Any latest development in the world of asphaltene inhibitor and asphaltene in general?
Last time I checked, asphaltene inhibitors are not that very effective (60 -70% effective in a good case) and hence a lot of asphaltene problems in the industry.
Does anyone have any new info to share on the latest development in the world of asphaltenes and asphaltene inhibitor?
Scott Lamb
Corrosion Inhibitor Chemical Manufacturer
As long as they could identify the value of the opportunity, then anyone with the funding could find a Universal Solution, regardless of national affiliation. My suspicion is that the costs associated with this solution have been weighed against the costs of the status quo, and the consensus may be that the less expensive option is to simply continue dealing with the asphaltene deposition problem using established methods.
Titus Sobisch
Senior Application Specialist at LUM seeking for new opportunity in R&D and customer support
Fully agree that the asphaltene problem is strongly associated with the solvent, i.e. crude oil composition. @Humberto I would assume that filtration efficiency based on compatibility of the filter (absorption) media to asphaltenes and the remaining crude oil would be more promising, i.e. finding out on which media or surfaces asphaltene deposition is strongest. Of course in any case problem of clogging would be the most serious one. Good luck.
Win Robbins
Advanced Characterization - petroleum at Carmagen Engineering
Humberto, Because asphaltenes precipitate as a function of solvent composition, there is no single size to remove by filtration. Although there are wide variations in detail, consensus analytical definition of asphaltenes is hepane insolubles toluene solubles. Numerous processes have been proposed for asphaltene removal, only a few have been found economic either due to filter plugging, energy costs or loss of "good" HC's. One such process is ROSE. Note that this process uses supercritical CO2 as a precipitating solvent (liquid CO2 is equivalent to nC6 in solvent power). Because asphaltenes are surface active they stabilize emulsions and foams. The latter is now used in froth processing Canadia tats sands. Rather than diluting with a "good solvent " like toluene, the tars sands are diluted with a paraffinic naphtha (solvency like heptane), frothed with gas vapor, and the froth enriched with asphaltenes and fine particulated skimmed away See.
Ahmed Helmi
Adjunct Professor at Pharos University
Win: The literature states that the molecular size of Colloidal Particles range from as small as 1 nanometer upto 1 micrometer. The consequent logic tells me that Humberto "should" use a filtration device having pores of 1 nanometer, ie. the smallest diameter for retaining the smallest particle. There is no role for any solvent in this rationale. But the logic tells me one further step: How Humberto would tackle / avoid plugging his filtration device in the very moment of the initial start up of his pilot plant?? Is it the role of high pressure? if so it may work in the beginning of a run but shortly the "high" pressure may cause getting the retained Asphaltenes as a compact layer on the surface of the filtration device. If Humberto could rely on intermittent operation meaning periodically stopping the run to skim the Asphaltene layer off his filtration device, could this be practically acceptable? I doubt. Humberto: Appreciate your elaboration.
Win Robbins
Advanced Characterization - petroleum at Carmagen Engineering
Ahmed,
Asphaltenes have no specific composition, rather the event of precipitation brought on by a change in solvent power (pressure drop, mixed crudes, or solvent addition) crashes a complex mixture of structures out solution. The precipitate includes not only insoluble compounds but a variety of trapped (occluded) solvent molecules. TWhereas the precipitated asphaltenes have a generic discotic (disk-like) character, the molecules within the precipitate slowly re-arrange. Kilpatrick has recently referred to the precipitates as "molecular velcro". In separate papers, Kilpatrick and Gray have published useful hypothetical models showing his type of aggregated material. Analytically, the size of the precipitate is a function of solvent composition and diluent volume; but no analytical technique has been able characterize a monomer of asphaltene. Most analytical methods use solvent/oil ratios >10, preferably >30, and allow the precipitate to age for several hours before filtration on disposable paper filters followed by extensive solvent washing. Such conditions are not economically feasible for a process. The ROSE process mentioned earlier is exception because the CO2 doesn't have to be recycled to be economic.
You are absolutely right about the filtration. Filtration through nano-porous ceramic membranes will remove some of the asphaltenes but at the expense of extreme pressure. After a few hours the pressure drop becomes excessive, recovery of precipitated material by backflush with a good solvent (toluene) is partially successful because the pressure has de-aggregated the asphaltene within the membrane pores leaving some insoluble deposit. After a few cycles, initial pressure drop is too high. In general, filtration is not a practical method for petroleum processing. If phase separation can be achieved predictably, then physical property separations( distillation, centrifugation, liquid/liquid extraction, etc) are more acceptable, especially if the phases can flow. Batch type operations like filtration are only practical for high value products.
Ahmed Helmi
Adjunct Professor at Pharos University
Win:
1- Glad that my previous comment draged you to tell valuable technical information, very educational to me from a subject-matter-expert. Thanks.
2- While reading your comment describing how difficult Asphaltenes detrmination is for the Analytical Chemists I recalled my first day at Prof Dr Mike Delaney's Artificial Intelligence Lab at Boston Univ close to the mid eighties as PhD student: Here we add intelligence to chromatographs and spectrophotometers to predict the structure and concentration of simple molecules as a beginning, Absolute No if you ever think of complex molecules of your Petroleum Industry, No for Asphaltenes or Aromatic Extracts!! At then I realized how carefully he read my CV where I wrote about my humble experimentation for their column chromatographic separation in Egypt, ambitious dreams/curiosity of a junior lab chemist equipped with only a glass column and a refractometer Russian-made.
Humberto:
Still waiting for your elaboration if you don't mind:
Colloidal particles molecular size range from 1 nanometer to 1 micron
Suspended Solids (Can I say "molecular size" here too???) around 10 micron
Which type of Solutes are you targetting for the separation? If there is no solvent added yet; I would expect the Ashaltenes suspended in the oil (dispersion medium) as a stabilized collodal system, meaning in Colloidal Dimensions (1 nano meter to 1 micrometer) not as Suspended Solids as we know the term in water chemistry. Please correct me if I were wrong.
Win Robbins
Advanced Characterization - petroleum at Carmagen Engineering
Ahmed,
Characterization of petroleum has certainly progressed from when you (and I) started with open columns and spectrophotometers. Advances in HPLC, diode arrays, and now high resolution MS (FT/ICR/MS) have allowed us to understand how little we understand about the complexity of petroleum. Petroleum originates from such a broad range of bio-matter, sedimentary conditions, and geo-thermal processes that contribute to this complexity. In the past decade, it has become apparent that many petroleum accumulations are alive with anaerobic and aerobic bio-organisms further complicating crude handling. Ancient bio-marker compounds are being supplemented with extensive genetic coding. Some of the bio-molecules may well be found within the material precipitating as asphaltenes. It's no longer sufficient to consider the origin of asphaltenes in terms of organic geochemistry; we now need to consider organic microbiological geochemistry! Some potential clues linking bioactivity to asphaltenes are now being found on the sea bed around "black smoker" seeps.
Ahmed Helmi
Adjunct Professor at Pharos University
Win: I hope to maintain communication with you. I will write here my website address and 2 publications in which I was coauthor named "Abdelfattah" , a grandfather I don't like as he had a second wife besides my sweet tender grandmom so my family name in Facebook and LinkedIn is "Helmi" my grand grandfather's name. 4- ElGayar, M., Mostafa, A., Abdelfattah, A., and Barakat, A. (2002) Application of geochemical parameters for classification of crude oils from Egypt into source-related types. Fuel Processing Technology, 79, pp. 13-28.
5- ElGayar, M., Abdelfattah, A., and Barakat, A. (2002) Maturity-dependent geochemical markers of crude petroleums from Egypt. Petroleum Science and Technology, Vol. 20, Nos 9&10, pp. 1057-1070.
www.ahelmiconsultant.com Will read your last comment with more concentration after dinner, my Dear Wife gets mad if she announces: Dinner is Ready and I pretend as if not hearing and continue with my Labtop!
Ahmed Helmi
Adjunct Professor at Pharos University
Gents: I appreciate the initiator of this discussion Mike Davis and all the Commentators for extending my vision of Asphaltenes from the macro-scale to the micro-scale. Appreciate Win for a deeper vision beyond the micro-scale, I may call it the Sub-MicroScale. I wrote in a previous comment the need for a joint R&D research program by the Biggies of the O&G Industry to have a universal solution for the Asphaltenes depositional problems. Thanks to the last comment of Win as the Search engine lead me to a valuable published academic report authored by a researcher from the University of Illinois that digs in finding a Universal Solution. Here, I post the Abstract of this report hoping for your comments: G. Ali Mansoori Departments of BioEngineering, Chemical Engineering & Physics, University of Illinois at Chicago, Chicago, IL 60607-7052, USA E-mail: mansoori@uic.edu Abstract: We present a coherent and unified group of general explanations for the various phase transitions, which may occur in the seven naturally occurring petroleum fluids with emphasis on their heavy organics. The seven petroleum fluids include, in the order of their fluidity, natural gas, near-critical gas-condensate, light crude, intermediate crude, heavy oil, tar sand and oil shale. At first the nature of every petroleum fluid is presented including their constituents and their heavy fractions. Then their main families of constituents are presented. The generalised petroleum fluid phase behaviour is introduced in light of the well-known theory of phase transitions. The effects of variations of composition, temperature and pressure on petroleum fluids phase behaviour are introduced. Their 11 distinct phase-transition points are presented and their relation with state variables and constituents are identified. This report is the basis for development of a unified phase behaviour prediction model of all the petroleum fluids. Keywords: asphaltene; diamondoid; heavy oil; heavy organic; hydrocarbon; oil shale; phase transition points; polydisperse fluid; resin; tar sand. Reference: Mansoori, G.A. (2009), ‘A unified perspective on the phase behaviour of petroleum fluids’, Int. J. Oil,Gas and Coal Technology, Vol. 2, No. 2, pp.141–167.
If you read in this report, please see Fig. 8, as I suspect a printing error that spoils my interpretation of this particular valuable data presentation/plot. What do you think?
Win Robbins
Advanced Characterization - petroleum at Carmagen Engineering
Ahmed,
Mansoori makes a valiant effort to come up with a universal model based on phase transitions; however, his references to asphaltene composition and structure is 10-20 years out of date. The only recent reference that he cites for the "continental" model is Mullins (2006). Over the past 20 years the consensus has grown to prefer a mixed model with both continental and "archipelago"( model with a maximum of 6 fused aromatic rings linked by short C-C bonds or naphthenes.) Rodgers (FSU) and Qian (Exxon) have separately used different MS techniques to demonstrate the latter is the dominant structure in most cases. The more open structure is supported by Exxon asphaltene models (Siskin, 2006) and Exxon papers by Freund supporting a patented model for the fragmentation of kerogen and asphaltenes.(US 7,334,889). As for Mansoori's Figure 8, GCP or SEC is not adequate for determining the MW of asphaltenes, it only reveals the apparent molecular size for the asphaltene aggregates at the concentration and in the solvent used for the test.
Ahmed Helmi
Adjunct Professor at Pharos University
Win: I was about to shutdown my Laptop, take a break, then I made a visit to the Group to see if any comment. I am now fully alert and thanks again and again for your generous information about the latest updates in Asphaltenes' research. Mansoori is depending on the PT diagram and its Gas Envelope to characterize the separation of different phase/s per given change in PT and I was about to consider the extension of his approach when it comes to Asphaltenes as exaggeration; but I recalled a scene during a visit to the Lab of a Gas Separation plant west of Alexandria a couple of years ago. An experimentalist chief chemist of that Lab showed me his separated Asphaltenes out of Natural Gas Condensates with Gas Oil at its tail end. He managed to concentrate these Asphaltenes by several consequent distIllations starting with a Large quantity of Condensates. I was shocked as I used to tell my students that Asphaltenes can be found only in Crudes/Residues. Could these separated Asphaltenes precipitated out of the Condensates according to the PT Diagram? Rephrasing; could this support Mansoori's claim? Win: it seems that I always manage to drag you for deeper insights, will this one work?
Manfred Eigner
Owner, ME Consultancy Services (MECS) and Oil & Energy Consultant
Hi Mike, During my active career with Shell we did excellent research into the phenomena of asphaltenes and what they actually are. Lately, I did some work for Maersk Angola for developing a new oil field offshore Angola comprising an extensive literature study. What resulted was rather disappointing in terms of availability of suitable asphaltene inhibitors. They are not available yet, mainly because the chemical industry does not look for suitable products. All what is available is based on suitable surfactants but non of them based on the principle properties of asphaltenes. Having said this, to find a solution will be difficult anyway: asphaltenes vary a lot in composition. I reckon that the industry discovered that as well and are now aiming at quantifying the phase behavior of asphaltenes under a variety of production conditions, even commingling. In that way may be operators will be able to manage troublefree production when asphaltenes are present. Sorry for the bleak picture, but these are the facts, unless the chemical industry will make a dedicated effort.
Manfred
Tom McCartney
Director of Chemical Development
Hello Mike. The work on asphaltene inhibitor and dispersants have been ongoing for a number of companies. Not to blow my own horn (but if I don't who will) we have an excellent dispersant product that is highly effective in suspension of asphaltenes. Check out Paratene S627 on my website paratene.com - we have a number of case studies you may find interesting available.
Humberto Miguel Mejía Pérez
New Business Development IOS Group / Independent BD + Technologist + Systems Thinker
Tom is it possible to send me infor on the Paratene S627, I cannot access the website.
Manfred- excellent insight.
By any chance do you have a particle size distributions of the asphaltenes?
Manfred Eigner
Owner, ME Consultancy Services (MECS) and Oil & Energy Consultant
Humberto, Particle size of asphaltenes is difficult to give. Their size depends very much of their state of flocculation, so their original size in crude oil is very much different from when the precipitate from crude oil. To overcome this problem we started to mimic actual field conditions in coreflow experiments. There were a few surprises, mainly in the area of plugging phenomena. Can you me tell what you need the size distribution for.
Cheers Manfred
Humberto Miguel Mejía Pérez
New Business Development IOS Group / Independent BD + Technologist + Systems Thinker
Thanks Manfred- I am designing a filtration device to capture the asphaltenes, I have powdered particle distribution of asphaltenes that are free of resid, however, I want to have the "real" particle size distribution of the asphaltenes + resid, in the clean up process I need to recover as much resid as I can and therefore a chemical that can take on this problem is highly desirable
Scott Lamb
Corrosion Inhibitor Chemical Manufacturer
Since we're blowing horns, I'll offer a subjective note: Lonza produces a chemical that when added to an asphaltene dispersant packages may significantly improve performance. Please do not hesitate to contact me if you have any interest: scott.lamb@lonza.com.Now, to be completely objective:Asphaltenes, as Manfred recognised, vary a lot in composition. Thus there is no One Magic Bullet, and there is no single, "excellent dispersant product," although I am sure that successful case studies can be offered for any one product. Because there are such varied physical and chemical characteristics among different sources of asphaltenes, the effective dispersent often must be chosen by trial and error. Even then, the test method may not quite match the application, and what will work in the lab may not be effective in the field. Much of the research into asphaltenes is not designed to create a perfect dispersant, but rather simply to determine how to analyze the particular asphaltene, how to test dispersants under more applicable conditions, and how to measure test results. For these reasons, the "dedicated effort" from the chemical industry is unlikely to arise until someone can actually identify the quantity and quality of the chemicals that are needed in asphaltene dispersants.
Manfred Eigner
Owner, ME Consultancy Services (MECS) and Oil & Energy Consultant
Dear Scott, I would like to comment on your remarks. Although I am convinced that you are doing your utmost in finding a suitable chemical solution for the apparent asphaltene deposition problem in the industry, it is the approach of the chemical industry that bothers me most. As we all know that the problem is caused mainly by the pressure reduction, hence change in molar volume of the solute, the method of identifying a suitable chemical solution of the problem is inadequate. May be your company is following a new testing method that mimics the actual pressure reduction of live crude oil better then the existing ones. In that case I am keen to find out and my comments are premature. In my reply to Humberto I was only reflecting my experience that goes back to 2010-2012. And the result of my literature study was not very favorable. I would be very pleased if you want to share with me what your company is doing in this field.
Regards Manfred
Scott Lamb
Corrosion Inhibitor Chemical Manufacturer
Dear Manfred, I agree with your assessment, but think that perhaps by "chemical industry" we mean different things: I mean chemical manufactures capable of producing large scale volumes of molecules. You might mean chemical service companies that cater to the oil industry. In the first case, unless a chemical molecule is specifically identified, and the market is well defined, then it is difficult to imagine investing resources to produce the chemical. This has been, and still appears to be the status quo, as each geologic formation seems to produce its own, unique asphaltene for which only a customized dispersant formulation seems effective for each application.
Prof. Dr. Hans-Jörg Oschmann
Prof. II Colloid and polymer chemistry at NTNU
Hello Mike, interesting you only found such low performance in the literature. From an application viewpoint I always found asphaltenes significantly less challenging than wax since the new chemistries developed over the last ten years have been more than sufficient to deal with all asphaltenes problems I have encountered (including such severe environments as asphaltenes precipitation in de-ethanizers. Some products perform better then others on specific crudes but there is a couple of chemistries which so far have always come out amongst the top three. So I have never seen it as an "unmet need" for the industry. However there is still room for improvement on the application side. F.I. the MIC of asphaltenes inhibitors is still higher then for comparable Scale Inhibitors impacting squeeze lifetime.
Prof. Dr. Hans-Jörg Oschmann
Prof. II Colloid and polymer chemistry at NTNU
@Humberto
If you are precipitating the asphaltenes + dry them to generate a powder you are very much moving away from the original colloidal system...
Manfred Eigner
Owner, ME Consultancy Services (MECS) and Oil & Energy Consultant
Dear professor Oschmann, It is good that the scientific world takes part in the discussions. I must point out that the chemical solutions offered to-day are not fully suitable. Especially not for offshore applications where we have to operate underwater completions, remotely operate valves etc., hence we can not accept a product that is will eliminate the problem of deposition for 60-70%. This is a no go as the deposition will take place and will hamper operation of underwater completions. In the field of scale inhibitors the world looks different as there are very effective products available. Moreover, there chemistry differs from what is being offered to counteract asphaltene precipitation.
Humberto Miguel Mejía Pérez
New Business Development IOS Group / Independent BD + Technologist + Systems Thinker
Dear Prof. Hans- Thanks for the note. Since Mike's post also inquires about asphaltene in general, I take the opportunity to interact with the Group in order to see if the conceptual design I am working on is valid. I am planning to deasphalt via mechanical filtration, the idea is not new, once the asphaltene flocs are trapped in the porous structure the idea is to see how to remove the resid content that binds to the asphaltene core in order to have recover as much resid as possible and mix with the DAO, this is where chemistry would come into play, I am considering Supercritical CO2 solvent extracting, ideally after that I would have "pure" asphaltenes granules trapped in the porrous stucture that I would oxidize to then afterward recover V and Ni from the water.
Mike Davis
Senior Technical Writer/Editor at OilfieldWiki.com
@Prof. Dr. Hans-Jörg Oschmann
The 60-70% reduction comes from experience as well. I agree, asphaltene is a little easier to treat than wax because wax inhibitor can also have poor performance, never 100%. asphaltene is also easier to dissolve than wax. A lot of times, asphaltene deposition is saved by high flow rate while wax doesn't benefit from it as much.
Prof. Dr. Hans-Jörg Oschmann
Prof. II Colloid and polymer chemistry at NTNU
Thanks Mike, I may have been lucky as I have a lot of cases where we had 100% efficiency (confirmed by monitoring/pigging inspection). All of them however are via continuous treatment below bubble point or early injection into incompatible crude (aliphatic condensate / black oil). Good point rgds the high flow rate / shear! This matches others experience as well and was one of the points brought up in the asphaltenes discussion at the recent SPE workshop on flow assurance in Norway (Tackling Tomorrow's Challenges 13 - 14 November 2013).
@Manfred - totally agree that 60-70% efficiency would be a killer for many subsea applications. That was why I was a bit surprised as many GoM projects rely on highly effective asphaltenes inhibition. Nobody can nowadays afford a "Prinos" asphaltenes disaster with wells blocking up quicker then you can look.
Prof. Dr. Hans-Jörg Oschmann
Prof. II Colloid and polymer chemistry at NTNU
Hi Humberto,
just to get this correct- do you want to focus primarily on the recovery of the metals? If yes you may be better of using iso-octane or similar medium mol. weight aliphatics as you will separate a lot of lower molecular weight colloids with the supercritical CO2. Also if you go with supercritical CO2 as opposed to liquid CO2 you will partially break down asphaltene agglomerates changing their properties.
Humberto Miguel Mejía Pérez
New Business Development IOS Group / Independent BD + Technologist + Systems Thinker
Thanks Prof Hans-
Actually v and Ni recovery is just an added bonus operation that has to be considered depending on the site economics.
The process would be run batch type
1- HO would cycle though a filtration media to capture the asphatenes.
2- Once asphaltenes are "trapped" a DAO (deasphalted oil) is obtained and removed.
3- The filtration media would be regenerated via SCCo2, other solvents to recover resid.
4- At this stage we should have solid asphaltene granules in the porous structure, that would be oxidized, if in water media the water would have the V and the Ni + other compunds such as S, etc.
Hope this helps
Win Robbins
Advanced Characterization - petroleum at Carmagen Engineering
Asphaltenes are not a compound or a class of compounds, they are an event cuased by solvent incompatibility. A solvent strength change can occur by pressure drop in the production tubing in the upstream or by blending with oils with different composition, i.e. both upstream and downstream. Asphaltene aggregation and precipitation causes problems in areas as diverse as emulsions in oil water separators/desalters, deposits & fouling in heat exchangers, poisoning& plugging hydroprocessing catalysts, and even creating hotspots in cokers. The "composition" and occurrence of asphaltenes has been studied extensively both academically and by the refining industry. Over my 30+ years working for Exxon, I followed processes have proposed for asphaltene and metals removal, including some of my own. In the past decade, more characterization has been achieved, but the problems remain.
Search the literature for papers by Mullins (Schlumberger) for discussions of size and pressure drop, Kilpatrick (Notre Dame) Rodgers (FSU-NationalHigh Field Magnet Lab) for compostion, Chapman (Rice) and Folger (U MIchigan) on phase behavior, Buckley(New Mexco Tech) and Jeff Creek (Chervon) on flow assurance, and Wiehe (Soluble Solutions) for discussion of solvent compatibility. All these individuals have been working closely with chemical service vendors in addressing asphaltene deposition. As Manfred has indicated, success is limited to specific cases because the "asphaltene event" can be induced by so many variables that there is no universal solution.
Manfred Eigner
Owner, ME Consultancy Services (MECS) and Oil & Energy Consultant
Thanks Win for your fine comments. They are 100% in line with my way of thinking about asphaltene deposition problems during oil production. There is no ideal solution and one has to look into each deposition problem separately. It may be possible to arrive at a solution for that particular case but the next problem may not fit. I hope you can agree to the new approach that people started to look into the phase behavior of native crude oil w.r.t. asphaltene solubility. By managing the phase behavior one may arrive at a more practical solution: how can we produce a life crude oil without initiating asphaltene precipitation or even deposition. Please note: I am using here two different physical phenomena on purpose: precipitation followed by deposition. Back in the eighties we were able to manage deposition thereby allowing precipitation (experience from wells in Kuwait). Mike was so kind to invite me to Oilfieldwiki to add some more practical information. I promised to do that, so watch the special page.
Win Robbins
Advanced Characterization - petroleum at Carmagen Engineering
Manfred,
A large number of excellent papers have been presented at the Petrophase conferences where many of the people I cited meet annually to discuss asphaltenes and other phase related problems. Meetings are annual; Petrophase 2014 will be in Galveston.
Growing agreement among attendees is that aggregation and adsorption are separate phenomena.
Ahmed Helmi
Adjunct Professor at Pharos University
Gents: Enjoyed very much the thoughts/insight in your discussion. I noticed mentioning the names of a few of the Biggies, EXXON & Shell, that some of you had been working in and faced/involved in the Asphaltenes' deposition problems. A thought came to my mind as I got to the last comment: If the Biggies have not yet met to set a joint R&D plan to find a universal solution to the Aspheltenes Deposition problems, why the prestigeous API has not done a Research Plan so far? I see the finding of a Universal Solution as lacking Management much more Technical capabilities. My students here in Egypt are used hearing me saying now and then a phrase: The Americans are the Pharoes of Petroleum Engineering as the Russians are the Masters of Petroleum Geochemistry. I am quite sure that America has more than needed of Technical capabilities to accomplish a Universal Solution for the Asphaltenes Deposition problems, just let someone/someauthority like the API take the role of Managing the needed Research. What do you think?
