Sustainable Chemistry

Metrics for Environmental Analysis and Eco Efficiency

Various metrics and methods in engineering design are used to evaluate and measure the different aspects of the environmental impact of industrial activities and services. These metrics differ in terms of approach to manage this complex problem, involving various kinds of interactions. An in-depth analysis of this problems is beyond the scope of the present chapter, which will thus be limited to the classification used by Seager and Theis 18 . Sustainable metrics may be characterized in a...

Other Integrated HPPO Processes

Hppo Process

An integrated process has also been reported, but not implemented at a commercial level, by ARCO (now Lyondell) 21 . In this case, the O-donor species is produced by the autoxidation of aryl-substituted secondary alcohols (a-methyl benzyl alcohol) to ketones, and the resulting solution is used to feed the epoxidation reactor. The alcohol is then recovered by hydrogenating the ketone. The main difference with respect to the EniChem process is the higher temperature of the autoxidation process...

Life Cycle Tools

Life Cycle Assessment Stages

Many assessment methodologies have been developed that include not only the product or process but also the entire supply chain and disposal, that is, the cradle-to-grave approach 68, 69 . Apart from life cycle assessment (LCA) and life-cycle costing (LCC) 70 , the energy-based sustainability index (ESI) 52, 53 , MIPS (materials input per unit service 71 ) and MFA (materials flow accounting) 72 are also cradle-to-grave approaches. The main differences among all these indices lie in the way they...

Shutting Down A Sulfuric Acid Alkylation Unit Reactor

Alky Unit Configuration Pfd

Figure 12.5 Key reaction paths for alkylation and related reactions 9 . Low temperature (e.g., 70 C and below) yields a higher TMP product slate. This is a kinetic effect, and isomerization reactions are lowered with decreased temperature. The distribution of TMPs is highly dependent on temperature. The preferred high octane, 2,2,4 isomer is abundant at lower temperatures. Figure 12.5 9 covers many reactions alkylation, dimerization, self-alkylation, b-scission and H-transfer. Figure 12.6 14...

Selective Oxidation Examples of Directions to Improve Sustainability

Selective Oxidation

Some main directions towards improving sustainability that should be highlighted are (i) the use of new and clear oxidants, which is exemplified by the use of H2O2, (ii) the use of new feedstocks, which can be illustrated by the substitution of alkenes with alkanes, and (iii) the process development, which can be discussed by showing the developments arising from using new reactor opportunities and an integrated reactor catalyst design, as well as by substituting air with oxygen. Together with...

New Process for the Production of Biodiesel by Transesterification of Vegetable Oils with Heterogeneous Catalysis

Heterogeneous Process

Transport fuels gasoline (for cars), diesel (for trucks and cars) and kerosene (for aircrafts) are entirely dependent on oil, with no possibility for carbon capture (and sequestration). Furthermore, if we consider the predicted growth of transport fuel on a world scale, as illustrated in Figure 9.1 and summarized in Table 9.1, we can expect, at least in the 20 years, that the use of all fuels will grow, with kerosene having the fastest growth. In addition, gasoline, the dominant fuel in 2005,...

BioEtbe A New Component for Gasoline

Mtbe Reactor

Marco Di Girolamo and Domenico Sanfilippo 11.1 To face the remarkable growth in worldwide demand for energy in a sustainable way requires strong integration between fossil and renewable fuels. In fact, the uncertainty as to the quantity of crude oil reserves, its availability limited to a few regions affect oil prices and energy supply security and, moreover, combined with need to reduce greenhouse gas emissions, creates pressure to search for renewable or non-CO2-emitting energy technologies...

POonly Routes Several Approaches for Sustainable Alternatives

Propylene Oxide Supply Shortage

Alternative routes that do not produce sizeable quantities of coproducts and that do not use chlorine-based chemistry have already been, or will be, implemented at the commercial level. In April 2003, Sumitomo Chemical commercialized the first PO-only plant in Japan, which produces PO by oxidation of propene with cumyl hydroperoxide (the latter being obtained by hydroperoxidation of cumene) without a significant formation of coproducts. Nowadays, the plant located at the Chiba factory, a joint...

Bio Based Economy

Industrial biotechnology is a key technology to realizing the knowledge-based bioeconomy by transforming the knowledge of life sciences into new, sustainable, eco-efficient and competitive products. This includes an optimized combination of the biotechnology processes with classical and new biochemical processes - especially in the chemical, materials and biofuels sectors. The following three topics have been identified as being of major importance to facilitate the development of a bio-based...

Ecofining New Process for Green Diesel Production from Vegetable

Green Diesel Production

Franco Baldiraghi, Marco Di Stanislao, Giovanni Faraci, Carlo Perego, Terry Marker, Chris Gosling, Peter Kokayeff, Tom Kalnes, and Rich Marinangeli Existing technology for producing diesel fuel from vegetable oil has largely centered on the production of FAME biodiesel 1-3 . While FAME has many desirable qualities, such as high cetane, there are other issues associated with its use such as poor stability and high solvency, leading to filter plugging problems. Moreover, there has been little...

Industrial Uses of Biocatalysis

Sustainable Chemistry

The earliest industrial application of biocatalysts began without a scientific foundation in 1874 Christian Hansen founded the first biocatalysts company, which supplied enzymes for cheese production. Now, over 130 years after the founding of this enzyme business and significant progresses in scientific understanding 143 , the world annual turnover of biocatalysts is worth well over US 2 billion. More than 130 industrial biotransformation processes had been launched by 2002 144 , but the...

Enlarged Uses of Membrane Concepts

From the above, many functions may be imagined based on the employment ofthin layers selective mass transfer, chemical or biological reaction, fluid distribution or even energy transfer. Up to now, thin porous layers have been used mainly for mass transfer purposes. But there would be no impediment to take advantaging, for example, of the specific microporous structure and geometry of certain kinds of thin layers to use them for energy (heat) transfer. These new devices differ from classical...

From the Dream Reaction to the Real Process the Implemented HPPO Process

Uhde Methanol

The HPPO process has been implemented recently by BASF and The Dow Chemical Company the first plant has been in operation since November 2008 in Antwerp, Belgium. Dow acquired its PO technology from its 2001 purchase of EniChem's polyurethane business. BASF had been exploring HP-based routes to PO since the mid-1990s Dow and BASF began collaborating in 2003. The two companies have established a long-term partnership with Solvay SA (supplier of HP to the new facility). The HPPO plant is fed with...

Microengineering and Microtechnology

Substantial progress in microtechnologies has largely pushed the development and availability of novel micro-sized chemical apparatus (reactors, mixers, separators, heat-exchangers and analyzers) in recent years, making possible the accurate control of reaction conditions with respect to mixing, quenching and temperature profile 33-35, 74, 75 . Microfabricated chemical systems are now expected to have several advantages for chemical kinetic studies, chemical synthesis and, more generally, for...

Sustainability through Chemistry and the F3Factory

A key driving force promoting this change from green to sustainable chemistry vision is the European Technology Platform on Sustainable Chemistry (ETP SusChem) 6 promoted by Cefic (European Chemical Industry Council) and EuropaBio (European Association for Bioindustries). To implement this vision, however, requires not only a concerted strategy of the stakeholders of the sector (objective of the cited platform), but also the progressive introduction of radical new approaches to chemical...

Safety and Sustainability of Chemicals

A chemical substance is safe for a certain use if it is demonstrated that it poses no risk when taking into consideration risk reduction measures that reduce exposure of man or environment 86-88 . However, this is not enough to indicate that it is also a sustainable chemical. A sustainability target consists of the development of inherently safe chemicals (ISCs), for example, without risks for human health and the environment, even without specific exposure control. We may distinguish two...

Sustainable Product and Process Design

The building blocks for sustainable product and process design are engineering, catalysis and chemical synthesis to achieve intensified, more eco-efficient, environmentally benign and competitive processes and production technologies. Five main areas need to be developed to implement innovative process technologies and knowledge-based design as well as plant operation methodologies in chemical, pharmaceutical and biotechnological production 1. Diversification of the feedstock base. 2....

Principles of Green Chemistry Sustainable Chemistry and Risk

The previous section outlined briefly the historical development of the Green Chemistry Movement, which started in the early 1990s as a means of encouraging industry and academia to use chemistry for pollution prevention. More specifically, the green chemistry mission was To promote innovative chemical technologies that reduce or eliminate the use or generation of hazardous substances in the design, manufacture and use of chemical products. Practical motivations, however, were to counteract the...

An Alternative Oxidant for Cyclohexene Oxygen

Cyclohexene

The main product of cyclohexene oxidation with oxygen in the absence of a reduction reagent is 2-cyclohexen-1-one 40a-c . This may finally be hydrogenated to cyclo-hexanone, but the route is clearly disadvantageous compared to the oxidation of cyclohexane to cyclohexanone. The reaction follows the classical autoxidation mechanism, with cyclohexene hydroperoxide being the first reaction product. When catalyzed by polyoxoanion-supported organometallic Ir(I), Ru(II), Re(I) complexes, in the...

Limits to Their

And Example Chemistry

All the indicators discussed above are based on mass intensity. These indicators have been developed specifically for their use in synthetic chemistry, either at the laboratory or industry level. They have in common the objective of showing to what extent a chemical reaction is wasteful in material terms simplicity is their main merit, as most of them can be easily calculated as soon as the chemical reaction is defined and quantified. However, they include neither information on energy issues...

Potential Future Solutions for PO Synthesis Gas Phase Hydrooxidation of Propene with Oxygen and Hydrogen HOPO

Examples Gas Phase Solutions

The hydro-oxidation reaction involves one mole of propene, one mole of oxygen and one mole of hydrogen, forming PO and water 6.2 PO-only Routes Several Approaches for Sustainable Alternatives 351 O Competing side reactions include propene hydrogenation to propane, and propene combustion to carbon dioxide and water. Additional hydrogen and oxygen consumption occurs to form water. The best systems for this reaction are based on Au0 nanoparticles supported either over TiO2 (anatase), or over...

Friedel Crafts Acylation of Aromatic Ethers Using Zeolites

Chlorobenzyl Chloride Process

RolandJacquot and Philippe Marion 14.1 The Friedel-Crafts reaction and the related Fries rearrangement of aromatics are the most important methods in organic chemistry for synthesizing aromatic ketones, which are of interest in the synthesis of numerous fine chemicals such as drugs, fragrances, dyes and pesticides. The conventional method for preparation of these aromatic ketones involves reaction of the aromatic hydrocarbon with a carboxylic acid derivatives using a Lewis acid (AlCl3, FeCl3,...

Sustainable Risk Reflections Arising from the Bhopal Accident

Bhopal Chemistry Accident

The focus of green chemistry on the reaction more than on the process and its industrial feasibility, even considering the attention given to aspects such as green chemistry and engineering 16 , indicates that aspects related to the safety of a chemical or manufacturing process, measured in terms of risk, are not given enough consideration. In its simplest form risk can be expressed as To date, legislation has sought to minimize risk by limiting exposure to chemicals, that is, controlling use,...

Towards the Direct Oxidation of Benzene to Phenol

Benzoquinone Formation Hydroquinone

Marco Ricci, Daniele Bianchi, and Rossella Bortolo 13.1 Phenol is one of the most important intermediates of the chemical industry. Its current global capacity is put at about 8 x 1061 yr_1 and is forecast to grow near 4.5 per year through to 2009. The main consumption of phenol, accounting for nearly 40 of its global demand, occurs in the synthesis of bisphenol A (mainly used to produce polycarbonate for compact discs). This is followed by phenol use in the production of epoxy resins (used,...

References

1 Reay, D., Ramshaw, C. and Harvey, A. (2008) Process Intensification - Engineering for Efficiency, Sustainability and Flexibility, Elsevier (Butterworth Heinemann) Pub., Amsterdam. 2 Ramshaw, C. (1985) Chem. Eng., 415, 30. 3 Hendershot, D.C. (2000) Chem. Eng. Prog., 96, 35. 4 Stankiewicz, A.I. and Moulijn, J.A. (2000) Chem. Eng. Prog., 96, 22. 5 Ramshaw, C. (1983) Chem. Eng., 389, 13. 6 Zheng, C., Guo, K., Song, Y., Zhou, X., Al, D., Xin, Z. and Gardner, N.C. (1997) Proceedings of the 2nd...

Introduction Current Industrial Propene Oxide Production

Industrial Manufacturing Propene

Propene oxide (PO) is one of the largest propene derivatives in production, ranking second behind polypropene it is used primarily as a chemical intermediate 1 . Worldwide, approximately 8 million tons are produced annually, the major suppliers are Dow (1.9 M-tonyr-1), Lyondell (2.1-ton yr-1) and Shell BASF (0.9M-tonyr_1) other key producers are Sumitomo, Repsol and Huntsman. One of the fastest growing markets is China in fact, nowadays there are more than 30 Chinese PO producers. From 1990 to...

Selective Oxidation

Catalytic selective oxidation processes play a central role in the chemicals industry as well as in the development of new catalysts as the key contributions to modern manufacturing, because a large proportion of materials and commodities in daily use undergo a selective oxidation process as a critical step in their production cycle. More than half of the products obtained using catalytic processes are obtained by selective oxidation, and nearly all the monomers used in the production of fibers...

Sustainable Chemistry and Inherently Safer Design

Inherently Safer Design Examples

Process safety, a discipline that focuses on the prevention of fires, explosions and accidental chemical releases at chemical process facilities, is a key element for a sustainable industrial chemistry, as indicated in the previous sections. There are three key elements for process safety behavior, system and process. Thorough and effective analyses of workplace incidents are critical components of a comprehensive safety management system. Yet, many incident analysis processes (i.e., accident...

Several Technologies for In Situ HPPO with TS1Supported Pd Catalysts

Hppo Process Reaction

A process for the epoxidation of propene with in situ generation of HP was proposed in the 1990s by the Tosoh Corporation 23 . It was suggested that PO could be made via a direct reaction between hydrogen and oxygen in the presence ofpropene, using a catalyst made of Pd supported on crystalline titanium silicate, in a flow system. The solvent for the reaction was t-butanol, and the reaction temperature was 45 C. A conversion of 0.8 was reported, with a selectivity for PO of 99 . ARCO Chem Tech...

Dshphppo Technology Developed by Degussa Evonik Headwaters

The DSHP has been developed jointly by Degussa-Evonik and Headwaters Nanoki-netix, USA 27 . A demonstration unit for the production of several thousand metric tons per year of dilute HP in methanol went on stream in 2006, in Hanau-Wolfgang, Germany commercial production will begin in 2009. The process operates below the explosion limit, and uses a Pd(Pt) nanocatalyst developed by Headwaters Technology Innovation, denominated NxCat . It was anticipated that investment costs for the direct...

N2O From a Waste Compound to a Reactant for Downstream Applications

Kreslen Podle Cisel Pro Deti

As an alternative, N2O can be recovered from the off-gas in pure form, either for selling or for use as an oxidant in some downstream processes. Within this context, an innovative solution has been developed by Solutia, together with the Boreskov Institute of Catalysis, in which N2O is the oxidant used for the hydroxylation of benzene to phenol in the presence of a ZSM-5 catalyst exchanged with Fe(III) 11 . Phenol can then be hydrogenated to yield cyclohexanol, hence completing the N2O cycle...

With Nitric Acid

Nitric Acid Oxidizing Agent Mechanism

The second step ofthe process from cyclohexane is the oxidation ofthe KA Oil with a large excess of 50-65 HNO3 (molar ratio HNO3 Ka Oil at least 7 1), and with a Cu(II) and ammonium metavanadate catalyst 2a, b . The formal stoichiometries are as follows (indeed, the reaction leads not only to N2O, but also to the formation of NO and NO2) cyclohexanone to AA, DHR 172 kcal mol 1 cyclohexanol to AA, Dhr 215 kcal mol 1 The reaction is carried out in two (or more) in-series reactors, the first one...

An Alternative Raw Material for AA Synthesis Cyclohexene

Cyclohexane Cyclohexene Synthesis

Cyclohexene can be synthesized by partial hydrogenation of benzene, by partial dehydrogenation of cyclohexane, or by dehydrohalogenation of cyclohexyl halides. The hydrogenation of benzene is the most viable route in the Asahi process, cyclohexene is obtained with a 60 yield and 80 selectivity, with the remainder being converted into cyclohexane. Asahi has developed a process for the addition of water to cyclohexene to produce cyclohexanol that can then be oxidized to AA using the conventional...

Green Sustainable Chemistry in the Production of Nicotinates

Nicotine Mild Oxidation Reaction

This chapter discusses the fulfillment of the requirements for a green process, together with the importance of the nicotinate vitamin B3. Lonza's contribution to green chemistry is then illustrated by its processes for producing nicotinates. The current niacinamide process running is China employs no fewer than six basic principles of green-sustainable chemistry. The acceptability of a process should not be governed solely by its cost. An economic process is not necessarily green, especially...

Replacement of Hazardous Chemicals the Case of DMC

Phosgene Production Process

Dimethyl carbonate DMC is a versatile compound that is an attractive alternative to phosgene 68, 69 and which could be synthesized in a eco-friendly process by catalytic oxidative carbonylation of methanol with oxygen Enichem, Italy 70 and Figure 1.9 Bhopal and alternative routes to N-methyl 2-naphthyl carbamate 67 . UBE, Japan 71 processes . DMC can act as a substitute for phosgene and toxic methylating agents like dimethyl sulfate and methyl chloride, and can also find use as a safe solvent...

Factor and Atom Economy

Previous sections have outlined the general aspects of evaluation of sustainability, and the value and limits ofthe different methodologies. Even though not exhaustive of the state of the art in this broad topic, which is beyond the scope of this book, the discussion can provide the elements for an evaluation of the specific indexes and methodologies proposed for green (sustainable) chemistry. We also remark that some of the indicators and methodologies discussed in the previous sections do not...

Basell Spherizone Technology

Basell Montedison Slurry Technology

The family of polymers, and in particular polyolefins, is important in the modern world because of the very high number of applications in all fields. Among plastic materials, polypropylene is one of the most important, having undergone rapid growth since its discovery in 1954 by the Nobel Prize winner G. Natta of Politecnico di Milano. Today, polypropylene demand is about 40 million ton per year with a market share, among all thermoplastic materials, of about 26 , which is second only to...

Highly Sour Gas Processing in a More Sustainable World

Equilibrium Solubility H2s Selexol

Fran ois Lallemand and Ari Minkkinen 10.1 For decades to come, natural gas will be the energy source of choice to meet evergreener worldwide environmental standards. Fortunately, gas reserves are growing but new gas is often found to be of substandard quality in remote and or stranded areas of the world. When natural wellhead or oil field associated gases are highly loaded with acid gases, the dilemma facing most operators is what to do, how and when to best exploit these poor quality...

Opportunities and Perspectives for a Sustainable Process Design

Higee Reactor

PI is a hot topic in chemical and process engineering, and is now reaching a maturity that is seeing PI concepts applied to a wide range of processes and technologies. Already, over 30 industrial examples are available, but this number is rapidly increasing. Originally developed for the bulk chemical industry, PI developments have more recently been focused on the higher added-value chemicals and pharmaceutical active ingredient sectors. Examples reported by the Process Intensification Network...

Hybrid Unit Operations

The first case deals with multifunctional equipment that couples or uncouples elementary processes (transfer-reaction-separation) to increase productivity and or selectivity with respect to the desired product and to facilitate the separation of undesired by-products. Numerous reactive separation processes involving unit operation hybridization exist. The concept of reactive or catalytic distillation has been commercialized successfully, both in petroleum processing, where packed bed catalytic...

Eni Chem Approach TS1 Allows the Integration of HP and PO Synthesis

Reactions With Propene

Since the early 1980s, EniChem has been a pioneer in the development of the process, holding a portfolio of patents 10c,d . The integration of HP synthesis by means of (RAQ RAHQ) cycle technology, with PO production, by means of propene epoxidation with HP, is possible because of the peculiar properties of the TS-1 catalyst (Scheme 6.5). TS-1 can selectively epoxidize propene using diluted HP 12 . A water- methanol mixture is the solvent for the epoxidation the alcohol is necessary to obtain a...

Two Step Oxidation of Cyclohexene to AA Via 12Cyclohexandiol

The syn dihydroxylation of olefins is usually performed in the presence of metal oxide, for example, KMnO4 or OsO4, and with t-BuOOH or HP as terminal oxidants. The anti dihydroxylation can be achieved with peracetic acid and m-ClC6H4CO3H in water. However, the atom efficiency of these oxidants is low, and they form equimolar amounts of deoxygenated compounds 36a, b . Osmium-catalyzed dihydroxylation of olefins involves an Os(VIII) Os(VI) substrate-selective redox system 36c-g . In this system,...

Olefin Paraffin Alkylation Evolution of a Green Technology

Angevine Today's gasoline has many refining sources fluid catalytic cracking (FCC) naphtha, straight-run naphtha, coker and visbreaker naphtha, reformate, isomerate and alkylate. High compression engines are pushing the market to increased amounts of high-octane gasoline, and environmental factors are constraining gasoline composition in many other ways. Table 12.1 lists some of the key specifications of gasoline - now and in the near future In addition to SOx...

Critical Toolbox for a Sustainable Industrial Chemistry

PI is more than just a series of novel reactors or equipments. It offers the full potential of redesigning industrial chemical process in line with sustainability concepts. PI presents a range ofexciting processing tools opportunities for chemists. The smaller footprints ofprocesses offer new opportunities to insert them in a factory, as visually illustrated in Figure 1.2 (Chapter 1), allowing thus a significant reduction in terms of an eyesore for the general public. In some cases the plant...

Inherently Safer Process Design

In general, there are two approaches to design safety into a chemical process - either handling the hazards with engineering and management controls or eliminating them altogether 47 . If a process hazard cannot be eliminated, it may still be possible to reduce its potential impact sufficiently as far it is not capable of causing major injury or damage. Whenever feasible, it is desirable to eliminate or minimize process hazards. Engineering and management controls have been effective in...

An Overview Several Possible Green Routes to AA Some Sustainable Others

Scheme 7.17 summarizes the possible routes for the synthesis of AA. Some of them are green but only a few of them can be considered truly sustainable, from Scheme 7.17 Summary of the various alternative pathways for AA synthesis. Scheme 7.17 Summary of the various alternative pathways for AA synthesis. both an environmental and economic point of view, if the cost of reactants and the complexity of the operation are taken into consideration. For instance, the direct oxidative cleavage of...

Introduction The Adipic Acid Market

Adipic acid (AA) is an important chemical intermediate 1 . The production of Nylon-6,6 (for fibers and resins) accounts for 63 of AA consumption the fibers are used in applications such as fishing lines, tires, carpets, home furnishings and in tough fabrics for parachutes, backpacks, luggage and business cases. Nylon engineering resins are chiefly used in electrical connectors, auto parts and items such as self-lubricating bearings, gears, and cams. The major non-nylon uses of AA are in...

High Gravity Fields

As commented in Section 3.1.1, the use of high-gravity fields generated by the centrifugal operation for process intensification started with the pioneering work of Ramshaw and Mallison from the ICI New Science Group (around 1980) on the application of high-gravity fields (so-called HiGee) in distillation processes 100 . Various other authors have later confirmed such a large increase in the mass transfer rates in the high-gravity field of rotating packed beds (RPBs). For example, Lin et al....

Aqueous Biphase Operations

Basf Oxo Process Flowsheet

An excellent example of sustainable chemical processes using homogeneous catalysts is Ruhrchemie Rhone-Poulenc's (RCH RPs) oxo process, which is a prototype of an aqueous biphasic process (Figure 2.3) 65, 66 . The first commercial oxo plant using the RCH RPs biphasic process went on stream in 1984 and has produced over 5 million tons of n-butanyraldehyde (as well as less than 4 iso-butyraldehyde). The oxo-active HRh(CO)4 catalyst is modified by trisulfonated triphenylphosphine (TPPTS) ligands....

Introduction

Graph Interpret

The concept of Green Chemistry was introduced in the early 1990s in the USA. After the introduction of the US Pollution Prevention Act, the Office of Pollution Prevention and Toxics (OPPT) explored the idea of developing new or improved chemical processes to decrease hazardous to human health and the environment. In 1991, OPPT launched a research grants program called Alternative Synthetic Pathways for Pollution Prevention. This program was focused on pollution prevention in the design and...

NHydroxyphthalimide as the Catalyst for the Oxidation of Cyclohexane to AA with Oxygen

Phosphatidyl Choline

One notable achievement is the process that makes use of N-hydroxyphthalimide (NHPI) as the catalyst for the aerial oxidation of cyclohexane 30 . NHPI is a cheap, nontoxic catalyst easily prepared by the reaction of phthalic anhydride and hydrox-ylamine. It acts as a precursor of the phthalimido-N-oxyl (PINO) radical, which is the effective abstracting species in the free radical process (Scheme 7.7). A 30tonyr 1 pilot plant has been constructed by Daicel Chemical Industry to produce AA with...

The First Industrial POOnly Synthesis the Sumitomo Process

Dot Dot Outer Space

The Sumitomo PO-only process consists of the following steps 5 (Scheme 6.4) 1. Oxidation, where cumene is oxidized in air to obtain cumyl hydroperoxide (CHP). 2. Epoxidation, where PO and a,a-dimethylbenzyl alcohol (cumyl alcohol, CA) are obtained from CHP and propene, in the presence of a proprietary heterogeneous epoxidation catalyst. Scheme 6.4 PO-only Sumitomo process. Scheme 6.4 PO-only Sumitomo process. 3. Hydrogenolysis, where the alcohol is first dehydrated to a-methylstyrene (AMS) and...

When Dense or Microporous Materials Control the Overall Process Performance

For membrane operations in which dense or microporous materials control the overall process performance there is no doubt that process intensification will follow directly from improvement of material properties. With the development of new materials having properties controlled at the nanoscale level, operations ofthis kind seem promised a really bright future. An example is provided by mixed matrix membranes (MMM). Basically they are constituted of inorganic molecular nanoparticles (such as...

Sustainable Chemical Production Metrics

The assessment of a complex phenomenon such as that of the sustainability of the chemical production requires integration of several indicators into a useful metric. The usefulness of a metric depends strongly on the number of indicators too few may not provide an adequate description of a phenomenon, whereas too many would make the cost of completing the metric prohibitively high. Several organizations have been actively involved in developing sustainability metrics. The most prominent efforts...

Cascade and Domino Catalytic Reactions

Prescribing Cascades Examples

This chapter has reported various examples to evidence how the new advances in catalyst design allow us to perform selectively in one-pot multistep reactions. These, which apply in particular for fine chemicals production, are often called cascade reactions, because they effectively involve the desorption from one site to react on another site physically distant from the first. It is thus a different concept from that shown in Figure 2.66 n-butane to maleic anhydride on (VO)2P2O7 catalysts,...

HPPO and In Situ HPPO Processes HP Generation by Direct Oxidation of H2 DSHP

The price of the HP for PO synthesis is a major factor determining the overall cost-effectiveness of the process. With DHSP, by direct reaction between hydrogen and oxygen, the epoxidation process might be coupled with the HP-producing process without intermediate concentration or purification. On the other hand, the selectivity to HP on a hydrogen basis is still low. The DSHP is carried out in an alcoholic solvent, and produces dilute solutions of HP. The dilute methanol solution obtained...

Supported Liquid Films

The discussion in the previous sections has evidenced that the use of biphasic systems has solved, at least in various cases, the problem of homogeneous catalyst recovery and recycle, but there still exists the problem of the cost of recycle and especially of reaction rate per volume of reactor, which derives in large part from mass- and heat-transfer limitations, but also from the low amount of catalytic centers per volume of reactor necessary to avoid side reactions and maintain a high...

Industrial Microreactors for Fine and Functional Chemistry

Microreactor technology is a tool used by most large chemical and pharmaceutical companies and also by some SMEs. Various examples are discussed by Hessel et al. 176 , based on the collaboration ofthe Institute for Micro-Technology at Mainz (Germany) with various companies. We recall here some relevant cases to further evidence how microreactors are not more only at a laboratory-scale stage of development, even though most of the applications are still on a small-size scale. 3.3.4.1 Phenyl...

Information and Communication Technologies

Information and communication technology (ICT) is a fast-moving consumer sector with a strong need for new materials and products to meet demands. The adoption of newly developed architectures and materials will lead to fundamental changes in the concepts and design paradigms of integrated circuits. Integration of nanostructures in device materials is thus a priority. Several new nanostructured materials, including carbon nanotubes, and silicon and germanium nanowires, are of potential interest...

Homogeneous Catalysis and the Role of Multiphase Operations

Several large-scale industrial processes use homogeneous catalysts e.g., hydrofor-mylation, hydrocyanation (DuPont), ethene-oligomerization (SHOP), acetic acid (Eastman Kodak), acetic acid anhydride (Tennessee-Eastman), acetaldehyde (Wacker) and terephthalic acid (Amoco) as well as smaller scale applications e.g., metolachlor (Novartis), citronellal (Takasago), indenoxide (Merck) and glycidol (ARCO, SIPSY) . However, homogenous catalysts are still far less used on an industrial scale than...

Role of Catalysis

Emphasis throughout this book is given to catalysis, because it is a driver for sustainability and societal challenges 8 . Catalysis plays a critical role in promoting the feasibility, eco-efficiency and economics of over 90 of chemical processes. However, catalysis is also one of the critical enabling factors for sustainability in the specific field of chemical processes. In the mobility sector, without the introduction of catalytic converters starting from the 1960s, it was not possible to...

New Operating Modes of Production

Several new operating modes of production allow process intensification, although they have been mainly investigated at a laboratory and or pilot stage. The more relevant for practical applications were the following according to Charpentier 7 reversed flow for reaction-regeneration, unsteady operations, cyclic processes, pultrusion (a variation of the extrusion process), low-frequency vibrations to improve gas-liquid contact in bubble columns, high-temperature and high-pressure technologies,...

Fundaments of PI

Process intensification is driven by four generic principles 1. Maximize the effectiveness of intra and intermolecular events. 2. Give each molecule the same processing experience. 3. Optimize the driving forces on every scale and maximize the specific areas to which those driving forces apply. 4. Maximize the synergistic effects from events and partial processes. Four main domains, which constitute the pillars of the PI scientific approach, may be identified 2. Energy (thermodynamic domain)....

Ionic Liquids

Ionic liquids (IL) 92 are a major topic in the area of multiphase homogeneous catalysis. ILs are characterized by the following three criteria (i) consist entirely of ions, (ii) have melting points below 100 C and (iii) exhibit no detectable vapor pressure below the temperature of their thermal decomposition. As a consequence of these properties most ions forming ionic liquids display low charge densities, resulting in a low intermolecular interaction. Figure 2.8b displays some of the most...