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Commercial Trial of Catalytic Pyrolysis Process for Manufacturing Ethylene and Propylene

Chaogang Xie and Xieqing Wang, Research Institute of Petroleum Processing, SINOPEC, China; Zhixiong Guo, SINOPEC Engineering Inc., China; Qiang Wei, PetroChina Daqing Refining & Chemical Co., China Abstract
A novel ethylene and propylene production technology, Catalytic Pyrolysis Process (CPP), has been developed by Research Institute of Petroleum Processing, SINOPEC on the basis of modification of DCC process via operating parameter, catalyst formulation and unit configuration. CPP is suitable for processing heavy feedstocks, such as VGO, VGO blended with residual oil, coker gas oil, deasphalted oil, and atmospheric residue, etc. A riser reactor and a specially designed zeolite catalyst are used in this technology. Both catalytic and thermal reactions take place on the dual-functional catalyst with carbonium ion and free radical reaction mechanism. Based on a great deal investigation from lab to pilot plant test, a commercial CPP unit with 80kt/a capacity was revamped from a DCC unit and the test was conducted in the last quarter of 2000 to early 2001 cooperated with SINOPEC Engineering Incorporation and PetroChina Daqing Refining & Chemical Company. The commercial results showed that 20.37wt% ethylene and 18.23wt% propylene were obtained under a reaction temperature of 913K with Daqing atmospheric residue as feedstock. CPP technology introduced some new engineering devices including quenching outlet reactants and heat recovery facilities, and paves a novel way to producing ethylene and propylene from heavy feedstock.

Introduction
Ethylene is the most important petrochemical raw material. Its production technology is the well known steam cracking with light hydrocarbons, such as ethane, propane, butane, naphtha and light gas oil as feedstocks. The proportion of various feedstocks worldwide is shown in Fig 1. Among these feedstocks, naphtha is the dominant one which amounts to 50~55% of the total steam cracking feedstocks. In North American and Middle East, ethane is used as a preferable feedstock which accounts for 25~30% of the total. The other feedstocks, such as propane, butane, light gas oil and condensate are less than 10%.

Propane

Butane

Naphtha

Ethane Other LGO

Figure 1 - Proportion of various feedstocks in steam cracking Propylene is second of importance only after ethylene as a raw material for petrochemical industries. Today about 70% of the global propylene is produced by steam cracking with light hydrocarbon feedstock. Most of the remaining propylene is recovered from FCC and Deep Catalytic Cracking (DCC), and a small amount by propane dehydrogenation and other processes.

In recent years, great attention has been paid to the technologies producing ethylene using heavy feedstocks. A series of FCC family technologies1, such as DCC for maximum propylene and butylenes production, MGG for maximum gaseous olefins plus high octane gasoline production and MIO for maximum isoolefins and high octane gasoline production, have been developed and commercialized by Research Institute of Petroleum Processing, SINOPEC since the middle of 1990s. The youngest member of FCC family technology named Catalytic Pyrolysis Process (CPP), which is a modification of DCC process on operating parameters, catalyst formulation and unit configuration, is developed successfully for directly converting heavy hydrocarbons into light olefins with ethylene and propylene as the major products. Based on a great deal investigation from lab to pilot plant test, a commercial CPP unit with 80kt/a capacity was revamped from a DCC unit and the test was conducted from the last quarter of 2000 to early 2001 cooperated with SINOPEC Engineering Incorporation and PetroChina Daqing Refining & Chemical Company. The characteristics of CPP process and the catalyst, as well as revamping of the commercial unit and its performance and operation were presented in this paper.

Process Description
CPP process is a novel technology for the production of ethylene and propylene from heavy hydrocarbons with a continuous reaction/regeneration system, which uses a riser reactor and a specially designed zeolite catalyst. The reaction temperature of CPP is much lower than that of steam cracking. Both thermal and catalytic reactions take place on the dual-functional catalyst with carbonium ion and free radical reactions resulted in maximum production for ethylene and propylene. The olefin yield of CPP in comparison with FCC and DCC from pilot plant testing using a paraffinic feedstock are shown in Figure 2. From the data in Figure 2, one can see that DCC has higher propylene and butylenes yields, and CPP exhibited both higher ethylene and propylene yields, its ethylene is about 4 times of DCC, propylene yield is 3 times of FCC and very close to DCC. Figure 2 CPP olefin yields in comparison with FCC and DCC
25 FCC DCC CPP

20 Olefin yield, m%

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0 Ethylene Propylene Butylenes

The characteristics of CPP are shown as follows: suitable for processing heavy feedstocks, such as VGO, VGO mixed with residual oil, CGO and DAO, etc., which expand the source of feedstock for ethylene production and reduce the cost of the feedstock; a riser reactor with continuous reaction/ regeneration circulation operation; a specially designed zeolite catalyst with dual-functional active sites for carbonium ion and free radical reactions to maximize the production of both ethylene and propylene;

flexibility of operating modes for maximum ethylene, maximum propylene and maximum ethylene plus propylene; reaction temperature in the range of 873~923K, which is significantly lower than that of steam cracking owing to the reduction of the cracking activation energy by using catalyst, thus the investment and energy consumption are lower; using a stripping device with reversing and crossing flow and short contact time to minimize the flue gas adsorbed on regenerated catalyst; the coke formed in the reaction is used as the main heat source for the reaction/regeneration system; a similar process scheme to that of FCC with tolerable reaction and regeneration temperature, which are below 923K and 1033K respectively, so that a simple modification of FCC unit can meet the demand of CPP unit without using of expensive alloy steel materials.

Catalyst Properties
There are two kinds of active sites on the acidic zeolite catalyst: one is Bronsted acid site, the other is Lewis acid site. Bronsted acid sites are probably responsible for carbonium ion reaction to produce propylene and butylene as the major gaseous olefin products, and Lewis acid sites may cause both carbonium ion reaction and free radical reaction that can produce more ethylene than that of Bronsted acid sites. Conventional FCC catalysts possess mainly Bronsted acid sites, so reactions take place via carbonium ion mechanism and result in the propylene and butylene as the major gaseous olefin product. When the catalyst has much more Lewis acid sites, ethylene can be produced significantly because Lewis acid sites enhance the free radical reaction2. Table 1 - Property of CEP catalyst Name Chemical composition, m% Al2O3 Na2O Fe2O3 Surface area, m2/g Pore volume, ml/g 3 Apparent bulk density, g/cm Attrition index, m%/h Particle size distribution, v% 0-40 micron 0-149 micron APS, micron ) Cracking activity index* *) After aged at 100% steam, 1073K, 4h. CEP commercial sample 46.3 0.04 0.27 152 0.24 0.86 0.91 17.7 91.8 71.1 70

Therefore, the catalyst used in the CPP process should be designed to have the following features: higher Lewis acid sites to Bronsted acid sites ratio, low hydrogen transfer activity and excellent thermal and hydrothermal stabilities. CEP catalyst was developed successfully for CPP process by Research Institute of Petroleum Processing, SINOPEC through the improvement of matrix, binder and catalyst manufacturing process. The property of CEP catalyst manufactured by Catalyst Factory of SINOPEC Qilu Petrochemical Company is shown in Table 1. From the data in Table 1, one can see that the physical property of CEP catalyst is similar to that of conventional cracking catalyst, but with an outstanding attrition index.

Unit Revamping
CPP commercial unit with capacity of 80kt/a was modified from an existed DCC unit3 in PetroChina Daqing Refining & Chemical Company with capacity of 120kt/a under the cooperation with Beijing Design Institute of SINOPEC Engineering Incorporation. To meet the demand of CPP, unit modification mainly included reactor/regenerator system, main fractionator, product recovery system and quenching system. Considering the high reaction temperature, the design of post-riser quench was vital both for heat recovery and termination of secondary reaction to avoid further thermal degradation of target products.
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A specially designed quench device was adopted for quenching the outlet products by direct heat exchange with a portion of feed. To avoid the flue gas carried over as less as possible from regenerated catalyst via reactor into the dry gas recovery system, a device was designed to remove flue gas carry-over and installed between regenerator and reactor. The carry-over of flue gas can be divided into two parts, i.e. those in catalyst pore and in the space between the catalyst particles. It has been found that the major portion of flue gas carry-over was caused in the space between catalyst particles. A special device was designed to replace the flue gas by small amount of steam in very short resident time to avoid catalyst deactivation as alight as possible.

Commercial Trial
The commercial trial of CPP was successfully carried out from the last quarter of 2000 to early 2001 in the revamped unit with capacity of 80kt/a. The fresh CEP catalyst was used in the start-up of the CPP unit and 45% Daqing VGO mixed with 55% vacuum residue, which is similar to Daqing atmospheric residue, was used in the CPP commercial trial. The feedstock properties, main operation conditions, product distribution and naphtha properties were listed in Table 2-4 respectively. In order to make a comparison, the results from pilot plant unit with 70% Daqing VGO mixed with 30% vacuum residue were also listed4. From the result of the commercial trial, the following statement can be drawn: 13.71m% ethylene and 21.45m% propylene were obtained under a reaction temperature of 883K; and at a reaction temperature of 913K, the ethylene and propylene yields were 20.37m% and 18.23m% respectively. The commercial results consisted with that of the pilot plant data. Table 2 - Feedstock Properties Feedstock Density@293K, g/cm CCR, m% Hydrogen, m% Sulfur, m% Nickel, ppm Group analysis, m% Saturates Aromatics Resin Asphaltene
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Commercial 1 0.9015 4.9 12.86 0.16 6.2 54.8 28.4 16.0 0.8 Commercial 1 2 913 0.08 0.51 37.13 28.46 14.82 7.93 0 10.66 1.00 20.37 18.23 2 0.9012 4.7 12.84 0.16 6.3 55.5 28.0 15.7 0.8

Pilot Plant 0.8826 2.9 13.02 0.12 2.9 59.8 26.4 13.2 0.6 Pilot Plant 913 0.07 0.54 40.15 26.43 11.72 8.53 3.75 8.51 0.91 22.82 15.96

Table 3 - Operating Conditions and Product Yields Operating conditions Reactor temp., K Reactor press, MPa(g) Steam/feed ratio Product yields, m% C2 minus C3+C4 C5+Naphtha LCO HCO Coke Loss Ethylene yield, m% Propylene yield, m%

883 0.08 0.37 26.29 36.55 17.61 8.98 0 9.67 0.90 13.71 21.45
4

Table 4 - Properties of Naphtha Commercial Density@293K, g/cm3 MON RON Group analysis, m% Paraffins Iso-paraffins Naphthenes Olefins Aromatics 1 0.8261 101.6 87.6 3.76 2.96 1.51 12.79 78.98 2 0.8315 102.5 87.8 1.24 2.63 0.76 16.25 79.12 Pilot Plant 0.8539 102.5 88.9 1.72 8.84 4.05 9.60 75.79

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25

20 Olefin yield, %

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0 Ethylene Propylene Butylenes Butadiene

CPP

Steam Cracking

Figure 3- CPP olefin yields in comparison with steam cracking

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BTX content, %

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0 Benzene CPP Toluene Steam Cracking Xylenes

Figure 4 BTX content of CPP naphtha comparison with steam cracking Figure 3 and 4 showed the light olefin yield and BTX content in naphtha fraction of CPP with Daqing atmospheric residue as feed in comparison with steam cracking using Daqing LVGO as feed. In comparison with steam cracking, the feedstock of CPP is obviously heavier than that of steam cracking, and the reaction temperature of CPP was about 160K lower than that of steam cracking. The ethylene yield of CPP process was lower that that of steam cracking, but the yields of propylene and butylenes in CPP process were higher than that of steam cracking, and total gaseous olefins yields were the same in both processes. The yields of diolefin and alkyne in CPP process were obviously lower than that of steam cracking. The yield of butadiene in CPP process was about 1/10 of that of steam cracking process, and the yields of acetylene, propadiene and methyl acetylene in CPP process was about 1/100 of that of steam cracking process respectively. The benzene content in CPP naphtha fraction is lower than that of steam cracking, and toluene and xylenes contents are more than that of steam cracking.

Conclusion
CPP commercial trial was successfully carried out in PetroChina Daqing Refining & Chemical Company. During the test, the unit operation was easy to control and kept stable and flexible. 13.71m% ethylene and 21.45m% propylene were obtained under a reaction temperature of 883K; and at a reaction temperature of 913K, the ethylene and propylene yields were 20.37m% and 18.23m% respectively. with 45% Daqing VGO and 55% vacuum residue mixture feedstock. The process scheme of CPP is similar to that of FCC, and the cracking temperature and regeneration temperature are below 923K and 1033K respectively. Simple revamping of the FCC unit can meet the demand of CPP unit without hardware replacement such as using of expensive alloy steel materials etc. CPP opens up a new route for producing light olefins with heavy feedstocks.

References
1. 2. 3. 4. Xie, C. G., Li, Z. T., Huo, Y. Q., et al, Block 3, Forum 16, 16th WPC, Calgary, Canada, 2000. Xie, C. G., Petroleum Processing and Petrochemicals, 2000, 31(7), 40. Xie, C. G., Shi, W. Y., Xu, Y. H., et al, Petroleum Processing and Petrochemicals, 1996, 27(7), 7. Zhang, Z. G., Xie, C. G., Shi, Z. C., et al, Petroleum Processing and Petrochemicals, 2001, 32(5), 21.