Application of Atomic Layer Deposition on Industrial Catalyst

Improved Catalyst Selectivity and Longevity for Propane Dehydrogenation Using Atomic Layer Deposition

Session Notes:


Zheng Lu 

Argonne National Laboratory




Propylene is regarded as a crucial chemical building block in the chemical industry and currently is produced primarily through either steam or fluidized catalytic cracking. However, these two commercial approaches do not meet the current or future global demands for propylene. With the price of propane at historic lows due to the availability of propane from shale gas, propane dehydrogenation (PDH) processes such as OleflexTM from UOP which utilizes a highly active and selective supported platinum catalyst have become economically attractive. However, at the high temperatures of PDH, the stability of platinum catalysts can be limited by sintering of the platinum nanoparticles. Pt sintering results in lower propane activity and selectivity. The goal of this project is to overcome catalyst degradation issues via atomic layer deposition (ALD) overcoating technology, which deposits protective layers over and around the active metal, preserving catalyst integrity under reaction conditions. 
In this project, industrial 1/16″ alumina extrudates were used as catalyst support. To investigate the optimal extrudates surface area and porosity for catalyst performance and ALD overcoating efficiency, the extrudates were calcined at several temperatures. TiO2 ALD was utilized as probe material to show that the ALD precursor is able to penetrate the internal pores of the extrudates equally. The gradual decrease of chemisorbed H2 amount on Pt nanoparticles with addition of the Al2O3 ALD cycles shows a very good control of layer-by-layer deposition. The similarity of the propane conversion for each catalyst after ALD overcoating shows the Al2O3 preferentially deposited on less active Pt sites for PDH reaction. The ALD overcoated catalyst shows improved performance in terms of resistance to sintering and appears to be optimized after five to ten ALD cycles. The selectivity to propylene is also increased as the number of ALD cycles.

0:00:02   Hello, everyone. My name is gender Sank the Year Postdoc and Argon National. Today I will present my
0:00:10   project and duty and album, which is used off time there. Preparation Air D to improve the
0:00:17   industrial catalysts, activity and lunch everything. Football pain. He had imagination.
0:00:27   So what is it for? Pain Cancer Foundation. It's a reaction. Convert propane to popping in the
0:00:33   hydrogen. Let's take a look. Can't figure on the left. The yellow bar is a popular supply from steam.
0:00:40   Cranky reaction. The Green Party in the popularly supply from flu ties to catch it. If you cracking
0:00:46   action, we see before year, could someone age the populist supply of bones? Those two processes can
0:00:53   SATs defined population revenge, which is a rather curved in the figure. But after year 2008 there
0:01:01   is a gap between popular demand public supply, which means we need your process for on purpose,
0:01:09   properly Production. The red figure shows well the processes from Honeywell Europea for propane t
0:01:16   hydrogenation the Pain Gas Coast with that happiness into those four floor bad reactors, and then
0:01:24   captain is separated from the products.
0:01:32   The catalyst used in this process is platinum based catalysts which has one major drawback. The
0:01:39   platinum particle center. After the action, we should overs PT surface area what we did in this
0:01:48   project to aluminum oxide a of the over coating those PT nanoparticles to prevent them from century
0:01:58   according to the lead richer. Starting before the propane hydrogenation reactions count. Sign those
0:02:04   over quality that had these in air. The Nano channel can be formed on the A R D layer, which can
0:02:11   provide access for acting properly and poor dr Pooping and protect properly to get in and get out.
0:02:21   But the Japanese this a healthy over coating technique has bean started before, like in the science
0:02:29   paper. After the women also a o. D over coated PD compiled a ghost Allstate, the hydrogenation off
0:02:37   asked internationally, the plate in the particle side were stabilized. This technique had also being
0:02:45   used in equal face reaction. The monoxide a rt over coated in copper nanoparticles can prevent
0:02:54   lesion off copper into water being wastewater treatment.
0:03:02   So this light shows how the capitalist system hard loose, like the Catholic support here, which he
0:03:09   used to support a PT Party coast is 1 16 inch diameter women. The oxide each two days, I put the
0:03:19   picture here. The same issue dates with calcite under fight. Differ in temperature two to the
0:03:27   surface area, of course. Eyes for the table. We can steal ways that increase off the house nation
0:03:33   temperature. The total surface area decreased from 2 82 80 square meter program and the poor side
0:03:41   increased from 7 to 16. 90 meter. We name those supporters out so high, high, medium low and ultra
0:03:52   low surface area support. After that, 25% off PT impregnated on each of those by supposed. So why we
0:04:03   investigated different surface area support Because for a o. D, we knew less materials and the
0:04:10   machine time will be used lower surface area substrate But for policies we need a high surface area
0:04:18   to fully disperse PT in the particle or the small as possible
0:04:27   from the SCM images those PT particle has ever exercised around 0.9 Nana meter So the gulf this
0:04:36   poacher to stabilize the size off those nanoparticles on The exception is for the catalyst Ultra low
0:04:46   surface area support particle size These Wadham 1212 centimeter with the wife distribution also fund
0:04:55   Can you saw how the amount on this catalyst his 15 29 which is the lowest value among those
0:05:04   catalysts. Again, she was not repeated. Particle performed has been cam. Assumption experiments is
0:05:12   to use hydrogen who came resolved on the surface. PT Adams. The larger the particle size the last
0:05:19   heart surgeon can use off based off the same PT of 1% this house for those of his area, Catalyst is
0:05:27   a good material for a R D. Norfolk analyses. So the idea of a Coty Ronal API applied on this
0:05:35   catalyst
0:05:38   for this year. Summary for the catalyst preparation for different surface area support synthesized
0:05:46   and then 25% of PT loaded on each off the and by GOP. After that, different cycles off women aqsa
0:05:56   ordeal was over. Coated on PT catalyst by Force Nano. Once we got those card, please. Where did a
0:06:04   fascination on performance test
0:06:10   the material? Importantly bio. The, um, poor or support like the extradited here is very complicated.
0:06:19   Then the planner materials to check the aluminum oxide can be departed here sued the issue days
0:06:27   Kyoto D, well utilized to understand the precursor of penetration behavior since it is not feel able
0:06:36   to distinguish aluminum oxide Depart by air D from aluminum oxide. Two days. We cannot ask the
0:06:44   monoxide people quietly by OD to raise their hands, Right Fielder explains the BDS mapping analyses
0:06:52   Medium surface area of the monoxide. Extra days off the final cycles off. Zero LD The two examples
0:07:00   show here were extracted from even in parts off the two days with the help off focused, I be right
0:07:09   here where finances a luminous signal. Green here represents the detainee in signal. We can see that
0:07:16   Titania homogeneous lead dispersed throughout the oxide.
0:07:26   The Nigerian fears option analyses will use to matter. On the surface, every change after aluminum
0:07:32   knocks a or the over coating, we can steer ways The increase off a odious ICoast. The surface area
0:07:39   decreased. Also high. High medium stuff is aggressive Park, which shows vertical control off
0:07:47   aluminum oxide Politics by Air D versus the LG cycle for no surface area support. The average four
0:07:56   sizes. 16 anime in previous table. We should too large for at least seven cycles. Aluminum oxide
0:08:06   charity to change the surface area. The goal off this project into stabilize the PT particle size
0:08:14   after a o D. One thing we need to check is there should be no pity. Sing Goring after a OT. We
0:08:23   picked this 10 cycle of human Achter, a ready on low surface area. Support Catalyst. You see the PD
0:08:31   particle size cause asked. He an image. The matter of average particle size is point hit. Three.
0:08:39   Nana Leader, which, yes, them before a are the overcoats. This shows there's no change after a R D
0:08:47   for those PT particles. This catalyst has the highest possibility for PT little Particle Sing Kering
0:08:55   because it's spent the longest time in a regular actor and has a low surface area, so it is safe to
0:09:03   conclude the audio recording. Thailand Change PT size.
0:09:11   The nitrogen fittest option analysis in previous lights shows with more air view cycles, more
0:09:17   aluminum oxide deposited on the support. But we are not assured, Eliminar said. Overcoat PT
0:09:25   particles are not. So again we used hydrogen chemist option to matter that exposed PT Adams on the
0:09:34   PT animal particles. For he. Figures here show the results for out high, high, medium and low
0:09:42   surface area cat These the black hair over here represents the cameras off hydrogen amount after a
0:09:50   are the overcoats so we can see it with the increase off a lot of psychos. The X axis that can be
0:09:58   solved. Heidi amongst decreased the y axis. This shows the graduate cover off PT no particles with
0:10:07   additional air. The cycles the record shows that came resolved hydrogen After a meeting, we see that
0:10:16   red curves above the black curves, which means that more surface PT atoms I supposed which is due to
0:10:26   that that China Information From the a o d day year.
0:10:35   This TM image shows the PD particle side for fresh catalyst. Important night for man a meter. How
0:10:43   this media service area support catalyst and after 20 over on the reaction condition the average
0:10:53   particle side for the spent catalyst 0.90 centimeters. So there is no PT and no particle chance size
0:11:01   change for coated cat least we realized that's those catalysts from your people who designed for
0:11:12   yearlong process. So steam treatment will use to force the Pitino particles to sing their mimics a
0:11:20   long term effect on the reaction condition. So the lower body figure shows larger peaky metal
0:11:27   particle formed after steaming
0:11:34   to evaluate the performance for each catalysts were divided. Each Cantonese into two equal amount
0:11:41   well past it without steamy went asking off. Steaming. Seems the PT non particle seem to and after
0:11:48   steam treatment, the propane conversion curve for the cat these are steamy will be under the one
0:11:56   with all steamy. The propane conversion means the percentage of propane converted into action wish
0:12:05   directly related to a longevity off the catalyst. So this project go into reduce. Don't have propane
0:12:13   conversion after steamy while minimizing activity reduction. After a of the overcoat E, I will use
0:12:21   bar chart to show the propane conversion at is a tense over for each catalyst. In other words, for
0:12:30   the bar chart, the goal for this project to reduce the green are height, which would have dances.
0:12:38   Don't off propane conversion off the steaming and increase orange bar heights, which represents to
0:12:45   the steam catalyst activity while maintain a total body height. Similar, which represents the
0:12:53   activity for the fresh catalyst after a are the overcoats.
0:13:02   This light shows the catalyst performance. Each figure represents the performance for catalysts on
0:13:11   the from the surface area. Get your Carlin each finger represent one Captain east. The X axis is the
0:13:20   any of the cycle number. The Y axis is the propane conversion we can see wears increase off the air.
0:13:27   The cycles the going far high decreased, which means the drop off propane conversion after steamy
0:13:36   and the orange power had increased with increase off a rowdy cycles, which represents the propane
0:13:43   conversion for the catalyst after steamy. Both shows the catalyst Non charity improved after LD
0:13:51   overcoat the total bar height with similar, which represents the pope in comparision for fresh
0:13:58   catalyst with all steamy. This shows the monoxide deposited by O. D. Minimally block the peaky size
0:14:08   for the reaction.
0:14:11   This is just like to show the popping, slighted bitty, which means the percentage off toppling a
0:14:18   month or the protects again the X axis nuts for the each catalyst. After a cycle where access
0:14:27   represents the pertains to the activity in this bar chart, the Orange bar here represents the
0:14:35   populace night activity. We can see that for post fresh and esteem catalyst with increased off the
0:14:43   cycles, the population of activity the orange for height slightly increased, so in conclusion,
0:14:53   aluminum oxide were deposited by a already to stabilize the pitching arm particles on the industrial
0:15:01   excluded capitalist after air and nearly more PT atoms were exposed on the steam treatment that we
0:15:08   use to mimics a long term effect. Founder reaction condition The catalyst. No charity improved after
0:15:16   the A are the overcoats and aluminum oxide partly bio. The only minimally blocks the PT activist
0:15:25   eyes on the popular things like here it here were slightly increased after the A are the overcoats.
0:15:35   So for this project, I don't rely to things craze. Jeff Peter from our international lab. Natalia
0:15:42   the craziest part for Honeywell, your P and the foot underling Ryan from 40 Nano. This project
0:15:52   funded by Advanced Manufacturing Office on video, he thank you, and I would like to answer any
0:16:01   question.