As brine composition profoundly influences reservoir wettability and hence microscopic sweep, careful design of injection brine is part of a strategy to improve on oil production in existing and future water flooding projects, in both sandstone and carbonate reservoirs and in combination with follow-up EOR projects. The following results were found:Formation water with higher salinity level correlates to a higher content of multivalent cations. This causes the (sandstone) reservoir wettability to be more oilwet;The field-observed temporary reduction in watercut during breakthrough of so-called "Designer Waterflood" water in a Middle Eastern sandstone reservoir with highly saline formation water was interpreted to be caused by an oil bank ahead of the slug of injected water;The oil bank results from improved sweep by wettability modification to more waterwet state. The interpretation was confirmed by laboratory experiments;Experiments in limestone core plugs demonstrate similar wettability modification, if the sulphate ion content in the invading brine is far in excess of the calcium ion content. Based on these results the following conclusions were drawn:Designer Waterflooding may increase the Ultimate Recovery of oil by at least a few percent;There is scope for further improvement in oil production by flood front stabilization by adding low concentration polymer to the optimised slug;If future EOR projects are planned, a Designer Waterflooding pre-flush is recommended to obtain more favourable oil desaturation profiles and savings on polymer costs;In case of seawater injection into reservoirs with formation water of low salinity level, removal of multivalent cations from the seawater should be considered to avoid the potential risk that the reservoir becomes more oilwet, which will result in reduced sweep. Introduction In the past decade, injection of brines with well-selected ionic composition in sandstone and carbonate reservoirs has been developed into an emerging IOR technology, aiming for improved microscopic sweep efficiency with reduction in remaining oil saturation as result (Tang and Morrow, 1997, 1999, 2002; Maas et al, 2001; Webb et al, 2003 and McGuire et al, 2005). Recently, some evidence of the beneficial impact of injection of brines with well-selected ionic composition from historical field data was published (Robertson, 2007). In-house research on this subject covered a broad range of disciplines, including core flow and Amott imbibition experiments, Colloid Chemistry and Petroleum Engineering. In this paper we describe the major results from our study and indicate where this technology can be most favourably applied.

Modifying the chemistry of injection water yields improved wettability behavior on carbonate rock surfaces. Previous work has focused on demonstrating the effect of modified brine formulation on particular carbonate samples. Here the results of a more general screening study consisting of Amott spontaneous imbibition experiments on the samples from oil-bearing zones and from outcrops of different carbonate formations are reported. Tertiary incremental oil production due to increased water-wetness was observed upon transition to brine of lower ionic strength. Additional oil recovery from the spontaneous imbibition tests ranged from 4 to 20% of OIIP (Oil Initially In Place), reflecting a large variability in the response and indicating a high complexity of the mechanism(s). Consistent with numerous published reports, Stevns Klint outcrop chalk samples were a clear exception and exhibited increased oil recovery with increasing sulfate ion concentration. These did not respond to lowering the salinity of the imbibing brine. Tertiary oil recovery from samples containing evaporites occurred simultaneously with dissolution of salt minerals, as evident from brine analysis. However, incremental oil recovery in the same range was measured for samples without evaporites but from the same geological formation. Hence, mineral dissolution as a mechanism for enhanced oil recovery could not be confirmed. The results show that injection of low salinity brine into carbonate reservoirs has potential as an EOR technology. However, additional research is needed to improve the understanding of the underlying chemical and physical mechanisms and improve a priori predictability.

Summary Low salinity water injection is an emerging EOR technology, applicable to mixed-to-oil-wet sandstone reservoirs. Flooding with low salinity water causes desorption of petroleum heavy ends from the clays present on the pore wall, resulting in a more waterwet rock surface, a lower remaining oil saturation and higher oil recovery. A secondary flood application is discussed in the Omar field in Syria showing a change of wettability from oil wet to a water-wet system. This change in wettability is supported by the observation of dual steps in watercut development. In between the two steps the watercut was constant. This behaviour is a known indicator of changing wettability. Moreover, direct connate water banking measurements confirm the change. The field observations are supported by spontaneous imbibition experiments in core material and a single well Log-Inject-Log test in an analogue field. From the field observations, the change in wettability is estimated to be nearly complete, leading to an associated incremental recovery of 10–15% of the Stock Tank Oil Initialy In Place (STOIIP). The significance of this work is that this is one of the very few documented proofs of concept on a reservoir scale. Work is ongoing to prove this concept in a tertiary flood as well.

Low-salinity water injection is an emerging IOR/EOR technique, applicable to mixed-to-oil-wet sandstone reservoirs. This paper describes the field response for two large fields: Omar (secondary flood) and Sijan (tertiary flood). The data were analyzed using analytical and numerical modelling tools. This included evaluation of scaling numbers, mixing and dispersion and calibration. Insight was obtained on relevant drive mechanisms. The responses to low-salinity flooding differ for the two fields: In Omar, a dual-step water-cut development was observed, which is characteristic for a change in wetting state. Our interpretation is that in this field, viscous forces provide the dominant drive mechanism, which is favorable to low-salinity flooding. We were able to history match the low-salinity response using a simple conceptual model.In Sijan, the low-salinity flood appears to be still immature and breakthrough of low-salinity water has not (yet) been observed. The reasons for the muted response thus far are explored, including a rather strong buoyancy effect caused by the higher permeability of the block, and the significant effect of injectant mixing with the highly saline aquifer. A proposal is made for a workflow on how to apply this analysis to future low-salinity flooding implementation in field cases.

Improved oil recovery by low salinity waterflooding (LSF) represents an attractive emerging oil recovery technology, as it is relatively easy to implement and low-cost compared to other Improved and Enhanced Oil Recovery (IOR and EOR, respectively) processes. Even though LSF leads to extra oil recovery in most laboratory experiments and some promising data from the field have been presented, the mechanism underlying LSF is still unclear. Therefore it is difficult to predict a favorable performance of LSF in one field a priori, while dismissing others. This paper describes a series of spontaneous imbibition experiments on Berea outcrop core plugs, and some reservoir rock core plugs, that were designed to determine the impact of formation water, imbibing water and crude oil composition on wettability and on wettability modification by LSF. The data presented in this paper lead us to conclude that: Spontaneous imbibition experiments with formation brine and low salinity brine executed on Berea outcrop material aged with a crude oil show excellent reproducibility;An increasing concentration of divalent cations in the formation brine makes a Crude Oil/Brine/Rock system more oil-wet;The extent of wettability modification towards more oil-wet upon aging also depends on the types of cations in the formation brine;Improved oil recovery by exposure of the aged plugs to NaCl brines occurred when the imbibing phase was either higher or lower in salinity than the formation brine;Aging of the same brine/rock system with different crudes having diverse physico-chemical properties led to:○A spread in wettabilities after aging○A crude oil-dependent low salinity effect These results are discussed within the context of several mechanisms that have been put forward previously as an explanation for the low salinity effect.

No abstract

Densely-fractured oil-wet carbonate fields pose a true challenge for oil recovery that traditional primary and secondary processes fail to meet. The difficulty arises from the combination of two unfavorable characteristics: First, the dense fracturing frustrates an efficient waterflood; second, because of the oil-wetness, the water pressure exceeds the oil pressure inside the matrix blocks, thus inhibiting spontaneous imbibition of water. In the past decade, using a new class of surfactants, enhanced oil recovery (EOR) researchers have studied the options to chemically revert the wettability of carbonate rock without drastically decreasing the oilwater interfacial tension. These chemicals, termed "wettability modifiers" (WMs), effectively reverse the sign of capillary pressure at the prevalent saturation. With the oil pressure exceeding the water pressure, the capillary pressure becomes the driving force for oil expulsion from the matrix and into the fracture system.Previous publications on chemical wettability modification focused on the performance of different chemical wettability modifiers for a chosen rock/oil/brine system. In some cases, they demonstrated an almost full oil recovery from core plugs. Little attention, however, has been given to the mechanism underlying the transport of the chemical into the matrix block and to the proper scaling of laboratory results to reservoir size. The present study aims to demonstrate that imbibition after wettability modification is diffusion-limited. To this end, the recovery profiles for spontaneous capillary imbibition, as well as for imbibition after wettability modification, are calculated. The results are then used to compare with the data of Amott cell imbibition experiments. It is confirmed that in both cases, the cumulative recovery is initially proportional to the square root of time. Imbibition after wettability modification, however, takes approximately 1,000 times longer than spontaneous capillary imbibition into a water-wet medium. The slow recovery observed in the case of imbibition after wettability modification is in excellent agreement with the assumption that, in the absence of significant spontaneous imbibition, the WM, to unfold its action, must first diffuse into the porous medium. In any diffusion process, the time scale is linked to the square of the length scale of the medium. Therefore, it would take up to 1,000 times longer (an equivalent of 200 years) before the same recovery is obtained from a meter-scale matrix block as is obtained from a centimeter-scale plug in a laboratory in 100 days.Consequently, unless a significantly faster transport mechanism for the wettability modifier is identified, or unless viscous forces or buoyancy enable forced imbibition, the chemical wettability modification of fractured oil-wet carbonate rock does not provide an economically interesting opportunity. TheoryCountercurrent spontaneous capillary imbibition and molecular diffusion obey differential equations of similar structure. The com-

Reservoir souring refers to the generation of hydrogen sulphide (H~) in originally sweet reservoirs that have been subjected to production operations such as (sea)water flooding. The most plausible cause of reservoir souring is the growth of sulphate-reducing bacteria (SRB) in the zone where seawater mixes with formation water. In the mixing zone the components that support the SRB's lifeoxidant and nutrients -are present.Inorganic reactions are not considered important in the generation of H 2 S. They are important, however, in the scavenging of H 2 S, since many ironcontaining minerals are capable of reacting with H 2 S, forming pyrite or pyrrhotite. For this reason, the types and quantities of iron-containing minerals within the reservoir have been studied using petrographic and isotopic techniques.As a first step towards quantifying the effects of H 2 S production by SRB, a 10 analytical transport model has been developed. It describes the production of H 2 S in the mixing zone and the compound's transport through a reservoir. The partitioning of H 2 S between the fluid phases and the possibility of scavenging by iron-containing minerals have also been included in the model.References and illustrations at end of paper. 369The model has served to calibrate a numerical simulator, which can be used for modelling souring under more realistic settings. It is demonstrated how the distribution of nutrients, sulphates and H 2 S actually observed in a producing field can be used to assess the existence of souring chemical reactions as well as the mechanisms that give rise to them.