Industrial chemistry new applications processes and systems

Industrial Chemistry New Applications, Processes and Systems Harold H Trimm, PhD, RSO Chairman, Chemistry Department, Broome Community College; Adjunct Analytical Professor, Binghamton University, Binghamton, New York, U.S.A William Hunter III Researcher, National Science Foundation, U.S.A Apple Academic Press © 2011 by Apple Academic Press, Inc CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 Apple Academic Press, Inc 3333 Mistwell Crescent Oakville, ON L6L 0A2 Canada © 2011 by Apple Academic Press, Inc Exclusive worldwide distribution by CRC Press an imprint of Taylor & Francis Group, an Informa business No claim to original U.S Government works Version Date: 20120830 International Standard Book Number-13: 978-1-4665-6265-3 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot 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Danvers, MA 01923, 978-750-8400 CCC is a not-for-profit organization that provides licenses and registration for a variety of users For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com For information about Apple Academic Press product http://www.appleacademicpress.com © 2011 by Apple Academic Press, Inc Contents Introduction 9   Trace Determination of Linear Alkylbenzene Sulfonates: Application in Artificially Polluted Soil—Carrots System Caroline Sablayrolles, Mireille Montréjaud-Vignoles, Jérôme Silvestre and Michel Treilhou   Are Biogenic Emissions a Significant Source of Summertime Atmospheric Toluene in the Rural Northeastern United States? 47 C Riverol and V Pilipovik   Tula Industrial Complex (Mexico) Emissions of SO2 and NO2 During the MCMA 2006 Field Campaign Using a Mobile Mini-DOAS System 23 M L White, R S Russo, Y Zhou, J L Ambrose, K Haase, E K Frinak, R K Varner, O W Wingenter, H Mao, R Talbot and B C Sive   Mathematical Modeling of Perfect Decoupled Control System and its Application: A Reverse Osmosis Desalination Industrial-Scale Unit 11 C Rivera, G Sosa, H Wöhrnschimmel, B de Foy, M Johansson and B Galle © 2011 by Apple Academic Press, Inc 56 6  Industrial Chemistry: New Applications, Processes and Systems   Hit from Both Sides: Tracking Industrial and Volcanic Plumes in Mexico City with Surface Measurements and OMI SO2 Retrievals During the MILAGRO Field Campaign B de Foy, N A Krotkov, N Bei, S C Herndon, L G Huey, A.-P Martínez, L G Ruiz-Suarez, E C Wood, M Zavala and L T Molina   Characterization of a β-Glucanase Produced by Rhizopus microsporus var microsporus, and Its Potential for Application in the Brewing Industry Klecius R Silveira Celestino, Ricardo B Cunha and Carlos R Felix   Chemical Analysis and Risk Assessment of Diethyl Phthalate in Alcoholic Beverages with Special Regard to Unrecorded Alcohol Jenny Leitz, Thomas Kuballa, Jürgen Rehm and Dirk W Lachenmeier   Effects of Photochemical Formation of Mercuric Oxide Evan J Granite, Henry W Pennline and James S Hoffman   Novel Sorbents for Mercury Removal from Flue Gas Evan J Granite, Henry W Pennline and Richard A Hargis 10 Toward a New U.S Chemicals Policy: Rebuilding the Foundation to Advance New Science, Green Chemistry, and Environmental Health Michael P Wilson and Megan R Schwarzman 11 Biofilm Reactors for Industrial Bioconversion Processes: Employing Potential of Enhanced Reaction Rates Nasib Qureshi, Bassam A Annous, Thaddeus C Ezeji, Patrick Karcher and Ian S Maddox 12 Techno-Economic Analysis for the Conversion of Lignocellulosic Biomass to Gasoline via the Methanol-to-Gasoline (MTG) Process S B Jones, Y Zhu 13 Aluminum Hydride: A Reversible Material for Hydrogen Storage Ragaiy Zidan, Brenda L Garcia-Diaz, Christopher S Fewox, Andrew Harter, Ashley C Stowe and Joshua R Gray 14 Solving the Structure of Metakaolin Claire E Whitea, John L Provisa, Thomas Proffenb, Daniel P Rileyc and Jannie S J van Deventera © 2011 by Apple Academic Press, Inc 75 109 125 142 151 176 202 242 263 274 Contents     15 An 8-Fold Parallel Reactor System for Combinatorial Catalysis Research Norbert Stoll, Arne Allwardt, Uwe Dingerdissen and Kerstin Thurow 16 Assessing the Reliability and Credibility of Industry Science and Scientists Craig S Barrow and James W Conrad Jr 288 306 Index 318 © 2011 by Apple Academic Press, Inc Introduction Industrial chemistry is the practical application of chemistry to industrial processes It is closely allied to the field of chemical engineering, where reactions are run on a large scale and the economics of the process are being constantly evaluated In industry, the main focus is to make a profit Industrial chemists take readily available raw materials and turn them into finished products for the consumer; the lower the price of the raw material, the better the economics of the process Common raw materials include salts, limestone, and petroleum Industrial chemists use their knowledge of chemistry to turn these substances into consumer products such as synthetic fibers, dyes, pigments, agricultural chemicals, drugs, packaging materials, plastics, and polymers One of the largest applications of industrial chemistry is the refining of crude oil into various products such as liquefied petroleum gas, naphtha, gasoline, kerosene, jet fuel, diesel, heating oil, greases, waxes, coke, and asphalt In oil refineries, crude oil is separated into various consumer products by the process of distillation The crude oil is heated and the vapors rise through a fractionating tower to a point corresponding to their boiling point There is a great deal of chemistry and research occurring at the cracking and reforming units, which can break down heavier molecules or reassemble smaller molecules to tailor the products formed to consumer demand The green revolution now allows farmers to produce as much as ten times the crop yield as before Much of this increase in the world’s food supply is due to © 2011 by Apple Academic Press, Inc 10  Industrial Chemistry: New Applications, Processes and Systems the production of chemical fertilizers by the agrochemical industry The Haber reaction allows agrochemists to turn the raw materials nitrogen and hydrogen into ammonia, which is then turned into fertilizer The process is very energy intensive, and there is intense research to improve the process Plastics are usually produced by disassembling fossil fuels into simple molecules (monomers), which are then reassembled into long polymers The properties of the plastic produced can be controlled by which monomers are selected, the length of the polymer chain, and how the chains interact (crosslinking) Plastics have become an integral part of everyday life They are used for packaging as well as major structural components of consumer products The majority of chemists are hired by industry Some of the areas where chemists are employed include agriculture, biotechnology, education, chemical sales, consulting, environmental, food and flavor, forensics, geochemistry, hazardous waste, health, pharmaceuticals, petroleum, polymer, paper, research, and water treatment Industrial chemists are constantly working on ways to produce consumer goods with less cost and less waste There is an increased focus on green chemistry, which is the design of chemical products and processes that reduce or eliminate the use or generation of hazardous substances Some of the fields that are studied by industrial chemists include agricultural, organic, pharmaceutical, soap, beauty aids, rubber, resin, paint, polymer, dye, pigment, inorganic, and household and office products By mass, the largest industrial chemistry products are petroleum, chloralkali, sulfuric acid, ammonia, and phosphoric acid Economists use the production of sulfuric acid as a means of estimating country’s manufacturing capabilities — Harold H Trimm, PhD, RSO © 2011 by Apple Academic Press, Inc Trace Determination of Linear Alkylbenzene Sulfonates: Application in Artificially Polluted Soil—Carrots System Caroline Sablayrolles, Mireille Montréjaud-Vignoles, Jérôme Silvestre and Michel Treilhou Abstract Surfactants are widely used in household and industrial products The risk of incorporation of linear alkylbenzene sulfonates (LAS) from biosolids, wastewater, and fertilizers land application to the food chain is being assessed at present by the European Union In the present work, a complete analytical method for LAS trace determination has been developed and successfully applied to LAS (C10–C13) uptake in carrot plants used as model These carrots were grown in soil with the trace organics compounds added directly into the plant containers in pure substances form LAS trace determination (μg kg-1 © 2011 by Apple Academic Press, Inc 12  Industrial Chemistry: New Applications, Processes and Systems dry matter) in carrots samples was achieved by Soxtec apparatus and highperformance liquid chromatography-fluorescence detection The methodology developed provides LAS determination at low detection limits (5 μg kg-1 dry matter) for carrot sample (2 g dry matter) with good recoveries rate (>90%) Transfer of LAS has been followed into the various parts of the carrot plant LAS are generally found in the carrot leaves and percentage transfer remains very low (0.02%) Introduction Linear alkylbenzene sulfonates (LASs) are synthetic anionic surfactants which were introduced in the 1960s as more biodegradable replacements for highly branched alkyl benzene sulfonates [1, 2] LASs are nonvolatile compounds produced by alkylation and sulfonation of benzene [3] LASs are a mixture of homologues and phenyl positional isomers, each containing an aromatic ring sulfonated at the para position and attached to a linear alkyl chain at any position except the terminal one (Figure 1) The product is generally used in detergents and cleaning products in the form of the sodium salt for domestic and industrial uses [2–4] Commercially available products are very complex mixtures containing homologues with alkyl chains ranging from 10 to 13 carbon units (C10–C13) It corresponds to a compromise between cleaning capacity, on the one hand and biodegrading and toxicity, on the other hand LASs have been extensively used for over 30 years with an established global consumption of millions tons per year [5] The properties of LASs differ greatly depending on the alkyl chain length and position on benzene sulfonate group It has been found that longer LASs homologues have higher octanol/water partition coefficient (Kow) values [6, 7] In fact, the homologues with long chain have a greater capacity of adsorption on the solids and a greater insolubility in the presence of calcium or magnesium [8] In general, a decrease in alkyl chain length is accompanied by a decrease in toxicity [5] Dermal contact is the first source of human exposure to LASs Minor amounts of LASs may be ingested in drinking water, on utensils, and food The daily intake of LASs via these media (exposure from direct and indirect skin contact as well as from inhalation and from oral route in drinking water and dishware) can be estimated to be about μg/kg body weight [9] Occupational exposure to LASs may occur during the formulation of various products, but no chronic effects in humans have been noticed In great concentration (500–2000 mg kg-1), LASs could have a long-term effect [8] Indeed, their dispersing capacity could induce the release of others compounds present in soil [10] Generated scrubbing could involve the biodisponibility of these new compounds [2] © 2011 by Apple Academic Press, Inc Trace Determination of Linear Alkylbenzene Sulfonates  13 Figure General chemical structure of linear alkylbenzene sulfonate (LASs), where x and y corresponds with the number of CH2 on each side of the benzene sulphonate group (7 • x + y • 10) After use, LASs are discharged into wastewater treatment plants and dispersed into the environment through effluent discharge into surface waters and sludge disposal on lands Moreover, LASs can be introduced directly into the grounds: their emulsifying and dispersing properties make them essential in the formulations of fertilizers and pesticides [11] They are thus present in many compartments of the environment (sediments, aquatic environments, grounds…) LASs have been detected in raw sewage with a concentration range of 1–15 mgL-1 [9], in sludge with concentrations between 3–15 g kg-1 of dry matter [5, 8, 9], in surface waters at 2–47 μgL-1 concentration range [9], and in soil at concentrations below mg kg-1 [9, 10] LASs can be degraded under aerobic conditions however are persistent under anaerobic conditions [9, 12] Moreover, Lara-Martín and colleagues have shown that this surfactant can be degraded in sulfate-reducing environments such as marine sediments [13] The determination of LASs in environmental samples is usually performed using liquid chromatographic methods with UV detection [4, 14, 15], fluorescence detection [16], or mass spectrometric detection [15, 17, 18] which allows the identification and determination of LASs isomers and homologues There are a more limited number of gas chromatography methods [19, 20] which can be due to the low volatility of these compounds, being necessary the use of derivatisation reactions of the sulfonate group to obtain more volatile compounds Capillary electrophoresis with UV detection has been also used for the determination of the sum, homologues and isomers of LASs in household products and wastewater samples [21] Methods for the quantification of LASs in soil [18], in sewage sludge [18, 19], in sediment [18, 22], in biological organisms [17, 23], or in water [14, 15, 20, 24] can be reported However, these methods cannot be directly applied to plant analysis Specific purification steps were needed The main problem for analysis of organic pollutants in plants comes from the complexity of the matrix Plants have a particular tissue structure, which depend on the species and the age, and are highly rich in pigments, essential oil, fatty acids, or alcohols © 2011 by Apple Academic Press, Inc Index  319 aluminosilicates, 152, 284 precursors, 275 sorbent, 157, 168 aluminum electrode, 268, 270 amalgamation, 152, 160 Ambient Air Monitoring Network, 65, 81 AMF See air mass factor (AMF) anaerobic gases, 210, 223 analog-digital converters, 301 Analysis of Variance (ANOVA), 131 anionic surfactants, 12 ANOVA See Analysis of Variance (ANOVA) anthropogenic toluene emission, 40 comparison with biogenic toluene emissions, 41 anthropogenic tracers, 25 A pasteurianus, 226 argon carrier gas sorbent, 161 asbestos, 187 ASPEN ICARUS 2006.5, for estimating capital costs for methanol synthesis, 252 ASU See Air Separation Unit (ASU) atomic absorption spectrophotometry (AAS), 143, 160 atomic fluorescence spectrophotometry (AFS), 143, 144, 153, 154, 159, 170 autoclave array, 292–93, 297 automated reaction technology, 290 autotrophic microorganisms, 215 B Bacillus clausii, 116 Bacillus halodurans, 115, 116 Bacillus polymyxa, 225 Bacillus sp., 111, 113 bacterial cells, 206 bacterial flocculation, 212 bacteriocides, 207 Bacteroides succinogenes, 113, 115, 116 “band-aging” mechanism, 249 barley β-glucans, 111, 112, 114, 118 hydrolysis of, 116 © 2011 by Apple Academic Press, Inc Battelle–Columbus Laboratory (BCL) process, 246 BBP See butylbenzyl phthalate (BBP) benzene, 25, 29 1,3-1,4-β-glucanase enzymes, 112 binary oxide, 166 bioaccumulative chemicals, 181–82 biochemical industry, 203 biochemical reactors, 203 comparison of different types of, 204 biofilm-based treatment system, 212 biofilm reactors, 204 in biological wastewater treatment, 211–15 industrial/pilot-plant level acetic acid/vinegar production, 231 butanol production, 231–32 other processes, 232 wastewater treatment, 230–31 production of industrial chemicals in 2,3-butanediol, 225 butanol, 219–25 ethanol, 217–19 other chemicals, 226–28 productivities of, 214 rates of production of chemicals in barriers for, 229 diffusion limitations, 229–30 length of operation, 228–29 schematic diagrams of various types of, 211 types of, 209–11 biofilms, 204 in 2,3-butanediol production, 225 formation of calculations and data presentation for, 208–9 factors enhancing, 207–8 mechanism for, 206–7 for gas and odor treatment, 215–17 industrial applications of, 205 multi-species, 205 stages for development of, 206 320  Industrial Chemistry: New Applications, Processes and Systems types of, 205–6 biofilters, 216 biogenic toluene emissions, 39–40 comparison with anthropogenic toluene emissions, 41 biological aerated filters, 212 biological oxygen demand (BOD), 212 biological waste gas treatment, 215 biomass, 27, 101, 215 conversion to synthesis gas by gasification, 244 granules, 206 Biomass MTG system capital and operating cost analysis, 255–56 performance analysis results, 254–55 process design and modeling approach for feed handling and preparation, 246–47 methanol synthesis and PSA unit, 248–51 process design basis, 245 sensitivity analysis feedstock cost, 257 sensitivity to capital cost and yield, 257–59 simulation and economic assumptions, 251–53 bioparticles, 204, 206, 230 bioscrubbers, 216, 217 Blacksville coal, 158, 169 BOD See biological oxygen demand (BOD) bonechar, 205, 208, 220–25 bovine serum albumin, 119 Bradford method, for determination of proteins, 119 Bragg reflections, 275 brewing industry, 110–12, 115, 117, 118 Brownian motion, 206 2,3-butanediol, 225 butanol production, 219–25 butylbenzyl phthalate (BBP), 127 © 2011 by Apple Academic Press, Inc C calcination, 275, 276, 282 calcium chloromercurate, 169 CAMx See Comprehensive Airquality Model with extensions (CAMx) capillary electrophoresis, 13 capillary viscosimetry, 117, 121 carbohydrates, 111, 219 carbon monoxide (CO), 27, 80, 83, 148, 290, 302 carbon sorbents, 152, 158, 163, 165, 169, 170 carbon-to-mercury weight ratios, 152 carbonylation reaction precision under comparison conditions, 302–3 screening examinations, 303 carrier gases, 145, 160, 170 cascade controllers, 54 catalytic activity, 168 hydrogenation, 265 hydrotreating reactor, 251 cationic macroreticular resin, 218 C beijerinckii, 225 biofilm formation characteristics of, 220 production of solvents in packed bed biofilm reactors of, 221 CBI See confidential business information (CBI) C1–C5 alkyl nitrates, 27 C1–C2 halocarbons, 27 C2–C10 nonmethane hydrocarbons (NMHCs), 27–28 celite, 271 celkate sorbent (Cl-celkate), 157, 166, 168 cell immobilization, 219 techniques for, 203 cell mass concentration, 203, 230 cell recycle continuous reactors, 219 cellulose, 111 extraction, 14 Index  321 centralized gas supply system, 294 CEPCI See Chemical Engineering Plant Cost Index (CEPCI) CFE See Federal Commission of Electricity (CFE) C2H2/CO ratio, 31 Chemical Engineering Plant Cost Index (CEPCI), 252 chemical hazard information, 189 chemical industry science, 308–10 chemical industry scientists, 310–12 chemical oxygen demand (COD), 212 chemical promoter, 163, 170 chemisorption, 152, 163, 164, 168 chemotaxis, 206 chitin, 111, 112, 118 chlorofluorocarbons, 187 chromium oxide (Cr2O3), 157, 168 Chromosorb-W, 168 13 C labeled toluene, 25 Clean Air Act (1963), 179 “clean-air” reference spectrum, 60 Clean Water Act (1966), 179 Clostridium acetobutylicum, 219 biofilm formation characteristics of, 220 biofilm particles of, 223 production of solvents in packed bed biofilm reactors of, 221 scanning electron micrograph of adsorbed cells of, 222 Clostridium cells, 208 Clostridium thermocellum, 113 CM-cellulose, 114, 118 CO See carbon monoxide (CO) coal-fired utilities, 143, 152, 162 coal-to-gasoline plants, 244 COD See chemical oxygen demand (COD) coke, 9, 220, 250 cold vapor atomic absorption spectrophotometry (CVAAS), 159 Comprehensive Airquality Model with extensions (CAMx), 83, 88 © 2011 by Apple Academic Press, Inc Concentration Field Analysis, 59, 65, 68 conductivity behavior, 53 confidential business information (CBI), 187–88 continuous stirred tank reactors (CSTRs), 204, 209 controller integrators, 55 controllers, inversion of, 54 control loops, 52 control system for RO unit, design of, 50–55 corona discharge, 143 coumarin, 137 covalent bond formation, 203 crude oil, 57 CSTRs See continuous stirred tank reactors (CSTRs) CVAAS See cold vapor atomic absorption spectrophotometry (CVAAS) cyclic voltammagrams, 266, 267, 270 cyclohexane, 128, 130, 131 D DBP See di-n-butyl phthalate (DBP) decoupled control system, 52, 54, 55 DEHP See di-2-ethylhexl phthalate (DEHP) dehydroxylation, 274, 278, 281–84 denatonium benzoate (bitrex®), 137 denaturing agent, 126, 136–37 density functional theory (DFT), 276 DEP See diethyl phthalate (DEP) Department of Toxic Substances Control, 183 desalination, 48, 51, 55 desalination plants, 51 detergents, 12 DFT See density functional theory (DFT) di-2-ethylhexl phthalate (DEHP), 127 diethyl phthalate (DEP), 126 regulation for use of, 136 toxicological evaluation of, 136 use as denaturing agent, 136 322  Industrial Chemistry: New Applications, Processes and Systems Differential Optical Absorption Spectroscopy (DOAS), 59, 60, 67, 77 dimethyl ether (DME), 249 di-n-butyl phthalate (DBP), 127 dioxins, 187 distributed control system, 295 DME See dimethyl ether (DME) DOAS See Differential Optical Absorption Spectroscopy (DOAS) dry matter production, 18, 19 Dudhia shortwave scheme, 82 Duke Forest vegetative flux measurements, 28–29 E early life exposures, to xenobiotic chemicals, 182 ECDs See electron capture detectors (ECDs) EC 3.2.1.73 enzyme category, 114 ECHA See European Union Chemicals Agency (ECHA) EDX See energy-dispersive x-ray (EDX) effluent discharge, 13 EISA See Energy Independence and Security Act (EISA) electrochemical cells, 269 electron capture detectors (ECDs), 26 electrophoresis, 13, 118, 120 electrostatic precipitators, 143 Emergency Planning and Community Right-to-Know Act, 179 emissions from refinery and power plants, models for studying meteorological measurements, 60–61 pilot balloons, 61 radiosondes, 61 mini-DOAS instruments, 59–60 simulation models, 61–63 Emissions Inventory Improvement Program, 66 empirical model, for design of control system for RO unit, 50–55 energy-dispersive x-ray (EDX), 145 © 2011 by Apple Academic Press, Inc Energy Independence and Security Act (EISA), 244 entrapment, 203 Environmental Defense Fund, 177, 191 environmental health sciences, implications for, 190–91 data gap, 191 safety gap, 191–92 technology gap, 192 enzyme activity, 111 assay, 118–19 half-lives of, 115 production, 111–12 purification, 113–14 specificity, 114 EPS See extracellular polymeric substances (EPS) Escherichia coli, 218, 228 ethanol production, 217–19 Ethics in Government Act, 310 ethyl alcohol, 126 Eulerian modelling, of Popocatepetl emissions, 79–80 Eulerian pollutant transport, 83 European Commission Seventh Framework Program, 137 European Union Chemicals Agency (ECHA), 180 European Union, new chemical and product laws in, 192–93 exopolysaccharide alginate, 207 expanded granular sludge bed (EGSB) reactors, 204, 206, 209, 213, 229 extracellular polymeric substances (EPS), 206 ExxonMobil, 244 F FACE See Free Atmospheric Carbon Enrichment (FACE) Faroes Statement of the International Conference on Fetal Programming and Developmental Toxicity, 182 Index  323 FAS See fluid automation systems (FAS) FAS Bacosol magnetic valves, 291, 295 FBBR See fluidized bed biofilm reactors (FBBR) FBRs See fluidized bed reactors (FBRs) Federal Advisory Committee Act (1972), 309, 311 Federal Commission of Electricity (CFE), 59 Federal Insecticide, Fungicide and Rodenticide Act (1972), 309 Federal Register Act (1935), 309 feed handling and preparation, for conversion of biomass to gasoline gasification, 246 gas purification and steam reforming, 247 tar reforming and gas scrubbing, 247 fermentation, 205, 206, 208, 210, 218–19, 223, 225, 227, 230, 232 ferric oxide sorbent, 157 FEV1 See Forced Expiratory Volume in s (FEV1) FIDs See flame ionization detectors (FIDs) field bus protocol, 295 filtration rate, 117, 121 Fischer–Tropsch liquid transportation fuels, 244 flame ionization detectors (FIDs), 26 FLD See fluorescence detector (FLD) flue gas, 143, 162, 164, 170, 246 technologies for removing mercury from, 152 fluid automation systems (FAS), 294 fluidized bed biofilm reactors (FBBR), 212, 213 fluidized bed reactors (FBRs), 204, 209, 211–12 anaerobic treatment of wastewater in, 213 for production of butanol, 224 fluorescence detector (FLD), 17 fly ash CERF-FA-#2, 158 © 2011 by Apple Academic Press, Inc CERF-FA-#4, 158 DCFA-1, 158 unburned carbons from, 169–70 8-fold parallel reactor system chemical application system test for, 302–3 concept of, 290 current state of technology for, 289 hardware solution for archiving and protocol logging, 300 autoclave array, 292–93 gas supply system, 294–95 general description, 291–92 hardware reactor control, 295 homogenization, 293–94 local control system, 297–98 process communication, 301 process management and control, 300 software reactor control, 296–97 temperature control, 293 visualization and operation function, 299–300 operating modes isobar mode, 301 isochoric mode, 301 Forced Expiratory Volume in s (FEV1), 58 Francisco Pérez Ríos Power Plant (FPRPP), 57, 71 Free Atmospheric Carbon Enrichment (FACE), 28, 42 fuel evaporation and emissions of toluene, 34, 38–39 sources, 25 fuel octane grades, 25 fumaric acid, 226, 227 G gas chromatography, 13, 128 gas fractionation, 250 and HGT, 250–51 gasification, 244, 246 gasifier, 245, 246 324  Industrial Chemistry: New Applications, Processes and Systems gaslift reactors, 210 gasoline, 25, 33, 245 effect of capital cost on price of, 258 effect of feedstock cost on price of, 257 gas purification, 247 gas scrubbing, 247 gas supply system, 294–95 gas-to-gasoline plant, 244 Gel White, 220 geopolymers, 275, 276, 282, 283 GFS See Global Forecast System (GFS) global chemical production chart, 178 Global Forecast System (GFS), 82 Global Ozone Monitoring Experiment (GOME), 78 Global Positioning System (GPS), 60 1,3-1,4-β-glucans, 110 analysis using mass spectrometry, 120 assayed by reducing-sugar method, 118–19 capillary viscosimetry and filtration rate, 117 effect of metal ions on activity of, 116, 120 effect of pH and temperature on activity of, 114–15, 120 electrophoresis, 120 enzyme production, 111–12 enzyme purification, 113–14 enzyme specificity, 114 hydrolysis of, 112, 115, 117 kinetic parameters, 116–17, 120 protein determination using Bradford method, 119 purification protocol of, 112 purifications of, 119 thermostability of, 116 time course of production of, 112 Gluconobacter oxydans, 226 β-D-glucosyl residues, 111 GOME See Global Ozone Monitoring Experiment (GOME) Good Laboratory Practice (GLP) regulations, 308 © 2011 by Apple Academic Press, Inc GPS See Global Positioning System (GPS) granular biofilms, 203, 206, 210 green chemistry, 10, 177–80, 184, 188–90, 192 H halide salts, 169–70 hardware reactor control, 295 hazardous chemicals, 179, 182, 184, 189, 192 hazardous waste, 10, 155, 183, 184 heat sinks, 291 Heavy Gasoline Treater (HGT), 248, 251 heterogeneous catalysis, 289 hexavalent chromium, 187 HGT See Heavy Gasoline Treater (HGT) high pass filters, 60 high-performance liquid chromatography (HPLC), 17 high production volume (HPV) chemicals, 186 homogenous catalysis, 289 HPLC See high-performance liquid chromatography (HPLC) HPLC-FLD chromatogram, 17 Huber Kältemaschinen GmbH Unistat Tango device, 293 human and environmental health consequences, of chemical industry bioaccumulative chemicals, 181–82 early life exposures, 182 hazardous waste, 183 link to green chemistry, 184 and new chemicals policy, 183–84 occupational disease, 182–83 hydrocarbons, 165 hydrodesulfurization catalysts, 157 hydrogen bonding, 284 hydrogen economy, 264, 265 hydrogen storage materials for, 264, 270 methods for, 264 Index  325 hydrostatic pressure, 48 hydroxyl radical (OH), 29 I ICP-AES See inductively coupled argon plasma atomic emission spectroscopy (ICP-AES) IMADA field campaign, 79 immobilized cell reactors, 203 inductively coupled argon plasma atomic emission spectroscopy (ICP-AES), 145, 153, 159, 160 industrial chemicals, 177 and Earth’s ecosystems, 181 governed by U.S law, 179 laws governing regulation of, 184–85 production in biofilm reactors 2,3-butanediol, 225 butanol, 219–25 ethanol, 217–19 other chemicals, 226–28 industrial plumes, 67–68, 70 industrial pollutants, laws governing, 179 industrial waste gases, 215 Information Quality Act (2000), 308–9 Institute of Gas Technology (IGT) gasifier, 246 intelligent microcontrollers, 295 Inventory Update Rule (IUR), 181 ion exchange chromatography, 113 ion exchange resins, 217 i-pentane, 25 IP protocol, 297 iron oxide, 167, 171 iron sulfides, 158, 169 isobar mode operation, of reactor system, 301 isochoric mode operation, of reactor system, 301 IUR See Inventory Update Rule (IUR) K Kain–Fritsch convective parameterisation, 82 © 2011 by Apple Academic Press, Inc kaolinite, 220, 275, 278 dehydroxylation of, 284 histograms of bond lengths in, 280 Kevex spectrometer, 145 Klebsiella pneumoniae, 225 L lactic acid, 226–27 Lagrangian particle trajectories, 61 LAI See leaf area index (LAI) laminarin, 112, 114, 118 land cover mapping, 87 LASs See linear alkylbenzene sulfonates (LASs) lattice oxygen, 165 leaf area index (LAI), 28 limestone, 9, 275 limit of detection (LOD), 130, 133 limit of quantitation (LOQ), 130, 133 linear alkylbenzene sulfonates (LASs), 12 bioavailability in carrots, 19 chemical structure of, 13 degradation under aerobic conditions, 13 determination in environmental samples, 13, 15 experimental results application methods, 18–19 extraction time, 16–17 separation, calibration graphs, and limits of detection, 17–18 experimental studies sample analysis, 16 sample extraction, 15–16 samples collection, 14–15 standards and reagents used, 14 levels in core, peel, and leaves of carrot plants, 19 percentage repartition of, 19 risk of incorporation of, 14 transfer towards plants by water absorption, 19 treatment stages for, 15 liquefied petroleum gas (LPG), 245, 250 326  Industrial Chemistry: New Applications, Processes and Systems liquid-liquid extraction (LLE) method, 127, 130 liquid transportation fuels, 244 liver-toxic agents, 137 loblolly pine (Pinus taeda), 28 local control system, 297–98 LOD See limit of detection (LOD) Long-Range Research Initiative, 307, 308 LOQ See limit of quantitation (LOQ) LPG See liquefied petroleum gas (LPG) M MABR See membrane-aerated biofilm reactor (MABR) magnetic stirring systems, 290 malts, 111 manan, 118 manganese dioxide (MnO2), 167 Mars–Maessen mechanism, 165, 167 mass spectrometer (MS), 26 Material Safety Data Sheets, 188 MCMA See Mexico City Metropolitan Area (MCMA) mechanical vapor compression (MVC), 48, 49 medical waste incinerators, 152 MEE See multiple-effect evaporation (MEE) membrane-aerated biofilm reactor (MABR), 215 membrane cell reactors, 225 mercaptans, 168 mercuric chloride, 152, 170 mercuric oxide, 143 mercury detection of, 143 breakthrough curve for I-AC using AFS for, 163 emission control, 152 photochemical oxidation of, 144–45 photochemical removal of, 146 as photo sensitizer for formation of ozone, 143 © 2011 by Apple Academic Press, Inc reaction mechanism for capture of, 165–66 as semi-noble metal, 166 sorbents for activated carbons, 163–65 metal oxides, 165–68 metal sulfides, 168–69 noble metals, 170 unburned carbons from fly ash, 169–70 technologies for removal from flue gas, 152 thermal oxidation of, 142 mercury vanadate (HgV2O6), 165, 168 mesoscale meteorological simulations, 82 metakaolin, 275, 276 atomic structure representation of, 279 bond length distributions in, 281 density functional modeling of, 284 histograms of bond lengths in, 280 pair distribution functions of, 277 synthesis of, 284 metal oxides, 165–68 methanol synthesis and PSA unit, 248 capital costs for, 252 gas fractionation and HGT, 250–51 methanol-to-gasoline (MTG) process, 249–50 power generation, 251 process flow diagram of, 248 methanol-to-gasoline (MTG) process, 244, 249–50 block diagram of, 250 Mexican Air Quality Standard, 58 Mexican National Weather Service (SMN), 82 Mexican Petroleum (PEMEX), 59 Mexican Petroleum Institute (IMP), 61 Mexico City Metropolitan Area (MCMA), 57 air quality, 59, 80 atmospheric monitoring network of, 58 basin-scale wind transport, 78–79 measured and simulated SO2 in, 83 Index  327 meteorological modelling, 82–85 MILAGRO field campaign, 76, 77 percentage of mean SO2 concentrations in, 100 pollutants measurements, 81–82 results of measuring SO2 concentrations, 85–86 double impacts, 96–99 industrial impacts, 89–90 industrial surface impacts with volcano plume, 94–95 OMI evaluation, 87–89 volcano impacts, 90–93 SO2 emissions and detection, 76–78 SO2 peaks observed in, 59 statistics diagrams of simulated vs measured SO2 in, 84 MHR See Miguel Hidalgo Refinery (MHR) Michaelis–Menten plot, 116 microbes, 206 microbial cells, 203 microbial metabolism, 215 micro reaction reactors, 289 Miguel Hidalgo Refinery (MHR), 57, 71 MILAGRO field campaign, 76, 77, 80 MIMO system, 54 MobileDOAS software, 60 mobile mini-DOAS instruments, 59–60 Moderate Resolution Imaging Spectroradiometer (MODIS), 82 molecular mass standard proteins, 118 molecular sieves, 275 molybdenum sulfide (MoS2), 157, 168–69 molybdenum trioxide, 166 monoterpenes, 27, 37 moving-bed biofilm reactors, 211 MS See mass spectrometer (MS) MSF See multistage flash desalination (MSF) MTG technology See methanol-to-gasoline (MTG) process multiple-effect evaporation (MEE), 48 multistage flash desalination (MSF), 48 © 2011 by Apple Academic Press, Inc municipal solid waste, 152 MVC See mechanical vapor compression (MVC) N National Academies’ Board on Environmental Studies and Toxicology, 310 National Inventory of Emissions, Mexico, 66 natural gas, 244, 249, 255 natural osmosis, 48, 49 n-butane, 25 NCAR Improved Moment Algorithm, 82 Newman–Keuls tests, 19 n-hexane, 130 nitrogen dioxide (NO2), 57 effects on human health, 58 measurements of Tula industrial complex, 66 nitrogen oxides (NOx), 24, 57 emission inventories, 68 NMHCs See C2–C10 nonmethane hydrocarbons (NMHCs) NOAA HYSPLIT transport and dispersion model, 32 NOAH land surface model, 82 noble metals, 152, 153, 170 non-aqueous solution regeneration cycle, 265 nonvolatile compounds, 12 nucleic acids, 206 O occupational disease, 182–83 Occupational Safety and Health Act (1970), 179 octanol/water partition coefficient, 12 OECD See Organisation for Economic Cooperation and Development (OECD) Office of Government Ethics (1997), 310 olivine, 246 328  Industrial Chemistry: New Applications, Processes and Systems OMI See Ozone Monitoring Instrument (OMI) OMI Evaluation, of SO2 concentrations, 87–89 OMI sensors, 87 operating modes, of reactor system, 301 oral reference dose (RfD), 135 organic pollutants, 13 Organisation for Economic Cooperation and Development (OECD), 308 organism and enzyme production, 118 osmosis, 48, 205 osmotic equilibrium, 49 osmotic flow, 48 osmotic flux, 48 osmotic pressure, 48 oxidation catalysts, 167, 168 oxidizing agents, 168 oxygen diffusion, 214 ozone (O3), 24, 57, 80, 143, 147–49 Ozone Monitoring Instrument (OMI), 76, 78, 82, 87, 88, 90, 92, 94, 100, 102 P packed bed reactors (PBRs), 169, 170, 204, 209 for butanol production, 223 pair distribution function (PDF), 276, 277 Paperwork Reduction Act (1980), 309 parallel reaction systems, advantage of, 289 Parker NOVA pneumatic membrane valves, 291 particle trajectories, 61, 62, 70, 79 particulate matter, 24 PBRs See packed bed reactors (PBRs) PCS See plastic composite support (PCS) PDF See pair distribution function (PDF) PDFGetN software, 284 PEMEX See Mexican Petroleum (PEMEX) pentachlorophenol (PCP), 214 permeable membrane, 203 © 2011 by Apple Academic Press, Inc PGI proteins, 113 PGII proteins, 113 phagocytes, 207 phospholipids, 207 photochemical reactions, 57 photosensitized ozone reaction, 143 phthalates See also phthalic acid esters as environmental contaminants, 126 retention time and selected ions for analysis of, 129 subchronic and chronic toxic effects of, 127 tolerable daily intake (TDI) values, 127 toxicity of, 127 phthalic acid esters, 126 Pico de Tres Padres (PTP), 78, 81, 90 PID controller, 54, 154 pilot balloons, 57, 61 plain-to-plateau density current, 79 planktonic bacterial cells, 206 plastic composite support (PCS), 227 plasticizers, 126 platinum sorbent (Pt/wool), 157, 170 PMNs See premanufacturing notices (PMNs) pneumatic actuators, 294 pole-zero cancellation method, 52 polyacrylamide slab gels, 120 polychlorinated biphenyls (PCBs), 187 polymeric matrix, 206 polysaccharides, 110, 111, 207 Popocatépetl volcano, 59, 77 Portland cement, 275, 276 potassium iodide, 170 potassium iodomercurate, 169–70 potassium superoxide (KO2), 168 powder x-ray diffraction, 269 premanufacturing notices (PMNs), 187 pressure swing adsorption (PSA), 245 process transfer function matrix, 51–52 proteins, 119, 207 proton transfer reaction mass spectrometry (PTR-MS), 27 PSA See pressure swing adsorption (PSA) Index  329 Pseudomonas aeruginosa, 207 Pseudomonas fluorescens, 207 Pseudomonas fragi, 226 PTP See Pico de Tres Padres (PTP) PTR-MS See proton transfer reaction mass spectrometry (PTR-MS) Q Quantum Superdry light element detectors, 145 quartz cells, 145, 147, 148 quartz reactors, 143, 144, 146 quenching, 145 quenching agents, 143, 148 R radar wind profilers, 82 radiosondes, 61, 82, 95, 102 RAMA See Red Automática de Monitoreo Atmosférico (RAMA) Raman spectroscopy, 269 rate of reaction, 203, 204 RBC See rotating biological contactors (RBC) REACH See Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) reaction mechanism, for capture of mercury by oxide catalysts, 165–66 reaction technology, current state of, 289 reactor control system, control software and document layout, 298 real space refinement, 285 recycle gas-to-DME reactor effluent ratio, 250 recycling fermentation, 223 Red Automática de Monitoreo Atmosférico (RAMA), 65, 81 Reflex IV mass spectrometer, 120 reformulated gasoline (RFG) hydrocarbon, 25 Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), 180, 183 © 2011 by Apple Academic Press, Inc Regulatory Flexibility Act (1980), 309 Reid Vapor Pressure (RVP), 25 relative standard deviation (RSD), 133 remote sensing, 80, 82 renewable energy, 244 Resource Conservation and Recovery Act (1976), 179 Responsible Care initiative, 307 reverse osmosis (RO), 48 control system based on empirical model, 50–55 decoupled control system, 55 desalination unit, 51, 55 principles of, 49 Rhizobium sp., 112 Rhizopus microsporus var microsporus, 112, 113 enzyme production using, 118 identification of, 111 purifications of 1,3-1,4-β-glucanase from, 119 Rhizopus oryzae, 116, 226 Risk Policy Report (2002), 311 RMSEc See root mean square error (RMSEc) RO See reverse osmosis (RO) root mean square error (RMSEc), 84 rotary continuous reactors, 209 rotating biological contactors (RBC), 211, 212 RRTM longwave scheme, 82 RSD See relative standard deviation (RSD) RVP See Reid Vapor Pressure (RVP) S Saccharomyces cerevisiae, 217 Santa Ana Tlacotenco (SATL), 81 satellite remote sensing, 80, 82 SATL See Santa Ana Tlacotenco (SATL) scanning electron microscopy (SEM), 145 Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY), 78 330  Industrial Chemistry: New Applications, Processes and Systems SDS See sodium dodecylsulfate (SDS) secondary organic aerosol (SOA), 24 seed germination, 111 SEM See scanning electron microscopy (SEM) semi-noble metal, 166 silver staining method, 120 simultaneous nitrification and denitrification (SND), 214 single-loop controllers, 52 single-reaction systems, 289 SISO systems, 54 SND See simultaneous nitrification and denitrification (SND) SOA See secondary organic aerosol (SOA) Society of Toxicology, 310, 311 sodium dodecylsulfate (SDS), 14, 118 sodium perchlorate (NaClO4), 14 software reactor control, 296–97 sorbents, 152 characterization of, 156 prepared from fly ash, 158 procedures for measuring capacities of, 153–59 sorbent screening unit, 153 Soxtec System HT2 apparatus, 16 steam reforming, 244, 247 Streptomyces viridosporus, 226 succinic acid, 226, 227 sugarcane bagasse, 217 sulfate aerosols, 79, 80, 101 sulfur dioxide (SO2), 58, 166 basin-scale wind transport, 78–79 biomass emissions of, 101 emission inventories at Tula industrial complex, 66 emissions and detection, 76–78 ground measurements of, 80 measurement by OMI sensor, 87–89 time series of measured concentrations of, 91, 95, 98 volcanic emissions of, 78 sulfur transport, 79–80 sweetgum (Liquidambar styraciflua), 28 © 2011 by Apple Academic Press, Inc syngas, 244, 245, 247, 258 synthesis gas See syngas T Talaromyces emersonii, 111–12, 113 tar reforming, 247 TBR See trickling bed reactors (TBR) TCP/IP protocol, 297, 298, 301 TDI See tolerable daily intake (TDI) TEAI See Tenango del Aire (TEAI) techno-economic analysis (TEA), of conventional biomass to gasoline process, 259–60 TEDA See triethylenediamine (TEDA) Teflon, 208 Tenango del Aire (TEAI), 81, 90, 91, 93, 94, 97 tetrachloroethylene, 206 TGA See thermal gravimetric analysis (TGA) themolybdenum sulfide sorbent, 157 theodolites, 61 thermal conductivity mass flow controller, 154 thermal desalination systems, types of, 48 thermal gravimetric analysis (TGA), 269 thermal oxidation of mercury, 142 thermal vapor compression (TVC), 48 Thermoactinomyces vulgaris, 226 thermophilic aerobic systems, 212 thin films, 212 Thiobacillus thiooxidans, 216 thiols, 168 Thiosphaera pantotropha, 214 Thompson Farm air mass source regions influencing, 31 alfalfa toluene production before and after harvesting, 35 ambient VOC measurements, 26–27 comparison of i-pentane and toluene mixing ratios from, 33 estimates of source contributions summer toluene enhancements biogenic emissions, 39–40 Index  331 fuel evaporation, 38–39 influence of various sources on toluene levels at, 33–38 toluene-to-benzene ratio in, 32 toluene vs i-pentane mixing ratios at, 35 vegetative flux measurements, 27–28 warm season toluene enhancements at, 29–32 time-of-flight neutron diffraction, 284 tolerable daily intake (TDI), 127 toluene biogenic and anthropogenic emissions in New England, 41 13 C labeled, 25 effects on human central nervous system, 24 emission rates for sunflowers and pine trees, 25 fluxes, 35, 37, 40 fuel evaporation emissions of, 34 influence of various sources on toluene levels at Thompson Farm, 33–38 vs i-pentane mixing ratios at Thompson Farm, 35 methods for measuring emission of Duke Forest vegetative flux measurements, 28–29 Thompson Farm ambient VOC measurements, 26–27 Thompson Farm vegetative flux measurements, 27–28 as pollutant and respiratory irritant, 24 seasonal cycle in urban anthropogenic emissions of, 25 sources of, 25, 34 warm season enhancements at Thompson Farm, 29–32 toluene-to-benzene ratios, 25, 29 observed in air masses, 32 seasonal pattern of, 31 at Thompson Farm, 32 as tracers of urban anthropogenic influence, 30 © 2011 by Apple Academic Press, Inc toxicological evaluation of alcohols materials and methods used for chemicals and reagents, 127–28 GC/MS method, 128–29 glassware and reagent control, 128 optimization and validation studies, 130–31 samples, 129–30 statistics, 131 results method validation and sample measurement, 133–35 parameter optimization for LLE method, 131–33 Toxics Release Inventory, 37, 179 Toxic Substances Control Act (TSCA), 177–79, 181, 182, 184–90, 192, 309 trade secrets, and industrial chemical policy, 187–88 triboelectrostatic method, 158 1,1,2-trichlorotrifluoroethane, 130 Trichoderma harzianum, 116 Trichoderma sp., 111 trickling bed reactors (TBR), 209, 210 trickling filters, 212, 216 triethylamine (TEA), 264, 268, 271 triethylenediamine (TEDA), 266 2,2,4-trimethylpentane, 25 TSCA See Toxic Substances Control Act (TSCA) Tula industrial complex, 57, 58, 79 comparisons between measured and simulated emissions from, 67–68 NO2 measurements of, 66 SO2 and NOx emission inventories of, 66 Tula–Vito–Apasco industrial corridor, 57 TVC See thermal vapor compression (TVC) U ultraviolet (UV) detector, for elemental mercury, 154 ultraviolet fluorescence detector, 145 332  Industrial Chemistry: New Applications, Processes and Systems ultraviolet radiation, 143 United States Environmental Protection Agency (US EPA), 24 Chemical Assessment and Management Program, 186 Emissions Inventory Improvement Program, 66 New Chemical Program, 186 requirements under chemical and pesticide regulatory statutes, 309 Science Advisory Board, 310, 311 upflow anaerobic sludge blanket (UASB) reactors, 204, 206, 209, 210, 213 urban fuel evaporation emissions, 33 urban plume, 32, 79 U.S Centers for Disease Control and Prevention (CDC), 181 U.S chemical industry contribution to national and global economy, 180–81 human and environmental health consequences bioaccumulative chemicals, 181–82 early life exposures, 182 hazardous waste, 183 link to green chemistry, 184 and new chemicals policy, 183–84 occupational disease, 182–83 scale of chemical production, 181 U.S chemicals policy, 183–84 data gaps existing chemicals, 186 logical paralysis, 185–86 development of, 180 effects of policy, safety and technology gaps on, 189–90 policy gaps, 184–85 safety gaps barriers to action, 186–87 new chemicals, 187 trade secrets, 187–88 technology gaps education and market, 188–89 minimal investment, 188 © 2011 by Apple Academic Press, Inc U.S Department of Energy (DOE), 264 U.S Department of Energy’s Fossil Energy Program, 152 U.S EPA See United States Environmental Protection Agency (US EPA) UV fluorescence, 81 V vacuum sensors, 295 vanadium pentoxide (V2O5), 166, 168 VARIOMAG MICRO stirrer drives, 293 vertical diffusion coefficients, 84 vertically moving biofilm reactors, 211 vinegar, 204, 226 volatile organic compound (VOC), 24–26, 58, 215 Thompson Farm, measurements at, 26–27 W waste water treatment, 203, 204, 205 anaerobic treatment systems for, 213 biofilm reactors in biological, 211–15 membrane bioreactors for, 215 plants, 13 waterflow behavior of manipulated variable in real conditions, 54 comparison of behavior of, 53 water flux, 48 water-soluble pollutants, 216 Weather Research and Forecast (WRF) model, 61 Weather Research and Forecast model version 3.0.1, 82 wind vectors, 81 Win32 MDI (multiple-document interface) application, 298 W.R Grace Co., 249 W.R Grace Report, for estimating capital costs for methanol synthesis, 252 WSM6 microphysics scheme, 82 Index  333 X xenobiotic chemicals, 182 XPS See x-ray photoelectron spectroscopy (XPS) x-ray diffraction (XRD), 157, 159 x-ray photoelectron spectroscopy (XPS), 157, 159 XRD See x-ray diffraction (XRD) xylan, 111, 118 © 2011 by Apple Academic Press, Inc Y YSU boundary layer scheme, 82 Z zeolites, 244, 249, 282 zygomycete microfungus, 111, 118 See also Rhizopus microsporus var microsporus Zymomonas mobilis, 217, 218 ... chemistry in coastal New England (Griffin et al., 2004; Mao et al., 2006; White et al., 2008), © 2011 by Apple Academic Press, Inc 26  Industrial Chemistry: New Applications, Processes and Systems. .. species and the age, and are highly rich in pigments, essential oil, fatty acids, or alcohols © 2011 by Apple Academic Press, Inc 14  Industrial Chemistry: New Applications, Processes and Systems. .. Inc 56 6  Industrial Chemistry: New Applications, Processes and Systems   Hit from Both Sides: Tracking Industrial and Volcanic Plumes in Mexico City with Surface Measurements and OMI SO2 Retrievals