High Pressure Reaction Vessel Research Articles

Experimental study on the effect of hydrate saturation in reservoir on microwave heating hydrate decomposition gas production

Microwave heating technology is an effective method to promote the decomposition of hydrates, with hydrate saturation being an important parameter influencing this process. This study has synthesized natural gas hydrates with different saturations within a high-pressure reaction vessel to conduct experiments on the decomposition of natural gas hydrates by microwave heating. The reservoir temperature, gas production dynamics, and energy utilization rate are investigated for hydrate saturations of 30.26 %, 35.63 %, and 39.61 %, respectively. The results indicate that increasing hydrate saturation enhances the microwave penetration depth, which in turn elevates the reservoir temperature and accelerates hydrate decomposition. When the hydrate saturation increases from 30.26 % to 39.61 %, the gas production time decreases. Simultaneously, both the volume and rate of gas production increase, accompanied by enhanced energy utilization rate. When the hydrate saturation is 39.61 %, the experiment achieves an average gas production rate of 1.17 L/min, a total volume of 19.73 L, and an energy utilization rate of 2.716. The research results can promote the application of microwave heating technology in the development of hydrates.

The Feasibility Study of In Situ Conversion of Oil Shale Based on Calcium-Oxide-Based Composite Materia Hydration Exothermic Reaction

Oil shale, as a vast potential resource, is considered an important alternative energy source, and its effective development and economic utilization are of significant importance in alleviating the contradiction between energy supply and demand. Presently, the in situ conversion technology for oil shale has gained significant global attention, with numerous extraction methods undergoing active research and development. One of these methods is the in situ conversion of oil shale based on the hydration reaction of calcium-oxide-based composite material (CaO-CM). This approach harnesses the heat produced by the reaction between CaO-CM and water as a heat source for the pyrolysis of oil shale. This paper conducted experiments to assess the feasibility of temperature associated with this method. The feasibility study mainly includes two aspects: First, it is necessary to investigate whether the temperature generated by the hydration reaction of CaO-CM can meet the temperature requirements for the pyrolysis of oil shale. Through pyrolysis experiments of Xinjiang oil shale, the minimum temperature required for oil shale pyrolysis was determined to be 330 °C. High-temperature and high-pressure reaction vessels were employed to explore the temperature generated by the hydration reaction of CaO-CM. The results show that with the increase in environment pressure, environment temperature, and reaction mass, the maximum temperature generated by the hydration reaction of CaO-CM also increases (reach 455.5 °C), meeting the temperature requirements for the pyrolysis of oil shale. Second, the study evaluates whether the hydration reaction of CaO-CM can induce pyrolysis hydrocarbons of the oil shale. Through the pyrolysis experiments of oil shale based on the hydration reaction of CaO-CM, the changes in the content of pyrolysis hydrocarbons (S2) in oil shale before and after pyrolysis are measured. The results show that under 10 MPa pressure, the content of pyrolysis hydrocarbons in the oil shale decreased from 40.96 mg/g to 0.08 mg/g after pyrolysis. This confirms the feasibility of the temperature conditions for the in situ conversion of oil shale based on the hydration reaction of CaO-CM.

Mechanism of pore expansion and fracturing effect of high-temperature ScCO2 on shale

To elucidate the mechanisms underlying the alteration of shale pore fractures by high-temperature supercritical carbon dioxide (ScCO2), this study employed medium–low maturity shale samples from a specific region as research subjects. The samples were subjected to high-temperature ScCO2 reactions in a corrosion-resistant high-pressure reaction vessel at various temperatures. A suite of analytical techniques, including X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), ImageJ image processing software, N2 and CO2 adsorption experiments, thermal gravimetric-differential thermal analysis (TG-DTG) of CO2 pyrolyzed shale oil, and gas chromatography (GC) analysis, were utilized to investigate and analyze the microstructural changes in the shale samples before and after ScCO2 treatment.The results reveal a subtle increase in the content of clay minerals and quartz, accompanied by a decrease in the content of carbonates, potassium feldspar, and calcite. These mineral transformations, encompassing dissolution, precipitation, and swelling processes, exert a substantial impact on the shale surface microstructure and modify the internal pore structure. Consequently, a shift in the mechanical properties of the rock is observed, which bears significance for its fracturing behavior.The experimental results reveal a steady growth in fracture area following high-temperature ScCO2 treatment. Importantly, the extent of initial fracture development plays a crucial role in determining the efficacy of hydraulic fracturing, indicating a positive correlation. Moreover, the connection between fracture area and temperature exhibits a clear trend marked by an initial rise, a subsequent decline, and finally, a resurgence. In particular, the thermal fracturing threshold temperature for the shale samples was found to be around 400 °C.From the analysis, it can be inferred that ScCO2, when subjected to an elevated temperature range of 100-200℃, exhibits mutual interactions with the shale. This results in effective extraction of organic matter and dissolution of mineral constituents within the shale matrix. Consequently, this treatment process leads to a significant reduction in the number of micropores (pore sizes less than 2 nm), while the quantities of mesopores (pore sizes between 2 and 50 nm) and macropores (pore sizes greater than 50 nm) display a noticeable increase.Upon exposure to a temperature range of 200-300℃, a remarkable affinity of the shale for CO2 adsorption becomes evident. The adsorption process contributes to the expansion of the matrix material and deposition of minerals, effectively filling the pore spaces. As a result, the contraction of mesopores and macropores is mitigated, with the predominant change being an increase in the number of micropores.When temperatures reach 300-500℃, the intensified heat initiates thermal decomposition of the kerogen, culminating in the release of pore spaces. This phenomenon prompts an increase in the number of micropores and mesopores, thereby augmenting the pore volume and specific surface area of the shale.

Low-temperature open-air synthesis of PVP-coated NaYF4:Yb,Er,Mn upconversion nanoparticles with strong red emission.

Cubic (α-phase) NaYF4:Yb,Er upconversion nanoparticles (UCNPs) are uniquely suited to biophotonics and biosensing applications due to their near-infrared excitation and visible red emission (λex approx. 660 nm), enabling detection via thick overlying tissue with no bio-autofluorescence. However, UCNP synthesis typically requires high temperatures in combination with either high pressure reaction vessels or an inert atmosphere. Here, we report synthesis of α-phase NaYF4:Yb,Er,Mn UCNPs via the considerably more convenient PVP40-mediated route; a strategy that requires modest temperatures and relatively short reaction time (160°C, 2 h) in open air, with Mn2+ co-doping serving to greatly enhance red emission. The optimal Mn2+ co-doping level was found to be 35 mol %, which decreased the average maximum UCNP Feret diameter from 42 ± 11 to 36 ± 15 nm; reduced the crystal lattice parameter, a, from 5.52 to 5.45 Å; and greatly enhanced UCNP red/green emission ratio in EtOH by a factor of 5.6. The PVP40 coating enabled dispersal in water and organic solvents and can be exploited for further surface modification (e.g. silica shell formation). We anticipate that this straightforward UCNP synthesis method for producing strongly red-emitting UCNPs will be particularly beneficial for deep tissue biophotonics and biosensing applications.

Construction of Position-Controllable Graphene Bubbles in Liquid Nitrogen with Assistance of Low-Power Laser

Graphene bubbles (GBs) are of significant interest owing to their distinguished electrical, optical, and magnetic properties. GBs can also serve as high-pressure reaction vessels to numerous chemical reactions. However, previous strategies to produce GBs are relatively elaborate and random. Therefore, their potential applications are severely restricted. Here, a facile and effective protocol is proposed to construct position-controllable GBs in liquid nitrogen (LN) with the assistance of laser and graphene wrinkles. Specifically, a film of graphene mounted on a SiO2 substrate (G@SiO2) is subjected to irradiation by a low-power laser in LN and then many GBs emerge from the surface of G@SiO2. Most impressively, the domain where GBs arise is the position of the laser beam spot. Hence, we demonstrated that the high collimation of laser facilitates the position definition of GBs. The microscopic results indicate that some GBs split into three parts when they were subjected to irradiation by an electron. Meanwhile, some GBs degenerate into pores with a diameter of 500 nm when they are exposed to air. To grasp the properties of GBs in depth, the molecular dynamics (MD) simulations are performed, and the corresponding results indicate that temperature has very little impact on the GBs' shape. A phase transition process of the substance inside GBs is also revealed. Moreover, a two-dimensional (2D) solid nitrogen is discovered by MD simulations. The simplicity of our protocol paves the way to engineer high-pressure microreaction vessels and fabricate porous graphene membranes.

Highly Stable and Rapid Switching Electrochromic Thin Films Based on Metal-Organic Frameworks with Redox-Active Triphenylamine Ligands.

Metal-organic frameworks (MOFs), known for their tailorable porous structures and large specific surface areas, are appealing for electrochromic applications as their abundant pores may greatly benefit the charge transport required for electrochromic switching. Herein, for the first time, a simple, scalable, and cost-effective electrochemical deposition method for fabrication of high-performance and durable MOFs-based electrochromic films with redox-active ligands was developed. The fabricated film can achieve rapid switching speed (both coloration and bleaching time <5 s) because the inherent cavities of the MOFs greatly facilitate ion insertion and extraction. In addition, the film constructed with optimized parameters shows a high optical contrast of 65%@700 nm and can be stably switched for 1000 cycles with <5% contrast attenuation, which is by far the best cycling performance for MOFs-based electrochromic materials ever reported. Furthermore, our method enables the scalable preparation of large-area MOFs-based electrochromic thin films without using large high-pressure reaction vessels, and the as-prepared film in this work could be switched well between colored and bleached states. This new method, therefore, opens up a new avenue to broaden the use of MOFs-based thin films for electrochromic applications.

Cambrex opens new labs in Karlskoga

Cambrex has completed construction of a 600 m2 facility at its Karlskoga, Sweden, site that incorporates process technology, quality control, and analytical development laboratories. The process technology section will accommodate R&D and production teams working together on scale-up demonstrations for highly potent molecules. The laboratory also includes high-pressure reaction vessels and crystallization equipment.

A Simple and Convenient Synthesis of Unlabeled and 13C-Labeled 3-(3-Hydroxyphenyl)-3-Hydroxypropionic Acid and Its Quantification in Human Urine Samples.

An improved method to synthesize the highly abundant and biomedically important urinary metabolite 3-(3-hydroxyphenyl)-3-hydroxypropionic acid (HPHPA) is reported. The modified protocol is based on an indium-mediated sonochemical Reformatsky reaction. The synthesis is a simple two-step route as opposed to a complex four-step route previously reported in the literature that requires specialized equipment, flammable materials, and high-pressure reaction vessels. The described procedure also provides an expedient route to prepare a 13C isotopically labeled HPHPA that can be used as a standard for quantitative LC-MS analysis. This report also illustrates how the synthesized metabolite standard was used to detect and accurately quantify its presence in human urine samples using both NMR and LC-MS techniques.

Monitoring the progress of the acetylation reactions of 4-aminophenol and 2-aminophenol in acetonitrile modified supercritical fluid carbon dioxide and pure acetonitrile using on-line supercritical fluid chromatography and on-line liquid chromatography

The progress of acetylation reactions of 4-aminophenol and 2-aminophenol in acetonitrile modified SF-CO2 or pure acetonitrile were monitored using on-line SFC or a non-conventional type of on-line normal phase liquid chromatography. For each reaction solvent, acetylations using acetic anhydride were performed at 323K, 333K and 343K. Reactions in SF-CO2 were monitored using a single valve recirculation interface that coupled a high pressure reaction vessel operated at 17.5MPa. Reactions in acetonitrile were monitored using a two valve interface to couple a reaction vessel operated under 0.1MPa nitrogen atmosphere. For both aminophenol isomers, acetylation proceeded more rapidly in acetonitrile modified SF-CO2 compared with acetonitrile. Also for each reaction solvent, the rate of acetylation of 4-aminophenol exceeded that of 2-aminophenol. On-line chromatographic analysis rapidly established that: (i) 4-aminophenol produced a diacetylated product only in acetonitrile modified SF-CO2, whereas (ii) 2-aminophenol produced a diacetylated product only in acetonitrile.

Supercritical water pyrolysis of sewage sludge

Municipal sewage sludge (SS) from wastewater treatment plant containing high water content (>85wt.%), lead to the difficulty of co-combustion with MSW or coal due to the high cost of drying. This study explores an alternative method by supercritical water (SCW) pyrolysis of sewage sludge (SS) in a high pressure reaction vessel. The effects of temperature and moisture content of SS on yield and composition of the products (bio-oil, bio char and non-condensable gas) were studied. A temperature of 385°C and moisture content of 85wt.% were found to be the optimum conditions for the maximum bio-oil production of 37.23wt.%, with a higher heating value of 31.08MJ/kg. In the optimum condition, the yields of aliphatic hydrocarbon and phenols were about 29.23wt.% and 12.51wt.%, respectively. The physical and chemical properties of bio-char were analyzed by using XRF and BET. Results of GC analyses of NCG showed that it has the maximum HHV of 13.39MJ/m3 at 445°C and moisture content of 85wt.%. The reaction path from SS to bio-oil through SCW pyrolysis was given. Moreover, carbon balance was calculated for the optimal condition, and finding out that 64.27wt.% of the carbon content was transferred from SS to bio-oil. Finally, this work demonstrates that the SCW pyrolysis is a promising disposal method for SS.

A comparison of a simplified cupric oxide oxidation HPLC method with the traditional GC‐MS method for characterization of lignin phenolics in environmental samples

AbstractA simplified method to characterize the lignin phenolic composition of environmental samples using alkaline CuO oxidation, solid‐phase extraction (SPE), and high performance liquid chromatography (HPLC) is described. Samples were oxidatively hydrolyzed in inexpensive, commercially available Teflon vials rather than expensive high‐pressure Teflon‐lined reaction vessels. We used milder hydrolysis conditions than conventionally used to avoid “over‐oxidation.” The monomeric lignin phenols released were extracted by SPE rather than liquid–liquid extraction and analyzed by reverse phase HPLC with ultraviolet (UV)‐visible diode array detection. Recoveries were 88% ± 6% for the overall procedure. The lignin phenolic composition of a wide variety of samples including plant tissues, isolated humic substances, soils, sediments, and freshwater dissolved organic matter are presented and compared with the conventional high pressure reaction vessel gas chromatography–mass spectrometry (GC‐MS) method. The agreement was generally good; the mean difference of nine diverse samples for a total of eight oxidation products was 4.5% with a relative standard deviation (RSD) of 23%. The advantages of this simplified method include no lengthy clean‐up and derivatization steps, no specialized reaction equipment, increased sample throughput, amenability to compound‐specific isotope analyses, and lower cost.

High-T, High-P Hydrothermal Synthesis of Uranium Silicates and Germanates

Most uranium minerals can be classified as oxidized species in which U is fully oxidized to U(VI), and reduced species, in which U occurs primarily as U(IV). Uranyl silicates are an important group of uranium(VI) minerals in the altered zones of many uranium deposits [1]. Uranyl silicates have also received attention because they form when spent nuclear fuel interacts with water containing silicon under oxidizing conditions. One naturally occurring uranium(IV) silicate exists, namely coffinite (USiO4), which is the most important ore mineral for uranium after uraninite. Numerous synthetic uranium(VI) silicates and germanates containing organic amines or alkali metals as countercations have also been reported [2]. In contrast to the uranium(VI) compounds, the chemistry of materials containing uranium(V) is considerably less developed owing to the tendency of U(V) to either oxidize to U(VI) or disproportionate to U(IV) and U(VI). We have synthesized a pentavalent-uranium silicate and a germanate by a high-temperature, high-pressure hydrothermal method in gold ampoules contained in a high-pressure reaction vessel at ca. 600 °C and 170 MPa [3a,b]. Following the synthesis of the U(V) compounds, a number of mixed-valence uranium silicates and germanates have been synthesized, for example, a mixed-valence uranium(IV,V) silicate, Cs2K(UO)2Si4O12 [3c], a uranium(IV,VI) germanate, Cs8U(UO2)3(Ge3O9)3·3H2O [3d], uranium(V,VI) silicates and germanates, A3(U2O4)Ge2O7 (A = Rb, Cs) and [Na9F2][(UO2)3(Si2O7)2] [3e,f], and a uranium(IV,V,VI) silicate, Na7UO2(UO)2(UO2)2Si4O16 [3g] in which three oxidation states of uranium co-exist in one compound. In addition, tetravalent-uranium compounds, Cs2USi6O15 and Cs4UGe8O20 [3h,i], were also synthesized. All members in the family of uranium silicates and germanates with the oxidation states of uranium from +4 to +6 have been observed. In this presentation the high-temperature, high-pressure hydrothermal synthesis, crystal structures, and XPS spectroscopy of these interesting compounds will be reported.

Preparation and application of coconut shell activated carbon immobilized palladium complexes

Coconut shell activated carbon (CSAC) granules were used as carriers to immobilize palladium complexes. Boehm titration showed that the hydroxyl content of the carbon surface reached 0.376 mmol g−1 after 20% HNO3 treatment. Ethylenediamine, benzyl malononitrile and propyl malononitrile were successfully grafted onto the oxidized CSAC. The bidentate nitrogen ligands complexed Pd2+ samples were characterized by FT-IR, XPS, ICP and N2 adsorption–desorption. In oxidative carbonylation of phenol, three bidentate ligand grafted catalysts were evaluated in a high pressure reaction vessel. The results showed that the ethylenediamine grafted catalyst had a phenol conversion of 12.06% and a diphenyl carbonate (DPC) selectivity of 91.03%. In comparison, the benzyl malononitrile grafted catalyst displayed a phenol conversion of 12.00% and a DPC selectivity of 90.65%. The propyl malononitrile grafted catalyst displayed a phenol conversion of 6.22% and a DPC selectivity of 81.02%. Additionally, the ethylenediamine and the benzyl malononitrile grafted catalysts were also investigated in a continuous packed-bed reactor. The results showed that the phenol conversion and the DPC selectivity were comparative to those obtained in a high pressure reaction vessel.

Laboratory Batch Experiments and Geochemical Modelling of Water-rock-super Critical CO2 Reactions in Gulf of Mexico Miocene Rocks: Implications for Future CCS Projects

Abstract Storage of CO 2 in deep saline formations in a super critical liquid state has been proposed as a way to mitigate the effects of increased atmospheric CO 2 levels. The ultimate fate of the CO 2 after injection requires an understanding of mineral dissolution/precipitation reactions occurring between the target formation minerals and the existing formation brines at formation temperatures and pressures in the presence of supercritical CO2. In this experiment core material taken from a Miocene age Gulf of Mexico core from a depth of 2806 m was reacted with synthetic brine at varied but high temperatures and pressures in the presence of super critical CO2. XRD and SEM analyses were conducted before and after reaction to identify dissolution of existing minerals and precipitation of authigenic mineral phases. Periodic geochemical analysis of the reaction fluid was used to quantify changes in the elemental composition of the reaction fluid which helps identify potential mineral dissolution/precipitation reactions. Reaction brine (140 ml) was loaded into a high pressure reaction vessel with 8 g of core sample. Experimental temperature was set to 70, 100 or 130 °C; pressure was set to 200 or 300 bar, and solution chemistry was changed from de-ionized (DI) water to a 1.88 M NaCl solution. After the introduction of CO 2 the Ca and alkalinity concentrations showed the largest increases, Ca concentrations increased ∼1000 ppm, suggesting carbonate dissolution was the dominant geochemical reaction. Final equilibrium Ca concentrations increased with decreasing reaction temperature because of greater CO 2 solubility. In addition, the reactions with the NaCl brine produced higher equilibrium Ca concentrations than the DI water experiment, likely due to the decrease in ion activity with higher ionic strength solutions. Pressure change from 200 to 300 bar did not significantly alter reaction rates. Unlike Ca, silicate dissolution reactions appear to be positively correlated with reaction temperature. Silicate dissolution rates are 2 orders of magnitude slower than carbonate dissolution rates. In this study, PHREEQC was used to simulate brine-rock-CO 2 interactions in batch experiments under high pressure and high temperature. Generally, the geochemical models reproduced concentration of Ca, Mg, K and Si seen in the water rock experiments suggesting that carbonate and K-feldspar dissolution are the dominant geochemical reactions. In addition, geochemical models show that dawsonite precipitates in higher salinity (higher Na+ concentration) experiments.

Natural Gas Hydrate Dissociation by Presence of Ethylene Glycol

In the current article, natural gas hydrate dissociation experiments have been conducted on a self-designed apparatus, which consists of a high-pressure reaction vessel, visualization system, chiller with circulation system, gas supplier, and data acquisition system. Gas hydrate was synthesized in the reaction vessel, and then the dissociation experiment was performed by addition of ethylene glycol (EG) as an inhibitor. The results show that dissociation rate depends on the concentration and flow rate of EG because it reduced the dissociation heat, and less energy is required for dissociation at higher ethylene concentration. Thus, EG concentration and flow rate can be optimized in practical utilization.

Microwave heating in high pressure reaction vessels

We report the use of microwave -hydrothermal processing to synthesize various ceramic powders. Microwave-hydrothermal processing is compared with conventional hydrothermal processing in the crystallisation of MoO2. The presence of microwave field leads to accelerated kinetics of crystallization of the finely divided molybdenum dioxide particles. Existing microwave heated pressure vessels for chemical synthesis cannot be used above 250 MPa and 270°C because they contain parts made of polymeric materials. The objective of this work is to associate a microwave source to a high pressure vessel in a way such that it might be used to carry out reactions in aqueous media at pressures around 100 MPa and temperatures above the critical point of water.

Remediation of Metal-Bearing Aqueous Waste Streams via Direct Carbonation

Direct carbonation using liquid carbon dioxide can be used for the remediation of aqueous streams or slurries while sequestering carbon dioxide in the form of metal carbonates. Carbonic acid (pH = 2.9), which formed when the aqueous phase was contacted with excess liquid carbon dioxide at ambient temperature (295 K) and elevated pressure (6.89 MPa), reacted with the metal cations to form metal carbonates in the agitated vessel. These metal carbonates precipitated out of solution as the pH returned to neutral when the system was depressurized. Electric arc furnace K061 dust, red mud from the Bayer process of alumina manufacture, and metal-bearing wastewater streams were amenable to this treatment. The treatment of a K061-dust slurry from a steel plant was semi-continuous. The dust particles were retained in the high-pressure reaction vessel as fresh water was continuously injected and high-pressure, metal carbonate-bearing water was withdrawn. The water residence time in the reactor was 12 min. About 30% o...

An automated high pressure reaction vessel for routine preparation of short-lived radiopharmaceuticals

A remote, automated high-pressure/temperature system for preparation of radiopharmaceuticals is described. The system was routinely employed in our laboratories in the production of multimillicurie amounts of 11C labeled d,l-amino acids in more than 90 production runs, with typical final d,l-product activities of 240–400 mCi. The high pressure system, however, is not restricted only to the production of 11C labeled amino acids, but for application in any synthetic procedure requiring high pressure (∼300 psia) and temperature (>300°C).