Benzene Process PFD Analysis

Turton/Bailie/Whiting/Shaeiwitz: Analysis, Synthesis, and Design of Chemical Processes Chapters 1, 2
The Structure and Synthesis of Process Flow Diagrams
Cheng-Liang Chen
LABORATORY
PSE
Department of Chemical Engineering National TAIWAN University
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Diagrams for Understanding Chemical Processes
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The most eective way of communicating information about a process is through the use of ow diagrams
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Block Flow Process Diagram

A Block Flow Diagram (BFD) Drawn for A Single Process Production of Benzene via the Hydrodealkylation of Toluene C7H8 + H2 C6H6 + CH4 BP (oC) H2 CH4 253 164 80.1
Compound Hydrogen Methane Benzene
Toluene
110.6
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A Block Flow Diagram (BFD) Drawn for A Single Process Production of Benzene via the Hydrodealkylation of Toluene C7H8 + H2 C6H6 + CH4
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BFD
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BFD Skeleton PFD

A Skeleton Process Flow Diagram Drawn for A Single Process Production of Benzene via the Hydrodealkylation of Toluene C7H8 + H2 C6H6 + CH4
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BFD Skeleton PFD PFD

A Process Flow Diagram (PFD) Drawn for A Single Process Production of Benzene via the Hydrodealkylation of Toluene C7H8 + H2 C6H6 + CH4
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Process Flow Diagram

Symbols for Drawing Process Flow Diagrams
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Conventions Used for Identifying Process Equipment
Equipment General format XX-YZZ A/B
XX are identication letters for equipment classication C - Compressor or Turbine (C-101A/B) E - Heat Exchanger (E-106) H - Fired Heater (H-101) P - Pump (P-102A/B) R - Reactor (R-101) T - Tower (T-101) TK - Storage Tank V - Vessel (V-104) Y designates an area within the plant ZZ is number designation for each item in an equipment class A/B identies parallel units or backup units Supplemental Information Additional description of equipment given on top of PFD
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Conventions Used for Identifying Process Equipment
Process Streams All conventions shown in Table 1.1 apply. Diamond symbol located in ow lines. Numerical identication (unique for that stream) inserted in diamond. Flow direction shown by arrows on ow lines. Utility Streams lps Low-pressure Steam: 3-5 barg (sat) mps Medium-pressure Steam: 10-15 barg (sat) hps High-pressure Steam: 40-50 barg (sat) htm Heat Transfer Media (Organic): to 400oC cw Cooling Water: From cooling tower 30oC returned at less than 45oC wr River Water: From river 25oC returned at less than 35oC rw Refrigerated Water: In at 5oC returned at less than 15oC rb Refrigerated Brine: In at 45oC returned at less than 0oC cs Chemical Waste Water with high COD ss Sanitary Waste Water with high BOD, etc. el Electric Heat (specify 220, 440, 660V service) ng Natural Gas fg Fuel Gas fo Fuel Oil fw Fire Water
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Information Provided in a Flow Summary
Required Information Stream Number Temperature (oC) Pressure (bar) Vapor Fraction Total Mass Flowrate (kg/h) Total Mole Flowrate (kmol/h) Individual Component Flowrates (kmol/h) Optional Information Component Mole Fractions Component Mass Fractions Individual Component Flowrates (kg/h) Volumetric Flowrates (m3/h) Signicant Physical Properties Density, Viscosity, Other Thermodynamic Data Heat Capacity, Stream Enthalpy K-values Stream Name
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The summary table for the Benzene process

Stream Temp (o C) Pressure (bar) Vapor Fraction Flow (ton/h) Flow (kmol/h) Hydrogen Methane Benzene Toluene Stream Temp (o C) Pressure (bar) Vapor Fraction Flow (ton/h) Flow (kmol/h) Hydrogen Methane Benzene Toluene 1 25. 1.90 0.0 10.0 108.7 0.0 0.0 0.0 108.7 11 147. 2.8 0.0 3.27 35.7 0.0 0.0 1.1 34.6 2 59. 25.8 0.0 13.3 144.2 0.0 0.0 1.0 143.2 12 112. 3.3 0.0 14.0 185.2 0.0 0.0 184.3 0.88 3 25. 25.5 1.00 0.82 301.0 286.0 15.0 0.0 0.0 13 112. 2.5 0.0 22.7 290.7 0.02 0.88 289.46 1.22 4 225. 25.2 1.0 20.5 1204.4 735.4 317.3 7.6 144.0 14 112. 3.3 0.0 22.7 290.7 0.0 0.0 1.22 5 41. 25.5 1.0 6.41 758.8 449.4 302.2 6.6 0.7 15 38. 2.3 0.0 8.21 105.6 0.0 0.0 0.4 6 600. 25.0 1.0 20.5 1204.4 735.4 317.3 7.6 144.0 16 38. 2.5 1.0 2.61 304.2 178.0 123.05 2.85 0.31 7 41. 25.5 1.0 0.36 42.6 25.2 16.95 0.37 0.04 17 38. 2.8 1.0 0.07 4.06 0.67 3.10 0.26 0.03 8 38. 23.9 1.0 9.2 1100.8 651.9 438.3 9.55 1.05 18 38. 2.9 0.0 11.5 142.2 0.02 0.88 106.3 35.0 9 654. 24.0 1.0 20.9 1247.0 652.6 442.3 116.0 36.0 19 112. 2.5 1.0 0.01 0.90 0.02 0.88 0.0 0.0 10 90. 2.6 0.0 11.6 142.2 0.02 0.88 106.3 35.0 -.-.-.-.-.-.-.-.-.-
Component Mole Flow (kmol/h)
289.46 105.2
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Equipment Summary for Toluene Hydrodealkylation PFD

Heat Exchangers Type Area (m2 ) Duty (MJ/h) Shell Temp. (o C) Pres. (bar) Phase MOC Tube Temp. (o C) Pres. (bar) Phase MOC Vessels/Tower/ Reactors Temp (o C) Pressure (bar) Orientation MOC Size Height/Length (m) Diameter (m) Internals E-101 Fl.H. 36 15,190 225 26 Vap. 316SS 258 42 Cond. 316SS V-101 55 2.0 Horiznl CS 5.9 1.9 E-102 Fl.H. 763 46,660 654 24 Par. Cond. 316SS 40 3 l 316SS V-102 38 24 Vertical CS 3.5 1.1 s.p. E-103 MDP 11 1055 160 6 Cond. CS 90 3 l CS V-103 38 3.0 Vertical CS 3.5 1.1 s.p. E-104 Fl.H. 35 8335 112 3 Cond. CS 40 3 l CS V-104 112 2.5 Horiznl CS 3.9 1.3 E-105 MDP 12 1085 112 3 l CS 40 3 l CS T-101 147 3.0 Vertical CS 29 1.5 42 sieve trays 316SS E-106 Fl.H. 80 9045 185 11 Cond. CS 147 3 Vap. CS R-101 660 25 Vertical 316SS 14.2 2.3 catalyst packed bed-10m
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Equipment Summary for Toluene Hydrodealkylation PFD

Pumps/ Compressors Flow (kg/h) Fluid Density (kg/m3 ) Power (shaft) (kW) Type/Drive Type/Drive Eciency (Fluid Power/Shaft Power) MOC Temp. (in) (o C) Pres. (in) (bar) Pres. (out) (bar) Key: MOC 316SS CS Vap Cond Recipr. MDP P-101 (A/B) 13,000 870 14.2 Recip./ Electric 0.75 CS 55 1.2 27.0 P-102 (A/B) 22,700 880 3.2 Centrf./ Electric 0.50 CS 112 2.2 4.4 C-101 (A/B) 6770 8.02 49.1 Centrf./ Electric 0.75 CS 38 23.9 25.5 Heater Type MOC Duty (MJ/h) Radiant Area (m2 ) Convective Area (m2 ) Tube P (bar) H-101 Fired 316SS 27,040 106.8 320.2 26.0
Materials of construction Stainless steel type 316 Carbon steel Stream being vaporized Stream being condensed Reciprocating Multiple double pipe
Par F.H. Fl.H. Rbl s.p. l Centrf.
Partial Fixed head Floating head Reboiler Splash plate Liquid Centrifugal
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Example 1.2: Check Overall Material Balance
Check the overall material balance for the benzene process shown in Figure 1.3 (PFD). From the gure, we identify the input streams as Stream 1 (toluene feed) and Stream 3 (hydrogen feed) and the output streams as Stream 15 (product benzene) and Stream 16 (fuel gas). From the ow summary table, these ows are listed as (units are in (103 kg)/h): Input Stream 3 Total 0.82 Stream 15 Stream 16 Stream 1 10.00 Output 8.21 2.61 10.82 103 kg/h
10.82 103 kg/h Total Output = Input.
Balance is achieved since
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BFD Skeleton PFD PFD

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The summary table for the Benzene process

Stream Temp (o C) Pressure (bar) Vapor Fraction Flow (ton/h) Flow (kmol/h) Hydrogen Methane Benzene Toluene Stream Temp (o C) Pressure (bar) Vapor Fraction Flow (ton/h) Flow (kmol/h) Hydrogen Methane Benzene Toluene 1 25. 1.90 0.0 10.0 108.7 0.0 0.0 0.0 108.7 11 147. 2.8 0.0 3.27 35.7 0.0 0.0 1.1 34.6 2 59. 25.8 0.0 13.3 144.2 0.0 0.0 1.0 143.2 12 112. 3.3 0.0 14.0 185.2 0.0 0.0 184.3 0.88 3 25. 25.5 1.00 0.82 301.0 286.0 15.0 0.0 0.0 13 112. 2.5 0.0 22.7 290.7 0.02 0.88 289.46 1.22 4 225. 25.2 1.0 20.5 1204.4 735.4 317.3 7.6 144.0 14 112. 3.3 0.0 22.7 290.7 0.0 0.0 1.22 5 41. 25.5 1.0 6.41 758.8 449.4 302.2 6.6 0.7 15 38. 2.3 0.0 8.21 105.6 0.0 0.0 0.4 6 600. 25.0 1.0 20.5 1204.4 735.4 317.3 7.6 144.0 16 38. 2.5 1.0 2.61 304.2 178.0 123.05 2.85 0.31 7 41. 25.5 1.0 0.36 42.6 25.2 16.95 0.37 0.04 17 38. 2.8 1.0 0.07 4.06 0.67 3.10 0.26 0.03 8 38. 23.9 1.0 9.2 1100.8 651.9 438.3 9.55 1.05 18 38. 2.9 0.0 11.5 142.2 0.02 0.88 106.3 35.0 9 654. 24.0 1.0 20.9 1247.0 652.6 442.3 116.0 36.0 19 112. 2.5 1.0 0.01 0.90 0.02 0.88 0.0 0.0 10 90. 2.6 0.0 11.6 142.2 0.02 0.88 106.3 35.0 -.-.-.-.-.-.-.-.-.-
289.46 105.2
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Example 1.3: Check Species Conversion
Determine the conversion per pass of toluene to benzene in R-101 in Figure 1.3. Conversion is dened as benzene produced = total toluene introduced From the PFD, the input streams to R-101 are shown as Stream 6 (reactor feed) and Stream 7 (recycle gas quench), and the output stream is Stream 9 (reactor euent stream).From the information in Table 1.5 (units are kmol/h): toluene introduced = 144 (Stream 6) + 0.04 (Stream 7) = 144.04 kmol/h benzene produced = 116 (Stream 9) 7.6 (Stream 6) 0.37 (Stream 7) = 108.03 kmol/h = 108.03/144.04 = 0.75
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Example 1.3: Check Species Conversion
Alternatively, we can write moles of benzene = toluene in - toluene out = 144.04 36.00 produced = 108.04 kmol/h 108.04 = = 0.75 144.04
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Combining Topology, Stream Data, and Control Strategy Example 1.4 We locate Stream 1 in Figure 1.5 and note that immediately following the stream identication diamond a sta is axed. This sta carries three ags containing the following stream data: 1. Temperature of 25oC 2. Pressure of 1.9 bar 3. Mass ow rate of 10.0 103 kg/h The units for each process variable are indicated in the key provided at the lefthand side of Figure 1.5.
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Combining Topology, Stream Data, and Control Strategy Example 1.6 In the benzene process, the feed to the reactor is substantially hotter than the rest of the process and is crucial to the operation of the process. In addition, the reaction is exothermic, and the reactor euent temperature must be carefully monitored. For this reason Stream 6 (entering) and Stream 9 (leaving) have temperature ags. Example 1.7 The pressures of the streams to and from R-101 in the benzene process are also important. The dierence in pressure between the two streams gives the pressure drop across the reactor. This, in turn, gives an indication of any maldistribution of gas through the catalyst beds. For this reason, pressure ags are also included on Streams 6 and 9.
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PFD Piping and Instrumentation Diagram

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PFD Piping and Instrumentation Diagram
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Summary: Block Flow Process Diagram

1. Operations shown by blocks 2. Major ow lines shown with arrows giving direction of ow 3. Flow goes from left to right whenever possible 4. Light stream (gases) toward top with heavy stream (liquids and solids) toward bottom 5. Critical information unique to process supplied 6. If lines cross, then the horizontal line is continuous and the vertical line is broken. 7. Simplied material balance provided
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Summary: Process Flow Diagram (PFD)

A typical commercial PFD will contain the following information: 1. All the major pieces of equipment in the process will be represented on the diagram along with a description of the equipment. Each piece of equipment will have assigned a unique equipment number and a descriptive name. 2. All process ow streams will be shown and identied by a number. A description of the process conditions and chemical composition of each stream will be included. These data will be displayed either directly on the PFD or included in an accompanying ow summary table. 3. All utility streams supplied to major equipment that provides a process function will be shown. 4. Basic control loops, illustrating the control strategy used to operate the process during normal operations, will be shown.
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Summary: Piping and Instrumentation Diagram

The P&ID is the last stage of process design and serves as a guide by those who will be responsible for the nal design and construction. Based on this diagram: 1. Mechanical engineers and civil engineers will design and install pieces of equipment. 2. Instrument engineers will specify, install, and check control systems. 3. Piping engineers will develop plant layout and elevation drawings. 4. Project engineers will develop plant and construction schedules. Before nal acceptance, P&IDs serve as a checklist against which each item in the plant is checked.
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The Structure and Synthesis of Process Flow Diagrams
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The evolution of every process follows a similar path. The resulting processes will often be quite dierent, but the series of steps that have been followed to produce the nal processes are similar.
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Hierarchy of Conceptual Process Design

1. Decide whether the process will be batch or continuous. 2. Identify the input-output structure of the process. 3. Identify and dene the recycle structure of the process. 4. Identify and design the general structure of the separation system. 5. Identify and design the heat-exchanger network or process energy recovery system.
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Step 1 Batch vs. Continuous Process
Factor Size Batch Processes Smaller throughput favors batch operations. As throughput increases, the required size of the process equipment increases, and the technical diculties of moving large amounts of chemicals from equipment to equipment rapidly increase. Continuous Processes Economies of scale favor continuous processes for large throughput.
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Factor Batch Processes Continuous Processes Continuous or periodic testing of product quality is carried out, but some potentially large quantities of o-specication product can be produced. If o-specication material may be blended or stored in dump/slop tanks and reworked through the process when the schedule permits, continuous processes are favored.
Batch When the product quality of Accountability/ each batch of material must Product be veried and certied, batch Quality operations are preferred. This is especially true for pharmaceutical and food products. If reworking (reprocessing) of o-specication product is not permitted, small batches are favored.
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Factor Operational Flexibility Batch Processes Often the same equipment can be used for multiple operations, for example, a stirred tank can be used as a mixer, then a reactor, then as a stage of a mixer-settler for liquid-liquid extraction. Continuous Processes Operational exibility can be built in to continuous processes but often leads to inecient use of capital. Equipment not required for one process but needed for another may sit idle for months. Often continuous processes are designed to produce a xed suite of products from a well-dened feed material. If market forces change the feed/product availability/demand, then the plant will often be retrotted to accommodate the change.
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Factor Standardized Equipment Multiple Products Batch Processes Often batch processes can be easily modied to produce several dierent products using essentially the same equipment. Examples of batch plants that can produce 100 dierent products are known [3]. For such processes the optimal control and sequencing of operations are critical to the success of such a plant. Continuous Processes The product suite or slate produced from continuous processes is usually xed. Equipment tends to be designed and optimized for a single or small number of operating conditions.
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Factor Batch Processes Continuous Processes Generally, as throughput increases, continuous processes become more ecient. For example, fugitive energy losses are reduced, and rotating equipment (pumps, compressors, etc.) operate with higher eciency. Recycle of unused reactants and the integration of energy within the process or plant is standard practice and relatively easy to achieve.
Processing Operation of batch processes requires Eciency strict scheduling and control. Because dierent products are scheduled backto-back, changes in schedules have a ripple eect and may cause serious problems with product availability for customers. If the same equipment is used to produce many dierent products, then this equipment will not be optimized for any one product. Energy integration is usually not possible, so utility usage tends to be higher than for continuous processes. Separation and reuse of raw materials is more dicult than for continuous processes.
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Factor Maintenance and Operating Labor Batch Processes There are higher operating labor costs in standard batch plants due to equipment cleaning and preparation time. These costs have been shown to be reduced for the so-called pipeless batch plants [4]. Continuous Processes For the same process, operating labor will be lower for continuous processes.
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Factor Feedstock Availability Batch Processes Batch operations are favored when feedstock availability is limited, for example, seasonally. Canneries and wineries are examples of batch processing facilities that often operate for only part of the year. Continuous Processes Continuous plants tend to be large and need to operate throughout the year to be protable. The only way that seasonal variations in feeds can be accommodated is through the use of massive storage facilities that are very expensive.
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Factor Product Demand Batch Processes Seasonal demand for products such as fertilizers, gas-line antifreeze, deicing chips for roads and pavements, and so on, can be easily accommodated. Because batch plants are exible, other products can be made during the o-season. Continuous Processes Dicult to make other products during the oseason. However, similar but dierent products, for example, a family of solvents, can be produced using the same processes through a series of campaigns at dierent times during the year. Each campaign may last several months.
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Factor Rate of Reaction to Produce Products Batch Processes Batch operations favor processes that have very slow reaction rates and subsequently require long residence times. Examples include fermentation, aerobic and anaerobic wastewater treatment, and many other biological reactions. Continuous Processes Very slow reactions require very large equipment. The ow through this equipment will be slow and dispersion can be a problem if very high conversion is desired and plug ow is required.
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Factor Equipment Fouling Batch Processes When there is signicant equipment fouling, batch operations are favored because cleaning of equipment is always a standard operating procedure in a batch process and can be accommodated easily in the scheduling of the process. Continuous Processes Signicant fouling in continuous operations is a serious problem and is dicult to handle. Operating identical units in parallel, one on-line and the other o-line for cleaning, can solve this problem. However, capital investment is higher, additional labor is required, and safety problems are more likely.
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Factor Safety Batch Processes Generally, worker exposure to chemicals and operator error will be higher (per pound of product) than for continuous processes. Operator training in chemical exposure and equipment operation is critical. Continuous Processes Large chemical plants operating excellent continuously have safety records, [6], and safety procedures are well established. Operator training is still of great importance, but many of the risks associated with opening equipment containing chemicals are eliminated.
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Factor Batch Processes Continuous Processes Generally, continuous processes are easier to control. Also, more work/research has been done for these processes. For complicated and highly integrated (energy and/or raw materials) plants, the control becomes complex, and operational exiblity is greatly reduced.
Controllability This problem arises because batch processes often use the same equipment for dierent unit operations and sometimes to produce dierent products. The ecient scheduling of equipment becomes very important. The control used for this scheduling is complicated, [3].
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Step 2 Process Input-Output Structure
Process Concept Diagram A diagram uses the stoichiometry of the main reaction pathway to identify the feed and product chemicals. The toluene hydrodealkylation process
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Generic Block Flow Process Diagram This chemical process broken down into six basic areas or blocks Each block provides a function necessary for the operation of the process. GBFPD for toluene hydrodealkylation process
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Process Flow Diagram The PFD, by convention, shows the process feed stream(s) entering from the left and the process product stream(s) leaving to the right. Toluene hydrodealkylation process
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Utility Streams Utility streams, such as cooling water, steam, fuel, and electricity, rarely directly contact the process streams. They usually provide or remove thermal energy or work. Utility streams for Toluene hydrodealkylation process
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Other Considerations: Feed Purity and Trace Components In general, the feed streams entering a process do not contain pure chemicals. The option always exists to purify further the feed to the process. (Purication before feeding ?) The question of whether this purication step should be performed can only be answered by a detailed economic analysis. However, some common-sense heuristics may be used to choose a good base case or starting point. The following heuristics are modied from Douglas [1].
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Heuristics: Feed Purity and Trace Components
If the impurities are not present in large quantities (say < 10
20%) and these impurities do not react to form by-products, then do not separate them prior to feeding to the process.
For example, the hydrogen fed to the toluene HDA process contains a small amount of methane (5 mol%see Stream 3 in Table 1.5). Since the methane does not react (it is inert) and it is present as a small quantity, it is probably not worth considering separating it from the hydrogen. If the separation of the impurities is dicult (for example, an
impurity forms an azeotrope with the feed or the feed is a gas at the feed conditions), then do not separate them prior to feeding to the process.
For example, again consider the methane in Stream 3. The separation of methane and hydrogen is relatively expensive (see Example 2.3) because it involves low temperature and/or high pressure. This fact, coupled with the reasons given above, means that separation of the feed would not normally be attempted.
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If the impurities foul or poison the catalyst, then purify the feed. For example, one of the most common catalyst poisons is sulfur. This is especially true for catalysts containing Group VIII metals such as iron, cobalt, nickel, palladium, and platinum [7]. In the steam reformation of natural gas (methane) to produce hydrogen, the catalyst is rapidly poisoned by the small amounts of sulfur in the feed. A guard bed of activated carbon (or zinc oxide) is placed upstream of the reactor to reduce the sulfur level in the natural gas to the low ppm level. If the impurity reacts to form dicult-to-separate or hazardous
products, then purify the feed.

For example, in the manufacture of isocyanates for use in the production of polyurethanes, the most common synthesis path involves the reaction of phosgene with the appropriate amine [8]. Because phosgene is a highly toxic chemical, all phosgene is manufactured on-site via the reaction of chlorine and carbon monoxide. CO + Cl2 COCl2 (phosgene)
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If carbon monoxide is not readily available (by pipeline), then it must be manufactured via the steam reformation of natural gas. The following equation shows the overall main reaction (carbon dioxide may also be formed in the process but it is not considered here): CH4 + H2O CO + 3H2 The question to ask is, at what purity must the carbon monoxide be fed to the phosgene unit? The answer depends on what happens to the impurities in the CO. The main impurity is hydrogen. The hydrogen reacts with the chlorine to form hydrogen chloride that is dicult to remove from the phosgene, is highly corrosive, and is detrimental to the isocyanate product. With this information, it makes more sense to remove the hydrogen to the desired level in the carbon monoxide stream rather than send it through with the CO and cause more separation problems in the phosgene unit and further downstream. Acceptable hydrogen levels in carbon monoxide feeds to phosgene units are less than 1%.
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If the impurity is present in large quantities, then purify the feed. This heuristic is fairly obvious as signicant additional work and heating/cooling duties are required to process the large amount of impurity. Nevertheless, if the separation is dicult and the impurity acts as an inert, then separation may still not be warranted. An obvious example is the use of air, rather than pure oxygen, as a reactant. Because nitrogen often acts as an inert compound, the extra cost of purifying the air is not justied compared with the lesser expense of processing the nitrogen through the process. An added advantage of using air, as opposed to pure oxygen, is the heat absorbing capacity of nitrogen, which helps moderate the temperature rise of many highly exothermic oxidation reactions.
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Addition of Feeds Required to Stabilize Products or Enable Separations Generally, product specications are given as a series of characteristics that the product stream must meet or exceed. Clearly, the purity of the main chemical in the product is the major concern. However, other specications such as color, density or specic gravity, turbidity, and so on, may also be specied. Often many of these specications can be met in a single piece or train of separation equipment. However, if the product stream is, for example, reactive or unstable, then additional stabilizing chemicals may need to be added to the product prior to it going to storage. These stabilizing chemicals are additional feed streams to the process. The same argument can be made for other chemicals such as solvent or catalyst that are eectively consumed in the process. If a solvent such as water or an organic chemical is required to make a separation take place, for example, absorption of a solvent-soluble chemical from a gas stream, then this solvent is an additional feed to the process. Accounting for these chemicals both in feed costs and in the overall material balance (in the product streams) is very important.
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Inert Feed Material to Control Exothermic Reactions
In some cases, it may be necessary to add additional inert feed streams to the process in order to control the reactions taking place. Common examples of this are partial oxidation reactions of hydrocarbons. For example, consider the partial oxidation of propylene to give acrylic acid, an important chemical in the production of acrylic polymers. The feeds consist of nearly pure propylene, air, and steam. The basic reactions that take place are: C3H6 + C3H6 + C3H6 +
3 2 O2 5 2 O2 9 2 O2
C3H4O2 + H2O Reaction 1 C2H4O2 + H2O + CO2 Reaction 2 3H2O + CO2 Reaction 3
All these reactions are highly exothermic, not limited by equilibrium, and potentially explosive. In order to eliminate or reduce the potential for explosion, steam is fed to the reactor to dilute the feed and provide thermal ballast to absorb the heat of reaction and make control easier.
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Inert Feed Material to Control Exothermic Reactions
In some processes, enough steam (or other inert stream) is added to move the reaction mixture out of the ammability limits, thus eliminating the potential for explosion. The steam (or other inert stream) is considered a feed to the process, must be separated, and leaves as a product, by-product, or waste stream.
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Inert Feed Material to Control Equilibrium Reactions
Sometimes it is necessary to add an inert material to shift the equilibrium of the desired reaction. Consider the production of styrene via the catalytic dehydrogenation of ethyl benzene: C6H5CH2CH3 C6H5CH=CH2 + H2 ethyl benzene styrene This reaction takes place at high temperature (600 750oC) and low pressure (< 1 bar) and is limited by equilibrium. The ethyl benzene is co-fed to the reactor with superheated steam. The steam acts as an inert in the reaction and both provides the thermal energy required to preheat the ethyl benzene and dilutes the feed. As the steam to ethyl benzene ratio increases, the equilibrium shifts to the right (LeChateliers principle) and the singlepass conversion increases. The optimum steam-to-ethyl benzene feed ratio is based on the overall process economics.
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Step 3 The Recycle Structure of the Process
This step basically involves the recovery of materials and energy from the process. It may be instructive to break down the operating costs for a typical chemical process. Peters and Timmerhaus suggest that raw materials make up between 10% and 50% of the total operating costs for processing plants; however, due to increasing conservation and waste minimization techniques this estimate may be low, and an upper limit of 75% is more realistic. Because these raw materials are so valuable, it is imperative that we be able to separate and recycle unused reactants. The extent of recycling of unused reactants depends largely on the ease with which these unreacted raw materials can be separated (and puried) from the products that are formed within the reactor.
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Eciency of Raw Material Usage Single-pass Conversion = Overall Conversion = Yield =
reactant consumed in reaction reactant fed to the reactor reactant consumed in process reactant fed to the process moles of reactant to produce desired product moles of limiting reactant reacted
Benzene Process: (for the most costly reactant, toluene) 144.0 36.0 = 0.75 or 75% Single-pass Conversion = 144.0 108.7 0.4 0.31 Overall Conversion = = 0.993 or 99.3% 108.7 105.2 + 2.85 = 0.9995 or 99.95% Yield = 108.7 0.4 0.31
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Recycle Feed and Product Together with
recycling both feed and product should be considered.
a Purge Stream
If separation of unreacted feed and products is not accomplished easily, then
Recycle structure of hydrogen stream. Methane is purged via stream 16.
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Recycle Feed and Product Together without a Purge Stream
This recycle scheme is only feasible when product can react further in reactor and therefore there is no need to purge it from the process. (2C6H6 C12H10 + H2)
Because diphenyl reacts back to benzene, it can be recycled without purging it from the system.
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Other Issues Aecting the Recycle Structure How many potential recycle streams are there? How does excess reactant aect recycle structure? How many reactors are required? Do unreacted raw material streams need to be puried prior to recycling? Is recycling of an inert warranted? Can recycling an unwanted product or an inert shift the reaction equilibrium to produce less of an unwanted product? Is recycling of an unwanted product or an inert warranted for the control of reactor operation? What phase is the recycle stream?
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Step 4 General Structure of Separation System Step 5 HEN or Process Energy Recovery System
Next Lecture
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Benzene Process PFD Analysis

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Benzene Process PFD Analysis

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Turton/Bailie/Whiting/Shaeiwitz: Analysis, Synthesis, and Design of Chemical Processes Chapters 1, 2

The Structure and Synthesis of Process Flow Diagrams

Department of Chemical Engineering National TAIWAN University

Diagrams for Understanding Chemical Processes

Block Flow Process Diagram

Compound Hydrogen Methane Benzene

Block Flow Process Diagram

Block Flow Process Diagram

BFD Skeleton PFD

BFD Skeleton PFD PFD

Process Flow Diagram

Process Flow Diagram

Process Flow Diagram

Process Flow Diagram

The summary table for the Benzene process

Component Mole Flow (kmol/h)

Component Mole Flow (kmol/h)

Equipment Summary for Toluene Hydrodealkylation PFD

Equipment Summary for Toluene Hydrodealkylation PFD

Par F.H. Fl.H. Rbl s.p. l Centrf.

Process Flow Diagram

10.82 103 kg/h Total Output = Input.

Balance is achieved since

BFD Skeleton PFD PFD

The summary table for the Benzene process

Component Mole Flow (kmol/h)

Component Mole Flow (kmol/h)

Process Flow Diagram

Process Flow Diagram

Process Flow Diagram

Process Flow Diagram

PFD Piping and Instrumentation Diagram

PFD Piping and Instrumentation Diagram

Summary: Block Flow Process Diagram

Summary: Process Flow Diagram (PFD)

Summary: Piping and Instrumentation Diagram

The Structure and Synthesis of Process Flow Diagrams

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

products, then purify the feed.

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design

Hierarchy of Conceptual Process Design