Resoures control and Environment control

380ppm

385ppm

大気中のCO2濃度の変遷

http://climate.nasa.gov/stateOfFlux/index.cfm

Division of Systems Research

Institute of materials and Systems for Sustainability (IMaSS)

Concurrent research group

Research Group on High-temperature Energy Conversion

Department of Mechanical Science and Engineering

Nagoya University

Prof. I. Naruse, Assoc.Prof. R. Yoshiie, Assis. Prof. Y. Ueki

1

Background

Reserve production ratio

Oil Gas Coal U

CO2 concentrations in the atmosphere

Problem in pulverized coal combustion boiler

Ash deposit phenomenon

2

・Slagging

・Fouling

Background

Solution of the behavior of the ash particle in the coal combustion process is necessary

Fig1 picture of pulverized coal combustion boiler

Fig2 fouling（after the two years operation ）

Enlarged

view

Ash deposit

Heat transfer tube

Lead to poor work performance of boiler

Mechanism of ash generated during pulverized coal combustion

Work content

①Coal combustion experiment by drop tube furnace ・sample in combustion process ・analysis combustion ratio and gas sampling ②SEM/EDX Analysis ・Ash particle classify Included mineral and Excluded mineral ・Particle diameter distribution ・Chemical composition distribution

Elucidation of basic behavior of the ash(Included Mineral and Excluded Mineral) in coal particle

Purpose

3

Excluded Mineral

Included Mineral resin

coal

Included Mineral Included Mineral are intimately surrounded by the carbon matrix

Excluded Mineral Excluded Mineral are ash particle which exists alone

Mechanism of ash generated during pulverized coal combustion

Background

Oxy-Fuel Combustion Group

• An energy source in the world is oil. • But, it is possible that the supply of oil will be

difficult because Almost oil is supplied by the district of the Middle East.

• And,it is worried that oil is exhausted after several decades.

So, • Recently,coal becomes the focus of public attention. • Ratio of reserves to production is a lot. • An area of coal deposits disperses.

• Caebon dioxide emissions of coal is more than that of other energy sources.

• Nitrogen and sulfur oxide break out due to N and S included in coal.

Problem

Oxy-Fuel Combustion Advantage • CO2 concentration in exhaust gas becomes more

than 90%. So,the separation and concentration is easy.

• A conversion rate of Nitrogen oxides decreases.

Solution

Oxy-Fuel Combustion

Drop Tube Furnace using electricity(DTF)

Purpose

・Solution of the behavior which coal is burned in Oxy-Fuel combustion and the formation mechanism of Nitrogen oxide

Research contents

Conduct combustion research using DTF in CO2-O2 atmosphere and Oxy-Fuel atmosphere. And, compare the experiment result with the result of simulation by calculation.

Recirculation imitation of exhaust gas

（Imitation of Oxy-Fuel combustion）

Experiment of coal combustion

Simulation by calculation

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64

219

40

61

227

41

67

192

41 60

133

46 59

118

53 56

109

0

50

100

150

200

250

Oil Natural gas Coal

Re

serv

es

to p

rod

uct

ion

rat

io

[ye

ar]

1997

2000

2003

2007

2010

2013

Oxy-Fuel combustion property of coal using fluidized bed

Background of research

• Reserves to production ratio: 118 years (2010) • Regional reserves are distributed around the world

Strong point

• Compared to other fossil fuels, CO2 emissions are large

• Generating NOx, SOx

Weak point

Utilization of primary energy resources

Oil has become a major in the world

• Reserves to production ratio: 46 years (2010) • Regional reserves are unevenly distributed. • Stable supply is anxiety.

Pay attention to coal

Development of high efficiency・CO2 capture

combustion technology

Fossil energy dependence of the major countries

Reserves to production ratio of fossil fuel

Oxy-Fuel combustion Fluidized bed

43 37 33 33 31 17 23

22 22

15 23

4

66 42

17 25 39 24

15

3

6

0102030405060708090

100

Natural gas

Coal

Oil

• Desulfurization in furnace available • A variety of fuel available • Low NOx emission

feature

Fluidized bed Oxy-Fuel combustion

rich CO₂ (over 90%)

• No need for separation and concentration of CO₂, liquefied and collected can be easily just cooling and compression

• With only add the path of exhaust gas recirculation, available in the remodeling of the boiler traditional

• There is a possibility of reduction of NOx

Strong point

• Elucidation of combustion characteristics of coal using bubbling fluidized bed

• Comparison of combustion characteristics in air, CO₂-O₂, Oxy-Fuel atmosphere

Purpose of research

Studies on behavior of trace element during coal gasification

• High-temperature corrosion of turbine blade • Degradation of fuel cell(IGFC) • Environmental pollution by exhaust gas → Effect on human health

Problem

・Exhaustion from fossil fuels

・Environmental problems

(Global Warming)

High-efficiency and clean uses of Coal

Coal gasification technology

Coal Compared with other fossil fuel • Vast resource reserves • Widely distributed in the world

Electric generation using coal gasification Generating efficiency • IGCC is approx.48% • IGFC is more than 55%

Require studies on behavior of trace elements during coal gasification process

Background

Experiment

Iso-kinetics sampling

Gas analysis

Particle analysis

Fuel injection part

Reaction part

Secondary gas

Coal feeder

Injector

Water

in

Water

out

Water

in

Water

out

Sampling probe

Primary gas

Dilution gas

Heater

unit

N2 CO2 Ar

Mass flow controller

Continuous feeding

Entraining gas : N2

Gasifying agent : CO2

Flow Meter

Pump

Pump

LPI unit

Micro-GC sample unit

Temperature

controlled

by electric heater

Residence time :

2s

Low Pressure Impactor

(LPI)

Filter

Experiment device (DTF)

• Thermo dynamic equilibrium calculation by FactSage

• Coal gasification experiment by

DTF 1. Analysis of produced gas by

Micro-GC 2. Collect according to particle diameter by LPI

→measure concentration of trace element by ICP

STUDY FOR SORBENTS OF TRACE

ELEMENTS IN COAL GASIFICATION

background

coal (C,H2O,…)

Gasification

gasification gas

(CO,H2,CH4,…,

trace elements)

Gas cleaning

Coal

gasification gas

(CO,H2,…)

Purpose

Elucidation of trace elements behavior

Control trace element compounds to retain these in fanes

Advantage

High supply stability

Lower CO2 emission

Disadvantage

Problems about small trace element compounds

High efficiency in electrical generation

CONTENTS

Thermodynamic

equilibrium calculation by

Factsage to calculate trace

elemental compounds

Evaluation the efficiency of

sorbents in gasification

gas by TG

Evaluation the efficiency of

sorbents in gasification

gas by packed bed

- to Measure trace element

concentrations by an atomic

absorption spectrometer

Fig. Experimental set up

SOFC

study

Purpose of study

・Analyze degradation characteristics of SOFC by trace elements in coal gasified gas

Study contents

・Thermodynamic equilibrium calculation By Factsage ・Electrical generation experiment

Artificial emissions of mercury in the world

Total emissions of mercury ▶1960 tons/year

Come from fossil fuel combustion ▶474 ton/year

about 25% of the total （ UNEP (2013) ）

Elucidation of mercury capture in exhaust gas

The Minamata Convention on Mercury

was signed in 2013

Need to reduce mercury emissions

Research Content

Experimental Equipment Control technical development of

the mercury discharged

Purpose

Reduce mercury emissions by

using adsorbents

1. Measure the amount of

mercury in the gas after the

adsorbent pass

2. Measure the amount of

mercury in the adsorbent

after the experiment

Evaluation of the performance

of the adsorbent

Elucidation of ash deposition behavior in pulverized coal-fired boiler

Ash deposition in pulverized coal-fired boiler causes some problems.

– Slagging

– Fouling

Fouling in pulverized coal-fired boiler

Decrease in thermal efficiency

Reducing heat transfer

Erosion of heat transfer tube

Purpose

In order to elucidate an ash deposition mechanism in pulverized coal-fired boiler.

Experimental apparatus

• SEM/EDX • FactSage ver. 6.4 • Thermomechanical analysis(TMA) • Vertical pulverized coal-fired boiler

Reduction technology of ash deposition in the waste combustion boilers

Efficient use of general waste

・use exhaust heat for the generation of electricity

18

Problem in waste material combustion boiler

Ash deposition trouble

by melting ash

・Fouling Phenomenon that a low melting point inorganic

matter becomes the binder and forms the

adhesion layer on the heat transfer pipe surface

Lowering of thermal efficiency

・Refuse Derived Fuel (RDF)

Need to solution of ash deposition

In the waste combustion ,it is concerned of fouling because ash have

a lot of chlorine

Fouling in waste material combustion boiler

Ni-alloy

SUS304

(Thickness：200μm)

Reduce ash deposition to spray Ni-alloy

Background

19

Experiment apparatus

Cooling water Thermo couple

Test piece

(desorption type)

Sampling port

Heat exchanger tube

Burner section

Reacting section

Deposit section

Exhaust section

Burner

Heat exchanger tube

Slag

Sampling port

Observation window

Burner section

Reacting section

Deposit

Exhaust section

Propane+O2

receiver

Feeder

Exhaust

window

Observation

Ash+N2

Elucidation of degradation mechanism of denitration catalyst by ash deposition

Background

Ash deposited on the denitration catalyst

NOX component is included in the flue gas, resulting in a air pollution when vented to the atmosphere as such.

Through denitration catalyst, I want to harmless 𝐍𝟐 and 𝐇𝟐𝐎 .

Combustion ash adheres to the denitration catalyst. Needto wash the catalyst, to replace

Greater efficiency of the denitration catalyst is made possible by elucidating the mechanism of degradation.

Research content

①Classification of the catalyst of age using ②Analysis deposits surface from a comparison of the surface properties of each catalyst using SEM ③Using the EDX, and analyze the deposit from the elemental analysis of the surface and cross-section

SEM image of catalyst surface

Analysis date of catalyst surface by EDX

Identification of the substance adhering to the catalyst surface and, to identify the cause of the catalyst deterioration

分類 発熱量

補正無水無灰基

kJ/kg (kcal/kg)

燃料比 粘結性 炭質 区分

無煙炭 (A)

Authracite

A1

--- 4.0 以上

非粘結 A2

瀝青炭 (B, C)

Bituminous

B1 35,160 以上

（8,400 以上）

1.5 以上

強粘結

B2 1.5 未満

C 33,910 以上 35,160 未満

（8,100 以上 8,400 未満） － 粘結

亜瀝青炭 (D, E)

Sub-Bituminous

D 32,650 以上 33,910 未満

（7,800 以上 8,100 未満） － 弱粘結

E 30,560 以上 32,650 未満

（7,300 以上 7,800 未満） --- 非粘結

褐炭 (F)

Lignite

F1 29,470 以上 30,560 未満

（6,800 以上 7,300 未満） ---

非粘結

F2 24,280 以上 29,470 未満

（5,800 以上 6,800 未満） ---

Background

Classification of coal (JIS M 1002)

Minable years(2005)

・Bituminous coal 97years

・Subbituminous coal 457years

・Lignite 172years

It is important to the

effective use of

subbituminous coal

Elucidation of the self-ignition characteristics of

subbituminous coal

Problems of subbituminous

coal

・Low calorific value

・Risk of self-ignition

Equipment

Thermobalance schematic

Analyzing the weight change behavior in constant heating rate field

Thermobalance

measuring the change in weight

of the coal using a

thermobalance

⇒analyze the oxygen adsorption

behavior

Cause of self-ignition is heat

generated by the reaction with

oxygen in the air

Analyze the oxygen adsorption

of the subbituminous coal,

evaluated by comparing the

results of bituminous coal

Objective

Oxygen adsorption experiment

Using solid fuel (limited) Include waste

Using waste instead of solid fuel

Advantage of using waste ・saving solid fuel ・use not only energy resource but also raw materials

・Reduction of Discharge about a toxic substance like dioxin

Becoming more serious

The 2013 44.87 million ton waste in Japan

出展：環境省 一般廃棄物の排出及び処理状況について

First combustion experiment

Second get date

Third modeling

Way to research

purpose

measurement of the burning velocity elucidation of mechanism about solid

fuel and waste

Enhance efficiency of Waste combustion

To use numeral simulation is acceptable.

Fig1: Schematic of stoker furnace Purpose of this study

To produce simplification reaction mechanism based on GRI-Mech3.0 26

Clarify the production of NOx by burning wastes

Low excess air ratio and high temperature combustion is the mainstream

・plobrem Highly emission of N2O and NO

Content

Output by calculation of provisional reaction mechanism

Experimental output of burning RDF by Butch furnace

Brush up for these two outputs into agreement

Fig2: Schematic of Butch furnace

Analysis and its reduction techniques of tar generated during thermal decomposition of carbon-based resources

If we could reduce tar ・・・

Increase product gas (H2, CO, etc.)

product material

Tar cause ・pipe clogging ・engine trouble

Plastics waste

What tar Tar is blended much chemical species that polycyclic aromatic hydrocarbon

28

Gasification of one method in thermal recycle

High efficiency gasification

High heat value similar to fossil fuel

important Substitution Energy resources

• Product gas (H2, CO, etc.) • Tar

セラミックヒーター サンプルホル

ダー ガラス管

マントルヒーター

サンプルロッド マスフロコントローラ

圧力ゲージ

真空ゲージ

水槽（氷冷） ジクロロメタン （CH2Cl2 ）

コットン ウォーター ポンプ

エアーポンプ

三方バルブ

ウォータータンク

バルブ

バルブ

温度コントローラー

ABS

PC PE

Tar capturing

Plastic waste

Tar CO

H2

Analysis and its reduction techniques of tar generated during thermal decomposition of carbon-based resources

steam injection ＋

gasification

• Plastics species • gasification temperature • Amount of steam injection

Experimental parameter

• Amount of tar • Analyze by mass spectrometry

Analysis method

Carbon neutral

Renewable

Big resources

Low energy density

Low production per unit density

Advantage Disadvantage

Fossil fuel

Reference: 2011年度の一次エネルギー国内供給量(経済産業省)

Global warming is caused by CO2 emission

Fossil fuel is limited

Alternative resource of fossil resource

Demand on high efficiency gasification technology

Biomass

REACTION BEHAVIORS IN PACKED-BED BIOMASS GASIFIER

Background

Air

Biomass

pellets

φ100m

m

PC

PC

Logge

r

Micro

GC

Tar

trap

Exhaust

gas burner

Thermo-

couples

Insulator

Ignition

ports Impinger

×3 Fire

grate

Coolin

g

tower

Co

olin

g

Wa

ter

Co

olin

g

Wa

ter

1000m

m

LP

Fig1. Packed bed gasifier

Optimization to injected steam

parameter(temperature, height,

quantity)

Biomass gasification packed

bed gasifier object be made to

suppress the occurrence of tar

Steam addition is effective in

the suppression of tar

Purpose

REACTION BEHAVIORS IN PACKED-BED BIOMASS GASIFIER

Purpose and devices

Study on technique for promoting oxidation of

low concentration hydrocarbon

• Healthy damage to the neighboring human beings in painting factories

• Cause of air pollution

low concentration

hydrocarbon such as

VOC

VOC : Volatile Organic Compounds (toluene, xylene etc.)

Background

We propose a method using ozone

Conventional technique using the catalyst ： High cost by the use of the catalyst

32

Study

Experimental apparatus

• Decomposition behavior analysis of low concentration

hydrocarbon using reaction kinetics

• Experiment of reducing low concentration hydrocarbon using O3

33

Examined various

temperatures to find the

optimum operation

conditions.

Add O3 to hydrocarbon

Heating

Analysis using GC-FID

Measurements of Trace Elements in Gas with Single-Pulse LIBS

Background

• Harmful elements(As, Se, etc...)come from plants.

• Real-time monitoring is needed.

Previous method

Preprocessing is needed for samples.

Single-pulse LIBS

• No preprocessing

• Direct detection

Single-pulse LIBS can detect and analyze elements in real time and in situ.

• Coal sample is excited by concentrated laser.

• Atomic elements in breakdown plasma are excited and emit excitation light with specific wavelength.

• Identify atomic elements by analyzing the spectrum.

Measurement principle

Coal sample

Furnace

Breakdown plasma

Spectro meter

Experimental system

Study

Coal sample is combusted in image furnace.

Measuring the combustion gas by LIBS

Making effect of Hydrogen for coal combustion clear

Due to global warming, it is important to

decrease CO2 emissions. The iron making

industries account for 15% of CO2

emissions in Japan. Most of it is from

process of making pig iron. So, iron

industries proceed new making iron

process.

Effect of Addition of Mixed Gas Including Hydrogen on

Combustibility of Pulverized Coal

Background

It is considered that using Hydrogen for

reduction of ironstone in new process.

Subject

Blast Furnace

Hot blast（1200℃）

+Pulverized coal

Ironstone

Coke

H2

Study

Combustion experiment by

DTF to research reaction of

pulverized coal with Hydrogen

・Analysis of combustion gas ・Calculation of conversion ・Inspection by SEM

blowpipe

rance coke

Hot blast(1200℃)＋Hydrocarbongas

PC

Reaction Behaviors of Carbon Composite Iron Ore in an Isothermal Process

38

Background

CO2 emissions from iron industries make up about 12% of total emissions in Japan. About 70% of them are exhausted in a pig iron-making process.

It is urgent task to reduce CO2 emissions in a pig iron-making process.

Energy 43%

Transportation 17%

Others 15%

Steel 12%

Chemistry 4%

Pulp,Paper 2%

Processing Food 1%

Others 6%

Manufacturing, Construction

25%

Classification of CO2 emissions in Japan

Sintered Ore

Coke

Pig Iron

Blast Furnace

Purpose

Study on reduction behavior of Fe2O3 with unused carbon resources

Contents

Mixtures of Fe2O3 and reducing agent (coal, biomass, waste)

Weight changes of samples by Electric balance

39

Experimental Equipment (Batch Furnace)

Sample

Measurement

Elucidation of ashes behavior in combustion and gasification of coke

Enlarged view of Tuyere

1. Heat supply 2. Reducing agent for iron oxide 3. Ensure the breathability and

liquid permeability 4. carburizing source for molten iron

Role of cokes in a blast furnace

The most important property for blast furnace

operation

Back ground

It is said that ashes included in cokes form the shell, but the combustion and gasification reaction of coke is not known well yet

One of the property causing the deterioration of breathability is ……

lumpy zone

Dripping zone

coke

Deadman

Raceway

Formation of Raceway shell cohesive zone

Make the combustion and gasification

interruption sample with Batch furnace.

Experiment

Analyze the particles of ash in the sample with CCSEM-EDX.

Analysis

Content

Purpose

Schematic view of batch furnace Principle view of EDX

Observation and analysis of size and composition of the ash particles in the combustion and gasification interruption sample

Elucidation of ashes behavior in combustion and gasification of coke

Elucidation of ashes behavior in combustion and gasification of coke