vulcan vgp series purification catalyst / absorbents operating manual

Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts / Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries

Web Site: www.GBHEnterprises.com

GBH Enterprises, Ltd.

VULCAN VGP Series Purification

Catalyst / Adsorbents Operating Manual

Process Information Disclaimer

Information contained in this publication or as otherwise supplied to Users is believed to be accurate and correct at time of going to press, and is given in good faith, but it is for the User to satisfy itself of the suitability of the Product for its own particular purpose. GBHE gives no warranty as to the fitness of the Product for any particular purpose and any implied warranty or condition (statutory or otherwise) is excluded except to the extent that exclusion is prevented by law. GBHE accepts no liability for loss, damage or personnel injury caused or resulting from reliance on this information. Freedom under Patent, Copyright and Designs cannot be assumed.



Contents Section 1 Introduction 2 Process design and modification considerations 3 Health and Safety precautions 4 VULCAN VGP CATALYST containers and storage

5 VULCAN VGP CATALYST handling

6 VULCAN VGP CATALYST charging / loading 7 VULCAN VGP CATALYST discharge 8 Vessel entry 9 System start-up / Shutdown / Standby / Upsets 10 General considerations for liquid and gaseous systems 11 VULCAN VGP Sulfur guards 12 VULCAN VGP Mercury guards 13 VULCAN VGP Chloride guards 14 VULCAN VGP Arsine and other guards 15 VULCAN VGP Reduced materials 16 Reclamation or disposal of used absorbent 17 Treatment options with VULCAN VGP Series Catalyst Materials



1 Introduction GBH Enterprises (GBHE) provide VULCAN VGP Series catalysts and Absorbents for a wide variety of different applications in many industries. There are a number of reasons why gas/liquid streams require purification. For example, sulfur and chlorine compounds are particularly severe poisons for nickel, iron and copper catalysts used in refinery applications, so their removal using VULCAN VGP Series catalysts and Absorbents can prevent catalyst and plant degradation. Mercury and sulfur levels can be significant in raw gas feedstock, and need to be reduced in order to meet tight sales gas specifications. VULCAN VGP Series catalysts and Absorbents products can reduce these contaminants down to parts per billion (ppbv) levels. Hydrogen sulfide (H2S) and carbonyl sulfide (COS) removal from CO2 streams is another area in which VULCAN VGP Series catalysts and Absorbents are well proven. VULCAN VGP Series catalysts and Absorbents products provide purification of process streams using a well-established fixed-bed technology. The flexibility of VULCAN VGP Series catalysts and Absorbents means that they can be effective over a range of temperatures and pressures; they can be used in plants with changing throughput for applications on-shore or off-shore. This manual discusses how to handle and operate the VULCAN VGP Series catalysts and Absorbents, for use in gas and liquid streams, in order to achieve the optimum performance. Every VULCAN VGP Series catalysts and Absorbents application is different, and the product selected is tailor made for each situation. It is important to discuss any proposed changes with the GBHE Technical Sales Manager, to prevent loss of product efficiency. Every care is taken to make sure that all absorbents which are produced by Haiso Technology Co., Ltd. leave our manufacturing site, and are transported to the final destination, in the best possible condition. However, to get the best service from any absorbent it must be handled and operated correctly after the time it arrives at the user’s site. This means that the absorbent should be subject to proper storage, charging and commissioning procedures and should be correctly operated once the plant is on line.



Absorbent handling should be done with care and considered in detail at an early stage. This will ensure that all equipment is available so that proper and safe procedures can be followed. Guidance is provided in this document which will allow the development of local operating procedures to ensure the safety of operators during VULCAN VGP Series catalysts and Absorbents charging and discharging operations. Process operating instructions should also be developed before commissioning of the VULCAN VGP Series catalysts and Absorbents and these should cover the start-up, normal operation, shut-down and emergency procedures associated with the use of VULCAN VGP Series catalysts and Absorbents products. It is strongly recommended that the normal operating boundaries of the VULCAN VGP Series catalysts and Absorbents are detailed and reviewed with GBHE before commissioning of any VULCAN VGP Series catalysts and Absorbents products. It is vital that any modifications to these operating boundaries are discussed with GBHE before any changes to process operating conditions are made on the plant. Failure to carefully review process modifications may result in a loss of process efficiency and could cause a range SHE issues.



2. PROCESS DESIGN AND MODIFICATION CONSIDERATIONS VULCAN VGP Series catalysts and Absorbents are by their very nature active materials. They remove small quantities of contaminants from a wide variety of liquid and gas streams, with high efficiency and effectiveness. As a result of their high activity, they are sensitive to changes in the composition of the process stream. At the project design stage it is therefore vital to consider any unusual or “upset” process conditions as well as the normal operating conditions. Any major differences in process conditions that could occur during start-up, shutdown, or mal-operating conditions should be discussed with GBHE before commissioning. On most new plants and many retrofits, a HAZOP, or Hazard and Operability study will be carried out. GBHE recommend that the use of a Hazard and Operability study is considered and that the VULCAN VGP Series catalysts and Absorbents are only installed following the development of local operating procedures. It is particularly important that any possible interactions of the VULCAN VGP Series catalysts and Absorbent reactors with all other units within the process flowsheet are reviewed. For sulfided materials the possible ingress of air (or pure oxygen) to the VULCAN VGP Series catalysts and Absorbent reactors during trip situations on other units is of particular importance. This situation should be avoided. Furthermore, during the Hazard and Operability study it should be noted that the VULCAN VGP Series catalysts and Absorbent may be chemically distinct in their fresh and in their spent state and the absorbents may therefore be sensitive to different components in the process stream at different stages of their life. The various VULCAN VGP Series catalysts and Absorbents are sensitive to different contaminants and GBHE will choose the most suitable VULCAN VGP Series catalysts and Absorbents for each project based on an understanding of the nature of the contaminants in each process stream.



Contaminants or components of particular interest are: Hydrogen Oxygen Carbon monoxide Unsaturated hydrocarbons Aromatic hydrocarbons Sulfur compounds ( H2S, COS, SO2, RSH, R2S, CS2) Halogen compounds (HF, HCl, Cl2, RCl ) Nitrogen compounds ( NOX, NH3, HCN, Organo – N ) Mercury Metals Arsine / Phosphine / Metal Carbonyls The more detail that can be given about the gas composition the better. GBHE will also need to consider the possibility of solid or liquid carry over into the VULCAN VGP Series catalysts and Absorbent reactor and any significant temperature and pressure changes which may be experienced during operation of the absorbents. Therefore, at the design stage a detailed composition of the normal running process stream should be supplied to GBHE and as much information as is available about unusual operating conditions should also be made available.



Process modifications A distinctive and discrete design will be prepared for each VULCAN VGP Series catalysts and Absorbent application. The choice of absorbent will be made to provide the user with the most economically attractive purification process and to ensure that the VULCAN VGP Series catalysts and Absorbents produces no unexpected SHE hazards during loading, beneficial operation and unloading. However, both the efficiency of the VULCAN VGP Series catalysts and Absorbents and the SHE risk analysis associated with the use of the absorbent can be compromised by uncontrolled process modifications. During the design stage of the project GBHE should be made aware of as wide a range as possible of likely operating conditions including those which could be experienced during start-up, shutdown and emergency operations. If any change to these conditions is expected to occur while the VULCAN VGP Series catalysts and Absorbents on-line then GBHE should be made aware of these changes before the modification is implemented. The range of modifications which should be reviewed with GBHE includes, but is not limited to: - Impurity concentrations - Operating pressures - Temperatures - Viscosity - Flow rates - Changes to the source of the process stream - Changes to the levels of contaminants such as oxygen, hydrogen, carbon monoxide, unsaturated hydrocarbons, Sulfur species and ammonia. - The design conditions should also be confirmed against the actual operating conditions to ensure that the bed is not exposed to unexpected challenges.



Other considerations that should be included at the design stage or as part of a modification are: - Provision of suitable non-isolatable pressure relief systems - Isolation of vessels for maintenance and bed change out (Double block

and bleeds are the usual standard for vessel entry) - Access for change outs - Sample points and monitoring systems - Process control and analytical systems to achieve required outlet specification - Provision of purge points and venting systems - Pipe layout - Fouling rates / liquid carry over - Provision of filters - Single phase or 2 phase / Dense phase operation - Up or down flow in the case of liquid treaters - Provision of hard standing areas for absorbent changeouts - Selection of absorbent loading system - Vessel inspection requirements - Corrosion rates - Impact of other unit operations



Examples of different modes of operation VULCAN VGP Series catalyst and Absorbent purification beds can be arranged in numerous different combinations, depending on the stream and the target contaminant. Single beds Lead lag beds Parallel beds Process control Pressure drop minimization Phased installation Beds used in combination with other processes

Vessel drawings

Vessel drawing of 2 or 3 typical vessels showing details of standard collector and distributor arrangements. Note, the collectors and distributors are individually sized for each case. It is important to ensure that the ceramic support balls are larger than the slots or holes in the collector



Monitoring of beds

It is recommended that the beds are monitored on a regular basis to assess ongoing operational performance

Many plants have DCS type systems which record process flows, temperatures and pressures but there are other variables which should also be recorded.

A typical list would include:

- Inlet impurity concentration - Outlet impurity concentration - Pressure drop - Flow rate (Typical, average and peak) - Temperature - Pressure - Any changes in stream composition - Any operational issues - Bed status – lead / lag, parallel, bypass etc.

This information is very useful if there are any issues with the bed as it allows a picture to be built up of the operation over an extended period. It is very helpful if these records can be forwarded to the relevant GBHE contact person as it is the best way of improving the understanding of the particular process stream and operation.



Health, Safety and Environmental Precautions 3.1 Working Practice Guidelines Operators should be aware of the hazards associated with the use of absorbents and draw up the appropriate safety measures. The Material Safety Data Sheet supplied by GBHE should be consulted for information on specific absorbents. The key areas to address include, but are not limited, to: 3.1.1 Training All personnel involved in absorbent handling should be instructed in the potential occupational health and safety hazards associated with both fresh and used absorbent, and the appropriate precautions to be taken. 3.1.2 Site Preparation The absorbent handling area should be roped off to exclude unauthorized personnel. The restricted area may have to be adjusted, depending on the wind strength and direction. Provision will have to be made for the access of forklift vehicles and dust extraction equipment etc. where necessary. 3.1.3 Ergonomics & Personal Protective Equipment Physical hazards arise from the handling of drums, materials and lifting equipment. Personnel should be aware of these, and appropriate precautions taken. Personnel working with the absorbent loading, unloading, screening, sealing drums, cleaning up spills etc. should wear protective overalls, goggles, hard hat, gloves, boots and appropriate dust masks.



3.2 Dust Control It is essential to control the inhalation of absorbent dust to levels below the appropriate occupational health exposure limits. Engineering methods should be employed as the primary means of controlling exposure to dust whenever this is reasonably practicable. If dust cannot be controlled to safe levels, suitable approved respiratory protection must be worn. All the activities involving absorbent dust must be assessed to gather information about health hazards, to evaluate the risks and to specify controls. The hazards associated with absorbents depend on the composition of the absorbent, and the Material Safety Data Sheets provided by GBHE should always be consulted. The potential short and long term health effects are described in these data sheets. It should be noted that the Material Safety Data Sheets apply to the unused absorbents. Absorbents discharged after use will usually have different physical and chemical properties and these properties will vary with the plant operating conditions. 3.2.1 Dust Masks The type of respiratory protection to be worn depends on the dust levels generated, and the exposure limits for the materials involved. However, experience suggests that personnel involved in charging and discharging operations inside a vessel should wear approved full-face air supplied breathing apparatus. If there is a danger of loss of consciousness or asphyxiation, powered respirators with high efficiency filters must be used. It is preferable to use positive pressure rather than demand systems. Personnel involved in other activities such as the screening of absorbents, filling socks and cleaning up spillages are advised to wear suitable dust masks. The maintenance of equipment that has contained catalyst/absorbent may also necessitate the wearing of suitable dust masks. All personnel required to wear respiratory protection should be instructed in its proper use, and limitations. A DUST MASK IS NOT A BREATHING APPARATUS AND MUST NOT BE USED AS PROTECTION AGAINST TOXIC GASES, OR IN AN ATMOSPHERE DEFICIENT IN OXYGEN ( <19.5%).



3.2.2 Monitoring Periodic air monitoring can be carried out to determine personal exposure levels to airborne dust. These monitoring results can be used to assess the effectiveness of the dust control measures and respiratory protection. An assessment of the performance of any local exhaust ventilation that is installed should be carried out. Monitoring should also be considered for other fugitive emissions and releases such as hydrocarbons, aromatics, mercury vapor or any other contaminants of the process stream. If an issue is identified, the work should be stopped until a safe way forward has been agreed amongst the parties involved 3.2.3 Housekeeping All absorbent spillages should be cleaned up promptly using methods that do not produce airborne dust e.g. with a vacuum cleaner with a high efficiency filter, or by wet mopping. Dry sweeping should be avoided. All sweepings and other debris should be disposed of in a suitable way. They should not go into the domestic waste. 3.2.4 Personal Hygiene To prevent the ingestion of absorbent dust, no eating, drinking or smoking should be allowed in the absorbent handling area. Personnel working with absorbents should practice good personal hygiene and wash their hands and faces prior to eating, drinking or smoking, and washing hands before using toilet facilities.



3.3 First Aid Measures In the event of direct exposure to absorbents, the following first aid measures should be taken: Eye Contact - flush the eyes with clean water for at least 15 minutes. If any irritation persists, medical attention should be obtained. Skin Contact - wash off immediately using soap and water. Ingestion - obtain medical attention. Give 250 ml of water to drink. DO NOT give anything to an unconscious person. Do not induce vomiting. See Material Safety Data Sheet for the specific recommendations for particular products. Check suitability of these generalized first aid measures 3.4 Entry into Inert Gas Atmospheres Operators should never enter an absorbent vessel filled with an inert gas unless they are fully trained in inert entry procedures. Without an approved breathing apparatus, the operator would lose consciousness within a few seconds and die soon afterwards. There have been a number of double fatalities when somebody outside a nitrogen filled vessel has entered without breathing apparatus, to assist a colleague already in difficulties. Even looking closely into the open manhole of a nitrogen filled vessel can be very dangerous without approved breathing apparatus. Openings into a vessel blanketed with inert gas should be kept closed, except when work is going on inside, and there should be prominent warning notices to alert everyone to the potential hazard. All personnel working in the area should be made aware of the nature and dangers of asphyxia, and should know how to attempt the rescue and resuscitation of anybody who may be overcome. If entry into a nitrogen filled vessel is unavoidable, it is essential to use a fully integrated life support system with adequate back up. There are a number of specialized companies that have teams of fully trained staff available for this type of work.



See also diagram and references in section 8 3.5 Discharge of catalyst/absorbent It is important to note that spent material may be contaminated with process fluid as well as any debris/contamination that has accumulated on the bed. The spent absorbent will also be chemically different from fresh material, so different handling precautions will be required. Issues associated with particular absorbents are detailed in the discharge section and the safety data sheet. 3.6 Discharge of Self-heating Absorbents Some VULCAN VGP Series catalyst and absorbents will be discharged in a self-heating state. In these cases the effect of oxidation on the absorbent can cause a significant temperature rise. There are 2 main potential causes of this, 3.6.1 Sulfided material Some sulfided materials may react with air to produce heat. In extreme cases, some decomposition may occur, releasing SO2. It is essential that the discharged absorbent is kept separate from flammable materials. The material should be discharged into approved UN drums so that it can be shipped to a reprocessing facility as a self-heating material. Appropriate local regulations should be adhered to for this activity.



3.6.2 Reduced material Some reduced materials may react with air to produce heat. In these cases local stabilization/re-oxidization of the material may be possible. It is essential that the discharged catalyst is kept separate from flammable materials. Transport of such absorbent should be in enclosed metal skips or enclosed metal-sided trucks. Dumps of the absorbent should be within easy reach of water hoses so that any overheating that occurs can be controlled. High temperatures can build up in heaps and it may be a prudent precaution to spread the absorbent thinly over the ground until oxidation is complete. This should be done in a banded area, to prevent any contaminated water going to drain. Under no circumstances should personnel be allowed to walk over the absorbent until it has been fully stabilized. 3.7 Discharged Spent Sulfur Absorbents The discharged absorbent contains sulfides and should not be stored near acids. Accidental contact of the spent absorbent and acid would result in the evolution of hydrogen sulfide (H2S). Similarly, accidental mixing of sulfided material with oxidizing agents could result in release of SO2 3.8 Discharged Spent Chloride Guards As with discharged sulfur guards, spent chloride guards should not be stored near acids or oxidizing agents, as accidental mixing could result in the release of HCl. 3.9 Ancillary Equipment For some applications, filters may be installed, either on the process stream or as part of the vacuum handling system. Due care should be taken when changing filters as dust contamination can be a source of self-heating. Used filter bags should be put into a sealed metal container, for disposal.



3.10 Environmental precautions Care should be taken to ensure that fresh or spent absorbents do not enter the environment. It is particularly important to note that sulfided absorbents oxidise to sulphates in air. Sulphates are much more soluble than sulfides and will readily enter water systems. Some absorbents contain components which are significant marine pollutants if discharged to water system and may affect fish or effluent treatment facilities For further information contact your local GBHE representative or:



4. VULCAN VGP SERIES CATALYST CONTAINERS AND STORAGE

Drums GBHE most commonly supplies VULCAN VGP Series catalyst and absorbents in steel drums with polythene liners. The drums can be banded on pallets to allow easier movement. The full drums weigh between 80 and 250kg (175 and 550lb) depending on the density of the product. The absorbent drums should be inspected on arrival on site for damage, so that any insurance claim can be substantiated. Drums should not be stacked on their sides, or stacked more than four drums high, even when supported on pallets. Taller stacks tend to be unstable, and the lower drums can be crushed. If the drums are to be stored on site, they should be kept under cover and away from damp walls and floors. The lids should be left on until just before the absorbent is to be charged. If lids are removed for any reason, e.g. to permit inspection, they should be replaced as soon as possible to prevent any contamination of the absorbent.

Figure 1. Stacked drums on pallets in a 40 CT Container



IBC’s GBHE absorbents can also be supplied in VULCAN Box containers on pallets. Typically, an VulcanBox will contain about 1m3 (35ft3) of absorbent. The absorbent is actually stored within the VULCAN Box in a Flexible Intermediate Bulk Container (FIBC or, commonly, a “big-bag”or “supersac”) which allows easy handling of the absorbent during lifting and transferring operations. If absorbents are supplied in VULCAN Box’s then time can be saved by avoiding the handling of a large number of drums during a shut-down period. VULCAN VGP Series catalyst and absorbents can be stored for long periods in VULCAN Box’s, provided they are suitably protected. Indoor storage is preferable.

Figure 2 : Picture of VULCAN Box

By special arrangement some absorbents can also be supplied in big bags without a VULCAN Box, 2m3 IBC hoppers or 25m3 bulk containers. Unless otherwise stated, GBH Enterprises VULCAN VGP Series Catalyst and Absorbents are not affected by extremes of temperature from -50°C to +50°C (-60°F to +120°F) provided that they are kept dry. In extremely humid conditions it may be necessary to store the absorbents in an air-conditioned building. Pre-reduced absorbents can overheat at temperatures above 100°C (212°F) and should therefore be stored below 50°C (122°F).



These materials should be kept out of direct sunlight, away from other sources of heat and away from combustible materials. Consideration should be given to the storage of other chemicals in the same area as GBHE VULCAN Series catalyst and absorbents.

It is particularly important that acids are not stored in the presence of sulfided materials, as accidental mixing could release toxic H2S. Oxidizing agents may cause the release of SO2 Similarly, spent chloride guards should not be mixed with acids or oxidizing agents as this may cause the release of HCl



Detailed information regarding product hazards are contained in the Material Safety Data Sheets. 5. VULCAN VGP SERIES CATALYST HANDLING

Drum handling VULCAN VGP Series Catalyst drums are supplied on pallets for ease of handling and to reduce the likelihood of damage in transit. A suitable fork-lift truck and a paved area are required to move the pallets. The fork-lift truck to be used for dismantling the pallets should be fitted with rim or body clamps to avoid damage to the drums. Standard fork-lift trucks must not be used to lift individual drums under the rolling hoops, as this inevitably damages the drums and absorbent. VULCAN VGP Series Catalyst drums should be handled as carefully as possible. If a mobile crane or suitable equipped fork-lift truck is to be used, a smooth paved area is desirable to facilitate movement. When drums are to be lifted to the charging manhole, it is usually more satisfactory to use a mobile crane rather than the individual lifting beam on the vessel. A crane can lift drums from a wide area, and this avoids multiple handling. Drums must not be rolled. If manhandling is unavoidable, suitable drum barrows, upending levers and skids should be used. More importantly, proper equipment is essential for the safety of the operators particularly when larger or heavier drums are involved. VULCAN Box / Big Bag handling Big bags, also known as IBC’s, typically contain 1m3 of absorbent. As a result they weigh around 1 tonne, and need to be moved by a suitable forklift truck. When the bags are being lifted to the top of the vessel for loading, spreader bars or extended hooks are required. If all 4 loops of the bag were fitted into a single crane hook, this applies excessive force on the bag which may result in a split bag.



Use of Cranes If a crane is to be used for catalyst/absorbent loading an appropriate lifting study should be carried out. Although these are not particularly big lifts, there can be a large number of small lifts in a short period of time. Use of forklift trucks Where forklift trucks are used, the work area should be cordoned off. For some sites, all terrain forklift trucks are required; otherwise a smooth paved area is preferable for the handling of drums and IBC’s. The zoning restrictions and control of sources of ignition in the work area should also be considered. It may be necessary to use diesel fork trucks, or fork trucks with flame arrestors in some process areas. Other equipment, such as tractor units for articulated lorries may need to operate under hot work permits. Control of work and risk assessments. Handling and loading operations should be controlled by local work permit systems. Where appropriate, a risk assessment may be required. This operating manual should answer most of the questions raised by a risk assessment, but if there are further questions, GBHE should be contacted to ensure that all issues are resolved.



6. VULCAN VGP SERIES CATALYST CHARGING / LOADING 6.1 Pre-charging Checks Before the VULCAN VGP SERIES CATALYST absorbent is charged, it is important to check the internal condition of the vessel. ln particular, checks should be made on the condition of the exit distributor, the absorbent support grid and any inert support material such as ceramic balls. Faults at these points cannot easily be rectified after the absorbent has been charged. If there has been any evidence of high pressure drop, or any operating problems, it may be worth removing any ceramic balls from the vessel head to remove any dust or scale. Dust accumulations in the ceramic balls can significantly raise the pressure drop across a vessel. The vessel should be clean, dry and free from loose scale and debris. It is important that the charging level is clearly defined to make sure that the correct volume of absorbent is charged. The required final level can be marked with chalk, before charging is started. A useful additional check can be made at this time by warming up any thermocouples, to make sure that the expected indication is being given on the control panel, and to check that any sample points are clear and undamaged. For vessels where a long bed life is expected, it is also worth checking that any vessel inspections are up to date, and doing any statutory internal inspections that are required while the vessel is empty. Some form of light metal grid or spider should be inserted into the discharge manhole to prevent inadvertent absorbent discharge when the manhole cover is eventually removed for discharging the vessel. The manhole should be securely tightened before the vessel is loaded, although it may not be necessary to fit all the bolts at this stage.



VULCAN Series Catalyst and Absorbents Reactor LoadingGrading Material Loading Diagram

ID = 7' 0"

design actual design actual

Dist Tray 8' Baskets are out9' 9'

26 ft3 active support, high void cylinder 16 mm9'8" 9'8"

active support, hollow cylinder 6.4 mm

13'2" 12'

catalyst 1/10"

catalyst 1/10" 14'10" 15'1"19 ft3 active support, ball 8.0 mm 15'4" 15'5" Top of Supp. Grid

Supp. Grid 15'8" Filled up dump chutew ith 1/8" support

Collector trayPerforate tray

Dist Tray 21'4" 21'4" Support beams extend 6"21'10" 21'10" to 8" below tray.

19 ft3 active support, high void cylinder 16 mm 22'4" 22'4"

19 ft3 active support, hollow cylinder 6.4 mm 22'10" 23'3"

19 ft3 active support, hollow cylinder 4.8 mm 23'4" 23'4"

272 ft3 catalyst 1/10"

30'5" 30'3"19 ft3 active support, ball 8.0 mm10 ft3 support balls 1/2" 30'8" 30'9" Top of stool

Elephant stool 31'8" 31'11" Btm of stoolBottom dump chutes w ere packed w ith kaow ool

Hollow cylinder 6.4 and 4.8 are the metric sizes

6"

Quench

6"

6"

Gear/Water w heel shape 16 is the metric size

Trilobe

Sphere 8.0 is the metric size

2'4"

8"

2'6"

7"

6"

85"

6"

Internals between the two beds are to be

6.2 Charging Vessels 6.2.1 General Issues A layer of heavy inert material (ceramic lumps or balls) or sometimes metal hold down grids should be placed on top of the absorbent, to prevent movement of the absorbent pellets by the incoming gases. A layer of inert material can be useful in trapping contaminants in the gas before they reach the absorbents. The VULCAN Series A2ST range of materials provides particularly good performance on those duties where occasional fouling may be an issue. Most absorbents produce some dust during the charging process. Therefore, suitably approved full-face air supplied breathing apparatus, or powered respirators, with high efficiency filters must be provided for all operators entering the vessel. Protection against dust is particularly important if the absorbent has any toxic properties. It is essential that the atmosphere in a vessel is checked before allowing entry.



There are two important general rules for charging VULCAN VGP Series Catalyst absorbents into vessels:

• The absorbents must not have a free fall of more than 50- 100 cm (20 - 40 inches).

• The absorbent must be distributed evenly as possible as the bed is filled. The distance that an absorbent pellet can fall without serious damage depends on its strength and shape. A hard spherical granule will withstand a fall better than a soft angular pellet or extrudate. Recent work indicates that some absorbents can be charged satisfactorily using a pneumatic conveyor, and this technique can shorten the charging time substantially. Generally, the absorbents and catalysts should be loaded via suitable hoppers and a loading sock. The materials should not be loaded via a vacuum system as this may lead to significant deterioration of the absorbent. In some cases, vacuum loading has been used, but use of this option should be discussed with GBHE before loading commences. 6.2.2 Loading procedures The absorbent must not be poured into the vessel at one spot, even if the resultant heap is raked level. This is because the particles tend to segregate as shown in Figure 3. Any small particles and dust stay mainly in the centre of the heap, while large pieces roll to the edges. This can lead to uneven distribution of the gas flow during plant operation. Care should be taken to ensure that the top of the absorbent bed is level after charging has been completed. If the bed is wide, and access is through a side manhole it can be difficult to get the absorbent distributed across the vessel without raking. However, raking is generally undesirable as it can lead to a concentration of fines near the manhole.



Figure 3: Particle Segregation during Charging



In practice, this type of maldistribution is most likely when the absorbent has been allowed to fall into one spot just beneath the charging manhole. This type of problem can occur also when operators walk on the absorbent bed, or vibrate it unevenly. When it is necessary to walk on the absorbent bed, the load should be spread as much as possible by using charging boards on top of the absorbent. The following equipment is required for manual absorbent charging: 1 Safe access to charging manhole - side or top as appropriate. 2 Crane, or local lifting beam, with suitable hoist. 3 Metal hopper or tundish plus section of flexible plastic tubing for top entry

manhole. 4 Canvas or plastic sock and rope - both of sufficient length to stretch from

the charging manhole to the lowest level of the absorbent. MANUAL ABSORBENT LOADING For outdoor installations it is recommended that manual absorbent charging is not carried out in heavy rain or high winds. The performance of the absorbent is not hindered by small amounts of water entering the reactor during absorbent charging. It is recommended that temporary weather protection is provided around the charging manhole. A hopper/tundish is usually supported above the charging manhole. The loading procedure should insist on the hopper/tundish being supported 1 m above the manhole to allow viewing access to the reactor. This can typically be done using temporary scaffolding. Ensure the absorbent support system has been installed as defined in the mechanical data sheet. This may require insertion of a wire mesh grid, ceramic balls or absorbent support material - see section 'Reactor Preparation'. Ensure the absorbent support system is horizontal and the top surface is free of debris. The absorbent charging procedure is as follows:



Empty the absorbent into the hopper or tundish and fill the sock with absorbent. The absorbent will flow into the reactor in a controlled manner. The rope attached to the free end of the canvas sock can be used to guide the sock so that it does not always discharge at the same point. As the level of the absorbent bed rises towards the free end of the absorbent sock, the reactor filling rate will be reduced. When this is observed the sock should be emptied of absorbent and shortened. This is most easily done by raising the free end of the sock with the rope and cutting 1 m off the sock with a knife.

When the absorbents have been charged to the correct height, the absorbent surface should be levelled using care. The ceramic ball loading should then be loaded as defined in the reactor mechanical data sheet. On completion of absorbent and ceramic ball loading, replace the charging manhole cover. If there is any delay during absorbent charging, the reactor manholes should be securely covered to prevent the ingress of water or other absorbent contaminants from the air. Once the reactor is boxed-up and mechanically complete GBHErecommend maintaining the reactor at pressure under an inert gas to prevent ingress of potential absorbent contaminants - see section 'System Start-up/Shutdown/Standby/Upsets'. A deep narrow bed is the easiest shape to charge satisfactorily, as irregularities are more likely to be evened out along the direction of the gas flow. Extra care is required with wide beds because it is more difficult to distribute the absorbent evenly over a large area. Radial flow beds are particularly susceptible to irregular packing and uneven gas flow. 6.2.3 Loading Problems Uneven packing of the absorbent and breakage during charging can seriously affect the gas distribution and the effectiveness of the absorbent bed. The degree of packing in the absorbent bed has a marked effect on the voidage. Even in a bed of regular pellets, the voidage can vary by +/-10%. If the particles are not all the same size, then the voidage variations can be considerably greater. The effect of packing on pressure drop is very marked.



To a first approximation the pressure drop is inversely proportional to the cube of the voidage and a +/-10% variation in voidage can result in a +/-30% variation in pressure drop. Furthermore, it is possible that a loosely packed bed will settle in use and the pressure drop may increase by up to 50% as this occurs. The effect of packing variations on the distribution of gas flow is more pronounced at low flow rates, because the flow becomes less turbulent, although the performance of the absorbent at low flow rates (when the inlet flow rate of contaminant is likely to be lower than the design value) may be less critical. 7 VULCAN VGP SERIES CATALYST Discharge Drawings of typical arrangements to be included in these sections Introduction The safe discharge of absorbent can be the most challenging phase in the life cycle of a bed. The absorbent will have changed its chemical composition, will be saturated in the process fluid and may have picked up other significant contaminants. As a result, this activity should be carefully considered and subjected to appropriate risk assessments Contamination Depending on the duty, other contaminants may have accumulated on the bed. These can include, mercury, aromatic hydrocarbons, oils, wax, metals, and iron sulfide among others. These contaminants can site or duty specific and will vary from case to case. Where necessary the bed should be sampled before discharge to ensure that appropriate PPE is worn. Where this is not possible, a higher level of PPE may be required for the job to ensure that the operators are not exposed to unacceptable levels of potentially harmful compounds. In such cases a COSHH (control of substances hazardous to health) assessment may be appropriate.



In general, the hazards associated with contamination of the bed will be similar to the hazards associated with a normal break in to the process lines. However, because of the high surface area of the absorbent, the concentrations may be higher than have been seen elsewhere in the process. Self Heating Materials. Materials which are either supplied in the sulfided form, or become sulfided in use can be self heating on discharge. In these cases the material should be discharged under nitrogen. Appropriate precautions for monitoring the nitrogen content of the work are and the provision of breathing apparatus should be considered. In some duties it is also possible for pyrophoric iron to accumulate on the top of the bed. This is scale which has become sulfided, broken off the inside of the pipe and washed down onto the bed Non-self heating materials Materials for the removal of chlorides are not generally self heating and do not usually need to be discharged under nitrogen once the vessel has been thoroughly purged There are three ways of discharging absorbent from a reactor:

- By gravity - By vacuum - Manually



Before discharge The following precautions should be taken before discharging the absorbent:

1 Ensure the reactor is isolated and purged with nitrogen for a suitable period. This reduces the quantity of any adsorbed hydrocarbons on the absorbent and eliminates potential for forming an explosive mixture with air. Purging is best achieved by repeated pressurisation and depressurisation.

It is recommended that the nitrogen specification should include a clause for an

oxygen level of less than 0.1% (mol).

2 Experience of VULCAN VGP Series Catalyst materials has shown that pyrophoric iron sulfide can accumulate in the bed from the process due to the long life of the absorbent.

Furthermore, the spent absorbents are themselves deemed liable to self heating in contact with air therefore DO NOT PURGE WITH AIR. Given enough oxygen and enough time the copper sulfide within the spent material will eventually oxidise giving off heat. The discharged absorbent should be sealed in the drums, to avoid ingress of air. Although the spent VULCAN VGP Series Catalyst material is not in itself pyrophoric, it is still recommended to handle it under inert conditions. Any inert entries into vessels must be undertaken with breathing apparatus and all appropriate precautions.

3 See section 'Absorbent Handling' for absorbent handling precautions.

4 See section 'Reactor Entry' if reactor entry is required.



7.1 ABSORBENT DISCHARGING USING GRAVITY The vessel should be under a nitrogen purge to prevent ingress of excessive amounts of air. As a result, operators working in the vicinity should be protected with appropriate PPE. Gravity discharge is the most common method. Manual discharge is usually only used as a last resort for small or part absorbent reactor volumes. In this particular case, the reactor is designed with a conical section in the bottom. This should allow complete absorbent discharge into the spent absorbent handling system. If there is sufficient headroom under the vessel, it may be possible to discharge direct into drums using a conventional double headed drum filling unit. If there is not sufficient room, it may be necessary to install a vacuum unit to transport the material to the area where it will be drummed up. The following equipment is required:

1 Container(s) for 'used' absorbent - empty metal drums

2 Tundish 2 Either plastic chutes/tubing or specialist vacuum equipment. 4 Drumming unit with dust extraction Set-up the absorbent discharging equipment - see figure for typical arrangement. A slip plate fitted in the discharge chute can control the rate of absorbent discharge.



When the majority of the absorbent is discharged it may be necessary to remove the following by hand or with specialised vacuum equipment : 1 Any remaining absorbent.

2 Ceramic balls plus associated wire mesh (if present) which were originally on top of the absorbent. Ceramic balls can be reused if their condition is satisfactory.

The side manhole should be removed and any absorbent, which is against the manhole, can be removed through the spider. Rotate discharge manhole spider to control absorbent flow: Spider webs horizontal - no absorbent discharge

Spider webs vertical - maximum absorbent discharge rate 7.2 ABSORBENT DISCHARGING USING VACUUM EQUIPMENT

Vacuum discharge may be carried out under nitrogen to avoid the risk of the used absorbent self-heating. Alternatively, several discharges have been successfully carried out with the vessels under nitrogen blanket, and air used as the fluid carrier only. The following equipment is required: 1 Safe access to the discharge manhole.

2 Specialised vacuum equipment with sufficient length of flexible plastic tubing to reach the lowest level of absorbent. A long length of rope attached to the free end of the tubing.

3 Container(s) for 'used' absorbent - may be combined with specialised vacuum equipment, otherwise empty drums, or container. Remove the discharge manhole cover. Set-up the absorbent discharging equipment - see figure for typical arrangement. Remove the ceramic balls that may be on top of the absorbent by hand and/or specialised vacuum equipment.



Discharge absorbent using specialised vacuum equipment using rope(s) to control flexible plastic tubing as necessary. In certain circumstances it may be necessary or more convenient for an operator to enter the reactor to direct the flexible plastic tubing of the vacuum equipment - see section 'Reactor Entry'. Since there is likely to be self-heating material present, a vacuum discharge is likely to be the most appropriate option. These operations should be carried out under inert conditions. It is possible to recycle the inert gas back into the reactor if required, although this is a more complex procedure. 8 VESSEL ENTRY Drawings of typical arrangements to be included in these sections Operators should never enter an absorbent vessel filled with an inert gas unless they are fully trained in inert entry procedures. Without an approved breathing apparatus, the operator would lose consciousness within a few seconds and die soon afterwards. There have been a number of double fatalities when somebody outside a nitrogen filled vessel has entered without breathing apparatus, to assist a colleague already in difficulties. Even looking closely into the open manhole of a nitrogen filled vessel can be very dangerous without approved breathing apparatus. Openings into a vessel blanketed with inert gas should be kept closed, except when work is going on inside, and there should be prominent warning notices to alert everyone to the potential hazard. All personnel working in the area should be made aware of the nature and dangers of asphyxia, and should know how to attempt the rescue and resuscitation of anybody who may be overcome. If entry into a nitrogen filled vessel is unavoidable, it is essential to use a fully integrated life support system with adequate back up. There are a number of specialized companies that have teams of fully trained staff available for this type of work.



Extreme caution must be exercised prior to reactor entry. Ensure that the permit to enter the reactor has been issued and signed, confirming that the reactor is positively isolated. If the reactor contains an inert (e.g. nitrogen) or toxic atmosphere then operators should be protected by an integrated life support system with an appropriate back up - specialist firms can be recommended by GBHE C2PT. If the reactor atmosphere is confirmed to be air and non-toxic GBHE recommends that operators wear suitable protective clothing - body clothing, gloves, goggles and dust mask. If there is the potential for absorbent dust generation such as during absorbent loading or discharging then GBHErecommends breathing sets. If breathing sets are used external back-up operators should monitor operators within the reactor at all times with spare breathing set(s) readily available. Please note that spent absorbents may contain adsorbed combustible or toxic components, which may not be completely removed during nitrogen purging. If there is any doubt about the presence of adsorbed combustible or toxic components GBHE recommends an inert gas entry using a specialist firm. Points to consider before vessel entry: Work permit / entry permit Risk assessment Rescue / Escape plan / Communication methods Purging plan Positive isolations – line breaks or slip plates on all process and service lines Full isolation of electrical drives, heating, radioactive sources, stirrers etc. Continuous atmosphere monitoring – LEL, O2 concentration, concentration of toxic compounds, temperature Breathing apparatus Harness / Lifelines Lifting tripod and winch Lighting Suitable tools Standby man Rest periods and ongoing review of risk assessment Training and instruction of personnel Qualified / experienced personnel



If a vessel entry is to be carried out, additional PPE includes - Breathing apparatus - Safety harness - Rope or wire to allow operator to be lifted out if required - Tripod and winch - Disposable overalls 9 SYSTEM START-UP / SHUTDOWN / STANDBY / UPSETS The following comments are prepared as recommendations for the operation of the unit. Operating companies should incorporate these recommendations as appropriate into the overall plant procedures. 9.1 SYSTEM PURGING The VULCAN VGP Series Catalyst process should be purged with nitrogen prior to the introduction of process feed, prior to absorbent discharge or prior to system maintenance. GBHE recommend that the VULCAN VGP Series Catalyst process is initially purged using a once through method followed by a number of repeated pressurisations / depressurisations to achieve the desired purge specification. Local instructions relating to the standard of purging should be followed, but typically the purging process is continued until the outlet stream is below 5% of the LEL (lower explosive limit)



9.2 SYSTEM STANDBY

Whenever the VULCAN VGP Series Catalyst process is not in use it should be maintained at pressure with either the feed or an inert gas such as nitrogen so as to prevent ingress of any contaminants from the atmosphere. Dedicated pressure relief that cannot be isolated is required for each vessel. For longer shutdowns (greater than one month) it is worth considering purging the vessel with nitrogen so that it is ready for restart when required. If the VULCAN VGP Series Catalyst process is connected to other high-pressure systems it is necessary to ensure no ingress of contaminants from these sources preferably with a positive isolation - slip plate or double block and bleed. Suitable non-isolatable pressure relief is required for all isolated pressurised systems. 9.3 SYSTEM START-UP The VULCAN VGP Series Catalyst process should only be operated within the agreed design conditions. If operation outside of these conditions is required, GBHEshould be consulted for advice. It is recommended that the system is pressurised at rates of not greater than 1 bar per minute below 10 barg and 10 bar per minute above 10 barg. This normally achieved by the use of small bypass valves. More details are included in the section describing vessel change over. Fresh absorbent will contain some water adsorbed in the pores from the atmosphere, which will be slowly released into the process fluid.



Sulfur guard Shutdown SYSTEM SHUTDOWN

The H2S removal vessels should be depressurised at a rate not exceeding 10 bar/minute above 10 barg or 1 bar/minute below 10 barg. The vessels should be purged with nitrogen until the purge gas is free of hydrocarbon. A heated nitrogen stream may allow the purging to be completed over a smaller time period. This should begin at the earliest stage that the shutdown procedure allows and will enable any hydrocarbons, which may be adsorbed onto the VULCAN VGP Series Catalyst, to vent off. During this period the operator will regularly monitor the vessel for signs of hydrocarbons in the purge stream. The vessel will be kept under a nitrogen blanket during discharge.

9.5 UPSETS

The VULCAN VGP Series Catalyst process is very robust but care should be taken to ensure that the process:

i is not subjected to significant flow variations (> 30%) above maximum design, which can cause deterioration in flow distribution.

ii is not subjected to significant water or liquid carryover.

iii is not subjected to undesirable poisons.

iv is monitored regularly to allow a record of normal reactor performance to be built-up.

FIGURE 3 : SIMPLIFIED PROCESS FLOW DIAGRAM



10 General considerations for liquid and gaseous systems Brief descriptions of the main points to consider in the operation of VULCAN VGP SERIES CATALYST beds, including: Blow down Isolations Double block and bleed Draining Upflow / downflow Purging Filling liquid vessels Gas locks Connection to relief system Different duties Control flow on outlet valves to avoid JT cooling effects VULCAN VGP SERIES CATALYST materials are used on both liquid and gaseous streams for the removal of Sulfur compounds, chlorides, mercury and arsine. These duties are individually considered depending on the customer’s process stream and the process conditions. 11 Sulfur guards Although this section repeats information that is available in other sections, it is included here to summarize the most important issues related to Sulfur guards on a single prompt sheet.

If you don’t read anything else, read this if you have a Sulfur guard.



Sulfur guards Sulfur guards are supplied as metal oxides and they react to form metal sulfides.

Sulfided materials will release H2S or SO2 on contact with acids or oxidising agents

Self-heating, Air and oxygen The absorbent will change from a metal oxide to a metal sulfide in use. Metal sulfides are self-heating, i.e. they heat up if air or oxygen is blown through them. Some absorbents are more self-heating than others DO NOT purge the bed with air, or allow air / oxygen to pass through the bed at any stage of the process operation.

Nitrogen for discharges As the absorbent is self heating it should be discharged under nitrogen The nitrogen used should be at least 99.9% pure. Nitrogen from membrane units is unlikely to be of sufficiently high quality. The hazards associated with working with nitrogen must also be considered to ensure that operators are protected from any oxygen deficient atmosphere

Vessel entry Vessel entry into an inert atmosphere should be avoided if at all possible If this is not possible, full breathing apparatus will be need, a full vessel entry and rescue plan should be prepared and the local work control procedures should be followed.



Metal containers As the spent material is self heating it should be discharged into suitable metal containers and sealed. Seal able UN drums or approved seal able IBC’s are usually used

Transportation Spent absorbent should be shipped to a suitable disposal site in accordance with local shipping regulations. These self heating materials would normally be ‘orange list’ and are subject to UN shipping regulations and transfrontier shipping regulations

MSDS’s Discharged material must be shipped under an MSDS which represents the material itself. GBHE can assist in the analysis of the discharged material so that an appropriate MSDS can be prepared. Small samples can be sent by DHL, Federal express and similar companies who are familiar with the shipment of samples. Generic MSDS’s can be supplied for the shipment of samples to GBHE for analysis.

Disposal Spent absorbent should be disposed of at a suitable outlet. Different regulations apply to different products and a number of different options are available.

Contamination It is important to note that beds may also be contaminated with other impurities such as mercury or benzene that are present in the stream in small quantities



Other contaminants or foulants in the stream can adversely affect the performance of the material

PPE Recommended personal protective equipment for handling fresh material includes: Suitable dust masks, Overalls, Gloves, Safety glasses, Safety boots For discharges the level of PPE required will be determined by the extent of contamination on the absorbent. For example, if benzene has accumulated on the bed, benzene filters will be required on gas masks and the other PPE requirements should be carefully reviewed.

Vessel entry If a vessel entry is to be carried out, read section 8

Loading Absorbent must be loaded using a sock to minimize breakage. Correct loading is vital to ensure the correct operation of the bed. Fresh Sulfur guards can be loaded in air.

Water / liquid carry over In operation, it is important to avoid water and / or liquid carry over on a bed that is in a gaseous duty

Steaming for purging will solidify the bed If a bed is steamed to purge it, as is done for some materials, a VULCAN VGP Series Catalyst bed is likely to solidify and it will then be very difficult to remove.



HAZOP It is recommended that a hazard and operability study is conducted on all processes which include a VULCAN VGP SERIES CATALYST bed. It should be noted that fresh and spent materials are chemically different and are sensitive to different process conditions

Work control In order to ensure that all operations associated with the beds are conducted in a safe manner, local work permit systems, risk assessments, lifting studies, COSHH assessments, and disposal regulations should be observed. 12 Mercury guards Although this section repeats information that is available in other sections, it is included here to summarize the most important issues related to Sulfur guards on a single prompt sheet.

If you don’t read anything else, read this if you have a mercury guard.

Mercury Guards Mercury guards are supplied in either a sulfided or an un-sulfided form (if H2S is present in the stream)

Sulfided materials will release H2S or SO2 on contact with acids or oxidising agents

Self-heating, Air and oxygen The absorbent will change from a metal oxide to a metal sulfide in use, or it will be supplied as a metal sulfide



Metal sulfides are self-heating, i.e. they heat up if air or oxygen are blown through them. Some absorbents are more self-heating than others DO NOT purge the bed with air, or allow air / oxygen to pass through the bed at any stage of the process operation.


Nitrogen for charging Sulfided material must be loaded under nitrogen.



Transportation Spent absorbent should be shipped to a suitable disposal site in accordance with local shipping regulations. These self heating materials would normally be ‘orange list’ and are subject to UN shipping regulations and transfrontier shipping regulations



Special disposal routes will bed required for mercury containing materials



Contamination It is important to note that beds may also be contaminated with other impurities such as organo-mercury compounds or benzene that are present in the stream in small quantities. Other contaminants or foulants in the stream can adversely affect the performance of the material

PPE Recommended personal protective equipment for handling fresh material includes: Suitable dust masks, Overalls, Gloves, Safety glasses, Safety boots For discharges the level of PPE required will be determined by the extent of contamination on the absorbent.



For example, if benzene has accumulated on the bed, benzene filters will be required on gas masks and the other PPE requirements should be carefully reviewed.


Loading Absorbent must be loaded using a sock to minimise breakage. Correct loading is vital to ensure the correct operation of the bed. Sulfided mercury guards must be loaded under nitrogen. Un-sulfided mercury guards can be loaded into air.


Steaming for purging will solidify the bed If a bed is steamed to purge it, as is done for some materials, a VULCAN VGP Series Catalyst bed is likely to solidify and it will then be very difficult to remove. HAZOP It is recommended that a hazard and operability study is conducted on all processes which include a VULCAN VGP SERIES CATALYST bed. It should be noted that fresh and spent materials are chemically different and are sensitive to different process conditions

Work control



In order to ensure that all operations associated with the beds are conducted in a safe manner, local work permit systems, risk assessments, lifting studies, COSHH assessments, and disposal regulations should be observed. 13 Chloride guards Although this section repeats information that is available in other sections, it is included here to summarise the most important issues related to chloride guards on a single prompt sheet.

If you don’t read anything else, read this if you have a chloride guard.

Chloride Guards Chloride guards are mixtures of metal oxides which react to form metal chlorides. They are not usually self-heating, although nitrogen should still be used for purging to avoid the formation of flammable mixtures. Spent chloride guards will release HCl or Cl2 on contact with acids or oxidising agents

Nitrogen for discharges Sometimes it is necessary to discharge under nitrogen if the hydrocarbon content of the material is very high and it is difficult to achieve less than 5% of the LEL (lower explosive limit). The hazards associated with working with nitrogen must also be considered to ensure that operators are protected from any oxygen deficient atmosphere




Metal containers The spent material is not generally self-heating, but it should be discharged into suitable metal containers and sealed. Seal able UN drums or approved seal able IBC’s are usually used

Transportation Spent absorbent should be shipped to a suitable disposal site in accordance with local shipping regulations. Spent materials may be corrosive on contact with water and are subject to UN shipping regulations and transfrontier shipping regulations


Disposal Spent absorbent should be disposed of at a suitable outlet. Different regulations apply to different products and a number of different options are available



Contamination It is important to note that beds may also be contaminated with other impurities such as or benzene that are present in the stream in small quantities Other contaminants or foulants in the stream can adversely affect the performance of the material


Vessel Entry If a vessel entry is to be carried out, read section 8

Loading Absorbent must be loaded using a sock to minimise breakage. Correct loading is vital to ensure the correct operation of the bed. Sulfided mercury guards must be loaded under nitrogen. Un-sulfided mercury guards can be loaded into air.




Steaming for purging will solidify the bed If a bed is steamed to purge it, as is done for some materials, a VULCAN VGP Series Catalyst bed is likely to solidify and it will then be very difficult to remove. HAZOP It is recommended that a hazard and operability study is conducted on all processes which include a VULCAN VGP Series Catalyst bed. It should be noted that fresh and spent materials are chemically different and are sensitive to different process conditions

Work control In order to ensure that all operations associated with the beds are conducted in a safe manner, local work permit systems, risk assessments, lifting studies, COSHH assessments, and disposal regulations should be observed. 14 Arsine and other guards 15 Reduced materials Although this section repeats information that is available in other sections, it is included here to summarize the most important issues related to reduced material on a single prompt sheet.

If you don’t read anything else, read this if you have a reduced material.



Reduced materials Reduced materials are supplied for a number of different duties. Depending on the material, they can be pyrophoric in air, i.e. they can burst into flame on contact with the oxygen in air. Special procedures are required for loading and handling these materials, and they are very specific to the particular operating conditions. Some materials are supplied as a metal and have to be reduced in-situ. Other materials are supplied in a pre-reduced form and need to be activated for the material to perform correctly. These guidelines some of the general issues associated with reduced materials and operating procedures for a particular process will be agreed with the plant.

Self-heating, Air and oxygen are self-heating, i.e. they heat up if air or oxygen are blown through them. Some absorbents are more self-heating than others DO NOT purge the bed with air, or allow air / oxygen to pass through the bed at any stage of the process operation.




Nitrogen for charging material must be loaded under nitrogen.



Transportation Spent absorbent should be shipped to a suitable disposal site in accordance with local shipping regulations. These self heating materials would normally be ‘orange list’ and are subject to UN shipping regulations and trans-frontier shipping regulations. Special disposal routes will bed required for mercury containing materials





Contamination It is important to note that beds may also be contaminated with other impurities such as organo-mercury compounds or benzene that are present in the stream in small quantities Other contaminants or foulants in the stream can adversely affect the performance of the material



Loading Absorbent must be loaded using a sock to minimise breakage. Correct loading is vital to ensure the correct operation of the bed.

- must be loaded under nitrogen. - can be loaded into air.




Steaming for purging will solidify the bed If a bed is steamed to purge it, as is done for some materials, a VULCAN VGP Series Catalyst bed is likely to solidify and it will then be very difficult to remove. HAZOP It is recommended that a hazard and operability study is conducted on all processes which include a VULCAN VGP Series Catalyst bed. It should be noted that fresh and spent materials are chemically different and are sensitive to different process conditions

Work control In order to ensure that all operations associated with the beds are conducted in a safe manner, local work permit systems, risk assessments, lifting studies, COSHH assessments, and disposal regulations should be observed.



16 Reclamation or Disposal of used absorbent The value of discharged VULCAN VGP Series Catalyst absorbents depends on the type of absorbent involved, prevailing metals prices, and on the location of the plant. Some absorbents (notably those containing nickel or copper) usually have a small positive value. Others (particularly those based on iron) have negative values, because the combined cost of freight and processing exceeds the value of the constituent metals. GBHE can assist in the environmentally friendly disposal of discharged VULCAN VGP Series Catalyst absorbents by recommending a number of metal recovery smelters who may be able to assist with metal recovery. Absorbents to be disposed of must be made safe for handling. In most cases this means that any VULCAN VGP Series Catalyst absorbents which are discharged in a potentially self-heating state must be made stable by exposure to air before they are moved from the factory site.

Disposal of spent materials A list of suitable disposal outlets can be supplied on request. This list is not published here to ensure that the most up to date information is provided when the material comes to be discharged Transportation of spent absorbents Local regulations should be followed for the transportation of spent absorbents to the selected disposal outlet. Some discharged materials will be classified as hazardous for various different reasons. Any such material need to be transported in accordance with the UN recommendations on the transportation of dangerous goods, also known as the ‘Orange book’. These regulations vary, but in Europe it is required that the material has a safety data sheet specific to that batch of spent material.



This means that the material needs to be discharged into suitable containers, sampled and stored on site for several days while the analysis is completed and the associated paperwork and permissions are prepared. GBHE are able to assist with the analysis of samples of discharged material if required. Samples of discharged material In order to generate a safety data sheet for the transportation of the discharged material, it will be necessary to send a sample for analysis to GBHE C2PT. These samples can be sent by freight forwarding companies such as Federal Express and DHL who have experience in handling such materials. There are requirements to send samples in UN approved containers with appropriate documentation. GBHE can supply a suitable MSDS for a small sample on request. Whenever possible samples should be taken which are representative of the bed profile. This is easy if the bed is being vacuumed out from the top of the vessel. If the bed is being discharged from the bottom, a grab sample from the top of the bed before the bed is discharged is very useful as it gives an indication of the highest absorbent loading and highest impurity concentration on the bed. In either case, samples every 10% of the bed are usually enough to give a good indication of the reaction profile down the bed. In cases such as mercury guards where high concentrations of an important impurity may be observed, it is worth taking samples at a higher frequency and retaining for later analysis if required.



17 Treatment options with VULCAN VGP Series Catalyst materials Impurities that can be removed by VULCAN VGP Series Catalyst processes, including precious metal catalyst options Sulfur compounds ( H 2S, COS, SO2, RSH, R2S, CS2 ) Halogen compounds (HF, HCl, CL2, RCl ) Carbon monoxide Unsaturated hydrocarbons Aromatic hydrocarbons Nitrogen compounds ( NOX, NH3, HCN, Organo – N ) Mercury Metals Arsine / Phosphine / Metal Carbonyls Hydrogen Oxygen Streams that can be treated by VULCAN VGP Series Catalyst processes Natural Gas Carbon dioxide Associated gas Synthesis gas Liquid hydrocarbons ( LPG, naphtha, Kerosene, NGL’s ) Industrial gases (H2, N2, CO2, CO, He ) Chemical feedstocks (propylene, ethylene) Air Obviously it will not be possible to remove every impurity from every stream, however, if is a stream with an impurity in it, drop us a line as we may be able to help.

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