Multiphase Reactor Engineering for Clean and Low-Carbon Energy Applications E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Fachliteratur
• Sprache: Englisch

Seitenzahl: 1280

Veröffentlichungsjahr: 2017

Beschreibung

Provides a comprehensive review on the brand-new development of several multiphase reactor techniques applied in energy-related processes * Explains the fundamentals of multiphase reactors as well as the sophisticated applications * Helps the reader to understand the key problems and solutions of clean coal conversion techniques * Details the emerging processes for novel refining technology, clean coal conversion techniques, low-cost hydrogen productions and CO2 capture and storage * Introduces current energy-related processes and links the basic principles of emerging processes to the features of multiphase reactors providing an overview of energy conversion in combination with multiphase reactor engineering * Includes case studies of novel reactors to illustrate the special features of these reactors

Leseprobe

Table of Contents

COVER

TITLE PAGE

PREFACE

LIST OF CONTRIBUTORS

1 NOVEL FLUID CATALYTIC CRACKING PROCESSES

1.1 FCC PROCESS DESCRIPTION

1.2 REACTION PROCESS REGULATION FOR THE HEAVY OIL FCC

1.3 ADVANCED RISER TERMINATION DEVICES FOR THE FCC PROCESSES

1.4 AN MZCC FCC PROCESS

1.5 TWO‐STAGE RISER FLUID CATALYTIC CRACKING PROCESS

1.6 FCC GASOLINE UPGRADING BY REDUCING OLEFINS CONTENT USING SRFCC PROCESS

1.7 FCC PROCESS PERSPECTIVES

REFERENCES

2 COAL COMBUSTION

2.1 FUEL AND COMBUSTION PRODUCTS

2.2 DEVICE AND COMBUSTION THEORY OF GASEOUS FUELS

2.3 COMBUSTION THEORY OF SOLID FUEL

2.4 GRATE FIRING OF COAL

2.5 COAL COMBUSTION IN CFB BOILER

2.6 PULVERIZED COAL COMBUSTION

REFERENCES

3 COAL GASIFICATION

3.1 COAL WATER SLURRY

3.2 THE THEORY OF COAL GASIFICATION

3.3 FIXED BED GASIFICATION OF COAL

3.4 FLUID BED GASIFICATION OF COAL

3.5 ENTRAINED FLOW GASIFICATION OF COAL

3.6 INTRODUCTION TO THE NUMERICAL SIMULATION OF COAL GASIFICATION

REFERENCES

4 NEW DEVELOPMENT IN COAL PYROLYSIS REACTOR

4.1 INTRODUCTION

4.2 MOVING BED WITH INTERNALS

4.3 SOLID CARRIER FB PYROLYSIS

4.4 MULTISTAGE FLUIDIZED BED PYROLYSIS

4.5 SOLID CARRIER DOWNER PYROLYSIS

4.6 OTHER PYROLYSIS REACTORS

4.7 CONCLUDING REMARKS

ACKNOWLEDGMENTS

REFERENCES

5 COAL PYROLYSIS TO ACETYLENE IN PLASMA REACTOR

5.1 INTRODUCTION

5.2 EXPERIMENTAL STUDY OF COAL PYROLYSIS TO ACETYLENE

5.3 THERMODYNAMIC ANALYSIS OF COAL PYROLYSIS TO ACETYLENE

5.4 COMPUTATIONAL FLUID DYNAMICS‐ASSISTED PROCESS ANALYSIS AND REACTOR DESIGN

5.5 CONCLUSION AND OUTLOOK

REFERENCES

6 MULTIPHASE FLOW REACTORS FOR METHANOL AND DIMETHYL ETHER PRODUCTION

6.1 INTRODUCTION

6.2 PROCESS DESCRIPTION

6.3 REACTOR SELECTION

6.4 INDUSTRIAL DESIGN AND SCALE‐UP OF FIXED BED REACTOR

6.5 INDUSTRIAL DESIGN AND SCALE‐UP OF SLURRY BED REACTOR

6.6 DEMONSTRATION OF SLURRY REACTORS

6.7 CONCLUSIONS AND REMARKS

REFERENCES

7 FISCHER–TROPSCH PROCESSES AND REACTORS

7.1 INTRODUCTION TO FISCHER–TROPSCH PROCESSES AND REACTORS

7.2 SBCR TRANSPORT PHENOMENA

7.3 SBCR EXPERIMENT SETUP AND RESULTS

7.4 MODELING OF SBCR FOR FT SYNTHESIS PROCESS

7.5 REACTOR SCALE‐UP AND ENGINEERING DESIGN

NOMENCLATURE

GREEK SYMBOLS

SUBSCRIPTS

REFERENCES

8 METHANOL TO LOWER OLEFINS AND METHANOL TO PROPYLENE

8.1 BACKGROUND

8.2 CATALYSTS

8.3 CATALYTIC REACTION MECHANISM

8.4 FEATURES OF THE CATALYTIC PROCESS

8.5 MULTIPHASE REACTORS

8.6 INDUSTRIAL DEVELOPMENT

REFERENCES

9 RECTOR TECHNOLOGY FOR METHANOL TO AROMATICS

9.1 BACKGROUND AND DEVELOPMENT HISTORY

9.2 CHEMISTRY BASES OF MTA

9.3 EFFECT OF OPERATING CONDITIONS

9.4 REACTOR TECHNOLOGY OF MTA

9.5 COMPARISON OF MTA REACTION TECHNOLOGY WITH FCC AND MTO SYSTEM

REFERENCES

10 NATURAL GAS CONVERSION

10.1 INTRODUCTION

10.2 REFORMING REACTIONS

10.3 SULFUR AND CHLORIDE REMOVAL

10.4 CATALYSTS

10.5 CHEMICAL KINETICS

10.6 FIXED BED REFORMING REACTORS

10.7 SHIFT CONVERSION REACTORS

10.8 PRESSURE SWING ADSORPTION

10.9 STEAM REFORMING OF HIGHER HYDROCARBONS

10.10 DRY (CARBON DIOXIDE) REFORMING

10.11 PARTIAL OXIDATION (POX)

10.12 AUTOTHERMAL REFORMING (ATR)

10.13 TRI‐REFORMING

10.14 OTHER EFFORTS TO IMPROVE SMR

10.15 CONCLUSIONS

REFERENCES

11 MULTIPHASE REACTORS FOR BIOMASS PROCESSING AND THERMOCHEMICAL CONVERSIONS

11.1 INTRODUCTION

11.2 BIOMASS FEEDSTOCK PREPARATION

11.3 BIOMASS PYROLYSIS

11.4 BIOMASS GASIFICATION

11.5 BIOMASS COMBUSTION

11.6 CHALLENGES OF MULTIPHASE REACTORS FOR BIOMASS PROCESSING

REFERENCES

12 CHEMICAL LOOPING TECHNOLOGY FOR FOSSIL FUEL CONVERSION WITH

IN SITU

CO

2

CONTROL

12.1 INTRODUCTION

12.2 OXYGEN CARRIER MATERIAL

12.3 CHEMICAL LOOPING REACTOR SYSTEM DESIGN

12.4 CHEMICAL LOOPING TECHNOLOGY PLATFORM

12.5 CONCLUSION

REFERENCES

INDEX

END USER LICENSE AGREEMENT

List of Tables

Chapter 01

TABLE 1.1 The Typical FCC Process Product Yields on Various Feedstocks

TABLE 1.2 Product Yield and Reaction Temperature at the Outlet of FCC Riser

TABLE 1.3 Prevailing Operation Conditions Before and After Quenching Agent Injection

TABLE 1.4 Product Distribution Before and After Quenching Agent Injection

TABLE 1.5 Prevailing Operation Conditions with Different Quenching Agent Injection

TABLE 1.6 Product Distribution with Different Quenching Agent Injection

TABLE 1.7 Experiment Results of High Oil and Catalyst Mixing Energy and Short Contact Time RFCC (Temperature of Regenerated Catalyst is 660°C)

TABLE 1.8 Experiment Results of High Oil and Catalyst Mixing Energy and Short Contact Time RFCC (Temperature of Regenerated Catalyst is 630°C)

TABLE 1.9 Product Yields of Physical and Chemical Stripping

TABLE 1.10 Composition of Cracked Gas in Physical and Chemical Stripping

TABLE 1.11 Changes in FBP and Heavy Components (Boiling Range >480°C) in the Liquid Product of Physical and Chemical Stripping

TABLE 1.12 Feedstock Properties Before and After MZCC Application

TABLE 1.13 Operating Conditions Before and After MZCC Application

TABLE 1.14 Material Balance Before and After MZCC Application

TABLE 1.15 Composition of Dry Gas and LPG Before and After MZCC Application

TABLE 1.16 Stable Gasoline Properties Before and After MZCC Application

TABLE 1.17 Light Diesel Properties Before and After MZCC Application

TABLE 1.18 Comparison of FCC Product Distributions Between the Stratified Injection of 1‐C

4

and AR in the First‐Stage Riser and Their Separate Reaction Process

TABLE 1.19 Comparison of FCC Product Distributions Between the Stratified Injection of LCN and HCO in the Second‐Stage Riser and Their Separate Reaction Process

TABLE 1.20 Results of Adopting Riser Reactor

TABLE 1.21 Results of Adopting Riser + Turbulent Bed

TABLE 1.22 Results of Pilot Plant of Naphtha Olefin Reduction Technology in Dagang Petrochemical Company (Micro‐Activity 56, Reaction Time 3 s, Catalyst‐to‐Oil Ratio 6)

TABLE 1.23 Composition of PONA Before and After Naphtha Olefin Reduction (Reaction Time 3 s, Catalyst‐to‐Oil Ratio, Reaction Temperature 450°C)

TABLE 1.24 Mass Balance Before and After Plant Revamping

TABLE 1.25 Main Operation Parameters

TABLE 1.26 PONA Analysis of Gasoline (Fluorescence, %)

TABLE 1.27 Properties of Gasoline

TABLE 1.28 Properties of Diesel

TABLE 1.29 Composition of Liquefied Gas, wt%

TABLE 1.30 Energy Consumption Before and After Plant Revamping

Chapter 02

TABLE 2.1 Classification of Power Fuel Coal

Chapter 03

TABLE 3.1 Comparison of Composition and Property Between Typical Raw Coal and Coal Water Slurry

TABLE 3.2 Operating Characteristics of Different Gasifiers

TABLE 3.3 Comparison of Gasification with Different Feeding Methods

TABLE 3.4 Experimental Equipment and Reaction Conditions Used for Gasification

TABLE 3.5 Performance of Winkler Gasifier When Processing Lignite

TABLE 3.6 Operating Data of Lurgi Circulating Fluidized Bed

TABLE 3.7 Operating Data of the U‐GAS Gasification Pilot Plant

TABLE 3.8 Typical Performance of the KRW Gasifier

TABLE 3.9 Performance of ICC Ash Agglomerating Fluidized Bed Coal Gasification

TABLE 3.10 Product Gas Composition of Several Typical Gasifier

TABLE 3.11 Operating Data of Texaco Coal Water Slurry Gasifier

TABLE 3.12 Operating Data of Shell Dry Coal Gasifier

TABLE 3.13 Operating Data of Opposed Multi‐burner Coal Water Slurry Gasifier

TABLE 3.14 Operating Data of Staged‐Oxygen Supply Coal Water Slurry Gasifier

TABLE 3.15 Main Operating Data of Tsinghua Gasifier

TABLE 3.16 Operating Data of Two‐stage Dry Pulverized Coal Gasifier

TABLE 3.17 Operating Data of Hangtian (HT‐L) Pulverized Coal Gasifier

TABLE 3.18 Numerical Simulations of Entrained Flow Gasification Device in Recent Years and the Typical Work with Corresponding Mathematical Models

Chapter 04

TABLE 4.1 A Highlight of Major Coal Pyrolysis Technologies Using Different Reactors

TABLE 4.2 Proximate, Ultimate, and Gray‐King Analyses for the Tested Yilan Coal

TABLE 4.3 Product Distribution from Pyrolyzing Yilan Coal in Reactors A–D at a Heating Furnace Temperature of 700°C

TABLE 4.4 Product Distribution at Different Furnace Temperatures in Reactor B

TABLE 4.5 Typical Results of Continuous Pilot Pyrolysis Using Moving Bed with Internals

TABLE 4.6 Properties of Tar Product from Last Two Pilot Tests Shown in Table 4.5

TABLE 4.7 Proximate and Ultimate Analyses of the Tested Coal Sample

TABLE 4.8 XRF Analyses of the Employed Coal Ash from a CFB Boiler

TABLE 4.9 Proximate and Ultimate Analyses of the Tested Fugu Bituminite

TABLE 4.10 Proxi mate and Ultimate Analyses of the Tested Lignite (wt.%)

TABLE 4.11 Proximate and Ultimate Analyses of Chars Made by Different Operation Modes

TABLE 4.12 Surface and Pore Properties of Chars Made by Three Operation Modes

TABLE 4.13 Classification Indexes of Raw Coal and Chars from Different Operation Modes

TABLE 4.14 Operating Conditions for the Reported Pyrolysis Tests in Downer

TABLE 4.15 Proximate and Ultimate Analyses of the Tested Coal

TABLE 4.16 Pyrolysis Results in Downer Comparing with Performance Data of Other Technologies

TABLE 4.17 Product Yields from Pyrolyzing Different Coal by DG Technology

Chapter 05

TABLE 5.1 Performance of Tianye 5 MW Pilot‐Plant Reactor Under Representative Operating Conditions

TABLE 5.2 Chemical Analysis Data of Long‐Flame Coal Before and After Pyrolysis

TABLE 5.3 Typical Operating Conditions and Performance of Lab‐Scale Pyrolysis Process

TABLE 5.4 Typical Operating Conditions and Performance of Pilot‐Scale Pyrolysis Process

TABLE 5.5 Coal‐Independent Kinetic Parameters for the CPD Model

TABLE 5.6 Chemical Analyses of Coals

TABLE 5.7 Chemical Structure Parameters of Coals for CPD Model

TABLE 5.8 Predicted and Experimental Yields of Volatiles and Light Gases for 28 Coals

Chapter 06

TABLE 6.1 Properties of DME in Comparison with Some Other Fuels

TABLE 6.2 Properties of DME and LPG

TABLE 6.3 Commercial Catalysts for Methanol Synthesis

TABLE 6.4 Summary of Primary Kinetic Models for Gas‐phase Methanol Synthesis

TABLE 6.5 Summary of Kinetic Models for Liquid‐phase Methanol Synthesis

TABLE 6.6 Summary of Kinetic Models for Methanol Dehydration

TABLE 6.7 Comparison of Pilot‐plant Results

Chapter 07

TABLE 7.1 Correlations for

k

l

a

TABLE 7.2 Correlations for Heat Transfer Coefficient

TABLE 7.3 Categories of SBCR Hydrodynamic Parameters Measuring Technologies

TABLE 7.4 Refractive Index of the Probe and Fluids

TABLE 7.5 Categories of Tomographic and Velocimetric Techniques

TABLE 7.6 Kinetics and Characteristics of the Iron‐based Catalysts

TABLE 7.7 WGS Kinetics and Characteristics of the Iron Catalysts

TABLE 7.8 Usual Drag Coefficient Correlations

TABLE 7.9 Correlations about Single Bubble

Chapter 08

TABLE 8.1 Comparison of Carbon‐Based Product Distributions of SAPO‐34 and ZSM‐5

TABLE 8.2 Comparison of the MTO and MTP Processes

Chapter 09

TABLE 9.1 Comparison of MTA with Other Technologies Using Methanol as Feedstock

TABLE 9.2 Product Distribution of MTA over Different Catalysts

TABLE 9.3 Comparison of the Aromatic Product of MTA with Other Technologies

TABLE 9.4 Comparison of Reaction System of MTA with Other Technologies

Chapter 10

TABLE 10.1 Constants Needed to Use Xu and Froment [6] Kinetics

TABLE 10.2 Typical Operating Conditions and Outlet Gas Composition of a Steam Methane Reformer

TABLE 10.3 Comparison of SMR, POX, and ATR, the Three Main Routes of Syngas Generation from Natural Gas

TABLE 10.4 Stoichiometric Capacities and Regeneration Temperatures for Various CO

2

Sorbents

Chapter 11

TABLE 11.1 Two‐Component Torrefaction Reaction Rate Constants for Wood

TABLE 11.2 Multiphase Reactors Explored for Biomass Torrefaction

TABLE 11.3 Known Pilot and Commercial Torrefaction Plants

TABLE 11.4 Some Reported Kinetic Constants for Single‐Component Biomass Pyrolysis

TABLE 11.5 Main Applications of Biomass Pyrolysis Products

TABLE 11.6 Preferred Reaction Conditions for Slow and Fast Pyrolysis and the Typical Product Yields

TABLE 11.7 Features of Main Types of Reactors for Biomass Fast Pyrolysis

TABLE 11.8 Commercial and Precommercial Fast Pyrolysis Facilities

TABLE 11.9 Summary of Biomass Gasification Catalysts Advantages and Disadvantages

TABLE 11.10 Characteristics of Different Categories of Gasification Process

TABLE 11.11 Comparison of Basic Characteristics of Different Types of Gasifiers

TABLE 11.12 Vienna Institute of Technology Commercial DFB Gasifiers

TABLE 11.13 An Overview of Advantages and Disadvantages of Various Biomass Combustion Technologies

Chapter 12

TABLE 12.1 Chemical Looping Development History

TABLE 12.2 Equilibrium Gas Compositions with Different Oxidization States of Iron at 850°C

TABLE 12.3 Performance of Key SCL Units from Thermodynamic Analysis and Process Testing

TABLE 12.4 Summary of OSU’s Bench‐ and Small Pilot‐Scale Unit Testing Results Using Different Fuels

List of Illustrations

Chapter 01

FIGURE 1.1 The basic “side‐by‐side” type FCC unit configurations.

FIGURE 1.2 The basic Orthoflow or stacked‐type FCC unit configurations.

FIGURE 1.3 Catalytic cracking reaction mechanisms for hydrocarbons in petroleum.

FIGURE 1.4 Product yield along the riser.

FIGURE 1.5 Gas–solid flow and reaction model in FCC riser.

FIGURE 1.6 Overview diagram for simulation calculation.

FIGURE 1.7 The gas‐phase flow diagrams for different sections in FCC riser.

FIGURE 1.8 Catalyst concentration contour plots for different sections in FCC riser (kg/m

3

).

FIGURE 1.9 The gas‐phase temperature contour plots for different sections in FCC riser (°C).

FIGURE 1.10 The gas and catalyst temperature along FCC riser.

FIGURE 1.11 Product yield, conversion, and the light oil yield along FCC riser.

FIGURE 1.12 The schematic diagram for reaction regeneration system in FCCU in Petrochemical Factory of Shengli Oilfield Company Ltd.

FIGURE 1.13 Close‐coupled cyclone systems: (a) Shell’s internal close‐coupled cyclone system and (b) KBR’s closed cyclone.

FIGURE 1.14 UOP’s (a) VDS and (b) VSS.

FIGURE 1.15 (a) RS

2

and (b) LD2.

FIGURE 1.16 Schematic of an efficient RTD system.

FIGURE 1.17 FSC system.

FIGURE 1.18 Rough cyclone RTD.

FIGURE 1.19 Cross‐flow prestripper.

FIGURE 1.20 Venturi connection geometry between the RTD gas exit tube and the downstream cyclone inlet tube.

FIGURE 1.21 CSC system.

FIGURE 1.22 Annular circulating prestripper.

FIGURE 1.23 VQS system.

FIGURE 1.24 First‐generation vortex head: (a) side view and (b) top view.

FIGURE 1.25 Second‐generation vortex head: (a) side view and (b) top view.

FIGURE 1.26 Third‐generation vortex head.

FIGURE 1.27 SVQS system.

FIGURE 1.28 The vortex head for SVQS.

FIGURE 1.29 Schematic diagram of MZCC process.

FIGURE 1.30 Comparison of prelift section between MZCC and routine FCC.

FIGURE 1.31 Temperature distributions in different preriser structures.

FIGURE 1.32 New array arrangement of FCC feed injectors.

FIGURE 1.33 Comparison of gas–solid two‐phase distribution within the conventional riser reactor with that of new array arrangement of feed injector.

FIGURE 1.34 New configurations of rapid separation: (a) FSC, (b) CSC, and (c) VQS.

FIGURE 1.35 Schematic diagram of chemical strippers.

FIGURE 1.36 Numerical simulation results of gas–solid two‐phase distribution within the conventional riser reactors.

FIGURE 1.37 Numerical simulation results of gas–solid two‐phase distribution within the riser reactor with new array arrangement of feed injector.

FIGURE 1.38 Reaction–regeneration system structures before and after MZCC application.

FIGURE 1.39 Parallel–sequential reaction network of heavy oil catalytic cracking.

FIGURE 1.40 Online sampling device.

FIGURE 1.41 Product yield as a function of riser height.

FIGURE 1.42 Effect of separate reaction on the product distribution.

FIGURE 1.43 Effect of separate reaction on the product distribution.

FIGURE 1.44 Diagram of the new idea.

FIGURE 1.45 Schematic of the TSR FCC process.

FIGURE 1.46 Schematic of the TMP process.

FIGURE 1.47 Effect of catalyst on product distribution.

FIGURE 1.48 Schematic diagram of reaction mechanism of naphtha olefin reduction.

FIGURE 1.49 Riser reactor.

FIGURE 1.50 Riser reactor + turbulent bed.

FIGURE 1.51 Effect of temperature on conversion of olefin and increase proportion.

FIGURE 1.52 Reaction network diagram of full‐range cracked gasoline olefin reduction.

FIGURE 1.53 Effect of olefin conversion on C

3

+

liquid yield.

FIGURE 1.54 Effect of olefin conversion on upgrading gasoline yield.

FIGURE 1.55 Effect of olefin conversion on liquefied gas.

FIGURE 1.56 Effect of olefin conversion on coke yield.

FIGURE 1.57 Effect of olefin conversion on dry gas yield.

FIGURE 1.58 Overview flowchart of auxiliary riser FCC for naphtha olefin reduction technology.

FIGURE 1.59 Profile of SRFCC in Fushun Petrochemical Company.

FIGURE 1.60 Profile of SRFCC in Harbin Petrochemical Company.

Chapter 02

FIGURE 2.1 Diffusion flame burner. (a) The picture of diffusion flame, (b) the structure of the diffusion flame, and (c) multishooting diffusion flame.

FIGURE 2.2 Premixed type gas burner—The Bunsen burner.

FIGURE 2.3 The flame shape of Bunsen flames.

FIGURE 2.4 Working principles of spreader stoker (a) mechanical spreader stoker with rotating blade, (b) mechanical spreader stoker with swing scraper, (c) wind power spreader stoker, and (d) wind‐power‐mechanical spreader stoker. 1, coal feeding equipment; 2, coal hitting equipment; 3, inclined plate; 4, wind power coal throwing equipment; and 5, air.

FIGURE 2.5 The 600 MW supercritical circulating fluidized bed in Baima, China.

FIGURE 2.6 The furnace types of pulverized coal boilers: (a) Π‐shaped boiler, (b) tower‐type boiler, and (c) W‐shaped flame boiler.

Chapter 03

FIGURE 3.1 Typical preparation process of coal water slurry.

FIGURE 3.2 Relationship between the water content of the slurry and the average diameter atomized droplets at different air/slurry mass ratio.

FIGURE 3.3 Several commonly used air atomizing nozzles for combustion: (a) T model nozzle, (b) standard Y model nozzle, and (c) divergent Y model nozzle. 1, Silicon carbide or ceramic casing.

FIGURE 3.4 Schematic diagram of the CWS swirl burner.

FIGURE 3.5 Schematic diagram of each layer in fixed bed gasifier.

FIGURE 3.6 Process flow diagram of pressurized fixed bed gasification.

FIGURE 3.7 Four types of fixed bed gasifier divided by the flow direction of gas: (a) Downflow type, (b) upflow type, (c) cross‐flow type, and (d) open center type.

FIGURE 3.8 Schematic diagram of UGI gasifier.

FIGURE 3.9 Schematic diagram of third‐generation Lurgi gasifier. 1, Apron board; 2, coal distributor; 3, agitator; 4, grate; 5, protective plate; 6, steam and oxygen; 7, coal lock; 8, upper transmission device; 9, spray cooler; 10, furnace body; and 11, ash lock.

FIGURE 3.10 Schematic diagram of BGL gasifier. 1, Coal scuttle; 2, upper transmission device; 3, spray cooler; 4, coal distributor; 5, agitator; 6, furnace body; 7, nozzle; 8, slag outlet; 9, slag quenching box; and 10, ash box.

FIGURE 3.11 Schematic diagram of chute working principle. (a) Loading coal state and (b) nonloading coal state.

FIGURE 3.12 Schematic diagram of furnace body.

FIGURE 3.13 Schematic diagram of coal distributor, stirrer, and cold cycle.

FIGURE 3.14 Schematic diagram of tower‐shaped grate. The numbers are showing the layers.

FIGURE 3.15 Schematic diagram of coal lock.

FIGURE 3.16 Schematic diagram of expansion condenser of coal lock.

FIGURE 3.17 Process flow diagram of first‐generation pressurized gasifier with no waste heat recovery.

FIGURE 3.18 Gasification process of anthracite in fluidized bed.

FIGURE 3.19 Schematic diagram of the temperature distribution.

FIGURE 3.20 Schematic diagram of Winkler gasifier.

FIGURE 3.21 Schematic diagram of Winkler gasification process.

FIGURE 3.22 Process flow diagram of HTW gasification.

FIGURE 3.23 Schematic diagram of Lurgi circulating fluidized bed gasifier.

FIGURE 3.24 Schematic diagram of U‐GAS gasifier.

FIGURE 3.25 Schematic diagram of KRW gasifier.

FIGURE 3.26 Process flow diagram of ICC ash agglomerating fluidized bed coal gasification.

FIGURE 3.27 Process flow diagram of the Texaco coal water slurry gasification technology.

FIGURE 3.28 Process flow diagram of Shell dry coal gasification technology.

FIGURE 3.29 Process flow diagram of opposed multiburner coal water slurry gasification technology.

FIGURE 3.30 Structure of the prefilming burner.

FIGURE 3.31 Influence of two‐staged oxygen supply to the temperature distribution of the gasification chamber.

FIGURE 3.32 Schematic diagram of staged‐oxygen supply gasification.

FIGURE 3.33 Influence of staged‐oxygen supply to the flow field of the gasification chamber: (a) without staged‐oxygen supply and (b) with staged‐oxygen supply.

FIGURE 3.34 Measurement of the flow field of the gasification chamber in different staged‐oxygen supply.

FIGURE 3.35 Schematic diagram of two‐stage dry pulverized coal gasifier.

FIGURE 3.36 Process flow diagram of Hangtian (HT‐L) pulverized coal gasification technology.

FIGURE 3.37 Prediction cloud picture of the concentration of solid phase with time variation in a fluidized bed gasifier. (a)

τ

 = 4 s, (b)

τ

 = 5 s, (c)

τ

 = 6 s, (d)

τ

 = 7 s, (e)

τ

 = 7.5 s, (f)

τ

 = 8 s, and (g)

τ

 = 8.25 s.

FIGURE 3.38 Fluidization phenomenon of the solid material in the fluidized bed gasifier simulated by DEM method.

FIGURE 3.39 Trajectories of particles with different diameter: (a)

d

p

 = 30 µm, (b)

d

p

 = 60 µm, (c)

d

p

 = 110 µm, and (d)

d

p

 = 175 µm.

Chapter 04

FIGURE 4.1 Schematic plots for four different fixed bed reactors A–D (left inset) and experimental system (right inset). (1) Furnace, (2) reactor, (3) pressure gauge, (4) condenser, (5) collection bottle, (6) acetone scrubbing bottle, (7) filter, (8) buffer flask, (9) suction pump, (10) wet gas meter, (11) sodium bicarbonate washing bottle, (12) silica gel drying bottle, (13) valve, (14) gas sampling, and (15) gas exhaust.

FIGURE 4.2 Heating curves for coal at reactor center or near the wall of the central gas collection pipe at heating furnace temperatures of (a) 700°C and (b) 900°C.

FIGURE 4.3 Light tar fraction in tar products from coal pyrolysis in four different reactors at a heating furnace temperature of 700°C.

FIGURE 4.4 Comparison of tar yield for coal pyrolysis in reactors A and D at different heating furnace temperatures.

FIGURE 4.5 Schematic plots for fixed bed reactors without (A) and (B) with internals (left) and pyrolysis experimental system (right). Reactors without (A) and with (B) internals: (1) furnace, (2) reactor, (3) pressure gauge, (4) water‐cooled condenser, (5) primary collection bottle, (6) valve, (7) coolant condenser, (8) secondary collection bottle, (9) suction pump, (10) gas meter, (11) gas sampling, and (12) gas exhaust.

FIGURE 4.6 Comparison of heating curve (a), product distribution (b), and pyrolysis gas composition (c) for 100‐kg pyrolysis in reactors A and B at a heating furnace temperature of 1000°C.

FIGURE 4.7 Comparison of tar yield and light tar content for reactors A and B.

FIGURE 4.8 A picture for the 1000 t/a continuous pyrolysis pilot plant and a flowsheet of the process shown in the control interface.

FIGURE 4.9 Typical time‐series composition of pyrolysis gas from pilot pyrolysis test.

FIGURE 4.10 A conceptual diagram of technical processes of pyrolysis gasification.

FIGURE 4.11 A schematic of experimental apparatus.

FIGURE 4.12 Variation of tar and gas yields with reaction temperatures in N

2

atmosphere.

FIGURE 4.13 Variation of gas product composition with reaction temperature: (a) SX and (b) XLT.

FIGURE 4.14 Pyrolysis product distribution for the two types of coals tested: (a) product distribution and (b) gas composition.

FIGURE 4.15 TG‐FTIR analysis of tars for the tested two types of coal (heating rate of TG: 30 K/min): (a) CO, (b) CO

2

, (c) aliphatic C–H, and (d) aromatic C=C.

FIGURE 4.16 Tar yields for coal pyrolysis with different bed materials.

FIGURE 4.17 Gas yields for coal pyrolysis with different bed materials: (a) XLT and (b) SX.

FIGURE 4.18 TG‐FTIR analysis of tars for coal pyrolysis with different bed materials: (a) CO, (b) CO

2

, (c) aliphatic C–H, and (d) aromatic C=C.

FIGURE 4.19 Tar yields in reaction atmosphere of simulated pyrolysis gas and N

2

.

FIGURE 4.20 TG‐FTIR analysis of tars for SX coal pyrolysis in the atmosphere of N

2

and SPG. (a) CO, (b) CO

2

, (c) aliphatic C–H, and (d) aromatic C=C.

FIGURE 4.21 Possible tar yield under reaction conditions simulating the coal topping process.

FIGURE 4.22 A schematic diagram of the 100 kg/h dual‐bed pyrolysis gasification pilot plant. AC, air conditioner; ETP, electric tar precipitator; HE, heat exchanger; IB, induction blower; LN, liquid nitrogen; LS, loop seal; RB, Roots blower.

FIGURE 4.23 Variation of temperature with operating time in (a) pyrolyzer and (b) gasifier in a typical pilot test for a Fugu bituminite.

FIGURE 4.24 Composition analysis by GC‐MS of pyrolysis tar product from the pilot test corresponding to Figure 4.23 for a Fugu bituminite.

FIGURE 4.25 Composition and HHV of (a) pyrolysis gas (N

2

free) and (b) gasification gas products from the pilot test corresponding to Figure 4.24.

FIGURE 4.26 A schematic diagram of experimental system. (1) Gas cylinders, (2) gas preheater, (3) water tank, (4) plunger pump, (5) steam generator, (6) gas mixer and preheater, (7) preheater, (8) electric furnace, (9) overflow standpipe, (10) reactor, (11) coal hopper, (12) screw feeder, (13) cyclone, (14) char receiver, (15) condenser, (16) tar collector, (17) ice‐water bath, (18) acetone trap, (19) wet gas meter, (20) gas bag, and (21) micro‐GC.

FIGURE 4.27 Three operation modes of the three‐stage fluidized bed. (a) Single‐stage mode, (b) two‐stage mode, and (c) three‐stage mode.

FIGURE 4.28 Product distribution (a) and gas composition (b) varying with temperature in N

2

atmosphere for single‐stage operation.

FIGURE 4.29 Product distribution (a) and gas composition (b) varying with steam/coal at 900°C and an excess air ratio (ER) of 0.2 in single‐stage operation.

FIGURE 4.30 Product distribution (a) and gas composition (b) varying with temperature of pyrolysis stage in the two‐stage operation (ER = 0.2, steam/coal = 0.09).

FIGURE 4.31 Comparison of product distribution in three operation modes at ER = 0.20 and steam/coal = 0.09.

FIGURE 4.32 Comparison of gas composition for three operation modes at ER = 0.2 and steam/coal = 0.09.

FIGURE 4.33 GC‐measured distillation curve (a) and fraction distribution (b) of tar obtained in three operation modes.

FIGURE 4.34 The oxidation reactivity of chars made by three operation modes.

FIGURE 4.35 Burning characteristics with air of chars from three operation modes measured in TG.

FIGURE 4.36 A schematic diagram of downer coal pyrolysis integrated into a riser combustor.

FIGURE 4.37 Pyrolysis product yield varying with pyrolysis temperature in downer.

FIGURE 4.38 Effect of pyrolysis temperature on distribution of liquid products.

FIGURE 4.39 Effect of pyrolysis temperature on groups in hexane‐soluble fraction.

FIGURE 4.40 Yields of gaseous hydrocarbons varying with pyrolysis temperature.

FIGURE 4.41 Production of major pyrolysis gas species varying with temperature.

FIGURE 4.42 A schematic diagram of the DG pyrolysis process. (1) Coal hopper, (2) riser, (3) dry coal hopper, (4) mixer, (5) reactor, (6) riser heater, (7) char receiver, (8) combustion fluidized bed, (9) cyclone, (10) scrubber tube, (11) gas–solid separator, (12) separation, (13) condenser, (14) tar removing unit, (15) desulfuration, and (16) air‐blaster.

FIGURE 4.43 A schematic diagram of the GF‐I technology. (1) Coal hopper, (2) preheating zone, (3) drying zone, (4) distillation zone, (5) cooling zone, (6) char, (7) cyclone, (8) double riser, (9) intercooler, (10) electrical tar precipitator, (11) phenol water tank, (12) original tar separator, (13) tar tank, (14) tar separator, (15) light tar tank, (16) final tar separator, (17) the gas pressure machine, (18) combustor, and (19) cooling tower.

FIGURE 4.44 A schematic diagram of the belt furnace technology.

FIGURE 4.45 A schematic diagram of the CSIRO pyrolysis reactor and process.

Chapter 05

FIGURE 5.1 Technology portfolio of chemical conversion processes from coal.

FIGURE 5.2 Schematic drawing of production routes to acetylene from coal.

FIGURE 5.3 Variations of Gibbs free energy of light hydrocarbons with temperature.

FIGURE 5.4 Variations of thermodynamic equilibrium composition with temperature at the mass ratio of C/H of 2 (solid carbon nonconsidered).

FIGURE 5.5 Schematic drawing of the cleaner production route to acetylene from coal (the pictures on the right side are taken from the 5 MW pilot‐plant plasma coal‐to‐acetylene process at Xinjiang Tianye Group Co. Ltd in China).

FIGURE 5.6 Schematic diagram of plasma jet apparatus for coal pyrolysis used in (a) British Coal Utilisation Research Association, (b) Sheffield University, and (c) Tsinghua University.

FIGURE 5.7 Effect of the coal and gas specific enthalpies on coal conversion and the yield of light gases: (a) coal‐specific enthalpy and (b) gas‐specific enthalpy.

FIGURE 5.8 Effect of the hydrogen concentration on the performance of coal pyrolysis to acetylene: (a) the conversion of reactant and yields of main gaseous products and (b) the conversions of C, H, O, and N elements in coal.

FIGURE 5.9 Effect of the volatile matter content in coal on (a) coal conversion and (b) the yield of carbon in light gases in slow pyrolysis, fast pyrolysis, and plasma pyrolysis processes.

FIGURE 5.10 Variations of thermodynamic equilibrium composition with temperature at mass ratio of C/H = 2: (a) solid carbon considered and (b) solid carbon nonconsidered.

FIGURE 5.11 Validation of thermodynamic equilibrium predictions with the representative 5 MW pilot‐plant data under the same initial mass fractions of C, H, and O atoms (C : H : O = 1.97 : 1.00 : 0.90).

FIGURE 5.12 Predictions of the gaseous composition at thermodynamic equilibrium with the temperature range of 1000–4000 K. The mass flow rate of water vapor is (a) 20 kg/h, (b) 50 kg/h, (c) 100 kg/h, and (d) 300 kg/h.

FIGURE 5.13 Decoking effect of the mixing section and reaction chamber in the 5 MW plasma reactor: (a) without online steam decoking and (b) with online steam decoking.

FIGURE 5.14 Variations of C

2

H

2

concentration at thermodynamic equilibrium with different mass flow rates of hydrocarbons under different quench temperatures. The hydrocarbons are (a) CH

4

, (b) C

3

H

8

, (c)

n

‐C

6

H

14

, and (d)

n

‐C

10

H

22

.

FIGURE 5.15 Variations of C

2

H

2

concentration at thermodynamic equilibrium with different effective mass ratio of C/H under different quench temperatures and predictions of C

2

H

2

concentration in different coal or hydrocarbons pyrolysis system.

FIGURE 5.16 Variations of quench temperature with different effective mass ratio of C/H and mole ratio of C

2

H

2

/CH

4

and evaluations of quench temperature in different coal or hydrocarbons pyrolysis system.

FIGURE 5.17 Chemical bridge reaction pathways treated in the CPD model [61].

FIGURE 5.18 Comparison among the experimental yields of volatiles, the original CPD predictions, and the improved CPD predictions as a function of temperature for coal 1–8.

FIGURE 5.19 Comparison among the experimental differential yields of volatiles, the original CPD predictions, and the improved CPD predictions as a function of time for coal 1–8.

FIGURE 5.20 Comparison between the experimental data and model predictions as a function of volatile matter content in coal: (a) yield of volatiles and (b) yield of light gases.

FIGURE 5.21 Comparison between the experimental yields of volatiles and model predictions as a function of heating rate.

FIGURE 5.22 Variations of (1) particle average temperature and (2) yield of volatiles with time in (a) H

2

atmosphere and (b) Ar atmosphere of different cases.

FIGURE 5.23 Predicted radial profiles of (a) temperature and (b) mass loss in at H

2

atmosphere at different times.

FIGURE 5.24 Pictures showing the initial distribution of the coal particles at the inlet of downer reactor using flat‐shaped nozzles: (a) 0°, (b) 45°, and (c) 90°.

FIGURE 5.25 Illustration of the modeling scheme of CFD–DPM approach considering heat, mass, and momentum transfer between the particle and gas phase.

FIGURE 5.26 Schematic of the 5 MW/2 MW plasma downer reactor.

FIGURE 5.27 Comparisons of model predictions with experimental data under typical operating conditions shown in Table 5.1: (a) 5 MW reactor and (b) 2 MW reactor.

FIGURE 5.28 Distribution of (1) gas temperature, (2) velocity magnitude, and (3) acetylene concentration in

x

 = 0,

y

 = 0 planes: (a) 5 MW reactor and (b) 2 MW reactor.

FIGURE 5.29 Distribution of coal particles together with the gas temperature field in a series of planes perpendicular to the

Z

‐axis: (a) 5 MW reactor and (b) 2 MW reactor.

FIGURE 5.30 Scale‐up methodology: parallel passage 4 × 1.5 MW plasma reactor.

Chapter 06

FIGURE 6.1 Current and future methanol demand by end use (a) 2011 demand 55.4 × 10

6

 t and (b) 2016 demand forecast 92.3 × 10

6

 t.

FIGURE 6.2 Haldor Topsøe DME process.

FIGURE 6.3 TOYO DME process flow for indirect DME synthesis.

FIGURE 6.4 Effect of reaction synergy on CO conversion.

FIGURE 6.5 Thermodynamic results of methanol/DME synthesis.

FIGURE 6.6 Fixed bed reactors for methanol synthesis: (a) multitubular fixed bed, (b) quench‐cooled fixed bed, and (c) Linde isothermal reactor.

FIGURE 6.7 Conversion profiles and equilibrium curve for three types of reactors: (a) boiling water reactor, (b) quench, and (c) indirectly cooled.

FIGURE 6.8 Types of slurry reactors: (a) bubble column, (b) internal‐loop airlift reactor, (c) external‐loop airlift reactor, and (d) spherical reactor.

FIGURE 6.9 Methanol synthesis reactors with different cooling designs: (a) cooling with water bath, (b) cooling with water coils, (c) cooling with cold feed, (d) feed gas quench, (e) feed‐effluent heat exchange by periodic flow reversal, (f) lateral flow, and (g) fluidized bed.

FIGURE 6.10 Simplified diagram of Lurgi’s MegaMethanol® Technology.

FIGURE 6.11 Flow regimes in a bubble column.

FIGURE 6.12 Influence of solid concentration on gas holdup.

FIGURE 6.13 Total gas holdup for nitrogen–water system as a function of superficial gas velocity at different pressures.

FIGURE 6.14 Influence of solid concentration on bubble size at the height of 0.65 m in a two‐dimensional (2D) column.

FIGURE 6.15 Influence of internals on gas holdup in an air–water–solid slurry system.

FIGURE 6.16 Photo of the internal bubble scraper.

FIGURE 6.17 Influence of bubble scraper on bubble size distribution in air–water system at

r

/

R

 = 0 and

U

g

 = 0.04 m/s.

FIGURE 6.18 Scale‐up strategy for bubble column reactors.

FIGURE 6.19 Two‐phase model for slurry reactor.

FIGURE 6.20 Influence of scale on the holdup of large bubbles and centerline liquid velocity.

FIGURE 6.21 Simulation of gas–liquid mass transfer with the framework of the CFD–PBM coupled model.

FIGURE 6.22 Bubble breakup and coalescence due to different mechanisms.

FIGURE 6.23 Comparison of measured and simulated average gas holdup (parameters of the simulated column: i.d. = 0.19 m,

H

 = 2.4 m). The results are for height of 2.0 m.

FIGURE 6.24 Bubble size distributions at different radial positions and superficial gas velocities.

FIGURE 6.25 Prediction of the variation of volume fraction of small bubbles with superficial gas velocity .

FIGURE 6.26 Comparison of the predicted and measured volumetric mass transfer coefficients .

FIGURE 6.27 Conversion of CO and selectivity to DME in the pilot plant.

Chapter 07

FIGURE 7.1 Possible reactors for FTS: (a) slurry bubble column reactor, (b) multitubular fixed bed reactor, (c) circulating fluidized bed reactor, and (d) fixed fluidized bed reactor.

FIGURE 7.2 Classification of slurry bubble column based on the axial slurry concentration. (a) HoSBC, (b) HeSBC, and (c) TFB.

FIGURE 7.3 Flow regime map for slurry bubble column reactors.

FIGURE 7.4 Typical construction of single‐tip conductivity probe.

FIGURE 7.5 A typical conductivity probe signal.

FIGURE 7.6 (a) Optical fiber probe and (b) schematic diagram of measurement.

FIGURE 7.7 Original and binarized signal of dual‐tip optical fiber probe.

FIGURE 7.8 Schematic diagram of the U‐shaped optical fiber probe.

FIGURE 7.9 Hot wire/film probes: (a) hot‐wire probe, (b) hot‐film probe, and (c) conical hot‐film probe [117].

FIGURE 7.10 Details and arrangement of Pavlov tube.

FIGURE 7.11 Normalized liquid velocity profile

u

L

(

r

)/

u

L

(0).

FIGURE 7.12 Typical variation of dynamic pressure gradient (

dP

) and gas holdup (

ε

G

) with time during the bed disengagement process.

FIGURE 7.13 Schematic of an EIT system applied to an electrically insulating (nonconducting) vessel.

FIGURE 7.14 Schematic of an EIT system applied to an electrically conducting vessel.

FIGURE 7.15 (a) Snap shot using high‐speed camera and (b) the digitalized image of the same shot using Adobe Photoshop software.

FIGURE 7.16 Laser Doppler anemometer setup [121].

FIGURE 7.17 Schematic of EIT system applied to Sandia’s SBCR [149].

FIGURE 7.18 Schematic diagram for high‐pressure and high‐temperature SBCR at OSU.

FIGURE 7.19 SBCR of 6 in. with ports used for overall gas holdup and DP measurements. CT1, CT2, and CT3 represent the scan levels used in this investigation.

FIGURE 7.20 Double‐bubble model considered axial dispersion.

FIGURE 7.21 Schematic of simulation for the whole FT process.

FIGURE 7.22 A typical simulation result for a pilot plant.

FIGURE 7.23 Schematic of gas sparger with cross‐shaped structure: (a) gas sparger in practical, (b) gas sparger in sumilation, and (c) reactor in simulation.

FIGURE 7.24 Simulation results of the reactor with cross‐shaped sparger: (a) 3D contour of slurry distribution, (b) 2D contour of slurry distribution at center profile, and (c) gas velocity vector in sparger.

FIGURE 7.25 Schematic of multistage sparger structure: (a) gas sparger in practical, (b) gas sparger in sumilation, and (c) reactor in simulation.

FIGURE 7.26 CFD simulation results of multistage sparger: (a) simulation result of general distribution of gas holdup, (b) profile of axial distribution of gas holdup, (c) profile of radial distribution of gas holdup, and (d) gas velocity vector around sparger.

FIGURE 7.27 Schematic of multiscale system.

FIGURE 7.28 The relation of multiscale drag coefficient and superficial gas velocity.

FIGURE 7.29 Structure of an SBCR reactor in a China patent [227].

FIGURE 7.30 Filtration systems of SBCR reactors [233, 234] (a) inner filtration method (16 slurry upper surface; 22 filtration zone; 30 filter elements; 50 restriction orifice; 51, 53 conduits; 52 shut‐off valve; 56 quick‐open valve) and (b) external separator (34, 38, 44 downcomers; 36 gas disengaging cup; 37 cone‐shape incline; 40 filtration vessel; 42 filter; 46, 48 valves; 50 baffle; 58 nozzle; 60 cover plate; 62 central line).

FIGURE 7.31 A graphic representation of a slurry phase reactor used with SSPD process in Sasol.

FIGURE 7.32 Demo plant with SBCR in China.

Chapter 08

FIGURE 8.1 Pore structures of the zeolites. (a) ZSM‐5. (b) SAPO‐34.

FIGURE 8.2 Side chain mechanism for the production of ethene and propene in methanol conversion.

FIGURE 8.3 Complex reaction routes of MTO.

FIGURE 8.4 Autocatalytic MTO performance in a fixed bed microreactor. Temperature: 350°C; pressure: normal; WHSV: 26 g MeOH/(gSAPO‐34·h).

FIGURE 8.5 Reaction heats of methanol and dimethyl ether (DME) to olefins. MTD, methanol to DME (based on 2 mol methanol or 1 mol DME); MTE, methanol to ethylene; MTP, methanol to propylene; MTB, methanol to butylene; DTE, DME to ethylene; DTP, DME to propylene; and DTB, DME to butylene.

FIGURE 8.6 Fixed bed reactors: (a) tubular fixed bed reactor, (b) multistage reactor with heat exchangers, and (c) multistage reactor with direct quenching.

FIGURE 8.7 Moving bed reactors: (a) axial concurrent flow, (b) axial countercurrent flow, and (c) radial cross flow.

FIGURE 8.8 Fluidized bed reactors: (a) turbulent reactor, (b) multistage turbulent reactor, (c) dense phase + dilute phase reactor, (d) dilute phase + dense phase reactor, and (e) riser.

FIGURE 8.9 Series connection of reactors: (a) series fast fluidized bed reactors and (b) series riser reactors.

FIGURE 8.10 Flow diagram of the MTO process. C, Compressor; C

2

, C

2

splitter; C

3

, C

3

splitter; CS, caustic srubber; D, dryer; DB, debutanizer; DE, deethanizer; DM, demethanizer; DP, depropanizer; OR, oxygen recovery; QT, Quench tower; R, reactor; and RE, regenerator.

FIGURE 8.11 DMTO plant in Baotou, China (1800 kt MeOH/year).

FIGURE 8.12 MTO/OCP plant in Nanjing, China (750 kt MeOH/year).

FIGURE 8.13 Flow diagram of the Lurgi‐MTP process. PR, pre‐reactor (methanol to DME); PRS, product recovery section; and R, MTP reactors (2 operating + 1 regenerating).

FIGURE 8.14 Lurgi‐MTP unit in China (1800 kt MeOH/year).

FIGURE 8.15 Flow diagram of the FMTP process. EBTP, ethene and butene conversion reactor; MCR, methanol conversion reactor; RE, regenerator; and PRS, product recovery section.

FIGURE 8.16 SAPO‐34 catalyst for FMTP. (a) SAPO‐34 zeolite and (b) spray‐dried catalyst.

FIGURE 8.17 FMTP pilot plant in Anhui, China (30 kt MeOH/year).

Chapter 09

FIGURE 9.1 Aromatic supply–demand in China (2013).

FIGURE 9.2 The increasing demanding rate of T and X from 2010 to 2015 (by CMAI, CEIC).

FIGURE 9.3 Weight ratio of aromatics in cracking products using different feedstocks.

FIGURE 9.4 Estimated aromatics supply and demand tree of China in 2020.

FIGURE 9.5 The formation route of hydrocarbon from methanol.

FIGURE 9.6 Reaction chain from methanol to hydrocarbons.

FIGURE 9.7 Structure of ZSM‐5 zeolite.

FIGURE 9.8 Consecutive reaction route from methanol to aromatics.

FIGURE 9.9 Temperature‐dependent yield of different products (spent Zn/ZSM‐5 catalyst, 0.3 h

−1

, 0.4 MPa).

FIGURE 9.10 Temperature‐dependent yield of aromatics, selectivity of PX in X, and selectivity of X (spent Zn/ZSM‐5 catalyst, 0.3 h

−1

, 0.4 MPa).

FIGURE 9.11 Profile of off gas and LPG under different temperatures (spent Zn/ZSM‐5 catalyst, 0.3 h

−1

, 0.4 MPa).

FIGURE 9.12 Effect of temperature on the aromatic product distribution (Ag/ZSM‐5(Si/Al ratio: 25), 475°C, 0.79 h

−1

, methanol partial pressure: 21.9 kPa).

FIGURE 9.13 Effect of methanol’s partial pressure on yield of aromatics (475°C, Ag/ZSM‐5, WHSV: 0.79 h

−1

, fixed bed).

FIGURE 9.14 Space velocity effect of methanol on yield of aromatics over Ag/ZSM‐5.

FIGURE 9.15 Space velocity effect on the product profiles from the conversion of methanol in TSFB (spent Zn/ZSM‐5 catalyst, 475°C, 0.25 h

−1

, 0.4 MPa).

FIGURE 9.16 Pressure effect on the product profiles (spent catalyst, 380°C, 0.3 h

−1

).

FIGURE 9.17 Reactor and catalyst regeneration of Ag/ZSM‐5 for two cycles using methanol with partial pressure of 20 kPa.

FIGURE 9.18 Four cycles of reaction‐catalyst regeneration of Ag/ZSM‐5 using pure methanol feedstock.

FIGURE 9.19 Illustration of single‐stage fluidized bed (SSFB) and two‐stage fluidized bed (TSFB).

FIGURE 9.20 Product profiles sampled at different stages of TSFB (fresh catalyst, 0.3 h

−1

, 0.4 MPa).

FIGURE 9.21 Reactor effect on the product profiles from the conversion of methanol (spent catalyst, 475°C, 0.25 h

−1

, 0.4 MPa).

FIGURE 9.22 Reactor effect on the product profiles (fresh catalyst, 475°C, 0.6 h

−1

, 0.4 MPa).

FIGURE 9.23 Flow sheet of CFB reactor system of MTA (1. catalyst regenerator; 2. MTA reactor; 3. stripper; 4. condensor; and 5. online GC).

FIGURE 9.24 Result of continuous reaction‐catalyst regeneration for 100 h in 20 t/a apparatus.

FIGURE 9.25 Primary and final product of MTA.

FIGURE 9.26 Flow sheet of MTA reactor system with 30 kt/a methanol feedstock (1. catalyst regenerator; 2. LHTA reactor; 3. MTA reactor; 4. stripper; 5. fine powder filter; 6. condenser; 7. gas–liquid–solid three‐phase separator; 8. compressor; 9. gas separation unit; and 10. liquid separation unit).

FIGURE 9.27 Photo of 30 kt/a pilot plant of MTA.

FIGURE 9.28 Result of continuous operation for 443 h in pilot plant test.

Chapter 10

FIGURE 10.1 Schematics of (left‐to‐right) top‐fired, side‐fired, and terraced‐wall‐fired steam reformers [15].

FIGURE 10.2 Schematic of processes taking place in ITM syngas technology.

FIGURE 10.3 Integrated OTM/HTM reactor separator.

FIGURE 10.4 Hydrogen content at equilibrium as a function of temperature for a pressure of 1.031 × 10

5

 Pa, a H

2

O : CH

4

molar ratio of 3, and a CaO : CH

4

molar ratio of 2.

Chapter 11

FIGURE 11.1 Schematic layout of self‐heat‐recuperation fluidized bed dryer with steam as fluidizing/drying medium.

FIGURE 11.2 A schematic of biomass property changes after torrefaction treatment.

Figure 11.3 Isothermal TG curves of British Columbia pine, pine bark, and three major components at 300°C.

FIGURE 11.4 A simple one‐component kinetics model accounting primary decomposition and secondary tar cracking reactions.

FIGURE 11.5 Illustration of dual‐fluidized bed allothermal biomass pyrolyzers: (a) BFB pyrolyzer + riser combustor and (b) riser pyrolyzer + BFB combustor.

FIGURE 11.6 Comparison of oil yield data from laboratory and pilot CFB pyrolyzers (symbols) and predicted by a simple biomass particle plug flow riser reactor model (line).

FIGURE 11.7 Syngas conversion technologies.

FIGURE 11.8 Effect of temperature and pressure (1–100 atm) on (a) H

2

, CO, CH

4

, and CO

2

equilibrium compositions (b) HHV contours for switchgrass steam gasification with steam‐to‐fuel mass ratio of 2.4 [97].

FIGURE 11.9 Equilibrium constants for major reactions in biomass gasification, calculated from the thermodynamic data correlations [93].

FIGURE 11.10 Catalytic oxidation–reduction mechanism of potassium carbonate on carbonaceous material steam gasification [144].

FIGURE 11.11 Diagram of a generic moving bed gasifier [156].

FIGURE 11.12 Diagram of a generic fluidized bed gasifier [156].

FIGURE 11.13 UBC dual‐fluidized bed steam gasifier configuration.

FIGURE 11.14 Two DFB biomass gasification systems: (a) dual‐fluidized bed gasification (DFBG) and (b) pyrolysis gasification (PG).

FIGURE 11.15 Schematic drawing of loop seal.

FIGURE 11.16 Equilibrium partial pressure of CO

2

for calcium carbonate.

FIGURE 11.17 Schematic of lime‐enhanced gasification process [172].

FIGURE 11.18 Diagram of a generic entrained flow gasifier [156].

FIGURE 11.19 Description of processes in a fluidized bed biomass gasifier.

FIGURE 11.20 Worldwide gasification capacity and planned growth cumulative by year.

FIGURE 11.21 Worldwide gasification capacity and planned growth product wise.

FIGURE 11.22 Developing growth strategies and market opportunities; BM, biomass.

FIGURE 11.23 Rate‐controlling regimes for heterogeneous char oxidation.

FIGURE 11.24 Principle of (a) decoupling and (b) process schematic diagram of the topping combustion technology.

FIGURE 11.25 Components of oxy‐combustion systems [203].

FIGURE 11.26 Oxygen transport capability of different redox systems.

FIGURE 11.27 A simplified schematic figure of the ash formation mechanisms during combustion of solid wood‐based biomass in CFB.

FIGURE 11.28 Modeling of physical and chemical processes interactions in biomass thermochemical conversion.

Chapter 12

FIGURE 12.1 Chemical looping processes for fossil fuel conversion.

FIGURE 12.2 Chemical looping concepts for fossil fuel conversion: (a) CLC for electricity production, (b) CLPO for syngas production, and (c) CLR for direct hydrogen production.

FIGURE 12.3 Oxygen partial pressure diagram of various metal oxides.

FIGURE 12.4 Structures of (a) Fe

2

O

3

, (b) Fe

3

O

4

, (c) FeO, and (d) Fe.

FIGURE 12.5 Gas–solid contacting patterns in chemical looping reactors.

FIGURE 12.6 Carbon distribution with various [O]:CH

4

ratio at 900°C, 1 bar: (a) Fe

2

O

3

/Fe and (b) Fe

2

TiO

5

–Fe/Fe

2

TiO

4

/FeTiO

3

.

FIGURE 12.7 Effects of (a) temperature on methane conversion and syngas purity and (b) steam addition on H

2

:CO ratio at 1 and 10 bar in ITCMO–CH

4

system. [O]:CH

4

is set to 3.

FIGURE 12.8 Multistage equilibrium model for a moving bed reactor.

FIGURE 12.9 Effects of molar flow‐rate ratio on a moving bed reducer performance at 900°C from multistage equilibrium model.

FIGURE 12.10 The comparison of the gases and solids conversions between the numerical results and the previous experimental data in the moving bed reducer.

FIGURE 12.11 The steady overall conversion profiles of syngas and solids when the reducer is shortened.

FIGURE 12.12 The gas and solids conversions verse the feed‐rate ratio between gases and solids.

FIGURE 12.13 Standpipe flow with the presence of a fine powder layer between bulk coarse solids.

FIGURE 12.14 The volume fraction of phase 2 in the combustor.

FIGURE 12.15 The static pressure in the combustor.

FIGURE 12.16 Comparison of axial velocities at two different flow regimes: (a) contours of axial velocity (phase 2) (m/s) (Time = 1.1615e + 02) and (b) contours of axial velocity (phase 2) (m/s) (Time = 1.1620e + 02).

FIGURE 12.17 Comparison of the static pressure at two different flow regimes: (a) contours of static pressure (mixture) (pascal) (Time = 1.1615e + 02) and (b) contours of static pressure (mixture) (pascal) (Time = 1.1620e + 02).

FIGURE 12.18 Picture of syngas chemical looping pilot‐scale unit.

FIGURE 12.19 (a) Diagram and (b) picture of the 25 kWth coal direct chemical looping system.

FIGURE 12.20 CDCL moving bed reducer layout.

FIGURE 12.21 Simplified process flow diagram of the shale gas‐to‐syngas system for liquid fuel synthesis.

FIGURE 12.22 STS subpilot cocurrent moving bed reactor.

Guide

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MULTIPHASE REACTOR ENGINEERING FOR CLEAN AND LOW‐CARBON ENERGY APPLICATIONS

Edited by

YI CHENG, FEI WEI, and YONG JIN

Department of Chemical EngineeringTsinghua University, Beijing, PR China

Copyright © 2017 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New JerseyPublished simultaneously in Canada

No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per‐copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750‐8400, fax (978) 750‐4470, or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748‐6011, fax (201) 748‐6008, or online at http://www.wiley.com/go/permissions.

Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages.

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Library of Congress Cataloging‐in‐Publication Data

Names: Cheng, Yi, 1970– editor. | Wei, Fei, 1962– editor. | Jin, Yong, 1935– editor.Title: Multiphase reactor engineering for clean and low‐carbon energy applications / edited by Yi Cheng, Fei Wei, Yong Jin.Description: Hoboken, New Jersey : John Wiley & Sons, Inc., [2017] | Includes bibliographical references and index.Identifiers: LCCN 2016041899 | ISBN 9781118454695 (cloth) | ISBN 9781119251088 (epub)Subjects: LCSH: Synthetic fuels. | Clean coal technologies. | Chemical reactors. | Clean energy.Classification: LCC TP360 .M79 2017 | DDC 662.6/25–dc23LC record available at https://lccn.loc.gov/2016041899

PREFACE

A multiphase reactor accommodates more than one phase (gas, liquid, or solid) coming into contact and resulting in a change in chemical composition of one or more phases. Almost all of the fuels, chemicals, and materials are produced through chemical transformations in multiphase reactors. Multiphase reactor engineering actually integrates fundamentals of transport phenomena and chemical reactions with reactor modeling, design, scale‐up, and process optimization quantitatively, and will continue to play a key role in the development of industrial processes.

This book pays special attention to the applications of multiphase reactor engineering in the energy‐related processes, especially to the emerging processes of clean, highly efficient conversion of fossil fuels as well as biomass to chemical products. The goal in editing the book is to provide the state‐of‐the‐art review on the historical development and characteristics of conventional and nonconventional multiphase reactors with the updated knowledge linked with the basic principles of some novel processes. In particular, for the limited reserves and poorer quality of oils nowadays, conventional refining processes meet new challenges, which calls for the new revolution in multiphase reactor technologies, for example, for clean coal utilization processes. Some emerging processes, such as coal to liquid fuels, coal to chemicals (e.g., acetylene, olefins, and aromatics) and the newly updated coal pyrolysis, gasification, and combustion, are being commercialized in industry. In parallel to the aforementioned processes, a perspective view on the CO2 capture and storage is also included as CO2 emission has become the bottleneck for sustainable future of the earth. The chapters are organized as follows: petroleum refining (Chapter 1), coal direct conversion (Chapters 2–5), syngas conversion (Chapters 6 and 7), methanol conversion (Chapters 8 and 9), natural gas conversion (Chapter 10), biomass conversion (Chapter 11), and CO2 control based on chemical looping technology (Chapter 12).

The editors would like to acknowledge the great efforts from all the contributors in preparing the chapters and their expertise in the specific areas. We anticipate that the book would help readers to deeply understand the fundamentals of multiphase reactors and the sophisticated applications related with key solutions to cleaner conversion techniques of fossil fuels and biomass.

Yi Cheng, Fei Wei, and Yong Jin

LIST OF CONTRIBUTORS

Xiaotao T. Bi, Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, British Columbia, Canada

Yi Cheng, Department of Chemical Engineering, Tsinghua University, Beijing, PR China

Chuigang Fan, State Key Laboratory of Multiphase Complex System, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, PR China

Liang‐Shih Fan, Department of Chemical and Biomolecular Engineering, Ohio State University, Columbus, OH, USA

Farzam Fotovat, Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, British Columbia, Canada

Jinsen Gao, College of Chemical Engineering, China University of Petroleum, Beijing, PR China

John R. Grace, Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, British Columbia, Canada

Jiangze Han, College of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang, Hebei Province, PR China

Yong Jin, Department of Chemical Engineering, Tsinghua University, Beijing, PR China

Xingying Lan, College of Chemical Engineering, China University of Petroleum, Beijing, PR China

Qiang Li, Department of Thermal Engineering, Tsinghua University, Beijing, PR China

Chunxi Lu, College of Chemical Engineering, China University of Petroleum, Beijing, PR China

Junfu Lv, Department of Thermal Engineering, Tsinghua University, Beijing, PR China

Mohammad S. Masnadi, Department of Energy Resources Engineering, School of Earth, Energy and Environmental Sciences, Stanford University, Stanford, CA, USA

Zhuowu Men, NICE, Beijing, PR China

Weizhong Qian, Department of Chemical Engineering, Tsinghua University, Beijing, PR China

Andrew Tong, Department of Chemical and Biomolecular Engineering, Ohio State University, Columbus, OH, USA

Gang Wang, College of Chemical Engineering, China University of Petroleum, Beijing, PR China

Jinfu Wang, Department of Chemical Engineering, Tsinghua University, Beijing, PR China

Tiefeng Wang, Department of Chemical Engineering, Tsinghua University, Beijing, PR China

Yao Wang, Department of Chemical Engineering, Tsinghua University, Beijing, PR China

Fei Wei, Department of Chemical Engineering, Tsinghua University, Beijing, PR China

Li Weng