Graphene a Review of Applications in the Petroleum Industry

i. Abstract

Graphene was attracted a widespread attending recently years because of its unique atom-thick two-dimensional structure and first-class backdrop. Graphene materials have been applied in energy storage and conversion, catalysis, electronic, loftier strength material, chemical and biosensor and biotechnology fields. With the decline of conventional oil and gas resource, unconventional oil and gas resource and complex well increased gradually. The drilling applied science encountered new claiming. We reviewed the research and awarding of Graphene materials in oilfield based on the requirement of drilling technology, and discussed the prospect of Graphene material in oilfield.

2. Keywords: Application Oilfield; Drilling Fluid; Graphene; Nano-Materials

1. Introduction

Graphene materials accept become a research hotspot in the field of materials because of its unique two-dimensional structure and excellent backdrop [one-3]. The basic and application Research of Graphene has become the electric current frontier and hot topic. At present, Graphene materials accept been widely used in free energy storage and conversion [iv-6], catalysis [vii,8], electronic devices [nine,10], loftier strength materials [11], chemical and biosensor [12,thirteen], biotechnology [xiv,15] and other fields. Two scientists at the University of Manchester, Andre Geim and Konstantin Novoselow, successfully stripped Graphene from graphite by mechanical ways in 2004, causing a worldwide awareness. Enquiry on Graphene shows explosive growth. By the end of May 8, 2017, the Spider web of Scientific discipline showed 144925 related reports after searching "Graphene". Graphene materials, the new favorite of the bombardment manufacture, are expected to cause a revolution in the battery industry. Graphene materials are considered to be the material with largest strength unit mass. With the increasing energy consumption and the failure of traditional free energy sources, the development of unconventional free energy and complex wells such as, deep wells, ultra-deep wells, extended achieve wells, wells with long horizontal department has increased year by year [16-18]. With the continuous development of oil and gas resources, the course of conventional oil and gas resources is getting worse and worse, and the difficulty of development is further increased [nineteen-20]. The evolution of unconventional free energy and wells with complex conditions is express past existing engineering science [21]. As the "Blood" of drilling industry, wellbore fluids face great challenges. Graphene material has get the new favorite of the material field subsequently carbon nanotubes, and the continuous innovation of Graphene material will greatly promote the development of the oilfield.

Co-ordinate to the evolution needs of petroleum manufacture, this paper discusses the cardinal technology of Graphene materials virtually applications and prospects on the basis of extensive investigation of inquiry status in oilfield. Four aspects, the characteristics of Graphene materials, research status, cardinal engineering science of application and the prospect in oilfield are reviewed.

1.1 Characteristics of Graphene material

Graphene structural features

Graphene is a monatomic layer of graphite that can exist independently in the external environs [22]. Graphene is obtained by stripping graphite in a physical or chemical manner. At present, the preparation methods of Graphene mainly include epitaxial grown method [23], mechanical stripping method [24], chemical vapor deposition method [25], thermal or oxidation stripping method [26]. The improved Hummer method is adopted by many scholars [27-28]. There are many dissimilar groups such as carboxyl grouping, epoxy group and hydroxyl group on the surface of Graphene oxide stripped past chemical method, as shown in Figure 1[29]. Graphene oxide Nano sheets are mainly equanimous of hexagons which are not oxidized, and some parts are oxidized.

The groups such every bit carboxyl groups are concentrated on the edges of Graphene oxide nanosheets. There are a large number of hydroxyl groups and epoxy groups in the middle zone of Graphene oxide nanosheets. The reduced Graphene is obtained when the Graphene oxide is reduced. The hydroxyl and epoxy groups in the middle zone of reduced Graphene nanosheets are reduced Hexagonal structure is destroyed and Graphene nanosheets with structural defects are formed. A large number of carboxyl groups, hydroxyl groups and epoxy groups are active groups, which are easy to be functionalized. The structural characteristics of Graphene make it easy to be functionalized. It laid the foundation for the extensive awarding of Graphene.

Applications of Graphene

Graphene is a new carbon textile after carbon nanotubes. Graphene has maximum strength per unit mass with unique electric conduction and is piece of cake to be functionalized, which all develop the application of grapheme. Now, Graphene composite materials have attracted great attention in the fields of free energy storage and conversion, catalysis, electronic devices, high strength materials, chemical and biological sensing, and biological applied science then on. Research and concerns nigh Graphene keep to heat upwards.

one.ii Applications in the oil industry

Some scholars take carried out enquiry on the application of Graphene in oilfield because of its fantabulous operation. In June 2011, James M. Tour invented a patent on the application of Graphene and modified Graphene in drilling fluid [thirty]. The patent reports the preparation of chemical modified grapheme, as in Figure 2.1.

The benzene was grafted onto the surface of Graphene by using hydrazine hydrate as reducing agent. Graphene and chemical modified grapheme are added to the drilling fluid, and Graphenenanosheets are adsorbed onto the surface of wellbore to reduce drilling fluid into the stratum, equally shown in Effigy two.2.

The cake with the addition of Graphene and modified Graphene is sparse and compact. Graphene and modified Graphene can effectively improve the quality of filter cake and reduce drilling fluid into the germination. The same year in September, James M. Tour publishes a paper about the research on Graphene oxide as filtrate reducer of high performance [31] in ACS Applied Materials & Interfaces. The newspaper describes the procedure of preparation for Graphene oxide by improved Hummer method in detail. The detailed study on property of Graphene oxide as filtrate reducer in drilling fluid shows that the filtration is 6.1mL in 0.ii wt% depression concentrations which is less than that of conventional filtration reducer, and the boilerplate filtration is 7.2 mL The thickness of the filter block is about twenty μ m, far less than that of conventional filtration reducer which is 280 μ m. Flexible Graphenenanosheets tin enter pores smaller than their size, and there is a large corporeality of Graphenenanosheets in the filtration of the drilling fluid, as shown in Figure ii.3. The addition of methanol modified Graphene oxide into drilling fluid results in lower filtration. Graphene oxide has excellent performance on filtration control.

In September 2013, Xuan Yang reported a paper nearly the preparation and evaluation of nano-Graphene oxide as a high-performance fluid loss condiment [32]. Filtration control properties of Graphene oxide according to the API standards are evaluated and the results show that Graphene oxide has excellent fluid loss performance. Compared with conventional filtrate reducers, Graphene oxide has the advantages of low dosage and thin cake.

In October 2013, Steve Young published a patent on Graphene material as shale inhibitor [33]. Based on James Yard. Bout chemical modified method, the patent evaluates rheological backdrop and rolling recovery rate after modifying Graphene oxide, the inhibition is characterized past rolling recovery rate.The inquiry about application of Graphene as lubricant was published by NorasazlyMohd Taha in IPTC in September 2015[34]. Graphene materials can form a dense movie on the surface of the metal under the pressure, temperature and mechanical strength. This Graphene film is formed under the synergistic activeness of concrete adsorption and chemic adsorption. Compared with traditional lubricants, Graphene materials accept much more excellent lubricity. In the aqueous polymer brine organisation, laboratory tests show that the friction of Graphene materials is at 70%-80% reduction, while it of conventional lubricant materials is generally at only 30%-40% reduction. At the same fourth dimension, the Graphene material still has splendid lubricity at 176 ℃ . In May 2016, our team studied the inhibition and the plugging performance for the nano pore of shale of amino modified Graphene[35]. As shown in Figure 2.4, we select sandstone with high permeability and shale with ultra-low permeability equally cores, downstream pressure is respectively recorded in 4%NaCl alkali system and 0.4% amino modified Graphene solution. The longer time the downstream pressure level reaches the upstream pressure level, the performance of plugging cores is better. The time which the upstream pressure level reaches the upstream pressure in brine system is about five minutes when sandstone is tested, while in modified Graphene system the time is about 24 hours.

This result shows that the amino modified Graphenehas the ability to seal pores in sandstone. When natural shale is called every bit core, in alkali system the time which the upstream pressure reaches the upstream pressure is nigh 5 hours, while the downstream force per unit area still does not increase later 66 hours in amino modified Graphene organisation.

The power of Graphene to plug nano pores is further revealed. Amino modified Graphene also has excellent ability to inhibit shale expansion. The mechanism of action betwixt amino Graphene and clay minerals is analyzed in item in the paper. Graphene is adsorbed on the surface of shale by hydrogen bonding and hydrophobic interaction, and a compact film is formed. This film prevents moisture entry and inhibits the hydration expansion of the clay. The experiment data shows that the amino modified Graphene has fantabulous power of plugging the nano pore of shale and inhibiting the hydration expansion of dirt.

1.three Prospects of Graphene in oilfield

Through the domestic and foreign literature investigation, 4 related literatures and 2 patents are retrieved well-nigh the application of Graphene materials in oilfield. Many scholars begin to explore the application of Graphene in the petroleum industry. Although a lot of work can be carried out, information technology is nevertheless in laboratory research at present. Lots of piece of work is just exam on functioning, not a thorough study of machinery. Graphene, as a new favorite in the field of materials, volition have broad application prospects in oilfield. Mainly in the following areas:

1.three.ane Drilling Fluid

Graphene materials as filtrate reducer for drilling fluid, showing excellent fluid loss agent performance, but the mechanism of Graphene materials and dirt minerals are non in-depth report, and not study compatibility with other additives for drilling fluid. Graphene material, as a shale inhibitor of drilling fluid, is only used for the determination of rolling recovery. The mechanism of action was non studied. Graphene material is a kind of monolayer graphite with many active groups. It has the post-obit application prospects in drilling fluid.

1.3.2 Tackifier and Shear Strength Agent

Intermolecular weak interaction between active groups of Graphene materials is formed past hydrogen bond, hydrophilic-hydrophobic interaction and π-π interaction. Graphene materials take splendid stimuli-responsiveness. High Shear thinning agents with high shear strength and low viscosity can be obtained past molecular pattern. At high shear rate, the viscosity is low specially nearly the nozzle. While at low shear rate, the viscosity is high, so it is easy to carry cuttings and forbid the settlement of the weighting materials.

1.three.3 Fluid Loss Agent

Previous piece of work has shown that Graphene is an first-class filtrate reducer. However, the mechanism of action has non been studied deeply. Temperature resistance needs further comeback. Graphene with one unmarried layer, when the salt molecules are shut to the border of Graphene, Graphene will curl to some extent, but the strong π-π interaction will limit its crimper. So,Graphene materials show excellent salt resistance, especially to divalent metallic ions. Graphene materials volition be widely used in the fields of filtration control with salt resistance and temperature resistance.

1.3.4 Shale Inhibitor

There are many agile groups such as carboxyl and hydroxyl groups on the edge of Graphene materials, and adsorption groups such as amino groups are obtained later being modified. The adsorption of Graphene materials on rocks is enhanced. Large areas of high strength canvass materials are adsorbed onto the stone surface to forestall wet from entering. Graphene is thin but has high strength, so information technology can effectively reduce costs with low dosage. Graphene materials are expected to get the unique shale inhibitors through advisable modification,

1.3.5 Nano-Pores Plugging Amanuensis

For plugging nano-pores in shale, there are no reports of industrial products at home and away. The permeability of shale is depression, and the pores are rich. The average size of nano-pores in shale is about 10nm. General rigid nanomaterials are easy to agglomerate in horizontal solution and difficult to enter nano-pores. Flexible organic materials, with large molecular weight and little interaction with stone, are difficult to adsorb to the surface of shale. Past molecular design, strong adsorption groups are introduced to increase the interaction between Graphene and rock. Graphene material is easy to be adsorbed on the surface of rock. It is hopeful to solve the bottleneck of plugging nano-pores in shale because of strong strength of Graphene materials and their pressure-bearing capacity.

1.3.6 Lubricant

By introducing groups which have interaction between metallic ions, Graphene materials tin be adsorbed onto the surface of the drilling tools and form a flexible movie which reduces the friction between drilling tools and drilling fluids, drilling tools and rocks. The lubrication performance of drilling fluids can be effectively improved. The forcefulness interim between drilling tools and drilling fluids can exist reduced by introducing hydrophobic groups which can prevent fleck balling, sticking of tool and other accidents effectively.

1.3.7 Wet Ability Reversal Amanuensis

As hydrophilic materials, the hydrophilicity and hydrophobicity of Graphene can exist inverse by introducing hydrophobic groups. These modified Graphene tin exist adsorbed onto the surface of the rocks and change the wettability of rocks. Graphene materials are expected to be an excellent wettability reversal agent

1.4 Completion Fluid and WorkOver Fluid

Completion fluid and workover fluid generally use brine systems to protect reservoirs. The adsorption of Graphene on the surface of rocks is beneficial to the stability of the borehole. Later on the performance, the Graphene is desorbed from surface of the rocks under the formation pressure and afterwards encountering the oil layer, and then reverse to the ground. Graphene materials are environmentally friendly, low-viscosity and easy to reverse.

1.5 Acidizing Fluid and Fracturing Fluid

Diverting acid is the cadre agent of acidizing fluid. Graphene is oxidized by strong acid and tin can exist stably under acidic conditions. Calcium sensitive Graphene materials tin exist prepared with molecular modification. It is expected to become a steering acid with footling amount, low cost and splendid functioning. Graphene and most polymers can course weak gel systems, which are environmentally responsive by the weak forces through not-covalent bonds. Information technology is expected to go a new generation of fracturing fluid system.

one.6 Plugging Agent

There are no mature technical countermeasures to severe leakage. The plugging functioning is carried out regardless of cost and times. Polymer gel has go the new material for plugging considering information technology is not limited by pore size, crosslinking time and breaking time are controllable. Graphene tin form the gel system with polyacrylamide, polyacrylic acid, polyvinyl booze and Carboxymethyl cellulose. Graphene tin can enhance the strength of gel, and also has excellent adsorption ability. Therefore, Graphene and polymer gel complex are expected to solve the problems of severe leakage.

ii.  Conclusions

The awarding of Graphene material in oilfield has been preliminarily explored. Many experimental achievements are notwithstanding in the laboratory research. The enquiry on the machinery of action is non thorough, and the range of application is still relatively narrow. The post-obit aspects need to exist studied:

one. Written report the mechanism of activity in depth and optimize the design of molecules.

ii. Expand the scope of inquiry, behave researches on drilling fluid, completion fluid, workover fluid, acidizing fluid, fracturing fluid, plugging agent.

iii. Accelerate the industrialization of Graphene materials.

Graphene materials with will excellent backdrop have wide application prospects in oilfield. It is expected to become a new generation of working fluid system. It is hopeful to play a unique role in the exploitation of unconventional oil and gas resources such as shale gas, coalbed methane and tight gas.

3.    Acknowledgements

We would similar to give thanks for the fiscal support from Prc Postdoctoral Fund (H29216)for this work.

Figure one: a) Graphene oxide; b) reduced Graphene[29].

Figure 2.1: preparation of modified Graphene [30].

Effigy two.ii: Schematic diagram of Graphene and modified Graphene [30].

Figure 2.3: SEM image of Graphene in mud filtrate [31].

Figure 2.4: pressure alter in brine system and amino modified Graphene system[35]. a, c) brine arrangement; b, d) amino modified Graphene arrangement.

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