Performances and mechanisms of the peroxymonosulfate/ferrate(VI) oxidation process in real shale gas flowback water treatment.

Shale gas flowback water (SGFW), which is an inevitable waste product generated after hydraulic fracturing during development, poses a severe threat to the environment and human health. Managing high-salinity wastewater with complex physicochemical compositions is critical for ensuring environmental sustainability of shale gas development. Desalination processes have been recommended to treat SGFW to adhere to the discharge limits. However, organic fouling has become a significant concern in the steady operation of desalination processes, and the effective removal of organic compounds is challenging. This study aimed to develop an effective oxidation method to mitigate membrane fouling in real SGFW treatment process. It adopted the peroxymonosulfate (PMS)/ferrate (Fe(VI)) process, involving both free and non-free radical pathways that can alleviate the negative effects of high-salinity environments on oxidation. The operating parameters were optimized and removal effects were examined, while the synergistic oxidation mechanism and organic conversion of the PMS/Fe(VI) process were also analyzed. The results showed that the PMS/Fe(VI) process exhibited a synergistic effect compared with the PMS and Fe(VI) processes alone, with a total organic carbon (TOC) removal efficiency of 46.8% under optimal reaction conditions in real SGFW. In the Fe(VI)/PMS process, active species such as Fe(V)/Fe(IV), ·OH, and SO4-· were jointly involved in the oxidation of organic matter. Additionally, 99.5% of the total suspended solids and 95.2% of Ba2+ in the SGFW were removed owing to the formation of a coagulant (Fe3+) and SO42- during the reaction. Finally, an ultrafiltration membrane fouling experiment proved that oxidation processes can increase the membrane-specific flux and alleviate fouling resistance. This study can serve as a reference for the design of real SGFW treatment processes and is significant for the environmental management of shale gas development.

Water and salt recovery from shale gas produced water by vacuum membrane distillation followed by crystallization.

A vacuum membrane distillation (VMD) followed by crystallization (VMD-C) was developed for the recovery of water and salts from shale gas produced water (SGPW). Before VMD, the pretreatment of SGPW with Fenton oxidation-flocculation is applied, with the chemical oxygen demand (COD) concentration reduction of 75% and the total removal of the total suspended solids (TSS), Ca2+, and Mg2+ in SGPW. The pretreatment of SGPW mitigated the membrane fouling in the VMD and effectively prevented the reduction of membrane flux over time. The average flux of the PTFE membrane reached 12.1 kg m-2 h-1 during the separation of the pretreated SGPW at a feed flux of 40 L h-1 and a feed temperature of 40 °C. The rejection rate of the membrane to TDS in SGPW was over 99%. Fresh water with a conductivity of below 20 µs cm-1 was produced by VMD-C. The salts concentrated upstream of the membrane were recovered by a stirring crystallization process. The VMD-C system resulted in a 61% cost savings compared to conventional SGPW treatment.

Composition and Origin of Surface Casing Fluids in a Major US Oil- and Gas-Producing Region.

Fluids leaked from oil and gas wells often originate from their surface casing─a steel pipe installed beneath the deepest underlying source of potable groundwater that serves as the final barrier around the well system. In this study, we analyze a regulatory dataset of surface casing geochemical samples collected from 2573 wells in northeastern Colorado─the only known publicly available dataset of its kind. Thermogenic gas was present in the surface casings of 96.2% of wells with gas samples. Regulatory records indicate that 73.3% of these wells were constructed to isolate the formation from which the gas originated with cement. This suggests that gas migration into the surface casing annulus predominantly occurs through compromised barriers (e.g., steel casings or cement seals), indicative of extensive integrity issues in the region. Water was collected from 22.6% of sampled surface casings. Benzene, toluene, ethylbenzene, and xylenes were detected in 99.7% of surface casing water samples tested for these compounds, which may be due to the presence of leaked oil, natural gas condensate, or oil-based drilling mud. Our findings demonstrate the value of incorporating surface casing geochemical analysis in well integrity monitoring programs to identify integrity issues and focus leak mitigation efforts.

Granular activated carbon (GAC) fixed bed adsorption combined with ultrafiltration for shale gas wastewater internal reuse.

Membrane processes are widely applied in shale gas flowback and produced water (SGFPW) reuse. However, particulate matters and organic matters aggravate membrane fouling, which is one of the major restrictions on SGFPW reuse. The present study proposed fixed bed adsorption using granular activated carbon (GAC) combined with ultrafiltration (UF) for the first time to investigate the treatment performance and membrane fouling mechanism. The adsorption of GAC for SGFPW was best described by the Temkin isotherm model and the pseudo-second-order kinetic model. GAC fixed bed pretreatment with different empty bed contact times (EBCT) (30, 60 and 90 min) showed the significant removal rate for dissolved organic carbon (DOC) and turbidity, which was 34.7%-42.4% and 98.1%-98.9%, respectively. According to characterization of UF membrane fouling layer, particulate matters and organic matters caused major part of membrane fouling. After being treated by GAC fixed bed, total fouling index (TFI) and hydraulic irreversible fouling index (HIFI) respectively decreased by more than 32.5% and 18.3% respectively, showing the mitigation effect of GAC fixed bed on membrane fouling. According to the XDLVO theory, GAC fixed bed also mitigated membrane fouling by reducing the hydrophobic interactions between the foulants and the UF membrane. The integrated GAC fixed bed-UF process produced high-quality effluents that met the water quality standards of SGFPW internal reuse, which was an effective technology of the SGFPW reuse.

Comparative life cycle assessment of cement, sintered bricks and non-sintered bricks manufacturing using water-based drilling cuttings from shale gas production in the Sichuan Basin, China.

This study determined the environmental impacts of three recycling pathways for water-based drilling cuttings (WDC), namely cement, sintered bricks, and non-sintered bricks, based on the life cycle assessment (LCA) method. A life cycle inventory was developed with based on the resource utilization of 1t drilling cuttings as the functional unit, and a sensitivity analysis was conducted to identify the essential materials and energy consumption. The results showed that the sequence of the environmental impact index for the three recycling pathways was cement, non-sintered brick and sintered brick. Primary energy demand and direct emissions were the main reasons for this difference. Direct emissions, electricity, and binder were the largest contributors to the inventory of cement, sintered bricks, and non-sintered bricks, accounting for 54%, 33.4%, and 62.1% of the environmental impact burden, respectively. Furthermore, a 5% reduction in direct emissions, electricity, and binder decreased the integrated impact index by approximately 2.67%, 3.04%, and 3.38% for cement, sintered bricks, and non-sintered bricks, respectively. Based on the LCA results, strategies for reducing emissions and conserving energy were proposed. These results provide a useful reference for creating a sustainable system for recycling water-based drilling cuttings.

Material Flows of Polyurethane in the United States.

Today, polyurethanes are effectively not recycled and are made principally from nonrenewable, fossil-fuel-derived resources. This study provides the first high-resolution material flow analysis of polyurethane flows through the U.S. economy, tracking back to fossil fuels and covering polyurethane-relevant raw materials, trade, production, manufacturing, uses, historical stocks, and waste management. According to our analysis, in 2016, 2900 thousand tonnes (kt) of polyurethane were produced in the United States and 920 kt were imported for consumption, 2000 kt entered the postconsumer waste streams, and 390 kt were recycled and returned to the market in the form of carpet underlayment. The domestic production of polyurethane consumed 1100 kt of crude oil and 1100 kt of natural gas. With the developed polyurethane flow map, we point out the limitation of the existing mechanical recycling methods and identify that glycolysis, a chemical recycling method, can be used to recycle the main components of postconsumer polyurethane waste. We also explore how targeting biobased pathways could influence the supply chain and downstream markets of polyurethane and reduce the consumption of fossil fuels and the exposure to toxic precursors in polyurethane production.

On-Site Treatment of Shale Gas Flowback and Produced Water in Sichuan Basin by Fertilizer Drawn Forward Osmosis for Irrigation.

Fertilizer drawn forward osmosis (FDFO) was proposed to extract fresh water from flowback and produced water (FPW) from shale gas extraction for irrigation, with fertilizer types and membrane orientations assessed. The draw solution (DS) with NH4H2PO4 displayed the best performance, while the DS with (NH4)2HPO4 resulted in the most severe membrane fouling. The DS with KCl and KNO3 led to substantial reverse solute fluxes. The FDFO operation where the active layer of the membrane was facing the feed solution outperformed that when the active layer was facing the DS. The diluted DS and diluted FPW samples were used for irrigation of Cherry radish and Chinese cabbage. Compared to deionized water, irrigation with the diluted DS (total dissolved solid (TDS) = 350 mg·L-1) promoted plant growth. In contrast, inhibited plant growth was observed when FPW with high salinity (TDS = 5000 mg·L-1) and low salinity (TDS = 1000 mg·L-1) was used for irrigation of long-term (8-week) plant cultures. Finally, upregulated genes were identified to illustrate the difference in plant growth. The results of this study provide a guide for efficient and safe use of FPW after FDFO treatment for agricultural application.

A review of membrane development in membrane distillation for emulsified industrial or shale gas wastewater treatments with feed containing hybrid impurities.

Investigations on membrane materials for membrane distillation (MD) and its applications have been ongoing since the 1990s. However, a lack of materials that produce robustly stable and up-to-the-mark membranes for MD for different industrial applications remains an ongoing problem. This paper provides an overview of materials developed for MD applications. Although key aspects of published articles reviewed in this paper pertain to MD membranes synthesized for desalination, future MD can also be applied to organic wastewater containing surfactants with inorganic compounds, either with the help of hybrid treatment processes or with customized membrane materials. Many industrial discharges produce effluents at a very high temperature, which is an available driving force for MD. However, there remains a lack of cost-effective membrane materials. Amphiphobic and omniphobic membranes have recently been developed for treating emulsified and shale gas produced water, but the problem of organic fouling and pore wetting remains a major challenge, especially when NaCl and other inorganic impurities are present, which further deteriorate separation performance. Therefore, further advancements in materials are required for the treatment of emulsified industrial wastewater containing surfactants, salts, and for oil or shale gas wastewater for its commercialized reuse. Integrated MD systems, however, may represent a major change in shale gas wastewater and emulsified wastewater that are difficult to treat.

The Application of Ferric Chloride-Lignin Sulfonate as Shale Inhibitor in Water-Based Drilling Fluid.

A series of ferric chloride-lignin sulfonate (FCLS) was prepared from ferric chloride and lignin sulfonate to be used as shale inhibitor. The swelling rate of clay with FCLS-2 (w/w = 0.3%) decreased to 41.9%. Compared with control, FCLS-2 displayed high inhibitive ability against the hydrating and swelling processes of clay. Thus, the swelling degree of samples with FCLS-2 was much lower than that of the control, as well as the mud ball was more stable in FCLS-2 solution. Essentially, these excellent performances in inhibitor were assigned to the hydrogen bonding, electrostatic interaction and anchoring between FCLS-2 and other components. In addition, FCLS-2 has good compatibility with other common drilling fluid additives, and it can reduce the viscosity of systems, regardless of the room temperature or high temperature.

Synthesis and Characterization of a Novel Microporous Dihydroxyl-Functionalized Triptycene-Diamine-Based Polyimide for Natural Gas Membrane Separation.

An intrinsically microporous polyimide is synthesized in m-cresol by a one-pot high-temperature condensation reaction of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and newly designed 2,6 (7)-dihydroxy-3,7(6)-diaminotriptycene (DAT1-OH). The 6FDA-DAT1-OH polyimide is thermally stable up to 440 °C, shows excellent solubility in polar solvents, and has moderately high Brunauer-Teller-Emmett (BET) surface area of 160 m2 g-1 , as determined by nitrogen adsorption at -196 °C. Hydroxyl functionalization applied to the rigid 3D triptycene-based diamine building block results in a polyimide that exhibits moderate pure-gas CO2 permeability of 70 Barrer combined with high CO2 /CH4 selectivity of 50. Mixed-gas permeation studies demonstrate excellent plasticization resistance of 6FDA-DAT1-OH with impressive performance as potential membrane material for natural gas sweetening with a CO2 permeability of 50 Barrer and CO2 /CH4 selectivity of 40 at a typical natural gas well partial pressure of 10 atm.

Omniphobic Polyvinylidene Fluoride (PVDF) Membrane for Desalination of Shale Gas Produced Water by Membrane Distillation.

Microporous membranes fabricated from hydrophobic polymers such as polyvinylidene fluoride (PVDF) have been widely used for membrane distillation (MD). However, hydrophobic MD membranes are prone to wetting by low surface tension substances, thereby limiting their use in treating challenging industrial wastewaters, such as shale gas produced water. In this study, we present a facile and scalable approach for the fabrication of omniphobic polyvinylidene fluoride (PVDF) membranes that repel both water and oil. Positive surface charge was imparted to an alkaline-treated PVDF membrane by aminosilane functionalization, which enabled irreversible binding of negatively charged silica nanoparticles (SiNPs) to the membrane through electrostatic attraction. The membrane with grafted SiNPs was then coated with fluoroalkylsilane (perfluorodecyltrichlorosilane) to lower the membrane surface energy. Results from contact angle measurements with mineral oil and surfactant solution demonstrated that overlaying SiNPs with ultralow surface energy significantly enhanced the wetting resistance of the membrane against low surface tension liquids. We also evaluated desalination performance of the modified membrane in direct contact membrane distillation with a synthetic wastewater containing surfactant (sodium dodecyl sulfate) and mineral oil, as well as with shale gas produced water. The omniphobic membrane exhibited a stable MD performance, demonstrating its potential application for desalination of challenging industrial wastewaters containing diverse low surface tension contaminants.

Natural Gas and Cellulosic Biomass: A Clean Fuel Combination? Determining the Natural Gas Blending Wall in Biofuel Production.

Natural gas has the potential to increase the biofuel production output by combining gas- and biomass-to-liquids (GBTL) processes followed by naphtha and diesel fuel synthesis via Fischer-Tropsch (FT). This study reflects on the use of commercial-ready configurations of GBTL technologies and the environmental impact of enhancing biofuels with natural gas. The autothermal and steam-methane reforming processes for natural gas conversion and the gasification of biomass for FT fuel synthesis are modeled to estimate system well-to-wheel emissions and compare them to limits established by U.S. renewable fuel mandates. We show that natural gas can enhance FT biofuel production by reducing the need for water-gas shift (WGS) of biomass-derived syngas to achieve appropriate H2/CO ratios. Specifically, fuel yields are increased from less than 60 gallons per ton to over 100 gallons per ton with increasing natural gas input. However, GBTL facilities would need to limit natural gas use to less than 19.1% on a LHV energy basis (7.83 wt %) to avoid exceeding the emissions limits established by the Renewable Fuels Standard (RFS2) for clean, advanced biofuels. This effectively constitutes a blending limit that constrains the use of natural gas for enhancing the biomass-to-liquids (BTL) process.

Changing the renewable fuel standard to a renewable material standard: bioethylene case study.

The narrow scope of the U.S. renewable fuel standard (RFS2) is a missed opportunity to spur a wider range of biomass use. This is especially relevant as RFS2 targets are being missed due to demand-side limitations for ethanol consumption. This paper examines the greenhouse gas (GHG) implications of a more flexible policy based on RFS2, which includes credits for chemical use of bioethanol (to produce bioethylene). A Monte Carlo simulation is employed to estimate the life-cycle GHG emissions of conventional low-density polyethylene (LDPE), made from natural gas derived ethane (mean: 1.8 kg CO2e/kg LDPE). The life-cycle GHG emissions from bioethanol and bio-LDPE are examined for three biomass feedstocks: U.S. corn (mean: 97g CO2e/MJ and 2.6 kg CO2e/kg LDPE), U.S. switchgrass (mean: -18g CO2e/MJ and -2.9 kg CO2e/kg LDPE), and Brazilian sugar cane (mean: 33g CO2e/MJ and -1.3 kg CO2e/kg LDPE); bioproduct and fossil-product emissions are compared. Results suggest that neither corn product (bioethanol or bio-LDPE) can meet regulatory GHG targets, while switchgrass and sugar cane ethanol and bio-LDPE likely do. For U.S. production, bioethanol achieves slightly greater GHG reductions than bio-LDPE. For imported Brazilian products, bio-LDPE achieves greater GHG reductions than bioethanol. An expanded policy that includes bio-LDPE provides added flexibility without compromising GHG targets.

Preparation and characterization of latex particles as potential physical shale stabilizer in water-based drilling fluids.

The poly(styrene-methyl methacrylate) latex particles as potential physical shale stabilizer were successfully synthesized with potassium persulfate as an initiator in isopropanol-water medium. The synthesized latex particles were characterized by Fourier transform infrared spectroscopy (FT-IR), particle size distribution measurement (PSD), transmission electron microscopy (TEM), and thermal gravimetric analysis (TGA). FT-IR and TGA analysis confirmed that the latex particles were prepared by polymerization of styrene and methyl methacrylate and maintained good thermal stability. TEM and PSD analysis indicated that the spherical latex particles possessed unimodal distribution from 80 nm to 345 nm with the D90 value of 276 nm. The factors influencing particle size distribution (PSD) of latex particles were also discussed in detail. The interaction between latex particles and natural shale cores was investigated quantitatively via pore pressure transmission tests. The results indicated that the latex particles as potential physical shale stabilizer could be deformable to bridge and seal the nanopores and microfractures of shale to reduce the shale permeability and prevent pore pressure transmission. What is more, the latex particles as potential physical shale stabilizer work synergistically with chemical shale stabilizer to impart superior shale stability.

Strength properties of preceramic brazed joints of a gold-palladium alloy with a microwave-assisted oven and gas/oxygen torch technique.

STATEMENT OF PROBLEM: The effect of microwave brazing on the strength properties of dental casting alloys is not yet known. PURPOSE: The purpose of this study was to compare the strength properties of preceramic brazed joints obtained by using a microwave oven and a conventional torch flame for a high noble alloy (Au-Pd). MATERIAL AND METHODS: A total of 18 tensile bars made of an Au-Pd ceramic alloy were fabricated. Six specimens were cut and joined with a high-fusing preceramic solder in a specially designed microwave oven, and 6 specimens were joined with a conventional natural gas/oxygen torch. The remaining 6 uncut specimens were tested as a control. All the specimens were subjected to testing with a universal testing machine. A 1-way ANOVA was performed for each strength property tested. RESULTS: The tensile strength of the uncut group was the highest (745 ±19 MPa), followed by the microwave group (420 ±68 MPa) and the conventional torch group (348 ±103 MPa) (P<.001); however, no significant difference in tensile strength was found between the microwave group and gas torch group. The tensile strength of the microwave group exceeded ANSI/ADA Standard No. 88, Dental Brazing Alloys (a joint standard of the American National Standards Institute and the American Dental Association). CONCLUSIONS: The microwave heating preceramic solder method demonstrated the excellent tensile strength of an Au-Pd alloy and may be an alternative way of joining alloys when a torch flame is contraindicated.

Two-stage thermal pyrolysis of plastic solid waste: Set-up and operative conditions investigation for gaseous fuel production.

In response to the escalating global challenge of mounting plastic waste and the imperative to adopt more sustainable practices for resource utilization, our study focuses on the utilization of plastic solid waste (PSW) through a two-stage thermal pyrolysis process. This aims to demonstrate its potential as a high-performance alternative to existing two-stage catalytic pyrolysis methods. The experimentation involved processing real scrap PSW material in a lab-scale batch set-up, emphasizing optimizing residence time in the cracking reactor to maximize gas yield and its lower heating value (LHV). The study underscores the advantages of the employed two-stage thermal pyrolysis apparatus through a comparative analysis with established set-up dedicated to maximizing gas yield. Once the operative conditions were explored, resulting pyrolysis products underwent detailed characterization to assess their suitability as a sustainable fuel source. The study also presents a practical application of the produced gaseous fuel, envisioning its combustion in an internal combustion engine (ICE), known for its flexibility regarding fuel properties. This application is demonstrated through a simulation conducted in Unisim Design©. The successful processing of real PSW material in the two-stage lab-scale experimental set-up showcased optimal gas yield achievements (>65 % w/w) with an LHV (∼41 MJ/kg), comparable to that of natural gas. This emphasizes the potential of these sustainable alternatives to replace fossil fuels, especially in the context of ICE applications. The integration of the pyrolysis plant with an ICE demonstrated promising prospects for generating electricity in the transportation sector and facilitating thermal power for heat integration in pyrolysis reactors.

New generation mixed matrix membrane for CO2 separation: Transition from binary to quaternary mixed matrix membrane.

Contemporary advances in material development associated with membrane gas separation refer to the cost-effective fabrication of high-performance, defect-free mixed matrix membranes (MMMs). For clean energy production, natural gas purification, and CO2 capture from flue gas systems, constituting a functional integration of polymer matrix and inorganic filler materials find huge applications. The broad domain of research and development of MMMs focused on the selection of appropriate materials, inexpensive membrane fabrication, and comparative study with other gas separation membranes for real-world applications. This study addressed a comprehensive review of the advanced MMMs wrapping various facets of membrane material selection; polymer and filler particle morphology and compatibility between the phases and the relevance of several fillers in the assembly of MMMs are analyzed. Further, the research on binary MMMs, their problems, and solutions to overcome these challenges have also been discussed. Finally, the future directions and scope of work on quaternary MMM are scrutinized in the article.

Simultaneous electrocoagulation and E-peroxone coupled with ultrafiltration membrane for shale gas produced water treatment.

Membrane fouling caused by the organics-coated particles was the main obstacle for the highly efficient shale gas produced water (SGPW) treatment and recycling. In this study, a novel hybrid electrocoagulation (EC) and E-peroxone process coupled with UF (ECP-UF) process was proposed to examine the efficacy and elucidate the mechanism for UF fouling mitigation in assisting SGPW reuse. Compared to the TMP (transmembrane pressure) increase of -15 kPa in the EC-UF process, TMP in ECP-UF system marginally increased to -1.4 kPa for 3 filtration cycles under the current density of 15 mA/cm2. Both the total fouling index and hydraulically irreversible fouling index of the ECP-UF process were significantly lower than those of EC-UF process. According to the extended Derjaguin-Landau-Verwey-Overbeek theory, the potential barriers was the highest for ECP-UF processes due to the substantial increase of the acid-base interaction energy in ECP-UF process, which was well consistent with the TMP and SEM results. Turbidity and TOC of ECP-UF process were 63.6% and 45.8% lower than those of EC-UF process, respectively. According to the MW distribution, the variations of compounds and their relative contents were probably due to the oxidation and decomposing products of the macromolecular organics. The number of aromatic compound decreased, while the number of open-chain compounds (i.e., alkenes, alkanes and alcohols) increased in the permeate of ECP-UF process. Notably, the substantial decrease in the relative abundance of di-phthalate compounds was attributed to the high reactivity of these compounds with ·OH. Mechanism study indicated that ECP could realize the simultaneous coagulation, H2O2 generation and activation by O3, facilitating the enhancement of ·OH and Alb production and therefore beneficial for the improved water quality and UF fouling mitigation. Therefore, the ECP-UF process emerges as a high-efficient and space-saving approach, yielding a synergistic effect in mitigating UF fouling for SGPW recycling.

Sustainability analysis of the use of natural gas in the iron and steel industry.

In this study, using natural gas instead of coke gas in the reheating furnace in a steelmaking company is investigated in terms of economic, social, and environmental impacts. A sample projection is prepared, and economic analyses are conducted in line with the production plan target for future planning periods of 144 months. The natural gas usage increases the production quantity by 914 tonnes and allows the company to produce 5,979,334 kWh of additional electric power from the metallurgical gases monthly. In the economic analysis, we use engineering economics techniques to examine the economic impacts of the modernization investment for reheating furnaces. Accordingly, a positive return for each month shows the feasibility of the renovation project. The self-paying time of the investment is calculated as a short period of 11 months. Besides, the social and environmental impacts are notable; the renovation project decreases occupational health and safety risks by using natural gas as a substitute fuel, preventing a potential explosion or poisoning risk in the production, storage, and distribution. The renovation project decreases the global warming potential of blast furnace gas constituents and carbon emissions by 0.84% per month.

Porous-layer columns with a poly(1-trimethylsilyl-1-propyne) stationary phase for determining of catalytic reactions components, natural gas and its processed products.

The presented review is devoted to methods for determining the component composition of the studied catalytic reactions, natural gas and its processed products using gas chromatography columns prepared on the basis of poly(1-trimethylsilyl-1-propyne) polymer (PTMSP). Methods of polymer modification are proposed in order to change the polarity and selectivity of separation of compounds of different chemical nature. The influence of the film thickness of the PTMSP stationary phase on the separation parameters and the loading capacity of the columns used is noted. Examples of the use of packed and capillary columns in solving various problems by gas chromatography are shown. The detection limits are determined and the repeatability for the analyzed compounds are calculated.