Flowsheet of Acrylonitrile Process

INTRODUCTION AND COURSE OBJECTIVES THROUGH MOTIVATING EXAMPLES
MOTIVATING EXAMPLE #1: ACRYLONITRILE PROCESS

5.0 kg AN/s 5.1 kg H2O/s + Gases Reactor Water 6.0 kg H2O/s B FW 1.2 kg H2O/s Boiler Tail Gases to Disposal Steam Steam-Jet Ejector Condensate 34 ppm NH3 0.2 kg AN/s 1.2 kg H2O/s
O2 NH3 C3H6
Scrubber
Off-Gas Condensate 14 ppm NH3 0.4 kg AN/s 4.6 kg H2O/s
18 ppm NH3 4.6 kg AN/s 6.5 kg H2O/s
AN to Sales 10 ppm NH3 4.2 kg AN/s 1.0 kg H2O/s 1ppm NH3 3.9kg AN/s 0.3 kg H2O/s
Distillation Column
Decanter
Aqueous Layer 25 ppm NH3 0.4 kg AN/s 5.5 kg H2O/s
Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s
20 ppm NH3 1.1 kg AN/s 12.0kg H2O/s Wastewater to Biotreatment
Flowsheet of Acrylonitrile Process Sold-out product with large profit/lb sold => need to expand. Biotreatment is a bottleneck (cannot tolerate more throughput). Also, need to reduce fresh water consumption.
TWO PROCESS-DESIGN OBJECTIVES: 1. DEBOTTLENECK (ENABLE MORE THROUGHPUT FOR) THE PROCESS. 2. REDUCE FRESH WATER CONSUMPTION.
Let's brain storm for some alternative solutions.
5.0 kg AN/s 5.1 kg H2O/s O2 + Gases NH3 Reactor C 3H 6
Steam-Jet B FW Water 1.2 kg H2O/s SteamEjector Condensate 6.0 kg H2O/s Boiler 34 ppm NH3 0.2 kg AN/s Tail Gases 1.2 kg H2O/s Scrubber to Disposal AN to Sales 1ppm NH3 3.9kg AN/s 0.3 kg H2O/s
18 ppm NH3 4.6 kg AN/s 10 ppm NH3 Off-Gas Condensate 6.5 kg H2O/s 4.2 kg AN/s 1.0 kg H2O/sDistillation 14 ppm NH3 Column 0.4 kg AN/s Decanter 4.6 kg H2O/s Aqueous Layer 25 ppm NH3 0.4 kg AN/s 5.5 kg H2O/s
Wastewater to Biotreatment
18 ppm NH3 4.6 kg AN/s 10 ppm NH3 Off-Gas Condensate 6.5 kg H2O/s 4.2 kg AN/s 1.0 kg H2O/sDistillation 14 ppm NH3 Column 0.4 kg AN/s Decanter 4.6 kg H2O/s Aqueous Layer 25 ppm NH3 0.4 kg AN/s 5.5 kg H2O/s 20 ppm NH3 1.1 kg AN/s 12.0kg H2O/s
Steam-Jet B FW Water 1.2 kg H2O/s SteamEjector Condensate 6.0 kg H2O/s Boiler 34 ppm NH3 0.2 kg AN/s Tail Gases 1.2 kg H2O/s Scrubber to Disposal AN to Sales 18 ppm NH3 1ppm NH3 4.6 kg AN/s 10 ppm NH3 Off-Gas 3.9kg AN/s Condensate 6.5 kg H2O/s 4.2 kg AN/s 0.3 kg H 2O/s 1.0 kg H2O/sDistillation 14 ppm NH3 Column 0.4 kg AN/s Decanter 4.6 kg H2O/s Aqueous Layer 25 ppm NH3 0.4 kg AN/s 5.5 kg H2O/s 20 ppm NH3 1.1 kg AN/s 12.0kg H2O/s Wastewater to Biotreatment
Steam-Jet B FW Water 1.2 kg H2O/s SteamEjector Condensate 6.0 kg H2O/s Boiler 34 ppm NH3 0.2 kg AN/s Tail Gases 1.2 kg H2O/s Scrubber to Disposal AN to Sales 18 ppm NH3 1ppm NH3 4.6 kg AN/s 10 ppm NH3 Off-Gas 3.9kg AN/s 4.2 kg AN/s 6.5 kg H O/s Condensate 2 0.3 kg H 2O/s 1.0 kg H2O/sDistillation 14 ppm NH3 Column 0.4 kg AN/s Decanter 4.6 kg H2O/s Aqueous Layer 25 ppm NH3 0.4 kg AN/s 5.5 kg H2O/s 20 ppm NH3 1.1 kg AN/s 12.0kg H2O/s Wastewater to Biotreatment
5.0 kg AN/s 5.1 kg H2O/s O2 + Gases NH3 Reactor C3H6
B FW Water 1.2 kg H2O/s Steam 6.0 kg H2O/s Boiler Tail Gases Scrubber to Disposal
Fresh Water
Condensate 34 ppm NH3 0.2 kg AN/s 1.2 kg H2O/s AN to Sales 1ppm NH3 3.9kg AN/s 0.3 kg H2O/s
18 ppm NH3 4.6 kg AN/s 10 ppm NH3 Off-Gas 6.5 kg H2O/s 4.2 kg AN/s Condensate 1.0 kg H2O/sDistillation 14 ppm NH3 Column 0.4 kg AN/s Decanter 4.6 kg H2O/s Aqueous Layer 25 ppm NH3 0.4 kg AN/s 5.5 kg H2O/s 20 ppm NH3 1.1 kg AN/s 12.0kg H2O/s
New Separation
Steam-Jet B FW Water 1.2 kg H2O/s SteamEjector Condensate 6.0 kg H O/s Boiler 5.0 kg AN/s 34 ppm NH3 2 5.1 kg H2O/s 0.2 kg AN/s O2 Tail Gases + Gases 1.2 kg H2O/s NH3 to Disposal Scrubber Reactor C 3H 6 AN to Sales 18 ppm NH3 1ppm NH3 4.6 kg AN/s 10 ppm NH3 Off-Gas 3.9kg AN/s 4.2 kg AN/s 6.5 kg H O/s Condensate 2 0.3 kg H Distillation 2O/s 1.0 kg H2O/s 14 ppm NH3 Column 0.4 kg AN/s Decanter New 4.6 kg H2O/s Aqueous Layer 25 ppm NH3 0.4 kg AN/s 5.5 kg H2O/s 20 ppm NH3 1.1 kg AN/s 12.0kg H2O/s Wastewater to Biotreatment
Separation
18 ppm NH3 4.6 kg AN/s 10 ppm NH3 Off-Gas Condensate 6.5 kg H2O/s 4.2 kg AN/s 1.0 kg H2O/sDistillation 14 ppm NH3 Column 0.4 kg AN/s Decanter 4.6 kg H2O/s Aqueous Layer New 25 ppm NH3 Separation 0.4 kg AN/s 5.5 kg H2O/s 20 ppm NH3 1.1 kg AN/s 12.0kg H2O/s
New Separation
New Separation
Extraction
Stripping
Ion Exchange
Steam-Jet B FW Water 1.2 kg H2O/s SteamEjector Condensate 6.0 kg H2O/s Boiler 5.0 kg AN/s 34 ppm NH3 5.1 kg H2O/s 0.2 kg AN/s O2 Tail Gases + Gases 1.2 kg H2O/s NH3 Scrubber to Disposal Reactor C 3H 6 AN to Sales 18 ppm NH3 1ppm NH3 4.6 kg AN/s 10 ppm NH3 Off-Gas 3.9kg AN/s Condensate 6.5 kg H2O/s 4.2 kg AN/s 1.0 kg H2O/sDistillation 0.3 kg H2O/s 14 ppm NH3 Column 0.4 kg AN/s Decanter 4.6 kg H2O/s
Stripping
Ion Exchange
Aqueous Layer 25 ppm NH3 0.4 kg AN/s 5.5 kg H2O/s 20 ppm NH3 1.1 kg AN/s 12.0kg H2O/s
Extraction
18 ppm NH3 4.6 kg AN/s 10 ppm NH3 Off-Gas 6.5 kg H2O/s 4.2 kg AN/s Condensate 1.0 kg H2O/sDistillation 14 ppm NH3 Column 0.4 kg AN/s Decanter 4.6 kg H2O/s Aqueous Layer 25 ppm NH3 0.4 kg AN/s 5.5 kg H2O/s 20 ppm NH3 1.1 kg AN/s 12.0kg H2O/s
Stripping
Ion Exchange
Extraction
Steam-Jet B FW Water 1.2 kg H2O/s SteamEjector Condensate 6.0 kg H2O/s Boiler 34 ppm NH3 0.2 kg AN/s Tail Gases 1.2 kg H2O/s Scrubber to Disposal AN to Sales 18 ppm NH3 Ion 1ppm NH3 4.6 kg AN/s 10 ppm NH3 Off-Gas 3.9kg AN/s Exchange Condensate 6.5 kg H2O/s 4.2 kg AN/s 1.0 kg H2O/sDistillation 0.3 kg H2O/s 14 ppm NH3 Column 0.4 kg AN/s Decanter 4.6 kg H2O/s Aqueous Layer 25 ppm NH3 0.4 kg AN/s 5.5 kg H2O/s 20 ppm NH3 1.1 kg AN/s 12.0kg H2O/s Wastewater to Biotreatment
Stripping
Extraction
and so on .. (infinite alternatives!) 5
And the optimum solution is
O2 NH3 C3H6 Reactor
5.0 kg AN/s 5.1 kg H2O/s + Gases Scrubber
Tail Gases to Disposal Tail Gases to Disposal Vacuum Pump AN to Sales 21 ppm NH3 4.7 kg AN/s 1.0 kg H2O/s 1ppm NH3 4.6 kg AN/s 0.3 kg H2O/s
Distillation Column
Decanter
To Regeneration and Recycle 10 ppm NH3 0.5 kg AN/s 5.3 kg H2O/s
Adsorption Column
Resin
Optimal Solution to the AN Case Study
How can we generate this optimum solution systematically?
What steps are needed to solve this problem? 1. Task Identifications: e.g. Stream rerouting (from where to where)? What transformations are needed (e.g. separation, biotreatment, etc.)? For example, should we use separations to clean up wastewater for reuse? To remove what? How much? From which streams? Should we change operating conditions of some units? Which units and which operating conditions? 2. Unit Selection: e.g., should we use extraction, stripping, ion exchange, or a combination adsorption? Which solvents? What type of columns? 3. Generation of Alternatives: e.g. reroute + extraction, stripping and ion exchange, etc. 4. Interconnection of Alternatives
Till the late 80's, the available approaches were: 1. 2. Brainstorming among experienced engineers Copy the last design we or someone else did!
Limitations of This Traditional Approach: Cannot enumerate the infinite alternatives Time and money intensive Is not guaranteed to come close to optimum solutions (except for very simple cases or extreme luck) Does not shed light on global insights and key characteristics of the process Severly limits groundbreaking and novel ideas.
State of the art: Systematic, fundamental, and generally applicable techniques can be learned and applied to synthesize optimal designs for improving process performance.
This is possible via Process Synthesis, Simulation, and Integration:
WHAT IS PROCESS SYNTHESIS? Process synthesis is concerned with the activities in which the various process elements are combined and the flowsheet of the system is generated so as to meet certain objectives. Hence, in process synthesis we know process inputs and outputs and are required to revise the structure and parameters of the flowsheet (for retrofitting design of an existing plant) or create a new flowsheet (for grass-root design of a new plant).
Process Inputs (Given)
Process Structure & Parameters (Unknown)

Process Synthesis Problems
Process Outputs (Given)
Process synthesis involves the following activities: 1. Task Identifications 2. Unit Selection 3. Generation of Alternatives 4. Interconnection of Alternatives and selection from among the alternatives.
WHAT IS PROCESS ANALYSIS/SIMULATION? Analysis is aimed at predicting how the synthesized process will perform. It involves the decomposition of the process into its constituent elements (e.g. units) for individual study of performance. Hence, once a process is synthesized, its detailed characteristics (e.g. flowrates, compositions, temperature, pressure, etc.) are predicted using analysis techniques. These techniques include mathematical models, empirical correlations and computer-aided process simulation tools (e.g. ASPEN Plus). In addition, process analysis may involve the use of experimental means to predict and validate performance. Therefore, in process simulation, we are given the process inputs and flowsheet and are required to predict process outputs. The lab will focus on ASPEN Plus.
Process Structure & Parameters (Given)

Process Simulation Problems
Process Outputs (Unknown)
PROCESS DESIGN = PROCESS SYNTHESIS + PROCESS ANALYSIS 8
MOTIVATING EXAMPLE #2: REFINERY

H2 To flare CH4
Steam Reforming CH4+ H2O = CO + 3H2
Exothermic @800 C
o
Shift Conversion CO+ H2O = CO2 + H2

Endothermic @350 C
o
Amine Separation
Crude Oil
C2-C4
Atmospheric Distillation
Gasoline
Steam
Steam
CO2
Naphtha
Gas Oil
Heavy Distillates to Vacuum Distillation
Problem: Naphtha and gas oil contain objectionable materials (e.g. sulfur, nitrogen, oxygen, halides) and unsaturated hydrocarbons (e.g. olefins and gum-forming unstable diolefins) that should be converted to paraffins. Design Objectives: Synthesize a revised process to remove sulfur (and other objectionable materials) and stabilize olefins and diolefins. Synthesis Activities: Example of a synthesized alternative: 1. Task Identifications: react naphtha and gas oil with hydrogen to remove objectionable materials and stabilize (saturate) olefins and diolefins. 2. Unit Selection: Hydrotreating and hydrodesulfurization catalytic processes. 3. Generation and interconnection of Alternatives: Add hydrotreating/hydrodesulfurization to each stream. Purchase fresh hydrogen and feed to units.
H2 To flare CH4
Steam Reforming CH4+ H2O = CO + 3H2
Exothermic @800oC
Shift Conversion CO+ H2O = CO2 + H2

Endothermic @350oC
Amine Separation
Crude Oil
C2-C4
Atmospheric Distillation
Gasoline Naphtha
Steam
Steam
Naphtha
CO2
Hydrotreating and Hydrodesulfurization
Fresh (purchased) H2
Gas Oil
Hydrotreating and Hydrodesulfurization
Gas Oil
Fresh (purchased) H2
Heavy Distillates to Vacuum Distillation
What is wrong with this synthesized process from the hydrogen perspective?
No integration of mass (hydrogen) MOTIVATING EXAMPLE #1 REVISITED

5.0 kg AN/s 5.1 kg H2O/s + Gases Reactor Water 6.0 kg H2O/s B FW 1.2 kg H2O/s Boiler Tail Gases to Disposal Steam Steam-Jet Ejector Condensate 34 ppm NH3 0.2 kg AN/s 1.2 kg H2O/s
O2 NH3 C3H6
Scrubber
AN to Sales 10 ppm NH3 4.2 kg AN/s 1.0 kg H2O/s 1ppm NH3 3.9kg AN/s 0.3 kg H2O/s
Distillation Column
Decanter
20 ppm NH3 1.1 kg AN/s 12.0kg H2O/s Wastewater to Biotreatment
Flowsheet of Acrylonitrile Process
10
MOTIVATING EXAMPLE #3: PHARMACEUTICAL PROCESS

Need to cool to 330 K before recovery Need to cool to 300 K before storage
H1
520 K
C1
300 KNeed
H2
380 K
to heat to 550 K before reaction
Adiabatic Reactor
C2
320 K
Separation
Need to heat to 380 K before washing

To Finishing Washing
Purification
Impurities
PROPOSED SOLUTION
Cooling utility (water) Heating utility H1 520 K (steam)
330 K To Recovery
Cooling utility (brine)

300 K To Storage
H2
380 K
C1
300 K 550 K
Adiabatic Reactor
C2
320 K
Separation
Heating utility (steam)

380 K To Finishing Washing
What is Wrong with the Energy Usage in this Synthesized Flowsheet?

No integration of heat
Purification
Impurities
11
WHAT IS PROCESS INTEGRATION? Process integration is a holistic approach to process design, retrofitting and operation which emphasizes the unity of the process.
Process integration = Energy Integration + Mass Integration. Energy integration is a systematic methodology that provides a fundamental understanding of energy utilization within the process and employs this understanding in identifying energy targets and optimizing heat-recovery and energy-utility systems.
Mass integration is a systematic methodology that provides a fundamental understanding of the global flow of mass within the process and employs this understanding in identifying performance targets and optimizing the generation and routing of species throughout the process.
TARGETING APPROACH OF PROCESS INTEGRATION Performance targets for the whole system can be determined ahead of detailed design Big Picture First Using Fundamental Chemical Engineering, Details Later! We will learn process synthesis, integration, and simulation. The lectures will focus on process synthesis and integration while the lab will focus on ASPEN simulation. We will learn: How to simulate complete flowsheets and predict their performance. How to identify best achievable performance targets for a process WITHOUT detailed calculations. 12
How to systematically enhance yield, maximize profit, maximize resource conservation, reduce energy, and prevent pollution? How to debottleneck a process? How to choose units and screen their performance? How to understand the BIG picture of a process and use it to optimize any plant? And much more
SUMMARY WHAT IS PROCESS ANALYSIS/SIMULATION?
Process Structure & Parameters (Given)
Process Outputs (Unknown)
WHAT IS PROCESS SYNTHESIS?
Process Structure & Parameters (Unknown)
Process Outputs (Given)
WHAT IS PROCESS INTEGRATION? Holistic approach emphasizing unity of the process.
13

Flowsheet of Acrylonitrile Process

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Flowsheet of Acrylonitrile Process

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INTRODUCTION AND COURSE OBJECTIVES THROUGH MOTIVATING EXAMPLES

MOTIVATING EXAMPLE #1: ACRYLONITRILE PROCESS

Off-Gas Condensate 14 ppm NH3 0.4 kg AN/s 4.6 kg H2O/s

18 ppm NH3 4.6 kg AN/s 6.5 kg H2O/s

Aqueous Layer 25 ppm NH3 0.4 kg AN/s 5.5 kg H2O/s

Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s

20 ppm NH3 1.1 kg AN/s 12.0kg H2O/s Wastewater to Biotreatment

Let's brain storm for some alternative solutions.

5.0 kg AN/s 5.1 kg H2O/s O2 + Gases NH3 Reactor C 3H 6

Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s

5.0 kg AN/s 5.1 kg H2O/s O2 + Gases NH3 Reactor C 3H 6

Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s

5.0 kg AN/s 5.1 kg H2O/s O2 + Gases NH3 Reactor C 3H 6

Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s

5.0 kg AN/s 5.1 kg H2O/s O2 + Gases NH3 Reactor C 3H 6

Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s

5.0 kg AN/s 5.1 kg H2O/s O2 + Gases NH3 Reactor C3H6

Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s

5.0 kg AN/s 5.1 kg H2O/s O2 + Gases NH3 Reactor C 3H 6

Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s

5.0 kg AN/s 5.1 kg H2O/s O2 + Gases NH3 Reactor C 3H 6

Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s

5.0 kg AN/s 5.1 kg H2O/s O2 + Gases NH3 Reactor C 3H 6

Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s

Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s

5.0 kg AN/s 5.1 kg H2O/s O2 + Gases NH3 Reactor C 3H 6

Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s

5.0 kg AN/s 5.1 kg H2O/s O2 + Gases NH3 Reactor C 3H 6

Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s

and so on .. (infinite alternatives!) 5

And the optimum solution is

O2 NH3 C3H6 Reactor

5.0 kg AN/s 5.1 kg H2O/s + Gases Scrubber

Off-Gas Condensate 14 ppm NH3 0.4 kg AN/s 4.6 kg H2O/s

23 ppm NH3 5.1 kg AN/s 5.8 kg H2O/s

To Regeneration and Recycle 10 ppm NH3 0.5 kg AN/s 5.3 kg H2O/s

12 ppm NH3 0.4 kg AN/s 4.6 kg H2O/s

Aqueous Layer 25 ppm NH3 0.4 kg AN/s 4.8 kg H2O/s

Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s

25 ppm NH3 0.4 kg AN/s 4.8 kg H2O/s

Optimal Solution to the AN Case Study

How can we generate this optimum solution systematically?

This is possible via Process Synthesis, Simulation, and Integration:

Process Inputs (Given)

Process Structure & Parameters (Unknown)

Process Outputs (Given)

Process Inputs (Given)

Process Structure & Parameters (Given)

Process Outputs (Unknown)

PROCESS DESIGN = PROCESS SYNTHESIS + PROCESS ANALYSIS 8

MOTIVATING EXAMPLE #2: REFINERY

Shift Conversion CO+ H2O = CO2 + H2

Heavy Distillates to Vacuum Distillation

Shift Conversion CO+ H2O = CO2 + H2

Hydrotreating and Hydrodesulfurization

Hydrotreating and Hydrodesulfurization

No integration of mass (hydrogen) MOTIVATING EXAMPLE #1 REVISITED

Off-Gas Condensate 14 ppm NH3 0.4 kg AN/s 4.6 kg H2O/s

18 ppm NH3 4.6 kg AN/s 6.5 kg H2O/s

Aqueous Layer 25 ppm NH3 0.4 kg AN/s 5.5 kg H2O/s

Bottoms 0 ppm NH3 0.1 kg AN/s 0.7 kg H2O/s

20 ppm NH3 1.1 kg AN/s 12.0kg H2O/s Wastewater to Biotreatment

Flowsheet of Acrylonitrile Process