Can Ionic Liquids Be Cheap?

Similar documents
Supplementary material

CHE 404 Chemical Reaction Engineering. Chapter 8 Steady-State Nonisothermal Reactor Design

Systems Engineering Spring Group Project #1: Process Flowsheeting Calculations for Acetic Anhydride Plant. Date: 2/25/00 Due: 3/3/00

1. (25 points) C 6 H O 2 6CO 2 + 7H 2 O C 6 H O 2 6CO + 7H 2 O

Mass Transfer Operations I Prof. Bishnupada Mandal Department of Chemical Engineering Indian Institute of Technology, Guwahati

Shortcut Distillation. Agung Ari Wibowo, S.T., M.Sc Politeknik Negeri Malang Malang - Indonesia

Fundamentals of Combustion

Process Classification

Simulation of Electrolyte Processes: Status and Challenges

CHEMICAL REACTORS - PROBLEMS OF REACTOR ASSOCIATION 47-60

Reactors. Reaction Classifications

PFR with inter stage cooling: Example 8.6, with some modifications

Chemical Engineering

Sulfuric Acid-Catalyzed Conversion of Alkynes to Ketones in an Ionic Liquid Medium under Mild Reaction Conditions

Mass Transfer Operations I Prof. Bishnupada Mandal Department of Chemical Engineering Indian Institute of Technology, Guwahati

INTRODUCTION: Shell and tube heat exchangers are one of the most common equipment found in all plants. How it works?

INDUSTRIAL EXPERIENCE WITH HYBRID DISTILLATION PERVAPORATION OR VAPOR PERMEATION APPLICATIONS

Chemical Reaction Engineering. Multiple Reactions. Dr.-Eng. Zayed Al-Hamamre

Comparison of distillation arrangement for the recovery process of dimethyl sulfoxide

Investigation of Petasis and Ugi Reactions in Series in an Automated Microreactor System

BOUNDARY VALUE DESIGN METHOD FOR COMPLEX DEMETHANIZER COLUMNS

EVAPORATION YUSRON SUGIARTO

CBE 142: Chemical Kinetics & Reaction Engineering

I. (20%) Answer the following True (T) or False (F). If false, explain why for full credit.

10.37 Exam 2 25 April, points. = 10 nm. The association rate constant

Approximate Methods Fenske-Underwood-Gilliland (FUG) Method Selection of Two Key Components

ChE 201 August 26, ChE 201. Chapter 8 Balances on Nonreactive Processes Heat of solution and mixing

Heat Integration - Introduction


Summary for TEP 4215 E&P/PI

Separation Trains. Sieder et. al. Chapter 9 and 13. Terry A Ring Chemical Engineering University of Utah

Process Unit Control System Design

Investigation of adiabatic batch reactor

C 6 H H 2 C 6 H 12. n C6H12 n hydrogen n benzene. n C6H6 n H2 100 C 6 H 6 n 2 n C6H H 2. n 1

Chapter 4. Problem SM.7 Ethylbenzene/Styrene Column

Ammonia Synthesis with Aspen Plus V8.0

Process Design Decisions and Project Economics Prof. Dr. V. S. Moholkar Department of Chemical Engineering Indian Institute of Technology, Guwahati

Process design decisions and project economics Dr. V. S. Moholkar Department of chemical engineering Indian Institute of Technology, Guwahati

SEM-2017(03HI MECHANICAL ENGINEERING. Paper II. Please read each of the following instructions carefully before attempting questions.

How to build and race a fast nanocar Synthesis Information

Integrated Knowledge Based System for Process Synthesis

CHE 425. Engineering Economics and Design Principles. Prof. Adnan Alamer Chemical Engineering Dept., KFUPM.

INTEGRATED PROCESS FOR γ-butyrolactone PRODUCTION

CHLORINE RECOVERY FROM HYDROGEN CHLORIDE

Lecture 25: Manufacture of Maleic Anhydride and DDT

Ways to Improve the Energy Efficiency of AN Solution Plants

CHAPTER 5 MASS AND ENERGY ANALYSIS OF CONTROL VOLUMES

Synthesis of renewable diesel with hydroxyacetone and 2-methyl-furan

Thermodynamics I - Enthalpy

Chemical Kinetics and Reaction Engineering

Esterification in CSTRs in Series with Aspen Plus V8.0

Chapter 4: Column Distillation: Internal Stage-by-Stage Balances

Comprehend and execute the 10 elements of effective problem

Principles of Chemical Engineering Processes

MAHALAKSHMI ENGINEERING COLLEGE

Continuous Flow Reactions. From idea to production size scale up in 3 steps

Thermochemistry: Calorimetry and Hess s Law

Supporting information

Production of Renewable 1,3-Pentadiene from Xylitol via Formic. Acid-Mediated Deoxydehydration and Palladium-Catalyzed

Chemical Engineering Thermodynamics Spring 2002

CHE 404 Chemical Reaction Engineering. Chapter 8 Steady-State Nonisothermal Reactor Design

Readings for this homework assignment and upcoming lectures

Enhanced Plant Design for the Production of Azeotropic Nitric Acid

regressing the vapor-liquid equilibrium data in Mathuni et al. and Rodriguez et al., respectively. The phase equilibrium data of the other missing pai

S.E. (Chemical) (Second Semester) EXAMINATION, 2011 HEAT TRANSFER (2008 PATTERN) Time : Three Hours Maximum Marks : 100

Separations and Reactors Design Project. Production of Allyl Chloride

Optimization of Batch Distillation Involving Hydrolysis System

THE FUTURE OF THE CHEMISTRY: CONTINUOUS FLOW REACTIONS BASEL 2016

Getting started with BatchReactor Example : Simulation of the Chlorotoluene chlorination

Abstract Process Economics Program Report 174A HIGH-OUTPUT FLUIDIZED-BED POLYETHYLENE TECHNOLOGY (July 1999)

H 0 r = -18,000 K cal/k mole Assume specific heats of all solutions are equal to that of water. [10]

Supporting Information. Silylated Organometals: A Family of Recyclable. Homogeneous Catalysts

DESIGN OF A SHELL AND TUBE HEAT EXCHANGER

Department of Mechanical Engineering ME 322 Mechanical Engineering Thermodynamics. Lecture 26. Use of Regeneration in Vapor Power Cycles

SIMULATION ANALYSIS OF FULLY THERMALLY COUPLED DISTILLATION COLUMN

SEM-2016(03)-II MECHANICAL ENGINEERING. Paper -11. Please read each of the following instructions carefully before. attempting questions.

Figure Q3. Boundary conditions for a tubular reactor.

Complex Compounds Background of Complex Compound Technology

Supplementary Figure 1. Structures of substrates tested with 1. Only one enantiomer is shown.

Lecture 35: Vapor power systems, Rankine cycle

Functional Genomics Research Stream. Lecture: February 17, 2009 Masses, Volumes, Solutions & Dilutions

Pre GATE Pre-GATE 2018

WINTER-15 EXAMINATION Model Answer

All rights reserved. Armando B. Corripio, PhD, PE Flash Distillation Flash Drum Variables and Specifications... 2

ME 354 THERMODYNAMICS 2 MIDTERM EXAMINATION. Instructor: R. Culham. Name: Student ID Number: Instructions

Experimental evaluation of a modified fully thermally coupled distillation column

Figure 1. Pore size distribution

Unit 10: Part 1: Polarity and Intermolecular Forces

Introduction to the Problem-Solving Methodology (PSM)

4.1 Derivation and Boundary Conditions for Non-Nipped Interfaces

SUMMER-18 EXAMINATION Model Answer

Chemistry 142 (Practice) MIDTERM EXAM II November. Fill in your name, section, and student number on Side 1 of the Answer Sheet.

How to Safely Quantify a Reaction Exotherm

Chemical Reaction Engineering Prof. Jayant Modak Department of Chemical Engineering Indian Institute of Science, Bangalore

A Novel Approach of Reduction of CO 2 into Methanol by Water Splitting with Aluminum over Copper Catalyst

Revamp of Saturated Gas Concentration Unit (SGCU)

Supporting Information

AE 205 Materials and Energy Balances Asst. Prof. Dr. Tippabust Eksangsri. Chapter 6 Energy Balances on Chemical Processes

"Thermodynamic Analysis of Processes for Hydrogen Generation by Decomposition of Water"

Analyzing Mass and Heat Transfer Equipment

Transcription:

Electronic Supplementary Material (ESI) for Green Chemistry. This journal is The Royal Society of Chemistry 2014 Electronic Supplementary Information (ESI) Can Ionic Liquids Be Cheap? Long Chen, a, b, Mahdi Sharifzadeh, c, Niall Mac Dowell, c Tom Welton, b Nilay Shah, c and Jason P. Hallett c* a State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China. b Department of Chemistry, Imperial College London, London, SW7 2AZ, UK. c Department of Chemical Engineering, Imperial College London, London, SW7 2AZ,UK *j.hallett@imperial.ac.uk Both of these authors contributed equally to this work. This document reports the details of the methods and results and consists of three main sections. In the first section, experimental details of ILs synthesis are reported. In the second section, details of the simulations and their results are presented for both the conventional and intensified process scenarios. In the third section, the details of the economic analysis and corresponding assumptions are discussed. 1. ILs synthesis [HNEt 3 ][HSO 4 ] (IL1) synthesis: Triethylamine (10.1 g, 0.1 mol) was mixed with 50 ml water and the mixture cooled to 0 C. Sulfuric acid (9.8 g, 0.1 mol) was added drop wise while stirring. The stirring was continued for 1 h at room temperature. 1 H-NMR and mass spectra are shown in Figures S1 and S2, respectively. [HC 1 im][hso 4 ] (IL2) synthesis: 1-methylimidazole (8.2 g, 0.1 mol) was mixed with 50 ml water and the mixture cooled to 0 C. Sulfuric acid (9.8 g, 0.1 mol) was added drop wise while stirring. The stirring was continued for 1 h at room temperature. 1 H-NMR and mass spectra are shown in Figures S3 and S4, respectively. 1 P age

Figure S1 1 H-NMR of IL1 ssm_3 111 (0.487) 100 102.1 TOF MS ES+ 87.5 L.CHEN IL1 % 283.2 83.0 282.1 125.1 264.1 283.2 281.2 284.2 75.1 81.9 86.1 90.5 93.6 97.1 100.1 102.2 109.9 105.1 115.5117.2 121.0 125.6 130.9 132.7 139.7141.4 147.1 150.6 153.6 157.5 159.5 167.9169.6 181.1 183.5 187.9 206.7 211.2 218.9 215.6 224.4 234.6 239.0 265.1 268.8 272.5 285.7 286.2 0 ssm_3neg 856 (3.776) Cm (853:856-24:69) 100 194.3 TOF MS ES- 667 194.3 % 96.7 194.3 194.3 0 77.7 95.7 79.7 81.2 86.2 87.690.2 98.7 100.1 104.4 109.6 113.5 117.0 122.6 136.8 124.6128.0 138.5 143.8 148.5 170.6 176.3 176.4 176.4 192.4 178.3 184.9 187.2190.5 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 195 200 205 210 215 220 225 230 235 240 245 250 255 260 265 270 275 280 285 194.4 196.3 196.4 198.3 210.8 216.1 Figure S2 Mass spectra of IL1 220.4 236.3 223.6 228.8 239.2 241.9 249.3 274.1 254.0 257.7 261.5 269.7 279.2 284.9 m/z 2 P age

HBimHSO4 1H-NMR 70000 65000 60000 55000 50000 45000 40000 35000 30000 25000 20000 15000 10000 5000 0-5000 13.5 13.0 12.5 12.0 11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 f1 (ppm) 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 Figure S3 1 H-NMR of IL2 ssm_3neg 959 (4.230) 100 96.7 TOF MS ES- 266 194.3 % 96.7 194.3 112.6 176.4 112.6 176.4 258.2 96.7 176.4 258.2 274.1 95.7 96.8 95.7 98.7 76.7 79.4 82.5 111.1 112.7 105.7 76.6 87.5 93.9 121.6 129.0 146.6 124.3 134.9 141.5 153.7 156.5 160.5 160.6 164.4 170.3 174.1 176.5 181.4 192.3 196.4 210.3 196.4 206.4 188.5 196.7 210.4 221.5 206.3 223.4 226.3 258.3 274.2 238.4 238.2 258.3 250.3 272.2 274.4 244.3 254.4 263.6 234.9 268.0 240.7 280.5 289.4 290.1292.1 296.9 301.5 308.1 314.9 318.1 319.8 0 m/z 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 195 200 205 210 215 220 225 230 235 240 245 250 255 260 265 270 275 280 285 290 295 300 305 310 315 320 3 P age

ssm_1b 845 (3.730) 100 311.0 TOF MS ES+ 54.7 313.0 310.0 % 83.0 315.0 309.0 245.0 264.1 307.5 70.0 81.2 95.9 105.5 110.1 118.5 123.0 71.6 73.3 84.6 87.1 96.0 99.6 105.9 118.8 123.3 92.5 112.4 74.0 92.6 96.1 106.1 132.5 157.0 149.0 136.8 145.7 161.8 179.5 136.8 149.1 163.1 172.8 179.6 184.6 142.7 169.6 137.0 152.3 207.1 219.3 229.0 201.0 209.4 232.9 233.4 238.6 215.0 223.1 238.8 248.8 256.3 253.4 249.4 256.6 264.3 268.6 281.2 281.5 288.0 301.2 288.4 293.9 285.9 316.0 319.6 0 m/z 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 195 200 205 210 215 220 225 230 235 240 245 250 255 260 265 270 275 280 285 290 295 300 305 310 315 320 Figure S4 Mass spectra of IL2 2. Simulation results The following section describes the simulation and reactor design for production of IL1 and IL2. The results are presented for the conventional process and intensified process, respectively. 2.1 The conventional process for IL1 The process configuration is shown in Figure S5 and consists of a single reactor which runs in adiabatic mode. This is because the heat transfer area of a CSTR reactor would be too small to remove the reaction heat and the temperature rise needs to be controlled by a diluting media. In this process water is added to the mixture to an extent that the temperature of the rector is limited to 90 o C. Then the pressure is reduced and the medium is heated up and enters a flash drum. The temperature of the flash drum is selected so the concentration of water is reduced from 58.6%wt to 20%wt. The remaining 20% is needed in order to reduce the IL viscosity to a convenient level (~3cP). The separated water needs to be condensed and pumped back for recycle/reuse. The required power for pumping is calculated based on the parameters in Table S2. The heat duties of coolers/heaters are calculated based on Table S2. The stream data is shown in Table S3. This information will be later applied to make a comparison with the intensified process. Table S1 Model summary (pumps) Name P-1 P-2 P-3 P-4 Electricity [kw] 2.56922 2.64357 4.65179 6.63282 Volumetric flow rate [cum/hr] 4.57766 4.87975 12.7403 21.3423 Calculated discharge pressure [bar] 7 7 7 7 Table S2 Model summary (coolers). Name CONDSR HTX PROD-CLR Specified pressure [bar] -0.3-0.3-0.3 Specified temperature [C] 25 25 Specified vapor fraction 0.766 Calculated heat duty [Gcal/hr] -13.228 12.1722-0.888768 4 P age

RCYL B5 WT R-RCYL CONDSR P-2 H2SO4FD H2SO4FD1 MIX OVHD WAT ER WAT ER1 P-1 MIX FLSHDRUM R-1 ETN3FD1 T O-FLASH ETN3FEED EFFLNT P-3 B4 ATMP IL1 IONIC-L1 HTX PROD-CLR Figure S5 Process flow diagram for the conventional process for IL1 production. Table S3 Stream table for Figure S5 Steam Tag ATMP EFFLNT ETN3FD1 ETN3FEED H2SO4FD H2SO4FD1 IL1 IONIC-L1 MIX OVHD RCYL TO-FLASH WATER WATER1 WTR-RCYL Temperature C 90 90 25.9 25 25 26.2 118.8 25 25.4 118.8 25.3 124.6 25 25.5 25 Pressure bar 2 6.7 7 1 1 7 1.4 1.1 7 1.4 7 1.7 1 7 1.1 Vapor Frac 0 0 0 0 0 0 0 0 0 1 0 0.766 0 0 0 Mole Flow kmol/hr 1521.385 1521.385 91.25 91.25 91.25 91.25 343.868 343.868 1521.385 1177.517 1177.517 1521.385 252.563 252.563 1177.517 Mass Flow kg/hr 43947.81 43947.81 9233.755 9233.755 8949.753 8949.753 22734.51 22734.51 34714.03 21213.29 21213.29 43947.81 4550 4550 21213.293 Mole Flow kmol/hr H2SO4 0 0 0 0 91.25 91.25 0 0 91.25 0 0 0 0 0 0 ETN3 0 0 91.25 91.25 0 0 0 0 0 0 0 0 0 0 0 H2O 1430.135 1430.135 0 0 0 0 252.618 252.618 1430.135 1177.517 1177.517 1430.135 252.563 252.563 1177.517 IL1 91.25 91.25 0 0 0 0 91.25 91.25 0 0 0 91.25 0 0 0 Mole Frac H2SO4 0 0 0 0 1 1 0 0 0.06 0 0 0 0 0 0 ETN3 0 0 1 1 0 0 0 0 0 0 0 0 0 0 0 H2O 0.94 0.94 0 0 0 0 0.735 0.735 0.94 1 1 0.94 1 1 1 IL1 0.06 0.06 0 0 0 0 0.265 0.265 0 0 0 0.06 0 0 0 5 P age

2.2 The intensified process for IL1 The simplified process configuration is shown in Figure S6 and consists of a series of reactors with interstage coolers. Each reactor operates in an adiabatic mode and is designed based on 100% conversion of sulfuric acid. Sulfuric acid is the limiting reactant and is fed between the stages. The heat of the exothermic reaction results in a temperature rise in the reactor which is a process design decision variable. The extent of interstage cooling is also another decision variable as it affects the temperature of the next reactor. Finally and most importantly, the number of stages is an important design variable and determines the extent of reaction in each stage so the overall reaction will reach completion at the end of the reactor network. The design specifications applied in this study are shown in Table 1. The IL is solid in the pure state at room temperature. Therefore, the sulfuric acid is diluted with water to maintain a liquid state. The extent of this dilution is adjusted so the ultimate product contains 20 wt % water. The justification for the other specification is to ensure safe operation. For example, the specification of maximum temperature of 90 o C and minimum pressure of 4 bar will ensure that no evaporation will happen inside the reactor. The analysis shows that avoiding such a limit without using diluting water requires that the extent of the reaction conversion be limited to less than 12.5%, therefore, at least eight reactors are needed. Table S4 reports the stream data. The required power for pumping is reported in Table S5. The heat duties of coolers are reported in Table S6. This information will be applied later for evaluating the operating and capital costs. The detailed design of reactors was conducted using the results from the simplified flow diagram. In this research, in order to avoid any uncertainty associated with the physical properties of the new ionic liquid product, the heat duties of all reactors are overdesigned up to 100%. The selected material was titanium, to prevent corrosion. The Exchanger Design and Rating software applied built-in optimization in order to minimize the total costs. The results for the detailed reactor design are shown in Table S7. In addition, Figure S3 shows the diagram of the 8 th reactor. The overall bare equipment cost is minimized to only 116800$ and there is no need for extra diluting water and associated costs of separation and recycling. 6 P age

P-2 H2SO4F D H2SO4F D1 MIX WAT ER1 MIX WAT ER SPLIT P-1 ACID-1 ACID-2 ACID-3 ACID-4 ACID-5 ACID-6 ACID-7 ACID-8 R-1 R-2 R-3 R-4 R-5 R-6 R-7 R-8 ET N3FEED ET N3FD1 EF 1 FEED2 EF 2 FEED3 EF 3 FEED4 EF 4 FEED5 EF 5 FEED6 EF 6 FEED7 EF 7 FEED8 EF 8 P-3 COOLER-1 COOLER-2 COOLER-3 COOLER-4 COOLER-5 COOLER-6 COOLER-7 IONIC-L Figure S6 Process flow diagram for the intensified process for IL1 production. PROD-CLR Table S4 Stream table for Figure S6 ACID-1 ACID-2 ACID-3 ACID-4 ACID-5 ACID-6 ACID-7 ACID-8 EF1 EF2 EF3 EF4 EF5 EF6 EF7 EF8 Temperature C 25.7 25.7 25.7 25.7 25.7 25.7 25.7 25.7 74.9 82.8 79.2 77.1 75.7 74.5 73.6 72.9 Pressure bar 7 7 7 7 7 7 7 7 7 6.7 6.4 6.1 5.8 5.5 5.2 4.9 Vapor Frac 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Mole Flow kmol/hr 42.949 42.949 42.949 42.949 42.949 42.949 42.949 42.949 122.793 154.336 185.879 217.422 248.965 280.508 312.051 343.593 Mass Flow kg/hr 1686.974 1686.974 1686.974 1686.974 1686.974 1686.974 1686.974 1686.974 10920.73 12607.71 14294.68 15981.66 17668.64 19355.61 21042.59 22729.56 Volume Flow cum/hr 1.372 1.372 1.372 1.372 1.372 1.372 1.372 1.372 14.788 16.341 17.881 19.523 21.222 22.957 24.717 26.495 Mole Flow kmol/hr H2SO4 11.406 11.406 11.406 11.406 11.406 11.406 11.406 11.406 0 0 0 0 0 0 0 0 ETN3 0 0 0 0 0 0 0 0 79.844 68.438 57.031 45.625 34.219 22.813 11.406 0 H2O 31.543 31.543 31.543 31.543 31.543 31.543 31.543 31.543 31.543 63.086 94.629 126.172 157.715 189.258 220.801 252.343 IL1 0 0 0 0 0 0 0 0 11.406 22.813 34.219 45.625 57.031 68.438 79.844 91.25 Mole Frac H2SO4 0.266 0.266 0.266 0.266 0.266 0.266 0.266 0.266 0 0 0 0 0 0 0 0 ETN3 0 0 0 0 0 0 0 0 0.65 0.443 0.307 0.21 0.137 0.081 0.037 0 H2O 0.734 0.734 0.734 0.734 0.734 0.734 0.734 0.734 0.257 0.409 0.509 0.58 0.633 0.675 0.708 0.734 IL1 0 0 0 0 0 0 0 0 0.093 0.148 0.184 0.21 0.229 0.244 0.256 0.266 7 P age

Table S4 Stream table for Figure S6 (continued) ETN3FEED FEED2 FEED3 FEED4 FEED5 FEED6 FEED7 FEED8 H2SO4FD IONIC-L MIX WATER Temperature C 25 50 50 50 50 50 50 50 25 25 25.7 25 Pressure bar 1 6.7 6.4 6.1 5.8 5.5 5.2 4.9 1 4.6 7 1 Vapor Frac 0 0 0 0 0 0 0 0 0 0 0 0 Mole Flow kmol/hr 91.25 122.793 154.336 185.879 217.422 248.965 280.508 312.051 91.25 343.593 343.593 252.343 Mass Flow kg/hr 9233.755 10920.73 12607.71 14294.68 15981.66 17668.64 19355.61 21042.59 8949.753 22729.56 13495.79 4546.038 Mole Flow kmol/hr H2SO4 0 0 0 0 0 0 0 0 91.25 0 91.25 0 ETN3 91.25 79.844 68.438 57.031 45.625 34.219 22.813 11.406 0 0 0 0 H2O 0 31.543 63.086 94.629 126.172 157.715 189.258 220.801 0 252.343 252.343 252.343 IL1 0 11.406 22.813 34.219 45.625 57.031 68.438 79.844 0 91.25 0 0 Mole Frac H2SO4 0 0 0 0 0 0 0 0 1 0 0.266 0 ETN3 1 0.65 0.443 0.307 0.21 0.137 0.081 0.037 0 0 0 0 H2O 0 0.257 0.409 0.509 0.58 0.633 0.675 0.708 0 0.734 0.734 1 IL1 0 0.093 0.148 0.184 0.21 0.229 0.244 0.256 0 0.266 0 0 Table S5 Model summary (pumps) Name P-1 P-2 P-3 Electricity [kw] 2.56825 2.64357 4.65179 Volumetric flow rate [cum/hr] 4.57368 4.87975 12.7403 Calculated discharge pressure [bar] 7 7 7 Table S6 Model summary (coolers). Please note that the heat duty of each cooler is equal to the heat generated by the reaction at that stage. Name COOLER-1 COOLER-2 COOLER-3 COOLER-4 COOLER-5 COOLER-6 COOLER-7 PROD-CLR Specified pressure [bar] -0.3-0.3-0.3-0.3-0.3-0.3-0.3-0.3 Specified temperature [C] 50 50 50 50 50 50 50 25 Specified vapor fraction Calculated heat duty [Gcal/hr] -0.154792-0.234397-0.22839-0.22583-0.22321-0.22012-0.21671-0.43641 8 P age

ream 1 73 C 129 Plates 526.08 mm Stream 1 25 C Horizontal Port Centres 260 mm 12 C Stream 2 Vertical Port Centres 1052.63 mm 25 C Stream 2 380 mm Plate Flow Width Actual surface area Number of passes Stream 1 / 2 Effective channels Stream 1 / 2 Number of exchangers 51.6 m2 2 / 1 64 / 64 1 Plate thickness Compressed plate pitch Area of each plate Chevron angle (to horizontal) Material type Port diameter 0.6 mm 4.11 mm.4 m2 45 Titanium 100 m m Figure S7 The geometric diagram of the final reactor (R-8). Table S7 The results of the detailed reactor design for IL1 (intensified). Heat duty (kw) Overdesign Heat duty (kw) Actual Maximum allowable temperature ( o C) Exit temperature ( o C) Overall heat transfer coefficient Effective Heat transfer area (m 2 ) Number of plates Material R-1-360 -180.02314 75 50 2017.5 5.3 29 Titanium 6130 R-2-540 -272.60389 83 50 1560.7 8.8 35 Titanium 9604 R-3-530 -265.62234 79 50 1475 8.8 35 Titanium 9604 R-4-520 -262.64477 77 50 1198.2 9.9 39 Titanium 10678 R-5-520 -259.58718 76 50 1526.2 8.6 21 Titanium 9300 R-6-510 -256.00292 75 50 1307.6 9.5 23 Titanium 10194 R-7-500 -252.03838 74 50 1316.4 9.5 23 Titanium 10194 R-8-1000 -507.5398 73 25 1033 50.8 129 Titanium 51095 Costs (USD) Total 116799 9 P age

2.3 The conventional process for IL2 The process configuration is shown in Figure S8 and consists of a single reactor which runs in adiabatic mode. The reason is that the heat transfer area of a CSTR reactor would be too small to remove the heat of reaction and the temperature rise needs to be controlled by adding a diluent. In this process water is added to the mixture to an extent that the temperature of the rector is limited to 90 o C. Then the pressure is reduced and the medium is heated up and enters a flash drum. The temperature of the flash drum is selected so the concentration of water is reduced from 65%wt to 20%wt. The remaining 20% is needed in order to reduce the IL viscosity to a level (~3cP) convenient for storage and transportation. The separated water needs to be condensed and pumped back for recycle / reuse. The required power for pumping is reported in Table S8. The heat duties of coolers are reported in Table S9. The stream data is shown in Table S10. This information will be later applied to make a comparison with the intensified process. Table S8 Model summary (pumps). Name P-1 P-2 P-3 P-4 Electricity [Watt] 2442.58 2698.08 2911.94 7613.68 Volumetric flow rate [cum/sec] 0.0011463 0.001272 0.00149883 0.00816004 Calculated discharge pressure [N/sqm] 730000 730000 730000 700000 Table S9 Model summary (coolers). Please note that the heat duty of each cooler is equal to the heat generated by the reaction at that stage. Name CONDSR HTX PROD-CLR Specified pressure [N/sqm] -0.3-30000 -30000 Specified temperature [C] 25 125.85 25 Specified vapor fraction Calculated heat duty [kw] -21284.5 19612.8-1451.6 10 P age

RC YL B5 WTR-RCYL CONDSR P-3 H2SO4FD H2SO4FD1 MIX MIX STEAM WATER1 WATER P-2 R-1 SEPARATN M-IM-FD 1 M-IM-FD V-1 TO-FLASH IL2 IONIC -L P-1 EF1 ATMSPH R PROD-CLR HTX Figure S8 Process flow diagram of the conventional process for IL2 production. Table S10 Stream table for Figure S8 ATMSPHR EFFLNT H2SO4 H2SO4FD H2SO4FD1 IL2 IONIC-L M-IM-FD M-IM-FD1 MIX RCYL STEAM TO-FLASH WATER WATER1 WTR-RCYL Temperature K 363.1 363.1 343.1 298.1 298.9 399 298.1 298.1 298.7 298.5 298.4 399 399 298.1 298.7 298.1 Pressure N/sqm 200000 700000 500000 100000 730000 170000 140000 100000 730000 700000 700000 170000 170000 100000 730000 169999.7 Vapor Frac 0 0 0 0 0 0 0 0 0 0 0 1 0.821 0 0 0 Mole Flow kmol/sec 0.548 0.548 0.001 0.028 0.028 0.098 0.098 0.028 0.028 0.548 0.45 0.45 0.548 0.07 0.07 0.45 Mass Flow kg/sec 14.425 14.425 0.098 2.749 2.749 6.314 6.314 2.301 2.301 12.124 8.111 8.111 14.425 1.264 1.264 8.111 Mole Flow kmol/sec H2SO4 0 0 0.001 0.028 0.028 0 0 0 0 0.028 0 0 0 0 0 0 H2O 0.52 0.52 0 0 0 0.07 0.07 0 0 0.52 0.45 0.45 0.52 0.07 0.07 0.45 M-IMIDAZ 0 0 0 0 0 0 0 0.028 0.028 0 0 0 0 0 0 0 IL2 0.028 0.028 0 0 0 0.028 0.028 0 0 0 0 0 0.028 0 0 0 Mole Frac H2SO4 0 0 1 1 1 0 0 0 0 0.051 0 0 0 0 0 0 H2O 0.949 0.949 0 0 0 0.715 0.715 0 0 0.949 1 1 0.949 1 1 1 M-IMIDAZ 0 0 0 0 0 0 0 1 1 0 0 0 0 0 0 0 IL2 0.051 0.051 0 0 0 0.285 0.285 0 0 0 0 0 0.051 0 0 0 11 P age

2.4 The intensified process for IL2 The simplified version of the process configuration is shown in Figure S9 and consists of a series of reactors with interstage coolers. Each reactor operates in an adiabatic mode and is designed based on 100% conversion of sulfuric acid which is the limiting reactant and is fed between the stages. The heat of the exothermic reaction results in a temperature rise in the reactor which is a process design decision variable. The extent of interstage cooling is also another decision variable as it affects the temperature of the next reactor. Finally and most importantly, the number of stages is an important design variable and determines the extent of reaction in each stage so the overall reaction will reach completion at the end of the reactor train. The design specifications applied in this study are shown in Table 1. The IL is a solid in the pure state at room temperature. Therefore, the sulfuric acid is diluted with water in order to maintain a liquid state. The extent of this dilution is selected so the ultimate product contains 20% wt water. The justification for the other specification is to ensure safe operation. For example, the specification of maximum temperature of 95 o C and minimum pressure of 4 bar will ensure that no evaporation will happen inside the reactor. The analysis shows that avoiding such a limit requires that the extent of the reaction conversion be limited to 9% and eleven reactors are needed. Table S11 reports the stream data. The required power for pumping is reported in Table S12. The heat duties of coolers are reported in Table S13. This information will be applied later for evaluating the operating and capital costs. The detailed design of reactors was conducted using the results from the simplified simulation. In this research, in order to avoid any uncertainty associated with the physical properties of the new product and materials, the heat duties of all reactors are overdesigned up to 100%. The selected material was titanium. The Exchanger Design and Rating software applied built-in optimization in order to minimize the total costs. The results for detailed reactor design are shown in Table S14. In addition, Figure S10 shows the diagram of the 11 th reactor. The overall equipment costs are minimized to only 110000$ and there is no need for extra diluting water and associated costs of separation and recycling. The costs are based on 2008 and will be later converted to 2012. 12 P age

P-3 H2SO4FD H2SO4FD1 MIX SPLIT MIX WATER1 WATER ACID-1 ACID-2 ACID-3 ACID-4 ACID-5 ACID-6 ACID-7 ACID-8 ACID-9 ACID-10 ACID-11 P-2 R-1 R-2 R-3 R-4 R-5 R-6 R-7 R-8 R-9 R-10 R-11 M-IM-FD1 M-IM-FD EF1 FEED2 EF2 FEED3 EF3 FEED4 EF4 FEED5 EF5 FEED6 EF6 FEED7 EF7 FEED8 EF8 FEED9 EF9 FEED10 EF10 FEED11 EF11 P-1 IONIC-L COOLER-1 COOLER-2 COOLER-3 COOLER-4 COOLER-5 COOLER-6 COOLER-7 COOLER-8 COOLER-9 COOLER10 PROD-CLR Figure S9 The flow diagram of the intensified process for IL2 production. Table S11 Stream table for Figure S9. ACID-1 ACID-2 ACID-3 ACID-4 ACID-5 ACID-6 ACID-7 ACID-8 ACID-9 ACID-10 ACID-11 Temperature K 298.8 298.8 298.8 298.8 298.8 298.8 298.8 298.8 298.8 298.8 298.8 Pressure atm 7.205 7.205 7.205 7.205 7.205 7.205 7.205 7.205 7.205 7.205 7.205 Vapor Frac 0 0 0 0 0 0 0 0 0 0 0 Mole Flow kmol/hr 35.434 31.891 31.891 31.891 31.891 31.891 31.891 31.891 31.891 31.891 31.891 Mass Flow kg/hr 1446.199 1301.579 1301.579 1301.579 1301.579 1301.579 1301.579 1301.579 1301.579 1301.579 1301.579 Mole Flow kmol/hr H2SO4 10.09 9.081 9.081 9.081 9.081 9.081 9.081 9.081 9.081 9.081 9.081 H2O 25.344 22.809 22.809 22.809 22.809 22.809 22.809 22.809 22.809 22.809 22.809 M-IMIDAZ 0 0 0 0 0 0 0 0 0 0 0 IL2 0 0 0 0 0 0 0 0 0 0 0 Mole Frac H2SO4 0.285 0.285 0.285 0.285 0.285 0.285 0.285 0.285 0.285 0.285 0.285 H2O 0.715 0.715 0.715 0.715 0.715 0.715 0.715 0.715 0.715 0.715 0.715 M-IMIDAZ 0 0 0 0 0 0 0 0 0 0 0 IL2 0 0 0 0 0 0 0 0 0 0 0 13 P age

Table S11 Stream table for Figure S9 (Continued). EF1 EF2 EF3 EF4 EF5 EF6 EF7 EF8 EF9 EF10 EF11 Temperature K 359.2 365.5 360.1 355.9 352.5 349.8 347.6 345.7 344 342.6 341.4 Pressure atm 7.205 6.908 6.612 6.316 6.02 5.724 5.428 5.132 4.836 4.54 4.244 Vapor Frac 0 0 0 0 0 0 0 0 0 0 0 Mole Flow kmol/hr 126.244 149.053 171.863 194.672 217.482 240.291 263.101 285.91 308.72 331.529 354.339 Mass Flow kg/hr 9730.141 11031.77 12333.39 13635.02 14936.64 16238.27 17539.9 18841.52 20143.15 21444.77 22746.4 Mole Flow kmol/hr H2SO4 0 0 0 0 0 0 0 0 0 0 0 H2O 25.344 48.153 70.963 93.772 116.582 139.391 162.201 185.01 207.82 230.629 253.439 M-IMIDAZ 90.81 81.729 72.648 63.567 54.486 45.405 36.324 27.243 18.162 9.081 0 IL2 10.09 19.171 28.252 37.333 46.414 55.495 64.576 73.657 82.738 91.819 100.9 Mole Frac H2SO4 0 0 0 0 0 0 0 0 0 0 0 H2O 0.201 0.323 0.413 0.482 0.536 0.58 0.616 0.647 0.673 0.696 0.715 M-IMIDAZ 0.719 0.548 0.423 0.327 0.251 0.189 0.138 0.095 0.059 0.027 0 IL2 0.08 0.129 0.164 0.192 0.213 0.231 0.245 0.258 0.268 0.277 0.285 Table S11 Stream table for Figure S9 (Continued). FEED3 FEED4 FEED5 FEED6 FEED7 FEED8 FEED9 FEED10 FEED11 H2SO4FD IL IONIC-L M-IM-FD MIX WATER Temperature K 323.1 323.1 323.1 323.1 323.1 323.1 323.1 323.1 323.1 298.1 343.1 298.1 298.1 298.8 298.1 Pressure atm 6.612 6.316 6.02 5.724 5.428 5.132 4.836 4.54 4.244 0.987 4.935 3.948 0.987 7.205 0.987 Vapor Frac 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Mole Flow kmol/hr 149.053 171.863 194.672 217.482 240.291 263.101 285.91 308.72 331.529 100.9 3.6 354.339 100.9 354.339 253.439 Mass Flow kg/hr 11031.77 12333.39 13635.02 14936.64 16238.27 17539.9 18841.52 20143.15 21444.77 9896.22 648.665 22746.4 8283.89 14461.992 4565.773 Mole Flow kmol/hr H2SO4 0 0 0 0 0 0 0 0 0 100.9 0 0 0 100.9 0 H2O 48.153 70.963 93.772 116.582 139.391 162.201 185.01 207.82 230.629 0 0 253.439 0 253.439 253.439 M-IMIDAZ 81.729 72.648 63.567 54.486 45.405 36.324 27.243 18.162 9.081 0 0 0 100.9 0 0 IL2 19.171 28.252 37.333 46.414 55.495 64.576 73.657 82.738 91.819 0 3.6 100.9 0 0 0 Mole Frac H2SO4 0 0 0 0 0 0 0 0 0 1 0 0 0 0.285 0 H2O 0.323 0.413 0.482 0.536 0.58 0.616 0.647 0.673 0.696 0 0 0.715 0 0.715 1 M-IMIDAZ 0.548 0.423 0.327 0.251 0.189 0.138 0.095 0.059 0.027 0 0 0 1 0 0 IL2 0.129 0.164 0.192 0.213 0.231 0.245 0.258 0.268 0.277 0 1 0.285 0 0 0 14 P age

Table S12 Model summary (pumps). Name P-1 P-2 P-3 Electricity [Watt] 2442.58 2701.75 2911.94 Volumetric flow rate [cum/sec] 0.001146 0.001276 0.001499 Calculated discharge pressure [N/sqm] 730000 730000 730000 Table S13 Model summary (coolers). Please note that the heat duty of each cooler is equal to the heat generated by reaction at that stage. Name COOLER-1 COOLER-2 COOLER-3 COOLER-4 COOLER-5 COOLER-6 COOLER-7 COOLER-8 COOLER-9 COOLER10 CWCAL HEATER PROD-CLR Calculated pressure [N/sqm] 700000 670000 640000 610000 580000 550000 520000 490000 460000 430000 670000 100000 400000 Calculated temperature [K] 323.15 323.15 323.15 323.15 323.15 323.15 323.15 323.15 323.15 323.15 298.15 284.2 298.15 Calculated vapor fraction 0 0 0 0 0 0 0 0 0 0 0 0 0 Calculated heat duty [kw] -186.36-258.263-258.279-258.292-258.302-258.311-258.319-258.326-258.331-258.337 150 0.29-603.929 15 P age

Stream 1 69 C 73 Plates 295.92 mm Stream 1 25 C Horizontal Port Centres 260 mm 12 C Stream 2 Vertical Port Centres 1052.63 mm 25 C Stream 2 380 mm Plate Flow Width Actual surface area Number of passes Stream 1 / 2 Effective channels Stream 1 / 2 Number of exchangers 29.2 m2 2 / 1 36 / 36 1 Plate thickness Compressed plate pitch Area of each plate Chevron angle (to horizontal) Material type Port diameter 0.6 mm 4.11 mm.4 m2 45 Titanium 100 m m Figure S10 The geometric diagram of the 11 th reactor. Table S14. The results of the detailed reactor design for IL2 (intensified). Heat duty (kw) Overdesign Heat duty (kw) Actual Maximum allowable temperature (oc) Exit temperature (oc) Overall heat transfer coefficient Effective Heat transfer area (m2) Number of plates Material R-1-370 -186.4 86 50 1072.6 7.1 49 Titanium 8074 R-2-520 -258.3 93 50 1021.1 9.9 39 Titanium 10678 R-3-520 -258.3 87 50 1477.6 7.8 31 Titanium 8529 R-4-520 -258.3 83 50 1695.8 7.8 31 Titanium 8529 R-5-520 -258.3 80 50 1485.7 7.7 19 Titanium 8407 R-6-520 -258.3 77 50 1710.3 7.2 29 Titanium 7991 R-7-520 -258.4 75 50 2017.5 6.1 25 Titanium 6916 R-8-520 -258.4 73 50 2127.8 6.1 25 Titanium 6916 R-9-520 -258.4 71 50 2132.7 6.8 17 Titanium 7512 R-10-520 -258.4 70 50 2212.4 6.8 17 Titanium 7512 R-11-1200 -603.6 69 25 2051.7 28.4 73 Titanium 28926 Total 109990 Costs (USD) 16 P age

3. Economic assessment The purchase cost for a given component reflects a baseline equipment size. As changes are made to the process, the plant capacity may be different from what was originally designed, which will accordingly affect the equipment purchased cost. A common guideline for extrapolation of cost estimation to a different volume is the six-tenths rule: New Cost = (Base Cost)( Base New Size Size) 0.6 So the new equipment purchased cost can be easily estimated as changes are made to the plant capacity. C OL is determined based on data obtained from five chemical companies and correlated by W.A. Alkayatet al. 9 According to this method, the operating labour requirement for chemical processing plants is given by N OL = (6.29 + 31.7 P 2 + 0.23N np ) 0.5 where N OL is the number of operators per shift, P is the number of processing steps involving the handling of particulate solids for example, transportation and distribution, particulate size control, and particulate removal. N np is the number of non-particulate processing steps and includes compression, heating and cooling, mixing and reaction. In this IL preparation process, there is no solid participating in the system. For instance, in the intensified process for ILs production, N np is determined as 8 (8 reactors). So N OL of this system is calculated as 2.85. A single operator is assumed to work on average 49 weeks a year (3 weeks time off for vacation and sick leave), with five 8-hour shifts a week. This amounts to (49 weeks/year 5 shifts/week) 245 shifts per operator per year. A chemical plant normally operates 24 hours/day. This requires (330 days/year 3 shifts/day) 990 operating shifts per year. The number of operators needed to provide this number of shifts is [(990 shifts/yr)/(245 shifts/operator/yr)] or approximately 4 operators. Four operators are hired for each operator needed in the plant at any time. This provides the needed operating labour but does not include any support or supervisory staff. The number of operators required per shift is 2.85. So 11.4 (4 2.85) operators are needed totally (rounding up to the nearest integer yields 12 operators). From the US Department of Labour (http://www.bls.gov/oes/current/oes_nat.htm#51-0000), it is known that the operators annual mean wages are generally around $50,000 in 2012. Herein, we adopt $50,000 for the labour cost calculation. 17 P age

2024 © sciencedocbox.com Privacy Policy | Terms of Service | Feedback