REVAMPS AND SHUTDOWNS

Converting VGO HDS units to moderate pressure hydrocracking

An introduction to the technology of MAK Moderate Pressure Hydrocracking (MPHC), together with details of a successful revamp at the Chiba refinery of Kyokuto Petroleum Industries, Japan

David A Pappal Mobil Technology Company

Michael G Hunter M W Kellogg Technology Company

temperature and between 350 and 1000 normal cubic metres of recycle gas per cubic metre of feed. The two companies have been actively engaged in moderate pressure hydrocracking research for more than 10 years. Mobils first commercial MPHC installation, a VGO HDS retrofit, was successfully started up in 1983. The company operates five hydrocrackers, two of which are partial conversion MPHC designs that process vacuum gas oils into middle distillate products. This research and operating experience has led to an advanced capability to apply hydrocracking conversion technology to heavy feedstocks under moderate pressure conditions. Akzo Nobel has commercialised a family of hydrotreating and hydrocracking catalysts which are combined to achieve the optimal balance between activity and selectivity for each specific refining application. Akzo Nobel zeolite-based hydrocracking catalysts have been selected for application in both of Mobils MPHC units as well as nine additional units around the world.

Lucas R Groeneveld Akzo Nobel Chemicals BV

from the recycle gas enhancing hydrogen partial pressure and catalyst HDS performance. Due to the low light ends make from MPHC, a simple stripper followed by the fractionating column can be specified for product recovery. Low pressure separators upstream of the stripper tower can be specified if hydrogen recovery from the flash gas is a design objective. Lower design pressure and a minimum equipment count result in substantial capital cost savings. The general equipment requirements for the MPHC unit are the same as for many existing VGO HDS units. The primary difference is the need for increased reactor volumes to provide sufficient catalyst to achieve the desired conversion and cycle life. The advanced reactor design capabilities developed by Mobil and available through the MAK hydrocracking technology alliance allow for the efficient and cost effective addition of catalyst volume while minimising incremental pressure drop in the reactor section. Reactor design Reactor performance is vital for the safe, reliable and profitable operation of any hydrocracking process. Multiple catalyst bed reactor designs which do not have adequate quench and redistribution internals are subject to reactant mal-distribution which can lead to reactor temperature instability (temperature excursions and runaways), poor catalyst efficiency (loss of catalyst cycle life) and decreased yields. These issues are as important in moderate pressure partial conversion hydrocracking as they are in high pressure high conversion hydrocracking. Mobil has maintained active research and development programmes in the area of hydroprocessing reactor design for more than 30 years. These programmes have resulted in the commercialisation of the Spider-Vortex quench and redistribution reactor internals together with advanced

arket demand for middle distillate transportation fuels is expected to maintain steady growth in the future. Together with this increasing demand, there will be continuous pressure to lower sulphur content and improve burning quality by increasing the average cetane index of the gas oil pool. Many refiners have found it profitable in recent years to modify existing vacuum gas oil (VGO) hydrodesulphurisation (HDS) units for mild hydrocracking (MHC) service. This is accomplished through the use of specialised MHC catalysts together with changes in the operations strategy for the unit which involve running at near maximum reactor temperatures and accepting shorter catalyst cycles between regenerations. Mobil Technology Company has developed and commercialised a new technology called Moderate Pressure Hydrocracking (MPHC) which is now being offered for license to the refining industry through the Mobil-Akzo Nobel-Kellogg (MAK) hydrocracking alliance. This process overcomes several of the key limitations experienced with MHC type operations and has been applied to the revamp of a 28 000bpsd VGO HDS unit at Mobils joint venture Kyokuto Petroleum Industries (KPI) refinery in Chiba Prefecture, Japan. Moderate pressure hydrocracking is a single-pass hydrocracking process for the partial conversion of vacuum gas oils to low-sulphur distillates and unconverted oil which is highly upgraded relative to the raw feed. Operating at lower pressure significantly reduces capital investment and results in lower operating costs and substantially less hydrogen consumption. Furthermore, the process requirements for MPHC are within the range of many existing VGO desulphurisation units. Typically, the operating conditions for MPHC range between 50 and 100 bar total pressure, 340425C reactor

Process description
MAK Moderate Pressure Hydrocracking is a single stage, single pass process configuration consisting of a reactor section and fractionation section designed to meet specific project objectives. The advanced Spider-Vortex reactor internals design technology allows the application of multi-bed reactors while maintaining stable operations and maximising catalyst utilisation. In most cases, catalyst requirements are such that only a single reactor vessel is needed. Both high temperature and low temperature high pressure separators are utilised in the reaction section to enhance operability and heat integration with the fractionation section. An amine contactor is utilised in the reactor section to remove hydrogen sulphide

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stantially reduced cost as compared to single catalyst hydrocracking systems.

MPHC pilot plant feed properties, yields and hydrogen consumption

Feedstock properties
Specific gravity @ 15.5C Sim Dis, D-2887 IBP 50% FBP Sulphur Nitrogen CCR, D-4530 Net conversion to 343C-minus 0.907 C 295 429 635 2.1 860 0.4 37 9.2 7.8 23.8 18.5 44.9 Nm3/m3 SCFB 84 500 46 13.7 10,4 26.6 17.1 37.1 103 610

Commercial MPHC experience

Mobils first application of MPHC technology was for the revamp of an existing VGO desulphuriser located at the joint venture KPI refinery at Chiba, already mentioned. Design feed for the MPHC unit there was approximately 4200tpd of Middle Eastern vacuum gas oil with sulphur content of 1.8 to 2.8wt%. Operating pressure at the high pressure separator is 55 barg and recycle gas is approximately 645 normal cubic metres of recycle gas per cubic metre of feed. The unit is presently achieving a twoyear operating cycle at 35 to 45wt% net conversion, using an Akzo Nobel catalyst system. The unit was started up in September 1983 and has met or exceeded all design expectations. Its long-term reliability is testimony to the operating expertise, the quality of the process design and the effective performance of the advanced Spider-Vortex reactor internals. The design and operation of the KPI MPHC unit has resulted in a leading edge application of hydrocracking at moderate pressures. A pilot plant programme was conducted at Mobils Paulsboro Research Laboratory in 1990 to evaluate new catalysts which could be used to extend the capabilities of the Chiba MPHC unit. Experiments were conducted at 54 bar hydrogen pressure and 500 normal cubic metres of recycle hydrogen per cubic metre of feed, using Akzo Nobel pretreat and zeolitic hydrocracking catalysts. Feedstock properties as well as yields and hydrogen consumptions at two conversion levels are shown in Table 1. Total middle distillate (166343C) yields of 31.6 per cent and 37.0 per cent were achieved at 37 per cent and 46 per cent net conversion, respectively.

wt% wppm wt% %

Liquid yields

vol% of feed

C5-166C, Naphtha 166-227C, Kerosene 227-343C, Lt gas oil 343-388C, Hvy gas oil 388C-plus, LSFO Hydrogen consumption

Table 1
design techniques to ensure the optimum performance of hydrotreating and hydrocracking process facilities. The commercially demonstrated improvements in temperature distribution and catalyst utilisation have translated into better yields, longer catalyst cycles and more efficient use of limited hydrogen resources throughout the refining system. A complete description of the Spider-Vortex development programme can be found elsewhere. Catalyst selection Another key feature of the process is the specification of an Akzo Nobel catalyst system. The system consists of a pretreat catalyst formulated for high hydrodenitrogenation activity followed by a hydrocracking catalyst with both activity and selectivity tailored to meet specific conversion objectives. Since organic nitrogen compounds are poisons to acidic hydrocracking catalysts, nitrogen must be substantially converted in order to achieve optimal hydrocracking activity. Hydrotreating catalysts are also significantly less expensive than hydrocracking catalysts and are less sensitive to temperature instability. Therefore, it is best to carry out the high heat release desulphurisation and denitrogenation reactions in the beds that contain only hydrotreating catalyst. A large family of catalysts are available to optimise pretreat performance, including highly specialised materials for metals and carbon residue conversion. Akzo Nobels hydrocracking catalysts exhibit a range of activity and selectivity response which can be used to optimise the desired hydrocracking performance on a case-by-case basis. In general, there is an inverse relationship between catalyst activity for conversion and the selectivity to heavier middledistillate products. Zeolite cracking catalysts with the highest activity for gas oil conversion tend to be less selective to the heaviest (middle distillate) products. The distribution of pretreating and cracking catalyst is an important MPHC design consideration. Generally, the percentage of pretreating catalyst in the total fill will range from 40 to 60 per cent. The optimal catalyst distribution will depend on many factors including feedstock properties and processing objectives. Lower overall catalyst requirements and the use of less expensive hydrotreating catalysts result in sub-

Figure 1 Normalised temperature vs catalyst age

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Figure 2 Moderate pressure hydrocracking revamp flowscheme

Hydrogen consumptions were only 84 and 103 normal cubic metres per cubic metre of feed. While these yields do not represent the maximum distillate selectivity for Akzo catalysts, the high activity and stability of KC-2600 allows for an extended operating cycle and better cumulative yield as compared with less active catalyst alternatives. All of the kerosene and gas oil fractions are good quality low sulphur (less than 300wppm) blending components for the distillate pool. The gas oil cuts have cetane indices ranging from 40 to 56. The heavy gas oil and unconverted bottoms are excellent low sulphur (less than 500wppm), low viscosity fuel oil components. The low density and nitrogen content (less than 50wppm) of the HGO and bottoms product also make them excellent feedstocks for fluid catalytic cracking (FCC). Based on these pilot plant evaluations, the Akzo Nobel dual catalyst system was chosen for the Chiba unit and installed in August 1991. The first cycle on KF-843 and KC-2600 was operated successfully until July 1993. The average catalyst temperature normalised to 45 per cent net conversion and constant feed nitrogen is plotted against days on stream in Figure 1. The least squares regression line through the data indicates an aging rate of only 1.2C per month. Also shown in Figure 1 is the actual 343C-plus net conversion. During the first 100 days of operation, the conversion was increased from about 30wt% in the first week of operation to the target level of 45wt%. From 100 days through the end-of-cycle at approximately 650 days on stream, the conversion was maintained essentially constant at 45 per cent. The distillate yield was also very stable throughout the cycle. A cetane index of 50 was also achieved for the gas oil distillate product throughout the catalyst cycle. The current cycle at Chiba was started up with regenerated KF-843 and KC-2600 and continues to operate successfully. Following the commercialisation of MPHC technology in the KPI refinery, Mobil installed a grassroots MPHC unit in 1991 to convert VGO at the Jurong Refinery, Singapore a decision demonstrating Mobils belief and financial commitment to the technology within its own refining system. Design feed for the Jurong MPHC unit was approximately 4700tpd of Middle Eastern vacuum gas oil with sulphur content of 1.8 to 2.8wt%. Operating pressure at the high pressure separator is 83 barg and recycle gas is approximately 674 normal cubic metres of recycle gas per cubic metre of feed. The unit is presently achieving a two-year operating cycle at 50 to 60wt% net conversion, using an Akzo Nobel catalyst system. The key design feature of this unit is a single large diameter multi-bed reactor utilising the MAK Spider-Vortex internals technology.

Hydrocracking costs
The high installed cost for hydrocracking equipment is related to high hydrogen partial pressure requirements and process conditions requiring the use of exotic materials of construction. The required operating pressure level is determined by a complex relationship between feed properties, desired conversion level, catalyst life and product quality constraints. To operate at near 100 per cent total conversion with extinction recycle, high hydrogen pressures are required to limit catalyst deactivation to acceptable rates. In general, heavier, higher end point feedstocks will necessitate higher design pressures for a given conversion level and catalyst life. Also, the aromaticity of hydrocracked products will be directly proportional to hydrogen partial pressure. Designing a hydrocracker with the objective of producing high smoke point specification jet fuel requires very high pressure and can result in significant product quality give-away in the naphtha and diesel fractions and inefficient use of hydrogen resources. While moderate pressure hydrocracking will yield a

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high quality diesel fuel component, the kerosene fraction in general will not have high enough smoke point to qualify as a specification turbine fuel. In many refining situations, however, the kerosene cut will be suitable for blending into the jet fuel pool or can be used for other fuel oil blending purposes and free-up better quality straight run kerosene for jet fuel products. Designing a hydrocracker for singlepass partial conversion operation mitigates to a large extent the need for high operating pressures. The single-pass hydrocracker is not subject to fouling or high catalyst deactivation rates which can result from the buildup of polynuclear aromatics in the recycle oil stream. The kinetic impact of lower hydrogen pressure is compensated by decreased conversion level and by lowering liquid hourly space velocity (LHSV) if necessary. The naphtha, diesel and unconverted bottoms products are not over-saturated and hydrogen consumption is thereby minimised. The economic keys to MPHC are the values of the low sulphur distillate and upgraded bottoms products relative to the untreated feed. For grassroots facilities, the investment required for a moderate pressure hydrocracker is only 50 to 80 per cent of a full conversion hydrocracker. A grassroots MPHC unit which utilises available refinery hydrogen can require less than half of the capital investment associated with a high pressure hydrocracker which in the majority of cases requires the addition of hydrogen manufacturing facilities. Even though the catalyst consumption for MPHC can in some cases exceed that of high pressure full conversion hydrocracking, the overall operating costs are generally only 60 to 70 per cent as high. As illustrated later in this article, it is possible to revamp existing moderate pressure hydroprocessing equipment to achieve conversion levels of 30 to 50 per cent. In these situations, the capital investment to achieve significant hydrocracking conversion can be a fraction of that required for a new unit. Many refiners have discovered that existing gas oil hydrodesulphurisation units can be modified to achieve incremental conversion to more valuable distillate products. In many cases, a change in catalyst system together with only minor modifications to the HDS product recovery equipment can result in 20 to 30 per cent net conversion. Without the addition of incremental catalyst volume, however, this level of conversion will in most cases result in substantially shorter operating cycles as compared to HDS only service. MAK-

Yield and revenue comparison: VGO HDS vs MAK-MPHC revamp

Operating Mode Existing VGO HDS BPSD 600 1620 28 380 MPHC revamp BPSD 4110 3120 7980 16 260 Incremental products BPSD 3510 3120 6360 12 120 Incremental revenue US$/day 65 848 69 264 138 266 224 583 +48 795

Liquid products Naphtha Kero Gas oil LSFO

Notes:Pricing per ARGUS Fundamentals, May 1995 Naphtha = $18.76/bbl, Kerosene = $22.2/bbl Gas oil = $21.74/bbl, LSFO = $18.53/bbl

Table 2
MPHC technology can be used to add reactor volume and achieve as much as 40 to 50 per cent conversion without sacrificing run length. A commercial example is presented here, illustrating the successful application of this concept at the joint venture KPI refinery. Case study Revamp of existing VGO HDS unit Kellogg has performed a simple case study to make a preliminary assessment of the economic value of a MAK-MPHC revamp of existing VGO HDS facilities at a European refinery site. A VGO hydrodesulphurisation unit is assumed to process 30 000bpsd (4400 tons/day) of VGO feedstocks derived from Middle Eastern crudes. The unit is revamped to MAK-MPHC technology with the installation of a new reactor vessel sized to achieve 45 per cent net conversion over a two-year operating cycle. The primary features of the revamp are illustrated in Figure 2. The existing reactors are converted to parallel instead of series flow and act as the lead pretreating catalyst bed. A new three-bed reactor is installed in series with the existing reactors and is loaded with the balance of the pretreating catalyst and all of the required zeolitic hydrocracking catalyst. Also, a new heat exchanger is added to preheat recycle gas against reactor effluent and bypass the existing combined feed heat exchangers and charge furnace. This scheme substantially reduces the recycle gas compressor head requirements and, together with a simple gear change to speed up the existing compressor, can result in a cost effective increase in gas capacity of as much as 25 per cent. Additional modifications include a new make-up compressor to supply the incremental hydrogen demand and the installation of a kerosene draw in the fractionator. The estimated total installed cost of the required revamp facilities is itemised below: (Millions) New reactor $9.1 Makeup hydrogen compressor $2.9 Bypass exchanger and recycle compressor revamp $0.8 Fractionator modifications $2.1 Estimated total installed cost $14.9 A simple comparison of yields and hydrogen consumption is presented in

Figure 3 Incremental revenue and payout vs hydrogen cost

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MAK Moderate Pressure Hydrocracking provides a profitable, minimum investment route to achieving incremental vacuum gas oil conversion while producing high quality low sulphur distillate products
Table 2 together with an analysis of the incremental revenues based on European pricing. Total distillate yield is increased by 12 990bpd with a corresponding increase in hydrogen demand of 380scfb. The expected annual increase in product revenues based on 350 stream days operation per year is US$17.1 million. The incremental annual operating costs for catalyst and utilities are estimated to be US$3.5 million. Total hydrogen demand, including chemical consumption and losses, is 370scf/barrel for VGO HDS and 750scf/barrel for MPHC. The simple payout of the initial revamp investment will be a strong function of the cost of incremental hydrogen, as can be seen in Figure 3. In order to achieve a three-year payout of capital for the study case, the cost of hydrogen should be approximately US$2.0/thousand scf or lower.

Conclusions
MAK Moderate Pressure Hydrocracking provides a profitable, minimum investment route to achieving incremental vacuum gas oil conversion while producing high quality low sulphur distillate products. Mobil has successfully commercialised and demonstrated this technology in both revamp and grassroots applications totalling more than 21 years of operating experience. Reactor design is a key element in the application of hydrocracking technology. Mobils investment in quench zone technology research and development has resulted in the commercialisation of superior reactor internals hardware. The SpiderVortex system allows for the construction of large diameter multi-bed reactor vessels while ensuring reliable and efficient operations. The Mobil KPI joint venture MPHC operation in Chiba demonstrates the high level of hydrocracking performance possible by revamping moderate pressure VGO HDS facilities. The combination of the two companies operating experience and design technology, together with Akzo Nobels state-of-the-art KF-843/KC-2600 catalyst system, has resulted in a two-year cycle length and 45wt% conversion at only 54 barg hydrogen partial pressure. The technology to achieve the results described here is available for license to the refining industry through the MobilAkzo-Kellogg hydrocracking alliance.

David A Pappal is an advanced senior associate at Mobils Paulsboro Technical Center, New Jersey, USA, and is hydrocracking technology leader in the hydroprocessing group for Mobil Technology Company. He holds a BS CHE degree from Pennsylvania State University. Dr Lucas R Groeneveld is a senior application specialist, hydrocracking catalysts, in the hydroprocessing group of the Akzo Nobel Catalyst Business Unit at Amersfoort, The Netherlands. He has a PhD in physics/inorganic chemistry. Michael G Hunter is product manager of hydroprocessing for The M W Kellogg Technology Company, where his principle experience is in hydrotreating and hydrocracking. He holds BS and MS degrees in chemical engineering from Arizona State University.

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