space velocity is 5h -1, water hydrocarbon mol ratio is 0.1.Product with gas chromatographic analysis, is calculated the selective of the conversion ratio of iso-butane and isobutene according to the result of analyzing after cooling.
Evaluation result: fresh catalyst is evaluated 7d continuously, iso-butane conversion ratio is 35.6%, selective isobutene is 98.5%.Catalyst after regeneration is evaluated 7d continuously, and iso-butane conversion ratio is 35.0%, and selective isobutene is 99.0%.
embodiment 4:
First under 80 ° of C, with cerous nitrate aqueous solution dipping γ-Al 2o 3bead 4h, after the dry 8h of 120 ° of C, then under air atmosphere 550 ° of C roasting 5h.With calcium nitrate aqueous solution dipping, 80 ° of C maintain 4h again.After the dry 8h of 120 ° of C, then under air atmosphere 550 ° of C roasting 5h.Then the liquid infiltration being made into the hydrochloric acid solution of chloroplatinic acid aqueous solution, the butter of tin aqueous solution and 2.5wt%, 80 ° of C maintain 4h.After the dry 8h of 120 ° of C, then under air atmosphere 500 ° of C roasting 5h, finally 550 ° of C reduction 8h in hydrogen atmosphere, make catalyst for dehydrogenation of low-carbon paraffin.The metal element weight of the load capacity of each component based in catalyst gross mass is just calculated as: Pt content is 0.5wt%; Sn content is 1.0wt%; Ca content is 1.0wt%; Ce content is 0.8wt%.
Decaying catalyst is made charcoal in tunnel cave, and charcoal temperature is divided into three steps, and 200 ° of C that are respectively low-temperature prewarming section maintain 1.5h, and 380 ° of C of middle temperature charcoal burning step maintain 2h, and 500 ° of C of high temperature charcoal burning step maintain 5h.The catalyst soakage dichloroacetic acid of burning-off coke and the mixed aqueous solution of hydrochloric acid, 80 ° of C maintain 6h, then in the dry 8h of 120 ° of C.The load capacity of chlorine is counted the 3wt% of catalyst gross mass with element
Subsequently, catalyst is moved in stainless steel reactor to 550 ° of C roasting 5h in air atmosphere.Then, continue blowing air, simultaneously to injected water steam in reactor, and maintain 4h at 550 ° of C.Wherein, the mass percent of steam and air is 5:10.Finally, by the catalyst after calcination activation, steam dechlorination in hydrogen atmosphere, 550 ° of C reduction 5h, the catalyst for dehydrogenation of low-carbon paraffin after both must having regenerated.
Appreciation condition: stainless steel reactor reacts, catalyst loading amount 1kg, prereduction temperature is 600 ° of C, time 10h.Iso-butane mixes with hydrogen and steam and by heater, is heated to predetermined temperature and enters beds and carry out catalytic dehydrogenating reaction.The initial temperature of dehydrogenation reaction is 550 ° of C, and reaction terminating temperature is 620 ° of C, and reaction pressure is 0.1Mpa, hydrogen hydrocarbon mol ratio 2.0, and propane mass space velocity is 5h -1, water hydrocarbon mol ratio is 0.1.Product with gas chromatographic analysis, is calculated the selective of the conversion ratio of iso-butane and isobutene according to the result of analyzing after cooling.
Evaluation result: fresh catalyst is evaluated 7d continuously, iso-butane conversion ratio is 34.2%, selective isobutene is 97.7%.Catalyst after regeneration is evaluated 7d continuously, and iso-butane conversion ratio is 34.6%, and selective isobutene is 97.3%.
embodiment 5:
By γ-Al 2o 3bead is placed in the liquid infiltration that the hydrochloric acid solution of lanthanum nitrate aqueous solution, the lithium nitrate aqueous solution, the strontium nitrate aqueous solution, chloroplatinic acid aqueous solution, the butter of tin aqueous solution and 5wt% is made into, and 80 ° of C maintain 6h.After the dry 8h of 120 ° of C, then under air atmosphere 550 ° of C roasting 10h, last 550 ° of C reduction 8h in hydrogen atmosphere, both catalyst for dehydrogenation of low-carbon paraffin.The metal element weight of the load capacity of each component based in catalyst gross mass is just calculated as: Pt content is 0.5wt%, and Sn content is 1.0wt%, and Li content is 0.8wt%, and Sr content is 0.2wt%, and La content is 1.0wt%.
Decaying catalyst is made charcoal in tunnel cave, and charcoal temperature is divided into three steps, and 200 ° of C that are respectively low-temperature prewarming section maintain 1.5h, and 380 ° of C of middle temperature charcoal burning step maintain 2h, and 500 ° of C of high temperature charcoal burning step maintain 5h.The catalyst soakage potassium chloride of burning-off coke and the mixed aqueous solution of magnesium chloride, 80 ° of C maintain 6h, then in the dry 8h of 120 ° of C.The load capacity of chlorine is counted the 2.5wt% of catalyst gross mass with element
Subsequently, catalyst is moved in stainless steel reactor to 550 ° of C roasting 5h in air atmosphere.Then, continue blowing air, simultaneously to injected water steam in reactor, and maintain 4h at 550 ° of C.Wherein, the mass percent of steam and air is 4:10.Finally, by the catalyst after calcination activation, steam dechlorination in hydrogen atmosphere, 550 ° of C reduction 5h, the catalyst for dehydrogenation of low-carbon paraffin after both must having regenerated.
Appreciation condition: stainless steel reactor reacts, catalyst loading amount 1kg.Iso-butane mixes with hydrogen and steam and by heater, is heated to predetermined temperature and enters beds and carry out catalytic dehydrogenating reaction.The initial temperature of dehydrogenation reaction is 550 ° of C, and reaction terminating temperature is 620 ° of C, and reaction pressure is 0.1Mpa, hydrogen hydrocarbon mol ratio 2.0, and propane mass space velocity is 5h -1, water hydrocarbon mol ratio is 0.1.Product with gas chromatographic analysis, is calculated the selective of the conversion ratio of iso-butane and isobutene according to the result of analyzing after cooling.
Evaluation result: fresh catalyst is evaluated 5d continuously, iso-butane conversion ratio is 32.2%, selective isobutene is 95.7%.Catalyst after regeneration is evaluated 5d continuously, and iso-butane conversion ratio is 31.6%, and selective isobutene is 96.3%.

Claims (5)

1. a renovation process for catalyst for dehydrogenation of low-carbon paraffin, is characterized in that comprising the following steps:
The catalyst for dehydrogenation of low-carbon paraffin of step 1. pair carbon distribution inactivation adopts device to make charcoal outward, in air atmosphere, carry out, charcoal temperature is divided into three steps, the 100-300 ° of C that is respectively low-temperature prewarming section maintains 0.5-2h, the 300-450 of a middle temperature charcoal burning step ° C maintains 1-5h, and the 450-550 of a high temperature charcoal burning step ° C maintains 2-10h;
Step 2. is by the muriatic aqueous solution of catalyst soakage of burning-off coke in step 1, make on catalyst chlorine element in load, dipping temperature is 30-150 ° of C, dip time is 0.5-8h, then through 80-150 ° of C, dry 5-8h, the load capacity of chlorine is counted the 0.05-5wt% of catalyst gross mass with element;
Step 3. moves into dried catalyst in step 2 in stainless steel reactor, 400-600 ° of C roasting 1-10h in air atmosphere, subsequently, continue blowing air, simultaneously to injected water steam in reactor, and maintain 1-6h at 400-600 ° of C, wherein, the mass percent of steam and air is 1:10-8:10, finally by catalyst in hydrogen atmosphere, 400-600 ° of C reduction 1-10h, the catalyst for dehydrogenation of low-carbon paraffin after both must having regenerated.
2. the renovation process of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, is characterized in that: step 1 is under air atmosphere, in swinging roaster or carry out in tunnel cave.
3. the renovation process of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, it is characterized in that: in step 2, the aqueous chloride solution that the dip operation of catalyst is used can be one or more the combination in aqueous hydrochloric acid solution, aqueous ammonium chloride solution, the alchlor aqueous solution, the chloroacetic acid aqueous solution, the dichloroacetic acid aqueous solution, trichloroacetic acid solution, the sodium chloroacetate aqueous solution, water lithium chloride solution, sodium-chloride water solution, potassium chloride solution, magnesium chloride brine, calcium chloride water, the strontium chloride aqueous solution.
4. the renovation process of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, the catalyst for dehydrogenation of low-carbon paraffin using is PtSn loaded catalyst, carrier is γ-Al 2o 3bead, also contains a kind of in rare-earth metals La, Ce in catalyst, and one or more the combination in alkali metal or alkali earth metal Li, Na, K, Mg, Ca, Sr is as auxiliary agent; The metal element weight of the load capacity of each component based in catalyst gross mass is just calculated as: the content of Pt element is 0.3-0.5wt%, the content of Sn element is 0.6-1.0wt%, the content of thulium is 0.8-1.0wt%, and the content of alkali metal or alkali earth metal is 0.2-1.0wt%.
5. the renovation process of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, low-carbon alkanes is C 2-C 5alkane, be mainly propane and iso-butane.
CN201410326939.7A 2014-07-10 2014-07-10 A kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin Expired - Fee Related CN104084218B (en)

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CN111790382A (en) * 2020-08-13 2020-10-20 福州大学 Active regeneration method for Pt-based catalyst for preparing propylene by propane dehydrogenation

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