2. PIR3502 and PUV3402 Process Photometer

3. Market Discussion
Ethylene and Propylene plants sometimes called Olefins plants
Most measurements have traditionally been done by Gas Chromatography in these processes
Why Process Filter Photometers?
Manufacturing ethylene is an extremely fast process
Continuous measurements are very beneficial in controlling a fast process
Filter photometers are very reliable
Need minimal support
No consumables

4. Applications to be Discussed
ABB Hydrogenation Solution
Acetylene
Methyl Acetylene and Propadiene
Ethylene Fractionator
Ethane Fractionator
Caustic Wash Tower Solution
Furnace Decoke

5. Industrial IT for Acetylene / MAPD Hydrogenation
Improve Acetylene / MAPD Hydrogenation Safety, Economic & Environmental Performance
Industrial IT for Acetylene / MAPD Hydrogenation

6. ABB Solution for Hydrogenation in Olefins Plants
Leverages already proven measurement capability
Feeds to the Hydrogenation reactors of Acetylene to Ethylene and MAPD to Propylene are very variable due to up-stream events
Multiwave Photometer provides continuous analysis of the stream feed streams
Allows operator to tightly control hydrogen ratio
Allows operator to track the ratio changes
Minimizes over-hydrogenation
Minimizes contaminate breakthrough (acetylene or MAPD)
ABB can provide advanced process control in addition if the customer needs it

7. What is Acetylene / MAPD Hydrogenation ?
Key unit operation within Ethylene Plants
Removes C2 & C3 acetylenic contaminants from olefin products
C2H2 + H C2H4
C3H4 + H C3H6

8. Why is Acetylene and MAPD Hydrogenation Important
Plants increasingly are using highly variable feedstocks
Makes process control more difficult due to fast nature of feedstock composition changes
Increased environmental regulations being implemented at the same time the feedstock is becoming more variable
Tight control of reaction is critical
Over hydrogenation converts ethylene to ethane or propylene to propane (Reduces yield)
Under hydrogenation allows acetylene and MAPD break though into the product
Immediate flaring of product occurs
Acetylene and MAPD are problems in the polyethylene and propylene markets
Very expensive event
Environmental liability

9. Industrial IT for Acetylene / MAPD Hydrogenation
ABB offers technologies that seamlessly combine to deliver a unique synergistic solution for Acetylene / MAPD Hydrogenation Units
Real-time characterization of lead & guard bed feeds
real-time, on-line determination of conversion & selectivity
Process analytical technology for hydrogen and olefin product quality
real-time hydrogen product quality measurements
Multivariable control that exploits all of our unique analytical capabilities
improved approach based upon the real time availability of lead & guard bed feed composition
A complete service portfolio to maintain the performance of the IndustrialIT solution :
field services
on-line support
training & parts / repair
Operating companies can obtain a combined analytical & control solution from one vendor
delivers unique synergistic benefits
enhances unit reliability & selectivity while maintaining safe operation

10. AAS Solution Components
Analytical (budgetary end-user prices)
2 x PIR3502 photometer for lead reactor feed & effluent characterization ($45KUSD)
1 x AO2000- Uras14 analysis of high purity hydrogen stream ($9 - 16KUSD)
1 x PGC2000 Analysis of Guard Reactor effluent ($ KUSD)
Advanced Process Control (budgetary end-user prices)
Multivariable, model-predictive control (MVPC) :
Meet <1ppm acetylene(s) specification in olefin products while :
minimizing hydrogen ratios
maximizing throughputs
maintaining acceptable catalyst cycle-lengths
increasing reactor selectivity to ethylene ( & propylene )
avoiding reactor runaways
Upgrade to existing ABB license & platform ($60KUSD)
Benefits FEED study of any unit to justify IIT solution ($20KUSD)
Implementation of (1 application license, server ) new APC scheme for
acetylene hydrogenation unit ($125KUSD)

11. Example - Hydrogen : Acetylene Ratio Control

12. Hydrogen : Acetylene Ratio Control - Common Problems
The majority of units run with poor hydrogen : acetylene ratio control resulting in :
lower reaction selectivity leading to reduced olefin gains ( or net losses )
acetylene slippage causing off-specification product & flaring
closer approaches to “runaway” conditions
higher “green-oil” production with increased regeneration frequency & shorter catalyst life
product downgrades to ethane (or propane) with associated recycle costs
Poor ratio control is further deteriorated by rapid feed compositional changes
acetylene content
heavy ends from upstream fractionation upsets
neither occurrence detected fast enough by conventional GC analyzers
During plant upsets, operators tend to ramp up to excessive H2 addition rates to maintain on-specification product
leads to extremely high olefin losses
greatly reduced selectivity
usually held in this condition for longer than the duration of the initial incident

13. ABB Solution
ABB multivariable control technology driven by our unique capability of real-time feed & mid-bed stream characterization
Feeds to lead & guard beds are characterized in real-time with a continuous process photometer providing a true hydrogen demand picture leading to optimum ratio control
Inherently more effective than traditional approaches that rely on slow feedback from gas chromatographs
As part of a wider multivariable control scheme, this approach leads to improvements in olefin yields compared to baseline traditional APC performance
Plant upsets are smoothly managed
eliminate operator “over hydrogenation” for excessive periods

14. Benefits of ABB approach to Hydrogen : Acetylene Ratio control
Setting hydrogen addition rates based upon real-time characterization of lead & guard bed feeds offers several advantages over conventional approaches
Average H2 : Acetylene ratios are lowered even in those operations that have already implemented advanced process control in an attempt to improve baseline performance
Flaring incidents are reduced as the H2 ratio is maintained consistently without analyzer dead time effects, resulting in higher availability of on-spec product
annualized savings associated with reduced flaring are $ M* (depending on baseline converter performance)
Ethylene yields are increased due to improvements in olefin selectivity across the beds
implementation of traditional APC can improve olefin yields ( as a percentage of feed ) by up to 0.5%
the enhanced ABB approach can improve olefin yield gain by an additional 0.2%.
this results in average benefits of $1 – 1.5 M* per annum
ethane recycle costs are also reduced
* Billion pounds per year facility

15. Benefits of ABB approach to Hydrogen : Acetylene Ratio control
Less frequent approaches to runaway conditions as precise hydrogen ratio control avoids “over hydrogenation” and rapid ethylene consumption
Plants can finally realize the expected gains of recent investments in state of the art catalysts
exploit catalyst capability for low H2 : acetylene ratios
avoid operating “ on the safe side”
Reduce green oil formation & the need for large inlet temperature increases to maintain unit conversion
reduce regeneration frequency & improve catalyst life
track catalyst performance throughout the operating cycle
Maintain optimum ratio control during plant upsets
real-time determination of acetylenes & “heavies”
avoid operator initiated “over hydrogenation” for excessive periods
Summary
For many years, operators have considered improved hydrogen ratio control
limited by measurement and control capability
ABB can now deliver this approach in a single analytical-control package

16. Analytical Measurements
The Backbone of the Solution!

17. Acetylene Converters: Lead Bed Inlet
Measurements:
0-2% Acetylene
0-30% Ethane
0-2% Propylene
0-100% Ethylene
Process Benefits
Fast acetylene analysis on the acetylene converter inlet
Provides feed forward control for the hydrogen addition to the inlet of the lead bed
Traditionally done with Gas Chromatography (3-6 minute analysis time)
Additional measurements provide additional information for control of over hydrogenation and thermal runaway
Benefits provided by Multiwave
PIR 3502 Multi-component capability allows for all measurements on one analyzer
PIR 3502 can compensate for the spectral interferences from the other stream components
Continuous online measurement for optimum control of a very
fast process

18. Acetylene Converters: Guard Bed Inlet (Midbed)
Measurements:
0-0.5% Acetylene
0-30% Ethane
0-100% Ethylene
Process Control Benefits
Fast acetylene analysis on the acetylene converter guard bed inlet
Provides feedback control to the lead bed
Provides feedforward control for hydrogen feed to the guard bed
Traditionally done with Gas Chromatography (3-6 minute analysis time)
Additional measurements provide additional information for control of over-hydrogenation and thermal runaway
Benefits provided by Multiwave
PIR 3502 Multi-component capability allows for all measurements on one analyzer
PIR 3502 can compensate for the spectral interferences from the other stream components
Continuous online measurement for optimum control of a
very fast process

19. Acetylene Converter Applications
Lead Bed Inlet
Measure Component:
Acetylene 0-2%
Ethane %
Propylene 0-2%
Ethylene %
Stream Composition:
Acetylene 1%
Methane 0.2%
Propane 0.2%
Propylene 0.5%
Ethane 25%
Ethylene Balance
Guard Bed Inlet
Measure Component:
Acetylene %
Ethane %
Ethylene %
Stream Composition:
Acetylene 0.2%
Methane 0.2%
Propane 0.2%
Propylene 0.5%
Ethane 25%
Ethylene Balance

20. Acetylene Converter: Spectra
REFERENCE
ETHYLENE COMP.
% TRANSMISSION
ETHANE MEASURE
BLACK: 70% ETHANE
BLUE: % ETHYLENE
RED: % ACETYLENE
ACETYLENE MEASURE
WAVENUBER (CM-1)

21. Acetylene Converter: Measurement Precision
Acetylene will have significant interference from Ethane
Uncompensated 30% Ethane would cause about a 8% of Full Scale error (0.12% Acetylene)
Using the compensation capability of most filter photometers will reduce this affect by approximately 10X – 15X or less than 1% of Full Scale error (<0.015% Acetylene)
Acetylene will have small interference from Ethylene
Uncompensated the 100% Ethylene would cause about a 2% interference (0.03% Acetylene)
Using interference compensation the ethylene interference would be reduced to about 0.2% of full scale error (0.003% Acetylene)
Ethane measurement is interference free from the other stream components

22. MAPD Converters: Lead Bed Inlet Measurements
0-2% Methyl Acetylene
0-2% Propadiene
0-2% MAPD
0-10% Propane
0-2% Butadiene
Process Control Benefits
Fast MAPD analysis on the converter lead bed inlet improves converter control and efficiency
Provides feedback control to the lead bed
Traditionally done with Gas Chromatography (10-13 minute analysis time)
Additional measurements provide additional information for control of over-hydrogenation and thermal runaway
Benefits provided by Multiwave
PIR 3502 Multi-component capability allows for all measurements on one analyzer
PIR 3502 can compensate for the spectral interferences from the other stream components
Continuous online measurement for optimum control of a
very fast process
Cell design allows for the sample to be run at pressure and then returned to process

23. MAPD Converters: Guard Bed Inlet Measurements
0-0.5% Methyl Acetylene
0-0.5% Propadiene
0-0.5% MAPD
0-10% Propane
Process Control Benefits
Fast MAPD analysis on the converter lead bed inlet improves converter control and efficiency
Provides feedback control to the lead bed
Provides feedforward control for hydrogen feed to the guard bed
Traditionally done with Gas Chromatography (10-13 minute analysis time)
Additional measurements provide additional information for control of over-hydrogenation and thermal runaway
Benefits provided by Multiwave
PIR 3502 Multi-component capability allows for all measurements on one analyzer
PIR 3502 can compensate for the spectral interferences from the other stream components
Continuous online measurement for optimum control of a
very fast process
Cell design allows for the sample to be run at pressure and then returned to process

24. MAPD Converters: Applications
Inlet Application
Measure Components:
0-2% Methyl Acetylene
0-2% Propadiene
0-2% MA + PD
0-10% Propane
0-2% Butadiene
Stream Composition:
Methyl Acetylene 1%
Propadiene 1%
Ethylene 0.4%
Propane 6%
Propylene Balance
Mid-Bed Applications
Measure Components:
0-0.5% Methyl Acetylene
0-0.5% Propadiene
0-0.5% MA + PD
0-10% Propane
Stream Composition:
Methyl Acetylene 0.2%
Propadiene 0.2%
Ethylene 0.4%
Propane 6%
Propylene Balance

25. MAPD Converter: Spectra
REFERENCE
% TRANSMISSION
PROPYLENE
COMP.
BLACK: 15% PROPADIENE
BLUE: % PROPYLENE
RED: % METHYL ACETYLENE
PROPADIENE
MEASURE
WAVENUMBER (CM-1)
METHYL ACETYLENE
MEASURE

26. MAPD Converter: Measurement Precision
Propadiene will have a significant interference from Propylene
Uncompensated 100% Propylene would cause about a 7% of Full Scale error (0.14% Propadiene)
Using the interference compensation capability will reduce this affect by approximately 10X – 15X or less than 0.7% of Full Scale error (<0.014% Propadiene)
Methyl Acetylene will have a small interference from Propylene
Uncompensated the 100% Propylene would cause about a –0.7% of full scale interference (0.014% Methyl Acetylene)
Using interference compensation the propylene interference would be reduced to about 0.07% of full scale error (0.0014% Methyl Acetylene)

27. Other Multiwave Applications in Olefins Plants

28. Ethylene Fractionator
Measurement:
0-30% Ethylene
Process Benefits
Purification part of the process
Ethylene is removed from the ethane
Fast analysis time important for the control of the fractionator tower
Benefits provided by Multiwave
Analysis can be made at elevated pressure so sample can be returned to the process
Provides continuous analysis
Precise measurement
Reliable Analyzer

29. Ethylene Fractionator: Application
Measurement:
Ethylene 0-35%
Stream Composition:
Ethylene 20%
Propylene 3%
Propane 3%
Ethane Balance

30. Ethylene Fractionator: Spectra
% TRANSMISSION
REFERENCE
ETHYLENE MEASURE
BLACK: 100% ETHANE
RED: % ETHYLENE
BLUE: % PROPYLENE
WAVENUMBER (CM-1)

31. Ethylene Fractionator: Measurement Precision
Very easy measurement for a filter photometer
No interferences
Expected precision ± 0.5% of full scale

32. Benefits Provide by Multiwave
Ethane Fractionator
Measurement:
0-30% Ethane
Process Benefits
Purification part of the process
Ethane is removed from the ethylene
Fast analysis important for the control of the fractionator tower
Benefits Provide by Multiwave
Analysis can be made at elevated pressure so sample can be returned to the process
Provides continuous analysis
Precise measurement
Reliable Analyzer

33. Ethane Fractionator: Application
Measurement:
Ethane 0-30%
Stream Composition:
Ethane %
Methane Trace
Ethylene Balance

34. Ethane Fractionator: Spectra
REFERENCE
% TRASMISSION
BLACK: 35% ETHANE
RED: % ETHYLENE
ETHANE MEASURE
WAVENUMBER (CM-1)

35. Ethane Fractionator: Measurement Precision
Very easy measurement for a filter photometer
No interferences
Expected precision ± 0.5% of full scale

36. Caustic Wash Tower Solution Application (Page 1)
Measurement:
0-10% Sodium Hydroxide
Process Benefits
Sodium hydroxide used to remove carbon dioxide from the furnace outlet streams
Scrubbing solution must have excess caustic at all times to prevent carbon dioxide from going to other parts of the process
A fast and accurate sodium hydroxide measurement allows the wash tower to be operated at lower excess caustic when controlled with an analyzer with cycle times
Operation cost savings by running at lower excess caustic

37. Caustic Wash Tower Solution Application (Page 2)
Benefits Provided by Multiwave
Precise and continuous measurement allows operation at lower excess cost
Can compensate for interferences
As carbon dioxide is removed from the process gas sodium carbonate builds up in the scrubbing solution
Sodium carbonate will interfere with the caustic measurement if it is not compensated
Isolated sample cell can be heated to help keep salts in solution
Cell can be made from Hastelloy C to handle the corrosive stream
Can provide timed flush for the SHS and cell with water by use of the zero benchmark functions
Can withstand some bubbles from the non-dissolved light hydrocarbons that get through the degasser in the SHS
No reagents to periodically replace
Low maintenance
Only one moving part

38. Caustic Wash Tower Solution Application
Measurement:
Sodium Hydroxide %
Stream Composition:
Sodium Hydroxide %
Sodium Carbonate %
Dissolved Hydrocarbons 0.1%
Water Balance

39. Caustic Wash Tower Solution: Spectra
BLACK: 100% WATER
RED: % NaOH IN WATER
BLUE: 5% Na2CO3 IN WATER
SODIUM CARBONATE
COMPENSATION
% TRASMISSION
REFERENCE
SODIUM HYDROXIDE MEASURE
WAVENUMBER (CM-1)

40. Caustic Wash Tower: Measurement Precision
Sodium hydroxide measurement will have a significant interference from sodium carbonate
Uncompensated 1.5% sodium carbonate will cause a 10% of full scale interference (1% sodium hydroxide)
Using interference compensation the interference would be expected to be reduced to less than ± 1% of full scale (± 0.1% sodium hydroxide)
Testing on installed analyzers has shown the interference to be less than ± 0.5% of full scale (± 0.05% sodium hydroxide)

41. Caustic Wash Tower Feed
Measurement:
0-200 ppm Carbon Dioxide
Stream Composition:
ppm Carbon Dioxide
ppm Carbon Monoxide
30-45% Hydrogen
5-9% Methane
30-40% Ethylene
15-35% Ethane
0.2-1% Propylene
% Propane
% 1,3 Butadiene

42. Caustic Wash Tower Overhead
Measurement:
ppm Carbon Monoxide
Stream Composition:
2-4% Water Vapor
ppm Carbon Dioxide
ppm Carbon Monoxide
30-45% Hydrogen
5-9% Methane
30-40% Ethylene
15-35% Ethane
0.2-1% Propylene
% Propane
% 1,3 Butadiene

43. Furnace Decoke Measurement: 0- 15% Carbon Dioxide Process Benefits
Pyrolysis reactors have a carbon build up from the cracking of the feedstock
Carbon build up reduces the heat transfer which reduces the cracking efficiency
Periodically need to remove the carbonaceous material
Done by injecting steam in combination with heat converts the carbon to carbon dioxide
Monitoring the decrease in CO2 concentration during decoke:
Optimizes the operation
Minimizes time and utilities spent on decoking

44. Furnace Decoke Benefits Provided by Multiwave
Straight forward spectroscopic measurement
Difficult to provide representative sample to analyzer
Sample contains high particulate loading
Sample contains free water droplets
Water vapor concentrations vary between 35 to 90%
Successful approach has been to use a reflux sampler to remove the particulate and free water prior to the Multiwave
Located at process line
Cools the sample to condense the water
Condensed water then removes the particulate
Particulate and condensed water go back into process line
Heated sample cell and optics not damaged if water break through occurs from DRS upset
Very reliable analyzer
Low Maintenance

45. Dynamic Reflux Sampler (DRS2170)

46. DRS: Principle of Operation
Primary sample conditioning occurs in a virtually in-situ fashion with the DRS approach. Condensable components are removed and are used to support particulate removal before they can present problems in the sample transport system’s downstream components and the analyzer.
The DRS is essentially a fixed temperature distillation derived from the need to remove water as a condensable component from low boiling point gases. Cooling is provided by way of a vortex cooler controlled by an electronic temperature controller.

47. Furnace Decoke: Application
Measurement:
Carbon Dioxide %
Stream Composition:
Carbon Dioxide %
Carbon Monoxide 5%
Water 8%
Oxygen 17%
Nitrogen Balance

48. Furnace Decoke: Spectra
% TRANSMISSION
REFERENCE
BLACK: 1% CARBON DIOXIDE
RED: 5% CARBON MONOXIDE
BLUE: 2% WATER VAPOR
CARBON DIOXIDE MEASURE
WAVENUMBER (CM-1)

49. Furnace Decoke: Measurement Precision
Very easy measurement for a filter photometer
No interferences
Expected precision ± 0.5% of full scale

50. Conclusions
PIR3502 Process Photometers can be used to provide several fast and continuous measurements in the manufacturing of ethylene and propylene
Inlet to the Acetylene converters
Mid-bed in the Acetylene converters
Inlet to the MAPD converters
Mid-bed in the MAPD converters
Ethylene fractionator tower
Ethane fractionator tower
Caustic wash tower
Furnace Decoke