Start Date
September 2016

Background
This project was established to continue the Deposit Analysis Protocol (DAP) work undertaken and funded by the following closed projects; NGL Fractionation, Iron Fouling, Oil sands Bitumen Processibility, Condensate Quality. All four projects had been working on identifying the nature and source of TIOM’s in various plant fouling deposits and feeds.

This CCQTA sponsored project is investigating the composition and potential sources of TIOM material that has been found throughout the industry.

TIOMs are commonly characterized as asphaltenes since they appear as a black deposit or sludge in tanks, exchangers, reboilers and numerous other systems. What is unique about this material is that it is not soluble in toluene or almost any conventional solvent so it is very problematic and difficult to remove without resorting to mechanical removal methods. TIOM’s also contain no functional chemistry (N, S, O, P, etc…) and are simply comprised of C and H which lead to an early consideration of drag reducing agent as a possible source.

The goal of the project is to locate and understand the source(s) of this material in an attempt to mitigate or eliminate the associated problems.

Milestones as of February 2024

• Omnicon developed an analytical protocol for evaluating solid deposits for the presence of TIOMs. Protocol uses both solubility as well as thermal gravimetric analysis (TGA) for identification. 2014
  
• TIOM material had been identified in numerous facilities over 15+ years including: NGL fractionation, bitumen blending, gas plants, pipeline and refineries. Most recently TIOM material was found at the wellhead post fracturing and completion operations. This was the first time TIOM was located in a wellhead scenario and that prompted investigation into the source properties, conditions and additives that may be potential sources of TIOM’s.
  
• Three working theories on the origin of TIOMs.


1. Material is broken polymer material such as polyacrylamide (PAM) or another polymer based additive used.
   
2. Material is kerogen (pyrobitumen) disturbed in the well during fracture/completions and then brought to the surface during early production.
   
3. Material is formed due to the interactions of toluene soluble asphaltenes and active clays forming a TIOM.


• Project obtained core materials from a well that showed evidence of TIOM’s in post fracturing flow-back tankage as well as the production facility immediately downstream. Results were presented at the December 2018 Condensate Quality Sub-Committee meeting.
  
• Terminal supplied deposit material collected from both a strainer and tank bottom during tank cleaning. Analysis is currently in progress. Results were presented at the March 2019 Condensate Quality Sub-Committee meeting.
  
• Data is beginning to show a pattern that may loosely identify the source of TIOM material. TIOM material boiling <500°C appears to be polymer additive related (DRA, friction reducer, etc…) while TIOM material boiling >500°C appears to be naturally occurring in the formation (kerogen, bitumen, etc…).
  
• New data is suggesting an alternate theory on the formation of TIOM’s. This theory involves the interaction of mineral clays and asphaltenes through a very strong interaction mechanism that alters the solubility of the asphaltenes so they are no longer soluble in toluene. A similar mechanism has been theorized where asphaltenes are converted to TIOM during the oil sands extraction process. Investigation continues on the formation mechanism, possible mitigation and/or remediation. Data was presented at the December 2019 Open Forum meeting.
  
• The TIOM analysis protocol has been extended to included XRD/EDS, and ICP.
  
• Two tank bottom samples have been received recently and were tested under the TIOM protocol. Results were presented at the June 2020 project meeting.
  
• Data was presented at the December 2020 Light Oil Fouling project meeting
  
• Work was completed using high-pressure extraction techniques to separate the organic and inorganic phases. Chevron employed multiple analytical techniques for characterization. This is a joint project between CCQTA, Chevron and National High Magnetic Field Lab at Florida State University. New data was presented during the June 2021 Light Oil Fouling/TIOM project meeting.
  
• Three samples of heat exchanger foulant material have been provided by two member companies. Pyrolysis GC/MS characterization of the samples has been completed and will be presented at the December project meetings.
  
• The characterization of 5 samples received from two refineries were presented at the March 2022 project meeting. The Gulf Coast refinery had significant TIOM and inorganics in the deposits while the Midwest refinery had more toluene soluble and inorganics with a lesser amount of TIOM.
  
• The TIOM deposit analysis protocol has been extended to include asphaltene, wax, and base oil on the toluene soluble fraction as well as the non-volatile and volatile components of the toluene insoluble fraction.
  
• A summary of all TIOM results has been compiled and was presented at the March 2022 project meeting.
  
• Cenovus provided a summary at the March 2022 project meeting of a findings from an internal investigation into fouling reduction in the refinery/upgrader based on changes made to the treatment and handling of production slop. That presentation is available in the March 2022 meeting minutes.
  
• High resolution mass spectrometry identified carbon allotrope (graphite) in two refinery samples. Graphite was also identified several years ago in an unrelated project deposit but was disregarded at the time. One of the refineries also reports that graphite has been identified in deposits since 2011 but was also disregarded. Graphite was the most abundant component in both the refineries deposits.
  

• The project group continues to seek samples of deposits from tanks, exchangers, pig traps, etc... that were initially identified as asphaltenes or as an unknown sludge.
  
• Two exchanger deposit samples were received, and characterization is in progress. Included in the characterization is the use of TGA-FTIR-MS to allow evaluation the organic portion of the deposit in narrow boiling ranges as opposed to on the bulk deposit. The FTIR will provide structural information while the MS will provide potential compound identification.
  
• Characterization results will be presented at the March 2024 project meeting.