Development of the Base-Case Design O Understand how to go about assembling design data and creating a preliminary data base. O Be able to implement the steps in creating flowsheets involving reactions, separations, and T-P change operations. In so doing, many alternatives are identified that can be assembled into a synthesis tree that contains the most promising alternatives. O Know how to select the principal pieces of equipment and to create a detailed process flowsheet, with a material and energy balance and a list of major equipment items. On completing this part of the course, you should: Preliminary Database Creation to assemble data to support the design. Experiments often necessary to supply missing database items or verify crucial data. Preliminary Process Synthesis top-down approach. to generate a synthesis tree of design alternatives. illustrated by the synthesis of processes for the manufacture of VCM and tPA (refer to text book, pg. 94). Development of Base-case Design focusing on the most promising alternative(s) from the synthesis tree.
Environmental and safety data toxicity data flammability data
Chemical Prices e.g. as published in the Chemical Marketing Reporter Companies carry out market studies and have a basis for projecting market size and chemical prices. Chemical market reporter, newspaper provide up-to-date for chemical commerce, but not reflect the market situation, just give a good starting point. To get the better estimation, contact manufacturers directly. For utility prices; steam, cooling water, electricity, it is desirable to estimate it during process creation.
Design concepts result from experiments Additional experiments at other conditions of compositions, temp, pressures and representative solvents. Rates of reactions and catalyst life estimations. Aid in the selection and preliminary design of separation operations. Synthesis of chemical processes involves: Selection of processing mode: continuous or batch Fixing the chemical state of raw materials, products, and by- products, noting the differences between them. Process operations (unit operations) - flowsheet building blocks Synthesis steps - O Eliminate differences in molecular types O Distribute chemicals by matching sources and sinks O Eliminate differences in composition O Eliminate differences in temperature, pressure and phase O Integrate tasks (combine tasks into unit operations)
Decide on the raw material and product specifications (states): Mass (flow rate) Composition (mole or mass fraction of each chemical species having a unique molecular type) Phase (solid, liquid, or gas) Form (e.g., particle-size distribution and particle shape) Temperature Pressure
Chemical reaction To effect differences in the molecular types between raw material and product streams. Positioning in the flowsheet involves many considerations (conversion, rates, side reactions, reactions in the reverse direction), related to T and P at which the reaction are carried out. Methods to remove or supply energy Catalysts (competitive reaction rates and selectivity). Separation of chemicals needed whenever there is difference between the desired composition of a product stream or intermediate stream and the composition of its source. (separation is needed when there is impurities in raw materials, or when products, byproducts and unreacted raw materials coexist in effluent stream). Choice of separations operations depends on the phase of the mixture and differences in the physical properties of chemical species. Distillation (volatilities are large differrent) (vapor-liquid separation); Crystallization (melting point s are large different) (solid-liquid separation) Liquid liquid separation (difference in volatilities and melting points are small): use solvent which is selective for some components (e.g. liquid- liquid extraction). Gases separation: adsorbent, absorbent, membrane separation
Phase separation - Flash drums (vapor-liquid separation) - Decanters (liquid-liquid separation) - Filters and centrifuge (liquid-solid separation) Throughout a chemical process, there are often: - Change of temperature - Change of pressure - Change of phase when enter or leave a process operation (e.g. reaction and separation operations) or during Mixing and splitting of streams and branches
Synthesis Step O Eliminate differences in molecular types O Distribute chemicals by matching sources and sinks O Eliminate differences in composition O Eliminate differences in temperature, pressure and phase O Integrate tasks (combine tasks into unit operations and decide between continuous or batch processing) Process Operation Chemical reaction Mixing Separation Temperature, pressure and phase change
1. Continuous - Dominant in chemical process industry (large-scale) for manufacture of commodity chemicals, plastic and etc - Combined chemical fed, processing and product removal continuously - When production rates are low, it is difficult to justify construction of continuous plant comprised of small vessels and pipes 2. Batch - Small scale production rates, production of many specialty chemical using batch processing - Batch chemical fed before and product are removed after processing - Fed-batch combined fed and process continuously, product removed after processing is finished - Batch-product removal chemical fed before processing. Then product is removed continuously as processing occurs - Fed- batch and batch-product removal semicontinuous process - The challenge in designing batch processing time and size of vessel Continuous and Batch Continuous Batch Fed-batch Batch-product removal Example 1:
Vinyl Chloride Manufacture Process Creation DESIGN AND ANALYSIS II - (c) Daniel R. Lewin 14
Chemical Molecular weight Chemical formula Chemical structure Acetylene 26.04 C 2 H 2 H - C C - H Chlorine 70.91 Cl 2 Cl-Cl
1,2-Dichloroethane
98.96
C 2 H 4 Cl 2 Cl Cl | | H-C-C-H | | H H
Ethylene
28.05
C 2 H 4 H H C = C H H Hydrogen chloride 36.46 HCl H-Cl
Vinyl chloride
62.50
C 2 H 3 Cl H Cl C = C H H
Chemicals participating in VC Manufacture: O Direct chlorination of ethylene:
Advantages: Attractive solution to the specific problem denoted as Alternative 2 (analysis of primitive problem in chapter 1). Occurs spontaneously at a few hundred o C. Disadvantages: Does not give a high yield of VC without simultaneously producing large amounts of by-products such as dichloroethylene Half of the expensive chlorine is consumed to produce HCl by- product, which may not be sold easily.
HCl Cl H C Cl H C 3 2 2 4 2
(2.1) O Hydrochlorination of acetylene:
Advantages: This exothermic reaction is a potential solution for the specific problem denoted as Alternative 3 (analysis of primitive problem in chapter 1). It provides a good conversion (98%) of C 2 H 2 to VC in the presence of HgCl 2 catalyst impregnated in activated carbon at atmospheric pressure. These are fairly moderate reaction conditions, and hence, this reaction deserves further study. Disadvantages: Flammability limits of C 2 H 2 (LFL = 2.5; UFL = 100%)
Cl H C HCl H C 3 2 2 2
(2.2) O Thermal cracking of C 2 H 4 Cl 2 from chlorination of C 2 H 4 :
Advantages: Conversion of ethylene to 1,2-dichloroethane in exothermic reaction (2.3) is 98% at 90 o C and 1 atm with a Friedel-Crafts catalyst such as FeCl 3 . This intermediate is converted to vinyl chloride by thermal cracking according to the endothermic reaction (2.4), which occurs spontaneously at 500 o C with conversions as high as 65% (Alternative 2). Disadvantage: Half of the expensive chlorine is consumed to produce HCl by- product, which may not be sold easily.
2 4 2 2 4 2 Cl H C Cl H C HCl Cl H C Cl H C 3 2 2 4 2
HCl Cl H C Cl H C 3 2 2 4 2
(2.3) (2.4) (2.1) O Thermal Cracking of C 2 H 4 Cl 2 from Oxychlorination of C 2 H 4 :
Advantages: Highly exothermic reaction (2.5) achieves a 95% conversion to C 2 H 4 Cl 2 in the presence of CuCl 2 catalyst, followed by pyrolysis step (2.4) as Reaction Path 3. Excellent candidate when cost of HCl is low Also a solution for specific problem denoted in Alternative 3. Disadvantages: Economics dependent on cost of HCl
(2.5) (2.4) (2.6) O H Cl H C O HCl 2 H C 2 2 4 2 2 2 1 4 2
HCl Cl H C Cl H C 3 2 2 4 2
O H Cl H C O HCl H C 2 3 2 2 2 1 4 2
O Balanced Process for Chlorination of Ethylene:
Advantages: Combination of Reaction Paths 3 and 4 - addresses Alternative 2. All Cl 2 converted to VC All HCl produced in the pyrolysis reaction is consumed in the oxychlorination reaction No by-products! (2.5) (2.3) (2.7) O H Cl H C O HCl 2 H C 2 2 4 2 2 2 1 4 2
HCl 2 Cl H C 2 Cl H C 2 3 2 2 4 2
(2.4) 2 4 2 2 4 2 Cl H C Cl H C O H Cl H C 2 O Cl H C 2 2 3 2 2 2 1 2 4 2
Chemical Cost (cents/lb) Ethylene 18 Acetylene 50 Chlorine 11 Vinyl chloride 22 Hydrogen chloride 18 Water 0 Oxygen (air) 0
Chemical Bulk Prices Reaction Path O is eliminated due its low selectivity. This leaves four alternative paths, to be compared first in terms of Gross Profit. Reaction path O C 2 H 4 + Cl 2 = C 2 H 3 Cl + HCl lb-mole 1 1 1 1 Molecular weight 28.05 70.91 62.50 36.46 lb 28.05 70.91 62.50 36.46 lb/lb of vinyl chloride 0.449 1.134 1 0.583 cents/lb 18 11 22 18
Gross profit = 22(1) + 18(0.583) - 18(0.449) - 11(1.134) = 11.94 cents/lb VC Reaction Path Overall Reaction Gross Profit (cents/lb of VC) O C 2 H 2 + HCl = C 2 H 3 Cl -9.33 O C 2 H 4 +Cl 2 = C 2 H 3 Cl + HCl 11.94 O C 2 H 4 + HCl + O 2 = C 2 H 3 Cl + H 2 O 3.42 O 2C 2 H 4 + Cl 2 + O 2 = 2C 2 H 3 Cl + H 2 O 7.68
Raw Materials Process Flowsheet? C 2 H 4 , Cl 2 Products C 2 H 3 Cl, HCl Cl 2 113,400 lb/hr C 2 H 4 44,900 lb/hr Direct Chlorination Pyrolysis C 2 H 4 Cl 2 HCl 58,300 lb/hr C 2 H 3 Cl 100,000 lb/hr HCl C 2 H 3 Cl C 2 H 4 Cl 2 C 2 H 4 Cl 2 C 2 H 3 Cl + HCl C 2 H 4 + Cl 2 C 2 H 4 Cl 2 800 MM lb/year @ 330 days/y 100,000 lb/hr VC On the basis of this principal sink, the HCl sink and reagent sources can be computed (each flow is 1,600 lbmol/h) Next step involves distributing the chemicals by matching sources and sinks. A conversion of 100% of the C 2 H 4 is assumed in the chlorination reaction. Only 60% of the C 2 H 4 Cl 2 is converted to C 2 H 3 Cl with a byproduct of HCl, according to Eqn. (2.4). To satisfy the overall material balance, 158,300 lb/h of C 2 H 4 Cl 2
must produce 100,000 lb/h of C 2 H 3 Cl and 58,300 lb/h of HCl. But a 60% conversion only produces 94,980 lb/h of VC and HCl. The additional C 2 H 4 Cl 2 needed is computed by mass balance to equal: [(1 - 0.6)/0.6] x 158,300 or 105,533 lb/h. Its source is a recycle stream from the separation of C 2 H 3 Cl from unreacted C 2 H 4 Cl 2 , from a mixing operation, inserted to combine the two sources, to give a total 263,833 lb/h. The effluent stream from the pyrolysis operation is the source for the C 2 H 3 Cl product, the HCl by-product, and the C 2 H 4 Cl 2 recycle. Reactor pressure levels: Chlorination reaction: 1.5 atm is recommended, to eliminate the possibility of an air leak into the reactor containing ethylene.
Pyrolysis reaction: 26 atm is recommended by the B.F. Goodrich patent (1963) without any justification. Since the reaction is irreversible, the elevated pressure does not adversely affect the conversion. Most likely, the patent recommends this pressure to reduce the size of the pyrolysis furnace, although the tube walls must be considerably thicker and many precautions are necessary for operation at elevated pressures.
The pressure level is also an important consideration in selecting the separation operations, as will be discussed in the next synthesis step.
The product of the chlorination reaction is nearly pure C 2 H 4 Cl 2 , and requires no purification. In contrast, the pyrolysis reactor conversion is only 60%, and one or more separation operations are required to match the required purities in the C 2 H 3 Cl and HCl sinks. One possible arrangement is given in the next slide. The data below explains the design decisions made.
Boiling point ( o C) Critical constants Chemical 1 atm 4.8 atm 12 atm 26 atm T c ,C P c , atm HCl -84.8 -51.7 -26.2 0 51.4 82.1 C 2 H 3 Cl -13.8 33.1 70.5 110 159 56 C 2 H 4 Cl 2 83.7 146 193 242 250 50
Boiling point ( o C) Critical constants Chemical 1 atm 4.8 atm 12 atm 26 atm T c ,C P c , atm HCl -84.8 -51.7 -26.2 0 51.4 82.1 C 2 H 3 Cl -13.8 33.1 70.5 110 159 56 C 2 H 4 Cl 2 83.7 146 193 242 250 50
There may be other, possibly better alternative configurations, as discussed in the following chapter. Summary of synthesis steps: 1. Reaction path 2. Distribution of chemical 3. Separations 4. Temperature, pressure and phase change 5. Task integration 1. Heuristics are the rules of thumb which must be obeyed for designing a process 2. Heuristics are used commonly by design team to expedite the generation of alternative flowsheet in preliminary process synthesis Detailed for heuristics will be covered on topic 4 Develop one or two of the more promising flowsheets from the synthesis tree for more detailed consideration. 1. Block flow diagram (BFD) - Represent the main processing sections in terms of functional blocks - Diagram indicates overall material balances and condition at each stage where appropriate - The detail is helpful to summarise principal processing section and appropriate to be used in early design stages, where alternative processes are usually under consideration 2. Process flow diagram (PFD) - Provide more detailed view of process - Display all major processing unit in the process (including HE, pump, compressor), provide stream info, include main control loops - Preliminary PFD constructed using process simulator, then more detailed prepared using software such as AUTOCAD and Microsoft Visio 3. Processing unit - Icon that represent units are links by line that represent the process stream - Unit for icon are taken from accepted standard (ASME: American Society for Mechanical Engineers) - Labeling refer textbook pg 103 (new version); pg 97 (old version) 4. Stream information - Directed lines represent stream, with flow direction from left to right wherever possible - By convention, when streamline cross, the horizontal line shown as continuous, vertical line broken - Mass flowrate, P, T may appear on PFD directly, but more often are placed in the stream table instead, for clarity - See table 4.6 pg 104 (new version); table 3.6 pg 100 (old version) 5. Utilities - Various utility streams are utilised for heating or cooling the process stream - For ex. See table 4.7 pg 105 (new version); table 3.7 pg 100 (old version)
6. Equipment summary table - Provides info for each equipment item in PFD (See table 4.8 pg 105 (new version); table 3.8 pg 101 (old version) - Materials of construction (MOC) and operating T and P, required for all units 7. Piping and Instrumentation diagram (P&ID) - Design document transmitted by process design engineers to engineers responsible for plant construction - To support start-up, operation of process and operator training - Contains item that do not appear in PFD such as location and type of measurement and control instruments, positioning of valves, size, schedule, material of construction of piping etc.
8. Calculation supporting flow diagram - The important calculation in flow diagram is mass and energy balance for each process - Other than that, engineer should know how to calculate number of stages and reflux ratio for distillation towers - The calculation could been completed using process simulators - Complete simulation not justified until design team is ready to begin detailed design - Gradually, additional detail is added to the simulation model. For ex.: number of stages and reflux ratio are selected for the distillation column and; material and energy balance are completed with recycle streams that are not assumed to be pure
Process Flow Diagram (PFD) development is central to the design task
The PFD depicts the process route, showing the flows of material and energy between those process units that make up the plant. It therefore
defines the role/task and operating conditions of each section or unit in the process line gives an overall view of the process route allows an insight into the overall operability of the process provides an initial assessment of potential sources of hazards forms the template for subsequent material and energy balances
A well thought out PFD simplifies unit process design and allows more accurate assessment of the overall viability of the plant
There are usually two stages to developing the PFD, namely:
operational specification functional specification Here, you decide upon the sections of the process that would be needed to manufacture the product. Typically, a proposed plant is divided into the following sections:
raw material storage feed preparation manufacturing separation purification effluent and waste treatment product packaging and storage These are shown in the following figure In most cases, the required sections would have been dictated by the chosen process route. It is during this stage of the design that you should be alerted to:
where recycles may be required to minimise wastage materials handling and transport requirements, and where loss containment systems (control) have to be installed The result at this stage is the process flowsheet Next, using process knowledge together with information obtained from the literature, you will have to provide details about the kind and number of main process units that are required to perform the various operations defined by the main sections of the plant. By convention, you should include only those units where composition, temperature or pressure changes occur. To do this, you will need data on reaction kinetics, physical and thermodynamic properties of the materials being handled at each section of the process and to call upon your knowledge about the capabilities of each type of processing equipment. Thus, it is during this stage of the PFD development, that you get an indication of the: probable materials of construction for each process unit utilities (steam, water, electricity) that will be required potential hazards that may occur at unit level impact of each unit on other units in the plant 1. Create a detailed database by refining and adding to preliminary database 2. A pilot-plant is constructed to confirm that the equipment items operate properly and provide data for detailed data bank and simulation model is prepared 3. It is common to add transport and kinetics data, as well as data concerning the feasibility of separation, the identity of any forbidden matches in HE, heuristic parameters and data for sizing equipment 4. Additional data for sizing equipment are typically maximum pressure drops, tube lengths and baffle spacing in HE, surface tension and drag coefficients for estimating flood velocities, specification for tray spacing in multistaged towers and residence times in flash vessel and surge tanks 1. As detailed database is assembled, the needs for pilot-plant testing become quite evident 2. For manufacture new chemical, pilot plant can produce quantities of product suitable for testing and evaluation by potential customers 3. Very few processes that include reaction steps are constructed without some form of pilot plant testing prior to doing detailed design calculation. Though it is an expensive and time consuming step. 4. In connection with the need for laboratory experiments, pilot plant test also help to identify potential problem that arise from small quantities of impurities in feed stream and etc 5. Pilot plant can also verify separation schemes developed during process design 1. When part of simulation model exist, it is common for design team to assemble a more comprehensive model, one that enable team to examine the effect of parametric changes on entire process 2. When process simulator have not been used for design, simulation model is created for comparison with pilot plant data and parametric studies Preliminary Database Creation needed to provide data to support the design. Experiments often necessary to supply missing database items or verify crucial data. Preliminary Process Synthesis Selection of processing mode Fixing the chemical state Process operation Synthesis steps: - Top-down approach. - Generates a synthesis tree of design alternatives. Development of Base-case Design Creating block flow diagram (BFD)/process flow diagram (PFD) focusing on the most promising alternative(s) from the synthesis tree. Symbols (or elements of symbols) for use in conjunction with other symbols Symbols (or elements of symbols) for use in conjunction with other symbols Pumps and Compressors