Thermochemical Conversion 3

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CONVERSION OF BIOMASS TO BIOFUELS

WSU ChE 481/581 & UI BAE 504

THERMOCHEMICAL CONVERSION SECTION

LECTURER: MANUEL GARCIA-PEREZ , Ph.D.

Department of Biological Systems Engineering

205 L.J. Smith Hall, Phone number: 509-335-7758 e-mail: mgarcia-perez@wsu.edu

CREDIT HOURS: 3

MEEETING PLACE: EME B46, TUESDAY AND

THURSDAY 1:25-2:40 AM

OUTLINE OF OUR PREVIOUS LECTURE

A.- TORREFACTION

B.- SLOW PYROLYSIS (CARBONIZATION)

C.- FAST PYROLYSIS

D.- CONCLUSION

OVERVIEW OF THE THERMOCHEMICAL SECTION

LECTURE 1

INTRODUCTION TO BIOMASS THERMOCHEMICAL CONVERSION

TECHNOLOGIES AND THERMO-CHEMICAL REACTIONS

LECTURE 2

TORREFACTION AND PYROLYSIS (SLOW AND FAST)

LECTURE 3

GASIFICATION, COMBUSTION AND HYDROTHERMAL CONVERSION

LECTURE 4

CHARACTERIZATION AND USES OF PRODUCTS OF THERMOCHEMICAL

REACTIONS

LECTURE OUTLINE

A.- GASIFICATION

B.- COMBUSTION

C.- HYDROTHERMAL CONVERSION

A.- GASIFICATION (700 -1400 o C)

THERMOCHEMICAL GASIFICATION IS THE CONVERSION BY PARTIAL OXIDATION AT ELEVATED

TEMPERATURES OF A CARBONACEOUS FEEDSTOCK INTO A GASEOUS ENERGY CARRIER

CONSISTING OF PERMANENT GASES AND TARS. DEVELOPMENT OF GASIFICATION

TECHNOLOGIES DATES BACK TO THE END OF THE 18 TH CENTURY WHEN HOT GASES FROM

COAL AND COKE FURNACES WERE USED IN BOILER AND LIGHTING APPLICATIONS .

GASIFICATION OF COAL IS NOW WELL ESTABLISHED , AND BIOMASS GASIFICATION HAS

BENEFITED FROM ACTIVITY IN THIS SECTOR . HOWEVER, THE TWO TECHNOLOGIES ARE NOT

DIRECTLY COMPARABLE DUE TO DIFFERENCES BETWEEN THE FEEDSTOCKS (E.G.

CHAR

REACTIVITY, PROXIMATE COMPOSITION, ASH COMPOSITION, MOISTURE CONTENT,

DENSITY ).

ALTHOUGH MANY BIOMASS GASIFICATION

PROCESSES HAVE BEEN DEVELOPED

COMMERCIALLY, ONLY THE

FLUID BED

CONFIGURATION ARE BEING CONSIDERED IN

APPLICATIONS THAT GENERATE OVER 1 MWe .

FLUID BED GASIFIERS ARE AVAILABLE FROM A

NUMBER OF MANUFACTURERS IN THERMAL

CAPACITIES RANGING FROM 2.5 TO 150 MW

FOR OPERATIONS AT ATMOSPHERIC AND

ELEVATED PRESSURE.

A.- GASIFICATION (700 -1400 o C)

SYNTHESIS GAS CONVERSION PROCESSES

Spath PL, Dayton DC: Preliminary Screening-Technical and Economic Assessment of Synthesis Gas to Fuels and Chemicals with

Emphasis on the Potential for Biomass-Derived Syngas. NREL/tp-510-34929

A.- GASIFICATION (700 -1400 o C)

The equivalent ratio ( f

) is used to quantify the proximity of a mixture (biomass + air

(oxygen) to its combustion stoichiometric conditions. The equivalent ratio is denoted as:

  the the actual biomass

 air biomass

 air ratio for ratio complete combustion

 

 m m f f

/

/ m o m o

 st

 m o st m o

Where: m f

: mass of biomass (fuel) m o

: mass of oxidizer (air)

St: Stoichiometric conditions

Φ > 1 The mixture is rich (Excess of Biomass)

Φ ≤ 1 The mixture is weak (Excess of air)

PYROLYSIS: Φ infinite

GASIFICATION: Φ between 3 and 5 (1/ Φ between 0.15 and 0.28)

COMBUSTION: Φ 0 to 1

The equivalent ratio is related to the air to fuel ratio ( AFR )

AFR

1

AFR st

A.- GASIFICATION (700 -1400 o C)

DISTRIBUTION OF ENERGY AND EXERGY TO THE PREODUCT GAS AND CHAR FOR BIOMASS CONVERSION BY AIR

(BIOMASS AND OXYGEN BROUGHT TO EQUILIBRIUM CONDITIONS)

1/ Φ

DISTRIBUTION OF ENERGY AND EXERGY TO THE PREODUCT GAS AND CHAR FOR BIOMASS CONVERSION BY

STEAM (STEAM TEMPERATURE 500 K) (BIOMASS AND STEAM BROUGHT TO EQUILIBRIUM CONDITIONS)

MARK JAN PRINS: THERMODYNAMIC ANALYSIS OF BIOMASS GASIFICATION. INCLUDING TORREFACTION AS A THERMAL PRETREATMENT. VDM VERLAG Dr. MULLER.

PhD THESIS UNIVERSITY OF EINDHOVEN , 2005

A.- GASIFICATION (700 -1400 o C)

BIOMASS

STEAM OR

OXYGEN

GASIFICATION

AIR

OPERATIONAL BIOMASS GASIFIERS

GÜSSING: 2 MWe, STEAM, AUSTRIA

HARBOØRE: 1.3 MWe, AIR, DENMARK

ARBRE: 8 MWe, AIR, UK

MHV

GAS

SYNTHESIS OR

CONVERSION

FUEL CELLS

TURBINES

LHV

GAS

ENGINE

BOILER

METHANOL

ETHERS

DIESEL

GASOLINE

HYDROGEN

AMMONIA

ELECTRICITY

HEAT

A.- GASIFICATION (700 -1400 o C)

1812: FOUNDATION OF THE LONDON GAS, LIGHT AND COKE COMPANY FOR THE PRODUCTION OF

TOWN GAS

1900: ELECTRIC BULBS REPLACED GAS AS A SOURCE OF LIGHT.

1920: ONLY GAS OF LOW HEATING VALUE (3.5-6 MJ/m 3 ) COULD BE PRODUCED

1920: CARL VON LINDE COMMERCIALIZED THE CRYOGENIC SEPARATION OF AIR ALLOWING TO

DEVELOP OXYGEN BLAST FOR THE PRODUCTION OF SYNTHESIS GAS AND HYDROGEN

1926: FRANZ FISCHER AND HANS TROPSCH DEVELOPED THE FISCHER-TROPSCH PROCESS IN

GERMANY.

1920-1940: DEVELOPMENT OF NEW GASIFICATION CONCEPTS: 1926THE WINKLER FLUID BED

PROCESS , 1931THE LURGI MOVING-BED GASIFICATION PROCESS , 1940THE KOPPERS-TOTZEK

ENTRAINED-FLOW PROCESS .

1920-1960: LITTLE FURTHER TECHNICAL PROGRESS IN THE GASIFICATION OF SOLID FUELS BUT THESE

TECHNOLOGIES PLAYED A CRITICAL ROLE IN GERMANY’S WARTIME SYNTHESIS FUEL PROGRAM AND

ON THE WIDER BASIS IN THE WORLDWIDE DEVELOPMENT OF THE AMMONIA INDUSTRY .

1950: TEXACO AND SHELL DEVELOPED THE OIL GASIFICATION PROCESS , DECLINE IN IMPORTANCE OF

GASIFICATION BECAUSE OF THE LARGE PRODUCTION OF NATURAL GAS AND NAPHTHA .

1970: SASOL USES COAL GASIFICATION AND FISCHER TROPSCH SYNTHESIS AS THE BASIS FOR ITS

SYNFUELS COMPLEX .

1970: FIRST OIL CRISIS INVESTMENT IN COAL HYDROGENATION (HYDROGASIFICATION) TO PRODUCE

METHANE AND LIQUID FUELS. LACK OF COMMERCIAL SUCCESS DUE TO THE NEED FOR HIGH

PRESSURE PROCESSED.

A.- GASIFICATION (700 -1400 o C)

1972PROTOTYPE GASIFICATION PLANTS TO PRODUCE ELECTRICITY FROM COAL GASIFICATION

VIA IGCC HAVE BEEN BUILT AND TESTED (COOL WATER, 1984; LUNEN, 1972, BUGGENUM, 1994;

WABASH RIVER, 1995; POLK, 1996; PUERTOLLANO 1998).

1978: KOPPERS AND SHELL JOINED FORCES TO PRODUCE A PRESSURIZED VERSION OF THE

KOPPERS-TOTZEK GASIFIER .

1981: REINBRAUM DEVELOPED THE HIGH TEMPERATURE WINKLER FLUIDIZED-BED REACTOR

1984: LURGI DEVELOPED A SLAGGING VERSION OF ITS EXISTING TECHNOLOGY IN PARTNERSHIP

WITH BRITISH GAS.

1984: TEXACO EXTENDED ITS OIL GASIFICATION PROCESS TO ACCEPT A SLURRIED COAL FEED .

1984- COAL TO CHEMICALS RECEIVED INCREASED ATTENTION ( EASTMAN METHANOL PLANT IN

KINSPORT STARTED UP IN 1984; Ube IN JAPAN BEGAN WITH COAL TO AMMONIA ).

1990- GASIFICATION OF HEAVY OIL RESIDUES IN REFINERIES.

FOUR PLANTS WERE BUILT IN ITALY .

2000sINCREASING IN ENERGY PRICES IS FUELING A RENAISSANCE OF GASIFICATION

TECHNOLOGIES .

MANY PLANTS ARE BEING BUILT IN CHINA .

A.- GASIFICATION (700 -1400 o C)

GASIFICATION REACTORS CAN BE GROUPED INTO THREE CATEGORIES:

1.- MOVING-BED GASIFIERS

2.-FLUID-BED GASIFIERS

3.-ENTRAINED-FLOW GASIFIERS

MOVING BED GASIFIERS (SOMETIMES CALLED FIXED-BED GASIFIERS) ARE CHARACTERIZED BY A

BED IN WHICH THE CARBONACEOUS MATERIAL MOVES SLOWLY DOWNWARD UNDER GRAVITY

AS IT IS GASIFIED BY A BLAST THAT IS GENERALLY BUT NOT ALWAYS, IN COUNTER-CURRENT

BLAST TO THE CARBONACEOUS MATERIAL . IN SUCH A COUNTER-CURRENT ARRANGEMENT,

THE HOT SYNTHESIS GAS FROM THE GASIFICATION ZONE IS USED TO PREHEAT AND PYROLYSE

THE DOWNWARD FLOWING SOLID . WITH THIS PROCESS THE OXYGEN CONSUMPTION IS VERY

LOW, BUT PYROLYSIS PRODUCTS ARE PRESENT IN THE PRODUCT SYNTHESIS GAS.

FLUID-BED GASIFIERS OFFER EXTREMELY GOOD MIXING BETWEEN FEED AND OXIDANT, WHICH

PROMOTES BOTH HEAT AND MASS TRANSFER. CERTAIN AMOUNT OF ONLY PARTIALLY REACTED

FUEL IS INEVITABLY REMOVED WITH THE ASH . THIS PLACES A LIMITATION ON THE CARBON

CONVERSION OF FLUID BED PROCESSES. THE OPERATION OF FLUID BED GASIFIERS IS GENERALLY

RESTRICTED TO TEMPERATURES BELOW THE SOFTENING POINT OF THE ASH , SINCE ASH

SLAGGING WILL DISTURB FLUIDIZATION . SIZING OF THE PARTICLE IS VERY IMPORTANT . THE

LOWER TEMPERATURE OPERATION OF FLUID BED PROCESSES MEANS THAT THEY ARE MORE

SUITED FOR GASIFYING REACTIVE FEEDSCTOCKS , SUCH AS BIOMASS AND LOW-RANK COAL .

Source: Higman C, van der Burgt: Gasification, Gulf Professional Publishing, Second Edition, 2008.

A.- GASIFICATION (700 -1400 o C)

ENTRAINED-FLOW GASIFIERS OPERATE WITH FED AND BLAST IN CO-CURRENT FLOW. THE

RESIDENCE TIME OF THESE PROCESSES IS SHORT (A FEW SECONDS).

THE FEED IS GROUND TO A

SIZE OF 100 m m OR LESS TO PROMOTE MASS TRANSFER AND ALLOW TRANSPORT IN THE GAS.

GIVEN THE SHORT RESIDENCE TIME, HIGH TEMPERATURES ARE REQUIRED TO ENSURE A GOOD

CONVERSION AND THEREFORE ALL ENTRAINED FLOW GASIFIERS OPERATE IN THE SLAGGING

RANGE .

ONE IMPORTANT POINT TO KEEP IN MIND IS THE SIGNIFICANCE OF THE SLAGGING BEHAVIOR OF

THE ASH . AT TEMPERATURES ABOVE THE ASH SOFTENING POINT , THE ASH BECOMES STICKY AND

WILL AGGLOMERATE, CAUSING BLOCKAGE OF BEDS OR FOULING THE HEAT EXCHANGE

EQUIPMENT .

TRADITIONAL PROCESSES:

GAS PRODUCER: HUMIDIFIED AIR IS BLOWN UPWARD THROUGH A DEEP BED OF COAL OR COKE .

THE AIR REACTS WITH THE COAL, THEREBY PRODUCING A GAS WITH A LOWER HEATING VALUE OF

ABOUT 6.5 MJ/m 3 . WHEN USING LOW RANK FEEDSTOCKS THE CALORIFIC VALUE CAN BE AS LOW AS

3.5 MJ/m 3 .

WATER GAS: STEAM REACTS IN A BATCH PROCESS WITH RED-HOT COKE TO FORM HYDROGEN

AND CARBON MONOXIDE .

FIRST THE COAL OR COKE IS HEATED BY BLOWING AIR UPWARD

THROUGH THE BED AT 1300 o C . THEN THE AIR IS STOPED AND THE STEAM IS PASSED TO PRODUCE

SYNTHESIS GAS. WHEN THE TEMPERATURE DROP TO ABOUT 900 o C THE CYCLE IS REPEATED.

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

-PARTIAL OXIDATION TO GIVE A LOW ( ~ 5 MJ/m 3 ) TO MEDIUM ( ~ 10 – 15 MJ/m 3 )

HEATING VALUE SYNTHESIS GAS (EQUIVALENT RATIO ( f 

~ 4 ) TEMPERATURES ( 700-1400 o C ). BIOMASS MOISTURE : LOWER THAN 15 mass %. PROBLEMS (GAS QUALITY , COST

REDUCTION)

GASIFICATION REACTORS

Winkler process

PRODUCT GAS CHARACTERISTICS

A.- GASIFICATION (700 -1400 o C)

REACTION ZONES IN A STANDARD UPDRAFT GASIFIER

BIOMASS

DRYING ZONE

PYROLYSIS ZONE

OXYGEN

A.- GASIFICATION (700 -1400 o C)

MOVING BED PROCESSES

MOVING-BED PROCESSES ARE THE OLDEST PROCESSES .

THE PATENT FOR THE LURGI DRY BOTTOM PROCESS OF “COAL PRESSURE

GASIFICATION” AS IT IS KNOWN WAS GRANTED IN 1927 .

IN 1931 LURGI STARTED TO

DEVELOP A PRESSURIZED VERSION OF EXISTING ATMOSPHERIC PRODUCER GAS

TECHNOLOGY.

THE DEVELOPMENT WAS MADE IN CLOSE COLABORATION WITH THE

TECHNICAL UNIVERSITY IN BERLIN UNDER THE DIRECTION OF PROFESSOR RUDOLF

DRAWE.

THE FIRST COMMERCIAL APPLICATION WAS BUILT IN 1936 . FURTHER

TECHNICAL DEVELOPMENT HAS BEEN PLACED IN A JOINT VENTURE BETWEEN LURGI

AND THE LARGEST OPERATOR OF THIS TECHNOLOGY “SASOL”. TODAY THE

TECHNOLOGY IS REFERED AS THE SASOL-LURGI DRY BOTTOM GASIFIER .

THE HEARTH OF THE LURGI PROCESS IS THE REACTOR IN WHICH THE BLAST AND

SYNGAS FLOW UPWARD IN COUNTER-CURRENT TO THE SOLID . THE REACTOR

VESSEL ITSELF IS A DOUBLE-WALLED PRESSURE VESSEL IN WHICH THE ANNUAL

SPACE BETWEEN THE TWO WALLS IS FILLED WITH BOILING WATER.

THE STEAM IS

GENERATED AT A PRESSURE SIMILAR TO THE GASIFICATION PRESSURE , THUS

ALLOWING A THIN INNER WALL , WHICH ENHANCES THE COOLING EFFECT. THE ASH

IS RECOVERED VIA A ROTATING GRADE IS PRECOOLED BY INCOMING BLAST (OXYGEN

OR STEAM) TO ABOUT 300-400 o C.

Source: Higman C, van der Burgt: Gasification, Gulf Professional Publishing, Second Edition, 2008.

A.- GASIFICATION (700 -1400 o C)

SASOL-LURGI DRY BOTTOM GASIFIER

PROCESS FLOWSHEET OF SASOL-LURGI DRY BOTTOM GASIFICATION

Source: Higman C, van der Burgt: Gasification, Gulf Professional Publishing, Second Edition, 2008.

A.- GASIFICATION (700 -1400 o C)

BRITISH GAS/LURGI SLAGGING GASIFIER (BGL)

THE BGL SLAGGING GASIFIER IS AN EXTENSION OF THE ORIGINAL LURGI PRESSURE GASIFIER

WITH THE ASH DISCHARGE DESIGNED FOR SLAGGING CONDITIONS. AN EXISTING LURGI

GASIFIER IN WESTFIELD SCOTLAND WAS MODIFIED FOR SLAGGING OPERATION AND

OPERATED FOR SEVERAL YEARS. THE UPPER PORTION OF THE BGL GASIFIER IS IDENTICAL TO

THAT OF THE SASOL-LURGI DRY BOTTOM GASIFIER.

THE BOTTOM IS COMPLETELY

REDESIGNED . THE MOTIVATION FOR THE DEVELOPMENT OF A SLAGGING VERSION OF THE

EXISTING LURGI INCLUDED THE DESIRE TO:

1.- INCREASE CO AND H

2

YIELDS (AT THE EXPENSE OF CO

2.- INCREASE SPECIFIC REACTOR THROUGHPUT

2

AND CH

4

)

3.- HAVE A REACTOR SUITABLE FOR COALS WITH LOW ASH MELTING POINT

4.- HAVE A REACTOR SUITABLE FOR ACCEPTING FINES

5.- REDUCE THE STEAM CONSUMPTION AND CONSEQUENT GAS CONDENSATE PRODUCTION

THE DECLINE IN INTEREST FOR COAL GASIFICATION IN THE 1980s PREVENTED

COMMERCIALIZATION OF THIS TECHNOLOGY. IN THE MID 1990s THE FIRST COMMERCIAL

PROJECT WAS REALIZED AT SCHWARZE PUMPE IN GERMANY TO GASIFY A MIXTURE OF

LIGNITE AND MUNICIPAL SOLID WASTES .

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

BGL GASIFIER

COMPARATIVE PERFORMANCE OF LURGI DRY

BOTTOM AND BGL GASIFIERS

THE LOWER PORTION OF THE REACTOR INCORPORATES A MOLTEN SLAG BATH . THE MOLTEN SLAG IS

DRAINED THROUGH A SLAG TAP INTO THE SLAG QUENCH CHAMBER, WHERE IT IS QUENCHED WITH WATER

AND SOLIDIFIED. THE SOLID SLAG IS DISCHARGED THROUGH A SLAG LOCK.

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

FLUID-BED PROCESSES

THE HISTORY OF DEVELOPMENT OF COAL GASIFICATION AND FLUID-BED

TECHNOLOGY HAVE BEEN INTIMATELY LINKED SINCE DEVELOPMENT OF THE WINKLER

PROCESS IN THE EARLY 1920s .

IN FLUID-BED GASIFICATION PROCESSES THE BLAST HAS TWO FUNCTIONS: (1) AS A

REACTANT AND (2) AS A FLUIDIZING MEDIUM FOR THE BED . SOLUTIONS WHERE ONE

VARIABLE HAS TO ACCOMPLISH MORE THAN ONE FUNCTION, WILL TEND TO

COMPLICATE OR PLACE LIMITATIONS ON THE OPERATION OF THE GASIFIER .

OPERATING TEMPERATURE: IF THE ASH CONTENT OF THE FUEL START TO SOFTEN

THEN THE INDIVIDUAL PARTICLES BEGIN TO AGGLOMERATE . THE LARGER PARTICLES

FORMED WILL FALL TO THE BOTTOM OF THE BED AND THEIR REMOVAL POSES A

CONSIDERABLE PROBLEM. FLUID BED GASIFIERS ALL OPERATE AT TEMPERATURES

BELOW THE SOFTENING POINT OF THE ASH WHICH IS TYPICALLY IN THE RANGE 950-

1100 o C FOR COAL AND 800-950 o C FOR BIOMASS.

FEED QUALITY: FLUID-BED GASIFIERS TYPICALLY OPERATE ON LOW RANK COAL SUCH

AS LIGNITE, PEAT OR BIOMASS (THESE MATERIALS HAVE HIGHER REACTIVITIES AND

CAN BE GASIFIED AT LOWER TEMPERATURES ). THESE REACTORS OPERATE WITH

GROUND COAL.

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

CARBON CONVERSION: THERE IS WIDE RANGE OF RESIDENCE TIMES OF THE INDIVIDUAL

PARTICLES, THUS REMOVAL OF FULLY REACTED PARTICLES, WHICH CONSIST ONLY OF ASH,

WILL INEVITABLY BE ASSOCIATED WITH REMOVAL OF UNREACTED CARBON .

MAXIMUM

CONVERSION EFFICIENCIES (97 %).

THE WINKLER PROCESS

WINKLER ATMOSPHERIC FLUID BED GASIFICATION THE WINLER ATMOSPHERIC FLUID-BED

PROCESS WAS THE FIRST CONTINUOUS

GASIFICATION PROCESS USING OXYGEN

RATHER THAN AIR AS BLAST . THE

PROCESS WAS PATENTED IN 1922 AND THE

FIRST PLANT BUILT IN 1925 . SINCE THEN

SOME 70 REACTORS HAVE BEEN NUILT

AND BROUGHT INTO COMMERCIAL

SERVICE BUT HAS NOW BEEN SHUT

DOWN FOR ECONOMIC REASONS .

IN

MOST SYSTEMS OPERATION

TEMPERATURE IS MAINTAINED BELOW THE

ASH MELTING POINT ( 950-1050 o C ).

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

THE HIGH-TEMPERATURE WINKLER (HTW) PROCESS

THE NAME “HIGH-TEMPERATURE WINKLER” FOR THE PROCESS DEVELOPED BY

RHEINBRAUN IS TO SOME EXTENT A MISNOMER. THE MOST IMPORTANT

DEVELOPMENT VIS-À-VIS THE ORIGINAL WINKLER PROCESS IS THE INCREASE OF

PRESSURE WHICH HAS NOW BEEN DEMONSTRATED AT 30 bar .

WINKLER (HTW) PROCESS

THE FEED SYSTEM COMPRISES A LOCK-

HOPPER FOR PRESSURIZED AND A SCREW

FEEDER FOR THE TRANSPORT OF COAL FROM

THE HIGH-PRESSURE CHARGE BIN INTO THE

GASIFIER. THE HTW PROCESS INCLUDES HEAT

RECOVERY IN A SYNGAS COOLER IN WHICH

THE RAW SYNTHESIS GAS IS COOLED FROM

900 TO ABOUT 300 o C . A CERAMIC CANDLE

FILTER IS USED DOWNSTREAM OF THE

SYNGAS COOLER FOR PARTICLE REMOVAL.

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

CIRCULATING FLUIDIZED BED (CFD) PROCESSES

THE CHARACTERISTICS OF A CIRCULATING

FLUIDIZED BED COMBINED MANY

ADVANTAGES OF THE STATIONARY FLUIDIZED

BED AND THE TRANSPORT REACTOR. THE

HIGH SLIP VELOCITIES ENSURE GOOD MIXING

OF GAS AND SOLIDS , AND THUS PROMOTE

EXCELLENT HEAT AND MASS TRANSFER .

SMALL PARTICLES ARE CONVERTED IN ONE

PASS, OR ARE ENTRAINED, SEPARATED FROM

THE GAS AND RETURNED VIA AN EXTERNAL

RECYCLE.

ONE ADVANTAGE OF THIS SYSTEM

IS THAT THE SIZE AND SHAPE OF THE

PARTICLES IS LESS IMPORTANT . THIS TYPE OF

GASIFIER IS EMINENTLY SUITABLE FOR THE

GASIFICATION OF BIOMASS AND WASTES , OF

WHICH THE SIZE, SHAPE, AND HENCE THE

FLUIDIZATION CHARACTERISTICS ARE MORE

DIFFICULT TO CONTROL.

LURGI CIRCULATING FLUID-BED GASIFIER

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

AGGLOMERATING FLUID-BED PROCESSES

THE IDEA BEHIND AGGLOMERATING FLUID-BED

PROCESSES IS TO HAVE A LOCALIZED AREA OF HIGHER

TEMPERATURE WHERE THE ASH REACHES ITS

SOFTENING POINT AND CAN BEGING TO FUSE . THE

PURPOSE OF THIS CONCEPT IS TO ALLOW A LIMITED

AGGLOMERATION OF ASH PARTICLES THAT AS THEY

GROW AND BECOME TOO HEAVY TO REMAIN IN THE

BED, FALL OUT AT THE BOTTOM. THIS PREFERENTIAL

SEPARATION OF LOW-CARBON ASH PARTICLES IS

DESIGNED TO PERMIT HIGHER CARBON CONVERSION

THAN CONVENTIONAL FLUID-BED PROCESSES .

THE

BURNERS IN THESE GASIFIERS HAVE TWO FUNCTIONS:

INTRODUCING THE FLUIDIZING GAS, AND ALSO

CREATING A HOT REGION WHERE THE ASH

AGGLOMERATION OCCURS.

TWO PROCESSES HAVE

BEEN DEVELOPED USING THIS PRINCIPLE: THE KELLOG

RUST WESTINGHOUSE (KRW) PROCESS , AND THE U-

GAS TECHNOLOGY DEVELOPED BY THE INSTITUTE OF

GAS TECHNOLOGY (GTI) ( 1970 ). A 1O t/DAY PILOT

PLANT OF A MODIFIED VERSION OF THE U-GAS FOR

BIOMASS ( RENUGAS ) WAS BUILD IN 1985 .

U-GAS GASIFIER

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

ENTRAINED-FLOW PROCESSES

THE PRINCIPAL ADVANTAGES ARE THE ABILITY TO

HANDLE PRACTICALLY ANY COAL , AND TO PRODUCE

A CLEAN, TAR-FREE GAS . THE ASH IS PRODUCED IN

THE FORM OF AN INERT SLAG OR FRIT . THIS IS

ACHIEVED WITH THE PENALTY OF A

REACTORS HAVE BECOME THE

OXYGEN . THESE

PREFFERED

GASIFIER FOR HARD COALS . THE FINE COAL

PARTICLES REACT WITH THE CONCURRENTLY

FLOWING STEAM AND OXYGEN . ALL ENTRAINED

GASIFIERS ARE OF THE SLAGGING TYPE WHICH

IMPLIES THAT THE OPERATING TEMPERATURE IS

ABOVE THE ASH MELTING POINT . THIS ENSURES

DESTRUCTION OF TARS AND OILS AND, A HGH

CARBON CONVERSION OF OVER 99 % . MOREOVER,

THESE REACTORS PRODUCE THE HIGHEST QUALITY

SYNTHESIS GAS WITH LOW METHANE

CONTENT . THE TWO BEST KNOWN REACTORS ARE

THE TOP-FIRED COAL-WATER SLURRY-FEED GASIFIER

( GEE PROCESS ) AND THE DRY COAL FEED SIDE FIRED

GASIFIER DEVELOPED BY SHELL AND KRUPP-

KOPPERS ( PRENFLO ).

TOP-FIRED COAL-WATER SLURRY FEED SLAGGING ENTRAINED-FLOW

GASIFIER

SIDE FIRED DRY COAL FEED SLAGGING ENTRAINED-FLOW GASIFIER

TOP FIRED DRY COAL FEED SLAGGING ENTRAINED FLOW GASIFIER

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

JUST AS WITH MOVING AND FLUIDIZED BED PROCESSES, THE FIRST ENTRAINED-

FLOW SLAGGING GASIFICATION PROCESS OPERATED AT ATMOSPHERIC PRESSURE .

THE ATMOSPHERIC PRESSURE KOPPERS-TOTZEK (KT) PROCESS WAS DEVELOPED IN

THE 1940s .

KOPPERS-TOTZEK (KT) PROCESS

THE KT REACTOR FEATURES SIDE-

MOUNTED BURNER FOR THE

INTRODUCTION OF COAL AND OXYGEN,

A TOP GAS OUTLET AND A BOTTOM

OUTLET FOR THE SLAG . THE GAS

LEAVING THE TOP OF THE GASIFIER AT

ABOUT 1500 o C IS QUENCHED WITH

WATER NEAR THE TOP OF THE REACTOR

TO A TEMPERATURE OF ABOUT 900 o C

TO RENDER THE SLAG NON-STICKY

BEFORE IT ENTERS A WATER TUBE

SYNGAS COOLER FOR THE PRODUCTION

OF STEAM.

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

SHELL COAL GASIFICATION PROCESS (SCGP)

SHELL AND KOPPERS JOINTLY DEVELOPED A

PRESSURIZED VERSION OF THE KOPPERS-TOTZEK

PROCESS. IN 1978 THEY STARTED TO OPERATE A 150 t/DAY GASIFIER IN HARBURG, GERMANY. FOR SHELL

THE MAIN INTEREST AT THE TIME WAS THE

PRODUCTION OF SYNTHETIC FUELS FROM COAL VIA

FISCHER-TROPSCH SYNTHESIS .

THE SCGP PROCESS

FEATURE AN EVEN AMOUNT OF DIAMETRICALLY

OPPOSED BURNERS IN THE SIDE-WALL AT THE

BOTTOM OF THE REACTOR . COAL IS GROUND IN A

MILLING AND DRYING UNIT TO A SIZE OF 90 %

BELOW 90 m m , PRESSURIZED IN LOCK-HOPPERS ,

TRANSPORTED AS A DENSE PHASE AND MIXED NEAR

THE OUTLET OF THE BURNER WITH A MIXTURE OF

OXYGEN AND STEAM .

THE REACTIONS ARE VERY

FAST , AND AFTER A RESIDENCE TIME OF 0.5-4

SECONDS THE PRODUCT GAS LEAVES THE REACTOR AT

THE TOP AND THE SLAG LEAVES THROUGH AN

OPENING IN THE BOTTOM OF THE REACTOR WHERE IT

IS QUENCHED IN A WATER BATH. THE TEMPERATURE

IS TYPICALLY 1500 o C AND THE PRESSURE 30 - 40 bars .

SHELL COAL GASIFICATION PROCESS

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

THE SIEMENS SFG PROCESS

THE SIEMENS SFG PROCESS WAS FIRST

DEVELOPED IN 1975 FOR THE

GASIFICATION OF LOCAL BROWN

COALS.

THE FIRST GSP GASIFIER WAS BUILT

IN 1984 AT SCHWARZE PUMPE, GERMANY.

THE SFG PROCESS FEATUIRES A TOP-FIRED

REACTOR , WHERE THE REACTANTS ARE

INTRODUCED THORUGH A CENTRALLY

MOUNTED BURNER . THIS USE OF A SINGLE

BURNER REDUCES THE NUMBER OF FLOWS

TO BE CONTROLLED TO THREE ( COAL,

OXYGEN AND STEAM ). THE SLANG AND HOT

GAS LEAVE THE GASIFICATION SECTION

TOGETHER WHICH REDUCES ANY POTENTIAL

FOR BLOCKAGES IN THE SLAG TAP. THE

FIGURE SHOWS A REACTOR WITH A

SPIRALLY-WOUND COOLING SCREEN ,

TYPICALLY USED FOR ASH CONTAINING

CONVENTIONAL FUELS AND LIQUIDS .

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

BIO-OIL GASIFICATION

GASIFIER

Wright MM, Brown RC, Boateng AA: Distributed Processing of Biomass to Bio-oil for Subsequent Production of Fischer-Tropsh liquids. Bio-fuels, Bioprod., Bioref 2:229-

238 (2008)

A.- GASIFICATION (700 -1400 o C)

WHEN LOOKING AT BIOMASS GASIFICATION IT IS INSTRUCTIVE TO LOOK AT COAL

CONVERSION , AS THERE ARE MANY SIMILARITIES. BIOMASS CAN BE CONSIDERED AS A

VERY YOUNG COAL . THE TEMPERTURE REQUIERED TO COMPLETE THERMAL

GASIFICATION OF BIOMASS IS AROUND 800 - 900 o C .

ON THE OTHER HAND, THERE ARE A NUMBER OF SIGNIFICANT DIFFERENCES BETWEEN

COAL GASIFICATION AND BIOMASS GASIFICATION . THE

BIOMASS ASH HAS A

COMPARATIVELY LOW MELTING POINT

,

IN THE MOLTEN STATE IS VERY

AGGRESSIVE

. BIOMASS IS GENERALLY HIGHLY REACTIVE .

BIOMASS IS FIBROUS

AND

AT LOW TEMPERATURE

IT PRODUCES A LOT OF TARS

.

ENTRAINED-FLOW PROCESSES MIGHT HAVE AN APPARENT ATTRACTION IN BEING ABLE

TO GENERATE A CLEAN, TAR-FREE GAS, HOWEVER THE AGGRESSIVE CHARACTER OF

MOLTEN SLAG SPEAKS AGAINST USING A REFRACTORY . THESE REACTORS REQUIERE

VERY SMALL PARTICLE SIZES THAT ARE DIFFICULT TO OBTAIN WITH BIOMASS.

MOVING BED PROCESSES HAVE BEEN APPLIED TO LUMP WOOD , BUT THEY ARE LIMITED

TO THIS MATERIAL. FURTHERMORE, IN A COUNTER-FLOW GASIFIER, THE GAS WOULD

BE HEAVILY LOADED WITH TAR.

THE ALTERNATIVE OF CO-CURRENT FLOW COULD REDUCE

THE TAR PROBLEM SUBSTANTIALLY, BUT THE NECESSITY TO MAINTAIN GOOD CONTROL

OVER THE BLAST DISTRIBUTION RESTRICT THIS SOLUTION TO VERY SMALL SIZES .

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

FLUIDIZED BEDS ARE THE MOST COMMONLY USED REACTORS TO GASIFY BIOMASS ,

MOST OF THE SYSTEMS TRY TO FIND A SOLUTION TO TAR PROBLEMS OUTSIDE THE

GASIFIER .

FLOW DIAGRAM OF THE VARNOMO IGCC

SYSTEM (20 BARS) (SWEDEN)

CARBONA PRESSURIZED FLUIDIZED

BED PROCESS (1996, U-GASIFIER, 30

BARS, DEVELOPED BY GTI)

(COMMERCIAL PLANT STARTED IN

DENMARK, IN 2007)

SILVAGAS (BATELLE)

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

CHOREN PROCESS

DESPITE THE GENERAL TREND OF USING FLUID-BED REACTORS FOR BIOMASS GASIFICATION,

CHOREN IS ONE EXAMPLE OF AN ENTRAINED-FLOW GASIFICATION OF BIOMASS . CHOREN

ADDRESSES THE TAR ISSUE OF BIOMASS GASIFICATION BY USING A THREE STAGE PROCESS .

IN THE

FIRST STAGE THE BIOMASS IS PYROLYSED IN THE PRESENCE OF OXYGEN AT TEMPERATURES

BETWEEN 400 AND 500 o C .

THE PYROLYSIS GAS AND CHAR ARE EXTRACTED SEPARATELY . THE

PYROLYSIS GAS IS SUBJECTED TO HIGH TEMPERATURE GASIFICATION IN THE SECOND STAGE AT 1400 o C . THE CHAR IS GASIFIED IN THE THIRD STAGE .

Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008

A.- GASIFICATION (700 -1400 o C)

PRODUCTION OF ELECTRICITY

HIGH PRESSURE BIOMASS GASIFICATION COMBINED

CYCLE

LOW PRESSURE BIOMASS GASIFICATION COMBINED

CYCLE

Craig K.R., Mann M.K. Cost and Performance Analysis of Biomass-Based Integrated Gasification Combined-Cycle (BIGCC) Power Systems.

NREL/TP-430-21657

B.- COMBUSTION (OVER 1500 o C)

COMBUSTION IS A CHEMICAL REACTION BETWEEN FUEL AND OXIDIZER INVOLVING SIGNIFICANT RELEASE OF

ENERGY AS HEAT.

COMPLETE OXIDATION OF BIOMASS TO CO

2 smaller than 1), TEMPERATURES (OVER 1,500

AND H

2

O WITH PRODUCTION OF HEAT (EQUIVALENT RATIO ( f o C)

COMMERCIALLY AVAILABLE, EMISSIONS PROBLEMS, LOW EFFICIENCY AT SMALL SCALE (η ≤ 30 %)

FLUE GAS

BOILER

BIOMASS

STORAGE

DRYER

SUBSTATION

TURBINE

GENERATOR

ELECTRICITY

DRYER

EXHAUST

AIR

BOILER

BLOWDOWN

MAKE-UP WATER

DIRECT-FIRED BIOMASS ELECTRICITY GENERATING SYSTEM

SCHEMATICS.

B.- COMBUSTION (OVER 1500 o C)

USUAL AMOUNT OF EXCESS AIR SUPPLIED TO FUEL-BURNING EQUIPMENT

B.- COMBUSTION (OVER 1500 o C)

THE COMBUSTION OF SOLID BIOMASS IS FULLY ESTABLISHED AND ALREADY WIDELY

USED IN BIOMASS APPLICATIONS. THE COMBUSTION PROPERTIES OF BIOMASS ARE

WELL UNDERSTOOD. THE MOST POPULAR COMBUSTORS FOR BIOMASS APPLICATIONS

ARE EITHER

STOKER-FIRED

AND

FLUID BED DESIGNS

, ALTHOUGH IN RECENT YEARS

THE OPTION TO CO-FIRE SMALL PROPORTIONS OF BIOMASS WITH COAL IN LARGE

SUSPENSION FIRED FURNACES HAS ATTRACTED WIDESPREAD INTEREST.

IN STROKER-FIRED COMBUSTORS THE FEED BURNS AS IT MOVES THROUGH THE

FURNACE WHILE RESTING ON A

STATIONARY OR MOVING GRATE

.

FLUID BED DESIGNS BURN THE FEED IN A TURBULENT BED OF INERT MATERIAL THAT IS

FLUIDIZED BY COMBUSTION AIR FLOWING THROUGH IT FROM UNDERNEATH.

ALTHOUGH THE GRATE-FIRED COMBUSTORS ARE THE NORM FOR OLDER BIOMASS

FIRED PLANTS ,

FLUID BED COMBUSTORS ARE RAPIDLY BECOMING THE

PREFERRED TECHNOLOGY FOR BIOMASS COMBUSTION

BECAUSE OF THEIR LOW

NOX EMISSIONS .

FLUIDIZED BED BOILERS HAVE BEEN COMMERCIALLY AVAILABLE FOR

OVER 20 YEARS, AT CAPACITIES RANGING FROM 15 TO 715 MW INPUT.

BUBBLING

FLUID BED TEND TO BE LIMITED TO THE LOWER SIZE RANGE , WHILE CIRCULATING

FLUID BEDS ARE REPORTED OVER THE ENTIRE CAPACITY RANGE . OVER 110 FLUID BEDS

ARE OPERATING IN U.S.

ALL WITH PERFORMANCE GUARANTEES FROM THE VENDOR.

B.- COMBUSTION (OVER 1500 o C)

DIRECT COMBUSTION SYSTEMS: DIRECT COMBUSTION SYSTEMS COMMONLY USED FOR

COMBUSTION OF BIOMASS FUELS CAN BE CLASSIFIED INTO PILE, SUSPENSION, AND FLUIDIZED

BED COMBUSTION SYSTEMS .

PILE COMBUSTION SYSTEMS BURN THE WOOD FUEL IN EITHER A HEAPED PILE SUPPORTED ON

A GRATE (USED FOR SMALLER SCALE SYSTEMS) WHICH ARE HORIZONTAL OR INCLINED, OR IN A

THINLY SPREAD PILE SPREAD ACROSS A GRATE WHICH MAY BE TRAVELING OR STATIONARY.

COMBUSTION AIR IS PROVIDED BOTH UNDER THE GRATE AND ABOVE THE FUEL PILE . THE

MAIN ADVANTAGES OF THESE BURNERS ARE: RELATIVELY SIMPLE TO DESIGN , LOW CAPITAL

AND OPERATING COSTS , ABILITY TO TAKE A FAIRLY WIDE RANGE OF WOOD PARTICLES AND

MOISTURE CONTENTS .

MOISTURE CONTENTS UP TO 65 % CAN BE BURNED . MINIMUM

PARTICLE SIZE DEPENDS ON THE GRATE OPENINGS WHILE THE MAXIMUM PARTICLE SIZE

DEPENDS ON THE FUEL FEED OPENING INTO THE COMBUSTION CHAMBER.

SUSPENSION COMBUSTION SYSTEMS ARE OF TWO TYPES, WITH BOTH REQUIRING FUEL

MOISTURE LESS THAN 15 PERCENT AND UNIFORM PARTICLE SIZES WITH MAXIMUM

DIMENSIONS LESS THAN 6 mm . SUSPENSION BURNERS INCLUDE CYCLONIC BURNERS AND

PNEUMATIC SPREADER-STOKER SYSTEMS THAT BURN FUEL PARTICLES SUSPENDED IN A

TUBULAR AIR STREAM .

CYCLONIC BURNERS CONSIST OF HORIZONTAL OR VERTICAL CYLINDERS

OF CYCLONES WITH WOOD PNEUMATICALLY INJECTED ALONG THE TANGENT OF THE BURN

CHAMBER . CENTRAL FORCE SUSPENDS THE PARTICLES WHILE THEY ARE BURNED.

B.- COMBUSTION (OVER 1500 o C)

FLUIDIZED BED COMBUSTION (FBC) SYSTEMS BURN THE WOOD FUEL ON A HIGH

TEMPERATURE BED OF FINELY DIVIDED INERT MATERIAL , SUCH AS SAND, THAT IS AGITATED

BY AIR BLOWN FROM BENEATH THE BED.

SOLID FUEL IS INTRODUCED INTO THE CHAMBER

VIA AN AIRLOCK, WHERE THE FUEL PARTICLE, WHERE THE FUEL PARTICLE BURN WHILE

SUSPENDED IN THE BED . A STREAM OF GASES PASSES UPWARDS THROUGH A BED OF FREE

FLOWING GRANULAR MATERIALS IN WHICH THE GAS VELOCITY IS LARGE ENOUGH THAT THE

SOLID PARTICLES ARE WIDELY SEPERATED AND CIRCULATED FREELY THORUGHOUT THE BED.

DURING OVERALL CIRCULATION OF THE BED THERE WILL BE TRANSIENT STREAMS OF GAS

FLOWING UPWARDS IN CHANNELS CONTAINING FEW SOLIDS AND CLUMPS OR MASSES OF

SOLIDS FLOWING DOWNWARDS. THE FLUIDIZED BED LOOKS LIKE A BOILING LIQUID.

THE BED

IS USUALLY SAND OR LIMESTINE . OVERFIRE IS NORMALLY INTRODUCED IN THE

DISENGAGING ZONE ( FREEBOARD)

B.- COMBUSTION (OVER 1500 o C)

CIRCULATING FLUID BED: IF THE AIR FLOW OF A BUBBLING FLUID BED IS INCREASED, THE AIR

BUBBLES BECOME LARGER FORMING LARGE VOIDS IN THE BED AND ENTRAINING SUBSTANTIAL

AMOUNTS OF SOLIDS. THIS TYPE OF BED IS REFERRED TO AS TURBULENT FLUID BED . IN A

CIRCULATING FLUID BED THE TURBULENT BED SOLIDS ARE COLLECTED , SEPARATED FROM THE

GAS AND RETURNED TO THE BED, FORMING A SOLID CIRCULATION LOOP . A CIRCULATING FLUID

BED CAN BE DIFFERENTIATED FROM A BUBBLING FLUID BED IN THAT THERE IS NO DISTINCT

SEPARATION BETWEEN THE DENSE SOLID ZONE AND THE DILUTED SOLIDS ZONE.

CIRCULATING

FLUID BED DENSITIES ARE ABOUT 560 Kg/M 3 COMPARED TO A BUBBLING BED DENSITY OF 720

Kg/M 3 . TO ACHIEVE THE LOWER BED DENSITY AIR RATES ARE INCREASED FROM THE 1.5 – 3.7 m/s

OF BUBLING BED TO ABOUT 9.1 m/s. THE RESIDENCE TIME OF THE SOLIDS IN A CIRCULATING

FLUID BED IS DETERMINED BY THE SOLIDS CIRCULATION RATE , THE ATTRITIBILITY OF THE SOLIDS,

AND THE COLLECTION EFFICIENCY OF THE SOLIDS SEPARATION DEVICE.

B.- COMBUSTION (OVER 1500 o C)

CIRCULATING FLUID BED:

B.- COMBUSTION (OVER 1500 o C)

STOKER COMBUSTORS IMPROVE ON OPERATION OF THE PILE BURNERS BY PROVIDING A

MOVING GRATE WHICH PERMITS CONTINUOUS ASH COLLECTION, THIS ELIMINATING CYCLIC

OPERATION CHARACTERISTIC OF TRADITIONAL PILE BURNERS .

IN ADDITION, THE FUEL IS

SPREAD MORE EVENLY, NORMALLY BY PNEUMATIC STOKER AND IN THINNER LAYER IN THE

COMBUSTION ZONE FIVING MORE EFFICIENT COMBUSTION . (STOKER FIRED BOILERS WERE

FIRST INTRODUCED IN THE 1920s FOR COAL AND IN THE LATE 1940s THE DETROIT STOKER

INSTALLED THE FIRST TRAVELLING GRATE SPREADER STOKER FOR WOOD. IN THE BASIC

STOKER DESIGN THE BOTTOM OF THE FURNACE IS A MOVING GRATE WHICH IS COOLED BY

UNDERFIRE AIR. UNDERFIRE AIR DEFINES THE MAXIMUM TEMPERATURE OF THE GRATE AND

THUS THE ALLOWABLE MOISTURE CONTENT OF THE FEED.

STAGED COMBUSTION PROCESSES

WERE DEVELOPED IN THE 1980’S TO MEET THE TIGHTER NO

X

EMISSION LIMITS . FOR 40 %

EXCESS AIR THE OVERFIRE AIR GAS BEEN INCREASED TO 50 %, LOWERING THE MAXIMUM

TEMPERATURE IN THE FURNACE.

B.- COMBUSTION (OVER 1500 o C)

STOKER COMBUSTORS

C.- HYDROTHERMAL CONVERSION

HYDROTHERMAL CONVERSION (HTC) IS A THERMO-CHEMICAL CONVERSION TECHNIQUE

WHICH USES LIQUID SUB-CRITICAL WATER AS AREACTION MEDIUM FOR CONVERSION OF

WET BIOMASS AND WASTE STREAMS.

HYDROTHERMAL CONVERSION (HTC) CAN BE PERFORMED WITH VARIOUS PURPOSES AND

DIFFERENT PRODUCTS CAN BE AIMED FOR. IN A CATALYTIC VERSION OF THE PROCESS

ALMOST COMPLETE CONVERSION OF BIOMASS TO METHANE IS REALIZED .

BIOMASS

CATALYTIC HTC

For decomposition of organic contaminants in water of gaseous fuel production

HTC

For production of fuel for combustion

METHANE RICH GAS

HYDROPHOBIC ORGANIC

FUEL

HTC

For production of products suitable for further upgrading

INTERMEDIATE PRODUCTS

TO BE REFINED

Knezevic D: Hydrothermal Conversion of Biomass. Ph D Thesis, University of Twente, 2009

C.- HYDROTHERMAL CONVERSION

TYPICAL HTC PROCESS

BIOMASS

WATER

SLURRY

ALKALI

SOLUTION

(OPTIONAL)

REDUCING

GAS

(OPTIONAL)

HEAT

HEAT

HEAT

PRODUCT

COOLER

GAS

PRESSURE

REDUCING

VALVE

LIQUID /

SOLID

HIGH

PRESSURE

PUMP

PREHEATER

PRIOR TO FEEDING INTO THE PROCESS BIOMASS IS PRETREATED TO ENSURE THAT THE FEEDSTOCK HAS DESIRED

PROPERTIES: RHEOLOGICAL PROPERTIES, WATER CONTENT. IN THE FEEDING SECTION, FEEDSTOCK IS PRESSURIZED

AND HEATED TO THE DESIRED TEMPERATURE (300-370 o C) . FEEDING BIOMASS-WATER SURRIES IS A PARTICULAR

CHALLENGE DUE TO THE PROBLEMS OF BIOMASS SETTLING AND BLOCKING THE PROCESS LINES. IN MOST CASES

TUBULAR REACTORS HAVE BEEN USED FOR CONTINUOUS INSTALLATIONS. TYPICALLY RESIDENCE TIMES OF 5-90

MINUTES ARE APPLIED. UPON COOLING THREE DIFFERENT PRODUCTS ARE OBTAINED : HYDROPHOBIC ORGANIC

PHASE , AND AQUEOUS PHASE WITH ORGANIC COMPOUNDS DISOLVED AND GASES (MAINLY CO

2

).

Knezevic D: Hydrothermal Conversion of Biomass. Ph D Thesis, University of Twente, 2009

C.- HYDROTHERMAL CONVERSION

1970’s:

1971:

1980’s:

1990’s

2000’s

INTEREST IN ALTERNATIVE ENERGY SOURCES INCREASES DUE TO THE OIL CRISES.

THE US BUREAU OF MINES STUDIED THE CONVERSION OF CARBOHYDRATES IN HOT COMPRESSED

WATER IN THE PRESENCE OF CO AND Na

2

DEVELOPMENT UNIT IN ALBANY.

CO

3

. DEVELOPMENT OF A 18 kg /h WOOD PROCESS

HTC USING BIOMASS/WATER SLURRIES WITH SPECIAL FEEDING SYSTEMS WAS STUDIED AT

THE UNIVERSITY OF ARIZONA, THE UNIVERSITY OF SASKATCHEWAN, PNNL AND SHELL.

AFTER A PERIOD OF REDUCED ATTENTION, THE INTEREST IN CONVERSION OF BIOMASS

INTO ENERGY WAS RENEWED IN THE MID 1990’s. THE HYDRO-THERMAL UPGRADING (HTU)

PROGRAM OF SHELL WAS RESTARTED AT BENCH AND LABORATORY SCALE.

THE FIVE TONS PER DAY STORS PROCESS DEMONSTRATION PLANT WAS BUILD IN JAPAN WITH

THE AIM OF CONVERTING SEWAGE INTO A COMBUSTIBLE ENERGY CARRIER. AFTER THE SUCCESS OF

THE PLANT TREATING MUNICIPAL WASTEWATER IN COLTON, CALIFORNIA , THE PROCESS IS NOW

COMMERCIALIZED BY THERMOENERGY (US) UNDER THE NAME: THERMOFUEL PROCESS .

ENERTECH

ENVIRONMENTAL INC (US) IS CURRENTLY BUILDING A COMMERCIAL SCALE FACILITY IN

RIALTO, CALIFORNIA TO PROCESS 170 tons/day OF BIO-SOLIDS FROM FIVE MUNICIPALITIES IN LOS

ANGELES AREA (IT IS BEING COMMERCIALIZED WITH THE NAME SLURRYCARB).

HYDROTHERMAL CONVERSION OF SPECIFIC FEEDSTOCK TO HYDROPHOBIC FUELS FOR

COMBUSTION IS NEARING COMMERCIAL OPERATION .

HTC FOR BROADER RANGE OF

FEEDSTOCKS AND FOR PRODUCTION OF PRECURSORS OF TRANSPORTATION FUELS IS

STILL IN THE DEVELOPMENT STAGE .

Knezevic D: Hydrothermal Conversion of Biomass. Ph D Thesis, University of Twente, 2009

C.- HYDROTHERMAL CONVERSION http://www.enertech.com/technology/efuel.html

C.- HYDROTHERMAL CONVERSION

HTC REACTION CHEMISTRY

HTC REACTIONS CAN BE CLASSIFIED ACCORDING TO THEIR MECHANISM AS: IONIC AND

FREE RADICAL REACTIONS .

HYDROLYSIS: IS A CLASS OF DECOMPOSITION REACTIONS OF ORGANICS INVOLVING

BREAKDOWN BY WATER. THIS IS A TYPICAL IONIC REACTION CATALYZED WITH BASES AND

ACIDS . THESE REACTIONS READILY OCCUR ALREADY IN THE TEMPERATURE RANGE OF 150

TO 250 o C WHEN AUTOCATALYSIS IS CAUSED BY ACIDIC HTC REACTION PRODUCTS.

HEMICELLULOSE UNDERGOES HYDROLYSIS DECOMPOSITION AT TEMPERATURES FROM

120 TO 180 o C ; HYDROLYSIS OF CELLULOSE OCCURS AT TEMPERATURES ABOVE 180 o C . AT

THESE TEMPERATURES IT IS ONLY POSSIBLE TO OBTAIN A PARTIAL HYDROLYSIS OF LIGNIN .

COMPLETE DISSOLUTION OF WHOLE BIOMASS CAN BE ACHIEVED WITH Na

2

CO

3

.

OXYGEN REMOVAL UNDER THE HTC CONDITIONS OCCURS VIA THE FOLLOWING

REACTIONS : DEHYDRATION, DECARBOXYLATION AND DECARBONYLATION .

FURTHERMORE WATER IS THE PRODUCT OF POLYCONDENSATION REACTIONS WHICH ARE

ONE OF THE MAIN ROUTES TOWARDS CHAR.

Knezevic D: Hydrothermal Conversion of Biomass. Ph D Thesis, University of Twente, 2009

C.- HYDROTHERMAL CONVERSION

CELLULOSE DECOMPOSITION IN SUPERCRITICAL WATER (SAKA MODEL)

Ehara K, Saka S: A comparative study on chemical conversion of cellulose between the batch-type and flow-type systems in supercritical water. Cellulose 9: 301-311, 2002

C.- HYDROTHERMAL CONVERSION

ROLE OF WATER

WATER UNDER THE HTC HAS SEVERAL ROLES. IT IS A REACTION MEDIUM AND

CAN SERVE AS A DISTRIBUTION MEDIUM FOR HOMOGENEOUS AND

HETEROGENEOUS CATALYSTS . MOREOVER, WATER ITSELF HAS A CATALYTIC

ROLE IN VARIOUS ACID/BASE CATALYZED PROCESSES DUE TO ITS HIGHER

DEGREE OF IONIZATION AT THE INCREASED TEMPERATURE . WATER IS ALSO

DIRECTLY INVOLVED IN CHEMICAL REACTIONS AS A REACTANT OR A

PRODUCT . WATER PARTICIPATES IN THE HYDROLYSIS OF CELLULOSE , IT CAN

ALSO OXIDIZE SOME ORGANIC SPECIES .

IT IS A POWERFUL POLAR ORGANIC

SOLVENT THAT CAN REMOVE THE REACTION INTERMEDIARIES FROM THE

SOLID MATRIX AND SERVE AS A PHYSICAL BARRIER BETWEEN THEM TO

REDUCE POLYCONDENSATION REACTIONS.

D.- CONLCUSIONS

TORREFACTION

,

CARBONIZATION

,

FAST PYROLYSIS

,

GASIFICATION

,

COMBUSTION

AND

HYDROTHERMAL

CONVERSION

ARE IMPORTANT THERMOCHEMICAL

TECHNOLOGIES TO CONVERT

LIGNOCELLULOSIC MATERIALS

INTO HEAT

,

PRECURSORS OF TRANSPORTATION FUELS

OR

CHEMICALS

.

COMBUSTION IS THE ONLY OF THESE

TECHNOLOGIES IN

COMMERCIALIZATION

THE OTHERS ARE

STILL AT THE

DEMONSTRATION STAGE

.

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