the actual need of a guideline for sampling and analysis ... · milan, 22.06.2012 the actual need...

Milan, 22.06.2012

The actual need of a guideline for sampling and analysis of chemical matter (not tars) from product gas, pyrolysis gas and synthesis gas

Milan, 22.06.2012Folie 2

Sampling conditions

Sampling-conditions at

measurement point:

■ temperature: 50 – 1500 °C

■ pressure: -2 – 60 bar

■ concentrations: < 1 mg/m³ to 30 g/m³

■ water-content: 0 – 0.1 kg/kggas,dry

■ dust: <50 mg/m³ - 30 g/m³

■ tar: < 1mg/m³ - 300 g/m³

■ valves for pressure reduction?

■ condenser?

■ heating?

■ filtering?

■ fittings?

■ …

Settings of equipment:


Sampling, detection, analysis methods

sampling

in situ

online

deposits-probes

conductivity

optical

....

extractive

online

GC (MS,FID,..)

FTIR

further optical methods

…

offline

accumulative

SPA

physical capture

Chemical capture

absorption in liquids

batch (impinger)

continously

Equal for organic and

inorganic components

e.g. sufur containing tar

focus Bioenergy2020+


Equipment at Bioenergy2020+ (extractive, accumulative

method)

■ probe: stainless steel, PTFE, glass

■ heated filters: planar or depth

■ absorption: impingers (250 ml)

■ pump: membrane pump

■ gas drying/cleaning: silica, activated carbon

■ volume detection: diaphragm gas-meter

■ water-content: from solvent-sample

PIFI

PI

FI

cooling unit (-20°C)

pump activated

char coal

flow rate

display

silica gel

volume

detection

ball valve

control valve

drain

impinger for inorganic

parameterssafety flask

cooled double jacket flasks

for organic parameters

probe

heated filter

heated tube

ball valve

PIPIFIFI

PI

FIFI

cooling unit (-20°C)

pump activated

char coal

flow rate

display

silica gel

volume

detection

ball valve

control valve

drain

impinger for inorganic

parameterssafety flask

cooled double jacket flasks

for organic parameters

probe

heated filter

heated tube

ball valve


Quality measures – gas-generating unit

■ gas flow: 50-500 l/h

■ stripping out: H2SO4 + N2

■ gas preheating: 120°C

■ dosage of liquid standard: 0.1 to 50 ml/h

■ absorption units: 1 -2 impingers

■ tested components:■ H2S: Na2S(aq) + H2SO4 → H2S(g) + SO42- + 2Na+

■ HCN: 2KCN(aq) + H2SO4 → 2HCN(g) + SO42- + 2K+

30%vol.

H2SO4

N2 liquid standard of

Na2S or KCN

drops of standard

gas with defined H2S(g) or HCN(g)

loading

fritheating

perfusing pump

30%vol.

H2SO4

N2 liquid standard of

Na2S or KCN

drops of standard

gas with defined H2S(g) or HCN(g)

loading

fritheating

perfusing pump

Gas-generating unit: Settings:


Results- validation of H2S-measurement

86,4%

9,1%

101,6%

0,5%

98,0%

9,1%

95,1%

8,7%

90,3%

5,8%

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

sta

nd

ard

reco

very

-rate

[%

]

16,73 15,54 12,63 12,66 12,66

feeding standard [mg H2S]

1st absorption-flask 2nd absorption-flask

�H2S causes:

Damage to catalyst, increases emissions, corrosion

�Main reactions of sampling procedure

Zn(CH3COO)2 + H2O → Zn2+ + 2CH3COO- + H2O

H2S(aq) + H2O → HS- + H3O+

HS- + H2O → S2- + H3O+

Zn2+ + S2- → ZnS(s)↓

Pb2+ + S2- → PbS(s)(black)

�Advantanges

�good retention rates

�CO2 has no influence

�Direct photometric analysis possible

�Optical check-up with PbAc

�Disadvantages

�Solid precipitation


Development of special method for HCN-sampling

7,8%9,5%

3,0%

5,9%

56,1%

3,3%

96,8%

10,6%

33,9%36,1%

39,5%

9,6%

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

sta

nd

ard

reco

very

-rate

[%

]

NaOH NaOH CuAc HgAc CdAc AgNO3

1st absorption-flask 2nd absorption-flask

85,3488,09

19,66 19,36

0

10

20

30

40

50

60

70

80

90

100

01.0

3.201

0

01.0

4.20

10

01.0

5.20

10

01.0

6.201

0

[mg

CN

-/l]

056/Nc/62 056/Nc/72

3 month

�Main reactions

Hg(CH3COO)2 + H2O → Hg2+ + 2CH3COO-+ H2O

Hg2+ + 2HCN +H2O → [Hg(CN)2]aq + 2 H3O+

�Advantanges

�Efficient capture

�CO2 has no influence

�Direct photometric analysis possible

�No solid precipitation

�Long time stabile

�Disadvantages

�H2S has to be removed before

�NH3 creates amido-mercury chains (..Hg-NH2-Hg-NH2..)

1,41

2,40

3,72

2,31

0

0,5

1

1,5

2

2,5

3

3,5

4

Cu(CN)2 Hg(CN)2 Cd(CN)2 Ag(CN)2

mg

HC

N /

l

actual value desired value (2,301 mg HCN /l)

Sampling H2S from pyrolysis-gas


cooling unit

samplingprobe

heated

filter

ball

valve

heated

cyclone

heated water(50°C)

three-neck

flask

2-propanol+ 30%- H2SO4

safety flask

ZnAc

PbAc

2-propanol

Sampling total sulfur - basics


�Causes: catalyst damage, increased emissions

�Observation of traces important for SOFC

�System (principle)

�Main reactions of sampling:

Combustion:

R-S + H2S + O2 → SO2(g) + CO2 + ...

Absorption:

SO2(aq) + 2H2O ↔ HSO3- + H3O

+

HSO3- + H2O ↔ SO3

2- + H3O+

SO32- + H2O2 → SO4

2- + H2O

�Detection of SO42- via IC (Ion Chromatography)

Extraction Combustion Absorption

ma

in s

tre

am

Sampling total sulfur - detail


sampling

probe

heated filter

heated tube

ball valve

FR

air

quartz-wool

heating

850°C

pressure control

capillarytube

heated teflon-

tube (180°C)

overflowquartz pipe

impingers with Na2CO3

+ H2O2

heated

pumpe

control valve

activated char coal

pump

thermal flowmeter

PIR

PDR165°C

heated box

cooling control valve

sampling

probe

heated filter

heated tube

ball valve

FRFR

air

quartz-wool

heating

850°C

pressure control

capillarytube

heated teflon-

tube (180°C)

overflowquartz pipe

impingers with Na2CO3

+ H2O2

heated

pumpe

control valve

activated char coal

pump

thermal flowmeter

PIRPIR

PDRPDR165°C

heated box

cooling control valve

Summary


�Organic parameters

�Gravimetric tar, BTXE, PAH,

Phenols, total sulfur

�Inorganic parameters

�H2S, NH3, HCN, HCl, NaCl,

KCl, metals

�Gases

�Pyrolysis-gas, crude-gas,

product-gas, syngas

�Sampling ranges

(no dilution, 100l gas volume, 100ml liquid volume,

1h sampling)

1-100.000

10-300.000

0,05-20

0,1-20

0,05-1.200

0,1-1.800

0,1-1.400

0 0 1 10 100 1.000 10.000 100.000 1.000.000

H2S

NH3

HCN

S total

HCl

dust

tar

clean gas crude gas

[mg/m³dry]

0,01 0,1


Constitution of working group

T1A: gas extraction & pre treatment

T2A: accumulation offlinesolvents & SPA

T1B: sample transport, Volume metering

T3A: analytical procedure: solvent & solids:

detection and quantification

T2B: online detection-systemsbasics

T3B: analytical procedure:detection and quantificationcalibration-reference

T5: safety / measuresgases/liquids/solvents/solids/dust

samples/treatment/wastessafety relevant tips and tricks

T4: result procedurescalibration & references (steps, full)quality insurance, guidelines

T1A: gas extraction & pre treatment

T2A: accumulation offlinesolvents & SPA

T1B: sample transport, Volume metering

T3A: analytical procedure: solvent & solids:

detection and quantification

T2B: online detection-systemsbasics

T3B: analytical procedure:detection and quantificationcalibration-reference

T5: safety / measuresgases/liquids/solvents/solids/dust

samples/treatment/wastessafety relevant tips and tricks

T4: result procedurescalibration & references (steps, full)quality insurance, guidelines

...equal for organic and inorganic components

A guideline or method library is recommended for chemical parameters

Situation:•For different types of Gases a large number of applied procedures is already reported.•Activities can be reported from ~1980 til now.•As example VTT has compiled their concepts of procedures already in 1996-1998.•2007 IEA Biom T33 has arranged a shortlist (N-param.)

Aim for the next future:•A application matrix should be proposed.

•A Pre-review of existing methods and a draft matrix should be made.

•Short information should be given in a Pre-Guideline.

•A program for validation of this methods, regarding: Availability, reproducability,

quality issues should be made.

Application Matrixchemical parameters:

type of the gas

parameter is looked for

e.g. Synthesis gascomplete treated

.

.

.

e.g. Product gasFluidised bed

.

.

e.g. Pyrolysis gasallothermal

e.g. water e.g. S as H2S e.g. S as organic bond Se.g. water e.g. S as H2Se.g. water e.g. S as H2Se.g. water

•Sub-types

•techn. Needs

•Conditions

•constrains

Application Matrixchemical parameters: (Detail of yellow box before)

type of the gas

e.g. S as H2S

Type #

‚online with

GC/SCD‘ T2C-B

‚Acc. on SPA

draeger‘Accumulative

(T2C-A)

Measures of

sample preparation

Of GAS= T1A/B

•Temperature

•Water

•Particle

•Tars

•others

Examples chosen freely

Procedure of T2, T3

Time behavior

Selectivity

Tested about:

Items 1

Items 2

Items 3

Items 4

How to calibrate multicomponent?

Calibration gasesTestgas generators

•Forced dosage•Thermodynamic dosage

Milan, 22.06.2012

Further questions? Please contact:

DI Johannes Zeisler

[email protected]

Thank you for your attention!

DI Markus Kleinhappl

[email protected]

the actual need of a guideline for sampling and analysis ... · milan, 22.06.2012 the actual need...

Documents