IBP1868_12 TECHNICAL UPDATE: PREPARING PRODUCTION EQUIPMENT, PROCESS EQUIPMENT, BENZENE, LEL AND H2S CONTAMINATED EQUIPMENT FOR

SAFER AND FASTER MAINTENANCE MARTHA SMITH1

Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP
This Technical Paper was prepared for presentation at the Rio Oi & Gas Expo and Conference 2012, held between September, 1720, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings. .

Abstract
United Laboratories International, LLC has developed a unique method to safely and rapidly decontaminate petroleum upstream and downstream process equipment. The process removes oil, gas, VOCs (Volatile Organic Compounds), LEL (Lower Explosive Limit) and Benzene while also eliminating hydrogen sulfide (H2S) and accessible pyrophoric iron sulfides (FeS), ensuring the equipment is safe for personnel entry. This is accomplished through the use of the Zyme-Flow Process, an environmentally-friendly solution, in a fraction of the time compared to conventional methods. This decontamination process has been successfully used in slug catchers in the Middle East and Asia, on offshore platforms in Venezuela, on tank farm crude oil pipeline in Portugal as well as in refinery process units in Colombia, Mexico, Chile and refineries around the world. This paper will present case studies that detail the procedures applied to successfully decontaminate these facilities focusing on the oxidation of the H2S and FeS and on the reduction of VOCs, LEL and Benzene to safe limits. It will also detail how these goals were achieved in greatly reduced time compared to conventional technologies resulting in significant savings to the owner companies. The Zyme-Flow chemistry is active in liquid, vapor and foam phases and can be applied as an aqueous solution in circulation, boil-out or through a proprietary Vapour-Phase decontamination process where the product is injected directly into the vessel or units steam source using the standard steam-out procedures. Zyme-Flow chemistry in conjunction with the Vapour-Phase application offers the fastest method for rendering vessels and process equipment safe for personnel entry with a minimal mechanical footprint and vastly reduced amounts of generated effluents that are compatible with waste water treatment facilities. Zyme-Flow chemistries are environmentally responsible formulations utilized in refineries worldwide.

1. Introduction
For 20 years, Zyme-Flow Process has offered the most complete decontamination solution for refining and petrochemical plants, and most recently for upstream applications. In a single step, this process removes oil, gas, LEL, and benzene while also neutralizing hydrogen sulfide (H2S) and pyrophoric iron sulfides (FeS). The chemistry can be applied whether in circulation, as an aqueous solution, or through a proprietary Vapour-Phase process where the product is injected directly into the vessel or units steam source. Using Zyme-Flow chemistry in conjunction with the Vapour-Phase procedure offers the fastest method for rendering process equipment ready to open with a minimal mechanical footprint and vastly reduced amounts of generated waste that are compatible with waste water treatment facilities. Zyme-Flow chemistries are environmentally responsible formulations utilized in refineries worldwide.

2. Decontamination Process - Fundamentals

______________________________ 1 Master, Oil Refining, Gas and Petrochemicals - United Laboratories International, LLC

Rio Oil & Gas Expo and Conference 2012 During a Plant turnaround, and before internal inspection or mechanical maintenance is performed on any vessel containing organic and/or inorganic materials, decontamination must be accomplished in order to assure there will be safe working conditions for personnel that will enter the vessel and perform the work. Decontamination is the process of making equipment safe for personnel entry and maintenance. Typically, refineries decontamination procedures are designed with the purpose to remove all residual hydrocarbon from the vessels internal surfaces (internal walls, column trays, packing beds, bottom sections, piping, etc.), removal of toxic and dangerous compounds (as volatile organic compounds-VOCs, lower explosive limit material- LELs, Benzene, hydrogen sulfide (H2S), Ammonia, besides others), and removal or control of any potential presence of pyrophoric iron sulfide. Iron sulfide is the most common substance found in petroleum-refinery distillation columns that is subject to spontaneous ignition. Refineries use to perform an oil viscosity wash using light cycle oil or any other flushing oil followed by steam out procedures and water washes to remove contaminants. However this entire process will take several days before the equipment is ready for entry. Also, heavy asphalteens, polymer deposits, H2S and iron sulfide are very difficult to remove by such traditional techniques and in most of the situations required special treatment. With a target to increase safety and efficiency, some refineries have introduced chemical products and cleaning practices into their normal decontamination procedure to address and control contaminants concerns. One of the basic cleaning methods involves: 1) The use of special solvents during the oil wash or water flush stage. This method consists to inject a strong solvent product (as a terpene or di-limonene base product) into the oil or water wash circulation phase. These products are used to enhance solvency strength in order to satisfactory remove organic material from vessels, but very often create dangerous situations when treating the effluents at the waste water treatment facility. Frequently, refineries need to collect the effluents in a separate containment and pre-treat them, using abrasive chemicals in order to break the stable emulsion before the water fluids are sent to the waste water treatment plant. 2) The use of common oxidizers compounds to neutralize H2S and treat FeS based deposits. A synopsis of common oxidizers compounds for industrial oxidation is provided as Table 1. Most of these compounds are very effective in neutralizing sulfides via oxidation mechanism but some of them address special safety concerns when oxidation reaction occurs in presence of light hydrocarbons. This is due to the exothermic mechanism of their oxidation reaction that might ignite the light hydrocarbons. Moreover, these oxidizers compounds are required to be applied in liquid circulation therefore large amount of onsite storages facilities are needed for blending in situ as well as additional pumps often leaving the Refinery with large volumes of waste that should be treated and disposed at additional cost, effort and time. Table 1. Synopsis of common oxidizers for industrial oxidation (From Chemical Engineering www.che.com July 2007) Oxidizer Potassium Permanganate (KmNO4) Yes Bleach Hydrogen Peroxide (H2O2) Yes Common sufide absorbers Not normally

Dangerous exotermic possible? Dangerous Gas emission possible? Dangerous Residue Possible? Safe with light Hydrocarbons? Liquid Application?

Yes

Yes Yes

Yes Yes

Yes No

Yes Yes

No Yes

No Yes

No Yes

Not always Yes

Steam Application?

No

No

No

No

pH restriction?

Yes

Yes

No

Yes 2

Rio Oil & Gas Expo and Conference 2012 Create additional or hazardous sludge? Penetration ability Secundary wastetreatment required? Corrosive? Long shelf life? Handling hazards (*) Yes Moderate Yes Yes No High Yes Moderate Yes Yes Yes High No Poor No Yes No High Sometimes Good Yes Yes Yes High

(*)Note: Always consult MSDS sheet before using or handling any chemical.

3. Zyme-Flow Process
Zyme-Flow UN657 is a blend of mild surfactant oxidizer and enzymes designed to decontaminate refineries process units, petrochemical plants and upstream process vessels. Zyme-Flow UN657 is patented to be used as part of the Zyme-Flow Process which allows for reactive sulfide oxidation, de-oiling, degassing and other functions which are performed in many types of decontamination. In a single step, the Zyme-Flow Process removes oil, gas, LEL, hydrogen sulfide, benzene and pyrophoric iron sulfides. At the same time, it reduces sludge and conditions the effluents for COD control. The patented formulation is highly effective, fast-acting and safe for personnel, plant equipment and the environment. As a result, Zyme-Flow treatment dramatically reduces the time required to prepare equipment for entry while eliminating safety and procedural concerns associated with cleaning, degassing and environmental compliance. The Zyme-Flow Process attacks, breaks down and emulsifies not only hydrocarbon liquids, but also vapors within process equipment. Active in liquid, vapor and foam phases, Zyme-Flow can be applied as an aqueous solution in circulation or through a proprietary Vapour-Phase steam cleaning process using the plants existing steam-out procedures. In a Vapour-Phase procedure, Zyme-Flow is injected or educted directly into a steam source, allowing contact and penetration of all surfaces. The Vapour-Phase process is the fastest method for entering process equipment and consistently reduces steam-out time up to 75%. It also avoids the costs of temporary circulation pumps, while reducing the amount of waste generated. The Zyme-Flow Process reduces hydrogen sulfide to near zero, LEL's to near zero and benzene exposure to less than 1 ppm. It eliminates pyrophoric iron sulfide and other reacting sulfides as an integral part of the decontamination process. Excessive steam-out times are no longer necessary and emulsions formed separate quickly without the need for a breaker. Zyme-Flow chemistry is non-toxic, nonhazardous and biodegradable. It contains no volatile compounds and has no flammability concerns. The Material Safety Data Sheet hazard rating for Zyme-Flow is 0-0-0. Unlike other products, it does not form toxic by-products of sulfides during the decontamination process. All reactions with sulfides are non-exothermic and safe with hydrocarbons. Zyme-Flow is not a solvent. It is a completely biodegradable, all-aqueous formula that is free of volatile organic compounds. When applied in the Vapour-Phase process, it eliminates the odor problems associated with conventional steaming. The effectiveness of Zyme-Flow treatment significantly reduces EPA regulated waste generated by hydroblasting. Zyme-Flow chemistry is near neutral pH and compatible with all common metals of containment and construction. It is safe for plant wastewater treatment systems and the chemical constituents are not a threat for reprocessing recovered hydrocarbons.

4. Case Studies
The Zyme-Flow Process has been proven in a wide variety of applications. For more than three decades in the Specialty Chemical industry, United Laboratories, Inc. forged a leadership position in the evolution of 3

Rio Oil & Gas Expo and Conference 2012 environmentally sound alternatives to hazardous cleaning compounds. In the 1980's, this initiative led to the introduction of a special degreasing agent featuring naturally occurring enzymes and surfactants which was developed for United's waste water treatment market. For several years, this environmentally benign product, ZymeFlow, was successfully marketed to Waste Water Treatment Plants across North America for general purpose degreasing and for tertiary filter media remediation. Early in the 1990's, United began to explore other markets for ZymeFlow. Its unique separation capabilities and inherent compatibility with waste stream requirements suggested potential application in the decontamination of petroleum fouled surfaces and equipment. From that point forward, ZymeFlow has enjoyed widespread use and success in the petroleum upstream and downstream industries. During the past 20 years, United Laboratories International, LLC has seen repeated success and benefits using the ZymeFlow Process in refineries and petrochemical plants worldwide. This paper will present case studies that detail the procedure applied to successfully decontaminate a slug catchers in the Middle East, an off-shore platforms facility in Venezuela, a tank farm crude oil piping in Portugal and a Refinery Topping unit in Chile, focusing on the oxidation of the H2S and FeS and on the reduction of VOCs, LEL and Benzene to well below safe limits. It will also detail how these goals were achieved in greatly reduced time compared to conventional technologies resulting in significant savings to the owner companies. 4.1. Decontamination of a Slug Catcher - Middle East A slug catcher is a large diameter piping structure that utilizes several kilometers of piping in a network that separates sour natural gas from liquids. Fig. 1 shows a typical lay-out of a finger type slug catcher.

Figure 1. Finger Type Slug Catcher On June 2010 United Laboratories International, LLC partnered with a major gas processing plant in the Middle East to successfully decontaminate a finger type slug catcher. The purpose of this decontamination process was to remove H2S and FeS throughout the equipment to safe entry levels. The past decontamination method on this facility used Nitrogen purging and after completion a fire resulted due to residual pyrophoric iron deposits. As shown in Fig. 1, the plant consisted in one slug catcher divided into two separate and identical halves: one half was isolated and scheduled maintenance while the other was going to be in service. A gamma scan of the pipe work revealed deposits of scale, and sand (most likely debris from sub-sea pipeline feeding the slug catcher) in sections of 48 inch pipe. This debris acts like an absorption cell for H2S and poses a personnel hazard upon entry. The H2S needed to be decontaminated to acceptable limits for personnel entry (<10 ppm) before the 24 inch man-ways could be opened. All neutralization of FeS was done before opening. In most hydrocarbon processing facilities, ULI uses the patented Vapour-Phase decontamination process as it is quick, effective and produces minimal waste streams. This method was not applicable to the slug catcher due to temperature limitations. ULIs engineering team went to work and successfully solved the problem posed by this remote, low temperature application. ULIs Zyme-Ox with the addition of an anti-foaming agent was determined to be the most efficient and effective method for the decontamination of the slug catcher liquid bottles. ULIs R&D team then developed a process for mixing in the field immediately prior to its use. This ensured the solution was delivered for decontamination at the job site at full strength. This was a first in the industry. The slug catcher was de-pressurized, isolated and flushed with water to push all remaining gas out of the system over a five day period. ULIs Zyme-Ox Z-20 was injected into the aqua milling stream used by the in-house contractor. The use of Zyme-Ox in this procedure ensured that all H2S and FeS exposed by the aqua milling process were neutralized immediately. Figure 2. indicates the mechanical set-ups and chemical injection point used during decontamination process All H2S, pyrophoric material and 40 cm of sludge were removed from the slug catcher. During the aqua milling process the contractors were able to come out of breathing apparatus. The job was completed three days ahead of schedule with no safety issues. 4

Rio Oil & Gas Expo and Conference 2012 Zyme-Ox Z-20 is a stronger oxidizer chemistry develop by United laboratories International, LLC and often included in the Zyme-Flow Process to decontaminate towers and vessels where high H2S levels and pyrophoric FeS are commonly found. Common applications include packed sections of towers and heavily fouled trays and drums. It has twice sulfide oxidizing capacity compared with Zyme-Flow and is intended to be used only in water based applications below 200o F and to near freezing temperature. Zyme-Ox has also been shown to be effective at removing hydrogen cyanide, polythionates and thiosulfates. It reacts completely to destroy sulfides and pyrophorics, while expending itself and increasing detergency without foam or residue

Figure 2. Finger type slug catcher decontamination diagram

4.2. Decontamination of an off shore flare knock-out drum - Venezuela A vaporliquid separator or commonly known as a knock-out drum is a device used in several industrial applications to separate a vaporliquid mixture. On October 2010, ULI was requested to decontaminate a 4.3 m x 12.9 m KO Drum on an off-shore platform at the Maracaibo Lake, Venezuela. Drum was about 40% filled with highly sour crude oil sludge and sediments very compacted since the unit was in service from 1999. The scope of work required by customer included: 1. Application of a chemical product with ability of degassing and reduce the content of H2S, aromatics and removal of remaining crude oil from the sludge conditioning the sediments precipitated and stratified in the bottom of the vessel for final environmental disposal. 2. Neutralization of pyrophoric iron sulfide particles to prevent any expontaneous ignition by presence of oxygen (O2). ULI technical staff reviewed the problem and recommended a decontamination procedure of circulation and boil-out to be performed just after the vessel was properly de-pressurized, isolated and drained. Vessel was filled with enough water so as to be above the height of the weir, sludge and sediment in its bottom. Simultaneously a blend of a stronger solvent (Rezyd-X Z67) and a concentrated oxidizer (Super Tank-Zyme Z21) was introduce into the solution and heated with 50 psi steam until temperature achieve 212 oF. Rezyd-X is an internal cleaner that dissolves and disperses heavy hydrocarbon sludge, asphalt, heavy lube oils and heavy residues in vessels, heat exchangers, process lines and tanks. When used in conjunction with an oxidation chemistry as Super Tank-Zyme and/or other Zyme-Flow Process compatible products, it solvency power allow the active oxidative component to easier penetrate and neutralize all sulfides potentially trapped in the sludge. Multiple steam injection points were needed so that to elevate the temperature up to the boiling point and to enhance agitation of the solution in contact with the sediments. Temporary piping and hoses were set up as well, to facilitate the circulation of the decontamination solution using an external pump on 2 nozzle. Figure 3. shows vessel P&ID (Piping and Instrument Diagram) detailing the mechanical set-up for steam and chemical injection as well temporary facility for recirculation used during decontamination process The decontamination solution was boiled inside of the equipment, allowing circulation of the liquid and rising vapors to decontaminate the entire equipment internals. Since steam pressure at the platform was about 50 psi,

Rio Oil & Gas Expo and Conference 2012 occasionally the conditions during decontamination service needed to use some N2 to help sludge agitation. That is why it is shown to be injected at same points at steam and on on/off mode as needed. Once Boil-Out Decontamination process was established ULI in conjunction with a company operator started testing various low point steams and high point vents for contaminant levels of H2S and LEL. This testing routine continued on a regular routine schedule until the stream contaminant levels are low enough to vent the equipment to the atmosphere. Final testing results showed 0 ppm of H2S and 0 ppm of LEL on the liquid and the vapor phase. Test on sediments showed 1 ppm of H2S above 90o C (194o F) which was recognized by customer as an outstanding result

Figure 3. Off-shore platform KO-drum decontamination diagram 4.2. Crude oil 36 pipeline cleaning - Portugal In a recent application, the ZymeFlow Process was used to successfully decontaminate an uninsulated 2.1 Km 36 pipeline network associated with the transfer of crude oil at a refinery tank farm in Portugal. This particular facility was located in an environmentally sensitive and residential area, so there was obvious concern for chemical releases and noise pollution. The pipeline had never been decontaminated in its 40+ year history, but inspection reports indicated the need for some spool replacements due to wall thinning. Industry standard is to use a liquid circulation chemical cleaning process followed by mechanical pigging. Using that methodology, estimates for completion of this project were two (2) months. Due to critical time constraints posed by ship unloading schedule and the environmental concerns, the facility instead chose an innovative alternative approach using ZymeFlow chemistry in a VapourPhase application in order to minimize wastewater for disposal. Prior to the implementation of the project, meetings were conducted between ULI and the Refinery personnel to discuss project planning, job scope definition and to develop a collaborative execution plan. ULI estimated duration of this decontamination was three (3) day shifts exclusive of the preparative steps of draining the pipeline and conducting a water flush. Since the pipeline was drained but never waterflushed, significant oil volumes were expected and present when the decontamination commenced. Using a single injection point, ZymeFlow chemistry was introduced to the plants 3 steam line with the use of a singlestroke pneumatic pump. Piping laterals from the main pipeline to the storage tanks were blocked in before the tank, but did not have drain points. Pipeline skin temperatures were in the range of 226 F (107 C) at the end section and on the lateral pipelines indicated adequate transfer of chemical throughout the system without the need for any supplemental steam injection. The VapourPhase of ZymeFlow continued for five (5) hours, after which a relative small amount of condensate was collected using two (2) vacuum trucks. Upon opening, the pipeline was found to be completely free of oil, LEL, benzene, H2S, and pyrophoric iron sulfides. The only foreign material present was a minor amount of iron oxide scale. Large circulation pumps, frac tanks, and mix tanks were not required. Any oil emulsions quickly break upon quiescence with no further chemical treatment. The ZymeFlow VapourPhase Process did not require pipe breaks that are normally associated with the use of pigs with 90o piping turns (eliminating concerns for possibility of chemical release). 6

Rio Oil & Gas Expo and Conference 2012 The total job duration was three (3) days and the total cost of the project using ZymeFlow Process was a fraction of the original budget utilizing conventional liquid chemical cleaning/pigging practices.

Figure 4. Crude Oil 36 Pipeline Portugal Refinery 4.2. Topping Unit Decontamination Chile The first step in the refining process is the separation of crude oil into various fractions or straight-run cuts by distillation in atmospheric and vacuum towers. The main fractions or "cuts" obtained have specific boiling-point ranges and can be classified in order of decreasing volatility into gases, light distillates, middle distillates, gas oils, and residuum. Atmospheric and Vacuum distillation units are energy intensive processes so feedstock must be heated throughout crude oil heaters and cross heat exchangers. On October 2011 United Laboratories International, LLC in partnership with NEXXO (ULI Licensee in Chile), successfully decontaminated a Crude Oil preheat train of exchangers, an Atmospheric Tower and a Vacuum Tower at a Refinery in Bio Bio Chile. The project aimed the elimination of H2S, pyrophoric iron sulfide, explosives compounds and benzene, as well as the mobilization of heavy hydrocarbon waste, asphalt and/or polymers present along the decontamination circuits to discard directly into the oily sewer and from there to a slop tank. A decontamination pre-engineering work was performed in advance of the job, carrying out detailed planning, adjusting procedures, timetable and schemes for the approval of the refinery. The procedure accomplished to decontaminate the units included the following sequence of events: 1. Viscosity flush of crude unit pre-heat train of exchangers and bottoms circuits. A combination of light cycle oil (LCO) and Rezyd-X Z67 was kept in circulation for about 4 hours at 194 oF (90 oC) on the equipment intended for the removal of heavy asphaltenes material from the crude unit front end and heavy ends circuits. 2. Water flush off all bottoms and heavy ends circuits and drainage. Fire water was injected for 10 minutes on all bottom circuits to displace as much residual crude oil and sludge from considered systems in preparation for Vapour-Phase decontamination. Additional volumes of Zyme-Flow and Rezyd-X were added into the water flush to enhance solvency and surfactancy effect to remove residual heavy hydrocarbons material throughout the system. All rinsing water volumes were discharged directly into the refinery oily waters sewer that ends into an API separator as per the refinery normal plant emptying procedure. 3. Vacuum Tower packing bed pre-treatment. Equal volumes of Zyme-Flow and Rezyd-X Z67 were injected into each packing bed distribution header followed by water flush to enhance the contact of the chemistry over the packing surface. Packing bed pre-treatment aim the dilution of sludge and heavy polymers over the packing bed as well as oxidation of pyrophoric iron sulfide commonly present. 4. Vapour-Phase decontamination of atmospheric and vacuum tower, all associated heaters, coolers, pumps and piping. Zyme-Flow volumes were injected into refinery normal steaming-out procedure to capitulate decontamination of intended equipment and circuits. Decontamination procedure completed in 12 hours. A summary of the results obtained during the decontamination procedure is shown in Table 2. Table 2. Topping Unit- Decontamination Monitoring Readings
Time Location Temp. (oC) 140o H2S (ppm) 11 LEL (%) 50 Active Zyme-Flow (ppm) 300 Notes

08:00

Atmospheric Tower Reflux Drum F-2A

Started Zyme-Flow injection on Heavy Naphtha stripper E-2 and Kerosene Stripper E-3

Rio Oil & Gas Expo and Conference 2012

08:30 11:23 13:30 13:45 14:30 15:30 15:30 15:30 16:30 17:00 20:00 Atmospheric Tower Reflux Drum F-2B Vacuum Tower Bottom Circuit Pumps J-51 Vacuum Tower Bottom Circuit Pumps J-51 Vacuum Tower Reflux Drum F-51 Vacuum Tower Bottom Circuit Pumps J-51 Atmospheric Tower Reflux Drum F-2A Atmospheric Tower Reflux Drum F-2B Atmospheric Overhead Reflux Pump J-3 Vacuum Tower Bottom Circuit Pumps J-51 Vacuum Tower E-51 Vacuum Tower E-51 140o 103o 103o 104o 104o 140o 140o 130o 104o 104o 104o 15 23 10 10 2 0 0 0 0 0 0 50 5 20 20 13 0 0 0 0 0 0 300 300 300 300 300 300 300 300 300 300 300

0 ppm on all contaminants

Decontamination declared completed

From the table above it is observed that the goal of eliminating all pollutants was achieved approximately 7 hours after Zyme-Flow was injected. Once recorded levels of contaminants were zero ppm at all accessible drainage and vent points, the refinery was instructed to open vents to the atmosphere and block the ventilation to the flare in order to prevent re-contamination of the system. Chemical injection was suspended at that time and steaming-out was continued for additionally 2-3 hours to officially declare the decontamination concluded. At this stage all equipment were released back to the refinery which secured the units as per their normal procedure to allow personnel entry.

5. References
- PHILIP A. VELLA, Improved Cleaning Method Safely Removes Pyrophoric Iron Sulfide. Oil and Gas Journal, Vol. 95, No. 8, February 24th, 1997. - DESIGN PRACTICES COMMITTEE, FRACTIONATION RESEARCH INC. Causes and Prevention of Packing Fires. Chemical Engineering Magazine, July 2007 - M. P. CASTRO, T. T. PINTO, Petrogal Matosinhos Refinery, D. SCOTT P.E.,M. SMITH M.SC., S. MATZA PhD, H. DAWSON, Zyme-Flow Technologies, Houston, Texas, Innovative alternative to conventional pipeline cleaning-Petrogal Matosinhos refinery, Hydrocarbon Processing Magazine, North American Turnaround And Maintenance 2011, p. T-81 - SAEID MOKHATAB, WILLIAM A. POE, JAMES G. SPEIGHT, Handbook of Natural Gas Transmission And Processing, n 5.6, p. 221-223, 2006