CN104084218B - A kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin - Google Patents
A kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin Download PDFInfo
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Abstract
The invention discloses a kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin.The method adopts outside device and makes charcoal, and first in air atmosphere, point 100-300 ° of C maintenance 0.5-2h, 300-450 ° of C maintenance 1-5h, a 450-550 ° of C maintains 2-10h three phases and burn deposition coke on a catalyst.Then by the muriatic aqueous solution of catalyst soakage after making charcoal, after drying, moved into by catalyst in stainless steel reactor, in air atmosphere, 400-600 ° of C roasting 1-10h, injects steam subsequently in reactor, and maintains 1-6h at 400-600 ° of C.Finally by catalyst 400-600 ° of C reduction 1-10h in hydrogen atmosphere, the catalyst for dehydrogenation of low-carbon paraffin after both must regenerating.
Description
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, but the overwhelming majority is but used as domestic fuel burns, and causes the huge waste of resource.By low-carbon alkanes catalytic dehydrogenating reaction, amount low-carbon alkanes inexpensive is greatly 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, needs to carry out under the condition of high temperature, low pressure.Catalyst be easy to by course of reaction the carbon distribution that produces cover, and then inactivation.Due to dehydrogenation mainly precious metals pt series catalysts, production cost and the processing charges of catalyst are higher, and therefore, the regeneration techniques of catalyst seems particularly important.
The regeneration techniques of the Pt system catalyst for dehydrogenation of low-carbon paraffin of current report, as patent USP4133743, USP4210519, USP5087792, USP6916756, USP7585803, CN1541140A, CN101765576A, CN101940959A etc., its regenerative process generally comprises following several step: first, in the reactor that catalyst is housed, pass into the gaseous mixture of air and inert gas, make charcoal; The second, make charcoal after terminating, continue blowing air, inject in reactor as the chlorine-containing compound such as liquid chlorine, carbon tetrachloride and a certain amount of steam with pump simultaneously, carry out oxychloride reaction at 500 ° of about C, the Pt metal on catalyst is disperseed again; 3rd, will mend the catalyst roasting in air atmosphere after chlorine, rear steam dechlorination, finally reduces catalyst in hydrogen atmosphere, obtains the catalyst after regeneration.
In first step coke combustion, catalyst is easy to the situation producing hot-spot, and namely so-called " temperature runaway " phenomenon, causes the permanent deactivation of catalyst.In order to avoid this phenomenon, need in coke combustion to pass in reactor a large amount of inert gases as nitrogen, steam etc. as diluent to reduce the oxygen content in mist.Thus the time of making charcoal is long, and energy consumption is high, and gas consumption is large.The benefit chlorine process of second step requires high, and energy consumption is high, and operate more complicated, equipment investment is large.Therefore, the regeneration techniques of catalyst has necessity of exploitation further.CN103801330A discloses the renovation process of catalyst for dehydrogenation of low-carbon paraffin, the catalyst after oxidation processes is carried out synchronous dechlorination and reduction treatment, shortens the recovery time, reduce energy consumption.CN101940959A discloses and a kind of first to be regenerated in atmosphere by catalyst for dehydrogenation of low-carbon paraffin, and then the two step in-situ regeneration methods regenerated in the mixed atmosphere of steam and air, shortens the time of regeneration.But 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 object of the present invention is to provide 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 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 mode of making charcoal outside device, carry out in air atmosphere, charcoal temperature is divided into three steps, the 100-300 ° of C being respectively low-temperature prewarming section maintains 0.5-2h, preferred 200-280 ° of C maintains 1-2h, and 300-450 ° of C of middle temperature charcoal burning step maintains 1-5h, preferred 320-400 ° of C and maintain 2-4h, and the 450-550 of high temperature charcoal burning step ° of C maintains 2-10h, preferred 480-520 ° of C maintenance 4-6h.
Step 2. is by the muriatic aqueous solution of catalyst soakage of burning-off coke in step 1, and to make on catalyst chlorine element in load, dipping temperature is 30-150 ° of C, preferred 50-120 ° C, and dip time is 0.5-8h, preferred 1-8h.Then through 50-200 ° of C, preferred 80-150 ° C, dry 1-10h, preferred 2-8h.The load capacity of chlorine counts the 0.05-5wt% of catalyst gross mass, preferred 0.2-3wt% with element.
Catalyst dried in step 2 moves in stainless steel reactor by step 3., 400-600 ° of C roasting 1-10h in air atmosphere, preferred 500-550 ° of C roasting 5-8h.Subsequently, continue blowing air, inject steam simultaneously in reactor, and maintain 1-6h, preferred 450-550 ° of C maintenance 2-5h at 400-600 ° of C, 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 reduces 1-10h, preferred 500-550 ° of C roasting 5-10h.Both the catalyst for dehydrogenation of low-carbon paraffin after must regenerating.
Making charcoal in the regeneration step 1 of above-mentioned catalyst for dehydrogenation of low-carbon paraffin is in air atmosphere, carries out in swinging roaster or 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 uses can be the combination of one or more 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, and adopt infusion process preparation, carrier is γ-Al
2o
3bead, also containing rare-earth metals La, one in Ce in catalyst, and the combination of one or more in alkali metal or alkali earth metal Li, Na, K, Mg, Ca, Sr is as auxiliary agent; The load capacity of each component is just calculated as based on the metal element weight in catalyst gross mass: 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, 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 being 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 controls evenly, can avoid " temperature runaway " phenomenon, ensure that the pore structure of catalyst is stable, activity over catalysts Pt metal is not sintered.In addition, without the need to the diluent gas such as nitrogen, steam in coke combustion, gas consumption is reduced.
(2) in renovation process of the present invention, the benefit chlorine step of catalyst is by the catalyst soakage chloride solution of making charcoal later, and in air atmosphere, roasting realizes again after drying.Contrast tradition mends the method injecting chloride solution and air in high-temperature reactor of chlorine process, and technological requirement of the present invention is lower, and can avoid equipment corrosion, incorporates oxychloride reactions steps and calcination activation step simultaneously, reduces 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.
Detailed description of the invention
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 550 ° of C roasting 5h in air atmosphere.Again with the nitrate aqueous solution dipping of alkali metal or alkaline-earth metal, 80 ° of C maintain 4h, after the dry 8h of 120 ° of C, then 550 ° of C roasting 5h in air atmosphere.Then with the liquid infiltration that the hydrochloric acid solution of chloroplatinic acid aqueous solution, the butter of tin aqueous solution and 2.5wt% is made into, 80 ° of C maintain 4h.After the dry 8h of 120 ° of C, then 500 ° of C roasting 5h in air atmosphere, finally in hydrogen atmosphere, 550 ° of C reduce 8h, 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
3the liquid infiltration that the hydrochloric acid solution that bead is placed in the nitrate aqueous solution of the nitrate aqueous solution of rare earth metal, alkali metal or alkaline-earth metal, chloroplatinic acid aqueous solution, the butter of tin aqueous solution and 5wt% is made into, 80 ° of C maintain 6h.After the dry 8h of 120 ° of C, then 550 ° of C roasting 10h in air atmosphere, finally in hydrogen atmosphere, 550 ° of C reduce 8h, both catalyst for dehydrogenation of low-carbon paraffin.
Following examples are further illustrating of being given the present invention by the renovation process of catalyst for dehydrogenation of low-carbon paraffin, but not limitation of the present invention.
embodiment 1:
First under 80 ° of C, flood γ-Al with lanthanum nitrate aqueous solution
2o
3bead 4h, after the dry 8h of 120 ° of C, then 550 ° of C roasting 5h in air atmosphere.Again with sodium nitrate aqueous solution dipping, 80 ° of C maintain 4h.After the dry 8h of 120 ° of C, then 550 ° of C roasting 5h in air atmosphere.Then with the liquid infiltration that the hydrochloric acid solution of chloroplatinic acid aqueous solution, the butter of tin aqueous solution and 2.5wt% is made into, 80 ° of C maintain 4h.After the dry 8h of 120 ° of C, then 500 ° of C roasting 5h in air atmosphere, finally in hydrogen atmosphere, 550 ° of C reduce 8h, obtained catalyst for dehydrogenation of low-carbon paraffin.The load capacity of each component is just calculated as based on the metal element weight in catalyst gross mass: 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 the 280 ° of C being respectively low-temperature prewarming section maintain 1h, and 350 ° of C of middle temperature charcoal burning step maintain 3h, and 500 of high temperature charcoal burning step ° of C 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 counts the 0.8wt% of catalyst gross mass with element
Subsequently, catalyst is moved in stainless steel reactor, 500 ° of C roasting 8h in air atmosphere.Then, continue blowing air, in reactor, inject steam simultaneously, 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 regenerating.
Appreciation condition: stainless steel reactor reacts, catalyst loading amount 1kg.Be heated to predetermined temperature through heater after propane mixes with hydrogen and steam to enter 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, calculates the conversion ratio of propane and the selective of propylene according to the result analyzed after cooling.
Evaluation result: fresh catalyst evaluates 7d continuously, conversion of propane is 31.8%, and Propylene Selectivity is 97.7%.Catalyst after regeneration evaluates 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 impregnation γ-Al
2o
3bead 4h, after the dry 8h of 120 ° of C, then 550 ° of C roasting 5h in air atmosphere.Again with Alkitrate dipping, 80 ° of C maintain 4h.After the dry 8h of 120 ° of C, then 550 ° of C roasting 5h in air atmosphere.Then with the liquid infiltration that the hydrochloric acid solution of chloroplatinic acid aqueous solution, the butter of tin aqueous solution and 2.5wt% is made into, 80 ° of C maintain 4h.After the dry 8h of 120 ° of C, then 500 ° of C roasting 5h in air atmosphere, finally in hydrogen atmosphere, 550 ° of C reduce 8h, obtained catalyst for dehydrogenation of low-carbon paraffin.The load capacity of each component is just calculated as based on the metal element weight in catalyst gross mass: 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 the 250 ° of C being respectively low-temperature prewarming section maintain 1.5h, and 400 ° of C of middle temperature charcoal burning step maintain 2h, and 520 of high temperature charcoal burning step ° of C 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 counts the 1.5wt% of catalyst gross mass with element
Subsequently, catalyst is moved in stainless steel reactor, 500 ° of C roasting 8h in air atmosphere.Then, continue blowing air, in reactor, inject steam simultaneously, 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 regenerating.
Appreciation condition: stainless steel reactor reacts, catalyst loading amount 1kg.Be heated to predetermined temperature through heater after propane mixes with hydrogen and steam to enter 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, calculates the conversion ratio of propane and the selective of propylene according to the result analyzed after cooling.
Evaluation result: fresh catalyst evaluates 6d continuously, conversion of propane is 32.3%, and Propylene Selectivity is 98.4%.Catalyst after regeneration evaluates 6d continuously, and conversion of propane is 31.9%, and Propylene Selectivity is 98.1%.
embodiment 3:
First under 80 ° of C, flood γ-Al with lanthanum nitrate aqueous solution
2o
3bead 4h, after the dry 8h of 120 ° of C, then 550 ° of C roasting 5h in air atmosphere.Again with magnesium nitrate aqueous solution dipping, 80 ° of C maintain 4h.After the dry 8h of 120 ° of C, then 550 ° of C roasting 5h in air atmosphere.Then with the liquid infiltration that the hydrochloric acid solution of chloroplatinic acid aqueous solution, the butter of tin aqueous solution and 2.5wt% is made into, 80 ° of C maintain 4h.After the dry 8h of 120 ° of C, then 500 ° of C roasting 5h in air atmosphere, finally in hydrogen atmosphere, 550 ° of C reduce 8h, obtained catalyst for dehydrogenation of low-carbon paraffin.The load capacity of each component is just calculated as based on the metal element weight in catalyst gross mass: 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 the 230 ° of C being respectively low-temperature prewarming section maintain 2h, and 320 ° of C of middle temperature charcoal burning step maintain 4h, and 480 of high temperature charcoal burning step ° of C 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 counts the 0.2wt% of catalyst gross mass with element
Subsequently, catalyst is moved in stainless steel reactor, 550 ° of C roasting 5h in air atmosphere.Then, continue blowing air, in reactor, inject steam simultaneously, 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 regenerating.
Appreciation condition: stainless steel reactor reacts, catalyst loading amount 1kg.Be heated to predetermined temperature through heater after iso-butane mixes with hydrogen and steam to enter 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, calculates the conversion ratio of iso-butane and the selective of isobutene according to the result analyzed after cooling.
Evaluation result: fresh catalyst evaluates 7d continuously, iso-butane conversion ratio is 35.6%, and selective isobutene is 98.5%.Catalyst after regeneration evaluates 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 impregnation γ-Al
2o
3bead 4h, after the dry 8h of 120 ° of C, then 550 ° of C roasting 5h in air atmosphere.Again with calcium nitrate aqueous solution dipping, 80 ° of C maintain 4h.After the dry 8h of 120 ° of C, then 550 ° of C roasting 5h in air atmosphere.Then with the liquid infiltration that the hydrochloric acid solution of chloroplatinic acid aqueous solution, the butter of tin aqueous solution and 2.5wt% is made into, 80 ° of C maintain 4h.After the dry 8h of 120 ° of C, then 500 ° of C roasting 5h in air atmosphere, finally in hydrogen atmosphere, 550 ° of C reduce 8h, obtained catalyst for dehydrogenation of low-carbon paraffin.The load capacity of each component is just calculated as based on the metal element weight in catalyst gross mass: 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 the 200 ° of C being respectively low-temperature prewarming section maintain 1.5h, and 380 ° of C of middle temperature charcoal burning step maintain 2h, and 500 of high temperature charcoal burning step ° of C 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 counts the 3wt% of catalyst gross mass with element
Subsequently, catalyst is moved in stainless steel reactor, 550 ° of C roasting 5h in air atmosphere.Then, continue blowing air, in reactor, inject steam simultaneously, 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 regenerating.
Appreciation condition: stainless steel reactor reacts, catalyst loading amount 1kg, pre-reduction temperature is 600 ° of C, time 10h.Be heated to predetermined temperature through heater after iso-butane mixes with hydrogen and steam to enter 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, calculates the conversion ratio of iso-butane and the selective of isobutene according to the result analyzed after cooling.
Evaluation result: fresh catalyst evaluates 7d continuously, iso-butane conversion ratio is 34.2%, and selective isobutene is 97.7%.Catalyst after regeneration evaluates 7d continuously, and iso-butane conversion ratio is 34.6%, and selective isobutene is 97.3%.
embodiment 5:
By γ-Al
2o
3the liquid infiltration that the hydrochloric acid solution that bead is placed in 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, 80 ° of C maintain 6h.After the dry 8h of 120 ° of C, then 550 ° of C roasting 10h in air atmosphere, finally in hydrogen atmosphere, 550 ° of C reduce 8h, both catalyst for dehydrogenation of low-carbon paraffin.The load capacity of each component is just calculated as based on the metal element weight in catalyst gross mass: Pt content is 0.5wt%, Sn content be 1.0wt%, Li content be 0.8wt%, Sr content be 0.2wt%, La content is 1.0wt%.
Decaying catalyst is made charcoal in tunnel cave, and charcoal temperature is divided into three steps, and the 200 ° of C being respectively low-temperature prewarming section maintain 1.5h, and 380 ° of C of middle temperature charcoal burning step maintain 2h, and 500 of high temperature charcoal burning step ° of C 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 counts the 2.5wt% of catalyst gross mass with element
Subsequently, catalyst is moved in stainless steel reactor, 550 ° of C roasting 5h in air atmosphere.Then, continue blowing air, in reactor, inject steam simultaneously, 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 regenerating.
Appreciation condition: stainless steel reactor reacts, catalyst loading amount 1kg.Be heated to predetermined temperature through heater after iso-butane mixes with hydrogen and steam to enter 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, calculates the conversion ratio of iso-butane and the selective of isobutene according to the result analyzed after cooling.
Evaluation result: fresh catalyst evaluates 5d continuously, iso-butane conversion ratio is 32.2%, and selective isobutene is 95.7%.Catalyst after regeneration evaluates 5d continuously, and iso-butane conversion ratio is 31.6%, and selective isobutene is 96.3%.
Claims (4)
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 outside device makes charcoal, carry out in air atmosphere, charcoal temperature is divided into three steps, 100-300 DEG C that is respectively low-temperature prewarming section maintains 0.5-2h, 300-450 DEG C of middle temperature charcoal burning step maintains 1-5h, and the 450-550 of high temperature charcoal burning step DEG C maintains 2-10h;
Step 2. is by the muriatic aqueous solution of catalyst soakage of burning-off coke in step 1, and to make on catalyst chlorine element in load, dipping temperature is 30-150 DEG C, dip time is 0.5-8h, then through 80-150 DEG C, dry 5-8h, the load capacity of chlorine counts the 0.05-5wt% of catalyst gross mass with element; Wherein, aqueous chloride solution is the combination of one or more 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;
Catalyst dried in step 2 moves in stainless steel reactor by step 3., 400-600 DEG C of roasting 1-10h in air atmosphere, subsequently, continue blowing air, in reactor, inject steam simultaneously, and maintain 1-6h at 400-600 DEG C, wherein, the mass percent of steam and air is 1:10-8:10, finally by catalyst in hydrogen atmosphere, 400-600 DEG C of reduction 1-10h, obtains the catalyst for dehydrogenation of low-carbon paraffin after regeneration.
2. the renovation process of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, is characterized in that: step 1 is in air atmosphere, carries out in swinging roaster or in tunnel cave.
3. the renovation process of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, the catalyst for dehydrogenation of low-carbon paraffin used is PtSn loaded catalyst, and carrier is γ-Al
2o
3bead, also containing rare-earth metals La, one in Ce in catalyst, and the combination of one or more in alkali metal or alkali earth metal Li, Na, K, Mg, Ca, Sr is as auxiliary agent; The load capacity of each component is just calculated as based on the metal element weight in catalyst gross mass: 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%.
4. the renovation process of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, low-carbon alkanes is C
2-C
5alkane.
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| 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 |
| CN111085199A (en) * | 2019-12-26 | 2020-05-01 | 四川润和催化新材料股份有限公司 | Catalyst for preparing propylene by propane dehydrogenation and preparation method and application 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 |
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| CN101940959A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Regeneration method of catalyst for dehydrogenation of low-carbon alkanes |
| 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 |
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| 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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