Emerging Technologies in the Petrochemical Refinery

A.R Johnson, W.S. Letszch, T.E. Swaty and C.P. Bowen Stone & Webster, Inc. - A Shaw Group Company Introduction
For many years, closer integration of petroleum refining and petrochemical production has been a favorite topic. One of the authors of this paper gave such presentations as early as the WPRA 1960 meeting as well as at the UN conference for Petrochemicals in Developing Countries in Tehran in 1964. More recently Stone & Webster, Inc. presented a paper entitled Future Directions of Petrochemical/Refinery Inter-relationships at the 1994 Stavangar WPC1 meeting and Business Opportunities in Refining and Ethylene Plants at Petrotech 2001 in Bahrain. Before embarking on this voyage one more time, it is incumbent upon us to present a case for once again tabling this subject. Traditional factors cited in the previous papers as arguments for closer relationships between the refinery and the petrochemical plant continue to be relevant. A basic element has always been achievement of optimum use of the hydrocarbon streams resulting from the basic conversion processes thermal and catalytic cracking, reforming, etc. Typical examples include recovery of refinery olefins for petrochemical products, reforming to produce either gasoline components or aromatics and use of refinery raffinates for petrochemical feed. Often these have been armslength transactions rather than attempts to obtain any synergy resulting from operational integration. It is the thesis of this presentation that there now exist several additional incentives for more closely integrated refining and petrochemical production. Further, by adding energy integration and power generation to the mix, operators can achieve an additional degree of synergy. These added factors include:

In countries affected by the Kyoto Protocols the goal is to reduce CO2 emissions approximately 5% below 1990 levels by 2012. At the same time, the IEA2 projects a gap between the Kyoto Protocol commitments and their projection of over 16%.

Efforts to reduce CO2 and other greenhouse gas emissions.

Increasingly stringent environmental regulations regarding refinery products.

Currently, it is proposed to reduce gasoline and diesel sulfur contents to 10 - 15 ppm., while simultaneously reducing aromatics contents of both products. Paradoxically, a CONCAWE study3 has shown that achievement of 10 ppm gasoline and diesel sulfur level in Europe alone will result in generation of an additional 12 million tons per year of CO2.

Raw material supply issues

Assured supply of minimum cost raw materials is a necessary pre-condition for economic production of basic petrochemicals. Based upon the following IEA projections2, there are several factors that will impact selection of feedstock and siting of petrochemical installations. World primary energy demand will grow 56% between 1997 and 2010 with oil demand growing from 75 mb/d to 115 mb/d over the same period. Crude prices (in current dollars) are projected to be flat at $21/b until 2010 and increase to $28/b by 2020.

Gas will increase its share of world primary energy demand from 22% today to 26% in 2020. In absolute terms this amounts to an 80% increase in gas consumption over the 1997-2020 period. Much of the incremental gas is far removed from its markets and substantial investment will be required for transportation. Over the period to 2020 nearly 3,000 GW of new electric generating capacity will be required. Over this period, developing regions including China will account for 70% of increased crude demand.

Demand for Basic Petrochemicals

Data presented by CMAI4 indicate that the demand for petrochemicals will increase at a rate greater than the energy demand growth. In the period to 2020, ethylene is projected to grow at a 3.5% rate, propylene at 5%, benzene at 4% and mixed xylenes at 5%. This amounts to a doubling in ethylene production and significantly higher growth rates in the other basic intermediates. Given these various supply/demand projections, it is apparent that meeting the requirements of a growing world economy will increasingly create conflicts with the measures required to simultaneously satisfy the requirements imposed by environmental issues. Also, the differing growth rates expected for transportation fuels and petrochemicals will impact the relationship between these industrial partners. In this presentation we will attempt a broad overview of the technologies both developmental and commercial which offer promise in providing the means and flexibility which will be needed to meet these challenges in the context of profitable enterprises. Using these developments as a framework we will then show some examples of how these approaches may be combined to meet certain specific situations.

Olefins & Aromatics

The half-century history of petrochemical production of light olefins has been a success story resulting in substantial replacement of natural products by polymers based upon olefins and aromatics. This scenario has been played against a background of a cyclical market involving periodic intense price competition leading to several shifts in feedstocks and siting preferences in order to take advantage of whatever low cost hydrocarbon the natural gas and refining industry currently makes available. Consideration of these various feedstock opportunities, coupled with the need for product slate flexibility, has led to development of a considerable suite of alternative technologies for olefin and aromatics production employing raw materials ranging across the entire spectrum from methane to residual oil.

Coil Pyrolysis
Following the global energy crisis of the 1973-84 period, there have been substantial improvements in the basic thermal pyrolysis process for production of ethylene/propylene. The process has become much more selective and thermally efficient and can process a wide range of various feed stocks from ethane up to heavy gas oils. Developments have included: various low-coking techniques, lower NOx burners, co-generation techniques (including gas turbine integration), and energy efficient separation designs - all coupled with the benefits of significant economies of scale. While furnace based pyrolysis will undoubtedly continue to play a major role in expansion of this market, incentives for alternative processing approaches are becoming stronger. These incentives include; (1) opportunities to consider methane and heavy hydrocarbons as feedstocks, (2) the need for a process to efficiently supply local specific olefin needs where a world scale cracker is not justified. In certain cases, these opportunities may justify closer integration with petroleum refining.

Fluidized Solids Processes

Fluid catalytic cracking (FCC) is a core process for refinery conversion of heavy oils into lighter products, and it has always been tempting to consider a fluid solids pyrolysis reactor for petrochemicals. This type of reactor/heat transfer system eliminates concerns over coking and greatly broadens the range of feedstock options. In its early stages, FCC was based upon fluidized bed cracking due to the longer residence times dictated by low activity catalysts. The back-mixing inherent in these reactor systems was inconsistent with the selectivity requirements of pyrolysis for olefins production. With the introduction of zeolite catalysts in the early 1960s, FCC designs began to adopt riser reactor systems involving less back mixing. In the wake of these system and catalyst developments, parallel developments have progressed in pyrolysis/catalytic olefins technologies. Inert Solids In the high crude cost environment of the late 1970s, Stone & Webster, in association with Gulf Oil Chemicals, undertook a development program based upon use of heavy oil feedstocks using inert solids in a short residence time downflow reactor. This system employed a circulating solids reaction system named QC (for quick contact). The design is analogous to a FCC operation, employing a solids circulation through a reactor/regenerator loop with supplemental fuel to the regenerator if required for heat balance. The essential design departure from FCC was the downflow reactor-separator system and the use of higher temperatures. A substantial demonstration unit (500 B/D) was built and operated at Cedar Bayou Texas giving results generally comparable to coil cracking. The crude price drop of the mid-1980s removed the incentive for heavy feed processing, and the process has not yet been employed in commercial practice. Employing elements of RFCC design (see below) feedstocks as heavy as residual oils could be processed in QC. Catalytic Solids In our Stavangar paper1, we reported on the development of the Deep Catalytic Cracking (DCC) process by the Research Institute of Petroleum Processing (RIPP) of the Peoples Republic of China. This FCC-type process employs a specifically developed catalyst, and operates at conditions designed to produce a substantial yield of propylene relative to normal FCC operations. Several DCC plants are being operated in China. Together with high yields of propylene, the process also produces a high octane - aromatics-rich gasoline fraction. Since that presentation, Stone & Webster has built a plant for Thai Petrochemical Industry Public Co. Ltd. (TPI) which produces the propylene feed for a world scale polypropylene plant. To our knowledge, this is the first instance outside China where an FCC-type unit has been built for the specific purpose of supplying a petrochemical need. Operation of this unit is described in a TPI/S&W paper6. Table 1presents process yields obtained on the TPI operating unit. DCC conversion of paraffinic atmospheric residues has been demonstrated in RIPP pilot plant operations and LSWR has been included in the feed for the TPI unit. It is now practical to consider a DCC unit based entirely on light atmospheric residue. RIPP has continued to be committed to development of catalysts and FCC designs predicated on high yields of olefins. In a further development RIPP has developed the Catalytic Pyrolysis Process (CPP) capable of producing significant yields of ethylene as well as propylene. This process, based upon a modified pentasil zeolite catalyst, integrates thermal and catalytic reactions. In a paper presented by RIPP6 ethylene/propylene yields of 24.3/14.7 wt.% were

reported from pilot plant operations employing a riser reactor and processing a feed containing a paraffinic VGO mixed with 30% vacuum residue. The naphtha produced in this operation contained 75% aromatics. Given these developments in systems and catalysts, it is now possible to consider efficient fluidized solids conversion systems which will permit operation over a wide range of product/coproduct ratios and employing feedstocks ranging from naphtha through residual oils. This capability provides the opportunity for a refiner to consider production of one or more olefin based chemical products employing a low valued internal stream. The TPI DCC/polypropylene integration cited above illustrates this approach.

Methane-to Olefins
Due to economies of scale, the cracker-based petrochemical industry has tended to spawn major complexes. There are occasions however, where it is desirable to have a local supply of an olefinic raw material but the demand is not large enough to justify a multi-product complex. The TPI case discussed above is such an example. In such cases a technology which could efficiently convert a commodity raw material into olefins could be an attractive option. Recent developments indicate that, under certain circumstances, methanol may be able to fill the role of a commodity feedstock for such operations. Considerable attention is being paid to the concept of monetization of stranded natural gas reserves by production of transportable liquids such as methanol or Fischer-Tropsch products. Employing methanol as the intermediate, several processes are under development for the conversion of methanol to light olefins. Developments have been announced by UOP, Lurgi and ExxonMobil. Pricing stranded methane at $US 0.75/MMBtu, and employing recent price ranges for ethylene and propylene, UOP7 has estimated a 20% ROI for their process. While the stranded gas opportunity has provided an impetus for this development, once these techniques are operational, the way is then open to consider production of methanol at refinery sites to provide feedstocks for dispersed petrochemical operations. Such production could be a logical by-product of refinery-based gasification based power production using low-cost heavy feeds.

Direct Conversion of Alkanes

Several technologies are under development for direct conversion of alkanes to added-value intermediates. Petzny and Mainusch8 summarized several activities in this field including: ethane based production of VCM and propane-based synthesis of acrylonitrile. Other alkane conversion technologies include ethane to acetic acid and butane to maleic anhydride. The VCM technology is under development by European Vinyls Corporation and has progressed to the point where a 1000 t/yr pilot plant was brought into operation in mid-1998. In the case of propane to acrylonitrile, Asahi Chemical, Mitsubishi Chemical and BP Amoco Chemicals are all reported to be active in this development. This approach again offers siting flexibility to the producer of a commodity intermediate.

Aromatics
Aromatics are typically produced by recovery from the gasoline by-product of steam cracking or by reforming virgin naphtha. Recently technologies have been developed for converting aliphatic and olefinic light hydrocarbons to aromatics. Cyclar, developed by BP and licensed by UOP is based upon conversion of propane and butane9. The Alpha process10 commercialized by Asahi Chemical Industry Co., Ltd. at Mizushima, Japan produces BTX from a pyrolysis C4/C5 fraction.

A combination of the DCC or CPP technologies discussed above, with aromatics extraction of the pyrolysis gasoline and recyle of raffinates, can be an effective means of co-producing propylene and BTX from vacuum gas oil or light residue with little, or no co-production of transportation fuels. Addition of a technology such as Alpha offers the opportunity to increase the BTX yield from such an operation.

Petroleum Refining
In discussions of the future, it is generally assumed that future crude supplies will increasingly involve heavier materials. Recent history has shown however that newer discoveries tend to favor the lighter crudes associated with deeper production zones. This element does not however, mitigate the need for producers of heavy crudes, such as Mexico and Venezuela, to move their product into market. This recent phenomenon, also does not alter the fact that at projected consumption growth rates, a large component in the incremental demand will need to be derived from the heavier crudes. Considering the North America/Caribbean region, the most extensive petroleum reserves are heavy crudes and tar sands, and their utilization will be an essential element in the energy equation of this high demand region. Relative to the theme of this presentation we will focus on the residue upgrading aspects of refining technology, with particular emphasis on integration with petrochemical production and/or with electric power generation.

Fluid Catalytic Cracking

The FCC process has been the refinery workhorse for conversion of heavier hydrocarbons into gasoline and gas oil boiling range materials. While the process is undoubtedly the most capital efficient means to accomplish heavy end conversion, the increasing stringency of product specifications and emission regulations have very specific impacts upon this technology. Issues include the following: (1) Gasoline quality in a modern refinery, FCC gasoline is the source of most of the sulfur and olefins found in gasoline blends. (2) SOx emissions Untreated, FCC regenerator stack gas will have a sulfur content reflecting the sulfur content of the feed. (3) CO2 emissions - up to 8% of FCC feed is consumed as coke and burned in the regenerator system with a consequent production of CO2. FCC has such an important position in the refiners kit of tools, that addressing these issues has attracted the required development. Among the results are: A number of new processing approaches now address desulfurization of FCC gasoline. These developments have effectively lowered the cost of reaching sulfur contents as low as 10 ppm while preserving octane number. Similarly, effective technologies are now available to remove SOx from regenerator stack gas. In the longer term, hydroprocessing of FCC feeds will play an important part in the sulfur issues - both product and emissions. Since hydrogen addition to the feed also improves process yields, its attractiveness is increased with decreased feed quality and with increased light/heavy crude price differential. In this regard it is noteworthy that in California which has a high crude differential and in which the FCC feed comprises a significant fraction of coker gas oil - virtually every FCC unit is integrated with feed hydrotreating. Beyond addressing the environmental issues, there have been several developments directed to extending application of the technology in terms of both product slate and feedstock capability.

As discussed above, the technology has recently been significantly extended to maximize light olefin production particularly propylene. These developments are based upon variations in the design of the process features coupled with catalyst modifications involving application of pentasil zeolites. Another important development has been the extension of the feedstock range to include asphalt processing up to full atmospheric residues (RFCC). Several RFCC units now operating are designed to process feeds as heavy as full range atmospheric residue from Light Arabian crude. Given the current capabilities of FCC technology, it can now be considered an overlap technology serving both the refiner and the petrochemical producer. Employing the technologies discussed above (QC, DCC, CPP) facilities can be designed to be capable of varying feed and product slate to reflect cyclical market factors in these two markets.

Residue Conversion Technologies

A broad range of well developed residual oil processing technologies are available to the refiner. Vacuum residue from crude distillation is a carbon-rich, hydrogen-deficient material. Consequently, upgrading technologies have been categorized into either carbon-rejection (e.g. RFCC, coking, deashalting) or hydrogen-addition (e.g. hydrotreating, residue hydrocracking). The carbon-rejection processes have generally been less expensive, but, with the exception of RFCC, leave the refiner with the problem of disposing of the low value asphalt or coke products. In addition to these developed technologies, there are a number of developmental processes for conversion of heavy oils. Examples include; Use of fine catalysts to achieve >90% asphalt conversion. Acquaconversion a technology developed by Intevep involving transfer of hydrogen from water vapor into the unconverted bottoms11. Biological processing BioCat,Inc is engaged in further development and commercialization of technology for biocatalytic processing of heavy petroleum developed at Brookhaven National Laboratory12.

Combination Processing Hydrogenation/Cracking

Under certain circumstances, combinations such as hydrotreating of VGO or residues followed by either FCC or coking are employed. These are particularly useful in reducing coke yield together with an improved yield of higher quality light products. As noted earlier this approach is quite common in markets such as California which are characterized by low feed quality and stringent product specifications. This combination is also beneficial in preparing refinery streams as petrochemical feedstocks. In order to achieve the desired propylene yields, the Thailand DCC unit discussed earlier processes a hydrotreated Middle East vacuum gas oil. There are also cases in which vacuum gas oil is partially hydrocracked and the unconverted, hydrogenated bottoms are employed as steam cracker feed.

Gasification Refinery Power Generation Process Plant Energy

Oxygen or air gasification of hydrocarbons as exemplified by the Texaco and Shell processes is over fifty years old. The first embodiment of the Texaco process was for production of synthesis gas for the Brownsville, Texas Fischer-Tropsch GTL plant built in the late 1940s. Since that time, and until recently, the technology found only occasional application. Recently however, gasification appears frequently in lists of new projects. Texaco13 lists 15 plants with start-up dates from 1996 onward. Geographic distribution of applications is global with units

in Europe, Asia and the USA. It is also interesting to note that in 10 of these cases electric power is a product, often with steam and hydrogen as co-products. Feedstocks for these plants range from heavy oil through petroleum coke. The drivers for such projects include decreased value for high sulfur coke and heavy oil as power plant fuels coupled with the availability of lower priced heavy, high sulfur crudes. In virtually all cases power generated from a gasifier will involve an Integrated Gasification Combined Cycle (IGCC) installation. In these cases the gasifier gas is first expanded through a gas turbine for basic power generation, the exhaust gas is then cooled in a heat recovery steam generator (HRSG). Steam generated in the HRSG is then used for additional power generation. Starting with this basic installation there is almost an infinite number of variants on the theme of co-production of products and energy. Following are a few obvious examples. If oxygen is used as the gasification medium, the gasifier product is synthesis gas a mixture rich in CO and H2. A portion of this synthesis gas can be withdrawn to produce several products including: Hydrogen Methanol as a chemical product or as a feedstock for MTO or other operations. Fischer-Tropsch liquid hydrocarbons for conversion to transportation fuels or petrochemical feeds. Dimethyl Ether (DME) for use as a diesel fuel. Ammonia/Urea All or a portion of the steam produced in the HRSG can be sent to the process plants for heating or process use. Heat can be removed from the turbine effluent by exchange with a heat transfer fluid. This hot loop can be used to supply a portion of the process heat normally supplied by fired heaters in units such as crude distillation. In addition to improving efficiency, this approach will contribute to CO2 reduction. Schemes of this nature were being planned in the early 1980s, and were cancelled when crude prices dropped. Once gasification of rejected carbon becomes a viable option based upon local economics, the process plant planner is faced with an optimization issue regarding the extent to which hydrogen addition should be practiced relative to carbon rejection. This decision will vary from case to case depending upon local factors. Typically, carbon-rejection/gasification will become the preferred option as the hydrogen-content of the feed decreases.

Gas to Liquids
There has been a resurgence of interest in technologies for producing liquid hydrocarbons by converting synthesis gas to methanol, DME, Fischer-Tropsch liquids, etc. Monetization of socalled stranded gas is currently an important driver. Bruce Burke of Chem Systems presented a review14 of these developments in a paper presented at the 2001 NPRA meeting. A number of technologies are reported to be either operational or approaching this status. Developers include Sasol, Syntroleum, Shell, Conoco and ExxonMobil. Including a 10% ROI, and based upon Middle East gas at $0.50/MMBtu, Burke estimates a production cost range of $22-$32/barrel for F-T liquids produced by these various technologies. At this level projects have been announced, and within the 20 year framework of the IEA $28/barrel crude price projection, production of F-T liquids may well be an accepted means for recovering value from isolated gas resources. While the stranded gas situations may in certain cases be of interest to the petrochemical producer (e.g. methanol as an olefin precursor), this technology is also mentioned here for its longer term potential in the petrochemical or transportation fuels markets based upon synthesis gas derived from gasification of coke or heavy oils. In effect, we are witnessing establishment of the necessary technology base for coal liquefaction being built upon a foundation supplied by the natural gas industry.

Applications
The foregoing sections constitute an attempt to present a fairly comprehensive list of the technologies having the potential to assist the refiner and the petrochemical producer in meeting regulatory and market challenges by more closely integrating their operations. To a degree, the approach involves re-drawing the boundary of the refinery to include production of light olefins, BTX, synthesis gas based products and intermediates together with the transportation fuels. The following cases have been developed to illustrate these concepts.

Case 1. Petrochemical refinery Light/Medium crude case (Figure 1)

The refinery/petrochemiucal plant can be viewed as a continuum of concepts ranging from all transportation fuels at one end to all petrochemicals at the other. This first case can be viewed as the latter extreme. In the simplest variant a light waxy crude such as Daqing or Minas can be processed as follows; The crude is separated by atmospheric distillation into naphtha, mid distillate and atmospheric residue. The naphtha and distillate are pyrolyzed by steam cracking employing either a normal coil furnace system or a QC circulating solids system. Conversion of the atmospheric residue is accomplished in either a DCC or CPP reaction system. Products from both the thermal and catalytic conversion systems are processed in a common gas recovery plant. Disposition of the products are as follows: Ethylene and propylene are sent to further processing to produce intermediates and/or polymers. C4+ cracked naphtha is sent to aromatics recovery. The aromatics system can be either simple hydrogenation and separation or it can include a process such as Asahis Alpha process to increase aromatic yields. Residual gases and cycle oils are used as process fuel and fuels for steam and power generation. This approach enables a petrochemical producer to effectively divorce itself from the transportation fuel market, and to have the flexibility of obtaining feed (crude) from a number of sources eliminating dependence upon a refiners ability to supply acceptable feed materials. This approach also enables the petrochemical producer to avoid the need to arrange for disposition of transportation fuels in competition with established producers/distributors. In the case of medium crudes such as Light Arabian, or heavier - it will probably be desirable to include atmospheric residue desulfurization before processing through DCC or CPP. Beyond the processing benefits to be derived from metals and CCR reduction, hydrogen addition will produce substantial yield benefits. Choice of these options will depend on the price differential between light waxy crudes and medium, higher sulfur crudes.

Case 2. Petrochemical Refinery Heavy Crude Case (Figure 2)

The approach taken in Case 1 basic petrochemical production with a minimum of involvement with the transportation fuel market can be applied to heavier, high sulfur crudes as well. Processing of the heavier residues however, will require investment in hydrogenation and residue conversion, and a significant light/heavy crude price differential is required to justify this approach. The processing sequence illustrated is as follows: In this case, vacuum distillation is added to the crude separation step and the vacuum residue is further separated, by deep deasphalting, into heavy gas oil (DAO) and asphalt.

The vacuum gas oil and DAO are hydrotreated and then processed by DCC or CPP to produce a naphtha and lighter gas stream, and cycle oils. Virgin naphtha and atmospheric gas oils are hydrotreated and then steam cracked in either conventional coil operation or using a QC reactor system. Gas products (naphtha and lighter) from both cracking systems are co-processed to separate then into fuel gas, ethylene, propylene and a C4+ naphtha stream. The C4+ naphtha stream is processed into BTX, either by conventional hydrogenation and separation, or to maximize BTX production, by integration with a process such as the Asahi Alpha process. Raffinates are recycled to steam cracking. Asphalt from the deasphalting step, together with cycle oils from the thermal and catalytic cracking operations, are gasified to produce a synthesis/medium Btu gas. This gas is then converted to steam and hydrogen for use in the complex and power for both internal use and export. Optionally, a portion of the synthesis gas can be converted to liquid products such as methanol, ammonia or Fischer-Tropsch liquids.

Case 3. Integrated Petrochemical/Fuels Refinery Figure3

The preceding two cases are extreme in that no transportation fuels are produced. In most environments, it will be more economic to take advantage of the synergism resulting from coproduction of these products. There has always been a significant degree of arms-length interaction between refining and petrochemical production based upon differing relative values of intermediate streams. By integrating the operation, this synergism is achieved without the necessity to base the interchange upon negotiated transfer prices. In setting the fuels products processing sequence, it has been assumed that, in the market being served, the transportation fuel demand is tilted in favor of diesel fuel. There is a perception that, on an overall cycle basis, maximization of diesel fuel in the mix will be more efficient from both energy efficiency and CO2 emission bases. For this reason, hydrocracking is the heavy oil conversion technology chosen for transportation fuel production. Fluid solids cracking is employed only for petrochemical production. This example has been built upon the framework of Case 2 the heavy crude petrochemical refinery. The processing steps which differentiate this case are; The virgin heavy naphtha is reformed to produce the basic component of the gasoline pool. Supplemental gasoline is produced by alkylation to the extent of internally generated isobutane possibly supplemented by hydrogenated product from a C3/C4 olefin oligimerization process. This blend will produce zero sulfur/zero olefins gasoline, in which the benzene/aromatics content can be controlled by the alkylate/reformate ratio and/or by extraction of aromatics to supplement the BTX pool. Vacuum gas oil is hydrocracked either completely to diesel fuel, or partially with coproduction of a hydrogen-rich gas oil for petrochemical production. The diesel pool will consist principally of desulfurized AGO and hydrocracker product. Again as with gasoline, hydrogenated oligimerization products produced from C3 and C4 olefins may also supplement the distillate pool. Hydrogenated DAO, together with unconverted bottoms from VGO hydrocracking, is processed in fluidized solids systems comprising one or more of QC, DCC and CCP. Gas from the cracking complex is separated and processed into fuel gas, ethylene, propylene, alkylate, oligimerization products, BTX and raffinate for recycling.

Case 4. Future Integrated Petrochemical, Fuels and Energy Complex Figure 4

The energy crisis decade of 1974-84 witnessed a wide range of technology developments to produce what were termed synthetic fuels. In large measure, these developments were extensions of refining technology. Examples include H-Coal which drew on H-Oil technology and

coal gasification demonstrations based upon the oil gasification technologies of Texaco and Shell. While specific government sponsored developments were de-emphasized following the 1985 crude price drop many entities have continued to commercialize critical aspects of these technologies. As a result we are now in a position where the following exist, and merely await an economic basis for commercial use. Coal/coke based IGCC. Such plants are currently operating on petroleum coke13 and coal based operations have been demonstrated e.g. the Cool Water project based upon Texaco Gasification. Coal based liquids production. Under the stranded gas impetus, several Fischer-Tropsch variants are being commercialized, as discussed above. While the synthesis gas of current interest is methane-derived, it is no great leap to base such operations upon coal gasification. As natural gas prices increase with time, a point will be reached where coal based IGCC should be an economic alternative to natural gas based combined cycle power generation. A US DOE study15, evaluating these options, estimates levelized busbar cost of advanced coal based IGCC in the range of 3.38-3.88 cents/KWh while estimates for the gas based combined cycle alternative were 3.32-3.59 cents/KWh. This analysis was based upon 1998 prices of $1.26/MMBtu for coal and $2.70/MMBtu for gas. The current trend to increasing use of gas for new power generation facilities will tend to increase this differential. When one factors into this equation increasing crude oil prices (projected by the IEA to reach $28/bbl in todays dollars by 2020), it is not a very big leap to consider power generation facilities as venues for co-production of a range of synthesis gas based derivatives. Depending on local economics one can imagine ammonia/urea in agricultural regions. In the US Gulf Coast region, with its summer peak in power demand, synthesis gas could be converted to SNG for pipeline transmission north during the winter season. Considering that LNG imports are now being considered for meeting natural gas peaks, justification for this option could be close at hand. Returning to the theme of this presentation, these developments in coal utilization lead to consideration of a not-to-distant future in which coal and heavy crude could be an optimum mix for a fuels/petrochemical/energy complex. This flow sheet would not depart greatly from the configuration of Case 3, but would have several variants. First, the power generation plant would probably be base load scale. On this scale synthesis gas would be a by-product and its production cost would benefit from economies of scale. In this configuration, coal, together with asphalt would be gasified to supply the fuel for power generation and synthesis gas. Synthesis gas would be converted to hydrogen for complex requirements, as well as one or more of a variety of products. These could include: Methanol for several purposes including possibly conversion to olefins at dispersed derivative market demand locations. Fischer-Tropsch liquids for; production of lubes, hydrocracker feed for diesel production, steam cracker/DCC/CPP feed. Ammonia/urea DME as a diesel fuel alternative. SNG for peak winter demands. Beyond petrochemicals and electric power, the other important product of such a complex will be transportation fuels. When one discusses a future installation of twenty years, or more, hence, one must comment on likely developments in vehicular motive power. At present considerable attention is being paid to fuel cells as a probable partial replacement for the internal combustion engine. Options for fuel cell base fuel under consideration include: distribution of hydrogen to fueling stations, production of hydrogen at fueling stations by reforming of gasoline or methanol,

on-board reforming in the vehicle and use of methanol directly in a fuel cell. In any of these options, there will be a place for the products of the integrated complex. The balance of the complex in this Case 4 is similar to Case 3 with the exception that the deasphalting step has been replaced with residual oil hydrocracking. It is likely that at the point where conversion of synthesis gas to liquids is economic, it will also be economic to increase liquid yields from petroleum using a high degree of hydrogen addition. In certain cases it may also be appropriate to consider some degree of coal liquefaction possibly by co-processing coal and residual oil in an ebullated bed reaction system.

Conclusions
Feedstock cost is an essential element in establishing the competitive position of a petrochemical venture. At the same time, production of petrochemicals does not consume a sufficient percentage of the worlds hydrocarbons to significantly impact prices in the petroleum or natural gas markets. As a result, the petrochemical producer has typically existed at the margin, depending upon low valued streams derived from the refinery or the natural gas plant. The ever-increasing range of technology options offers the petrochemical producer a number of opportunities to achieve a level of independence coupled with an ability to possibly integrate back to the point of raw material production. Cases 1 and 2 above illustrate how a petrochemical producer can divorce itself from the transportation fuels market while still consuming crude oil. This option offers the opportunity to integrate with a crude producer and possibly to participate in the benefits of crude acquisition at production cost rather than be subject to market clearing prices for derivative hydrocarbons. This could provide valuable insulation from the effects of the inevitable petrochemical market cycles. This might mean sharing the thrill of the upswing with the crude producer, but the cushion on the downside may be well worth the trade-off. On the other hand, as is illustrated by Cases 3 and 4, this same range of technology options offers the refiner or even the power producer the opportunity to participate in the petrochemical market on a basis that permits modifications in emphasis in response to these same cyclical impacts. In these cases the refiner/power producer and the petrochemical producer will have thrown in their lot together and will gain the benefit of the capability to swing the processing emphasis in order to capitalize on any counter-cyclical aspect of these three markets power, fuels and petrochemicals. Before closing, a word is in order on the remarkable capability of this industry to catalyze innovation. It is apparent that starting with World War II, the hydrocarbon processing industry embarked on what must be seen as a very remarkable half century of technology development. These developments encompass reaction systems such as fluid solids, continuous reforming, high-pressure technologies, cryogenics and pyrolysis, - all supported by an extraordinary range of catalyst developments. During the war the US and Britain developed in very short order several technologies - catalytic cracking, alkylation and synthetic rubber among them. On the other side Germany made remarkable progress in developing Fischer-Tropsch and Bergius chemistry based technologies for conversion of coal to fuels. Much of what we process today was built upon those foundations. We believe we can rest assured that in the future, as in the past, technology will be made available to meet the energy and petrochemical challenges of the day.

References
1. Johnson, A.R., Hallee, L.P. and Bowen, C.P., Future Directions Petrochemical/Refinery InterRelationships. Proceedings of the 14th World Petroleum Congress 2. CONCAWE, Document no. 99/01 3. International Energy Agency, World Energy Outlook 2001

4. Hydrocarbon Processing, September 2001 23 5. Fu, A., Hunt,D., Bonilla,J.A. and Batachari, A. Deep Catalytic Cracking Plant Produces Propylene in Thailand Oil & Gas Journal Jan. 12, 1998. 49-54 6. Shi,W., Xie,C., Huo,Y. and Zhong, X. FCC Family Technology for Producing Light Olefins from Heavy Oils. China Petroleum Processing and Petrochemical Technology No.2 June 2001 15-21 7. UOP reference re 20% ROI basis the Bowen/Ried AiCHE paper 8. Petzny,W.J. and Mainusch,K.J. Novel Routes to Petrochemicals. OIL GAS European Magazine January 2000 21-26 9. Doolan,P.C. and Pujado,P.R. Hydrocarbon Processing, September 1998 p72 et seq. 10. Tsunoda,T., Kizuka,T., Kiyama,T., and Kawase,M. Alpha Process: Conversion of Light Olefin Hydrocarbons to Aromatics. Presented at 1995 DeWitt Poetrochemical Review. Houston, March 21, 1995. 11. Pereira,P., Flores,C., Zbinden,H., Guitan,J., Solari,R.B., Feintuch,H. and Gillis,D. Acquaconversion Technology Offers Added Value to /E. Venezuela Synthetic Crude Oil Production Oil & Gas Journal May 21, 2001 79-85 12. Premizic,E.T., Lin,M.S. and Manowitz,B. Fuel processing Technology 40 (1994) 227-239 13. Weissman,R.C., Brooker,D. and Garza,A. A New Role For Refineries in Meeting Americas Clean Energy Challenge, Paper AM-01-52 NPRA 2001 Annual Meeting 14. Burke, B.F. Emerging Technologies to Develop Stranded Gas, Paper AM-01-44 NPRA 2001 Annual Meeting 15. US Department of Energy Market Based Advanced Coal Power Systems May 1999

TABLE 1 COMMERCIAL DCC YIELDS (THAI PETROCHEMICAL INDUSTRIES) FEED YIELDS C2 & Lighter C3/C4 C5-220 C Naphtha LIGHT OLEFINS Ethylene Propylene Butylenes NAPHTHA PROPERTIES API RON MON 31.4 API Hydrogenated Mid East VGO wt % 11.6 41.5 35.7 5.3 18.5 13.3

49.9 98.5 85.3

Figure 2 Heavy Crude Petrochemical Refinery

Fuel Gas Atmospheric Distillation Naphtha Pyrolysis Coil or QC Ethylene

Atm. Gas Oil Heavy Crude

Recovery
Propylene

Raw Pygas Catalytic Cracking DCC or CPP

Recycles Pyrolysis Gas Oil

Vacuum Distillation

VGO

HydroTreat

Aromatics Recovery

BTX

DAO Deasphalter Gasifier Power Generation SynGas Production

Process Heat Steam H2 Power Liquid Products (Methanol DME Ammonia)

Figure 3 Integrated Petrochemical / Fuels Refinery

Atmospheric Distillation Naphtha Reforming Gasoline

Hydrotreating

Diesel Fuel

650 F and Lighter Vacuum Distillation VGO

HydroCracker

Cracking
Coil / QC, DCC / CPP, Gas Processing

Ethylene Propylene BTX Process Heat Steam Power H2 Liquid Products (Methanol, DME Ammonia)

Bottoms

DAO Deasphalter

HydroTreat

Gasifier Power Generation SynGas Production

Figure 4 Future Oil & Coal Based Integrated Petrochemical Fuels & Energy Complex
Light Naphtha to Cracking Heavy Naphtha H2 Reforming Alkylate and Polygasoline Hydrotreating Diesel Fuel Gasoline Atmospheric Distillation

650 F and Lighter Vacuum Distillation VGO

HydroCracker

Cracking
Coil / QC, DCC / CPP, Gas Processing

Ethylene Propylene BTX Process Heat Steam Power H2 Liquid Products (Methanol, DME Ammonia)

Bottoms

Resid / Coal Hydroprocessing Gasifier Power Generation SynGas Production

Coal

World Petroleum Congress Block 2 Forum2

Emerging Technologies in the Petrochemical Refinery

A.R Johnson, W.S. Letszch, T.E. Swaty and C.P. Bowen Stone & Webster, Inc. - A Shaw Group Company

Presentation Text
(Slide 1 Introduction)
For many years, closer integration of petroleum refining and petrochemical production has been a favorite topic of many papers. While we are dealing with two quite separate businesses in terms of customers and end products they are joined together by a common basic raw material source fossil hydrocarbons. Due to this commonality of raw material there is also considerable overlap in the basic technologies both thermal and catalytic. In spite of these common features, the two business are often only arms-length trading partners, even when under common ownership. In this presentation we will focus upon technologies both developmental and commercial which offer promise in providing the means and flexibility to accomplish closer integration of refining and the production of basic petrochemicals. Also we will consider the potential for making this a three party game by adding power generation as a player. Using these developments as a framework we will then show some examples of how these approaches may be combined to meet certain specific situations.

(Slide 2 Olefins/Aromatics Coil)

Steam cracking of hydrocarbons has been the basic technology for production of light olefins and co-production of aromatics. While steam cracking will undoubtedly continue to play a major role in expansion of this market, incentives for alternative processing approaches are becoming stronger. These incentives include; first, the need for a process to efficiently supply local specific olefin needs where a world scale cracker is not justified, and second, opportunities to consider methane and heavy hydrocarbons as feedstocks,

(Slide 2 Olefins/Aromatics - Fluidized solids/thermal)

Fluid catalytic cracking (FCC) is the most common process for refinery conversion of heavy oils into lighter products. It has always been tempting to consider a fluid solids pyrolysis reactor for petrochemicals. This type of reactor/heat transfer system eliminates concerns over coking and greatly broadens the range of feedstock options.

(Slide 3 QC Reactor sketch)

In the high crude cost environment of the late 1970s, Stone & Webster, in association with Gulf Oil Chemicals, undertook development program of a short residence time downflow reactor employing inert solids. This system employed a circulating solids reaction system named QC (for quick contact). The design is analogous to a FCC operation, employing a solids circulation through a reactor/regenerator loop with supplemental fuel to the regenerator if required for heat balance. The essential design departure from FCC was the downflow reactor-separator system and the use of higher temperatures.

(Slide 4 QC Photo)
A substantial demonstration unit (500 B/D) was built and operated at Cedar Bayou Texas giving results generally comparable to coil cracking. The crude price drop of the mid-1980s removed the incentive for heavy feed processing, and the process has not yet been employed in commercial practice.

(return to Slide 2 Olefins/Aromatics - fluidized solids/catalytic)

In an earlier paper we reported on the development of the Deep Catalytic Cracking (DCC) process by the Research Institute of Petroleum Processing (RIPP) of the Peoples Republic of China. This FCC-type process employs a specifically developed catalyst, and operates at conditions designed to produce a substantial yield of propylene relative to normal FCC operations. Several DCC plants are being operated in China. Together with high yields of propylene, the process also produces a high octane - aromatics-rich gasoline fraction.

(Slide 5 TPI photo/yields)

Since that presentation, Stone & Webster has built a plant for Thai Petrochemical Industry Public Co. Ltd. (TPI) which produces the propylene feed for a world scale polypropylene plant. To our knowledge, this is the first instance outside China where an FCC-type unit has been built for the specific purpose of supplying a petrochemical need. Operation of this unit is described in a TPI/S&W paper6. The process yields show a very substantial yield of propylene together with a highly aromatic gasoline product. RIPP has continued development of catalysts and FCC designs predicated on high yields of olefins. In a further development RIPP has introduced the Catalytic Pyrolysis Process (CPP) capable of producing significant yields of ethylene propylene and butylenes from very heavy feeds. Given these developments in systems and catalysts, it is now possible to consider efficient fluidized solids conversion systems which will permit operation over a wide range of product/coproduct ratios and employing feedstocks ranging from naphtha through residual oils

(return to Slide 2 Olefins/Aromatics - MTO)

Considerable attention is being paid to the exploitation of stranded natural gas reserves by production of transportable liquids such as methanol or Fischer-Tropsch products. Employing methanol as the intermediate, several processes are under development for the conversion of methanol to light olefins. Developments have been announced by UOP, Lurgi and ExxonMobil.

(Slide 2 Olefins/Aromatics - Aromatics)

Aromatics are typically produced by recovery from the gasoline by-product of steam cracking or by reforming virgin naphtha. Recently technologies have been developed for converting aliphatic and olefinic light hydrocarbons to aromatics. Cyclar, developed by BP and licensed by UOP is based upon conversion of propane and butane9. The Alpha process10 commercialized by Asahi Chemical Industry Co., Ltd. at Mizushima, Japan produces BTX from a pyrolysis C4/C5 fraction. A combination of the DCC or CPP technologies discussed above, with aromatics extraction of the pyrolysis gasoline and recycle of raffinates, can be an effective means of co-producing propylene and BTX from vacuum gas oil or light residue with minimum co-production of transportation

fuels. Addition of a technology such as Alpha offers the opportunity to increase the BTX yield from such an operation.

(Slide 6 Residue Conversion)

We will now consider the refinery side of the equation. Most predictions generally assume that future crude supplies will increasingly involve heavier materials. Considering the North America/Caribbean region, the most extensive petroleum reserves are heavy crudes and tar sands. Utilization of these resources will be an essential element in the energy equation of this high demand region. Relative to the theme of this presentation we will focus on the residue upgrading aspects of refining technology, with particular emphasis on integration of Residual Oil Fluid Catalytic Cracking and heavy oil gasification with petrochemical production and/or with electric power generation.

(Slide 7 FCC)
The FCC process has been the refinery workhorse for conversion of heavier hydrocarbons into gasoline and gas oil boiling range materials. While the process is undoubtedly the most capital efficient means to accomplish heavy end conversion, the increasing stringency of product specifications and emission regulations have very specific impacts upon this technology. Issues include product quality particularly sulfur content and regenerator emissions. A number of new processing approaches now address desulfurization of FCC gasoline and upgrading of the cycle oil product. Technologies are now available to remove SOx from regenerator stack gas. In the longer term, hydroprocessing of FCC feeds will play an important role in the sulfur reduction of both product and emissions..

(Slide 8 RFCC photo)

FCC feedstock range has been expanded to include the processing of atmospheric residues. Several RFCC units now operating are designed to process feeds as heavy as full range atmospheric residue from Light Arabian crude. One such unit is shown in the photo. Given the current capabilities of FCC technology, it can now be considered an overlap technology serving both the refiner and the petrochemical producer. The QC, DCC, CPP technologies discussed above are capable of varying feed and product slates to reflect cyclical market factors in these two markets.

(Slide 9 Power Generation - CC )

As a low capital cost option to meet ever-increasing demands for power, the last decade has seen many installations of gas fired power generation. These plants often employ combined cycle configurations to maximize efficiency. In areas such as the United States the fuel of choice has generally been natural gas.

(Slide 9 Power Generation IGCC)

In other cases, gasification of heavy hydrocarbons an old technology which lay dormant for many years is being utilized for new power generation projects.. Power is often generated with steam and hydrogen as co-products. Feedstocks for these plants range from heavy oil through petroleum coke. The drivers for such projects include decreased value for high sulfur coke and heavy oil as power plant fuels coupled with the availability of lower priced heavy, high sulfur

crudes. Extension of this configuration to coal could be a next logical step given the necessary economic driving force.

(Slide 9 Power Generation - IGCC/GTL)

In parallel with these gasification and IGCC developments, there has been a resurgence of interest in technologies for producing liquid hydrocarbons by converting synthesis gas to methanol, DME, Fischer-Tropsch liquids, etc. Anticipating that facilities will be installed local to the petrochemical market to convert methanol to olefins the way is then open to consider production of methanol at refinery sites to provide feedstocks for dispersed petrochemical operations. Such production could be a logical by-product of refinery-based gasification-based power production using low-cost heavy feeds. While the stranded gas situations may in certain cases be of interest to the petrochemical producer (e.g. methanol as an olefin precursor), this technology is mentioned here for its longer term potential in the petrochemical or transportation fuels markets based upon synthesis gas derived from gasification of coke or heavy oils or coal. Because of these two developments power generation by IGCC and natural gas to liquids, we are witnessing establishment of the necessary technology base for coal liquefaction being built upon a foundation supplied by the natural gas industry. Given the above background, in olefins production from heavy feeds, aromatics production and gasification developments, we will turn to consideration of applications to the petrochemical producer.

(Slide 10 - Petrochemical refinery Light/Medium crude case)

We will first consider the simplest case one in which essentially the entire output consists of light olefins and aromatics. In this case ; Crude is separated by atmospheric distillation into naphtha, mid distillate and atmospheric residue. Naphtha and distillate are pyrolyzed by steam cracking employing either a normal steam cracking system or a QC circulating solids system. Conversion of the atmospheric residue is accomplished in either a DCC or CPP reaction system. Products from both the thermal and catalytic conversion systems are processed in a common gas recovery plant. Disposition of the products are as follows: Ethylene and propylene are sent to further processing to produce intermediates and/or polymers. C4+ cracked naphtha is sent to aromatics recovery. The aromatics system can be either simple hydrogenation and separation or it can include a process such as Asahis Alpha process to increase aromatic yields. Residual gases and cycle oils are used as process fuel and fuels for steam and power generation. This approach enables a petrochemical producer to effectively divorce itself from the transportation fuel market, and to have the flexibility of obtaining feed crude) from a number of sources thereby eliminating dependence upon a refiners ability or willingness to supply acceptable feed materials. This approach also enables the petrochemical producer to avoid the need to arrange for disposition of transportation fuels in competition with established producers/distributors.

(Slide 10 Petrochemical refinery - ARDS)

In the case of medium crudes such as Light Arabian - it is desirable to include atmospheric residue desulfurization before processing through DCC or CPP. Beyond the processing benefits to be derived from metals and CCR reduction, hydrogen addition will produce substantial yield benefits. Choice of these options will depend on the price differential between light waxy crudes and medium, higher sulfur crudes.

(Slide 10 Petrochemical Refinery Heavy Crude Case)

The approach taken so far basic petrochemical production with a minimum of involvement with the transportation fuel market can be applied to heavier, high sulfur crudes as well. Processing of the heavier residues however, will require investment in hydrogenation and residue conversion, and a significant light/heavy crude price differential is required to justify this approach. The added steps are: vacuum distillation and deep deasphalting, into heavy gas oil (DAO) and asphalt. The vacuum gas oil and DAO are hydrotreated and then processed by DCC Asphalt from the deasphalting step, together with cycle oils from the thermal and catalytic cracking operations, are gasified to produce a synthesis/medium Btu gas. This gas is then converted to steam and hydrogen for use in the complex and power for both internal use and export. Optionally, a portion of the synthesis gas can be converted to liquid products such as methanol, ammonia or Fischer-Tropsch liquids.

(Slide 11 - Integrated Petrochemical/Fuels/Power Refinery present case)

The preceding cases are extreme in that no transportation fuels are produced. In most environments, it will be more economic to take advantage of the synergism resulting from coproduction of these products.. In setting the fuels products processing sequence, fuel production has been tilted in favor of diesel fuel. This example has been built upon the framework of the previous case the heavy crude petrochemical refinery. The added processing steps are: The virgin heavy naphtha is reformed to produce the basic component of the gasoline pool. Supplemental gasoline is produced by alkylation of C3/C4/C5 olefins to the extent of internally generated and purchased iso-butane. Further, hydrogenated product from a C3/C4 olefin oligimerization process may also be produced. This blend will produce zero sulfur/zero olefins gasoline, in which the benzene/aromatics content can be controlled by the alkylate/reformate ratio and/or by extraction of aromatics to supplement the BTX aromatics products. Vacuum gas oil is hydrocracked either completely to diesel fuel, or partially with coproduction of hydrogen-rich gas oil for petrochemical production. Hydrogenated DAO, together with any unconverted bottoms from VGO hydrocracking, is processed in fluidized solids systems comprising one or more of QC, DCC and CPP. Gas from the cracking complex is separated and processed into fuel gas, ethylene, propylene, alkylate, oligimerization products, BTX and raffinate for recycling. This configuration produces: Environmentally benign transportation fuels A very significant amount of basic petrochemical products Electric power for the complex

(Slide 12 Coal Processing)

The energy crisis decade of 1974-84 witnessed development of a wide range of processes to produce what were termed synthetic fuels. In large measure, these developments were extensions of refining technology. Examples include: H-Coal which drew on HRI now Axens H-Oil technology, coal gasification demonstrations based upon the oil gasification technologies of Texaco and Shell and Fischer-Tropsch gas-to-liquids. While specific government sponsored developments were de-emphasized following the 1985 crude price drop many entities have continued to commercialize critical aspects of these technologies. As a result we are now in a position where the following exist, and merely await an economic basis for commercial use. Coal/coke based IGCC. Such plants are currently operating on petroleum coke13 and coal based operations have been demonstrated e.g. the Cool Water project based upon Texaco Gasification. Coal based liquids production. Ebullated bed reactor systems which provided the basis for Bergius-type coal liquids processes are in commercial operation using heavy crude feedstocks. Fischer-Tropsch variants are being commercialized, as discussed above. While the synthesis gas of current interest is methane-derived, it is no great leap to base such operations upon heavy oil or coal gasification and produce: Methanol Fischer-Tropsch liquids Ammonia/urea DME as a diesel fuel alternative. SNG for peak winter demands.

(Slide 11 - Integrated Petrochemical/Fuels/Power Refinery future case)

Integration of such coal-based technologies with the earlier heavy crude case processing leads to an integrated complex producing transportation fuels both for both conventional and fuel cell based vehicles, petrochemicals including olefins, aromatics and synthesis gas based products and electric power for distribution to the grid.

(Slide 13 Conclusions)
The ever-increasing range of technology options offers the petrochemical producer the opportunity to achieve a level of independence by integration back to crude oil processing without involvement in fuels markets. This option offers the opportunity to integrate with a crude producer and possibly to participate in the benefits of crude acquisition at production cost rather than be subject to market clearing prices for derivative hydrocarbons. This could provide valuable insulation from the effects of the inevitable petrochemical market cycles. On the other hand this same range of technology options offers the refiner or even the power producer the opportunity to participate in the market for basic petrochemicals. Application of such technologies will promote increased collaboration between the three key sectors refining/petrochemicals/power. In this manner these industries should be able to adjust processing parameters in order to insulate themselves against market price swings.