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1 Systems and methods for the determination of odorants and other sulfur components in natural and liquid gas Axel Semrau GmbH & Co KG Dipl.-Ing. Frank.

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Presentation on theme: "1 Systems and methods for the determination of odorants and other sulfur components in natural and liquid gas Axel Semrau GmbH & Co KG Dipl.-Ing. Frank."— Presentation transcript:

1 1 Systems and methods for the determination of odorants and other sulfur components in natural and liquid gas Axel Semrau GmbH & Co KG Dipl.-Ing. Frank Sasse

2 2 Topics Axel Semrau GmbH & CO, the company Odorization ODOR handy ODOR on-line Field Study

3 3 The company Axel Semrau®, a company of 44 employees, with a technical staff of 34, comprising mostly chemists (PHD) and also some electronic and information technology engineers. Since 1973 Axel Semrau as a person later his company is involved in sales and support for analyzers of odorant sulfur compounds

4 4 Lab for odorization control and gas analysis

5 5 Axel Semrau GmbH & Co services Hardware service, repair and maintenance Supply of calibration gas Training on site and in the AS training center Seminars on all topics related to the analysis and monitoring of odorants in gas.

6 6 Odorization Methane CH4 (major component of natural gas) is without any smell. Natural gas is also often without any smell. If it smells, that is caused by natural sulfur. The concentration of natural sulfur is continuously changing. For a constant and typical smell an odorant is added. Main reason: Everybody should be able to detect (smell) any leak in a house installation.

7 7 Gas production sometimes strong smell, very high sulfur content (sour gas) Desulfurization not always necessary Transport Odorization Distribution

8 8 Odorants Strong and typical smelling organic sulfur components of the substance classes –Sulfides R-S-R –Mercaptans R-S-H

9 9 Odorants for natural gas THT (Tetrahydrothiophen) TBM (Tertiary butyl mercaptan) Blends Scentinel® E and Spotleak® 1009 (TBM 75%, IPM 16%, NPM 8% ) Scentinel® TB (50% TBM, 50%THT)

10 10 Odorants for LPG (liquid gas) LPG: Propan / Butan EM Ethylmercaptan MM Methylmercaptan

11 11 German Regulation G280 Level of odorant intensity

12 12 German Regulation G280 Gas should reach a warning smell (level 2) before it reaches a concentration of 20% from LEL (lower explosion limit). Similar regulations in other countries

13 13 Calculation of the minimum odorant concentration in gas K C = ---------------- mg/m3 20% * LEL (LEL = Lower explosion limit) Example: TBM in natural gas 0,03 mg/m³ C= ------------------= 3.8 mg/m³ TBM Minimum conc- 0,20 * 0,04 entration in Germany

14 14 Odorization control Why do we have to check the odor level at all?

15 15 Mechanical problems Odorant rate is not correct –Bypass odorizer (difficult to adjust) –Injection pump (mechanical failure) –Pump injects only air –Pump is getting no impulse –Remote control broken –Failures caused by operators

16 16 Chemical and physical problems Chemical oxidization (especially mercaptans) and adsorption (specially THT) The loss of odorant is depending on the flow and temperature. New PE pipes can also cause a problem. =>This means you have a big loss of odorant from the point of injection to the households! e.g: Injection 20mg/m³ THT Concentration at the last point 9mg/m³ =>It is very important to measure the concentration at the end point of the distribution net!

17 17 Measuring methods Smell the gas –Advantage: You smell it! –Disadvantages: different results from different people –Lower results after several measurement in a short time –Inaccurate –Good as an additional backup. –In European Countries are not used any longer

18 18 Measuring methods Measuring tubes Advantage: simple to handle, low investment costs Disadvantage: Many cross sensitivities, Very inaccurate Due to low accuracy not allowed in Germany any longer

19 19 ODOR handy

20 20 Proofed by extensive testing by many well recognized gas institutes, DVGW institute (Germany Gas Institute) for instance Proofed by hundreds of companies, using it in daily routine work all over the World eg. (Italy, Spain, France, Poland, Czech Rep., Mexico, Argentina, Brazil, Chile, Bolivia) Several customers have more than 20 units in use ODOR handy

21 21 ODOR handy TBM Display 00.1 Measuring range 0 to 50 mg/m³ For all mercaptans and blends with a high mercaptan concentration Special version with US units (lbs/MMFC) and display 0.01 available ODOR handy THT Display 000 Measuring range THT 0 to 100 mg/m³ For THT and blends with high THT concentration Differences between THT and Mercaptan version

22 22 ODOR handy in the field 1.Connect direct to the gas pipe if pressure is 20 mbar (approx. 15 inch of water, 0.5 psi) or with a rotameter if the pressure is higher. 2.Wait just a few minutes 3.Read the result 4.Ready for next measurement after 10 minutes

23 23 Odorant concentration direct in mg/m³

24 24 Operation state No OFF switch Sensor should always have voltage In case of empty battery or new sensor: => let the sensor stabilize up to 12h => then calibrate the ODOR handy

25 25 ODOR handy Ex-proof Can be used everywhere on site Easily connected to the gas pipe by means of a very short non adsorptive tube Weight approx. 100g Selective alarm levels Simple calibration procedure Ex-proof battery (6 months continuous work) Rechargeable battery ex-proof optional

26 26 Calibration gas set ISO 19739 (ISO 6326 T2)

27 27 ODOR handy

28 28 Calibration 1.Battery check 2.Zero point check, adjust if necessary (screw 7) 3.Pure calibration gas pressure regulator 4.Connect calibration gas to ODOR handy 5.Wait till the reading is stable 6.In case of differences: - adjust span/amplification (screw 8) - disconnect calibration gas and wait 10 minutes. - Repeat in case of bigger differences.

29 29 Life time sensor Sensor has to be replaced if: 1.THT: Ce-value is higher 200 TBM: Sensor has not enough sensitivity to adjust during calibration 2.H2S filter is saturated. Life time of sensors is about 1-2 years, depending on usage. (Sensors age, even if they are not been used.)

30 30 ODOR on-line

31 31 conform to ISO 19739 ( German standard DIN 51 855-07-GC/ASTM D7493-08) gas chromatographic procedure for online measurement (stationary and mobile) for more than 30 years successful operating since 1996 with ODOR on-line systems are always on the latest technical standard 2010 about 300 instruments on the market

32 32 Major applications 1. Natural sulfur compounds (e.g H2S, mercaptans) in natural gas –Underground gas storages –Gas power plants –Transmission pipes –Gas quality stations H2S causes corrosion to pipes and turbines

33 33 Major applications 2.Odorization control –City gates –Pressure regulation stations –Mobile measurement Odorants fade during transportation!

34 34 Installation In the field for on-line application In the lab for manual operation (analyzing of samples)

35 35 References E-on Ruhrgas (Germany) RWE (Germany) Fluxys (Belgium) Gas de France TIGF (France) Italgas (Italy) Gas Natural (Spain, Brazil) Peoples gas (USA) Kindermorgan (USA) Polish Oil and Gas Company (Poland) Société Tunisienne de l’Electricité et du Gaz (Tunisia) VCP Vychodoceska plynarenska, a.s (Czech Republic) Igdas (Turkey) EWE, Bayern Gas …… (Germany)

36 36 Stationary measurement On-line measurement in a pressure regulation station

37 37 Stationary measurement Processing with a special PC Software ODOR control

38 38 ODOR on-line Chromatograph designed to fulfill the demands of ISO 19739 (ISO 6326 T2) packed column electrochemical detector 10 ml gas sampling loop

39 39

40 40 Packed column

41 41 Heated column

42 42 An electrochemical detector uses the oxidation ability of a substance as its proof. In the case of H2S and mercaptans the oxidation power of the chrome trioxide is used as the specific proof. Electrochemical detection Explanation of the expression

43 43 Detector

44 44 Detector tank front view

45 45 Insulated column and detector tank

46 46 Reservoir with distillated water for automated refill

47 Manual injection of low pressure samples 47

48 48 Injector for manual gas injections

49 Taking samples 49

50 50 ODOR control Software Easy to operate Real-time chromato- gram User defined reports

51 51 ODOR control Software Database with all measure- ments Search filters Export function to Excel™

52 52 ODOR control Reportgenerator User specific reports

53 Data output: 3 x 4-20mA (standard) or Modbus (optional) 53

54 Option Modbus All results with name of the substances, retention time, areas and … Groups of substances 8 different alarms Status of the instrument Information about the last run 54 26.02.2010 16:22:24--------------- Update of Bus-Memory --------------- 26.02.2010 16:22:24File: F:\ODO000005.Results.xml 26.02.2010 16:22:24 26.02.2010 16:22:24Parameter: Substance name TBM 26.02.2010 16:22:24Value: TBM 26.02.2010 16:22:24Type: String 26.02.2010 16:22:24Start address: 0 26.02.2010 16:22:24---------------------------------------------------- 26.02.2010 16:22:24Parameter: Retention time TBM 26.02.2010 16:22:24Value: 94 26.02.2010 16:22:24Type: Single 26.02.2010 16:22:24Start address: 10 26.02.2010 16:22:24---------------------------------------------------- 26.02.2010 16:22:24Parameter: Peak area TBM 26.02.2010 16:22:24Value: 409305 26.02.2010 16:22:24Type: Int32 26.02.2010 16:22:24Start address: 20 26.02.2010 16:22:24---------------------------------------------------- 26.02.2010 16:22:24Parameter: Concentration TBM 26.02.2010 16:22:24Value: 2.8 26.02.2010 16:22:24Type: Single 26.02.2010 16:22:24Start address: 30

55 THT in natural gas 55

56 THT and TBM in natural gas 56

57 Natural Sulfur and THT 57

58 58 complex mercaptan blends

59 59 Elution sequence of odorants

60 60 Measuring range –THT 0.1 mg/m³ - about 100 mg/m³ –H2S 0.1 mg/m³ - about 100 mg/m³ –Mercaptans 0.01 mg/m³ - about 100 mg/m³ Carrier gas –Nitrogen or compressed oil free air Automatic and manual injector Odor on-line

61 61 Advantages of the electrochemical detector The detector is not sensitive to other compounds in natural gas Low detection limits 0.1 mg/m³ Linear within the normal measuring range Extremely robust and stable in on-line applications

62 62 Mobile measurement 12 V use Heated column No cross sensitivities Option: Electronically flow controller

63 electrochemical detector 63 operation position park / transport position

64 64 Mobile sampling No sample transport. Connect the instrument direct to the gas pipe

65 Service company: Schütz 65

66 66

67 67

68 measureing point 68

69 69 Measureing point

70 70

71 71 Comparission ODOR handy / ODOR on-line

72 Total Sulfur a)1 ODOR on-line For H2S, natural mercaptans (and odorant) b)2 ODOR on-lines One for H2S, natural mercaptans (and odorant) One for Carbonylsulfid (COS) c)ODOR on-line plus ODOR total S II 72

73 73 Project with RMG Container for BTU and sulfur measurement a)1 ODOR on-line For H2S, natural mercaptans (and odorant) Total Sulfur

74 b.) 2 ODOR on-lines One for H2S, natural mercaptans (and odorant) One for Carbonylsulfid (COS) 74

75 Total Sulfur c.) ODOR on-line plus ODOR total S II 75

76 ODOR total S II 76

77 77 Field study Gas distribution net from Mark E Length: 563 km Sales volume: 2.300 Mio. kWh customers: 48.000 City and area of Hagen Stand December 2002

78 78 Measuring methods 1.Stationary on-line measurement 2.Mobile measurement with a car 3.On demand: quick check with an ODOR handy

79 79 Sample sites

80 80 1. Stationary on-line measurement Data transmission to the central control station

81 81 2. Mobile measurement with a car factory Public building (school) Small pressure regulation station Sampling point on the street

82 82 Summary field study Mark E Optimum control procedure for odorization level by: On-line measurement (24h) ODOR on-line Good positioning of sample sites Flexible through a mobile gas chromatograph Quick results from new sites with the handheld instrument (ODOR handy)

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