IBP2161_12 ENHANCEMENT OF BOILER FEED WATER QUALITY WITH MEMBRANE TECHNOLGY FOR OIL SANDS AND POWER GENERATION

APPLICATIONS Dr. Ramraj Venkatadri1, Mr. Raphael Bim2

Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP

This Technical Paper was prepared for presentation at the Rio Oil & 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
Two distinct case studies will be presented in this paper. In the first case study, we discuss the conventional water treatment scheme for ground water at a major oil sands facility that was augmented with Reverse Osmosis (RO) systems before the boilers in order to produce high-quality steam. Due to the ineffectiveness of the conventional treatment system, the Silt Density Index (SDI) on the RO feed exceeded 10. A pressurized mobile Microfiltration (MF) unit was delivered and installed to replace the existing pretreatment system. After installation of the MF system, the SDI values on the feed to the RO unit dropped to less than 3. The oil sands customer has enjoyed trouble-free operation for over two years and is currently using three mobile MF units for treating the feed water. In order to optimize the performance of the RO membrane system, a pressurized microfiltration membrane system was delivered and commissioned within five days to replace the existing pretreatment system. The new unit contained an automated Polyvinylidene Fluoride (PVDF) hollow fiber microfiltration membrane system mounted in a trailer. SDI values in the range of 1.0-2.5 were immediately observed in the feed water to the RO system. The end user has enjoyed significant cost savings and ease of operation. In the second case study, the problems associated with the operation of conventional treatment involving clarifier/sand filter/cation/anion/mixed bed demineralizer at a major power plant in North America are described. The key problems identified had been high chemical costs for lime softening and frequent regeneration of the demineralizer beds, accordingly high chemical consumption and costs as well as considerable amounts of waste water production. The plant used variable quality surface water as feed. An integrated membrane system (MF/RO) was installed to produce high-quality permeate water and to maximize ion exchange run times at minimum chemical costs.

CASE STUDY #1: PRODUCTION OF HIGH-QUALITY WATER FOR OIL SANDS A. Oil Sands Deposits
The Oil and Gas Journal has reported nearly 175 billion barrels of reserves from oil sands in Alberta, Canada in 2005, making it one of the largest oil reserves in the world. The oil sands are located in three distinct areas in northern Alberta the largest deposits are along the Athabasca River. Current production of approximately 1 million bbl/day of crude oil from bitumen is predicted to increase to over 3 million bbl/day by 2015.

B. Extraction Methods
Currently, two-thirds of the bitumen output is produced by strip mining and the remaining portion by in-situ methods such as Steam Assisted Gravity Drainage (SAGD). But since 80% of the recoverable bitumen is buried too deep for strip mining, the in-situ methods are expected to dominate the scene in the coming years. In the SAGD process, two horizontal wells are drilled into the oil sands, one near the bottom of the formation and another one, typically five meters above it. These wells can extend up to a kilometer in all directions. Steam is injected into the

______________________________ 1 Ph.D., Chemical Engineering, Global Marketing Manager PALL CORPORATION, USA 2 Water System Specialist PALL DO BRASIL

Rio Oil & Gas Expo and Conference 2012 upper well. The heat decreases the viscosity of the bitumen, which allows it to flow into the lower well, from where it is produced. Upgraders are then used to convert the heavy bitumen into light sweet crude. Enormous amounts of steam are required to operate the upgrader facility and for the SAGD process. Incoming water of high-quality is required for the boilers generating medium and High Pressure (HP) steam and for the upgrader operation.

Membrane Technology
The conventional clarifier/multimedia filters for the treatment of incoming fresh water into plants suffer from several drawbacks. The primary one is the inability of these systems to cope with sudden upset conditions that could result in increases in total suspended solids in the feed water. This is also reflected in an increase in SDI, conductivity or in turbidity (NTU values) in the feed water to the unit. Technological improvements since the 1990s have resulted in processes such as Microfiltration (MF) and Ultrafiltration (UF) becoming economical and popular. In a typical application, the incoming water passes through several thousand spaghetti-like hollow fiber polymeric membranes, which remove suspended solids and bacteria. The effluent performance for turbidity of MF and UF is similar. For removal of dissolved solids, the treated water from the MF/UF unit passes through the RO membranes. This technology is employed before the demineralizers. The pores in the RO membrane are only a few angstroms in size and can remove a majority of the dissolved salts.

Modes of Operation
The MF and UF filtration systems can be operated in the dead-end mode or in crossflow mode. The RO units operate in the crossflow mode. The MF unit described in this paper uses a hollow fiber membrane operated in the conventional dead-end filtration mode wherein the feed water flows in from the outside to inside of the hollow fiber and the suspended particles and bacteria are captured within the filter and the permeate is sent to the RO unit. These filters have a unique air cleaning method and are regularly cleaned with chemicals (described in a later section). The RO unit operates in the crossflow mode, in which the feed water flows parallel to the membrane surface. The water that is filtered through the fine pores (permeate) is mostly devoid of dissolved salts.

Analysis of Incoming Water

The source of the feed water to this oil sands site is groundwater from 13 different wells located in the vicinity of the site. Groundwater from four different wells is drawn on a daily basis and thus, there is daily variation in the quality of the incoming water. The key data from the 13 wells is shown in Table 1 below. Only the minimum, maximum and average numbers are shown. Table 1. Analysis of raw water used for boiler feed at the site Parameter Total Dissolved Solids, mg/l Conductivity, microSiemens/cm Total Suspended Solids, mg/l Alkalinity, mg/l Bicarbonate, mg/l Total Organic Carbon, mg/l pH Dissolved Iron, mg/l Dissolved Magnesium, mg/l Dissolved Sodium, mg/l Dissolved Boron, mg/l Dissolved Chloride, mg/l Minimum 503 866 <1 503 614 12.2 7.6 0.03 0.9 93 0.5 0.9 Maximum 2270 4600 95 843 934 12.2 8.7 4.96 34.9 956 4.61 891 Average 1281 2198 21 701 800 12.2 8.4 0.6 10.1 480 2.4 284

The MF system used in the plant is shown in Figure 1 below. It is a unique system and it is fully automated. It features more than 6000 hollow fibers made of PVDF in a single module. Up to 60 modules can be stacked in one unit. It has superb membrane integrity and it operates in the dead-end mode. Feed water enters the bottom of the module and is distributed uniformly to the outside of the hollow fibers. It operates under low pressure, typically 45 psig. The water, 2

Rio Oil & Gas Expo and Conference 2012 under pressure, flows through to the membrane core and the permeate flows to the top of the module, from where it is conveyed by a filtrate header to the next unitin this case, the RO membrane. An increase in Trans Membrane Pressure (TMP) occurs with passage of time as fouling materials obstruct flow across the membrane.

Figure 1. The pressurized Microfiltration system

Cleaning and Maintenance of the Filter Element

Flux Maintenance is done constantly to lower the TMP values. Air scrub involves the injection of air at low pressure into the feed side of the module. Clean filtrate is also pumped in a reverse direction through the hollow fibers to dislodge the foulants and deposits. Enhanced Flux Maintenance uses hot water with mild chemical solutions and is done periodically to lower TMP. As the TMP approaches 1.7-2.0 bar (25-30 psi), chemical Clean-in-Place (CIP) is performed. This is a two-step protocol, first using a caustic and then an oxidant solution, to return the modules to nearly new condition. This is done hundreds of times over the lifetime of the element.

Mobile Microfiltration Units

The MF units are sometimes mounted in mobile units, shown in Figure 2. Mobile units were originally introduced in the late 1990s to handle emergency water situations at remote industrial plants, but are increasingly becoming the industry workhorse for advanced water treatment. They provide flexibility of operation, are reliable, and performance is excellent even during process upsets. The unit in use at this site comprises of a complete, automated packaged system that is 15.9 m long, 4 m high, and 2.6 m wide (53 feet long, 13 feet 6 in high, and 8 ft 6 in wide). It has two sets of racks each containing 40 PVDF modules and a total flow rate capacity of 180 m3/hr (800 gpm). Both racks can be operated simultaneously or one rack can be redundant. It has the additional feature of PLC controls, including data collection and remote access capabilities.

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Figure 2. Mobile units containing pressurized microfiltration systems

Performance
The boiler feed water production was commenced late in 2007 using the clarifier and multimedia filter. The design called for SDI values in the incoming water to the RO units to be around 3.0. However, SDI values of the permeate from the multimedia filter typically were in the range of 12-20, which indicated that the units upstream of the RO unit were malfunctioning. This led to a lack of production of the boiler feed water, since a continuation would result in catastrophic fouling of the RO unit. Losses can be considerable for the plant in such a scenario. An operating loss of USD$1.2-1.5 million/day would be typical for boiler feed water not being available to this plant. A Mobile Microfiltration Unit was available immediately and the commissioning was done in five business days. The plants water treatment specialist was familiar with the unit and had confidence in its performance and approved its use. Installations took place in late 2007 and operations were re-started in November 2007 by bypassing the multimedia and sand filter and passing the raw well water directly through the MF unit, with the MF permeate being sent to the RO unit. Within six hours of initial water processing, the SDI values in the permeate were recorded to be in the range of 1.0-2.5 and turbidity values in the permeate were consistently below 0.1 NTU. This excellent performance has been sustained since then and spot-checks of permeate SDI values over the past six months have been consistently below 3.0. Increased flow rates to the boilers have now resulted in three (3) units being commissioned. The variation of Trans Membrane Pressure is studied over a period of time. The TMP values show a slow upward trend and appear to increase only after 60 days. This indicates very good performance and also that the membranes do not require frequent CIP process. Normally, the CIP is initiated as the TMP approaches 1.7-2.0 bar (2530 psi). Eventually, in the case of this plant, the CIP procedure was performed by a service professional in order to prolong membrane life. Only two CIPs were performed in the first six months of operation.

Conclusions
The microfiltration system has performed well since commissioning at this oil sands site and has consistently provided the necessary high-quality water for reverse osmosis. The conventional multimedia filters could not meet the performance specification of the RO feed water and this problem has been overcome with the microfiltration unit. The microfiltration system has provided ease and flexibility of operation. Performance has been reliable regardless of the feed water quality and flow rate. Membrane performance has been enhanced with the standard chemical CIP program. Due to excellent performance, the membranes do not require frequent CIP.

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CASE STUDY #2: INTEGRATED MEMBRANE SYSTEM OPERATION IN POWER PLANT BOILER FEED WATER TREATMENT Introduction
A major North American utility station deploys conventional lime softening and demineralizers to produce high-quality water for boiler make-up. The conventional system uses coagulant, lime, acid, and caustic in large quantities to produce demineralized water. Pall Corporation and plant personnel worked together to develop an integrated membrane-based system to produce high-quality permeate water to maximize ion exchange run times. This article focuses on the conventional approach and the new membrane approach in treating the lake water to produce demineralized water, as well as the challenges faced, and direct and indirect benefits gained with the new system.

Background Information
Raw surface water from an adjoining lake is the fresh water source for the power plant. In the original treatment scheme, about 340 m3/hr (1500 gpm) of this water was being treated with a conventional clarification and cold lime softening process followed by sand/gravel bed filtration. Demineralization units were subsequently used to produce the required water quality for the HP boilers. These units consisted of a conventional cation bed using sulfuric acid for resin bed regeneration, and weak and strong base anion beds as well as a mixed-bed demineralizer using caustic soda for resin regeneration. The driving forces to consider alternate treatment schemes in lieu of the conventional clarifier/sand bed were: 1. Chemical costs required to regenerate the demineralizer beds were extremely high since regeneration of the resin was carried out once a day or even more frequently. The ion exchange run time needed to be improved significantly. 2. Operational simplicity: frequent upset in the clarifiers would result in frequent regeneration. 3. Although the plant was designed with a three-bed demineralizer followed by mixed-bed polishers to meet boiler feed water quality, silica breakthrough in the strong base bed was frequent and beds were regenerated more often. Pall water treatment experts performed a detailed analysis of the plant conditions and decided to recommend an integrated membrane (MF/RO) system (IMS) to replace the cold lime softening clarifiers and sand/gravel filter beds. Since the power plant was on line, an additional challenge was to install the systems without shutting down the demineralizer trains or negatively impacting the amount of treated water while the new IMS plant was brought on line. Pall recommended installing the IMS in parallel with the clarifiers and sand/gravel filters and reusing the existing filtered water tanks. One filtered water tank was used as an MF/RO break (filtrate tank), and the other as an RO permeate water storage tank (the new demineralizer train feed tank). After commissioning the IMS, the plant personnel bypassed the clarifier/sand bed system and fed the incoming water from the feed system directly into the MF system. The MF and RO product water quality that the units were designed for is shown below: Giardia and Cryptosporidium Suspended Solids Turbidity RO Product Water Quality TDS <25 ppm pH 5-7 Undetectable Undetectable <0.1 NTU

Integrated System Details

The integrated system was commissioned in February 2008. The microfiltration system consists of two independent treatment trains of 42 modules each. This system is 2 x 100% capacity 175 m3/hr (770 gpm) maximum each and allows for an average production of 320 m3/hr (1400 gpm), input of 350 m3/hr (1540 gpm) with 95% recovery with both trains in service.

Rio Oil & Gas Expo and Conference 2012 Since the IMS system was installed along with the existing system, the space available for the RO skid was limited. Therefore, the RO skid had to be custom designed to fit in the available space. To accomplish this, the RO system consisted of three stages (single train), arranged in a 16:8:4 array with five membrane elements each. The inlet flow to the RO system was 140 m3/hr (625 gpm). The system was designed for a total permeate production of 113 m3/hr (500 gpm), the average capacity of the boiler.

Results and Discussion

Table 2 lists the existing costs for chemical addition and power requirements with the clarifier/sand-gravel bed operation prior to the plant switching over to the MF/RO system. The costs for caustic soda and sulfuric acid are extremely high, owing to the fact that the demineralizer train was regenerated at least once a day. Sodium aluminate/lime was used for the lime softening operation. The sludge treatment/disposal costs and some other costs have not been quantified. The chemical costs were considerable, exceeding USD$3500/day. Table 2. Existing chemical costs and power requirements Component Sulfuric Acid 93% Caustic Soda 50% Sodium Aluminate 40% Lime 100% Power Total Daily Cost Total Yearly Cost Daily Consumption 3665 kg (8064 lb) 7270 kg (16,000 lb) 454 kg (1000 lb) 340 kg (750 lb) 1630 KWH Total Cost in U.S. Dollars $402 $2880 $200 $45 $81 $3609 $1,317,285

Table 3 lists the chemical addition and power costs in the plant after the integrated system was operational. There was a dramatic lowering of the chemical costs. Table 3. Chemical costs and power requirements after the integrated system was operational Component Sodium Hypochlorite 12% Citric Acid 50% Caustic Soda 50% Sodium Bisulfite 38% Antiscalant 100% Sulfuric Acid 93% Power Total Daily Cost Total Yearly Cost Daily Consumption 11.8 kg (26 lb) 9.5 kg (21 lb) 82 kg (181 lb) 26 kg (58 lb) 1 kg (2.2 lb) 0 kg (0 lb) 2800 KWH Total Cost in U.S. Dollars $3.40 $11.60 $32.60 $24.90 $77.00 $0 $140.00 $289.50 $105,650

The principal benefit of the Pall system is the significant improvement in the regeneration of the ion exchange units. The regeneration cycle in the demineralizers improved from daily to once every 5-6 days. This led to a steep decrease in the use of caustic soda and sulfuric acid used in the resin bed regeneration. The use of sodium aluminate and lime was eliminated by bypassing the clarifier operation. The chemicals used to clean the MF/RO system during EFM and CIP (sodium hypochlorite, caustic soda and citric acid) are commodity chemicals and usage quantities are negligible compared to the chemicals used in the conventional system. Antiscalant was used to prevent LSI scaling in the RO unit, while sodium bisulfite was used for dechlorination. As indicated in Tables 2 and 3, the resulting daily savings in chemical/power costs is USD$3310 per day (USD$3609 - $289.50), or about USD$1.2 million per year. Figure 3 shows the variation of the turbidity of the incoming surface water and the turbidity of the filtered water from the MF unit with time over a period of several months. The incoming water varies in the range of 1.5 - 4 NTU, with occasional higher values. MF filtrate always exhibited turbidities below 0.05 NTU, with a majority of the readings less than 0.02 NTU.

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Figure 3. Turbidity of incoming water and permeate from the MF unit The classic SDI method was used to determine the fouling potential of the RO membrane. SDI is measured manually before the RO guard filter. Figure 4 demonstrates the variation of SDI. All the readings were in the range of 1-3, with a majority of the SDI values being below 2.0. This again demonstrates consistent MF performance and fouling protection for the RO.

Figure 4: Variation of silt density index after microfiltration Figure 5 shows the operation of Stage 1 of the RO unit. The outlet pressure over several months is steady and actually declines slightly. The figure also demonstrates the pressure drop across the elements in Stage 1 and it shows no increase. This demonstrates the excellent RO performance of Stage 1 and is characteristic of a very low fouling tendency. Although not shown here, similar results were obtained for Stages 2 and 3 of the RO unit.

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Figure 5. Variation of outlet pressure and differential pressure (RO-1)

Return on Investment
The cost of the Pall Integrated System was approximately USD$1.2 million. Savings from the chemical costs from installation of the system: USD$1.2 million/yr. Savings from the improved performance of the polishing system: USD$250,000/yr. (not described here). Total savings to the plant: USD$1.2 + USD$0.25 = USD$1.45 million/yr. The return on investment was achieved in less than 10 months of operation.

Conclusion
Palls integrated system resulted in considerable direct savings on chemical costs and improved ion exchange unit run times.