GUIDELINES FOR PRESULFIDING OF STARS CATALYSTS

1. INTRODUCTION STARS catalysts (e.g. KF 757/760/767/848/857/905) have superior activity for sulfur and nitrogen removal and hydrogenation reactions. They are designed with a maximum number of so-called Super Type II Active Reaction S ites (STARS ). Type II Ac tive Sites exhibit extraordinarily high intrinsic activity and are therefore preferred over Type I active sites found on conventional catalysts. STARS catalysts require a slightly adjusted presulfiding procedure to obtain the maximum activity. In this Technical Information Bulletin we will provide background information and guidelines for the presulfiding of STARS catalysts with feed-only presulfiding, as well as with spiked feed presulfiding. Safety : STARS catalyst may emit a little CO (carbon monoxide), especially if stored for a long time or at elevated temperatures. Read the safety instructions before handling.

2. CHEMISTRY OF PRESULFIDING Sulfiding of the metal oxides MoO3, NiO and CoO will result in the metal sulfides MoS2, Ni3S 2 and Co 9S 8. These reactions are exothermic and release water. High temperature and high hydrogen pressure without the presence of sulfur compounds favor reduction of the metals and should be avoided at all time s. The lower valence oxides or metals are catalytically inactive and are only very slowly converted into sulfides. Proper presulfiding is therefore done by addition of the required amount of sulfur in the shortest period of time at a low temperature. 3. PRESULFIDING STEPS There are four steps to a successful in-situ presulfiding: catalyst drying soaking with oil conversion of the oxides to sulfides saturation of the catalyst with sulfur at high temperature

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3.1 Catalyst drying The most active metals are metals with a low metal-support interaction. These metaloxides can be leached out of the catalyst with water. Consequently, the catalyst should be stored and handled in such a way that it remains dry. It is very critical that the feed is dry during start up. Note that water may also affect particle strength. Condensation of water at cold spots in the reactor should also be avoided. Although condensed water is more harmful than steam, we also recommend to minimize the concentration of water vapor during start up and normal operation. As delivered on site, STARS catalysts contain about 12-20 wt% of a proprietary organic compound that will be removed during activation. When loaded slowly in rainy weather, the catalyst may absorb water. Precautions should be taken to protect the catalyst from coming into direct contact with water. If the catalyst cannot be adequately protected, loading should not take place when it is raining. It is necessary to remove the water carefully during the dry-out. The catalyst bed is heated slowly to about 110-130 C (230-265 F) with nitrogen or hydrogen treat gas. To avoid reduction of metal oxides and hydrogen embrittlement of the reactor, the pressure should never exceed metallurgical constraints and preferably not be more than 60 bar (870 psi). Bed temperatures above 140o C (284F) in the absence of liquid feed must be avoided to obtain the maximum activity of STARS catalysts. Since the temperature during gas phase dry-out is difficult to control and temperature overshoot must be avoided, we strongly recommend taking in liquid feed at catalyst bed temperatures of approximately 110oC (230F) . We do not recommend lower temperatures so as to minimize the risk of non-vaporized water carry-over to the reactor (which would deteriorate the catalyst strength and activity). 3.2 Soaking with oil The sulfiding reactions generate heat. In order to limit the exotherm and preserve the high intrinsic activity of Type II Active Sites, dry liquid feed must be present during sulfiding of the catalyst. To obtain a good wetting of the catalyst, the feed rate during wetting and sulfiding should be high, preferably at the design feedrate. Never use cracked feedstocks during wetting and sulfiding of the catalyst, because this will result in a significant lower activity of the catalyst due to premature coking.

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3.3 Conversion of the oxides to sulfides Active metals are converted to metal sulfides during presulfiding: MoO3 + H2 + 2H2S 9CoO + H2 + 8H2S 3NiO + H2 + 2H2S MoS2 Co 9S8 Ni3S2 + 3 H2 O + 9 H2 O + 3 H2 O

The amount of sulfur required for STARS catalysts can be found on the data sheets. Since the conversion of oxides to sulfides is kinetically controlled, H2S breakthrough will occur at a specific moment. This breakthrough is usually observed when about 75% of the required sulfur has been added. During the sulfiding reaction water is released. For every liter of SPIKING AGENT added, approximately 0.6 liter s of water will be formed. It is important for the water to be constantly drained from the system, usually at the high-pressure separator. Note that this water is acidic. It is recommended to check with your corrosion expert whether any precautions need to be taken. The organic component on the STARS catalyst is completely removed during the presulfiding process. Reactions between H2S and the organic components may result in the formation of polar components such as mercaptans, which have a odor at low concentrations. They are readily detectable as their odor levels are far below the danger point, but they have a moderate toxicity and may cause some irritation and headache. It is therefore recommended to drain the water to a closed system. Temporarily, the product may have a yellow/orange color, which disappears during the start up. The color is also caused by polar, probably sulfur containing components, which disappear upon reprocessing it under normal hydrotreating conditions. Water return with the liquid feed to the reactor, either as free water or cloudy gas oil, must be avoided since it may interfere with the presulfiding reactions and affect the catalyst strength and activity. The feed drum should be regularly checked for water and drained as appropriate.

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3.4 Saturation of the catalyst at high temperature The catalyst will reach maximum activity when fully sulfided. After H2S breakthrough, the remaining sulfur needs to be added at higher temperatures. The presulfiding is finished at 320C (610 F), and the unit is then ready to begin normal processing. Cracked feedstock should not be added to the unit for at least three days after completion of the sulfiding . The catalyst is very active, and early addition of a cracked feedstock can lead to excessive coke lay-down and premature pressure drop build-up. After three days, cracked feedstock can be gradually phased in over several days.

4.

PRESULFIDING METHODS 4.1 "Feed-only" presulfiding STARS catalysts have unique Type II Active Sites, which accept sulfur quite easily. It has been found that catalyst activity of STARS catalysts after feed-only presulfiding is equivalent to the activity obtained with DMDS presulfiding. STARS catalysts can be successfully sulfided with feed only, without use of spiking agents. Of course, when desired, the catalyst can also be successfully presulfided with spiked feed. Feed-only presulfiding saves costs and avoids handling of bad smelling and dangerous presulfiding agents. In practice, a total presulfiding time of about 24 hours has been achieved with feed-only, which is close to the time normally required for spiked feed presulfiding. The feed should be a dry light LGO with an endpoint no greater than 380oC (715 F) and a sulfur content of at least 0.8 wt%. If such a feed is not available, or if the presulfiding time is critical, a spiked feed presulfiding can be applied. Note: For regenerated catalyst, a feed only presulfiding is not recommended. The procedure with a spiking agent as indicated below should be used.

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4.2 "Spiked feed" presulfiding In this procedure, a sulfur compound that dissociates easily is added to the feedstock in appropriate quantities. A dry (light) straight run atmospheric gasoil is preferred with a FBP not exceeding 380C (715F) (ASTM D86). For STARS catalysts we recommend the use of DMDS or TBPS. In case you would like to use another spiking agent, please contact Albemarles Technical Service group. As most spiking agents have a high coking tendency under presulfiding conditions, the spiking level is restricted to a maximum 1 wt% extra sulfur in the feedstock. Important : If polysulfides are heated up without H 2 being present, uncontrolled situations may occur because polysulfides can dissociate in to components like elementary sulfur. If H2 is added only after the liquid feed with the spiking agent passes the furnace, it is not recommended to apply polysulfides. If under presulfiding conditions a major part of the feed evaporates while applying polysulfides, hydrogen abstraction reactions can create reactive and less volatile species including olefins, cyclic olefins, and cross-linked or fused aromatics. These reactive materials may continue reacting to ultimately form high molecular weight materials or solids, which may cause increased pressure drop. In case polysulfides are applied, we recommend using a high-boiling feed. We recommend consulting the supplier of the spiking agent for further details (safety, application know-how, etc.).

Table 1 Spiking agent

Sulfur %wt

Presulfiding temperature C 230 220

Density kg/l 1.06 1.15

di-Methyl di-Sulfide Tertiairy-Butyl-PolySuflide

DMDS TBPS

68 53

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5.

GUIDELINES FEED-ONLY PRESULFIDING

Feed-only Presulfiding
Inlet Temperature (C) 350 300 250 200 150 100 50 0 0.0 10.0 20.0 T ime (hrs) 30.0 40.0

1. Order sufficient detection tubes for measuring H2S in the recycle gas. This is usually done with Drger tubes. The following ranges are suggested: 100-2000 ppm (ref CH 29101)-required to check breakthrough 0.2-7 vol% (ref CH 28101)-required to monitor at >0.2 vol% level.

Although the compressor should be designed to handle some H2S, we recommend checking the maximum allowable H2S concentration. 2. Pressurize the reactor system (within its metallurgical constraints) with treat gas to 60 bars (870 psi) maximum. 3. Start recycle gas circulation at normal rates. If necessary, purge and add fresh hydrogen at a sufficient rate to maintain hydrogen purity of the recycle gas at a minimum of 60 vol% during the whole activation procedure. The recycle gas scrubber, if present, must not be in service throughout the whole presulfiding stage. 4. Raise the reactor inlet temperature at 20C/h (36F/h) to 130 C (265F) for dry-out. Do not exceed 140oC (285F) . Temperatures higher than 140oC (285F), at any point in the catalyst bed, may result in less than optimum catalyst activity . Decrease the heating rate to 10oC/h (18F/h) when the furnace outlet temperature reaches 90 oC (195F) to minimize the risk of temperature overshoot. Maintain the temperature at 130oC (265F) for a minimum of two hours. Continue with step 4 when the reactor outlet temperature of 90C (195F) is reached.

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In case the available gas flow is too low to heat up the unit at an acceptable rate, oil may be introduced at an earlier stage, as described under point 5. The only risks of an early oil introduction are: Cold gasoil may create some pressure drop temporarily. The pressure drop will disappear with time while the viscosity of the feed drops with temperature. Limit the feed rate if the pressure drop becomes too high. Liquid water is very detrimental to the catalyst at this stage and any water at cold temperatures should be avoided. Before any feed is introduced, ensure that the feed is dry and that no slugs of water enter the reactor.

Note: On a few occasions, an exotherm has developed after the compressor needed to be shut down before liquid feed was introduced, which left the catalyst under pressurized hydrogen without gas flow for more than one hour. Temperatures might increase to values above 200C (390F) under these conditions. Such an exotherm can be prevented by cooling and depressurizing the unit if the start up needs to be postponed for more than one hour. 5. Start straight run feedstock to the unit (once-through during the whole presulfiding procedure) and stabilize at 80-100% of the design feed rate. Watch pressure drop and reduce feed rate if the pressure drop is too high. Route the product to slop. Use a light, dry straight-run atmospheric gasoil (FBP maximum 380 C, 715F ASTM D86) which is easy to desulfurize and has a minimum sulfur content of 0.8 wt% (preferably higher to shorten the presulfiding time). After the feed rate has stabilized and a liquid level has been established in the HP -separator, continue the catalyst wetting for a period of at least 3/LHSV hours with a minimum of 2 hours and a maximum of 6 hours at 130C (265F). Raise the reactor inlet temperature from 130 o C to 290 C (265 F to 555 F) at a rate of 25 C/h (45 F/h), and maintain the unit pressure at the target level of 60 bar (870 psi). Watch for water formation to start at 180oC (355F). Begin to measure feed sulfur (every 4 hours) and product sulfur (on an hourly basis), either by a calibrated on-line sulfur analyzer or in your laboratory. Begin to measure H2S in the recycle gas every hour. This is usually done with Drger tubes. Different ranges are available and the following is suggested : 100-2000 ppm (ref CH 29101)-required to check breakthrough 0.2-7 vol% (ref CH 28101)-required to monitor at >0.2 vol% level.

6.

Ensure availability of lab technicians on a round-the-clock basis. Also , ensure that the online H 2 and H2S analyzer s, if available, are operational and can be put into service as soon as recycle gas circulation has started.

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7. Maintain the reactor inlet temperature at 290 C (555 F) or lower so as to not exceed a 10-15 C (18-27 F) exotherm over the reactor. Maintain unit pressure at the target level. Measure hydrogen purity of the recycle gas every hour and keep it higher than 60 vol% by purge and fresh gas addition. Do not use unnecessarily high gas purge to minimize the loss of H2S. 8. Calculate the sulfur uptake on the catalyst by making sulfur balances across the reactor. It is expected that H2S break-through (H2S> 0.5 vol%) will occur when about 75% of the required sulfur (Table 1) has been added. If after 2 hours at 290oC (555 F) the %HDS is lower th an 25%, increase the reactor inlet temperature in steps of 5oC (9F) to achieve 25% HDS.

9. After H2S breakthrough and when at least 75% of the required sulfur is laid down on the catalyst, increase reactor inlet temperature from 290oC to 320 C at 10 C/h (555F to 6 10F at 18F/h). If the H2S content in the recycle gas drops below 0.5 vol%, hold the temperature until it is above 0.5 vol% again for at least hour. Hold the temperature at 320C (610F) until the required sulfur (Table 1) has been absorbed on catalyst. The minimum time at 320 oC (610 F) is two hours. In the case where the expected start-of-run temperature is below 320C (610C), it is not recommended to exceed the SOR temperature. However, the final presulfiding temperature should always be at least 300C (570F). 10. Go to normal operating pressure and switch to normal feedstock, if applicable. Increase the temperature to expected start-of-run temperature at a heat-up rate of no more than 10oC/hour (18F/h). If possible, do not put the gas recycle scrubber into operation for the next 12 hours. 11. Do not add cracked feedstock for at least three days . Run on virgin feed only. After three days, the cracked feed may be phased in over several days. 12. Several parameters need to be monitored during presulfiding. A worksheet to facilitate this calculation is presented in Attachment 2.

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6.

GUIDELINES SPIKED FEED PRESULF IDING

DMDS Presulfiding
Inlet Temperature (C) 350 300 250 200 150 100 50 0 0.0 10.0 20.0 30.0

Time (hrs)

1.

Calculate (see attachment 1) and order the required spiking agent in advance. Order sufficient detection tubes for measuring H2S in the recycle gas. This is usually done with Drger tubes. The following ranges are suggested: 100-2000 ppm (ref CH 29101)-required to check breakthrough 0.2-7 vol% (ref CH 28101)-required to monitor at >0.2 vol% level. Although the compressor should be designed to handle some H2S, we recommend checking the maximum allowable H2S concentration.

2. Ensure availability of lab technicians on a round-the-clock basis. Also, ensure that the online H2 and H2S analyzer s, if available, are operational and can be put into service as soon as recycle gas circulation has started. 3. In absence of experience with other presulfiding agents at the time of issue of this document, Albemarle recommends the use of DMDS or TBPS. Please contact Albemarle if you wish to use another presulfiding agent. 4. Ensure that the spiking agent injection facilities are on stand-by and check that the injection point is made at the right location. Test the spiking agent injection pump in advance. 5. Pressurize the reactor system (within metallurgical constraints) with treat gas to 60 bar (870 psi) maximum. The recycle gas scrubber, if present, must not be in service throughout the whole presulfiding process.

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6. Commission the charge heater at minimum duty and raise reactor inlet temperature at 20 C/h to 130C (36 F/h to 265 F) for catalyst dry-out. Do not exceed 140 oC (285F). Optimum catalyst activity will not be achieved if temperatures higher than 140oC (285F) occur at any point in the catalyst bed. Decrease the heating rate to 10 oC/h (18F) when the charge heater outlet temperature reaches 90oC (195 F) to minimize the risk of temperature overshoot. Maintain the temperature at 130 oC (265F) for a minimum of two hours. Continue with step 7 when the reactor outlet temperature of 90C (195F) is reached. In case the available gas flow is too low to heat up the unit at an acceptable rate, oil may be introduced at an earlier stage, as described under point 7. The only risks of an early oil introduction are: Cold gasoil may create some pressure drop temporarily. The pressure drop will disappear with time while the viscosity of the feed drops with temperature. Limit the feed rate if the pressure drop becomes too high. Liquid water is very detrimental to the catalyst at this stage and any water at cold temperatures should be avoided. Before any feed is introduced, ensure that the feed is dry and that no slugs of water enter the reactor.

Note: On a few occasions, an exotherm has developed after the compressor needed to be shut down before liquid feed was introduced, which left the catalyst under pressurized hydrogen without gas flow for more than one hour. Temperatures might increase to values above 200C (390F) under these conditions. Such an exotherm can be prevented by cooling and depressurizing the unit if the start up needs to be postponed for more than one hour. 7. Start straight run feedstock to the unit (once through) and stabilize at 80-100% of the design feed rate. Watch pressure drop and reduce feed rate if the pressure drop is too high. Run the product to slop. Light, dry straight-run atmospheric gasoil (FBP maximum 380C (715 F) ASTM D86) is required with a minimum sulfur content of 0.3 wt%, but preferably higher. After the feed rate has stabilized and liquid level has been established in the HP-separator, continue the catalyst wetting for a period of at least 3/LHSV hours for a minimum of 2 hours and a maximum of 6 hours at 130C (265F). 8. Raise reactor inlet temperature from 130 to 215oC (265 to 420F) for DMDS or to 205C (400F) for TBPS at a rate of 25 C/h (45 F/h). Watch for water formation to start at about 180 oC (355F). 9. When the reactor outlet temperature has reached 190 oC (375F), the feedstock is put on internal circulation (provided, of course, a visual inspection shows that the reactor run-down is free of particulates and does not contain free water).

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10. With the reactor inlet temperature at 215 or 205oC (420 or 400 F), reactor outlet at 190oC (375 F), feed on circulation, and the unit stable, begin with injecti on of DMDS or TBPS at 35% of the calculated rate (see attachment 1). Start measuring feed and product sulfur content on an hourly basis, either by a calibrated on-line Sulfur analyzer or in your laboratory. Begin to measure H2S in the recycle gas every hour. 11. Immediately after establishing stable injection, raise reactor inlet temperature to 230C (445 F) for DMDS or 220C (430 F) for TBPS at the rate of 15C/h (27F/h). 12. When the reactor inlet temperature has reached 230 or 220oC (445 or 430 F), increase spiking agent injection rate to 100% of the calculated rate (see attachment 1). 13. Maintain reactor inlet temperature at 230 or 220 oC (445 or 430F). Adjust the spiking agent injection rate as necessary to limit the exotherm to 10-15 C (18-27 F) maximum. Maintain the unit pressure at the target level of 60 bar (870 psi) maximum. Measure the hydrogen purity every hour and keep it higher than 60 vol% by appropriate purge and make-up gas. Do not use unnecessarily high purge as to minimize loss of H2S. 14. Calculate the sulfur uptake on the catalyst by making sulfur balances across the reactor. It is expected that H 2S break-through (H 2S> 0.5 vol%) will occur when the catalyst has absorbed about 75% of the required sulfur (Table 1). 15. If breakthrough occurs prematurely at sulfur levels considerably lower than 75% of the required sulfur (Table 1), then decrease the spiking agent injection rate to half of the calculated rate. If the H2S level still remains > 0.5 vol%, then increase the reactor inlet temperature to 240C (465 F). Continue under these conditions until about 75% of the required sulfur is laid down on the catalyst. 16. Fix the spiking agent injection rate so that there is sufficient spiking agent available for a total of 8 hours (heating-up period of 6 hours and another 2 hours at 320 oC (610 F)). In any case, do not exceed 1 wt% sulfur added to the feed. Raise the reactor inlet temperature to 320 C (610 F) at a rate of 15C/h (27 F/h). If the H2S content in the recycle gas drops below 0.5 vol%, hold the temperature until it is above 0.5 vol% again for at least hour. Hold at 320C (610F) for at least two hours or as long as necessary to inject all of the spiking agent. In the case where the expected start-of-run temperature is below 320C (610C), it is not recommended to exceed the SOR temperature. However, the final presulfiding temperature should always be at least 300C (570F). 17. Stop the addition of spiking agent and introduce feed in once-through operation.

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18. Go to the normal operating pressure and switch the feed to normal feedstock, if applicable. Increase the temperature to the expected start-of-run temperature at a heat-up rate of 10 oC/hour (18F/h) maximum. If possible, keep the recycle gas scrubber out of service during the first 12 hours of the normal operation. 19. Do not add cracked feedstock for at least three days after presulfiding . Run on virgin feed only. After 3 days, the cracked feed may be gradually phased in over several days. 20. Several parameters need to be monitored during the p resulfiding. A worksheet to facilitate this is presented in Attachment 2.

7.

INFORMATION In case you cannot follow the above guidelines, please contact your Albemarle Technical Service Representative: Albemarle Catalysts Company L.P. 2625 Bay Area Blvd. Suite 250 Houston, Texas 77058 Tel 281-480-4747 Fax 281-283-1519 Albemarle Catalysts Company B.V. Hydroprocessing Catalysts P.O. Box 103 3800 AC AMERSFOORT Tel. : 31-33-4676-310 Fax. : 31-33-4676-104

Please always check with your Technical Service Representative for an updated version of this Technical Information Bulletin.

8.

ADDITION AL INFORMATION

The information in this document is based upon our current knowledge and experience and is believed to be true and correct. However, no warranty (including as to completeness, accuracy, merchantability of the product or fitness for any particular purpose) or performance guarantee is given or implied unless explicitly agreed otherwise in writing. The information is furnished with the express understanding that the customer shall make its own assessment, by preliminary tests or otherwise, to determine the suitability of such information for this purposes. The use of the product(s) and the information, data and recommendations provided herein shall be for the users sole risk and account and unless explicitly agreed otherwise in writing we disclaim any liability, including for patent infringement, incurred in connection with any such use. The information in this document supersedes all previously issued versions of the same. Changes can be made without prior notice.

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ATTACHMENT 1
WORKSHEET TO CALCULATE THE REQUIRED AMOUNT OF SPIKING AGENT AND INJECTION RATE
(Example for KF-757) CATALYST TYPE SULFUR REQUIRED CATALYST QUANTITY (Dry Basis) SULFUR REQUIRED SPIKING AGENT SULFUR CONTENT DENSITY AMOUNT OF SPIKING AGENT KF-757 15 B = 100000 C = 15 x 100000/100 = 15000 DMDS or TBPS D = 68 (DMDS), 53 (TBPS) E = 1.06 (DMDS), 1.15 (TBPS) Example, in case of DMDS: F = 15000/68 x 100 = 22059 G = 22059/1.06 = 20810

% kg kg

(A) (B) (C=A x B/100)

% kg/l kg liter

(D) (E) (F=C/D x 100) (G=F/E)

SULFUR FEED BELOW 0.3 wt%? ONCE THROUGH GAS ? ORDER 15% EXTRA SPIKING AGENT EST. FOR INJECTION RATE (at 240 C)

liter l/h

(G=F/E x 1.15) (H=G/ 10) (I) (J=I/D/E)

G = 22059/1.06x1.15 = 23932 H = 20810/10 = 2081 I = 100000 (LHSV = 1.0) J = 100000/68/1.06 = 1387 (J < H, thus injection rate is 1387 l/h)

FEEDRATE kg/h MAX INJECTION RATE (1 %wt S on feed) l/h (IF "J" EXCEEDS "H", USE "H" FOR INJECTION RATE!)

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ATTACHMENT 2 WORKSHEET FOR MONITORING OF PRESULFIDING

CATALYST TYPE QUANTITY S P I K I N G TYPE A G E N T QUANTITY ORDERED SULFUR CONTENT DENSITY INJECTION RATE PRESULFIDING TEMPERATURE

kg

liter % kg/l liter/h C

DAY

TIME

FEED RECYCLE M A K E - U P PURGE H2 H2S H 2 S FURNACE REACTORREACTORR E A C T O RR E A C T S O PR IKING A SG PE IK N IN T G A G ES NU T L F U R SULFUR SULFUR S U L F U R O NS U L F U R RATE GAS FLOW GAS FLOW GAS FLOW RECYCLE RECYCLE P U R G E OUTLET INLET OUTLET INLET OUTLET INJECTED I N J E C T I O N FEED PROD A D D E D CATALYST % O F GAS GAS GAS TEMP TEMP T E M P PRESSURE P RESSURE RATE TOTAL STOICH kg/h Nm3/h Nm3/h Nm3/h %vol %vol %vol C C C bar g bar g liter liter/h %wt %wt kg kg %

Albemarle Catalysts Company L.P. 2625 Bay Area Blvd. Suite 250 Houston, Texas 77058 Tel 281- 480-4747 Fax 281- 283-1519

Albemarle Catalysts Company B.V. Hydroprocessing Catalysts P.O. Box 103 3800 AC Amersfoort Tel. : 31-33- 4676- 310 Fax. : 31- 33- 4676-104

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HPC-31 11/2005 7 14 of 14