Industrial Chemistry: New Applications, Processes and Systems

330 Pages·2011·7.721 MB·English

by  Harold H. Trimm (ed.), William Hunter Jr. (ed.)

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.
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Contents
Introduction 9
1. Trace Determination of Linear Alkylbenzene Sulfonates: 11
Application in Artificially Polluted Soil—Carrots System
Caroline Sablayrolles, Mireille Montréjaud-Vignoles,
Jérôme Silvestre and Michel Treilhou
2. Are Biogenic Emissions a Significant Source of Summertime 23
Atmospheric Toluene in the Rural Northeastern United States?
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
3. Mathematical Modeling of Perfect Decoupled Control System 47
and its Application: A Reverse Osmosis Desalination
Industrial-Scale Unit
C. Riverol and V. Pilipovik
4. Tula Industrial Complex (Mexico) Emissions of SO and 56
2
NO During the MCMA 2006 Field Campaign Using a Mobile
2
Mini-DOAS System
C. Rivera, G. Sosa, H. Wöhrnschimmel, B. de Foy, M. Johansson
and B. Galle
© 2011 by Apple Academic Press, Inc.
6 Industrial Chemistry: New Applications, Processes and Systems
5. Hit from Both Sides: Tracking Industrial and Volcanic Plumes 75
in Mexico City with Surface Measurements and OMI SO
2
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
6. Characterization of a β-Glucanase Produced by Rhizopus 109
microsporus var. microsporus, and Its Potential for Application
in the Brewing Industry
Klecius R. Silveira Celestino, Ricardo B. Cunha and
Carlos R. Felix
7. Chemical Analysis and Risk Assessment of Diethyl Phthalate 125
in Alcoholic Beverages with Special Regard to Unrecorded Alcohol
Jenny Leitz, Thomas Kuballa, Jürgen Rehm and Dirk W. Lachenmeier
8. Effects of Photochemical Formation of Mercuric Oxide 142
Evan J. Granite, Henry W. Pennline and James S. Hoffman
9. Novel Sorbents for Mercury Removal from Flue Gas 151
Evan J. Granite, Henry W. Pennline and Richard A. Hargis
10. Toward a New U.S. Chemicals Policy: Rebuilding the 176
Foundation to Advance New Science, Green Chemistry,
and Environmental Health
Michael P. Wilson and Megan R. Schwarzman
11. Biofilm Reactors for Industrial Bioconversion Processes: 202
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 242
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 263
Ragaiy Zidan, Brenda L. Garcia-Diaz, Christopher S. Fewox,
Andrew Harter, Ashley C. Stowe and Joshua R. Gray
14. Solving the Structure of Metakaolin 274
Claire E. Whitea, John L. Provisa, Thomas Proffenb,
Daniel P. Rileyc and Jannie S. J. van Deventera
© 2011 by Apple Academic Press, Inc.
Contents  77
15. An 8-Fold Parallel Reactor System for Combinatorial 288
Catalysis Research
Norbert Stoll, Arne Allwardt, Uwe Dingerdissen and Kerstin Thurow
16. Assessing the Reliability and Credibility of Industry Science 306
and Scientists
Craig S. Barrow and James W. Conrad Jr.
Index 318

© 2011 by Apple Academic Press, Inc.
IntroduCtIon
Industrial chemistry is the practical application of chemistry to industrial pro-
cesses. 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. Indus-
trial chemists use their knowledge of chemistry to turn these substances into con-
sumer 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 frac-
tionating 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 mol-
ecules (monomers), which are then reassembled into long polymers. The proper-
ties 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 chem-
ists 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 pro-
duction of sulfuric acid as a means of estimating country’s manufacturing capa-
bilities.
— 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, waste-
water, 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 ap-
plied 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 high-
performance 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]. Commer-
cially 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 2 millions tons per year [5]. The prop-
erties 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 homo-
logues 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 4 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 1. 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 formula-
tions of fertilizers and pesticides [11]. They are thus present in many compart-
ments 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 sur-
face waters at 2–47 μgL-1 concentration range [9], and in soil at concentrations
below 1 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 us-
ing 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 wastewa-
ter 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 ap-
plied to plant analysis. Specific purification steps were needed. The main problem
for analysis of organic pollutants in plants comes from the complexity of the ma-
trix. 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.