Determination Determination ofof HH22SSin in WasteWaste WaterWater andand
PetrochemicalPetrochemical ProductsProducts
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Dr. Michael Hahn (Chemistry) Dr. Dorit Wilke (Chemistry)
ECH Elektrochemie Halle GmbH, Germany
Bildquelle: ECHwww.detmolder-abwasser.de
Outline
1. ECH – Area of Business
2. H2S Analyzer by ECH- Basics
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- Basics
- Applications for petrochemical products,
e.g. liquids, viscous samples, solids and gases
- Applications for water, typical measurements and
methods for waste water treatment
3. Summary
1. ECH – Area of Business� Development, manufacturing and marketing of analyti cal
instruments and measurement methods
� Main fields of application are:(A) laboratory analysis(B) factory - and process monitoring for technical control
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(B) factory - and process monitoring for technical control(C) on-site, online and mobile analysis
(A) Products for Laboratory Analysis
Titrator AQUA 40.00Gas Module
ECH Laboratory GC
Titrator AQUA 40.00
H2S-Analyzer ElectrochemicalAnalyzer SnLayer
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(B) Typical On -Site ProductsB.2 Analyzer including sample preparationB.1 Analyzers
ECH MobilGC
H2S-Analyzer: automatic gas analyzer for 2 sample points (e.g.: biofilters or waste water tanks)
H2S-Analyzer (manual injection)5
(C) Typical Online ProductsOnline H 2S-Analyzer Online gas chromatograph
online monitoring systembased on the measuring principle of
gas chromatography
liquid samples
gaseous samples6
2. H2S-Analyzers by ECH
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Applications for the determination of H 2S:
� water and waste water
� solids, oil and gas
� in the laboratory, on-site or online
http://www.deutschebp.de
Problems caused by H2S
1. Odour trouble- sensitization of population
2. Health risk- toxicity is comparable to hydrogen cyanide (HCN)hydrogen cyanide (HCN)
3. Sulphuric acid corrosion - concrete reducing up to 10 mm per year- high investment costs to repair
4. Blocking of biological activity of microorganism s- increasing of bulking sludge inside aeration tanks of waste water treatment plants
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Effects of H2Sc(H2S)
[ppm ]
Effect
0.002 – 0.2 Odour threshold
3 – 5 Odour nuisance
10 MAC (Maximum Allowable Concentration)10 MAC (Maximum Allowable Concentration)
> 10 Irritation to eyes and respiratory tract
> 50 Serious eye defect (damage of cornea)
150 – 250 Loss of sense of smell
300 – 500 Damage of breathing
>1000 Mortal danger in minutes or seconds
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Different Types of H 2S-containing Samples in Refineries
Sample Example Method
#1 liquid gasoline, kerosene, diesel fuel, crude oil, mineral oil, hydraulic oil, engine oil, transformer oil
indirect by oven and gas extraction
chamber
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oil, engine oil, transformer oil chamber
#2 highly viscous and solid
tar, oil sludgebitumen, sulphur
indirect by oven and headspace-technique
#3 gaseous LPG, LNG, CNG gas injection module
#4 water extraction and washing solutions,waste water
indirect by gas extraction chamber
and acidification
Principle of H 2S-Analyzer
Advantages:
� no sample preparation
� fast gas extraction procedure of H 2S from
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procedure of H 2S from sample
� low cross sensitivity
� H2S is purged completely from sample and transferred to the sensor
H2S-Analyzer Cubiform
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Features:
� short measuring time 5 – 10 min
� free adjustable sample volume 0.01 – 20 mL
� wide measuring range and low detection limit of 0.0 1 ppm
� automatic peak evaluation at the end of the measure ment
H2S – Analyzer with Autosampler
Advantages:� fully automated analytical
procedure
� sample volume 0.01 – 20 mL
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0.01 – 20 mL
� low demand of chemicals
� robust and fast analysis(up to 40 measurementsper hour)
Headspace -Module for the Determination of H 2S
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Without sample
preparation
Headspace vial is inserted into the oven and the
measurement is started
Principle of the Headspace -Module
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Temperature: up to 250°C
Application: Determination of H 2S in Oil
16Determination of H 2S in a mineral oil sample
Application : Determination of H 2S in heavy Oil
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Determination of H 2S in heavy oil
Determination of H 2S in Oil
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Result listshows the high repeatability
of the measurement
Calibration function
Features:� automatic sampling
� direct analysis of sulphide/H 2S-content of waste water and light oils
Online H 2S- Analyzer
� low demand of chemicals (H3PO4)
� data transfer via 4-20 mA or modem/internet
� alarm settings
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Online application directly in the waste water
Typical Applications� surface water
� ground water
� mineral water
� leachate
� seweage water
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� seweage water
� pressure pipes
� pump sumps
� grease separators
� refineries, chemical industries
� mineral oil, crude oil
Special Features� detector is separated from the
sample by the gas extraction chamber
� high sensitivity (>0,01 ppm )
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� high accuracy of the sample injection (1%)
� sample inlet can be rinsed backwards to prevent biofouling and sedimentation
Self Cleaning Sampling
Problem:
Biofouling on surface of electrodes or measuring systems
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Answer:
� back flushing of sample tubes with fresh water (4 b ar)
� immediate cleaning after injection of waste water s ample
� low maintenance and high robustness
Determination of Sulphide in the Waste Water of Refineries
23Online-analysis of waste water
Comparison of Results from the Laboratory and Online H 2S-Analyzer
200
250
300
350
Online-Sulfid
Laborwerte
Back flush cleaning of the waste water pipe
Online-sulphide
Lab results
0
50
100
150
200
2.6
3.6
4.6
5.6
6.6
7.6
8.6
9.6
10
.6
11
.6
12
.6
Su
lph
ide
[m
g/L
]
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Typical H 2S- ProfileThe odour nuisance was caused by peaks of H2S from the waste water
60
70
80
90
100
S [p
pm]
--- inlet of pressurized sewer pipe --- outlet of pressurized sewer pipe 25
0
10
20
30
40
50
28.8 29.8 30.8 31.8 1.9 2.9
H2S
[ppm
]
Self-Learning Treatment System
Formation of H 2S depends on:
- flow rate of waste water - residence time of waste water in pressure pipes
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- ageing characteristics of waste water- inflowing H 2S-content - weather conditions, temperature and season
Optimized Waste Water Treatment
30
40
50
60
70
80
90
100
6
8
10
12
14
16
18
20
H2S
[ppm
]
H2S
[ppm
]
waste water chemical: Fe(II)-salt-solutionconsumption: 1.800 L / dwaste water: 10.000 m3 / dlength of pressure pipe: 3 km
Mean H2S value at outlet: 1,1 ppm
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--- inlet of pressurized sewer pipe --- outlet of pressurized sewer pipe
0
10
20
30
0
2
4
6
25.7 26.7 27.7 28.7 29.7 30.7 31.7 1.8 2.8 3.8 4.8
SummaryHigh sensitivity and accuracy
Wide linear measuring range
Low demand of chemicals
Low detection limit
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Low demand of chemicals
Low maintenance effort
No sample preparation is needed
For laboratory, on-site and online applications
ECH Elektrochemie Halle GmbH
Weinbergweg 23D-06120 Halle/S.
Tel: 0345/5583711Internet: www.ech.de
Email: [email protected]
Different kinds of petrochemical samples
Experts in Analysis
ECH Elektrochemie Halle GmbHWeinbergweg 23D-06120 Halle/S.Tel: +49 (0)345 5583 711Fax: +49 (0)345 5583 710web: www.ech.de
… and we will take care ofyour analytical problem …
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web: www.ech.deEmail: [email protected]
