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Examples For Process Synthesis
Examples For Process Synthesis
Examples For Process Synthesis
The state selections can be changed later with modifications to the flowsheets.
4. Form, if solid phase (e.g., particle size distribution and particle shape)
5. Temperature
6. Pressure
Synthesis steps
Process synthesis involves the selection of processing operations to convert the raw
materials to products. In other words, each operation can be viewed as having a role in
eliminating one or more of the property differ-ences between the raw materials and the
desired products. As each operation is inserted into a flowsheet, the effluent streams
from the new operation are closer to those of the required products.
It involves positioning the process operations in the following steps to eliminate the
differences:
Example of Process Synthesis: Manufacture of Vinyl Chloride
an important polymer (usually referred to as just vinyl) that is widely used for rigid plastic
piping, fittings, and similar products. Over the years, large commercial plants have been
built, some of which produce over 1 billion lb/yr. Hence, polyvinyl chloride, and the
monomer from which it is derived, is referred to commonly as a commodity chemical
that is produced continuously, rather than in batch, virtually everywhere. Historically,
vinyl chloride was discovered in 1835 in the laboratory of the French chemist Regnault,
and the first practical method for polymerizing vinyl chloride was developed in 1917 by
the German chemists Klatte and Rollett (Leonard, 1971). Vinyl chloride is an extremely
toxic sub-stance and, therefore, industrial plants that manufacture it or process it must
be designed carefully to satisfy government health and safety regulations.
In this example, only the production of the monomer is considered, with a focus on
alternatives 2 and 3. In the concept stage, the objective is to create several promising
flowsheets, as candidate solutions.
The first major subproblem in the process synthesis involves the selection and analysis
of the reaction. The reaction links the product of processing with cheap and readily
available materials, and generates wastes and by-products with which we must contend.
For example in the production of vinyl chloride following reactions are used and need to
choose any one best of these.
2. Hydrochlorination of Acetylene
This two-step reaction path has the advantage that the conversion of ethylene to 1,2-
dichloroethane in exothermic reaction is about 98% at 90°C and 1 atm with a Friedel-
Crafts catalyst such as ferric chloride (FeCl3). Then, the dichloroethane intermediate is
converted to vinyl chloride by thermal cracking according to the endothermic reaction,
which occurs spontaneously at 500°C with conversions as high as 65%. Unreacted
dichloroethane is recovered entirely from the vinyl chloride and hydrogen chloride and
recycled.
Given this information, it seems clear that the design team would reject reaction path 1
on the basis of its low selectivity with respect to the competing reactions (not shown)
that produce undesirable byproducts. This leaves the other reaction paths as potentially
attractive to be screened on the basis of the chemical prices. Although it is too early to
estimate the cost of the equipment and its operation, before the remaining process
operations are in place, the design team normally computes the gross profit (i.e., the
profit excluding the costs of equipment and the operating costs) for each reaction path
and uses it as a vehicle for screening out those that cannot be profitable.
Then, the gross profit is 35(1) + 25(0.583) - 30(0.449) - 18(1.134) = 15.69 cents/lb of
vinyl chloride. Similar estimates are made for the overall reaction in each of the reaction
paths, it being assumed that complete conversion can be achieved without any side
reactions (not shown).
Gross Profit for Production of Vinyl Chloride (Based on Chemical Prices in Table
Even without the capital costs (for construction of the plant, purchase of land, etc.) and
the operating costs (for labor, steam, electricity, etc.), the gross profit for reaction path 2
is negative, whereas the gross profits for the other reaction paths are positive. This is
principally because acetylene is very expensive relative to ethylene. The fairly high price
of HCl also contributes to the inevitable conclusion that vinyl chloride cannot be
produced profitably using this reaction path. It should be noted that the price of HCl is
often very sensitive to its availability in a petrochemical complex. In some situations, it
may be available in large quantities as a byproduct from another process at very low
cost. At a much lower price, reaction path 2 would have a positive gross profit, but would
not be worthy of further consideration when compared with the three reaction paths
involving ethylene. Turning to these paths, all have sufficiently positive gross profits, and
hence are worthy of further consideration. It is noted that the price of HCl strongly
influences the gross profits of reaction paths 3 and 4, with the gross profit of reaction
path 5 midway between the two. Before proceeding with the synthesis, the design team
would be advised to examine how the gross profits vary with the price of HCl.
Figure shows the first step toward creating a process flowsheet for reaction path 3. Each
reaction operation is positioned with arrows representing its feed and product
chemicals. The sources and sinks are not shown because they depend on the
distribution of chemicals, the next step in process synthesis. The flow rates of the
external sources and sinks are computed assuming that the ethylene and chlorine
sources are converted completely to the vinyl chloride and hydrogen chloride sinks.
Here, a key decision is necessary to set the scale of the process, that is, the production
rate at capacity. In this case, a capacity of 100,000 lb/hr (800 million lb/yr, assuming
operation 330 days annually-an operating factor of 0.904) is dictated by the opportunity.
Given this flow rate for the product (principal sink for the process), the flow rates of the
HCl sink and the raw material sources can be computed by assuming that the raw
materials are converted to the products according to the overall reaction. Any unreacted
raw materials are separated from the reac-tion products and recycled. By material
balance, the results in Figure 3.4 are obtained, where each flow rate in lbmol/hr is 1,600.
Environmental Issues
Because fossil fuels are the predominant sources of power worldwide, their combustion
products are a primary source of several pollutants, especially in the urban centers of
industrialized nations. More specifically, effluent gases from burners and fires contain
sizable con centrations of SO2, the nitrogen oxides (NOx), CO, CO2, soot, ash, and
unburned hydrocarbons. These, in turn, result in many environmental problems,
including acid rain (principally concentrated in H2SO4), smog and hazes (concentrated in
NOx), the accumulation of the so-called greenhouse gas (CO2), volatile toxic
compounds (e.g., formaldehyde, phenol), and organic gases (e.g., CO), which react
with NOx, especially on hot summer days, altering the O3 level. As the adverse impacts
of pollutants on animals, plant life, and humans are being discovered by scientists and
engineers, methods are sought to reduce their levels significantly.
As a rule of thumb, it should be noted that the cost of cleaning combustion products is
approximately an order of magnitude less than the cost of removing contaminants from
fuel. This is an important heuristic, especially when designing processes that are energy
intensive, requiring large quantities of fuel.
In the chemical and nuclear power industries, large quantities of toxic wastes are
produced annually, largely in wastewater streams, which in 1988 amounted to 97% of
the wastes produced, as shown in the pie chart of Figure. While a small portion is
incinerated (on the order of 3 % in the late 1980s), the bulk is disposed of in or on the
land, with a variety of methods having been introduced over the past century to bury
these wastes. In this regard, studies by the state of California have shown that aqueous
waste streams from the processing of electronic materials are posing widespread
threats to the groundwater in California's Silicon Valley. In fact, this area has a leading
number of sites on the U.S. National Priority List of toxic waste dumps (which is
comprised of approximately 10,000 sites throughout the United States). In process
design, it is essential that facilities be included to remove pollutants from waste-water
streams.
Bioaccumulated Chemicals
Probably the most well-known cases of chemicals that have been discovered to
bioaccumulate in the soil and plant life are the insecticide DDT (1,1-bis(4-chlorophenyl)-
2,2,2-trichloroethane; C14H9Cl5) and the solvent PCBs (polychlorinated biphenyls).
DDT was sprayed in large quantities by low-flying airplanes to kill insects and pests
throughout the 1950s. Unfortunately, although effective for protecting crops, forests, and
plant life, toxic effects in birds, animals, and humans were strongly suspected.
Consequently, DDT was banned by the U.S. EPA in 1972. Its effect, however, will
remain for some time due to it having bioaccumulated in the soil and plant life.
In this category, major changes have taken place since the late 1960s in response to the
dis-coveries of the toxic effects of lead, mercury, cadmium, and asbestos on animals
and humans. After lead poisoning (accompanied by brain damage, disfigurement, and
paralysis) was related to the ingestion of lead-based paints by children (especially in
older buildings that are not well maintained), the EPA banned lead from paints as well
as from fuels. In fuel, tetraethyl lead had been used as an octane enhancer throughout
the world. It was subsequently replaced by methyl tertiary-butyl ether (MTBE), which is
also being replaced due to reports that it can contaminate groundwater. Mercury, which
has been the mainstay of manometers in chemistry laboratories, has similarly been
found to be extremely toxic, with disastrous effects of accidental exposure and ingestion
reported periodically. In the case of asbestos, its toxic effects have been known since
the late 1940s, yet it remains a concern in all buildings built before then. Gradually, as
these buildings are being renovated, sheets of asbestos insulation and asbestos ceiling
tiles are being removed and replaced by nontoxic materials. Here, also, the incidents of
asbestos poisoning are associated most often with older buildings that have not been
well maintained.
Objectives:
1. Understand the importance of selecting reaction paths that do not involve toxic or
hazardous chemicals, and when unavoidable, to reduce their presence by shortening
residence times in the process units and avoiding their storage in large quantities.
4. Be able to distribute the chemicals, by using excess reactants, inert diluents, and
cold (or hot) shots, to remove the exothermic (supply the endothermic) heats of reaction.
These distributions can have a major impact on the resulting process integration.
Although experienced engineers know where to find information and how to make
accurate computations, they also keep a minimum body of information in mind on the
ready, made up largely of shortcuts and heuristics. The present compilation may fit into
such a minimum body of information, as a boost to the memory or extension in some
instances into less often encountered areas.
Heuristic 1: Select raw materials and chemical reactions to avoid, or reduce, the
handling and storage of hazardous and toxic chemicals.
The selection of raw materials and chemical reactions is often suggested by chemists,
biologists, biochemists, or other persons knowledgeable about the chemical
conversions involved. In recent years, with the tremendous increase in awareness of the
need to avoid handling hazardous and toxic chemicals, in connection with
environmental and safety regulations, raw materials and chemical reactions are often
selected to protect the environment and avoid the safety problems that are evident in
Material Safety Data Sheets (MSDSs).
For example, recall that when the vinyl chloride process was synthesized in before, the
reaction of acetylene with HCl was rejected because of the high cost of acetylene.
Today, in addition, this reaction path would be rejected on the basis of the high reactivity
of acetylene and the difficulty of ensuring safe operation in the face of unanticipated
disturbances.
In connection with the handling of hazardous chemicals, the 1984 accident in Bhopal,
India, in which water was accidentally mixed with the active intermediate methyl
isocyanate, focused worldwide attention on the need to reduce the handling of highly
reactive intermediates. Within an hour of the accident, a huge vapor cloud swept across
Bhopal, leading to the death of over 3,800 victims in the vicinity of the Union Carbide
plant. This accident, together with the discovery of polluted ground waters adjacent to
chemical plants, especially those that process nuclear fuels, have led safety and
environment experts to call for a sharp reduction in the handling of hazardous
chemicals.
For these reasons, societal needs are increasingly being formulated that call for new
processes to avoid or sharply reduce the handling of hazardous chemicals. As an
example, consider the manufacture of ethylene glycol, the principal ingredient of
antifreeze. Ethylene glycol is produced commonly by two reactions in series:
The first reaction involves the partial oxidation of ethylene over a Ag-gauze catalyst.
Since both reactions are highly exothermic, they need to be controlled carefully. More
important from a safety point of view, a water spill into an ethylene oxide storage tank
could lead to an accident similar to the Bhopal incident. Yet it is common in processes
with two reaction steps to store the intermediates so as to permit the products to be
generated continuously, even when maintenance problems shut down the first reaction
operation.
Given the societal need (or primitive design problem) to eliminate the storage of large
quantities of reactive intermediates, such as ethylene oxide, four alternative processing
con-cepts (or specific problems) are possible:
2. Use costly chlorine and caustic (compared to oxygen from air) in a single reaction
step:
This alternative requires more expensive raw materials, but completely avoids the
intermediate.
3. As ethylene oxide is formed, react it with carbon dioxide to form ethylene carbonate,
a much less active intermediate. This reaction occurs smoothly over a
tetraethylammonium bromide catalyst. Ethylene carbonate can be stored safely and
hydrolyzed to form the ethylene glycol product as needed.
4. Carry out reactions (R1) and (R4) consecutively over a Ag-gauze catalyst by reacting
ethylene in a stream containing oxygen and carbon monoxide. To consider this as an
alternative processing concept, laboratory or pilot-plant data on the rates of reaction are
necessary.
Block Flow Diagram (BFD)
The block flow diagram represents the main processing sections in terms of functional
blocks. As an example, Figure 4.18 shows a block flowdiagram for the vinyl-chloride
process, in which the three main sections in the process— namely, ethylene
chlorination, pyrolysis, and separation— are shown, together with the principal flow
topology. Note that the diagram also indicates the overall material balances and the
conditions at each stage, where appropriate. This level of detail is helpful to summarize
the principal processing sections and is appropriate in the early design stages, where
alternative processes are usually under consideration.
Process flow diagrams provide a more detailed view of the process. These diagrams
display all of the major processing units in the process (including heat exchangers,
pumps, and compressors), provide stream information, and include the main control
loops that enable the process to be regulated under normal operating conditions. Often,
preliminary PFDs are constructed using the process simulators. Subsequently, more
detailed PFDs are prepared using software such as AUTOCAD and VISIO, the latter
having been used to prepare Figure 4.19 for the vinyl-chloride process. The conventions
typically used when preparing PFDs are illustrated using this figure and are described
next.