Title of Innovation: Next Generation Environmentally Acceptable Inhibition

Transcription

1 Title of Innovation: Next Generation Environmentally Acceptable Inhibition Category: Chemical Treatment Nominee(s): Dr. Jonathan J Wylde Clariant Oil Services Global Head of Application Development Aberdeen, Scotland, U.K. Alistair Kirkpatrick Clariant Oil Services Senior Development Chemist Aberdeen, Scotland, U.K. Melanie Reid Clariant Oil Services Senior Development Chemist Aberdeen, Scotland, U.K. Dr. Nihal Obeyesekere Global Integrity Manager Houston, TX, USA Dr. Dirk Leinweber Head of R&D Center Surfactants and Alkoxylates Frankfurt, Germany Web site: Date of Innovation: June 2012

2 Full Description: When and how was it developed? Clariant Oil Services has pursued an innovation initiative for the last 18 months in the area of environmentally acceptable corrosion inhibitors. This initiative is to develop a range of new corrosion inhibitors with acceptable environmental profiles. There is an unmet need in the market for base chemistries with >60% biodegradation and low aquatic toxicity that are also excellent metal film formers and display suitable corrosion inhibition properties. The project has made excellent progress through a combination of formulation development, base chemistry performance assessment and ecotox testing, examining base chemistries that exist in the market place, as well as developing bespoke and novel molecules. Final formulations have now begun to result from this research initiative and individual field applications are being evaluated as part of this project with CORRTREAT DF being initially formulated on 16th February The project has been performed in house by Clariant Oil Services and, in part, by a Knowledge Transfer Partnership (KTP) scheme. KTP is a U.K. wide program enabling industry to improve their productivity and performance. A KTP achieves this through the forming of a Partnership between industry and an academic institution (such as university, further education college, or research and technology organization), enabling access to skills and expertise to help develop innovative solutions. The knowledge sought is embedded into industry through a project, or projects, undertaken by a recently qualified person (known as the Associate), and recruited to specifically work on that project. How does it work, in basic terms? Corrosion inhibitors work by forming passivating films, or chemisorbed layers of corrosion inhibitor molecules, onto metal surfaces to prevent the attack of corrosive species such as CO 2, H 2 S, and O 2. How or why is the innovation unique? CORRTREAT DF is unique because it contains a combination of several different patented corrosion inhibitor molecules that is only available to Clariant Oil Services. This combination of novel corrosion inhibitor molecules yields a totally bespoke synergy like none other seen in this area before that has resulted in a step change in corrosion control. What type of corrosion problem does the innovation address? The development of CORRTREAT DF has been to address internal pipeline corrosion for use in the oil and gas production industry manifested during transportation of produced fluids from the reservoir to refinery. Application of CORRTREAT DF prevents general corrosion caused by the dissolution of sweet (CO 2 ) and sour (H 2 S) gases into the liquid phase, localized pitting corrosion, and preferential weld corrosion under conditions of high (>30 Pa) shear.

3 What is the need that sparked the development of the innovation? The need of the industry that the development of CORRTREAT DF has met is the availability of high performance corrosion inhibitors that are at the same time environmentally acceptable and from a sustainable source. The oil industry to date has relied heavily upon environmentally hazardous chemistries such as toxic imidazolines and quaternary ammonium compounds that exhibit poor biodegradation and can bioaccumulate. Clariant Oil Services has a commitment to operate in a safe and sustainable manner and this development is in line with our corporate vision because, in addition to protecting oil and gas transportation pipelines from integrity failures, it also has a low environmental impact if it is discharged into the environment. Are there technological challenges or limitations that the innovation overcomes? CORRTREAT DF has overcome the challenge of having high corrosion inhibition performance with environmental acceptability; to date an elusive combination. An independent study proved that CORRTREAT DF has overcome this performance challenge and GLP approved laboratory data shows the environmental ecotox properties of CORRTREAT DF to be very favorable and environmental impact modeling (CHARM software) show a low impact to the environment through its use. What are the potential applications of the innovation? CORRTREAT DF can be used in many corrosive liquid environments. It has been specifically designed for use in a multiphase oilfield production system over a wide range of oil to water ratios, specifically for high CO 2 corrosive environments compounded by the presence of small amounts of H 2 S. Evaluation of CORRTREAT DF for preventing corrosion in any oilfield pipeline that transports water containing liquids would be indicated. How does the innovation provide an improvement over existing methods, techniques, and technologies? The improvement is very much about the minimal environmental impact the manufacture, application, and ultimate fate of CORRTREAT DF when compared to typical chemistries used for corrosion control where high toxicity and poor biodegradation result in a poor environmental footprint/impact. In terms of corrosion control and efficacy, CORRTREAT DF differs from other environmentally acceptable solutions because it has been shown in independent testing to be up to an order of magnitude higher in performance. What type of impact does the innovation have on the industry/industries it serves? The impact upon the oil and gas production industry is significant. More and more focus is placed upon the safe and responsible use of production chemicals to aid the development of oil and gas fields. The North Sea is a good example of best practice in terms of environmental protection through regulation and control on the use of toxic and hazardous chemicals. This best practice is now being adopted around the world the inception of REACh and new regulations offshore in several geographies where a similar approach to the UKs CEFAS regulations and the SFT regulations employed in Norway have been adopted. Does the innovation fill a technology gap? If so, please explain the technological need and how it was addressed prior to the development of the innovation. The technology gap filled is the unique combination of high corrosion inhibition performance and an excellent environmental profile that has a minimal impact on the environment in which it is applied. Prior to development of CORRTREAT DF the gap was addressed by

4 either high performance but environmentally hazardous chemicals or from poorly performing environmentally acceptable products being injected in an order of magnitude larger amounts. Has the innovation been tested in the laboratory or in the field? If so, please describe any tests or field demonstrations and the results that support the capability and feasibility of the innovation. CORRTREAT DF has been tested extensively in the laboratory and field injection and evaluation is currently ongoing offshore in the U.K. Sector of the North Sea and onshore in California. The laboratory testing program initially screened the products for their effect on fluid separation and foam formation propensity. Partitioning LPR bubble tests were then performed at a variety of water cuts in order to rank the products against one another. The top two performing products, along with the incumbent CORRTREAT , were flow loop tested. Finally, performance tests were repeated with the best performing product in the presence of a Clariant Oil Services scale inhibitor. Emulsion and foaming tendency tests used 100 ml of fluid in total. For the foaming tests, a 50:50 oil water mixture was used. The fluid was placed in a measuring cylinder and nitrogen introduced via a sintered frit for one minute at a flow rate of 250 liters per hour. Foam formation (height and onset time) was recorded via visual observations and then the time taken for foam collapse was measured. Initially, 1,000 mg/l of corrosion inhibitor was added to the test and further testing was performed on the final selected product after the effective field dose rate was determined. For emulsion tests, a 50:50 oil water mixture was used. Again, 1,000 mg/l of corrosion inhibitor was added to the fluid and the bottles shaken vigorously 10 times. The time for complete separation of the two phases was recorded and observations made every five minutes. Further testing was performed on the final selected product after the effective field dose rate was determined. Partitioned LPR testing was performed in water cuts of 10%, 25% and 75% with real field crude. The electrodes were ASI 1080 carbon steel and the solution was saturated with CO 2 at atmospheric pressure and a temperature of 30 C. Incremental corrosion inhibitor additions were made in order to determine the dose rate at which a corrosion rate of less than 0.1 mm per year was achieved. For the scale inhibitor test, the scale inhibitor was added at 100 mg/l after four hours into the test. Flow loop testing used the same brine as the partitioned LPR tests with an additional 1% field crude added. An electrode manufactured from actual field welded pipe was utilized to measure the corrosion rate independently on the parent metal (x2), heat affected zones (2x) and the weld material. The temperature was maintained at 30 C, the partial pressure of CO 2 was 2.5 bars and flow rates yielded a shear rate of 30 Pa. After a base line corrosion rate was determined, corrosion inhibitor was sequentially added to determine the dose rate required to achieve less than 0.1 mm/yr. At the end of the flow loop test, the fluids were replaced with completely fresh fluids without corrosion inhibitor. The corrosion rates were monitored for a further 48 hours to determine

5 the persistency of the protective corrosion inhibitor film, i.e., to mimic a chemical injection pump failure in the field. CORRTREAT DF was ranked number one overall in partitioned LPR tests, as it gave more consistent performance across all water cuts; every other product tested either did not perform, or required a very large amount at one of the water cuts. Flow loop testing showed that the amount of CORRTREAT DF required to achieve 0.1 mm/yr was half that of the incumbent and the next best performing competitive product. CORRTREAT DF did not cause emulsions or foam even when overdosed at 1,000 ppm. Based upon these results, CORRTREAT DF was recommended by the third party as the most appropriate product for field testing. Field testing is currently being performed subsea with side stream monitoring occurring at the receiving separator on the host facility. Is the innovation commercially available? If yes, how long has it been utilized? If not, what is the next step in making the innovation commercially available? CORRTREAT DF is commercially available and has been for over 3 months. It has been utilized by the oil and gas industry since becoming commercially available. Are you aware of other organizations that have introduced similar innovations? If so, how is this innovation different? Other competitive products are available on the open market. CORRTREAT DF differs by possessing superior performance as shown by the industry recognized independent test facility that evaluated this and four other companies products in a cross industry study. Are there any patents related to this work? If yes, please provide the patent title, number, and inventor. Corrosion Inhibitors Containing NonIonic Surfactants US2009/ A1. Dirk Leinweber and Michael Feustel. Supporting Photos:

6 Figure 1: Flow loop test results for the incumbent product CORRTREAT on a weldment electode. Figure 2: Flow loop test results for the incumbent product CORRTREAT DF on a weldment electode. Figure 3: Flow loop test results for the next best performing competitive product on a weldment electode.