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

Method for regenerating light alkane dehydrogenation catalyst Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
catalyst
low
dehydrogenation
temperature
aqueous solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410326939.7A
Other languages
Chinese (zh)
Other versions
CN104084218B (en
Inventor
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Wo Laide Energy Science Co Ltd
Original Assignee
Nanjing Wo Laide Energy Science Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Wo Laide Energy Science Co Ltd filed Critical Nanjing Wo Laide Energy Science Co Ltd
Priority to CN201410326939.7A priority Critical patent/CN104084218B/en
Publication of CN104084218A publication Critical patent/CN104084218A/en
Application granted granted Critical
Publication of CN104084218B publication Critical patent/CN104084218B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410326939.7A CN104084218B (en) 2014-07-10 2014-07-10 A kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410326939.7A CN104084218B (en) 2014-07-10 2014-07-10 A kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin

Publications (2)

Publication Number Publication Date
CN104084218A true CN104084218A (en) 2014-10-08
CN104084218B CN104084218B (en) 2016-03-02

Family

ID=51632035

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410326939.7A Expired - Fee Related CN104084218B (en) 2014-07-10 2014-07-10 A kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin

Country Status (1)

Country Link
CN (1) CN104084218B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016069918A1 (en) * 2014-10-29 2016-05-06 Flint Hills Resources, Lp Methods for dehydrogenating one or more alkanes
CN106391138A (en) * 2016-08-31 2017-02-15 中国科学院福建物质结构研究所 In-situ regeneration method of Pd catalyst for CO dehydrogenation purification
CN107497420A (en) * 2017-09-07 2017-12-22 浙江卫星能源有限公司 A kind of renovation process of carbon containing noble metal catalyst
CN110841726A (en) * 2019-12-02 2020-02-28 西安凯立新材料股份有限公司 Regeneration method of catalyst for isobutane dehydrogenation
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
WO2021128867A1 (en) * 2019-12-26 2021-07-01 润和催化材料(浙江)有限公司 Catalyst for preparing propylene by propane dehydrogenation, preparation method therefor, and use thereof
CN113968767A (en) * 2020-07-23 2022-01-25 中国石油天然气股份有限公司 Method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4210519A (en) * 1971-11-16 1980-07-01 Intitut Francals du Petrole Process and apparatus for hydrocarbon conversion
CN101623633A (en) * 2009-08-17 2010-01-13 清华大学 Catalyst for preparing olefin by dehydrogenating low-carbon alkane, and preparation method and application thereof
CN101773850A (en) * 2010-01-28 2010-07-14 清华大学 Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and application thereof
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
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4210519A (en) * 1971-11-16 1980-07-01 Intitut Francals du Petrole Process and apparatus for hydrocarbon conversion
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
CN101623633A (en) * 2009-08-17 2010-01-13 清华大学 Catalyst for preparing olefin by dehydrogenating low-carbon alkane, and preparation method and application thereof
CN101773850A (en) * 2010-01-28 2010-07-14 清华大学 Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and application thereof
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

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016069918A1 (en) * 2014-10-29 2016-05-06 Flint Hills Resources, Lp Methods for dehydrogenating one or more alkanes
CN106391138A (en) * 2016-08-31 2017-02-15 中国科学院福建物质结构研究所 In-situ regeneration method of Pd catalyst for CO dehydrogenation purification
CN106391138B (en) * 2016-08-31 2019-05-17 中国科学院福建物质结构研究所 A kind of CO dehydrogenation purification in situ regeneration method of Pd catalyst
CN107497420A (en) * 2017-09-07 2017-12-22 浙江卫星能源有限公司 A kind of renovation process of carbon containing noble metal catalyst
CN107497420B (en) * 2017-09-07 2021-03-05 浙江卫星能源有限公司 Regeneration method of carbon-containing noble metal catalyst
CN110841726A (en) * 2019-12-02 2020-02-28 西安凯立新材料股份有限公司 Regeneration method of catalyst for isobutane dehydrogenation
WO2021128867A1 (en) * 2019-12-26 2021-07-01 润和催化材料(浙江)有限公司 Catalyst for preparing propylene by propane dehydrogenation, preparation method therefor, and use thereof
CN113968767A (en) * 2020-07-23 2022-01-25 中国石油天然气股份有限公司 Method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane
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

Also Published As

Publication number Publication date
CN104084218B (en) 2016-03-02

Similar Documents

Publication Publication Date Title
CN104084218B (en) A kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin
CN105251486A (en) Supported platinum group catalyst applied to propane dehydrogenation propylene preparation and preparation method of supported platinum group catalyst
CN102049267B (en) Catalyst for preparing propylene by dehydrogenating propane as well as preparation method and applications thereof
CN101380587B (en) Propane dehydrogenation catalyst to produce propylene and preparation method thereof
CN102000593B (en) Catalyst for preparation of isobutene by isobutene dehydrogenation as well as preparation process and dehydrogenation process thereof
CN101259408B (en) Catalyst for removing flue gas NOx under low temperature and preparation and application
CN103990454A (en) Low-carbon alkane dehydrogenation catalyst as well as preparation method and low-carbon alkane dehydrogenation process thereof
CN101513613B (en) Propane dehydrogenation catalyst with hetero atom molecule sieve as carrier and preparation method thereof
CN104084197B (en) A kind of be carrier ruthenium system ammonia synthesis catalyst and the preparation thereof of graphitization active carbon
CN103801330B (en) A kind of renovation process of dehydrogenation
CN104174396A (en) Silver-containing light alkane dehydrogenation catalyst and preparation method thereof
CN105032503A (en) Regeneration method of noble metal catalyst
CN102836722B (en) Catalyst used in preparation of fluorine-containing olefin through dehydrohalogenation of halohydrofluoroalkane and preparation method of catalyst
CN103418367A (en) Catalyst used for preparing fluorinated alkene with chloro-fluoro alkane and preparation method thereof
CN109012676A (en) A kind of catalyst and the preparation method and application thereof preparing HF hydrocarbon for hydrofluoroalkane gas phase removal HF
CN101543781B (en) Catalyst for preparing propylene by oxidizing and dehydrogenating propane and preparation method thereof
CN102806095A (en) Multi-component non-mercury accelerant for preparing vinyl chloride through acetylene hydrochlorination and application method of multi-component non-mercury accelerant
CN102553585B (en) Sulfur-tolerant catalyst for gas deoxidation as well as preparation method and application thereof
CN105396582A (en) Propane dehydrogenation propylene preparation catalyst, preparation method and applications thereof
CN109261142A (en) A kind of catalyst and preparation method thereof preparing tetrafluoroethene and hexafluoropropene for fluoroform catalytic pyrolysis
CN103801331A (en) Regeneration method for low-carbon alkane dehydrogenation catalyst
CN102188985B (en) Carbon four-fraction selective hydrogenation catalyst and preparation method thereof
CN104941638B (en) A kind of dehydrogenation and its preparation and application
CN1322922C (en) Platinum catalyst for preparing cyclohexane by hydrogenating benzene and its preparing process
CN104190456A (en) Regeneration method for nickel phosphide dehydrogenation catalyst and application method of regenerated catalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160302

Termination date: 20160710