Amines in Crude

Start Date
December 2017

Background
Over the last several years a number of refiners have reported plant issues (crude tower overhead corrosion control) linked to the use of amine based scavengers in crude to help reduce H₂S levels during crude production and transportation (truck, rail, pipeline). In December of 2017, one refiner provided plant tests data indicating high levels of MonoEthanol Amine (MEA) in the crude tower overhead boot water.

The project was launched with the aim of providing direction to the crude transportation community on additive usage.

Milestones as of February 2024

• Letter to CAPP on Use of Amine Based H₂S Scavengers published. August 2018
  
• Draft version of Best Practices was reviewed at September 2018 meeting. Decision was made to rename document as an Information Bulletin.
  
• Published CQCTA Information Bulletin titled “H₂S Scavenger in Crude Oil – Factors Affecting the Selection and Use of H₂S Scavengers”. Available on the CCQTA website under Publications/White Papers. Jan 2019
  
• Information bulletin “Sour vs. Sweet Designation within the Petroleum Industry” was published in August 2019. This document provides a clear distinction between the terms “sweet” and “sour” and their implication(s) on H₂S in crude.
  
• Marathon Petroleum work related to extraction of amines from crude oil for use in further analysis is in progress. Approved by ASTM D02.03 to proceed with drafting the standard practice under WK#68878.
  
• A revision to the “Information Bulletin - Use of H₂S Scavenger in Crude Oil” was published in December 2019 to include additional information related to test methods.
  
• Project group began an investigation into the levels and types of amines in tank bottom water as a measure of the baseline levels of H₂S scavenger. Tank water amine concentration, over time, may be a lagging indicator of scavenger use in the industry.
  
• One tank bottom sample was collected, and results were presented at the December 2020 project meetings. Data so far is inconclusive. It appears the pH of the water may be too high for amine extraction into the water phase therefore using the water for baseline monitoring may not be effective.
  
• Project was moved to “Project Maintenance Activities” as opposed to a stand-alone project.
  

• ASTM standard practice on amine extraction from crude oil (WK81967) is pending revision and ballot.
  

Start Date
December 2017

Background
This committee was formed at the close of the Condensate Quality Project to provide a forum for members to participate, get updates and provide feedback to and from the numerous projects that relate to condensate quality. These projects currently include but are limited to:

• TIOM
  
• TVP/RVP
  
• H2S PVT
  
• Phosphorus
  
• Organic Chlorides

• No recent activity.
  
• Project was moved to “Project Maintenance Activities” as opposed to a stand-alone project.
  

Start Date
March 2021

Background
In 2010, the CCQTA discussed the development of Crude Quality Tutorials designed to help educate and train CCQTA members and to provide a general overview of crude quality issues for use and distribution to uninformed audiences. In the 2011, a presentation was developed to address the latter, while the former remained on the Association’s work item list.

In March 2021, the CCQTA launched the "Centre of Learning" on the CCQTA website. This new initiative was started as an effort to find new ways to engage with our existing members as well as summarize historical information for new members. This should allow new members to get up to speed quickly and engaged in new discussions. Content is targeted at 25-40 minutes to fit into a typical lunch hour.

Several formats are planned including:

• Presentations
  
• Panel discussions
  
• Interviews
  

• Light Ends and Vapour Pressure (2 episodes)
  
• Crude Oil Stability/Compatibility & Blending Practices (2 episodes)
  
• H₂S in Crude Oil
  
• What is the CCQTA – An Introduction
  
• Chlorides in Crude Oil
  

• The Vapour Pressure series launched in March 2021 and was released publicly. The first episode is focused on the basics of vapour pressure including theory, terminology and applications. Vapour Pressure - Episode 2 was released in August 2021 is focused on sampling and testing methods impacting vapour pressure. Both episodes are available publicly.
  
• The "Crude Oil Stability, Compatibility & Blending" series launched in October 2021and is in our member’s catalog. Episode 1 focused on the following:
    - Hydrocarbon Structural Basics & Classification (SARA)
    - Solubility and Stability Related to SARA — CII
    - Blending predictions using SARA & CII
    - Solubility Testing by D8253
    - Relationship between CII and P₀
    - Blending predictions using D8253 solubility parameters
    - CII and solubility parameters in blending operations
  
• Episode 2 of the "Crude Oil Stability, Compatibility & Blending" Lunch and Learn Series was released on Feb 2022 is in our members catalog. This is the second episode in this series. This episode of this series discusses the following:
    - Review of Episode 1 including how the SARA impacts asphaltene solubility.
    - Asphaltene Stability, its dependence on the SARA ratios and how they impact the asphaltene micelle.
    - An in-depth tutorial of the ASTM D8253 solubility measurements.
  
• H₂S in Crude was released in August 2022 and was released publicly. This Lunch & Learn focuses on the following:
    - H₂S basics
    - CCQTA background with H₂S
    - H₂S in crude sampling and measurement
    - H₂S control methods
  
• What is the CCQTA – An Introduction was released publicly in February 2023. This Lunch & Learn is an introduction to the CCQTA for prospective members and as a way for existing members to introduce their colleagues to CCQTA. This episode features the following:
    - Origins and founding guidelines:
    - Project structure
    - Director testimonials
    - Synopsis of key projects
  
• Chlorides in Crude Oil was released publicly in October 2023. This Lunch & Learn focuses on the following:
    - Types of chlorides
    - Sources of chlorides
    - Corrosion and fouling issues
    - Test methods and their nuances
    - Experiences and cautionary notes
  
  

• Other Topics Suggested by Members:
    - Crude by Rail
    - Bitumen Blending and Shrinkage
    - Partial Upgrading — Thermal chemistry impacts on compositions.
    - Etc...
  
  If you have ideas for additional topics please send them to secretary@ccqta.com
  

Start Date
June 2022

Background
In the past, the CCQTA has completed numerous projects where sediment contamination in crude (filterable solids) have been linked to a number of operability issues (e.g. tank bottoms, equipment wear, plant unit fouling, operability issues, catalyst poisoning, product contamination). The Association has been advocating for decades for a filterable solids specification in crude since the present S&W test method is inadequate for identifying solids issues. To provide perspective, 0.05% = 500 ppm and NACE recommends, in a crude unit corrosion guide, that filterable solids in raw crude not exceed 60 ppm.

Recent information provided by a CCQTA member re-confirmed the link between the quantity of production solids within crude and refinery fouling issues. This information, along with parallel concerns by transmission pipelines regarding the role of solids in tank bottom sludge accumulation, rekindled an interest in looking at filterable solids in crude.

Two transmission line operators have been collecting filterable solids data, via ASTM D4807, regularly on all pipelined commodities. Crude monitor has also been reporting D4807 results over the past 10 years. The combined average levels of the 2300 samples tested is 210 wppm. Refinery feed data is slightly lower at 195 wppm.

Project objectives are to:

• Determine if a limit for filterable solids should be placed on crude oil,
  
• What the limit should be,
  
• Should it be product specific (medium vs. heavy crude),
  
• Identify key variable of concern (inorganic sediment, TIOM, particulates, particle size, etc…), and
  
• Determine suitable test method(s).
  

• Compile available plant data connecting operability issues (production/pipeline/refinery) with solids/particulate in crude.
  
• Establish the “problematic level”. What limit would be appropriate?
  
• Collect available measured data on crude solids/particulate content Establish baseline data for crude(s). Where are we now?
  
• Recommend limits/targets for solids/particulates in crude.
  
• Assess capabilities of on-line monitoring methods e.g. Dynamic Imaging Technology, Magnetic Filtration, etc…
  

• Project was proposed at the June 2022 Open Forum meeting.
  
• Filterable solids data from both midstream and refiners were presented at the September 2022 project meeting.
  
• A refiner specific meeting was held on October 24, 2022 to understand the most pressing issues refiners have with filterable solids.
  
• A summary of refiner concerns was presented at the December 2022 project meeting. Primary concern is desalter upset followed by process unit fouling.
  
• A water washing protocol was developed to evaluate filterable solids for water solubility to determine the crystalline salt content vs insoluble solids. Two laboratories (Bureau Veritas and Agat) are currently performing this additional test under pipeline operator direction.
  
• The initial water washed results were presented at the March 2023 project meeting.
  
• To date, water washing reduced filterable solids between 11 % and 100 % and averaged 60 % reduction. In theory, only water insoluble solids (sediments, asphaltenes, etc…) will result in desalter upset and downstream unit fouling. See September 2023 meeting minutes for details.
  
• The LSB Quality project merged with Filterable Solids in September 2023 since both were on a similar trajectory and collecting complimentary data.
  
  

• Summary and findings from the LSB Quality project were provided at the December 2023 project meeting.
  
• Focusing attention on desalter upsets with correlations to filterable solids and particle size impacts.
  
• Feedback was received from chemical suppliers and refiners regarding their experiences with filterable solids in the refinery. (See
  
• One refiner reported that approximately 60% of desalter upsets are related to slop injection.
  
• Much of the information provided by refiners and additive suppliers to date is based on anecdotal evidence or perceptions as opposed to real data.
  
• Project members agree that standardization of a method for filterable solids testing and developing criteria for determining desalter solids capacity would be very helpful for the industry in managing solids.
  
• Details on the member supplied filterable solids methods will be provided at the March 2024 filterable solids meeting. The intention is to discuss and agree on a methodology that all can be applied across the industry which would allow comparisons between refineries when troubleshooting.
  

Start Date
June 2011

Background
This participant-based project was launched as a follow up to the H₂S Measurement in Crude project with the goal of developing methods for understanding H₂S in vapor phase based on liquid phase data. Initially the work attempted to estimate vapor levels from liquid data modeling. That approach was found inadequate and the project switched focus to investigating and develop methods for the direct measurement in vapor.

This project became a CCQTA sponsored project in 2015.

Milestones as of August 2023

• Assess the capabilities of the data/model obtained from the Sour Service Pipeline Industry group. Model determined to be inadequate. 2012 - 2013
  
• Refocus efforts on H₂S evolution risk led to the development of a proof of concept H₂S evolution field testing unit (AITF apparatus). Preliminary results looked promising however the equipment was too large and cumbersome for practical application in the field. 2014
  
• Explore the development of a miniaturized unit. Secure CCQTA funding for Wilson Analytical to proceed with proof of concept work. 2015
  
• Obtain additional grants funding support from Engage/IRAP & CCQTA. 2015 – 2016.
  
• Undertake design & optimization work on H₂S detector and H₂S isolation MOF. 2016 -2017
  
• Obtain additional funding support from Transport Canada. 2017
  
• Working prototype (alpha) completed and preliminary lab trials indicate show promising results. 2018
  
• Beta prototype completed in August 2018 with upgraded electronics and detector.
  
• Extended trial completed in September and October 2018 with beta prototype testing ~36 crude streams to get baseline H₂S evolution data. Trial included: condensate, synthetic, conventional sweet, conventional sour, and dilbit.
  
• Trial results illustrated the wide variability in H₂S between streams and between liquid and vapor phase results. 2018
  
• Next generation prototype “Peter” developed in the summer of 2019 underwent functional testing between September and November. Initial results looked promising however there was still evidence of H₂S adsorption impacting successive results.
  
• Extensive materials testing was conducted to identify materials that may be adsorbing H₂S and a revised version is ready for additional functional testing. 2019
  
• Performance testing using gas standards for detection limits, linearity, dilution performance, etc… was completed in May 2020. Data was presented at the June 2020 project meeting. (See meeting minutes for details).
  
• Preliminary detection limits indicates an LOQ of 5ppm and upper detection limit of 10,000 ppm.
• Preliminary repeatability ranges between 0.2 ppm at 1.8 ppm H₂S and 33 ppm at 140 ppm H₂S. Results are reported on a ppm (mol/mol) basis.
  

• No further progress on the H₂S analyzer to date.
  
• Project was moved to “Project Maintenance Activities” as opposed to a stand-alone project.
  

Start Date
December 2018

Background
Currently there are several critical measures in Western Canada where light ends are measured for marketing valuation by producers and refiners and for compliance to specs.
Even though there have been developments these last years across CCQTA, ASTM , API etc, there is still no formal standardization across industry labs and facilities and we are exposed to misalignment of light end measures in crude oil which influence, regulations, marketing and upstream/downstream operations. It is proposed to bring forward some expertise across industry to align and push for implementation of improved light end crude measurements.

Past work by CCQTA on best practices can use some extensions to leverage updated insights by CCQTA and Sandia Labs and pipeline company current data with a goal of more exact sampling and method alignment. Note that we continue to have facilities using inappropriate/conflicting RVP and sampling methods in addition to some pipelines leveraging RVP bounds for emission and operation compliance that can be misled by ongoing increases in light ends. Note that many crudes continue to be challenging the upper end of light end composition pushing industry closer to requiring more investment in capital to manage them. In addition, Labs and operators are developing their own new practices for sampling and analytical techniques that expose industry to conflicting data.

The proposal is to consolidate the expertise already present in CCQTA membership and leverage the wide industry representation to deliver a single, updated, fit for purpose position on crude oil and diluent sampling and testing for use in such services as Equalization, Crude Monitor, and Regulatory custody transfer measures. The consolidated information is intended as a publicly available best practice similar to the recently published Vapor Pressure Best Practice

Link to Vapor Pressure Best Practice

Milestones as of February 2024

• Sub-Committee had its first meeting in December 2018.
  
• Initiated CCQTA/CQI/ITC sampling and testing project in July 2019 with agreement on the project objective, scope and project execution plan in September 2019.
  
• Study will focus on ASTM D8003, ASTM D7900 and the GPA2177M light ends test methods.
  
• Phase 1 summary data was presented to members at the March 2022 project meeting.
  
• Based on the results of phase 1, the decision was made not to proceed with phase 2. The group in attendance felt further sampling and analysis would not provide additional value and that the conclusions from phase 1 were sufficient.
  
• Phase 1 Report was released publicly on the CCQTA website in March 2023.
  

• A request has been made for CCQTA to conduct an interlaboratory study to establish the precision of GPA 2177M as it applies to crude oils. This was be discussed at the September 2023 Project Maintenance Meeting. An ILS proposal was presented at the December Project Maintenance meeting and accepted.
  
• Sample collection, homogenization and distribution for the ILS will begin late March 2024. Results will be presented as soon as they are available.
  
• GPA Midstream has been approached to include the CCQTA modifications into the next revision of GPA2177 as a Procedure B or appendix however they have a revision in progress and are not willing to disrupt that process.
  
• Potential to draft a new standalone ASTM standard, however there are a limited number of laboratories that perform this method on crude oils so it likely wouldn’t meet the ILS requirements for generating the method precision. Will discuss further at the March 2024 Project Maintenance meeting.
  

Start Date
November 2021

Background
This project is intended to evaluate overall quality of Light Sour Blend (LSB) and investigate intermittent incidents that occur between multiple refiners in a similar timeframe.

This is a participant funded (closed) project therefore information and data will only be available to those members that participate. The initial cost to join the project is $5,000 and will be used for the initial baseline sampling and testing phase of the project. Please contact secretary@ccqta.com if you wish to participate.


Milestones as of February 2024

• Initial project meeting held in November 2021.
  
• Meeting held in January 2022 had the following outcomes:
    - Finalized the initial 6 participants with 4 additional pending confirmation;
    - Project participation fees;
    - Identified sampling locations and frequency for baseline study. 2022
  
• Baseline sampling was completed at Enbridge terminal locations in Cromer, MB; Superior, WI; and Sarnia, ON. 2022
  
• Two samples related to an upset were received. One taken during the upset and one taken during normal operating conditions June/September 2022.
  
• Results of the baseline and incident testing were presented at the December 2022 project meeting.
  
• A recent sample of LSB flagged as high water cut (June 2023) was characterized and the results discussed at the September 2023 project meeting.
  

• At the September 2023 project meeting, participants agreed to merge the LSB Quality with the CCQTA sponsored Filterable Solids projects. There is an obvious connection between the two projects as they are on similar paths and collecting similar data.
  
• See the Filterable Solids project for updates.
  

Start Date
June 2022

Background
This project was initiated to evaluate new technologies that may be of benefit to the industry. This project is not intended to promote any specific vendor and is strictly looking at the technical impact and viability of a technology within the CCQTA membership. These individual technologies may not warrant a stand-alone project so this project group provides a vehicle for evaluation.

Technologies Currently Under Evaluation as of February 2024

1. Magnetic Filtration
This was proposed at the March 2020 Open Forum meeting and initiated at the June 2020 Open Forum. This will investigate the implementation of magnetic separation technology as it applies to various midstream and downstream applications.

• The project is seeking member(s) that would be willing host a pilot project using a slipstream. This could potentially be installed inline in the densitometer or similar instrumentation fast loop.
  
• Anyone interested in participating in please contact secretary@ccqta.com.
  
• Black Powder Solutions (BPS) presented a case study on slop system clean-up at the March 2023 project meeting. Details of that presentation are available in the meeting minutes.
  

The CCQTA Open Forum meetings have been in place since 2016 and are being held in conjunction with our regular quarterly project meetings. The original intent of Open Forum was as a forum for members to voice concerns with internal issues and problems and to seek other members with similar issues, concerns with the intent to potentially launch projects based on similar interests. Primarily it was for issues that did not fall within the existing project slate and there was no forum for discussion.

The Open Forum format has evolved over the last six years and has been used for several different purposes:
1. Introduce ideas and launch new projects (6+).
2. Discuss numerous specific issues to illicit participants help and/or suggestions for solutions.
3. Introduce new emerging technologies that could be useful and applicable to some and/or all participants.
4. Provide updates on research, test method development and validation work outside of the specific project frameworks.
5. Discuss existing or future crude quality issues viewed to be of concern to CCQTA members.
6. Other matters deemed to be of value to members.

The last bullet above emphasizes that Open Forum meetings can be used to introduce any crude quality item, technology and/or new development deemed to be of value to the membership.

We encourage members to propose future presentations on any item(s) they believe is of interest to the membership, providing it incorporates an element of crude quality and is void of any commercial elements. That may include new chemistries, analytical techniques, technology innovations or improvements, etc…

If you have something you wish to present to CCQTA members at the Open Forum please forward your presentation(s) to secretary@ccqta.com. The Technical Director and I will do a preliminary review of the material and if necessary, suggest revisions to ensure the material is directed at an aspect of crude quality and is not commercial in nature. If there is concern regarding the suitability, we will seek input further input from the CCQTA Executive.

Start Date
June 2016

Background
A member company approached the participant based Organic Chloride project group in April of 2016 with the idea of pursuing the development of test method for measuring organic chlorides in distillate/gas oil streams. Following a data review and discussion, project members suggested that the CCQTA support ongoing work previously undertaken by Marathon and XOS.

Milestones as of February 2024

• Gas oil samples were requested in June 2016.
  
• Low level (estimated at 4 - 5 wppm) contaminated distillated samples were provided by Suncor in late 2016. Samples were tested by Marathon and XOS. There were insufficient quantities of TOX in the samples to undertake further method assessment/development work. Samples with higher concentrations are required.
  
• In June of 2019, evidence was provided at the Open Forum meeting that a “false positive” for organic chlorides had recently been reported in a sample of heavy crude (>940kg/m3). Follow up work further suggested that excessive heating of the sample during the naphtha distillation step might be responsible for thermal cracking, olefin generation, salt hydrolysis and subsequent organic chloride formation. This mechanism is now being investigated by the project group.
  
• In December 2019, additional data was presented based on the continuing investigation. New observations indicate incomplete combustion, high sulfur content in the recovered naphtha as well as the orientation of the combustion furnace may also be contributing to false positive readings. Further work in in progress.
  
• It was reported at the December 2019 project meeting, that there have also been false positives observed on lighter US gulf coast crudes.
  
• Results presented in June 2020, were inconclusive for “false positives” however the work did highlight the wide variation in results that could be encountered on the same naphtha sample run at different laboratories. Please see the June 2020 meeting minutes.
  
• Project was moved to “Project Maintenance Activities” as opposed to a stand-alone project.
  
• A lengthy discussion took place at the March 2023 Open Forum meeting regarding performing ASTM D4929 on samples with low naphtha content (<5%). The discussion centered around false positives and potential revisions to the test method to avoid them.
  
• CCQTA Lunch & Learn on “Chlorides in Crude Oil” was released on Oct 31, 2023.
  

• A revision to ASTM D4929 was submitted for ballot to sub-committee D02.03 in September 2023. The revision includes two notes added to section 12.1 which refers to the distillation procedure. The first note provides guidance for low naphtha content samples with a focus on avoiding cracking. The second note clarifies that the distillation rate is not critical to the success of the subsequent analysis, but prevention of decomposition is.
  
• The September ballot received several negatives that have been addressed and the revision is in concurrent ballot closing February 19, 2024.
  
  

Start Date
December 2019

Background
This project was initiated to evaluate PUB materials for risks to transportation and refinery processes. The project is focused on developing standardized test protocols to allow comparison of PUB materials produced via different technologies/conditions. This project is an extension of the 2016 Alberta Innovates initiated a project focused on Bitumen Upgrading which was completed in 2018.

Milestones as of February 2024

• In June of 2019, a proposal for a follow up project focussing on the Transportability and Processability of Partially Upgraded Bitumen (PUB) was presented. Presenter (scott.r.smith@cenovus.com) requested feedback/expressions of interest from the membership to determine if the project should be participant of Association funded.
  
• First meeting for the new project “Transportability and Processability of Partially Upgraded Bitumen (PUB)” was held on Dec 3rd, 2019.
  
• PUB Workshop was held on March 12, 2020. Workshop focus was the selection of samples and tests for study to address areas of concern with refining and/or transport of PUB. Output of the workshop was a survey/worksheet sent to participants to prioritize activities.
  
• Sample selection and testing survey results were presented at the June 2020 project meeting.
  
• A survey was sent to refiners to gather information regarding what the key areas of concern are for processing PUB products.
  
• Refiner survey results were presented at the September 2022 project meeting. The following were the key area of concern:
    — Exchanger fouling (high priority)
    — Emulsion stability (high priority
    — Desalter operation (medium priority)
    — Olefins in PUB (medium priority)
    — Migration of contaminants, specifically metals (medium priority)
    — Odor (low priority)
  
• The six phases of the project have been identified based on the priorities and discussions with the various stakeholders. The phases are listed below:
    Phase 1 — Basic Characterization
    Phase 2 — Fouling
    Phase 3 — Blend Fouling
    Phase 4 — Emulsion Stability
    Phase 5 — Migration of poisons into distillates
    Phase 6 — Changes in PUB during storage due to reactions of olefins/diolefins
  
• Nine types of PUB samples have been identified plus a dilbit reference material. These include hydrotreated and non-hydrotreated PUBs.
  
• Refinements were made to the testing matrix at the June 2022 project meeting.
  
• A preliminary budget has been developed and was discussed at the June project meeting.
  
• Based on the prop\osed budget, the CCQTA Board of Directors has agreed to provide funding support to this project as a CCQTA sponsored project. Sept 2022.
  
• A questionnaire was sent to refiners in October 2022 looking for feedback regarding the quality of PUB’s for FCC Feed.
  
• A meeting was held with the CCQTA chemical suppliers in November 2022 to discuss emulsion testing methods, use of de-emulsifiers as well as the interest of companies to work with the project team on experimental work.
  
• Results of both the refiner questionnaire and the chemical supplier meeting were discussed at the December 2022 project meeting.
  
• A funding application has been approved by Alberta Innovates to support the project work. The premise of the application is the development of the sampling and testing protocol to allow any PUB materials to be tested and then compared to each other based on the characteristics of most concern to refiners. The comparative data provided by the protocol should improve market access for PUBs by alleviating refiner concerns about processability problems.
  

• Sample selection is complete and sampling is in progress. WDB will be used as the reference crude and will be collected from Cenous along with the PUB samples. The PUB samples are currently being collected and blended, with anticipated delivery by the end of February 2024. KDB will be used for the PFT and has been received. Suncor OSP has been received as a cracked stock comparator because of the long history of refiners running it as a segregated product.
  

Start Date
February 1997

Background
Since 2017, regular updates on volatile phosphorus testing, carried out by Pembina Pipelines, have been provided at Condensate Quality project meetings. Pembina has been providing regular updates for over two decades.

No volatile phosphorus above the 1.5 wppm limit has been detected during the regular testing of ~2400 samples during 2018 and 2019. As of 2020, Pembina scaled back testing however they are still testing delivery points at some key nodes along the mainline.

Milestones as of February 2024

• In 2022, several US refiners reported issues with phosphorus deposits over the past year related to US domestic production. Phosphorus has also been recently detected in both the crude feed and deposits from several Canadian refineries.
  
• Data was presented at the September 2022 Project Maintenance meeting highlighting the recent phosphorus related observations from the impacted refineries. A follow-up meeting was held on October 12 to focus on phosphorus specifically.
  
• Key Points:
  - Monitor both the total phosphorus and volatile phosphorus. Midstream companies report no volatile phosphorus results in their testing however refiners are testing and finding total phosphorus in raw crudes. The volatile phosphorus testing distillation cut point at 250°C may not be capturing the current phosphorus species.
  - Current phosphorus fouling appears in the hotter tower sections than the previous fouling issues.
  
• The above were discussed at the December 2022 Project Maintenance meeting.
  
• At the March 2023 Project Maintenance meeting, a US refiner provided a dataset with ~2200 total phosphorus results from their various operations in North America over the past 5 years. The dataset showed a significant amount of phosphorus reporting from both North American and international sources. 56% of results are 1 wppm and 8% of the results are >1 wppm.
  
• Deposits from both two refineries were discussed at the September 2023 Project Maintenance meeting. Although phosphorus was detected in the deposits, the analysis indicated it was inorganic based and not organically bound like historical deposits.
  
• Deposits also have a different morphology/texture than those found during the alkyl phosphate ester fouling issues of the past. Those deposits were hard and adherent while the current deposits are powdery and easily removed.
  

• Nine sample were received from fouled tower trays. Seven had sufficient material for characterization.
  
• Included in the characterization is the novel 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.
  
• The results of the characterization will be presented at the March 2024 Project Maintenance meeting.
  

Start Date
December 2013

Background
In late 2013 a two-step proposal was presented to the CCQTA membership. Step 1 involved the development of a method for measuring specific contaminants (CO₂, O₂, H₂S) in crude. Step 2 would focus on methods to monitor on a regular basis for these or other contaminants. Monitoring for these gases was deemed important to both pipelines and railcars.

The project was launched late in December 2013 and became a CCQTA sponsored project in 2016.

Milestones as of August 2023

• AITF/Enbridge present modified TM0172M method. 2014
  
• The initial gas chromatography test method development work for CO₂, O₂, H₂S undertaken by Canmet Energy was unsuccessful however in 2015 AITF (InnoTech) agreed to take over method development work. 2015
  
• Omnicon/Enbridge/IPL developed test method and results presented for O₂ measurement in condensates & other hydrocarbons by optical probe in pressurized streams. 2016
  
• Draft corrosivity evaluation protocol presented combining multiple tests to evaluate different parameters contributing to corrosion. 2016
  
• Enbridge presented a proposal for the development of a corrosion assessment model for oxygen in hydrocarbon. 2017
  
• Innotech completed GC HPLIS direct injection test method for measuring for O₂ and CO₂ with H₂S capability in development. 2018
  
• Completed O₂ and CO₂ sampling program on the Enbridge Norlite system. Results were presented at the December 2018 CCQTA meeting. 2018
  
• Decision at March 2020 meeting to discontinue efforts to add H₂S separation and detection to the scope of the current O₂ and CO₂ method.
  
• Enbridge sponsored sampling and testing campaign on both the Norlite diluent system as well as Edmonton terminal crudes (MSW, WDB and SYN) has concluded. Samples were collected for both O₂ and CO₂ as well as H₂S, water content and sediment. Study results were presented at the March 2021 project meeting.
  
• Results of the 2021 sampling campaign were presented at the March 2022 project meetings.
  
• The target for this sampling campaign is to gather samples of crude oil that would represent the maximum concentration of CO₂ that could be expected. Regions that have active EOR (tertiary recovery) using CO₂ flooding are anticipated to have the highest concentrations.
  
• At the March 2022 meeting, preliminary OLI modeling results on a CO₂/Oil/Water system was presented. The modeling work was intended to estimate the impact of CO₂ on in-situ water pH and if transmission pipelines are at risk from CO₂ related corrosion.
  
• The initial model over predicted the CO₂ partial pressure however, even with over predicted values the corrosion rate was very low.
  
• A comparison was also made between fresh water and water containing chlorides and bicarbonate. The additional of bicarbonate lowered the corrosion rate by ~100 x.
  
• The second set of samples collected in 2022 showed similar CO₂ results for WCS and CL however the MD result was significantly higher (1800 wppm vs 800 wppm previously). Equation of State (EOS) simulations using the MD composition showed beyond 1800 wppm CO₂ the vapor pressure of the crude would exceed atmospheric pressure and would no longer be stabilized.
  
• Revised OLI modeling was conservatively performed at 2000 wppm CO₂.
  
• At the September 2022, the results of latest sampling, testing and OLI modeling were presented. These results confirmed the findings of the earlier work, that CO₂ at levels found in stabilized crude oil are at or below the NACE 1 mpy threshold in the presence of bicarbonate.
  

• The final report for this project was released in May 2023. The full report and an abbreviated version are both available under the projects directory of the CCQTA website. This report has not been released publically.
  
• This project is now closed.
  

Start Date
June 2015

Background
This project was officially established as a major pipeline participant-based project in 2015. It was based on initial work performed outside the CCQTA from 2009 to 2011 and then within the CCQTA Pipeline Corrosion project from 2014 to 2015. A project proposal was circulated to the membership in mid 2015 encouraging additional participation at reduced fees or under a Work-in-Kind agreement.

This project was initiated in response to the National Energy Board requirement for transmission pipelines to meet the CSA Z662 standard for Sour Service. The project focus is the evaluate the conditions required that would allow sulfide stress cracking to occur which will allow transmission pipeline operations to evaluate their systems and whether the conditions exist to promote SSC.

The project scope involved the collation of H₂S in crude test data, testing of available pipeline water samples, and the development of a Sulfide Stress Cracking (SSC) test protocol for transmission lines.

The project became a CCQTA funded project in June 2017.

Milestones as of February 2024

• Determined that under acidic conditions, oil contact with the SSC test solution prior to testing using NACE TM0177 significantly altered failure rates. Similar testing using a slightly basic brine (ASTM D1141) contacted with crude prior to TM0177 testing did not see significant variation from blank. 2017
  
• Project group presented to the NACE MR0175 maintenance panel in March 2016, March 2017, April 2018 and most recently in March 2019. The maintenance panel was engaged to make them aware of the work that was going on relating to differentiating transmission pipelines conditions from conventional gathering system conditions and how those conditions may affect SSC and to seek feedback.
  
• H2S partitioning testing determined that H₂S migration from oil to brine in the absence of a gas phase (no bubble point) results in significantly lower H₂S concentrations in water than those observed during a direct gas/brine exchange. Results were inconclusive regarding the effect of dissolved versus free H₂S on the SSC mechanism.
  
• Determined that pre-coating of coupons with both heavy and light oils, inhibited SSC failures in the ASTM D1141 solution - over the full 30-day test period.
  
• Enlisted the participation of NEB and AER in project work.
  
• The survey form for use with field experience data collection was finalized and sent to pipeline operators in November 2019.
  
• Available survey data was presented at the June 2020 project meeting.
  
• Ballot proposal presented to NACE MR0175/ISO 15156 maintenance panel in early October 2020.
  
• NACE MR0175/ISO15156 Maintenance Panel ballot passed in December 2020 and moved on to the TG299 Oversight Committee for review and ballot in 2021.
  
• A presentation was made to the TC299 OSC in January 2021 to provide context to the ballot. Presentation is available in the members area of the Sour Service project.
  
• NACE ballot has passed both the MR0175 Maintenance Panel and TG299 Oversight Committee. Next step will be to formally approve the revision in October 2021.
  
• A NACE technical bulletin (ISO_15156_3_2020_Cir_1_2021) was issued on 2021-12-09 including the new exclusion clause for transmission pipelines. The bulletin This bulletin has been added to the Sour Service director of the CCQTA website.
  
• Project was moved to “Project Maintenance Activities” as opposed to a stand-alone project
  
• Two ballots have been submitted to CSA for revision to Z662. These ballots are intended to harmonize the recent MR0175/ISO15156 revision with CSA Z662.
  
• The first ballot item is a revision to § 2.2 (Definitions) regarding “Pipeline System, Sales Quality Liquid Hydrocarbons” item b. The revised definition removes the ambiguous bubble point statement as well as the associated note.
  
• The § 2.2 revision also requests an update to the definitions of low vapor pressure (LVP) and high vapor pressure (HVP) to replace ASTM D323 with ASTM D6377.
  
• The second ballot item is a revision to §16.1.2 a) to remove the dissolved H₂S criteria from the exclusion requirements.
  
• The public review of the revisions to CSA Z662, closed on March 5, 2022. The CSA ballot will take place in late summer/early fall 2022. Ballot comments are then dispositioned, and changes are finalized at the Feb 2023 Technical Committee meeting, at which point they would be considered final and included in the 2023 edition.
  

• A new revision to ISO 15156 is currently in review and there are some concerns in the draft revision relating to conflicts with the previous exclusion for transmission pipeline that was issued in ISO_15156_3_2020_Cir_1_2021.
  
• Comments on the draft were submitted before the Oct 31, 2023 deadline.
  
• AMPP MR0175/ISO15156 maintenance panel is meeting on March 3 so additional information may be available at the March Project Maintenance meeting.
  

There are numerous projects which have limited activity and have not been closed because of ongoing maintenance work items. For example, projects that have spawned ASTM or other standards need to be maintained (revisions, ILS, etc...). These projects don't warrant individual meetings and budgets but there are still ongoing activities. To manage these work functions these projects have been combined into a single project identified as "Project Maintenance Activities". This consolidated project has been given a budget to manage the various sub-projects.

List of included projects

• Amines in Crude
  
• Condensate Quality
  
• Compatibility Test Method
  
• Light Ends Characterization
  
• Organic Chlorides
  
• Phosphorus
  
• Sour Service
  
• Water Content
  

Start Date
December 2018

Background
This sub-committee has been initiated to:

• Provide a more streamlined path to obtaining samples from CCQTA member companies for CCQTA project work.
  
• Provide guidance to members and industry regarding sampling best practices.
  
• Provide advice to members and industry on sampling practices that are best fit for their testing application.
  
• Sub-committee meetings will be held to coincide with quarterly project meetings. This sub-committee meeting will be scheduled as the last meeting of the week to allow discussion of any sampling needs that may have developed during the course of the project meetings.
  

• Sub-Committee had its first meeting in December 2018.
  
• Currently have authorizations from: Suncor, Flint Hills, Gibson. These three authorizations cover the bulk of the products requested by projects. Authorizations are valid to February 2025.
  

• Current Sampling Projects:
  — PUB project sampling is in progress. KDB and OSP samples have been collected/received. PUBs will be supplied by Cenovus.
  — Light Ends Characterization project will be conducting an interlaboratory study which will require collection of large (18L) sample volumes for homogenization and distribution into pressurized cylinders. The individual samples will be randomized and sent to the three laboratories for GPA 2177 analysis. Sampling is anticipated in late March 2024.
  

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.
  

Start Date
December 2021

Background
Fouling in crude tower overheads and pump around circuits can be linked to multiple sources and chemistries. Project will focus on common issues between refiners and methods to identify the fouling mechanism(s) and source materials.

Milestones as of February 2024

• Initial project meeting held in December 2021.
  
• Three samples were received from three different refineries. The deposit characterizations were presented at the June 2022 project meeting.
  
• At the September 2022 meeting, a review of the previous sample analysis included a discussion on the origin of the elemental sulfur found in all three deposits.
  
• Results of the characterization of two new deposits were presented at the September 2022 meeting. One tower overhead and one LVGO reflux cooler. Both refiner and the CCQTA characterizations of the deposits were presented. Elemental sulfur was also identified in the overhead deposit.
  
• Analysis of 8-12 deposits from the another refinery were presented.
  
• After the September 2022 meeting information was provided indicating the decontamination process prior to opening the units to collect the samples was the likely source of elemental sulfur. More details were provided at the December 2022 project meeting.
  
• Characterization data from additional deposit samples were received was presented at the December 2022 project meeting.
  

• Seeking additional tower top deposit samples.
  
• At the December 2023 meeting a summary was provided on the findings to date including:
  — Crude tower top fouling
  — Crude overhead emulsion
  — Crude overhead water pump strainer fouling
  — Crude tower fouling
  — Discussion on the carbon allotrope (graphite) found in recent deposits and possible origins.
  
• See the December 2023 meeting minutes for details.
  

Start Date
June 2013

Background
A project proposal for improving crude vapor pressure measurement was initially presented by TransCanada Pipelines (TCPL) in early 2012. During the remainder of the year both TCPL and Imperial Oil (IOL) presented additional data supporting the need for improved measurement methods. This was largely in part due to conflicts between measured vapor pressure data and the API nomograph conversions from RVP that were used for EPA tank emission calculations.

A workshop hosted by the Alberta Research Council (now InnoTech Alberta) in February of 2013 solidified the need for work in this area and the project was launched a few months later as a participant based project.

A significant volume of data was presented comparing ASTM D323 RVP data versus ASTM D6377 VPCR4(37.8°C) data as well as comparisons of vapor pressure variations due to sampling methods.

This project became a CCQTA sponsored project in 2016.

Milestones as of February 2024
The following publications/standards have been developed as part of project activities:

1. ASTM D7975-14 — Crude Oil Vapor Pressure Field Tester (VPCR-F). 2014
   
2. ASTM D8003-15a — Determination of Light Hydrocarbons and Cut Point Intervals in Live Crude Oils and Condensates by Gas Chromatography. 2015
   
3. ASTM D8009-15 — Manual Piston Cylinder Sampling for Volatile Crude Oils, Condensates, and Liquid Petroleum Products. 2015
   
4. CCQTA Letter to Industry Regarding Vapor Pressure and Light Ends Measurement. 2015
   
5. CCQTA Temperature Correction of D7975 Field Vapor Pressure Measurement. 2016
   
6. CCQTA Vapor Pressure Best Practice published. 2017
   
7. ASTM D8236-18 — “Standard Practice for Preparing an Equilibrium Liquid/Vapor Sample of Live Crude Oil, Condensates and Liquid Petroleum Products using a Manual Piston Cylinder for subsequent liquid analysis or gas analysis by Refinery Gas Analyzer”. 2019
   
8. Transport Canada (TC) is collaborating with the Canadian Crude Quality Technical Association on the Inter-laboratory Study for ASTM D7975 and D8003, by providing in-kind support (collection of crude oil samples during TC’s Task 4 sampling and analysis campaign), as well as financial support for the required subsampling and characterization of the crude oil samples.
   
9. Sampling for the ILS is complete with 8 samples captured by single phase sampling method. Both D8003 and D6377 have been completed on each sample and results were sent to the ASTM statistician for evaluation for the ILS.
   
10. An advisory was published in November 2021 regarding ASTM D6377 and the impact of agitation on vapour pressure measurement.
    
11. A revised CCQTA advisory was published in April 2021 regarding ASTM D6377 and the impact of agitation on measurement. This revision followed significant discussion at both the December 2020 and March 2021 meetings regarding details of the initially published advisory. Feedback from members as well as vapour pressure instrument manufacturers was incorporated into the revised version. The outcome was that increased agitation is a short-term mitigation strategy however the test method equilibrium criteria is the root cause.
    
12. Project was moved to “Project Maintenance Activities” as opposed to a stand-alone project.
    





Recent Updates



• The planned D8003/D7975 ILS has been delayed so that a revision to the D8003 method to include injectors other than the HPLIS. Once the revision has been approved, the ILS will be conducted as a “mixed system” ILS which will hopefully have a larger range or participants available.
  
• Based on the typical ASTM method review and ballot cycle the ILS will likely not proceed until Q4 of 2024 at the earliest.
  








Link to Vapor Advisory

Start Date
December 2017

Background
In December 2016, the issue of proper water measurement in crude surfaced and was discussed at all subsequent Open Forum meetings during 2017. The capabilities and limitations of available methods were discussed suggesting a need to provide some direction to industry on fit-for-purpose testing and the potential use of a referee method.

Milestones as of February 2024

• The project group will prepare and publish a “White Paper” on the subject of water testing in crude oil. The work scope will include reviewing previously published work, collecting available data from members, and providing recommendations for test method selection, based on a fit for purpose review.
  
• Nova Analytics and Validere conducted studies using visible and UV quantification of centrifuge method sediment and water layers to compare with Karl Fisher titration results. Study results were presented in December 2018 and updated at the March 2019 meetings.
  
• White paper titled “Water in Crude – Factors Affecting Water Content Measurement” was published in December 2019.
  
• Interlaboratory Study to incorporate an evaporative method into ASTM D4928 is complete and results were presented at the September 2020 project meeting (see meeting minutes).
  
• Project was moved to “Project Maintenance Activities” as opposed to a stand-alone project. 2021
  
• Revision to ASTM D4928 / API MPMS Chp 10.9 test method ballot failed by one vote in March 2021. The ASTM sub-committee ballot passed in October 2021. A working group was formed to polish the statistics.
  
• The changes to the scope, because of outlier interpretation, prompted API to require the method be sent back to ballot again.
  

• Concurrent D4928 ballot resolution is nearing completion and once completed it will be sent to ASTM/API for editorial review and publishing. Anticipate publishing in 2nd quarter of 2024.