《京都议定书》要减排哪些温室气体

悄然兴起的亚临界萃取中的液化石油气、 丙烷、二甲醚、四氟乙烷、六氟化硫萃取剂令业内人士担忧        http://www.sfst.net.cn 编辑部稿

    在防火防爆类的工厂设计规范中明文规定，凡是闪点＜28℃的易燃液体，凡是爆炸下限＜10%的可燃性气体均应列为甲级(最高级)防火防爆等级，而目前在国內悄然兴起的亚临界萃取中，个別企业却选用闪点及爆炸下限均远远低于这两个指标的 LPG(液化石油气)、DME(二甲醚)、丙烷、R600a(高纯度异丁烷)等易燃易爆危险品，用作亚临界萃取的主溶媒，其用于固体物料的间隙式萃取，由于要频繁的装卸物料需不断的打开 、关闭萃取槽顶盖，易燃易爆气体的洩漏在所难免，同时在频繁打开 、关闭萃取槽顶盖的过程中，产生静电火花的概率也较高，在规模化的工业生产中使用这些气体，危险性是显而易见的。 在连续密闭的大规模化的生产 LPG(液化石油气)、DME(二甲醚)、丙烷、R600a(高纯度异丁烷)等 的易燃易爆气体时，相对而言由于是在连续全密闭的条件下进行操作则较为安全。
      而R134a(1，1，1，2-四氟乙烷) 的亚临界萃取，由于R134a是温室气体，它能阻挡红外辐射能返回天空，对全球气候变暖直接影响较大，其全球温室效应潜能值GWP高达1300。因此早在1997年12月11日联合国气候变化框架公约缔约国第三次会议通过的《京都议定书》中，R134a是明确规定要控制与削减排放量的六 类温室气体中的一种，其排放(散发)、使用、生产也将受到严格的国际管制。再者工业级R134a的单价高于食品级二氧化碳50倍以上,作为萃取剂使用,生产成本偏高，这也是工业化生产中企业难以接受的。
    更有甚者，全氟化碳PFC(如CF₄和C₂F₆)和六氟化硫SF₆也是人为产生的气体，它们大气寿命非常长，对红外辐射有强吸收。所以这些化合物虽然排放量较小，但对未来气候的影响很大。CF₄在大气中可以至少存留50000年。它有自然源，但目前的人为排放是自然源的1000多倍，并且是观测到浓度增加的主要原因。一个SF₆分子的温室效应是一个CO₂分子的22200倍。虽然它目前的大气浓度较低(4.2×10^-12)，但它的增长速率明显(0.24×10^-12/年)。观测到的SF₆增长率与根据销售和储存数据而计算所得的排放十分一致。 

[200820053135.4]超声强化超临界或亚临界流体萃取装置
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[ 200510048681 ]-青蒿素提取的方法* /本专利以DME作为亚临界流体萃取剂，提取温度20～60℃提取压力0.5～3MPa[编者按DME：Tc：127.228℃；Pc：5.3558MPa；闪点 -41℃存在安全隐患等诸多问题]
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[200410022307.8]亚临界DME精制废弃烟草初提物的方法/ 2005.10.19公开/本专利以DME作为亚临界流体萃取剂，萃取温度10～60℃萃取压力0.1～1.5MPa[编者按DME：Tc：127.228℃；Pc：5.3558MPa；闪点 -41℃存在安全隐患等诸多问题，而在萃取温度10～60℃萃取压力0.1～1.5MPa的气态DME状况条件下怎能具有萃取功能？而气态DME又怎么能称之为亚临界DME？]
[200410022306.3]亚临界DME萃取废弃烟草的方法/ 2005.10.19公开/本专利以DME作为亚临界流体萃取剂，萃取温度30～90℃萃取压力0.5～3MPa[编者按DME：Tc：127.228℃；Pc：5.3558MPa；闪点 -41℃存在安全隐患等诸多问题]
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[ 02133470 ]-印楝油提取工艺 *
[ 01108701 ]-亚临界液化石油气萃取除虫菊酯的方法*

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Subcritical

Subcritical water chromatography: A green approach to high-temperature liquid chromatography.
At temperatures and pressures lower than 374 degrees C and 218 atm, subcritical water has widely tunable properties such as dielectric constant, surface tension, viscosity, and dissociation constant achieved by simply adjusting the temperature with a moderate pressure to keep water in the liquid state. At elevated temperatures, water acts like a weak polar organic solvent. Thus, subcritical water has been used as a green eluent to replace hazardous solvents commonly used as organic modifiers in RPLC. Subcritical water chromatography (SBWC) is capable of separating polar, moderately polar, and even some nonpolar analytes. Most of these low molecular weight solutes are stable at elevated temperatures during a chromatographic run. Some new packing materials are also quite stable and robust at mild temperatures ranging from 80 to 150 degrees C. Advantages of SBWC include the elimination of hazardous organic solvents used in traditional RPLC, rapid analysis time, improved selectivity, temperature-dependent separation efficiency, temperature-programmed elution, and compatibility with both gas- and liquid-phase detectors. In this paper, the technical aspects as well as the applications of SBWC are reviewed. Topics addressed in this review include the unique characteristics of subcritical water, analytes separated by SBWC, packing materials tested for SBWC, the application of GC and LC detection techniques in SBWC, SBWC instrumentation development, temperature effects on SBWC separation, and models developed for separation in SBWC.

Rapid column heating method for subcritical water chromatography.
A novel resistive heating method is presented for subcritical water chromatography (SWC) that provides higher column heating rates than those conventionally obtained from temperature-programmed gas chromatography (GC) convection ovens. Since the polarity of water reduces dramatically with increasing temperature, SWC employs column heating to achieve gradient elution. As such, the rate at which the mobile phase is heated directly impacts the magnitude of such gradients applied in SWC. Data from the current study demonstrate that the maximum column heating rate attainable in a typical SWC apparatus (i.e. using a GC convection oven) is around 10 degrees C/min, even at instrument oven settings of over three times this value. Conversely, by wrapping the separation column with ceramic insulation and a resistively heated wire, the column heating rates are increased five-fold. As a result, elution times can be greatly decreased in SWC employing gradients. Separations of standard alcohol test mixtures demonstrate that the retention time of the latest eluting component decreases by 35 to 50% using the prototype method. Additionally, solute retention times in this mode deviate by less than 1% RSD over several trials, which compares very well to those obtained using a conventional GC convection oven. Results suggest that the developed method can be a useful alternative heating technique in SWC.

Hydrolysis kinetics of trisaccharides consisting of glucose, galactose, and fructose residues in subcritical water.
The hydrolysis kinetics of trisaccharides consisting of glucose, galactose, and fructose residues with different glycosidic bonds, 1-kestose, d-melezitose, d-raffinose, and lactosucrose, in subcritical water were conducted over the temperature range of 150-230 degrees C and at a constant pressure of 10 MPa. The hydrolysis of trisaccharides in subcritical water proceeded consecutively, i.e., one cleavage of the two bonds antedated the other. The preceding cleavage was not expressed by the first-order kinetics, but by the kinetics considering the concentration of the acidic compounds, which were produced by the degradation of the constituent monosaccharides. The hydrolysis of the constituent disaccharides, except sucrose composed of the alpha-Glc-(1-->2)-beta-Fru bond, obeyed first-order kinetics. All of the rate constants of the hydrolytic kinetics were determined, and the values were found to depend on the type of bond.

Subcritical water extraction of nutraceuticals with antioxidant activity from oregano. Chemical and functional characterization.
In the present work, oregano leaves (Origanum vulgare L.) are explored as natural source of nutraceuticals with antioxidant activity. To do this, subcritical water extraction (SWE), a new environmentally friendly technique, is employed as extraction procedure and HPLC coupled to DAD is used for the chemical characterization of the extracts. Moreover, the radical scavenging 1,1-diphenyl-2-picrylhydrazyl (DPPH) method and the determination of the total phenolic content (measured with the Folin test) are applied to evaluate the antioxidant activity of the extracts. The extraction of antioxidants from oregano leaves by SWE is studied considering different temperatures (25, 50, 100, 150 and 200 degrees C) to investigate the selectivity of the process. The highest antioxidant activity is observed for the extract obtained at the highest temperature, 200 degrees C (EC(50) equal to 10 microg/ml). Moreover, the extraction yield was also the highest (54% dry weight) at these extraction conditions. The total phenolic content showed no differences among the different extracts, concluding that the amount of phenolic compounds extracted was similar but the type and structure of the phenolics was different, providing in this way different antioxidant activity. Some compounds could be tentatively identified, proposing some probable chemical structures for some of them, such as flavanones, dihydroflavonols, favonols and flavones.

Development of pressurized subcritical water extraction combined with stir bar sorptive extraction for the analysis of organochlorine pesticides and chlorobenzenes in soils.
An analytical method for the determination of several organochlorine pesticides (OCPs) like hexachlorocyclohexanes (HCHs), cyclodiene derivates (dieldrin, aldrin, endrin, heptachlor, heptachlor epoxide, endrin aldehyde, endosulfan and ensodulfan sulphate) and DDX compounds (p,p'-DDE, p,p'-DDD and p,p'-DDT) as well as chlorobenzenes in soils has been developed. The procedure is based on pressurized subcritical water extraction (PSWE) followed by stir bar sorptive extraction (SBSE) and subsequent thermodesorption-gas chromatography/mass spectrometry analysis. Significant PSWE and SBSE parameters were optimized using spiked soil and water samples. For the PSWE of the organochlorine compounds, water modified with acetonitrile as the extraction solvent, at an extraction temperature of 120 degrees C, and three cycles of 10 min extraction proved to be optimal. Under optimized conditions, the figures of merit, such as precision, accuracy and detection limits were evaluated. The detection limits obtained for soil samples were in the range 0.002-4.7 ng/g. Recoveries between 4.1 and 85.2% were achieved from samples spiked at a concentration level of 25-155 ng/g. The main advantages of this method are the avoidance of clean-up and concentration procedures as well as the significant reduction of the required volume of organic solvents. The described method was applied to the determination of the pollutants in soil samples collected from a polluted area, the Bitterfeld region (Germany). The results obtained by PSWE-SBSE were in a good agreement with those obtained by a reference method, a conventional pressurized liquid extraction (PLE).

Efficient decomposition of environmentally persistent perfluorooctanesulfonate and related fluorochemicals using zerovalent iron in subcritical water.
Decomposition of perfluorooctanesulfonate (PFOS) and related chemicals in subcritical water was investigated. Although PFOS demonstrated little reactivity in pure subcritical water, addition of zerovalent metals to the reaction system enhanced the PFOS decomposition to form F-ions, with an increasing order of activity of no metal approximately equal Al < Cu < Zn << Fe. Use of iron led to the most efficient PFOS decomposition: When iron powder was added to an aqueous solution of PFOS (93-372 microM) and the mixture was heated at 350 degrees C for 6 h, PFOS concentration in the reaction solution fell below 2.2 microM (detection limit of HPLC with conductometric detection), with formation of F-ions with yields [i.e., (moles of F- formed)/(moles of fluorine content in initial PFOS) x 100] of 46.2-51.4% and without any formation of perfluorocarboxylic acids. A small amount of CHF3 was detected in the gas phase with a yield [i.e., (moles of CHF3)/(moles of carbon content in initial PFOS) x 100] of 0.7%, after the reaction of PFOS (372 microM) with iron at 350 degree C for 6 h. Spectroscopic measurements indicated that PFOS in water markedly adsorbed on the iron surface even at room temperature, and the adsorbed fluorinated species on the iron surface decomposed with rising temperature, with prominent release of F- ions to the solution phase above 250 degrees C. This method was also effective in decomposing other perfluoroalkylsulfonates bearing shorter chain (C2-C6) perfluoroalkyl groups and was successfully applied to the decomposition of PFOS contained in an antireflective coating agent used in semiconductor manufacturing.

Resource recovery from excess sludge by subcritical water combined with magnesium ammonium phosphate process.
The amount of excess sludge produced in municipal wastewater treatment plants in Japan is increasing every year as the urban population increases. Phosphorus in excess sludge could be a potential phosphorus resource since at present, phosphate rock is being exhausted all over the world. Every year, Japan imports large quantities of phosphorus from abroad but much is discharged as excess sludge. Therefore, the solubilization process, one method of recovering phosphorus from sludge, could be a promising solution. In this study, a subcritical water process, a new technology that solubilizes sludge under subcritical conditions, was applied before the phosphorus in sludge was recovered with the magnesium ammonium phosphate (MAP) process. As a result, the solubilization rate of excess sludge achieved approximately 80% and about 94-97% of the phosphorus could be recovered.

Rapid determination of inorganic elements in airborne particulate matter by using acidified subcritical-water extraction and inductively-coupled plasma-optical-emission spectrometry.
A rapid and simple method has been developed for determination of inorganic elements in airborne particulate matter (PM10) by using acidified subcritical water and ICP-OES. Elements such as Al, As, B, Ba, Cd, Cu, Fe, Mn, Pb, Se, and Zn were rapidly and efficiently extracted from PM10 samples with a solution of 0.1 mol L(-1) HNO(3) under subcritical conditions. The method requires approximately 5% of the amount of acid used in the standard microwave extraction procedure. The material selected for the subcritical extraction manifold was poly ether ether ketone (PEEK), to avoid sample contamination with elements present in previously reported stainless-steel manifolds. The extraction temperature, time of static and dynamic extraction, and flow rate of acidified water were studied keeping the pressure controlled at about 1,500 psig. The efficiency of extraction of most of the analytes increased with temperature, tending to quantitative extraction at temperatures near 150 degrees C. After the extraction process the analytes were determined directly in the extract by ICP-OES. When the method was compared with the USEPA counterpart, the results indicate that under optimized conditions (static extraction time: 15 min, dynamic extraction time: 30 min, flow rate: 2 mL min(-1)) the analytes were extracted with recoveries between 73 and 158%. Alternatively, by using an extraction time of 15 min, the method could be used to screen for all the elements, with recoveries over 50%. The developed method was applied to the determination of inorganic elements in airborne particulate matter in the atmosphere of Santiago, Chile.

Decomposition kinetics of maltose in subcritical water.
The decomposition process of maltose in subcritical water was studied using a tubular reactor in the temperature range of 180 to 260 degrees C and at 10 MPa. The formation of glucose and 5-hydroxymethyl-2-furaldehyde during the maltose decomposition was also observed. The decomposition rate of maltose was faster at higher temperatures. The rate was approximated by first-order kinetics during the early stage of the decomposition, but was accelerated and deviated from these kinetics at the later stage. The effluent pH decreased as the residence time in the reactor increased and the decrease of pH affected the maltose decomposition rate and glucose formation. Low pH of a feed solution accelerated maltose decomposition. A good correlation was obtained between the pH of the effluent and the rate constant of the first-order kinetics.

Hydrolysis of ginger bagasse starch in subcritical water and carbon dioxide.
Ginger bagasse from supercritical extraction was hydrolyzed using subcritical water and CO(2) to produce reducing sugars and other low molecular mass substances. Response surface methodology was used to find the best hydrolysis conditions; the degree of hydrolysis and the yield were the two response variables selected for maximization. The kinetic studies of the hydrolysis were performed at 150 bar and temperatures of 176, 188, and 200 degrees C. The higher degree of hydrolysis (97.1% after 15 min of reaction) and higher reducing sugars yield (18.1% after 11 min of reaction) were established for the higher process temperature (200 degrees C). Different mixtures of oligosaccharides with different molecular mass distributions were obtained, depending on the temperature and on the reaction time. The ginger bagasse hydrolysis was treated as a heterogeneous reaction with a first-order global chemical kinetic, in relation to the starch concentration, which resulted in an activation energy of 180.2 kJ/mol and a preexponential factor of 5.79 x 10(17)/s.

Subcritical (hot/liquid) water dechlorination of PCBs (Aroclor 1254) with metal additives and in waste paint.
No disposal option exists for "mixed wastes" such as paint scrapings that are co-contaminated with polychlorinated biphenyls (PCBs) and radioactive metals. Either removal or destruction of the PCBs is required prior to disposal. Comparison of subcritical water dechlorination (350 degrees C, 1 h) of Aroclor 1254 in paint scrapings (180 ppm) and of standard Aroclor 1254 showed significantly enhanced dechlorination in the presence of paint. While no significant degradation was observed for standard Aroclor (no paint), the dechlorination of PCBs in paint was 99, 99, and 80% for the hepta-, hexa-, and pentachlorinated congeners, respectively, indicating that metals in the paint enhanced the dechlorination reactions. Adding metals to the standard Aroclor (no paint) reactions enhanced PCB dechlorination in subcritical water in descending order of activity: Pb approximately = Cu > Al > Zn > Fe. In the presence of both zerovalent and divalent lead and zerovalent copper in subcritical water (350 degrees C, 1 h), 99% of the Aroclor 1254 mixture (tetra- to heptachlorinated biphenyls) was dechlorinated. High dechlorination (ca. 95%) was also achieved with zerovalent aluminum. In contrast to other metals, lead retained its degradation ability at a lower temperature of 250 degrees C after 18 h. The high degradation efficiency achieved using metal additives in water at reasonable temperatures and pressures demonstrates the potential for subcritical water dechlorination of PCBs in paint scrapings and, potentially, in other solid and liquid wastes.

Off-line coupling of subcritical water extraction with subcritical water chromatography via a sorbent trap and thermal desorption.
In this study, the off-line coupling of subcritical water extraction (SBWE) with subcritical water chromatography (SBWC) was achieved using a sorbent trap and thermal desorption. The sorbent trap was employed to collect the extracted analytes during subcritical water extraction. After the extraction, the trap was connected to the subcritical water chromatography system, and thermal desorption of the trapped analytes was performed before the SBWC run. The thermally desorbed analytes were then introduced into the subcritical water separation column and detected by a UV detector. Anilines and phenols were extracted from sand and analyzed using this off-line coupling technique. Subcritical water extraction of flavones from orange peel followed by subcritical water chromatographic separation was also investigated. The effects of water volume and extraction temperature on flavone recovery were determined. Because a sorbent trap was used to collect the extracted analytes, the sensitivity of this technique was greatly enhanced as compared to that of subcritical water extraction with solvent trapping. Since no organic solvent-water extractions were necessary prior to analysis, this technique eliminated any use of organic solvents in both extraction and chromatography processes.

Subcritical water extraction of antioxidant compounds from rosemary plants.
Subcritical water extraction at several temperatures ranging from 25 to 200 degrees C has been studied to selectively extract antioxidant compounds from rosemary leaves. An exhaustive characterization of the fractions obtained using subcritical water at different temperatures has been carried out by LC-MS, and the antioxidant activities of the extracts have been measured by a free radical method (DPPH). Results indicate high selectivity of the subcritical water toward the most active compounds of rosemary such as carnosol, rosmanol, carnosic acid, methyl carnosate, and some flavonoids such as cirsimaritin and genkwanin. The antioxidant activity of the fractions obtained by extraction at different water temperatures was very high, with values around 11.3 microg/mL, comparable to those achieved by SFE of rosemary leaves. A study of the effect of the temperature on the extraction efficiency of the most typical rosemary antioxidant compounds has been performed.

Alkaline subcritical-water treatment and alkaline heat treatment for the increase in biodegradability of newsprint waste.
This work describes two alkaline semicontinuous processes for the conversion of refractory organic materials into biodegradable substances. Newsprint was used as a lignocellulosic waste. Methane conversion efficiencies and cellulose removals were investigated for the two following processes: alkaline subcritical-water treatment (ASWT) coupled with methane fermentation and alkaline heat treatment (newsprint heated with steam in an autoclave; AHT) coupled with methane fermentation with a neutral subcritical-water treatment (NSWT) recycle. Results showed that for ASWT coupled with methane fermentation higher methane conversion efficiencies and higher cellulose removals were achieved as HRT increased. At HRT = 20 days, average CH4 conversion efficiency and average cellulose removal reached 26% and 44%, respectively. After a final HRT of 40 days, average CH4 conversion efficiency and average cellulose removal reached 50% and 60%, respectively. On the other hand, for AHT coupled with methane fermentation, methane conversion efficiencies did not show a greater improvement using this pretreatment process. Average conversion reached 9% with an average cellulose removal of 20%. In order to improve the yield of the reactor, approximately one-third of the effluent was recycled using NSWT (150 degrees C; neutral pH). Methane conversion efficiency of this process increased as more recycles were performed. For the fifth operation, the total average methane conversion efficiency was 44% with a total average cellulose removal of 55%.

A novel process utilizing subcritical water and nitrilotriacetic acid to extract hazardous elements from MSW incinerator fly ash.
An effective process for hazardous element extraction from municipal solid waste incinerator fly ash was developed. The key trait of the process was to extract most of the hazardous elements out of the ash but leave Ca and Si inside the residue. In the extraction process, the ash was firstly pre-washed with water, then subjected to subcritical water (SC water) treatment and nitrilotriacetic acid (NTA) extraction. SEM images indicated that SC water is strong enough to destroy the ash particles, thus greatly improving hazardous elements extraction efficiency in the subsequent NTA extraction process. The extraction percentages for Cr, As, Se, Cd and Pb under SC water+NTA treatment were around 2-6 times higher than those treated by NTA at room conditions. The preferable SC treatment temperature was 573 K and the treatment time was 3 h. The optimum NTA concentration, vibration time and liquid/solid ratio were 0.8 M, 5 h and 10:1 (ml/g), respectively. Furthermore, it was found that introduction of a suitable amount of sulfuric acid into the extraction solution could extract more than 90% of most of the hazardous elements out of the ash.

Reductive dechlorination of polychlorinated dibenzo-p-dioxins by zerovalent iron in subcritical water.
A new method for reductive dechlorination of polychlorinated dibenzo-p-dioxins (PCDDs) and remediation of contaminated soils is described that uses zerovalent iron as the dechlorination agent and subcritical water as reaction medium and extractive solvent. It is found that the zerovalent iron can be applied for stepwise dechlorination of octachlorinated dibenzo-p-dioxin (OCDD) on various matrixes in subcritical water. By using iron powder as matrix higher chlorinated congeners were practically completely reduced to less than tetra-substituted homologues. A significant part of residual OCDD, when it was spiked in to soils, and formed less chlorinated congeners are extracted with water in the given conditions. The solubility of OCDD was increased by a 4-6 orders over its solubility at ambient conditions. The new method of contentious-flow extraction is described.

Subcritical water extraction and determination of nifedipine in pharmaceutical formulations.
A rapid and simple continuous method for the extraction of nifedipine from tablets was developed by using pressurized hot water at 150 degrees C. This is the first time that subcritical water was applied to the extraction of low-polarity compounds in pharmaceutical analysis. The method is based on the increment in solubility of nifedipine in subcritical water. Extraction temperature and static and dynamic extraction time were optimized in order to reach quantitative extraction of the drug from the tablets. After extraction, the drug was determined by spectrophotometry by measuring absorbance at 338 nm. Accuracy and precision of the method were determined by analysis of 10 synthetic samples of pharmaceutical formulations prepared with common tablet excipients. Recovery was found to be 99.2% with a relative standard deviation of 1.9%, which indicates that the excipients of the formulation do not interfere in the determination. The method was applied to the determination of the drug content uniformity in tablets.

Subcritical water extraction of essential oils from coriander seeds (Coriandrum sativum L.)
Subcritical water extraction (SCWE), hydrodistillation and Soxhlet extraction were compared for the extraction of essential oil from coriander seeds (Coriandrum sativum L.). The extraction efficiencies of different temperatures (100, 125, 150 and 175 °C), mean particle sizes (0.25, 0.50 and 1 mm), and water flow rates (1, 2 and 4 ml/min) were investigated. Separation and identification of the components were carried out by GC–FID and GC–MS. The results showed that the optimum temperature, mean particle size, and flow rate were 125 °C, 0.5 mm, and 2 ml/min. The SCWE was compared with both conventional methods in terms of the efficiency and the essential oil composition. Hydrodistillation and Soxhlet extraction showed higher extraction efficiencies, but the SCWE resulted to the essential oils more concentrated in valuable oxygenated components.

Ethanol-modified subcritical water extraction combined with solid-phase microextraction for determining atrazine in beef kidney.
The determination of the levels of pesticides in food products has prompted the development of sensitive and rapid methods of analysis that are solvent-free or utilize solvents that are benign to the environment and laboratory worker. In this study we have developed a novel extraction method that utilizes ethanol-modified subcritical water in combination with solid-phase microextraction (SPME) for the removal of atrazine from beef kidney. In situ sample cleanup was achieved using the technique of matrix solid-phase dispersion. A cross-linked polymer, XAD-7 HP, was utilized as a dispersing material for kidney samples. Subcritical water extractions were performed with a pressurized solvent extraction unit at 100 degrees C and 50 atm. Experimental parameters investigated were the volume of solvent and amount of modifier required for the complete extraction of atrazine and optimization of the extraction time. It was determined that 30% ethanol in water (v/v) is adequate for the complete extraction of atrazine. A Carbowax-divinylbenzene SPME fiber was used to sample the aqueous extracts. Analysis of the fiber contents was by ion-trap GC/MS utilizing the single ion mode. The total time of analysis for a single kidney sample is 90 min. The average percent recoveries from samples spiked to the concentrations of 2 and 0.2 microg/g were 104 and 111, respectively. The average relative standard deviations were 10 and 9, respectively. The method limit of detection for beef kidney spiked with atrazine was found to be 20 ng/g of sample.

Extraction of tricyclazole from soil and sediment with subcritical water.
The use of subcritical water to extract tricyclazole from soils and sediments was examined. Extraction efficiency and kinetics were determined as a function of temperature, sample age, sample matrix, sample size, and flow rate. Extraction temperature was the most influential experimental factor affecting extraction efficiency and kinetics, with increasing temperature (up to 150 degrees C) yielding faster and higher efficiency extractions. Higher extraction temperatures were also important for quantitative recovery of tricyclazole from aged samples. Extraction at 50 degrees C yielded 97% recoveries from samples aged 1 day but only 30% recoveries for samples aged 202 days, whereas extraction at 150 degrees C yielded recoveries of 85-100% that were independent of incubation time and sample matrix, with the exception of one sediment that contained a large amount of organic matter. Sample extracts from subcritical water extraction were generally a pale yellow color, contrasted with a dark brown color from organic solvent extractions of the same matrixes. Less sample cleanup was therefore required prior to analysis, with the total time for the extraction and analysis of a single sample being approximately 2 h. Subcritical water extraction is an effective technique for the rapid and quantitative extraction of tricyclazole from soils and sediments.

Continuous subcritical water extraction of medicinal plant essential oil: comparison with conventional techniques
A subcritical extractor equipped with a three-way inlet valve and an on/off outlet valve has been used for performing subcritical water extractions (SWE) in a continuous manner for the isolation of the essential oil of fennel, a medicinal plant. The target compounds were removed from the aqueous extract by a single extraction with 5 ml hexane, determined by gas-chromatography-flame ionization (GC-FID) and identified by mass spectrometry (MS). The proposed extraction method has been compared with both hydrodistillation and dichloromethane manual extraction. Better results have been obtained with the proposed method in terms of rapidity, efficiency, cleanliness and possibility of manipulating the composition of the extract.

Characteristics of lithium iron phosphate (LiFePO₄) particles synthesized in subcritical and supercritical water
The effect of temperature, pH, time, and reactant concentrations on the size and morphology of lithium iron phosphate (LiFePO₄) particles synthesized in a batch hydrothermal reactor was investigated in this work. It was found that LiFePO₄ could only be synthesized at neutral or slightly basic pH in both subcritical and supercritical water. Synthesis in subcritical water resulted in micron-sized particles of high crystallinity, whereas synthesis in supercritical water produced submicron particles. A more uniform particle size distribution was obtained at low reactant concentrations, irrespective of the synthesis temperature. Qualitative explanations for these observations are provided in terms of nucleation, growth, and agglomeration phenomena at subcritical and supercritical conditions.

Results of Search in US Patent Collection db for:
"Subcritical": patents.
　

	PAT. NO.		Title
1	7,387,761		Method for manufacturing a glass infiltrated metal oxide infrastructure
2	7,386,985		Detection of refrigerant charge adequacy based on multiple temperature measurements
3	7,385,057		Method and device for producing melamine in a single-phase tubular reactor
4	7,384,484		Substrate processing method, substrate processing apparatus and substrate processing system
5	7,381,439		Method and composition for washing poultry during processing
6	7,381,320		Heavy oil and bitumen upgrading
7	7,381,278		Using supercritical fluids to clean lenses and monitor defects
8	7,374,900		Fluorescent substrates for detecting organophosphatase enzyme activity
9	7,365,236		Generation of a creosote-like mixture, or recovery of metals, or both from preserved wood by reaction in supercritical water
10	7,365,234		Tuning product selectivity in catalytic hydroformylation reactions with carbon dioxide expanded liquids
11	7,364,839		Method for forming a pattern and substrate-processing apparatus
12	7,361,231		System and method for mid-pressure dense phase gas and ultrasonic cleaning
13	7,360,420		Method and bearing for balancing rotors without journals
14	7,353,113		System, method and computer program product for aquatic environment assessment
15	7,349,517		System for measuring burn-out of fuel elements of a high-temperature reactor
16	7,347,193		Method and device for determining the mass flow rate passing through the air-bleed valve of an internal combustion engine tank
17	7,344,746		Process for the hydrogenation of hop resin acids
18	7,337,742		Twin fin fairing
19	7,337,356		Systematic and random error detection and recovery within processing stages of an integrated circuit
20	7,335,296		System and device for processing supercritical and subcritical fluid
21	7,335,287		Solid electrolyte sensor for monitoring the concentration of an element in a fluid particularly molten metal
22	7,334,430		Refrigerating cycle
23	7,331,313		Continuous steam generator with circulating atmospheric fluidised-bed combustion
24	7,326,756		High temperature bulk polymerization of branched crystalline polypropylene
25	7,326,337		System for oxidation of organic bodies present in an aqueous effluent
26	7,326,001		Wave forming apparatus and method
27	7,323,096		Method for treating the surface of object and apparatus thereof
28	7,322,101		Turbine engine disk spacers
29	7,320,229		Ejector refrigeration cycle
30	7,320,091		Error recovery within processing stages of an integrated circuit
31	7,319,125		Supercritical polymerization process and polymers produced therefrom
32	7,316,824		Method and composition for washing poultry during processing
33	7,316,769		Length-dependent recoil separation of long molecules
34	7,314,942		Methylenelactones syntheses in supercritical fluids
35	7,311,003		Method and device for balancing journal-less rotors
36	7,310,755		Data retention latch provision within integrated circuits
37	7,304,309		Radiation detectors
38	7,300,527		Method for activating surface of base material and apparatus thereof
39	7,299,913		Drive unit for a vibrating spiral conveyor
40	7,294,353		Methods and compositions comprising ilex
41	7,293,403		Combustion chamber with internal jacket made of a ceramic composite material and process for manufacture
42	7,291,890		Gate dielectric and method
43	7,291,296		Method for making very fine particles consisting of a principle inserted in a host molecule
44	7,288,237		Epoxidation catalyst
45	7,287,725		Missile control system and method
46	7,287,541		Method, apparatus and system for controlling fluid flow
47	7,287,381		Power recovery and energy conversion systems and methods of using same
48	7,285,312		Atomic layer deposition for turbine components
49	7,282,099		Dense phase processing fluids for microelectronic component manufacture
50	7,281,484		Multimission transonic hull and hydrofield

51	7,279,184		Methods and compositions comprising Ilex
52	7,279,127		Continuous steelmaking plant
53	7,278,264		Process to convert low grade heat source into power using dense fluid expander
54	7,276,184		Surfactant assisted nanomaterial generation process
55	7,275,400		Washing apparatus
56	7,273,826		Epoxidation catalyst
57	7,270,795		Method for producing nano-carbon materials
58	7,267,727		Processing of semiconductor components with dense processing fluids and ultrasonic energy
59	7,264,710		Process and apparatus for treating heavy oil with supercritical water and power generation system equipped with heavy oil treating apparatus
60	7,263,727		Hygienic high detergency toilet
61	7,262,422		Use of supercritical fluid to dry wafer and clean lens in immersion lithography
62	7,261,529		Apparatus for preparing biodegradable microparticle formulations containing pharmaceutically active agents
63	7,260,001		Memory system having fast and slow data reading mechanisms
64	7,259,231		Extraction and fractionation of biopolymers and resins from plant materials
65	7,259,136		Compositions and methods for treating peripheral vascular disease
66	7,258,791		Method of reducing volume of sludge
67	7,252,719		High pressure processing method
68	7,244,461		Method of preparing liquid smoke
69	7,243,618		Steam generator with hybrid circulation
70	7,243,501		Expansion device for an air-conditioning system
71	7,238,833		Production of aromatic carboxylic acids
72	7,237,574		Controlled dispersion multi-phase nozzle and method of making the same
73	7,235,421		System and method for developing production nano-material
74	7,235,224		Process for preparing fine metal oxide particles
75	7,232,053		Seam-welded air hardenable steel constructions
76	7,229,979		Hypoestoxides, derivatives and agonists thereof for use as stent-coating agents
77	7,226,771		Phospholipases, nucleic acids encoding them and methods for making and using them
78	7,217,750		Process for incorporating one or more materials into a polymer composition and products produced thereby
79	7,216,830		Wing gull integration nacelle clearance, compact landing gear stowage, and sonic boom reduction
80	7,216,498		Method and apparatus for determining supercritical pressure in a heat exchanger
81	7,216,427		Surface treatment of prefinished valve seat inserts
82	7,214,394		Policosanol compositions, extraction from novel sources, and uses thereof
83	7,211,553		Processing of substrates with dense fluids comprising acetylenic diols and/or alcohols
84	7,211,145		Substrate processing apparatus and substrate processing method
85	7,208,181		Isolation of polyphenolic compounds from fruits or vegetables utilizing sub-critical water extraction
86	7,201,804		Cleaning of hydrocarbon-containing materials with critical and supercritical solents
87	7,201,019		Light gas component separation from a carbon dioxide mixture
88	7,197,876		System and apparatus for power system utilizing wide temperature range heat sources
89	7,197,404		Computation of radiating particle and wave distributions using a generalized discrete field constructed from representative ray sets
90	7,195,676		Method for removal of flux and other residue in dense fluid systems
91	7,193,120		Colloid-catalyzed gas transfer in supercritical phases
92	7,193,097		Method of producing a fatty acid ester
93	7,192,995		Homogenous compositions of polymers and crystalline solids or cross-linking agents and methods of making the same
94	7,192,217		Baffle apparatus
95	7,189,350		Method of sterilizing medical instruments
96	7,189,196		Method of separating materials with a concentric tubular centrifuge
97	7,183,229		Semiconductor thin film forming method, production methods for semiconductor device and electrooptical device, devices used for these methods, and semiconductor device and electrooptical device
98	7,182,861		System for separating electrophotographic carrier compositions and recycling the compositions
99	7,181,862		Sol-gel process for the production of glassy articles
100	7,178,362		Expansion device arrangement for vapor compression system

101	7,175,886		Apparatus and method for micron and submicron particle formation
102	7,174,713		Method for determination of composition of the gas mixture in a combustion chamber of an internal combustion engine with exhaust gas recirculation and correspondingly configured control system for an internal combustion engine
103	7,169,857		Homogenous compositions of fluoropolymers and crystalline solids or cross-linking agents and methods of making the same
104	7,169,179		Drug delivery device and method for bi-directional drug delivery
105	7,166,753		Process for production of hydrogen and carbonyl compounds by reacting sub- or super-critical water with alcohols
106	7,166,658		Rubber reduction
107	7,164,197		Dielectric composite material
108	7,163,989		Processes and apparatus for continuous solution polymerization
109	7,162,661		Systematic and random error detection and recovery within processing stages of an integrated circuit
110	7,160,492		Orthopaedic device for implantation in the body of an animal and method for making the same
111	7,160,380		Organic pigment fine-particle, and method of producing the same
112	7,159,409		Method and apparatus for controlling the load placed on a compressor
113	7,157,886		Power converter method and apparatus having high input power factor and low harmonic distortion
114	7,157,534		Polymerization process for producing copolymers
115	7,157,002		Process for the recovery of surfactants
116	7,156,925		Using supercritical fluids to clean lenses and monitor defects
117	7,148,387		Process for producing hydroxyl group-containing compound
118	7,147,670		Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent
119	7,147,436		Turbine engine rotor retainer
120	7,144,498		Supercritical hydrocarbon conversion process
121	7,144,461		Method of removing acid component in deteriorated acetate film
122	7,140,197		Means and apparatus for microrefrigeration
123	7,131,294		Method and apparatus for control of carbon dioxide gas cooler pressure by use of a capillary tube
124	7,131,291		Compression system for cooling and heating purposes
125	7,131,259		High density combined cycle power plant process
126	7,129,200		Domestic fabric article refreshment in integrated cleaning and treatment processes
127	7,127,905		Vapor compression system startup method
128	7,118,696		Method of forming light dispersing fiber and fiber formed thereby
129	7,114,508		Cleaning apparatus having multiple wash tanks for carbon dioxide dry cleaning and methods of using same
130	7,111,630		High pressure processing apparatus and method
131	7,108,867		Process for preparing particles
132	7,108,223		Missile control system and method
133	7,105,185		Kavalactone profile
134	7,101,499		Method of and apparatus for producing pellets from heavy hydrocarbon liquid
135	7,097,715		Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent
136	7,096,679		Transcritical vapor compression system and method of operating including refrigerant storage tank and non-variable expansion device
137	7,091,366		Recovery of residual specialty oil
138	7,091,288		Polymerization of vinylidene fluoride (VF.sub.2) in a supercritical fluid medium
139	7,090,871		Composition containing pyrrolizidine-alkaloid-free petasites
140	7,084,269		Process for producing lactam
141	7,084,181		Method for decomposing nonmetallic honeycomb panel, and method for recycling the same
142	7,082,355		Wake wash severity monitor for high speed vessels
143	7,081,486		Method of producing polymer
144	7,081,133		Antibiotic treated implantable medical devices
145	7,080,651		High pressure processing apparatus and method
146	7,078,731		Gallium nitride crystals and wafers and method of making
147	7,078,359		Aerogel composite with fibrous batting
148	RE39,171		Simulated wave water sculpture
149	7,074,881		Methods of synthesis of polysuccinimide, copolymers of polysuccinimide and derivatives thereof
150	7,074,369		Method and apparatus for decoupled thermo-catalytic pollution control

151	7,072,229		Memory system having fast and slow data reading mechanisms
152	7,070,146		Aircraft thickness/camber control device for low sonic boom
153	7,067,640		Cross-linked chiral compounds and methods of making thereof
154	7,064,834		Method for analyzing impurities in carbon dioxide
155	7,063,795		Method for starting up a system for treating waste by hydrothermal oxidation
156	7,063,750		Domestic fabric article refreshment in integrated cleaning and treatment processes
157	7,059,831		Turbine engine disk spacers
158	7,059,512		Solder alloy material layer composition, electroconductive and adhesive composition, flux material layer composition, solder ball transferring sheet, bump and bump forming process, and semiconductor device
159	7,058,100		Systems and methods for thermal management of diode-pumped solid-state lasers
160	7,057,055		Process for preparing a deuterated or tritiated compound
161	7,056,887		Treatment of acute coronary syndrome with GLP-1
162	7,049,475		Organic compound decomposing method
163	7,049,030		Battery
164	7,045,642		Process for preparing a deuterated or tritiated compound
165	7,045,622		Process for producing lactam
166	7,039,565		Method and system for developing a numerical dynamic sanitary sewer and storm water drainage simulation model
167	7,039,528		Method for detecting leak before rupture in a pipeline
168	7,038,000		Process for preparing propylene copolymers
169	7,037,524		Oral delivery of a botanical
170	7,037,420		Anodic oxidation method and treatment apparatus thereof
171	7,034,092		Process for producing bimodal polyethylene resins
172	7,034,084		Process and apparatus for the hydrogenation of polymers under supercritical conditions
173	7,033,985		Domestic fabric article refreshment in integrated cleaning and treatment processes
174	7,033,068		Substrate processing apparatus for processing substrates using dense phase gas and sonic waves
175	7,032,373		Device for cooling coolant in a gas turbine and gas and steam turbine with said device
176	7,029,707		Method of producing a processed kava product having an altered kavalactone distribution and processed kava products produced using the same
177	7,028,494		Defrosting methodology for heat pump water heating system
178	7,025,992		Pharmaceutical formulations
179	7,022,863		Production method of pyrrolidone carboxylic acid and salt thereof
180	7,021,106		Apparatus and method for forming internally ribbed or rifled tubes
181	7,018,902		Gate dielectric and method
182	7,009,215		Group III-nitride based resonant cavity light emitting devices fabricated on single crystal gallium nitride substrates
183	7,008,528		Process and system for continuously extracting oil from solid or liquid oil bearing material
184	7,005,301		Piecewise uniform conduction-like flow channels and method therefor
185	7,003,968		Motor vehicle air-conditioning installation equipped with an electronic control device
186	7,001,620		Kavalactone product
187	7,001,581		Method for producing nanocarbon materials
188	7,000,870		Laminar flow wing for transonic cruise
189	7,000,653		High pressure processing apparatus and high pressure processing method
190	7,000,413		Control of refrigeration system to optimize coefficient of performance
191	6,989,123		Methods to produce gel sheets
192	6,978,638		Nitrogen rejection from condensed natural gas
193	6,977,767		Plasmonic nanophotonics methods, materials, and apparatuses
194	6,977,520		Time-multiplexed routing in a programmable logic device architecture
195	6,972,271		Supported catalyst systems
196	6,968,708		Refrigeration system having variable speed fan
197	6,966,874		Concentric tubular centrifuge
198	6,964,787		Method and system for reducing microbial burden on a food product
199	6,964,168		Advanced heat recovery and energy conversion systems for power generation and pollution emissions reduction, and methods of using same
200	6,962,714		Critical fluid antimicrobial compositions and their use and generation

201	6,962,629		Method for moving contaminants from gases
202	6,960,672		Processes for producing alkyl ester of fatty acid
203	6,960,618		Preparation method for rigid polyurethane foam
204	6,958,123		Method for removing a sacrificial material with a compressed fluid
205	6,958,122		High pressure and high temperature reaction system
206	6,956,140		Hydrothermal hydrolysis of halogenated compounds
207	6,955,051		Steam generation apparatus and methods
208	6,953,564		Method for producing fullerenes
209	6,952,346		Etched open microchannel spray cooling
210	6,948,238		Method for dissociating metals from metal compounds
211	6,946,150		Pharmaceutical formulation
212	6,944,067		Memory system having fast and slow data reading mechanisms
213	6,943,461		All-weather energy and water production via steam-enhanced vortex tower
214	6,941,854		Sliding pairing for machine parts that are subjected to the action of highly pressurized and high-temperature steam, preferably for piston-cylinder assemblies of steam engines
215	6,939,837		Non-immersive method for treating or cleaning fabrics using a siloxane lipophilic fluid
216	6,939,651		Electrophotographic photoconductor, and process cartridge and electrophotographic apparatus using the same
217	6,936,843		Fixture used to prepare semiconductor specimens for film adhesion testing
218	6,936,292		Deodorized yellow colorant of safflower
219	6,935,592		Aircraft lift device for low sonic boom
220	6,932,541		Wave forming apparatus and method
221	6,931,372		Joint multiple program coding for digital audio broadcasting and other applications
222	6,929,752		Method for treating waste by hydrothermal oxidation
223	6,924,407		Pressure-tuned solid catalyzed heterogeneous chemical reactions
224	6,924,004		Apparatus and method for synthesizing films and coatings by focused particle beam deposition
225	6,923,011		Multi-stage vapor compression system with intermediate pressure vessel
226	6,921,820		Method for forming cellulose
227	6,921,420		Apparatus and methods for conserving vapor in a carbon dioxide dry cleaning system
228	6,919,421		Methods of synthesis of polysuccinimide, copolymers of polysuccinimide and derivatives thereof
229	6,913,779		Process for the preparation of accelerated release formulations using compressed fluids
230	6,908,660		Shaped body made of fiber-reinforced composites having a segmented covering layer, its production and its use
231	6,906,423		Mask used for exposing a porous substrate
232	6,905,556		Method and apparatus for using surfactants in supercritical fluid processing of wafers
233	6,905,555		Methods for transferring supercritical fluids in microelectronic and other industrial processes
234	6,903,181		Methods of synthesis of polysuccinimide, copolymers of polysuccinimide and derivatives thereof
235	6,902,999		Pattern formation method
236	6,901,814		Fuselage pitot-static tube
237	6,898,951		Washing apparatus
238	6,898,941		Supercritical pressure regulation of vapor compression system by regulation of expansion machine flowrate
239	6,898,936		Compression stripping of flue gas with energy recovery
240	6,893,995		Supported catalyst systems
241	6,890,660		Combustion chamber with internal jacket made of a ceramic composite material and process for manufacture
242	6,887,992		3-cephem derivative crystal
243	6,887,971		Synthesis of polysuccinimide and copoly(succinimide-aspartate) in a supercritical fluid
244	6,887,516		Method and apparatus for applying a powder coating
245	6,886,487		Thruster apparatus and method for reducing fluid-induced motions of and stresses within an offshore platform
246	6,884,911		Material processing by repeated solvent expansion-contraction
247	6,884,900		Method for producing fatty acid alcohol ester
248	6,884,737		Method and apparatus for precursor delivery utilizing the melting point depression of solid deposition precursors in the presence of supercritical fluids
249	6,881,800		Processes and apparatus for continuous solution polymerization
250	6,881,700		Dealuminized catalyst carrier, method of production, and method for hydrating C2 or C3 olefins with water

251	6,881,699		Method for producing a dealuminized catalyst support
252	6,880,560		Substrate processing apparatus for processing substrates using dense phase gas and sonic waves
253	6,880,326		High regression rate hybrid rocket propellants and method of selecting
254	6,878,466		Method for improving the reliability of brittle materials through the creation of a threshold strength
255	6,874,513		High pressure processing apparatus
256	6,858,179		Process for producing sterile water for injection from potable water
257	6,857,437		Automated dense phase fluid cleaning system
258	6,849,678		Polymerization, compatibilized blending, and particle size control of powder coatings in a supercritical fluid
259	6,848,269		Process and apparatus for the recovery of krypton and/or xenon
260	6,846,562		Method of forming light dispersing fiber and fiber formed thereby
261	6,845,900		Methods for producing weld joints having thermally enhanced heat-affected-zones with excellent fracture toughness
262	6,844,561		Rotating aperture system
263	6,843,193		Transonic hull and hydrofield (part III)
264	6,841,031		Substrate processing apparatus equipping with high-pressure processing unit
265	6,828,292		Domestic fabric article refreshment in integrated cleaning and treatment processes
266	6,825,588		Uninterruptible power supply using a high speed cylinder flywheel
267	6,825,260		Nanoporous interpenetrating organic-inorganic networks
268	6,823,880		High pressure processing apparatus and high pressure processing method
269	6,821,554		Polyol-based method for forming thin film aerogels on semiconductor substrates
270	6,821,485		Method and structure for microfluidic flow guiding
271	6,821,481		Continuous processing method and continuous processing apparatus for liquid-form substance, and liquid-form substance processed thereby
272	6,821,429		Method and device for capturing fine particles by trapping in a solid mixture of carbon dioxide snow type
273	6,821,413		Method and apparatus for continuous separation and reaction using supercritical fluid
274	6,818,072		High-strength heat-resistant steel, process for producing the same, and process for producing high-strength heat-resistant pipe
275	6,818,021		Domestic fabric article refreshment in integrated cleaning and treatment processes
276	6,817,193		Method for operating a refrigerant circuit, method for operating a motor vehicle driving engine, and refrigerant circuit
277	6,813,895		Supercritical pressure regulation of vapor compression system by regulation of adaptive control
278	6,805,801		Method and apparatus to remove additives and contaminants from a supercritical processing solution
279	6,801,593		Subcritical reactivity measurement method
280	6,800,773		Chemical process
281	6,800,316		Method for fractionating cooking oil
282	6,800,272		Process for the preparation of ZSM-5 catalyst
283	6,799,587		Apparatus for contaminant removal using natural convection flow and changes in solubility concentrations by temperature
284	6,797,738		Open pore biodegradable matrices
285	6,796,275		Method and apparatus for calculating minimum valve lift for internal combustion engines
286	6,796,137		Air conditioning system comprising an electronic control device
287	6,795,991		Apparatus for conserving vapor in a carbon dioxide dry cleaning system
288	6,795,780		Fluid energy pulse test system--transient, ramp, steady state tests
289	6,794,544		Method for the preparation of tetrahydrobenzothiepines
290	6,794,522		Process for preparing a deuterated or tritiated compound
291	6,793,975		Methods of chemical vapor deposition and powder formation
292	6,793,793		Electrochemical treating method such as electroplating and electrochemical reaction device therefor
293	6,792,759		High density combined cycle power plant process
294	6,790,790		High modulus filler for low k materials
295	6,790,707		Method of preparing a sample of a semiconductor structure for adhesion testing
296	6,774,421		Gapped-plate capacitor
297	6,774,262		Method of novel noncatalytic organic synthesis
298	6,773,581		System and method for solids transport in hydrothermal processes
299	6,766,810		Methods and apparatus to control pressure in a supercritical fluid reactor
300	6,765,113		Production of aromatic carboxylic acids

301	6,764,552		Supercritical solutions for cleaning photoresist and post-etch residue from low-k materials
302	6,763,271		Tracking sustained chaos
303	6,755,871		Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent
304	6,751,959		Simple and compact low-temperature power cycle
305	6,750,336		Method of production of lactam
306	6,750,062		Method and device for studying the effect of a supercritical fluid on the transition of a material from one condensed phase to the other and their application in the case of a polymer material
307	6,749,816		High-pressure treatment apparatus, feeding method thereto and protection method thereof
308	6,746,788		Concentration cells utilizing external fields
309	6,746,695		Pharmaceutical preparations of bioactive substances extracted from natural sources
310	6,741,669		Neutron absorber systems and method for absorbing neutrons
311	6,740,785		Catalytic oxidation of organic substrates by transition metal complexes in organic solvent media expanded by supercritical or subcritical carbon dioxide
312	6,740,416		Aerogel substrate and method for preparing the same
313	6,740,414		Magnetic recording media and magnetic recording apparatus used thereof
314	6,740,216		Potentiometric sensor for wellbore applications
315	6,739,141		Supercritical pressure regulation of vapor compression system by use of gas cooler fluid pumping device
316	6,738,446		System and method for radioactive waste destruction
317	6,737,254		Supercritical extraction of taxanes
318	6,736,859		Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent
319	6,733,586		High throughput non-photochemical laser induced nucleation
320	6,730,370		Method and apparatus for processing materials by applying a controlled succession of thermal spikes or shockwaves through a growth medium
321	6,728,092		Formation of thin film capacitors
322	6,723,363		Coating foods and pharmaceuticals with an edible polymer using carbon dioxide
323	6,718,915		Horizontal spiral tube boiler convection pass enclosure design
324	6,717,009		Method for making high-purity naphthalenedicarboxylic acid
325	6,716,663		Method for removing foreign matter, method for forming film, semiconductor device and film forming apparatus
326	6,716,107		Containerless sheet flow water ride
327	6,715,450		Fossil-fuel fired continuous-flow steam generator
328	6,713,316		Method for removing foreign matter, method for forming film, semiconductor device and film forming apparatus
329	6,712,973		Process and device for separation with variable-length chromatographic zones
330	6,712,081		Pressure processing device
331	6,709,602		Process for hydrothermal treatment of materials
332	6,709,595		Method and installation for setting in adsorbed state on a porous support active compounds contained in a product
333	6,708,513		CO2-module for cooling and heating
334	6,707,205		High-speed, high-power rotary electrodynamic machine with dual rotors
335	6,706,689		Treatment of acute coronary syndrome with GLP-1
336	6,705,103		Device and method for cooling
337	6,701,721		Stirling engine driven heat pump with fluid interconnection
338	6,699,808		High-solids SiO2 dispersions, process for producing them, and their use
339	6,698,234		Method for increasing efficiency of a vapor compression system by evaporator heating
340	6,698,214		Method of refrigeration with enhanced cooling capacity and efficiency
341	6,694,763		Method for operating a transcritical refrigeration system
342	6,693,222		Process for splitting water-soluble ethers
343	6,691,536		Washing apparatus
344	6,691,430		High-pressure drying apparatus, high-pressure drying method and substrate processing apparatus
345	6,689,311		Method and apparatus for manufacturing sinter, method for measuring concentration of plasticizer, evaluation method, and evaluation apparatus
346	6,685,394		Partial shroud with perforating for VIV suppression, and method of using
347	6,684,643		Process for the operation of a gas turbine plant
348	6,684,624		High regression rate hybrid rocket propellants
349	6,680,554		Aircraft, particularly a helicopter, transmission system
350	6,673,234		Combined process of low degree solvent deasphalting and delayed coking

351	6,673,171		Medium carbon steel sheet and strip having enhanced uniform elongation and method for production thereof
352	6,672,732		Micromechanical oscillating device
353	6,670,407		Biofunctional polymers prepared in supercritical fluid
354	6,667,019		Rare earth oxide fluoride nanoparticles and hydrothermal method for forming nanoparticles
355	6,666,074		Apparatus for conducting high-temperature liquid chromatography analysis
356	6,666,050		Apparatus for conserving vapor in a carbon dioxide dry cleaning system
357	6,660,176		Molecular imprinting of small particles, and production of small particles from solid state reactants
358	6,658,888		Method for increasing efficiency of a vapor compression system by compressor cooling
359	6,656,436		Device for transforming chemical structures in a fluid comprising a solvent and salts by ultrasonic action
360	6,649,776		Methylenelactone synthesis in supercritical fluids
361	6,649,516		Method for manufacturing a composite member from a porous substrate by selectively infiltrating conductive material into the substrate to form via and wiring regions
362	6,649,091		Electrically conducting ruthenium dioxide aerogel composite
363	6,649,062		Fluid-membrane separation
364	6,647,742		Expander driven motor for auxiliary machinery
365	6,642,407		Production, purification and polymerization of aromatic dicarboxylic acids
366	6,642,330		Supercritical fluid pressure sensitive adhesive polymers and their preparation
367	6,641,678		Methods for cleaning microelectronic structures with aqueous carbon dioxide systems
368	6,638,749		Carbon dioxide soluble surfactant having two fluoroether CO2-philic tail groups and a head group
369	6,634,576		Milled particles
370	6,632,878		Production process for polymers with hydroxyl groups and polymers obtained by the process
371	6,630,761		Combination mechanical and magnetic support for a flywheel power supply
372	6,628,002		Heat transfer system with supracritical fluid
373	6,627,246		Process for coating stents and other medical devices using super-critical carbon dioxide
374	6,624,299		Process for producing cellulose acetate
375	6,624,092		Method for forming low dielectric constant insulating layer with foamed structure
376	6,620,559		Photomask, method of lithographically structuring a photoresist layer with the photomask, and method of producing magnetic memory elements
377	6,619,368		Method for imaging inclusions in investment castings
378	6,619,041		Steam generation apparatus and methods
379	6,616,849		Method of and system for continuously processing liquid materials, and the product processed thereby
380	6,615,587		Combustion device and method for burning a fuel
381	6,613,945		Resolution method for a racemic mixture of aldehydes
382	6,613,358		Sustained-release composition including amorphous polymer
383	6,613,157		Methods for removing particles from microelectronic structures
384	6,610,251		Method of sterilizing medical instruments
385	6,608,878		Method and device for monitoring the power rise during startup of a nuclear reactor (diversitary excursion monitoring)
386	6,606,848		High power density combined cycle power plant system
387	6,602,545		Method of directly making rapid prototype tooling having free-form shape
388	6,602,351		Methods for the control of contaminants following carbon dioxide cleaning of microelectronic structures
389	6,601,438		Apparatus for conducting high-temperature liquid chromotography analysis
390	6,598,358		Use of aerogels for deadening structure-borne and/or impact sounds
391	6,596,093		Methods for cleaning microelectronic structures with cyclical phase modulation
392	6,596,077		Controlled nucleation of protein crystals
393	6,592,938		Method for coating particles
394	6,590,053		Supercritical fluid pressure sensitive adhesive polymers and their preparation
395	6,589,592		Methods of coating articles using a densified coating system
396	6,589,355		Cleaning processes using hydrofluorocarbon and/or hydrochlorofluorocarbon compounds
397	6,588,285		Fuselage pitot-static tube and the aerodynamic profile of its strut
398	6,586,434		Method for the preparation of tetrahydrobenzothiepines
399	6,585,958		Medicinal aerosol formulations
400	6,585,890		Process for producing sterile water for injection from potable water

401	6,582,666		Apparatus for high flux photocatalytic pollution control using a rotating fluidized bed reactor
402	6,582,508		Process for fine division of organic pigments
403	6,577,697		Field analysis of geological samples using delayed neutron activation analysis
404	6,576,185		System and method for hydrothermal reactions-three layer liner
405	6,576,066		Supercritical drying method and supercritical drying apparatus
406	6,574,138		Memory cell configuration and method for operating the configuration
407	6,572,759		Method and apparatus for treating aqueous medium
408	6,569,480		Liquefied gas extraction process
409	6,569,245		Method and apparatus for applying a powder coating
410	6,568,199		Method for optimizing coefficient of performance in a transcritical vapor compression system
411	6,565,682		Process for producing high-strength heat-resistant pipe
412	6,564,567		Method and device for heating and cooling a compartment of a motor vehicle
413	6,562,914		Process for making propylene homo or copolymers
414	6,562,898		Resin composition and manufacturing method therefor
415	6,562,605		Extraction of water soluble biomaterials from fluids using a carbon dioxide/surfactant mixture
416	6,562,146		Processes for cleaning and drying microelectronic structures using liquid or supercritical carbon dioxide
417	6,558,622		Sub-critical fluid cleaning and antimicrobial decontamination system and process
418	6,558,432		Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent
419	6,554,774		Method and apparatus for assessing hemodynamic properties within the circulatory system of a living subject
420	6,551,626		Composition containing pyrrolizidine-alkaloid-free petasites
421	6,551,561		Apparatus for decoupled thermo-photocatalytic pollution control
422	6,551,517		Method for transforming chemical structures in a fluid under pressure and in high temperature
423	6,550,974		Bearing assembly for a helicopter rear transmission shaft
424	6,548,647		Process for preparing azo colorants
425	6,541,278		Method of forming film for semiconductor device with supercritical fluid
426	6,539,536		Electronic design automation system and methods utilizing groups of multiple cells having loop-back connections for modeling port electrical characteristics
427	6,537,395		Process for producing gray cast iron for use in high speed machining with cubic boron nitride and silicon nitride tools
428	6,537,364		Process for fine division of organic pigments by precipitation
429	6,536,380		Fossil-fuel heated steam generator, comprising dentrification device for heating gas
430	6,532,550		Process protection system
431	6,531,035		Apparatus and method for low flux photocatalytic pollution control
432	6,528,669		Recovery of polyunsaturated fatty acids from urea adducts
433	RE38,001		Cleaning with liquid gases
434	6,526,115		Supercritical-pressure water cooled reactor and power generation plant
435	6,520,767		Fuel delivery system for combusting fuel mixtures
436	6,519,926		Hydrothermal conversion and separation
437	6,519,847		Surface treatment of prefinished valve seat inserts
438	6,517,840		Production of a product enriched in isoflavone values from natural sources
439	6,517,752		Surface reforming method for plastic molded product
440	6,517,694		Yttria-stabilized zirconia membrane electrode
441	6,514,556		Method and composition for washing poultry during processing
442	6,514,454		Sol-gel process using porous mold
443	6,510,739		Apparatus for continuously monitoring liquid level conditions in a liquid-vapor separating device
444	6,507,191		NMR cell system for supercritical fluid measurements and high-pressure cell for NMR
445	6,505,807		Blower motor with annular damping element
446	6,503,360		Etching method and apparatus
447	6,500,350		Formation of thin film resistors
448	6,499,463		Dual fuel source diesel engine
449	6,499,440		Fossil-fired steam generator
450	6,499,313		Process and apparatus for generating high-purity nitrogen by low-temperature fractionation of air