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Liquid-liquid equilibrium (LLE) data for poly (ethylene glycol) (PEG) of different molecular weights (600, 1500, 3000, 6000) + sodium formate (NaCHO2), potassium formate (KCHO2) + water at different temperatures (298.15 and 308.15 K) and for PEG (1500) + sodium formate + water at different pH values (8.05, 9.06, 10.92), were determined experimentally. The tie lines and plait point are reported at different PEG molecular weight, pH, temperature and type of cation. Furthermore, the effect of those parameters on binodal curve, tie-line length (TLL) and slope of tie line (STL) are discussed in detail by comparing the results to that of literature data. The effective excluded volume (EEV) values obtained from the LLE data were used to study the effect of the parameters on the binodal curves. The phase composition and the tie-lines’ ends were obtained by measuring the density ( ρ ) and refractive index ( n D ). Furthermore, the binodal curves and the tie-line compositions were well-fitted by using some semi empirical equations.

A ruthenium porphyrin-based porous organic polymer (POP) was synthesized, characterized, and used to reduce CO2 to a formate salt. We demonstrate that Ru-BBT-POP can be utilized to reduce CO2 to a silyl formate and then converted to potassium formate with a respectable turnover number and frequency.

Metal formates sometimes occur as degradation products on heritage objects due to the use of wood products or other sources of formic acid and formaldehyde. They are often related to alkaline surfaces which transform formaldehyde directly into formate. The dominant role of formate on alkaline surfaces, for example in glass-induced metal corrosion (GIM) or calcium carbonate degradation, was explored in the Stuttgart research on rare heritage corrosion products. This review discusses these findings together with those from the literature: ocurrences of sodium and potassium formate on glass, calcium formate and calcium acetate-formate phases on calcareous materials, magnesium formate on Sorel cement and dolomitic sandstone, lead formate on metal and pigments, cadmium formate on coated objects, as well as various copper and zinc formates on copper alloys. In the latter cases, formates dominate as glass-induced metal corrosion products. The formation of formates constitutes irreversible damage, degrading the material of heritage objects. Therefore, preventive conservation needs to remove all sources of carbonyl pollutants in order to avoid such corrosion.

This work examines formate salts as potential phase change materials (PCMs) for middle-high temperature (≤250 °C) latent heat thermal energy storage applications. The thermophysical properties of three formate salts were characterized: pure sodium formate and binary blends of sodium/potassium formate and sodium/calcium formate. The stability of formate PCM’s was evaluated by thermal cycling using differential scanning calorimetry where sodium formate and sodium/potassium formate appeared stable over 600 cycles, while sodium/calcium formate exhibited a monotonic decrease in heat of fusion over the test period. A longer test with sodium formate led to gas release and decomposition of the salt. FTIR analysis of the PCM showed degradation of formate to oxalate. T-history experiments with 50-g PCM quantities demonstrated a bulk supercooling of only 2–3 °C for these salts. Thermal conductivity enhancement of over 700% was achieved by embedding aluminum in the solid PCM. Finally, mild carbon steel was immersed in molten sodium formate for up to 2000 h. Sodium formate was found to be non-corrosive, as calculated by mass loss and confirmed by cross-sectional high-resolution microscopy. FTIR analysis of the PCM after 2000 h shows oxidation at the free surface, while the bulk PCM remained unchanged, further indicating a need to protect the formate from atmospheric exposure when used as a PCM.phase change materials; formate salts; latent heat thermal energy storage; thermal cycling; supercooling; thermal conductivity enhancement; corrosion

Xanthan gum solutions have gained increasing interest for their use as environmentally friendly chemicals in the oil industry. Xanthan is compatible with most concentrate brines used for controlling formation damage and fluid loss. Particularly, formate brines reinforce the ordered structure of the biopolymer in solution, gel strength, and the specific gravity of the resulting fluid. In this paper, we studied the effect of thermal aging on the rheological behavior of xanthan solutions as a function of the concentration in potassium formate. Ionic strength below a threshold concentration does not prevent the degradation of the structure of xanthan after being submitted to aging at 165 °C. Aged solutions show an important loss of strength in their mechanical properties, lower pH, and higher content in furfural and hydroxymethylfurfural. Highly concentrated formate brines are necessary to maintain the strength of the rheological properties after exposure to high-temperature environments, This research was funded by the EU-FEDER Program, grant numbers P18-RT-4684 and CTQ-2017-89792-R

Drilling and completion operations in HP/HT environments demand the use of environmentally friendly fluids with suitable properties such as solid-free high-density and pseudoplastic behavior. Xanthan gum solutions in different brines may be an interesting alternative to ensure a suitable thermo-rheological behavior and biodegradability. Nevertheless, xanthan exposed at high temperature experiences thermal degradation that can modify the flow properties over time and limits the ceiling temperature of oilfield applications. To gain insight on this issue, this paper characterizes the flow behavior of low concentration XT solutions in calcium and potassium brines, evaluating the effect that potassium formate exerts on both the flow properties and the resistance to thermal degradation of xanthan solutions as a function of the biopolymer concentration. Xanthan in formate brine retains the pseudoplastic behavior up to 190 °C, however, low concentrate solutions undergo a thermal degradation that decreases the recovery of pseudoplasticity after being exposed to high temperature.

Nowadays, the widespread application of formate fluids in petroleum industries due to its feasibility and its high potential to have more compatibility with the several formation characteristics would become a revolution to control the drilling inefficiencies and provide lower drilling expenditures. Formate fluids have the ability to maintain the property of drilling fluid on the high temperatures and high pressures, reduce the resistance of hydraulic flow, and decrease the rate of corrosion rate for the contact of drilling pipe with drilling fluid. The objective of this comprehensive study is to investigate the visual laboratory measurements of rheological characteristics, consider the profound impact of different types of pollutants on the rheological property, pore pressure transmission (henceforth; PPT) tests to measure formation pressure, and analyze the different concentration of salts for each drilling fluid. The drilling fluids are utilized in this study are silicate muds, glycol muds, sodium and potassium formate muds, and base muds. Consequently, regarding the results of this investigation, it is clarified that NaoH has performed the least impact on the rheological properties of formate fluids and sodium/potassium formate fluids has the minimum formation pressure (PPT tests) which leads to be operated as the best choice in drilling operations. Moreover, the more concentration of salts in the drilling fluid would be a weakening point which indicated that formate fluids would not be appropriate in higher salts concentration.

Recently, the utilization of formic acid (FA) or formate as promising hydrogen carriers through the interconversion between CO2 and HCOOH or HCO3– and HCOO–, respectively, has attracted increasing research interest. In this work, a PdAu bimetallic catalyst supported on phenylenediamine-alkalized reduced graphene oxide (Pd0.50Au0.50/PDA-rGO) was developed for catalyzing bicarbonate hydrogenation under basic conditions as well as FA/formate dehydrogenation under acidic and basic conditions. Without any additives, a very high yield (94%) of potassium formate (PF) can be achieved from the hydrogenation of potassium bicarbonate at 50 °C for 16 h. On the other hand, initial TOFs of 1.63 × 103 and 6.98 × 103 h–1 were accomplished in the dehydrogenations of 6 mol/L PF and 8 mol/L FA, respectively, at 80 °C. This work successfully demonstrates highly efficient CO2 hydrogenation and is the first report of a Pd-based heterogeneous catalyst for the additive-free dehydrogenation of concentrated (>6 mol/L) PF or FA sol...

Small organic molecules such as alcohols and formate salts can be readily transformed into hydrogen and carbon dioxide through electrochemical reforming at low energy cost. In this article methanol and potassium formate are studied for hydrogen production in alkaline anion exchange membrane electroreformers using two anode electrocatalysts, nanoparticle Pd and Rh supported on carbon (5 wt%). Firstly, we report a study of the electrochemical activity of both catalysts in electrochemical test cells at 80 °C. Formate oxidation kinetics are found to be fast on both catalysts. Rh/C shows the best performance for methanol electrooxidation with an onset potential 200 mV lower than Pd/C and a specific activity almost double reaching the value of 2600 A g −1 Rh . The energy cost and conversion efficiency for hydrogen production was determined in complete electrochemical reforming cells at 80 °C using both anode catalysts. The energy costs are low for both substrates ( −1 H2 ) with Pd/C producing hydrogen from potassium formate at an energy cost of 5 KWh kg −1 H2 . Considering both the energy consumption and conversion efficiency (substrate to hydrogen), it is shown that the Rh/C catalyst performs best with methanol as substrate.

Using the methods of design of experiments, filtration properties of the bentonite-free mud system that contains xanthan gum, starch, sodium and potassium formate salts, calcium carbonate and Alevron agent at temperature range of 130–170 °C, differential pressure of 1–5 MPa and initial permeability of ceramic filters of 0.95–7.20 D were studied. Regression models were built for the НТНР filtration loss and permeability of a ceramic filter after mud cake build-up depending on mud additives concentrations, temperature, differential pressure and initial filter permeability, which provide high accuracy of experimental data approximation.

Fabric-based microfluidic fuel cells (MFCs) serve as a novel, cost-efficient alternative to traditional FCs and batteries, since fluids naturally travel across fabric via capillary action, eliminating the need for an external pump and lowering production and operation costs. Building on previous research with Y-shaped paper-based MFCs, fabric-based MFCs mitigate fragility and durability issues caused by long periods of fuel immersion. In this study, we describe a microfluidic fabric-based direct formate fuel cell, with 5 M potassium formate and 30% hydrogen peroxide as the anode fuel and cathode oxidant, respectively. Using a two-strip, stacked design, the optimized parameters include the type of encasement, the barrier, and the fabric type. Surface contact of the fabric and laminate sheet expedited flow and respective chemical reactions. The maximum current (22.83 mA/cm2 ) and power (4.40 mW/cm2 ) densities achieved with a 65% cotton/35% polyester blend material are a respective 8.7% and 32% higher than previous studies with Y-shaped paper-based MFCs. In series configuration, the MFCs generate sufficient energy to power a handheld calculator, a thermometer, and a spectrum of light-emitting diodes.

Direct conversion of aldehydes to ketones is achieved via rhodium-catalyzed vinyl triflate-aldehyde reductive coupling-redox isomerization mediated by potassium formate. This method circumvents premetalated C-nucleophiles and discrete redox manipulations typically required to form ketones from aldehydes. [Image: see text]

Formate fluids are considered as one of the most efficient drilling fluids in petroleum industries, especially in shale to minimize the drilling inefficiencies during the operational performances. The objective of this study is to compare the profound impact of sodium and potassium formate fluids on the rheological properties such as apparent viscosity, plastic viscosity, yield point, fluid loss and shale recovery percentage of different drilling fluid samples. To do this, six samples with different compositions are conducted into the investigation in the laboratory conditions to measure each parameter statistically. According to the results of this experimental evaluation, potassium formate fluid has the lowest shale recovery percent (about 87%), which is indicated the shale preventive property of potassium. The mixture of sodium–potassium has the highest shale recovery (approximately 95%). Addition of Polyanionic Cellulose-Regular (PAC-R) and Polyanionic Cellulose-Ultralow (PAC-UL) has caused to increase the rheological properties of the formate fluids. Consequently, due to the excellent compatibility of formate fluid with reservoir rock, the minimum damaged has occurred to the formation. Keywords: Formate fluids, Shale reservoirs, Shale recovery, Rheological properties, Drilling inefficiencies

Nowadays, the adverse effect of drilling operations on the ecological system pushed the oil industry specialists to achieve optimum drilling performances. Volume and toxicity of discharged materials evaluate surface discharge severity. The ubiquitous utilization of formate fluids has revolutionized the way petroleum industries have conquered the lower drilling inefficiencies. As an objective of this extensive study, the profound impact of different pollutants on the potassium/sodium formate fluids was investigated by experimental tests. The particular sample for mud pollution test was formate fluid with starch biopolymers. To do this, five samples of formate fluids were made, and each one of them was polluted by several contaminants such as cement, lime, acid, alkali and stucco. Consequently, the rheological properties and the pH changes, as well as their effects on the formate fluids were evaluated.

An interesting contribution to solving the climate crisis involves the use of CO2 as a feedstock for monomers to produce sustainable plastics. In the European Horizon 2020 project “OCEAN” a continuous multistep process from CO2 to oxalic acid and derivatives is developed, starting with the electrochemical reduction of CO2 to potassium formate. The subsequent formate-to-oxalate coupling is a reaction that has been studied and commercially used for over 150 years. With the introduction of superbases as catalysts under moisture-free conditions unprecedented improvements were shown for the formate coupling reaction. With isotopic labelling experiments the presence of carbonite as an intermediate was proven during the reaction, and with a unique operando set-up the kinetics were studied. Ultimately, the required reaction temperature could be dropped from 400 to below 200 °C, and the reaction time could be reduced from 10 to 1 min whilst achieving 99 % oxalate yield.

The reaction of carbon dioxide with Et3SiH in the presence of catalytic amounts of [Ru3(CO)12] as a catalytic precursor was achieved to produce silyl formate (Et3SiOCOH) 1s with a TON of 9000. A similar reaction in the presence of KF yielded potassium formate (8s) in a one-pot protocol with high selectivity using water or MeCN as the solvent. In the current report the complete reduction of carbon dioxide to methane was achieved, with the use of a more reactive silane (phenylsilane). A catalytically relevant species was the ruthenium cluster [H4Ru4(CO)12]. This is the second report on the hydrosilylation of carbon dioxide catalyzed by highly active and readily available ruthenium clusters and this is the first report of hydrosilylation of CO2 to methane.

[Poly (N-Vinyl Pyrrollidone)] (PVP) (K30, average Mol. Wt., 40 kDa) stabilized gold nanoparticles with four different size (mean diameter) of 1.4 ± 0.2, 3.8 ± 0.4, 5.5 ± 0.8 and 7.8 ± 1 nm were synthesized using solution based chemical reduction method and used as catalysts for transfer hydrogenation reaction. Transfer hydrogenation of several organic functional groups (>C=O, –CH=O, –NO2, –CH=CH2, –C≡C–H, –C≡N) were studied using potassium formate (HCOOK) as hydrogen source in water. The major focus of this work was on catalytic activity, product selectivity and recycling ability of Au:PVP nanoparticles as a transfer hydrogenation catalyst. The size specific catalytic activity showed that up to 3.8 nm sized gold nanoparticles are highly active catalyst and afterwards its activity diminishes sharply with increasing particle size. Mechanistic insight showed that formate ions are activated on gold surface and produced bound hydride species, which is the active intermediate for this catalytic transformation.

Nowadays, the adverse effect of drilling operation performances on the environment is considered as one of the major concern of petroleum industries which should be taken into the consideration to virtually eliminate the unnecessary expenses of improving the wasting quality before entering to the environment. Volume and toxicity of discharged materials evaluate surface discharge severity. The ubiquitous utilization of formate fluids has revolutionized the way petroleum industries have conquered the lower drilling inefficiencies. We investigated the profound impact of different pollutants on the potassium/sodium formate fluids using experimental tests. The particular sample for mud pollution test was formate fluid with starch biopolymers. To do this, five samples of formate fluids were made, and each of them was polluted by several pollutants such as cement, lime, acid, alkali and stucco. Consequently, rheological properties and the pH changes and their effect on the formate fluids were evaluated.

This paper summarizes the experiences of Total E&P's first use ever of a low-solids cesium formate reservoir drill-in and screen-running fluid. The unique 2.07 SG formate brine-based mud system was used by Total E&P Norge as reservoir drill-in fluid (RDF) and screen running fluid in a Brent high permeability, high pressure gas well No. 4, in the Martin Linge field on the Norwegian Continental shelf. The fourth gas well was the first Martin Linge well completed openhole with 250-micron stand-alone sand screens (SAS). The previous Martin Linge gas wells were drilled and completed with 230-micron expandable sand screens (ESS), using non aqueous based mud (NABM).The low-solids cesium formate fluid was chosen for its known ability to produce easily through sand screens. The final fluid formulation, which consisted of concentrated cesium/potassium formate brine, included xanthan gum, high-temperature modified starch, and calcium carbonate bridging material, successfully underwent a series of qualification testing, including fluid loss control, rheology, formation damage, and production screen testing (PST).The main benefits seen with the formate fluid system compared with the solids laden NABM fluid systems when drilling the 8½-in. reservoir sections were significantly higher rate of penetration (ROP) with lower weight on bit (WOB), better drilling dynamics, significantly lower (0.016 SG) equivalent circulating density (ECD), 35% lower stand pipe pressure (SPP), and 5°C lower bottom hole circulating temperature (BHCT).The drilling fluid properties were easily maintained within specifications. Compared with the NABM, the main benefits were improved rheology, lower solids content, and much thinner, non-elastic filter cake.Improved wellbore stability was experienced for the well No. 4 compared with previous reservoir sections, and there was no indication of poor hole cleaning during drilling, tripping, or during lower completion operations, and no stuck-pipe incidents were experienced. In the previous reservoir sections, a stuck-pipe incident had been experienced in a coal section, requiring a sidetrack to be drilled.The only performance issue with the formate fluid was its higher mechanical friction, which caused a 25% increase in drilling torque compared with the previous sections drilled with NABM.A short cleanup of the well was conducted before the well was suspended. Despite the shorter cleanup time of the well No. 4 compared with the previous wells, the well's stipulated productivity index (PI) was twice as high. The pressure build-up response indicated full connection to the reservoir and no indication of partial plugging, which had been the problem during the cleanup attempts of the previous gas wells.Disregarding the significant increase in fluid cost compared to the previous reservoir sections that were drilled and completed with NABM, well No. 4 was a technical and commercial success based upon drilling and tripping operations, completion operations, and cleanup results.

In this article, the inhibitive properties of polyether diamine and formate salts (mainly sodium formate and potassium formate) were compared through a bentonite inhibition test, a shale hot-rolling dispersion test, and a particle distribution test. The inhibitive mechanism of polyether diamine and formate salts was analyzed via zeta potential measurement, X-ray diffraction analysis, modified montmorillonite water adsorption test, and activity test. The results indicated that, compared with formates, polyether diamine can reduce the interlayer spacing of hydrated clay utmost and lead to clay dehydration with low concentration. Meanwhile, adsorption of polyether diamine onto a clay surface renders the clay surface more hydrophobic, while formate salts prevent clay hydration mainly through lowering the solution activity.

This paper reports on a single alkaline exchange membrane direct formate fuel cell (AEM DFFC) consisting of a carbon-supported palladium catalyst at the anode, a quaternized polysulfone membrane, and a non-precious Fe–Co catalyst at the cathode. It is demonstrated that the AEM DFFC yields a peak power density of 130 mW cm−2 with 5 M potassium formate (HCOOK) at 80 °C. It is further shown that with the addition of KOH to the anolyte, the peak power density rises to as high as 250 mW cm−2 at the same operating temperature. In addition, the AEM DFFC was also tested at 100 mA cm−2 for more than 130 h and no significant degradation in performance is found. The results reported in this work suggest that formate salt (HCOOM, M+ = Na+ or K+) is a potential fuel for alkaline-type direct liquid fuel cells.

Dietary inclusion of salts of organic acids may modulate intestinal microbiota and enhance performance of pigs. Published data on the effects of potassium formate (KF; pH 6.0-8.5) on pig performance are scarce compared with that of potassium diformate (KDF; pH 4.1-4.5). Therefore, the objective was to evaluate the effects of KDF or KF supplementation on performance of 8- to 22-kg pigs. A 35-d growth trial was conducted with 144 PIC pigs (initial BW of 7.9 ± 0.69 kg) with 6 pigs (3 gilts and 3 barrows) per pen and 8 pens per treatment. Pigs were assigned to 3 diets based on corn (Zea mays), wheat (Triticum aestivum), and soybean (Glycine max) meal for each of the prestarter (days 1-14) and starter phases (days 15-35). The basal diet was supplemented with KDF at 1.20% or KF at 1.56% replacing corn starch to create diets 2 and 3, respectively, to provide a constant formate content. The ADG and feed conversion ratio (FCR) were not affected by the addition of KDF or KF during the prestarter phase. Addition of KDF or KF to the basal diet increased (P0.01) ADG and final BW and improved FCR (P0.05) during the starter and the overall 35-d period. The ADFI was not affected by the treatments. Performance of pigs fed diets supplemented with KF and KDF were similar. Diarrhea incidences were observed during week 1 but no differences were observed (P0.05) among treatments in term of the number of antibiotic treatments or fecal consistency scores. Overall, the supplementation of 1.56% KF or 1.20% KF improved performance of weaned pigs.

A formate-based fluid has been successfully used in many high pressure High temperature (HPHT) well operations since they were introduced in field practice. The laboratory research was carried out to determine composition of formate-base drilling fluid. It was formulated using sodium and potassium formate salts, Carboxymethyl Cellulose (CMC), Polyanionic Cellulose (PAC) and other types of polymers. In this research, the compatibility of different polymers with fluids, including potassium/sodium formate salts is being studied. Having said this, however, polymers, when taken to high temperatures, lose their properties. Therefore, this experimental procedure has been done at a temperature of 250°F over a period of 16 h. For doing these tests, six types of potassium/sodium formate fluids were made by different polymers. All samples formulation regarding their type and amount of water used in preparing fluids and the volume of salts used are simultaneously kept constant. On the contrary, the only differences were the types of polymers used in the different formulations. Formulation of formate-base fluids gives the best rheological properties in terms of AV/PV, YP and shale recovery than other fluids.

Conversion of carbon dioxide utilizing protons from water decomposition is likely to provide a sustainable source of fuels and chemicals in the future. We present here a time-evolved infrared reflection absorption spectroscopy (IRAS) and temperature-programmed desorption (TPD) study of the reaction of CO2 + H2O in thin potassium layers. Reaction at temperatures below 200 K results in the hydrogenation of carbon dioxide to potassium formate. Thermal stability of the formate, together with its sequential transformation to oxalate and to carbonate, is monitored and discussed. The data of this model study suggest a dual promoter mechanism of the potassium: the activation of CO2 and the dissociation of water. Reaction at temperatures above 200 K, in contrast, is characterized by the absence of formate and the direct reaction of CO2 to oxalate, due to a drastic reduction of the sticking coefficient of water at higher temperatures.

A novel air dehumidifier using HCOOK solution has experimentally been tested to be feasible and effective. Air flow rate and its relative humidity have big impacts on air dehumidification. The decrease of relative humidity could be over 25% using a strong HCOOK solution to desiccate highly humid air (>75% RH). However, it does not dehumidify efficiently the air with a relative humidity lower than 43% even if strong HCOOK desiccant solution is used. In highly humid spaces, such as bathroom, swimming pool, or kitchen, air dehumidification using a liquid desiccant is very efficient.

The influence of typical *OH radical scavengers as potassium formate and isopropanol on the radiation-induced removal of lead was individually studied. The lead can be completely removed from aqueous solutions containing 1x10(-2) mol/L of formate already at the dose of 2.5 kGy. With increasing concentration of formate (5x10(-5)-1x10(-2) mol/L) increases the amount of Pb(formate)(+) species in the solution before irradiation. The radiation product is metallic lead at low concentration of formate to PbCO(3) at higher concentration of scavenger. In the system with 10% isopropanol dominates the species Pb(2+) and the product of radiation reduction is then metallic lead.

This article describes the development of a high power density Direct Formate Fuel Cell (DFFC) fed with potassium formate (KCOOH). The membrane electrode assembly (MEA) contains no platinum metal. The cathode catalyst is FeCo/C combined with a commercial anion exchange membrane (AEM). To enhance the power output and energy efficiency we have employed a nanostructured Pd/C-CeO2 anode catalyst. The activity for the formate oxidation reaction (FOR) is enhanced when compared to a Pd/C catalyst with the same Pd loading. Fuel cell tests at 60 °C show a peak power density of almost 250 mW cm−2. The discharge energy (14 kJ), faradic efficiency (89%) and energy efficiency (46%) were determined for a single fuel charge (30 mL of 4 M KCOOH and 4 M KOH). Energy analysis demonstrates that removal of the expensive KOH electrolyte is essential for the future development of these devices. To compensate we apply for the first time a polymeric ionomer in the catalyst layer of the anode electrode. A homopolymer is synthesized by the radical polymerization of vinyl benzene chloride followed by amination with 1,4-diazabicyclo[2.2.2]octane (DABCO). The energy delivered, energy efficiency and fuel consumption efficiency of DFFCs fed with 4 M KCOOH are doubled with the use of the ionomer.

Molar conductivities, Λ, of dilute aqueous solutions (c = (≈3·10−4 to ≈5·10−3) mol·dm−3) of sodium formate, potassium formate, and formic acid in the temperature range T = (278.15 to 313.15) K are reported. The experimental data are examined by applying the Quint−Viallard conductivity equations and the Debye−Huckel equations for activity coefficients. Limiting conductivities of formate anion in the investigated temperature range were obtained from the data for salts, and then the dissociation constants for formic acid were estimated. Results were compared with the available literature data.

The activity of a binary catalyst in alcoholic solvents for methanol synthesis from CO/H 2 /CO 2 at low temperature was investigated in a concurrent synthesis course. Experiment results showed that the combination of homogeneous potassium formate catalyst and solid copper–magnesia catalyst enhanced the conversion of CO 2 -containing syngas to methanol at temperature of 423–443 K and pressure of 3–5 MPa. Under a contact time of 100 g h/mol, the maximum conversion of total carbon approached the reaction equilibrium and the selectivity of methanol was 99%. A reaction pathway involving esterification and hydrogenolysis of esters was postulated based on the integrative and separate activity tests, along with the structural characterization of the catalysts. Both potassium formate for the esterification as well as Cu/MgO for the hydrogenolysis were found to be crucial to this homogeneous and heterogeneous synergistically catalytic system. CO and H 2 were involved in the recycling of potassium formate.

KNpO2(OOCH)2 was isolated from neutral Np(V) solutions with a high concentration of potassium formate. The crystal structure of this compound was determined. The structure consists of infinite anionic chains [NpO2(OOCH)2] − . Potassium cations are located between these chains. The Np coordination polyhedron is a hexagonal bipyramid whose equatorial plane is formed by the oxygen atoms of four HCOO− ions. The Np bipyramids in the chains are bound via common equatorial edges. The anionic chains in the structures of KNpO2(OOCH)2 and NH4NpO2(OOCH)2 studied previously have similar composition but different structure.

This paper reports experimental and modeling work for the laboratory scale-up of continuous “trickle-bed” reactors for the electro-reduction of CO2 to potassium formate. Two reactors (A and B) were employed, with particulate tin 3D cathodes of superficial areas, respectively, 45 × 10−4 (2–14 A) and 320 × 10−4 m2 (20–100 A). Experiments in Reactor A using granulated tin cathodes (99.9 wt% Sn) and a feed gas of 100% CO2 showed slightly better performance than that of the tinned-copper mesh cathodes of our previous communications, while giving substantially improved temporal stability (200 vs. 20 min). The seven-fold scaled-up Reactor B used a feed gas of 100% CO2 with the aqueous catholyte and anolyte, respectively [0.5 M KHCO3 + 2 M KCl] and 2 M KOH, at inlet pressure from 350 to 600 kPa(abs) and outlet temperature 295 to 325 K. For a superficial current density of 0.6–3.1 kA m−2 Reactor B achieved corresponding formate current efficiencies of 91–63%, with the same range of reactor voltage as that in Reactor A (2.7–4.3 V), which reflects the success of the scale-up in this work. Up to 1 M formate was obtained in the catholyte product from a single pass in Reactor B, but when the catholyte feed was spiked with 2–3 M potassium formate there was a large drop in current efficiency due to formate cross-over through the Nafion 117 membrane. An extended reactor (cathode) model that used four fitted kinetic parameters and assumed zero formate cross-over was able to mirror the reactor performance with reasonable fidelity over a wide range of conditions (maximum error in formate CE = ±20%), including formate product concentrations up to 1 M.

Our research focuses on the hydrothermal conversion of carbon dioxide into formate with the aid of zerovalent iron. Conventionally, a one-step approach is applied wherein both (i) the production of hydrogen gas, through the oxidation of zerovalent iron in an aqueous medium and (ii) the conversion of carbon dioxide with this hydrogen gas into formate/formic acid, are performed under the same reaction conditions at a temperature of approximately 300 degrees C. Until now, the yields of formate/formic acid mentioned in the literature are, in the absence of a catalytic substance, low (13.5%). Recently, we developed a hydrothermal hydrogen gas production method based on the oxidation of zerovalent iron and performed under mild conditions (temperature of 160 degrees C). This synthesis method produces hydrogen gas with a high purity (>99 mol%) and a significant yield (approximately 80 mol%). These experimental results suggested that the optimal hydrothermal reaction conditions for the production of hydrogen gas and the conversion of carbon dioxide, are strongly different in case of applying zerovalent iron as the reducing agent. Therefore, this paper studies the potential of a two-step approach to enhance the carbon conversion yields. The first step is the production of hydrogen gas via the developed method at 160 degrees C. The second step is the conversion of carbon dioxide at higher temperatures (250-350 degrees C). This study reveals that the solubility of hydrogen gas into the aqueous solution is a key parameter in order to achieve a high amount of carbon conversion. Therefore, a high temperature, the degree of filling and the initial hydrogen gas amount are necessary to successfully perform the carbon dioxide conversion step with high carbon conversion yields. Applying these insights have led to the experimental observation that via a two-step approach the conversion of potassium hydrogen carbonate into potassium formate can be successfully performed with higher carbon conversion yields, up to 77.9 wt%, and a selectivity of at least 81% when applying a reaction temperature of 280 degrees C for 24 hours, a degree of filling with water of 50 vol% and an initial amount of hydrogen gas of 100 mmol.

This paper reports an experimental investigation into the effects of five process variables on the performance of a bench-scale continuous electrochemical reactor used in the reduction of CO2 to potassium formate, and interprets the data in terms of reactor engineering for a (speculative) industrial process for electro-reduction of CO2. The process variables: temperature, catholyte species, catholyte conductivity, cathode specific surface area and cathode thickness were studied, along with CO2 pressure and current density, in a set of factorial and parametric experiments aimed to unravel their main effects and interactions. These variables showed complex interdependent effects on the reactor performance, as measured by the current efficiency and specific energy for generation of formate (HCO 2 − ). The “best” result has a formate current efficiency of 86% at a superficial current density of 1.3 kA m−2, with a product solution of 0.08 m KHCO2 and specific electrochemical energy of 260 kWh per kmole formate. The combined results indicate good prospects for process optimization that could lead to development of an industrial scale reactor.

Aromatic and aliphatic aldehydes are selectively reduced to primary alcohols under mild conditions with potassium formate in the presence of Pd/C catalyst. The high selectivity obtained is attributed due to the presence of the basic potassium bicarbonate generated in situ from the formate salt via the hydrogen transfer process. Molecular hydrogen shows similar activity in the presence of potassium carbonate salts. Ketones did not react under these conditions; therefore, this method is used to separate aldehydes selectively from a mixture of aldehydes and ketones.

A direct formate fuel cell (DFFC) operated with a fuel of alkaline potassium formate has been studied using Pd anode and Ag cathode electrocatalysts in an intermediate temperature range of 80 to 120 °C by means of cyclic voltammetry and single cell measurements. Voltammetric studies clearly show that the kinetics of the formate electrooxidation on Pd in alkaline media is substantially increased with increasing temperature, leading to a high apparent activation energy of around 74.3±6.2 kJ mol−1. Preliminary single cell measurements show that increasing operating temperature and the formate concentration obviously increase the performance. A DFFC operated with 6 mol dm−3 HCOOK and at 120 °C demonstrates a peak power density of around 160 mW cm−2 over a current density range of 250 to 550 mA cm−2 without Ohmic resistance correction. The DFFC is therefore a promising high performance, environmentally benign and low cost fuel cell technology. Keywords: Direct formate fuel cell, Electrooxidation of formate, Electrocatalysis, Alkaline electrolyte, Activation energy

During snowmelt, the infiltration of large amounts of propylene glycol (PG), the major compound of many aircraft deicing fluids, affects redox processes and poses a contamination risk for the groundwater. To gain a better understanding about the degradation of PG and the associated biogeochemical processes under these conditions, we conducted saturated soil column experiments at 4 °C. During two successive PG pulses, we monitored the effect of the runway deicer formate (FO) and changing redox conditions on PG degradation. Furthermore, we applied first-order and simplified Monod kinetics to describe PG and FO transport. The transport of 50 mg l(-1) PG showed three stages of microbial degradation, which were defined as lag phase, aerobic phase, and anaerobic phase. During the second pulse, lag effects diminished due to the already accomplished microbial adaption, and the initial degradation rate of PG increased. Degradation of PG was most efficient during aerobic conditions (aerobic phase), while the subsequent drop of the redox potential down to -300 mV decreased the degradation rate (anaerobic phase). Formate addition decreased the overall degradation of PG by 50 and 15 % during the first and second pulse, illustrating the inhibitory effect of FO on PG degradation. The concurrent increase of Fe(III), organic carbon, and the turbidity in the column effluent after PG and FO application suggest the combined export of Fe adsorbed to fragments of detached biofilm. Neither the first-order nor the simplified Monod model was able to reconstruct the dynamic breakthrough of 50 mg l(-1) PG. The breakthrough of 1,000 mg l(-1), however, was described reasonably well with first-order kinetics. At low temperature and high water saturation, the application of first-order degradation kinetics seems therefore appropriate to describe the transport of high concentrations of PG.

The natural microbial activity in the unsaturated soil is vital for protecting groundwater in areas where high loads of biodegradable contaminants are supplied to the surface, which usually is the case for airports using aircraft de-icing fluids (ADF) in the cold season. Horizontal and vertical distributions of microbial abundance were assessed along the western runway of Oslo Airport (Gardermoen, Norway) to monitor the effect of ADF dispersion with special reference to the component with the highest chemical oxygen demand (COD), propylene glycol (PG). Microbial abundance was evaluated by several biondicators: colony-forming units (CFU) of some physiological groups (aerobic and anaerobic heterotrophs and microscopic fungi), most probable numbers (MPN) of PG degraders, selected catabolic enzymatic activities (fluorescein diacetate (FDA) hydrolase, dehydrogenase, and β-glucosidase). High correlations were found between the enzymatic activities and microbial counts in vertical soil profiles. All microbial abundance indicators showed a steep drop in the first meter of soil depth. The vertical distribution of microbial abundance can be correlated by a decreasing exponential function of depth. The horizontal trend of microbial abundance (evaluated as total aerobic CFU, MPN of PG-degraders, and FDA hydrolase activity) assessed in the surface soil at an increasing distance from the runway is correlated negatively with the PG and COD loads, suggesting the relevance of other chemicals in the modulation of microbial growth. The possible role of potassium formate, component of runway de-icers, has been tested in the laboratory by using mixed cultures of Pseudomonas spp., obtained by enrichment with a selective PG medium from soil samples taken at the most contaminated area near the runway. The inhibitory effect of formate on the growth of PG degraders is proven by the reduction of biomass yield on PG in the presence of formate.

peer-reviewed Doping a 1 wt.% Pd/C catalyst with alkali metal carbonates has a very significant promotional effect on its activity in hydrogen production from the decomposition of formic acid vapour (2 vol.%, 1 bar), potassium and caesium carbonates giving the largest effects. The K carbonate species present on the fresh catalysts react with formic acid to form formate ions, these being dissolved in a formic acid/water solution condensed in the pores of the support. The steady-state activities of the samples containing formate ions were 1-2 orders of magnitude greater than those of the unpromoted Pd/C and CO content was lower than 30 ppm. The activation energies for the reaction increased with doping from 66 to 88-99 kJ mo1-1, relatively independent of the cation of the dopant. Similar but lesser effects were found with unsupported Pd nanocrystals doped with K carbonate. The rate-determining step for the promoted samples appears to be the decomposition of formate ions on the Pd surface. (C) 2014 Elsevier B.V. All rights reserved. ACCEPTED peer-reviewed

Phase equilibria in the sodium formate—potassium formate—water system below 0°C along the NaHCOO : KHCOO = 5 : 1, 4 : 1, 3 : 1, 2 : 1, and 1 : 1 w/w sections have been investigated, the onset temperatures of ice crystallization from the aqueous solutions have been determined, and ice melting polytherms have been constructed for each section. The ice-melting capacity of the formate mixtures at —5 to —10°C has been calculated.

The properties of aqueous fluid of potassium formate were studied theoretically and experimentally in order to find an improved secondary refrigerant for indirect refrigeration systems. The most important advantages compared to the traditional aqueous solutions of alcohols and glycoles are good thermodynamic properties, low toxicity and non-flammability. A remarkable benefit is a reduced change of a laminar flow. Volumetric heat is lower, which brings about a higher rate of mass flow, if the temperature change of the fluid is maintained constant. However, because of the clearly lower values of viscosity, the pumping power demand is at same level. Good thermal conductivity promotes good heat transfer.

As a prelude to the study of surface formate species with inelastic neutron scattering (INS) we have used INS to obtain the vibrational spectra of the model compounds potassium formate (KHCOO), anhydrous copper formate [Cu(HCOO) 2 ], hydrated copper formate [Cu(HCOO) 2 ·4H 2 O] and formic acid. These data are compared to IR and Raman spectra. In INS we observe vibrational modes for both potassium and copper formate not previously reported in IR and Raman studies, including a librational mode of copper formate at ca. 600 cm -1 . The relative intensities of the formate bands are very different from those observed in IR and Raman spectra and vary considerably between the three compounds studied. The two most intense formate fundamental vibrations in the INS spectrum are the C–H out-of-plane bend and the C–H in-plane bend, both of which have low intensity in IR and Raman spectra. In the INS spectrum the relative intensities of these modes vary considerably between the compounds studied indicating a structural dependency of the INS intensities.

A new synthetic method of producing α-MnO2 was investigated. Calcination of a mixture of either manganese carbonate and potassium formate and/or manganese carbonate and potassium butoxide yielded α-MnO2 with potassium selective adsorption properties. The temperatures and other conditions to synthesize the materials were determined in advance by DTA-TG and XRD analyses. The product which was synthesized from manganese carbonate and potassium butoxide showed better crystallinity of α-MnO2 and higher adsorption selectivity for potassium ion than that from manganese carbonate and potassium formate. It will be an applicable adsorbent in potassium separation for industrial usage.

The formation and decomposition of formate species on the clean and on potassium‐modified Ru(001) surfaces have been investigated with time‐resolved vibrational spectroscopy and thermal desorption mass spectrometry (TDMS). Utilizing Fourier transform‐infrared reflection absorption spectroscopy (FT‐IRAS) we have characterized chemisorbed formate produced by the decomposition of formic acid on clean Ru(001), Ru(001)–(√3×√3)R30° K and on a K‐multilayer adsorbed on Ru(001). The vibrational spectra show that formate is adsorbed on both clean Ru(001) and Ru(001)–(√3×√3)R30° K with C2v symmetry indicative of a bridged or bidentate species. There are, however, characteristic differences in the vibrational spectra, which indicate that for the Ru(001)–(√3×√3)R30° K surface the formate is directly bound to potassium. The vibrational spectrum of the latter species is found to be in good agreement with that of bulk potassium formate adsorbed on Ru(001).Based on the agreement with literature data for bulk formate, we p...

Potassium formate was extracted from airport storm water runoff by headspace solid-phase microextraction (HS-SPME) and analyzed by GC-MS. Formate was transformed to formic acid by adding phosphoric acid. Subsequently, formic acid was derivatized to methyl formate by adding methanol. Using sodium [(2)H]formate (formate-d) as an internal standard, the relative standard deviation of the peak area ratio of formate (m/z 60) and formate-d (m/z 61) was 0.6% at a concentration of 208.5 mg L(-1). Calibration was linear in the range of 0.5-208.5 mg L(-1). The detection limit calculated considering the blank value was 0.176 mg L(-1). The mean concentration of potassium formate in airport storm water runoff collected after surface de-icing operations was 86.9 mg L(-1) (n=11) with concentrations ranging from 15.1 mg L(-1) to 228.6 mg L(-1).

Herein we report the conversion of aldehyde-containing potassium and tetrabutylammonium organotrifluoroborates to the corresponding amines through reductive amination protocols. Potassium formate facilitated by catalytic palladium acetate, sodium triacetoxyborohydride, and pyridine borane have all served as effective hydride donors, reducing the initially formed imines or iminium ions to provide the corresponding amines.

In-situ Fourier Transform-Infrared Reflection Absorption Spectroscopy (FT-IRAS) FT-IRAS has been utilized to characterize a reaction intermediate observed during CO hydrogenation at high pressures over potassium promoted Ru(001). This intermediate is identified as a potassium formate by vibradonal spectra obtained under reaction conditions. Vibrational spectra of formate obtained from the decomposition of formic acid on clean Ru(001) and K-Ru(001) allow us to further characterize this intermediate with respect to its symmetry, configuration and K-OOCH bond formation. The presence of potassium thermally stabilizes the formate on the surface in comparison to clean Ru(001). The observation of such a formate intermediate is an important step in elucidating the role of alkali promoters for the synthesis of oxygenates in the CO hydrogenation in catalysis where they have been proposed to be active intermediates.

This paper presents results from a lysimeter experiment on the fate of potassium formate, an alternative deicing agent. The experiment was performed through the winter and spring to identify any thermal sensitivity in the transport and biodegradation of formate in the lysimeter. Ninety-eight percent of the total quantity of formate applied was degraded while percolating through the 1.7-m-thick unsaturated sand layer within the lysimeter. Concomitantly, the bicarbonate concentration of the percolating water increased. The low concentrations of nitrogen (0.02 mg L(-1)) and phosphorous (

We present here an aquifer scale study on the fate of potassium formate, an alternative, weakly corrosive deicing agent in soil and subsurfaces. Potassium formate was used to deice a stretch of a highway in Finland. The fate of the formate was examined by monitoring the groundwater chemistry in the underlying aquifer of which a conceptual model was constructed. In addition, we determined aerobic and anaerobic biodegradation rates of formate at low temperatures (-2 to +6 degrees C) in soil microcosms. Our results show that the formate did not enter the saturated zone through the thin vadose zone; thus, no undesirable changes in the groundwater chemistry were observed. Furthermore, the conceptual model explained the distribution of chloride in the aquifer used in deicing for the past 30 years. We recorded mineralization potential up to 97% and up to 17% within 24 h under aerobic and anaerobic conditions, respectively, in the soil and subsurface samples obtained from the site. This demonstrates that biodegradation in the topsoil layers was responsible for the removal of the formate. We conclude that the use of potassium formate can potentially help diminish the negative impacts of road winter deicing on groundwater without jeopardizing traffic safety.

Aromatic and aliphatic aldehydes are selectively reduced to primary alcohols under mild conditions with potassium formate in the presence of Pd/C catalyst. The high selectivity obtained is attributed due to the presence of the basic potassium bicarbonate generated in situ from the formate salt via the hydrogen transfer process. Molecular hydrogen shows similar activity in the presence of potassium carbonate salts. Ketones did not react under these conditions; therefore, this method is used to separate aldehydes selectively from a mixture of aldehydes and ketones.

In plants, environmental adversity often leads to the formation of reactive oxygen species (ROS) because of excess light energy. We found that incubation of rice leaves under high light intensity together with CO2-depleted air seriously damaged photosynthesis; however, the application of potassium formate (2 mM) before the photoinhibitory treatment protected the photosynthesis of the plant from photoinhibition. Further analysis revealed that formate protects PSII, RuBisCO, and FBPase from photoinhibition. Formate is thought to be involved in endogenous radical scavenging and/or in the supply of CO2, derived from the formate, thereby reducing oxidative damage to the photosystems under photoinhibitory conditions.