Shutting Down A Sulfuric Acid Alkylation Unit Reactor

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

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...

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...

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...

With Nitric Acid

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...

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....

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...

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...

Aqueous Biphase Operations

Family Tree Template

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....

BioEtbe A New Component for Gasoline

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...

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,...

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...

Opportunities and Perspectives for a Sustainable Process Design

Reactor Jet Caco3

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...

Ecofining New Process for Green Diesel Production from Vegetable

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...

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...

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,...

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...

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...

Index

Acetic acid 180, 385, 389, 390, 395 acetone cyanohydrin (ACH) process 176,177 - sulfuric acid (H2SO4) 130, 141 - soluble oils (ASO) 493 acrylamide 110, 111 - biocatalytic production, Mitsubishi's - cyclohexane transformation 369-372 - KA oil oxidation with air 385-389 - twenty-first century Co RPC 392 - production 374, 378, 385, 402 - emerging developing technologies 402-413 - methyl acrylate dimerization 402 - production technologies 368-384 - commercial vs. proposed bioroute 111 - cyclohexene...

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,...

V

Figure 12.1 Conceptual mechanism for olefin paraffin alkylation 10 . to form higher molecular weight hydrocarbons or break into smaller products such as an olefin and a sorbed carbocation. The olefin rapidly reacts with the acid sites to form another carbenium ion. Since hydrogen transfer is essential for the desired product formation, a high isobutane-to-olefin (I O) ratio is required in the feed. A high hydride transfer rate lowers the formation of non-C8 (e.g., C5-C7 and C9 + ) products,...

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...

Highly Sour Gas Processing in a More Sustainable World

H2s Partial Pressure Temperature

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...

Introduction Current Industrial Propene Oxide Production

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...

Replacement of Hazardous Chemicals the Case of DMC

Oligomer Phosphorus Reaction Isocyanate

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...

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...