IBP1598_12 MINOX – COMPACT AND CHEMICAL FREE DEOXYGENATION OF INJECTION WATER Hans Evald Henriksen1

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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
The Minox Deoxygenation process is developed for effective removal of oxygen from water, mainly to be used for Deoxygenation of injection seawter in oil fields, in connection with enhanced oil recovery. The process, initially developed during 1980s by Minox and Norsk Hydros Resaerch Centre, is based on stripping of oxygen from a closed loop circulating nitrogen gas. The process is a physical gas stripping process that does not need oxygen scavengers to reach very low levels of residual oxygen. To date more than 30 system have been delivered and is regarded as a proven and robust technology. The main advantages of the process are:  Weight savings  Space savings  Increased plant-out flexibility  Chemical free process  Regeneration of stripping gas  This paper describes the concept, plant build up, performance and lessons learned.

1. Concept
The Minox Deoxygenation Systems are based upon gas stripping of dissolved oxygen from water by a closed loop circulating nitrogen gas, in which the oxygen is being removed in a low temperature catalytic process. Exposed to an atmosphere containing a certain level of oxygen, the oxygen content in water will eventually reach an equilibrium value. Examples of O2 equilibrium in fresh water:

Case Temperature, °C O2 content in atmosphere O2 equilibrium, ppm

A 10 °C 23% 11,4

B 10 °C 10 ppm 0,0005

______________________________ 1 BSc Chemical Engineering – Grenland Group AS

Rio Oil & Gas Expo and Conference 2012 To obtain reasonable degree of equilibrium, which is necessary for the Minox Deoxygenation Systems to work, the following factors are vital:    Gas to water –ratio Oxygen content in purified cycling gas Number of stripping stages

As the nitrogen gas used for stripping is being circulated, the oxygen stripping out of the water and into the gas has to be removed before re-used as stripping gas. Removal of oxygen is done by exothermic catalytic reaction between oxygen and a fuel in a reactor tank, the Deoxydiser. Catalyst being palladium coated Al2O3 sphere balls and fuel being hydrogen, methanol or ethanol. The catalyst is expected to last four to six years, but has proven to last longer if the recommended maintenance procedure were followed. The table below gives normal operating temperatures for the different system fuels. Fuel Hydrogen Methanol Ethanol Temperature °C Atmospheric 160-250 200-300

In most offshore cases methanol seems to be the most suitable and preferred fuel, and hydrogen for onshore applications. In practical plant operation the consumption of methanol is approximately 18-liters/1000 m3 water treated and for hydrogen approximately 25-m3/1000 m3 water treated. The reaction is exothermic and the generated energy is re-used thorough a heat exchanger to preheat the incoming stripping-gas to the Deoxydiser, see detail flow diagram page 3 & 4. The reaction products with methanol as fuel:    H2O (as vapour) CO2 (gas) CO (very low content, just small traces)

No untreated methanol has been found in the cycling N2. When using hydrocarbon as fuel for the catalytic process, the CO2 created is lowering the pH of water treated. By using methanol, reduction of pH by less than 1 has been found which helps prevent scaling. By using hydrogen as fuel only water vapour will be created and so this has no effect on pH. To circulate the nitrogen stripping gas Minox uses a blower or compressor depending on the required pressure ratio. Where applicable the heat generated from the blower (or compressor) is used for pre-heating the nitrogen gas before entering the Deoxydiser. The compressor can either be volumetric or centrifugal depending on preference and system specifications. In the systems where the blower (or compressor) energy can’t be re-used for preheating the Deoxydiser or where there isn’t enough energy, Minox uses a heater to either preheat the catalytic mass during start-up or for continuous heating if preferred. As listed in the table above the preferred temperature in the Deoxydiser depending on the fuel, has to be reached during start-up and preserved under continues operation. This can be reached in different ways, either by: 1. Using a pre-heater continuously upstream the Deoxydiser. 2. Using a smaller heater inside the Deoxydiser along with a heat exchanger. Meaning non-continuous use of the heater. 3. Using an even smaller heater and a bigger heat exchanger to minimize the use of the heater. 2

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Advantages of the Minox Deoxygenation Systems are: - They can be designed to meet any practical demand for reduction of oxygen content in water. - There is no need for chemical scavengers for final O2-reduction. Occasionally antifoam is needed. - The plants can be designed for and operate at different pressure levels. - The discharge pressure of the water from plants may be high enough to eliminate the need for booster pumps upstream the water injection pumps. - A plant can be placed in a non-hazardous area. - The practical operation range of the Minox Deoxygenation Systems is normally 25100%. - The Minox Compact Tower System can be used in the conversion of conventional deaerators. - Flexible plant lay-out - Smaller surface areas than conventional systems, also reducing heat losses. - Requirement for low overall weight/height may be met and also giving very low flooded weight. - Sytems can easy be assembled in multiple skids for transportation and installation. - Fully automatic operated systems.

2. The Ultra Compact Minox ®-stage edition
A key process feature of this deoxygenation process is the method of contacting the nitrogen stream with the incoming liquid (most cases being water). This is done in static mixers, cocurrent turbulent flow is achieved, producing highly efficient mixing of liquid and gas and simultaneous stripping of the dissolved oxygen from the water to very low concentrations. Vertical or horizontal installation, length and the number of mixing elements are a function of the desired degree of stripping. The number of stripping stages needed is a function of desired oxygen content and gas: water-ratio. Normally a 1 or 2-stage system will be sufficient to achieve desired oxygen content in treated water, see figure 1 underneath.

Figure 1; The Ultra Compact Minox® 2-stage edition 3

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The resulting gas phase contains both nitrogen and oxygen. These are separated from the deoxygenated water in separators, the water passing directly to the 2nd stage mixer, while the gases are recycled for oxygen removal. This is achieved by reacting oxygen with for instance methanol, MeOH, at 160-250 0C in a catalytic bed, converting the oxygen to mainly water vapour and carbon dioxide, CO2.

The small portion of the circulating nitrogen steam absorbed into the water during the stripping process is made up from air, its oxygen content also being removed in the catalytic stage. For start-up, bulk nitrogen can be supplied from an external supply, but the principal and common method is to produce nitrogen from air. With cold starts from air, target oxygen removal is achieved in a few hours. The main components of the system are:        Compressor(s) that are circulating gas, normally screw or centrifugal. Static mixers, that are forming the stripping zone where interaction between water and gas takes place. Separators, separates water and circulating gas. Deoxydiser, for catalytic oxygen removal from the circulating gas. Methanol unit. Methanol tank and pump to provide methanol for the catalytic reaction. Heat exchanger, pre heats the circulating gas before entering the Deoxydiser. Heater, heating up Deoxydiser to optimal fuel reaction temperature.

The Ultra Compact Minox® 2-stage edition does not require any chemical scavenger to obtain residual oxygen level. To avoid foaming in the separators, antifoam is sometimes added continuously or periodically with algae/blooming seasons.

In addition to the obvious attractions of weight and space saving, the process offers a number of other benefits. Although compact, it is also flexible in terms of equipment design. There are no large equipment items. Hence, the system can be skid-mounted or stacked, while the separators can be horizontal or vertical. All of which means that each unit can be tailor-made to slot into a given space.

This is a particularly attractive advantage when considering installation on existing platforms where interest is being shown for upgrading conventional deaeration systems. In such cases, the process will not only enable injection water volumes to be increased with a reduced oxygen content, but the need for a chemical scavenger is eliminated, as well as saving natural gas for stripping.

Another positive feature of the system is elimination of the traditional booster pumps upstream of the main injection pumps. The net positive suction head, following the second separation stage, is sufficient to feed the injection pumps directly, a situation not possible after a vacuum deaeration tower. Further, if required, the system is capable of operating without an internal fine-filtration stage.

Normally in deoxygenation of seawater, a two-stage system in used to lower oxygen content to 20 ppb or lower. In the first stage, raw seawater is introduced at a pressure form 2-6 barg. The overall pressure drop across the two stages is about 1 bar. The purified nitrogen is divided 4

Rio Oil & Gas Expo and Conference 2012 into two parallel flows, for the first and second stage, respectively. Chlorine, that is normally added to the water at the platform’s seawater intake for bacteria control, is unaffected by the oxygen removal process. As the catalyst is immune to chlorine poisoning above 160 0C, problems have not been seen in the any of the plants currently in operation.

A study conducted by Veritas (5) also stated the systems positive feature related to not being so sensitive to vessel motions or list as for vacuum and fuel stripping towers. This is due to the fact that the mass transfer takes place in the static mixers and not in a high tower so system performance is not sensitive to dynamic movements, as opposed to tower mass transfer devices.

3. The Minox® Compact Tower
Based upon the same basic principle of cycling and purifying a carrier gas, the Minox Compact Tower system is an alternative to the Ultra Compact MinoxTM 2-stage system. The Minox Compact Tower system also offers a direct competitive alternative to vacuum deaerators, yielding very low residual O2 content and better energy economy. The system can operate under atmospheric, or a few barg pressure, with N2 as stripping gas. See diagram underneath showing the flow in the system.

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With the Minox Compact Tower it is possible to:      

Obtain more than 30% increase of water flow through the tower (using structured packing compared to random ring fillings or trays) Bring residual O2 content down to 20 ppb or less, without applying scavenger. Reduce weights Lower energy consumption Increase discharge pressure By installation of small skid, comprising a blower and catalytic Deoxydiser plus supplementary equipment the conversion is completed.

The danger related to using natural gas as stripping gas is removed.

References

1. Experience and data from a 377000 BPD (2500 m3/h) Sea Water Deoxygenation Plant, by Norolf Henriken, Norsk Hydro ASA 2. Hydro Minox Systems for seawater deoxygenation, by Norolf Henriksen 3. Deoxygenation process treats seawater for injection, by Kjell Skar Minox Technology AS 4. Efficient and chemical free system for water deoxygenation, by Harald Ulleberg, Grenland Group 5. Veritas Offshore Technology and Services AS report 411172, 16.12.1991.

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