Improve Naphtha Quality For Olefins Cracking

Improve naphtha quality for olefins cracking | Hydrocarbon Proce...
http://www.hydrocarbonprocessing.com/IssueArticle/2598164/Ar...
COPYING AND DISTRIBUTING ARE PROHIBITED WITHOUT PERMISSION OF THE PUBLISHER
Improve naphtha quality for olefins cracking

04.05.2007 | Bhirud, V. L., Ethylene Consultants, Katy, Texas
Integrating an economy-of-scale extraction unit can yield naphtha suitable for ethylene production Keywords:
Over 50% of the world's ethylene capacity is naphtha based. As crude prices increase, so does the cost of naphtha for liquid crackers. Ethylene producers shun naphtha feedstocks containing high-aromatics content. Aromatics provide no net value to the cracking process. Integrating an aromatics-extraction unit with a naphtha hydrotreater can remove the problematic aromatics from heavy feedstreams. Pretreating off-grade naphtha can yield a high-quality feed for liquid olefins crackers. Feed of choice. For ethylene cracking, one of the most important issues is feedstock selection.1 Ethylene crackers are designed for feed flexibility so that they can process a predefined range of feedstocks. Since the ethylene cracker is the heart of many petrochemical complexes, the financial stakes are very high. For a petrochemical complex based on a world-scale ethylene cracker with a capacity of 800,000 metric tons per year (800 Mmtpy), the petrochemical complex investment can range from $2 billion to $5 billion. Keeping the ethylene cracker running at full capacity is critical for operating all downstream plants at full capacity. Loss of ethylene capacity can occur if the design feeds are in short supply and off-design feeds are processed through the ethylene cracker. Thus, the choice of feedstock to run the ethylene cracker is a critical issue. For naphtha-based ethylene crackers, integration with an aromatics extraction unit is proposed to extend the feed flexibility to off-grade naphthas that can be upgraded economically with little or no loss of ethylene capacity. This will provide more freedom of choice to naphtha cracker operators. Naphtha quality. Fifty percent of the world's ethylene capacity is based on naphtha.2 Naphtha with high paraffin content is preferred for ethylene cracking. As a traded commodity, full-range open-spec naphtha (OSN) is specified for a minimum of 65% paraffins for use as ethylene cracker feed.3 Naphtha that does not meet the OSN paraffin content specification is termed here as off-grade naphtha. Naphthas derived from several Middle East sources are rich in paraffins making them highly suitable as ethylene cracker feeds.4 Most newer worldwide naphthas are poor in paraffins (< 65% paraffins) as listed in Table 1.5 Many paraffin poor naphthas in Table 1 have significant amounts of aromatics.
1 of 9
9/3/2555 11:17
Aromatics extraction integration. It is well recognized within in the ethylene community that aromatics in naphtha are unwanted since they do not add any ethylene value and produce undesired fuel oil.6,7 As ethylene cracking capacities have increased, many olefins crackers are designed to have their own dedicated aromatics-extraction unit to recover aromatics from byproduct pyrolysis gasoline. New processing methods can add synergy by integrating an ethylene cracker aromatics-extraction unit to remove aromatics from paraffin-poor, off-grade naphtha. The treated naphtha is suitable as an ethylene feedstock. The main advantage of this processing is the investment savings with a dual-function economy-of-scale aromatics extraction unit. Obviously, off-grade naphtha must be hydrotreated before forwarding to aromatics extraction. Yet, dearomatizing paraffin-poor, off-grade naphtha can be cost-effective. Base plant. Fig. 1 is a block flow diagram for a typical large-scale, naphtha-based ethylene cracker with its own dedicated aromatics extraction unit. Fresh-feed naphtha and internal recycle streams are cracked in the furnace section. The furnace effluents are sent to the recovery section to produce main products ethylene and propylene. Normally, C2 (ethane) and C3 (propane) streams are recycled to the furnaces since they have high potential to produce olefins.
Fig. 1 Typical world-scale naphtha cracker with the material balance for the Base Case.
2 of 9
9/3/2555 11:17
One of the byproducts is raw pyrolysis gasoline that is rich in aromatics. To recover aromatics from the raw pyrolysis gasoline, it is hydrotreated in a gasoline hydrogenation unit. The heart cut containing C6C8 compounds is sent to the aromatics-extraction unit, where aromatics are separated from non-aromatics. The non-aromatics from the extraction unit are called raffinates. Raffinates plus the C5 recycle stream from the gasoline-hydrogenation unit are sent to the furnaces to produce additional olefins. The C4 -mix stream is assumed to be a battery-limit product. Other byproducts of less value are C9+ stream and fuel oil. Table 2 lists the characteristics of OSN used in the Base Case. Using a well-recognized ethylene yield model, total material balance for the 800-Mmtpy ethylene unit with propylene to ethylene ratio (P/E) of 0.5 is calculated.8 The results are shown in Fig. 1. Aromatics production is significant with an aromatics to ethylene ratio of 0.46. The total material balance is also summarized in Table 4.
3 of 9
9/3/2555 11:17
Off-grade naphtha. Two off-grade naphthasnaphtha A and naphtha B, which are paraffin poor but aromatics rich as listed in Table 2are selected for this evaluation. We will assume that the aromatics-extraction unit can completely remove all aromatics from the naphtha streams. Dearomatized naphtha A has a paraffin content of 72 wt%, which exceeds the OSN paraffin specifications and would be suitable as an ethylene-cracker feed. Conversely, dearomatized naphtha B has a paraffin content of 55 wt%, which does not meet OSN paraffin specifications and would be rejected as an olefins feedstock. Compositions of naphtha A and B are prorated from the composition of OSN naphtha.
Since the plant is designed for OSN, an ethylene owner would have a secure supply of at least 80% OSN and the balance 20% ethylene capacity would be at risk. Accordingly, 20% ethylene capacity could be derived from dearomatized, off-grade naphthas A and B. Table 3 summarizes the cases.
4 of 9
9/3/2555 11:17
The main intent is to integrate dearomatization off-grade naphtha A or B with the ethylene-cracker aromatics-extraction unit. However, naphtha A or B must be pretreated in a naphtha hydrotreater just as the C6C8 heart cut from the pyrolysis gasoline is hydrotreated. Fig. 2 shows the complete integration. The aromatics-extraction unit will produce a non-aromatics stream containing C6C8 pyrolysis gasoline raffinate plus the dearomatized naphtha A that is fed to the ethylene furnaces.
Fig. 2 World-scale naphtha cracker for off-grade naphtha upgrade with material balances for Base Case and Case 1.
Case 1. The total material balance for Case 1 is shown in Fig. 2 along with the Base Case. Production of hydrogen, fuel gas and C4 mix is almost identical in both cases. The aromatics production in Case 1 accounts for the aromatics removed from off-grade naphtha A. Aromatics production in Case 1 shows an increase in aromatics production. Fuel-oil production for Case 1 is lower than that for the Base Case, as desired and expected. Accordingly, C9+ production is also lower in Case 1 as compared to the Base Case. Furnace effluents from the Base Case and Case 1 are used to calculate the relative size of the main processing units to evaluate capacity bottlenecks. Table 4 summarizes the main area size factors for the evaluation. Most of the area size factors are within 0.5%. The largest area size factor in Case 1 is 1.006 for the debutanizer; thus, the debutanizer will be bottlenecked at about 99.4% capacity. The dearomatized off-grade naphtha A would be able to produce almost 100% ethylene capacity from the plant designed for OSN. Cost vs. feed flexibility. Investment costs must include the inside battery limit (ISBL) costs for the naphtha hydrotreater and expanded aromatics-extraction unit. Cost data of the naphtha hydrotreater and aromatics-extraction unit are available in literature.9,10 Cost data is adjusted to a June 2004 basis using the Nelson-Ferrar Refinery Index.11 The costs in 2004 are high due to large fabrication material costs. The calculated ISBL investment costs are summarized in Table 4. For the Base Case, there is no naphtha hydrotreater, and the aromatics-extraction unit investment is $10.5 million. For Case 1, the total ISBL investment for a naphtha hydrotreater and an expanded aromatics-extraction unit is $34.9 million. Thus, Case 1 will need additional ISBL investment of $24.4 million. Obviously, we are partly benefiting from the economy of scale for the aromatics-extraction unit. Payout. To determine the investment payout period, the gross margin is calculated. Prices for the main products are taken from the "bottom of cycle" basis using an average over a four-week period in September 2001.12 We believe this provides a conservative analysis. Normally, OSN is priced at a $4/bbl premium over the crude prices. For off-grade naphthas A and B, this premium is not expected in several locations globally. Thus, the price of off-grade naphtha A and naphtha B is
5 of 9
9/3/2555 11:17
discounted by $4/bbl or $36/t (assuming 9 bbl/t) from that of the OSN naphtha price. All stream prices are listed in Table 4. Gross margin for the Base Case is $209.6 million vs. $241.8 million for Case 1; the resulting gross margin is the difference of +$32.3 million for Case 1. The calculated investment payout period for Case 1 is 0.8 years, thus indicating a very strong justification to consider the aromatics-extraction integration process in which off-grade naphtha discounts are available. Case 2. Similar analysis of Case 2 is presented in Table 4 using off-grade naphtha B. The dearomatized off-grade naphtha B could produce 98%+ ethylene capacity in a plant designed for OSN. The investment payout period in Case 2 is 0.7 years. If the discount for off-grade naphthas A and B is reduced to $2/bbl, the payout period increases to 1.1 and 1 years for Cases 1 and 2, respectively, which is still highly attractive. Full dearomatization. As expected, the payout period reduces as percent dearomatization of naphtha is increased. For full dearomatization of naphtha, the payout period is less than 0.5 year for both naphtha A and naphtha B. Bottleneck analysis shows maximum 5% capacity bottleneck, which is usually covered by normal over design margin. This means that practically no changes are required to cracker as designed for the Base Case to process fully dearomatized naphtha A or naphtha B. We should use the most experienced aromatics extraction licensors to design such units since the amount of aromatics in the feed the extraction unit will be at the lower end of commercial practice. Aromatics-extraction integration operating range. Fig. 3 compares naphtha cracker operating range of Base Case OSN vs. naphtha B. The cross-hatched portion denotes the additional naphtha operating range possible by using aromaticsextraction integration.
Fig. 3 Naphtha operating range increase by using an integrated aromatics extraction unit.
Heavy naphtha. The aromatics-extraction integration process can be easily extended to heavy naphthas used in aromatics production. Table 1 lists a few worldwide heavy naphthas that are usually paraffin poor and aromatic rich. Fig. 4 is a block flow diagram of an integrated ethylene-aromatics facility. Heavy naphtha, either supplementary or excess, can be sent directly to the aromatics-extraction unit after hydrotreating and produce a dearomatized-heavy naphtha, which is suitable as ethylene-cracker feed. The economics of heavy naphtha with aromatics-extraction integration (Fig. 4) would
6 of 9
9/3/2555 11:17
benefit from the economy of scale of the hydrotreater as well as the aromatics-extraction unit. It would be superior to a stand-alone aromatics-extraction integration in Fig. 2.
Fig. 4 Ethylene-aromatics integration with dearomatized excess heavy naphtha in an ethylene plant.
Quench-oil tower fouling. Ethylene licensors have continued to successfully meet clients' increasing demands of run lengths as high as five years. But unexpected quench-oil tower fouling can curtail run length significantly. Fouling can be severe; for example, quench-oil tower fouling was the cause for an unscheduled shutdown after only a 24-month run.13 Ethylene producers have used chemical injection as needed to mitigate quench-oil tower fouling. Some ethylene producers do not have access to chemical injections. The primary cause of quench-oil tower fouling is polymers formed from styrene, indene and di-vinylbenzene, which are all aromatics in nature. Condensation reactions can form polycyclic compounds from aromatics.2 The high molecular-weight polycyclic compounds can also contribute to quench-oil tower fouling by forming tar.2 Ethylbenzene in the feed dehydrogenates into styrene.2 Thus, if aromatics, which are precursors to fouling compounds, are minimized or removed, then quench-oil tower fouling could be substantially mitigated. Thus, dearomatizing 20% of the feed using aromatics-extraction process can control quench-oil tower fouling. Obviously, fouling compounds will still be formed to a lesser degree by aromatics created through cracking reaction even if no aromatics are present in the feed. Furnace run length. Cracker operators are always looking for ways to increase furnace run lengths. Modifications such as coated or finned tubes are tried at significantly high costs. The root cause of fouling is the formation of fuel oil. Dearomatization reduces fuel oil formation, which will directly increase the furnace run length. Compared to Base Case, fuel oil fraction in Cases 1 and 2 is 0.92 and 0.96, respectively, which implies increased furnace run lengths in both cases. For fully dearomatized naphtha A and naphtha B, fuel oil fractions are 0.6 and 0.8, respectively. Removal of feed contaminants will also increase furnace run length. Feed contaminants. Contaminants in feed are becoming an important issue.14 Newer naphthas have significant levels of contaminants, especially heavy condensates.15 For more than 50 years, refiners have used naphtha hydrotreating in front of catalytic reformers to protect catalyst from contaminants. By hydrotreating off-grade naphthas A or B, ethylene plants can be protected from the contaminants and thus reduce investment for contaminant-removal equipment inside ethylene plant. Obviously if the entire naphtha feed is hydrotreated, then the ethylene plant could possibly run in "clean" mode at all times. Naphtha suppliers. Power exerted by the feedstock suppliers can be very stressful due to the limited supply of quality naphtha, although naphtha consumption by chemical users is small as compared to fuel usage. The ability to use off-grade
7 of 9
9/3/2555 11:17
naphthas provides choices to ethylene producers. They are no longer solely dependent on on-grade quality naphtha. Feed flexibility. There are many excellent articles on ethylene cracker flexibility of which a few are noted.1619 An 800-Mmtpy ethylene cracker based on naphtha feed would cost about $650 million for ISBLapproximately 10% will be pre-invested on feed flexibility. Thus, the feed flexibility pre-investment cost for an 800-Mmtpy ethylene capacity naphtha cracker is about $60 million. Incorporating the aromatics integration concept in an ethylene cracker design would require ISBL investment of about $25 million in Cases 1 or 2. Thus, compared to the $60 million ISBL investment for normal flexibility design, a $25 million investment in the aromatics-extraction integration provides a cheaper alternative to achieve feed flexibility and adds insurance against supply disruptions of on-grade naphthas. Feedstock options. The aromatics-extraction integration combines well-proven naphtha hydrotreater and aromaticsextraction technologies. This method can cost-effectively upgrade off-grade naphtha to an ethylene-cracker feed at "bottom of the cycle" pricing and very high ISBL cost basis. The aromatics-extraction integration could be easily incorporated in new grassroots unit or retrofitted in the existing facilities. HP
ACKNOWLEDGMENTS
The author appreciates the review and comments by George Nowowiejski, Equistar Corp., and Chris Wallsgrove, Selasfluid Corp. LITERATURE CITED
1
Hallee, L. P., et al., "Finding desirable feedstocks is problem for ethylene producers," Manufacturing Ethylene, Oil & Gas Journal, 1970. 2 Ethylene Report, "International Survey of Ethylene from Steam Crackers2003," Oil & Gas Journal, March 31, 2003, p. 47. 3 Platt's Guide to Petroleum Specifications, Products-Asia, 2001. 4 Mol, A., "Industry trend indicate need to optimize propylene yield will grow," Oil & Gas Journal, March 28, 1983, p. 78. 5 "Data Book," Oil & Gas Journal, 1997 Ed. 6 Hallee, L. P., et al., "Here's more on how cracking occurs in ethylene pyrolysis," Manufacturing Ethylene, Oil & Gas Journal, 1970. 7 Halle, L. P., et al.,"Here's more on hydrocarbon pyrolysis conversion products," Manufacturing Ethylene, Oil & Gas Journal, 1970. 8 Pycos, Pycos Engineering (UK) Ltd., London, UK. 9 Maples, R. E., Petroleum Refinery Process Economics, Second Ed., Pennwell Publishing. 10 Refining Processes 2002, Hydrocarbon Processing, November 2002, p. 92. 11 Oil & Gas Journal, Oct. 4, 2004, p. 52. 12 Chemical Week issues dated September 5, 12, 19 and 26, 2001. 13 Martin, J. F., "Reduce olefin plant fouling," Hydrocarbon Processing, November 1988, pp. 63-67. 14 Baumgartner, A. J., et al., "Feedstock Contaminants in Ethylene Plantsan Update," 2004 AIChE Meeting, April 2529, 2004, New Orleans, Louisiana. 15 Zehnder, S., "What are Western Europe's petrochemical feedstock operations?" Hydrocarbon Processing, February 1998, p. 59. 16 Becdelievre, C. and V. Kaiser, "Needs dictate olefin-plant flexibility," Oil & Gas Journal, April 3, 1978, p. 94. 17 Hayward, G. J. and P. N. Hoggett, "Ethylene-plant feedstock flexibility is justified," Oil & Gas Journal, July 28, 1975, pp. 81-84. 18 Lee, A. K. K. and A. M. Aitani, "Saudi ethylene plants move toward more feed flexibility," Oil & Gas Journal, Sept. 10,
8 of 9
9/3/2555 11:17
1990, pp. 60-62. 19 DeHaan, S., "Feedstock flexible olefins plants can be efficient," Oil & Gas Journal, Sept. 26, 1983, p.72.
The author {short description Vasant Bhirud is the president of Ethylene Consultants located in Katy, Texas. He has 30+ years of experience. Dr. Bhirud consults in process due diligence of the cracking furnaces to recovery section, plant of image} troubleshooting, techno-economic feasibility studies as well as refinery-ethylene integrations. He has consulted on acquisition of a cracker. Dr. Bhirud has worked at ABB Lummus and Stone & Webster in the ethylene business. At UOP, he worked on refinery-ethylene integrations. He earned his BS degree from the Indian Institute of Technology, Mumbai, and his PhD from the University of Michigan, Ann Arbor, in 1973, all in chemical engineering. He is a member of the American Institute of Chemical Engineering. Dr. Bhirud has authored or co-authored five papers on thermo-physical properties. He can be reached at vbhirud@ethyleneconsultants.com.
Please read our Term and Conditions and Privacy Policy before using the site. All material subject to strictly enforced copyright laws. 2011 Hydrocarbon Processing. 2011 Gulf Publishing Company.
9 of 9
9/3/2555 11:17

Improve Naphtha Quality For Olefins Cracking

Diunggah oleh

Informasi Dokumen

Deskripsi Asli:

Judul Asli

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

Improve Naphtha Quality For Olefins Cracking

Diunggah oleh

Hak Cipta:

Format Tersedia

Improve naphtha quality for olefins cracking | Hydrocarbon Proce...

COPYING AND DISTRIBUTING ARE PROHIBITED WITHOUT PERMISSION OF THE PUBLISHER