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A study on acetylene reactor performance with partial catalyst replacement
Table of contents
1. Abstract. 2. Introduction 3. Acetylene hydrogenation technique. 4. Hydrogenation in front end acetylene Reactor.. 5. Front End Acetylene Reactor system. 6. Acetylene reactor operation Philosophy 7. A UNITED Approach 8. Acetylene Reactor Performance Study. 9. cost benefit analysis. 10. Conclusion 9. References. 10. Author biographies. 11. Co-Authors biographies.

Though. Moreover. Secondly it will provide the confidence of longer life cycle of Chevron Philips E-series catalyst with this operation philosophy. Since some operational upsets will inevitably occur. KBR is the process licensor who has deigned to process up to 142 . There are two key parameters to be considered for study of acetylene convertor performance of an olefin cracker: select the right acetylene hydrogenation catalyst and maintain stable operation of reactor. INTRODUCTION: Jubail United Petrochemical Company (UNITED) an affiliates of SABIC has ethane cracker. United ethane cracker has two acetylene reactor beds in series with intercooler to control the bed inlet temperature. poison can influence the successful operation of catalyst. a provision was made to dispose off only the top bed catalyst and re-use bottom bed catalyst in the top bed. the inter cooler has adequate capacity to control the second reactor inlet temperature. new operation philosophy which is adopted to maximize the acetylene conversion in the top bed and very minimal acetylene conversion is to be maintained in the bottom bed to meet the acetylene specification in ethylene product. carbon monoxide (CO) generation from furnaces is optimized. ABSTRACT: The effective removal of acetylene in the front end hydrogenation using palladium based chevron Philips E-series catalyst is a challenge to ethylene producer. This paper will present the actual acetylene convertor performance with this option over the entire life of E-series catalyst. A fresh E-series catalyst is to be used in the bottom bed. The convertor catalyst utilized must be robust enough to manage these changes without degradation of the catalyst performance and unit profitability. If. 2. Then.  A study on acetylene reactor performance with partial catalyst replacement 1. The above mentioned option has been practiced in UNITED ethane cracker and successfully demonstrated acetylene reactor performance as accepted per study. It will provide the two fold benefits. Consequently reduce the production cost per ton of ethylene. It will provide the option to change the partial catalyst after 5-yrs of catalyst life cycle. Therefore. was designed to produce 1350 KTA of ethylene along with C3+ & tail gas as by products. firstly it will directly save one bed catalyst cost.

which is recycled back to furnace. are designed to thermally crack ethane into ethylene in seven (7) furnaces. while eighth furnace will be in different mode of operation. The remaining mixed C2s enter a heat pumped. hot steam standby. low pressure C2-spliter that separate the ethylene product from ethane. preheating furnace feed. the de-ethanizer is the first distillation column and the reactors are on the overhead stream of de-ethanizer column. 3. these reactor feed contained a large amount of hydrogen typically in the range of 10~35 mole percent. where a hydrogen rich tail gas is separated. In a front end deethanizer design. ACETYLENE HYDROGENATION TECHNIQUE: In front end selective catalyst hydrogenation reactors. H2 +C2H2 = C2H4 (In presence of catalyst) . the acetylene reactor precede the de-methanizer in the process. The crack gas from furnace is quenched successively in primary and secondary quench exchangers. The de-ethanizer overhead gas flow to highly selective front end acetylene reactor integrated within the de-ethanizer reflux loop. treated for acid removal. A process block diagram is shown in figure-1.e. The separation system starts with low pressure de-ethanizer that removes the C3 and heavier cut from crack gas. decoke or maintenance.  MMSCFD of ethane of 95% purity based on 8000 hrs to produce 4050Ton/day of ethylene. Crack gas composition as a function of reactor location is shown in table-1. i. Finally in water quench tower where Dilution steam & heavy boiling hydrocarbon are condensed and separated. Pyrolysis section include eight 200KTA SC-I Furnaces. As a result. The cracked gas then compressed. dried and sent forward for acetylene conversion and product separation. The reactor effluent flows to cold box and de-methanizer.

HYDROGENATION IN FRONT.Crack gas composition as a function of reactor location) Sr.  (Table-1.32 .02 2500 8. The absorption process activates the reactants. It is accepted that reactants like acetylene first absorb on the palladium metal site on the catalyst. 3.No Crack gas components 1. 6. 2.53 41. 5. Chevron Philips E-series catalyst is proven to be the most effective removal of acetylene via front end selective hydrogenation using supported palladium based catalyst.C  Value 26. Which subsequently react .5 65~75 4. 11 Hydrogen Carbon monoxide Acetylene Methane Ethylene Ethane Methyl Acetylene/Propadiene Propylene Propane Total Process Parameter Pressure Temperature unit Mol% Mol%  ppm  Mol%  Mol%  Mol%  Mol%  Mol%  Mol%  Mol%    barg  Deg.17 100% 27.END ACETYLENE REACTOR: UNITED had loaded the first charge in August’2004 of Chevron Philips E-series catalyst.72 23 . which is a palladium based on alumina with promoter.2 0.0012 0. 9. 10. 4. 7.

It is known from E-series catalyst literature that relative strength of adsorption on palladium as reflected by heat of absorption is as listed below. MAPD will replace the acetylene at the reaction site as the acetylene hydrogenated. Even the acetylene concentration is reach reduced to a very low level in the course of the hydrogenation reaction. it will prevent the absorption ethylene on reaction site. it desorbs from reaction site and will be replaced by another acetylene molecule. Thus hydrogenation product will be mainly ethylene. The high partial pressures of hydrogen permit using a . The acetylene reactor consists of two reactor beds in series with a cooling water exchanger between the two beds. Both CO and acetylene will be absorbed on reaction sites. Reaction takes place in the cracked gas stream which contains an excess of hydrogen needed for the hydrogenation of acetylene. When the carbon monoxide concentration in the feed reaches to minimum level. CO> Acetylene>>Conjugated di olefins>=Alkyl acetylene>di-olefins>>olefins Carbon mono oxide at low concentrations is a reaction modifier in the front end acetylene convertors. CO competes with acetylene for the reaction site. 5. the hydrogen of ethylene is suppressed. As long as there are sufficient acetylene molecules are available to cover all palladium site. Alternatively. FRONT END ACETYLENE REACTOR SYSTEM: The compressed vapor from crack gas compressor (CGC) fifth stage is preheated in Acetylene Reactor feed/effluent exchanger and then further heated up by LP steam heated acetylene reactor feed heater. thus reducing the activity of the catalyst. As soon as ethylene is formed. The absorption mechanism also explains the tempering effect of methyl acetylene and Propadiene (MAPD) in the front end de-propanizer acetylene convertor.  with hydrogen to form the hydrocarbon product? The activity of catalyst for a particular reactant is controlled by the availability of palladium site. Even. Acetylene will be absorbed more strongly on palladium than is ethylene. though the intrinsic rate of hydrogenation of ethylene is two time of magnitude faster than that of acetylene. then only acetylene will be hydrogenated. and selectivity depends on the preferential absorption of the reactant. As long as there is methyl acetylene (or Propadiene) remaining.

Acetylene is undesirable impurities in the ethylene product and must be removed. The reactor was operated very smoothly expect the one accident of runways. The acetylene reactor inter stage cooler is used to control the temperature of the feed to the bottom reactor bed. . start of run and end of run. Temperature higher than necessary can cause the ethylene loss by converting ethylene to ethane and increase the danger of runway reaction. including start up. bed inlet temperature must be maintained as low as possible. The most critical operating variable is the temperature of the process gas entering each catalyst bed. The detail operating parameters are tabulated here. The final acetylene removal will be in the lower catalyst bed. About 98 percent of the hydrogenation reaction occurs in the top bed. The advantage of removing the acetylene in front end hydrogenation is excess hydrogen. which is required for reaction and carbon mono oxide which serve as selectivity moderator.m) was loaded to both the beds and was commissioned on 1st-April’2005. Since the hydrogenation of acetylene is exothermic reaction. 6. especially in the first bed. shutdown. For optimum performance. United adopted operation philosophy that maximum acetylene is to be converted into the ethylene in the first bed and very fractional amount is to be cleaned up in the second bed of reactor. the most critical operating variable is the temperature of the process gas entering each catalyst beds. especially first bed. thus improving the selectivity of the catalyst for acetylene hydrogenation to ethylene. While achieving the desire acetylene clean up in the reactor effluent. All exchanger around the acetylene reactor are designed to accommodate a wide variety of situations.  relatively low operating temperature. First charge of chevron Philips E-series catalyst (88 Cu. upsets. ACETYLENE REACTOR OPERATION PHILPOSPHY: Acetylene reactor in front end hydrogenation is used to remove the acetylene which is being produced as one of byproducts of the cracking ethane in furnaces. Bed inlet temperature must be maintained as low as possible so long as sufficient hydrogenation can be achieved to meet the desire concentration of acetylene in reactor effluent.

03 unit Ton/hr Deg. it is understood that maximum acetylene conversion taking place in the top bed and very low acetylene conversion is taking place in the bottom. .C PPMV PPMV PPMV values 486 76 84 8 106 2200 50 It is to be noted that Furnaces have special feature of online steam water decoking. Extra amount of carbon mono oxide (CO) impacted the acetylene reactor performance.C Deg. The acetylene concentration at first bed outlet goes occasionally even less than 50ppmv.C Deg. which generate excessive amount of carbon dioxide & carbon monoxide (CO2/CO).C Deg.C Deg. It revealed the fact that bottom bed catalyst was not fully utilized. Therefore.  (Table-2: Acetylene Reactor operating Parameters) Top Bed Parameters Flow Inlet temperature Outlet Temperature Delta T Inlet Carbon mono oxide Inlet acetylene Outlet Acetylene Bottom Bed Parameters Inlet temperature Outlet Temperature Delta T Inlet acetylene Outlet Acetylene Deg.C PPMV PPMV 77 79 2 50 0.

where as the bottom bed work as guard bed and was not fully utilized. adequate capacity is available in inter cooler to avoid the runways. This is based past data analyzed and concluded as Description Design Intercooler heat absorption capacity Unit KW Value 11517 11000 346 7700 Heat absorption duty required for Max flow of 495 KW T/hr with 2580ppm of acetylene Plant capacity will be 70% during the start up. Then following question arises 1. the current catalyst in the top bed will be deposed off and 4-year old catalyst from bottom bed will be reloaded into the top bed. How to maintained inlet temperature of bottom bed. Bottom reactor bed still appeared to be fresh.  7. This option was discussed with catalyst vendor and their data narration are shown below in the tables. Therefore. It has been noted that if incoming acetylene is around 2580 ppm into the top bed. even after 4-year of catalyst life cycle including the continuous operation of 789 days. with outlet acetylene is 200ppmv and bottom bed is operating with fresh E-series catalyst.e. A UNITED APPROACH: It has been revealed from the acetylene reactor operation philosophy that most of hydrogenation reaction take place in the top bed of reactor . . flow is T/hr Heat absorption duty required for this flow at 2580 KW ppm of Acetylene (11000/495)X349 This heat duty is well below the design capacity (11517 KW). A fresh of Chevron Philip E-series catalyst will be loaded into the bottom bed. Will the inter cooler provide the adequate cooling to control bottom bed temperature. Therefore. UNITED has planned to replace the one bed catalyst in the coming schedule turnaround in March ‘2009 i.

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End Deethanizer Ethane Cracker) Ethane from ARAMCO Feed Saturation Furnaces Quench Water Section   5th Stage Compressor   Acid Removal unit  Dryers  Four stage Compressor  Tail Gas (H2.  (Figure-1: Simplified Front. CH4 etc)  De‐Ethanizer   Acetylene Removal unit   De‐Methanizer    Ethylene     C2‐Splitter   Recycle Ethane     .

But excessive amount of carbon monoxide is being generated during this process.C as calculated. The detailed performance of reactor is presented in the graph below. it was identified that few tube plugged during the early stage of furnace cracking. even after achieving the on specification ethylene product. Bottom bed reactor inlet temperature 8. Reactor top bed outlet temperature 4.series catalyst of the bottom bed. ACETYLENE REACTOR PERFORAMCE STUDY: UNITED kept monitoring the reactor parameters as listed below. UNITED has demonstrated that reloading of the bottom catalyst to the top bed and fresh catalyst loading in the bottom bed is possible. The carbon monoxide (CO) is acetylene & ethylene adsorption inhibitor and as its concentration increases. in order to minimize the potential of runway to happen to fresh E. Top Bed Inlet CO concentration 7. This technique helps to avoid furnace off line decoking. which disturb the reactor drastically and lead to increase reactor inlet temperature. 1. if. carbon monoxide. Flow to reactor 2. It is agree to keep leaking the acetylene up to 500 PPMV and slightly high carbon di oxide around 200PPMV during the 1st week of the operation. All the parameters around reactor were settled in a couple of week. 8. The start up of plant was initiated on 23rd March’2009 as per the above scenario and try to keep the bottom bed temperature as low as possible as stated above. methyl acetylene and Propadiene commonly impact the operation of the acetylene convertors. With this fact. intercooler has adequate capacity to control bottom bed temperature and carbon monoxide generation from furnace is optimized. UNITED has achieved 792 days of continuous operation since start up of plant on 23rdMarch’2009. The on line steam water decoking is being used whenever. the temperature needed to accomplish the same level of acetylene . The bottom bed temperature settle around 62 ~67 deg.  Moreover. In front end acetylene hydrogenation reactors. Bottom bed outlet acetylene concentration It is to be noted that UNITED ethane cracking furnace has distinct feature of on line steam water decoking apart from off line steam air decoking. Bottom bed reactor outlet temperature. Reactor top bed inlet temperature 3. Top bed inlet Acetylene concentration 5. 9. Top Bed outlet Acetylene concentration 6.

during the .C. but due to steam water decoking and excessive CO generation from furnaces has impacted to increase the reactor inlet temperature to offset the acetylene conversion. Figure -3 Plot displays. during the normal operation. the variation in the carbon monoxide concentration on the right axis. the reactor inlet temperature also raise.C at inlet temperature of 68 ~ 72 deg. It is quite interesting to note that how carbon monoxide (CO) influence a palladium based acetylene hydrogenation. we don’t observe such changes. As CO absorbs to palladium based catalyst more strongly than acetylene. the inlet temperature must also rise to offset the reduced number of active sites available to the acetylene. It is revealed from the plot that reactor maintained acetylene concentration. (Figure-2: Effect of carbon monoxide (CO) on let temperature) This graph attempts to qualitatively outline the effects of changing the carbon monoxide concentration on catalyst that has an operating Window of inlet 5 deg. Therefore. it was agreed. is crucial to the successful operation of this type of reactors with this option. The figure-2 illustrates this point of carbon monoxide (CO). Therefore.  conversion will also increase. even try to operate the furnace in such manner that CO generation should be minimize. As the carbon monoxide (CO) concentration rises. as the CO concentration increase. This has been noted over entire monitoring of reactor parameters. while top bed outlet acetylene concentration is plotted on left axis. not to encourage the steam water decoking. the influence that it exert on the catalyst can be extremely strong. Though.

  entire operation & monitoring of the reactor.0ppmv. one can also note that acetylene concentration at the outlet of bottom bed was less than 0. (Figure-3: Top bed outlet Acetylene concentration as function of CO concentration) (Figure-4: Effect of carbon monoxide & Rx inlet temperature over entire operation days) . It is clear indication of potential of over hydrogenation of acetylene to ethylene. Moreover.

the variation in the carbon monoxide concentration on the right axis. (Figure-5A: Top Bed Delta T as a function of CO concentration over the entire operation days) (Figure-5B: Bottom Bed Delta T as a function of CO concentration over the entire operation days) . while top bed inlet temperature is plotted on left axis.  Figure -4 Plot shows. The increase of reactor inlet temperature is the offset of hydrogenation reaction. the reactor inlet temperature increased accordingly. It is revealed from the graph that as carbon monoxide (CO) concentration increase over the entire operational days due to one or another reason. This offset was even maintained during all the operational days.

one bed catalyst cost will be saved. Cost saving estimate 1. 3. complete catalyst changed is recommended by vendor or process licensor. 2. COST BENEFITS ANALYSIS: It is well known fact that catalyst is one of heavy cost item in the process plant and play vital role in complete operation of the plant. 3.C. the delta T across the top reactor bed remain within the acceptable operating window 5 to 8 deg. Catalyst is to be changed as soon as catalyst life expired. 7. 9. It adds cost to final product. 1. 5. The similarly the bottom bed has also shown consistency over the entire operation in two step. But process optimization & operation philosophy studied has indicated that catalyst still has potential life.  This graph shows that even carbon monoxide (CO) concentration increased due to one or another reason as indicated in the graph. Expected life of ethane cracker Expected life of E-series catalyst E-series catalyst required for one Bed Total Catalyst required prior to new operation Philosophy Total E-series catalyst charge required over ethane cracker life Total Catalyst required after the new operation Philosophy Total Cost saved as per new operation Philosophy 30-Years 5-Year 51 Ton 51X2=102ton 5 51 Ton 3. It will provide two step benefits. Therefore. There are few exception persist. It will allow changing one bed of catalyst instead two beds as per new operational philosophy. 6. It will provide the technology benefit confidence on catalyst life. 2. The steady delta T for reactors indicates that the selectivity of the catalyst was remarkably constant during the entire operation. 4. Therefore.5MMUSD .

Even small saving in the production cost wills the producer to stand firm in the market. UNITED acetylene front end hydrogenation reactor has adopted new operation philosophy and demonstrated successful operation that one bed of catalyst replacement in every turn around is possible. 11. CONCLUSION: Today. 9. It has to be noted that cracking furnaces should be vigorously monitored to generate less carbon monoxide. 2. Total Number of Time catalyst saved Total Cost of catalyst saved 4 3. it will provide the technology confidence to catalyst manufacturer and process licensor. 4. Even there are some technology supplier offer on line steam water decoking is to be monitored and carried out at controlled rate or avoided. in turn has increased the entire petrochemical product across the globe in highly vibrant& oscillating crude oil prices . Therefore. in petrochemical competitive market as energy & utilizes price are soaring high.5X4 = 14MMUSD 10. 3. which will not only saved the catalyst but also reduced the production cost in the competitive petrochemical market. The new adopted operation philosophy and controlled parameters monitoring will always benefit to reduce the production cost. if furnace tube life reached to its end life. Moreover.  8.Monthly Monitoring report . UNITED-Acetylene Reactor data of 800 days Consultation with Chevron Philips for new operation philosophy & Intercooler UNITED – Technical & Operation Past experienced with Acetylene Convertor UNITED. REFERENCES: 1.

SABIC.P. 13.F. Working with UNITED (SABIC).S (Chemical) from K. Ethylene Glycol & Linear Alpha olefin (LAO) processes of Petrochemical and Chemical industry.Tech. If you have any questions or doubts need to clarify.sabic. India and having more than 22 years of industrial experience in Process Engineering of olefin crackers. AUTHOR BIOGRAPHIES M.U.T Nagpur.com. Al-Jubail KSA. Al–Anazi: B. Methyl Tertiary butyl ether (MTBE). (Chemical) from L. as Manager –Operation of Olefin Plant.wahab@united. You can reached to me on AnaziNH@UNITED. then author can be reached to me on abdul. Saudi Arabia and having more than 17 years of industrial experience in operation of Olefin & Air Separation Plant.  12. CO-AUTHOR BIOGRAPHY Abdul Wahab: Nayef. A. Working with UNITED (SABIC).com . Dhahran. as Staff Process Engineer.M.I. Al-Jubail KSA.