CLoupD PoINt & CRUDE O1L WASHING By T.J.Gunner@ @ @) @ List OF CONTENTS INTRODUCTION WHAT Is CRUDE OIL? ‘THE PHYSICAL BEHAVIOUR OF CRUDE OIL, (A) The Physical Behaviour of Aromatic Crude Oils (B) _. The Physical Behaviour of Paraffinic Crude Oils (C) The Cloud Point Determination (@) The Practical Implications of the Cloud Point Determination ‘THE CRUDE OIL WASHING OF SLUDGE AND SOME PRACTICAL IMPLICATIONS (A) What is Sludge? (B) The Basics of Cnade Oil Washing Procedures (C) Crude Oil Washing of Sludges (2) The Theory and Background (®) An Altemative and Practical Programme CONCLUSIONS APPENDICES ‘THE “BONDI” TEST PROCEDURE TO ESTABLISH CLOUD POINT GLOossARY OF TERMS : APPROXIMATE DENSITIES OF SUBSTANCES WoRrKED EXAMPLES FOR FORMULAE 27 27 34 34 38 4 42 43 44 451 INTRODUCTION Crude Oil Washing (COW) of a crude oil carrier's cargo tanks is a requirement to comply with the International Pollution Regulations known as MARPOL. These. regulations mandate that a minimum of twenty five percent of every crude oil carrier's cargo tanks are washed in the prescribed manner every voyage for sludge control. Subject to the operational design of a particular vessel the extent of tanks to be washed may be increased in order to comply with the additional objectives of the procedure, namely to render sufficient cargo tanks clean enough (as defined by the regulations) to take the required/stipulated water ballast tonnage for the ensuing ballast voyage. It is a requirement of the MARPOL regulations that every crude oil cartier has onboard a reference manual, commonly referred to as the COW Manual, in order to guide the responsible tanker officer for the presoribed COW operation. This manual typically contains information in seventeen sections relating to:- (1) The Text of the Revised Specifications This section contains the complete text of the revised Specifications for the Design, Operation and Control of Crude Oil Washing Systems and the agreed interpretations of certain of the provisions of the revised Specifications. (2) Drawing of the Crude Oil Washing System This section contains line drawings showing: (2) crude oil washing lines and valves (b) cargo pumps, lines and valves (©) ballast systems (where fitted) (d) stripping systems (© position of tank washing machines (©) position of facilities for hand dipping and tank gauges @ __ inert gas deck distribution system @) Description of the crude oil washing system and operational and equipment parameters . This section contains a description of the cargo, ballast, washing and . stripping system and in addition specifies: (@) _ types of tank washing machines and their standpipe length inside the tanks (©) _ revolutions of the machines (©) methods of checking the operation of tank washing machines (@) minimum operation pressure for crude oil washing (©) maximum permitted oxygen level in cargo tanks (® duration of tank washing machine cycles (@) results of tests performed in accordance with paragraph 4.2.10 (b) of the revised Specifications and the method of computation 1@ © © o ® ® (10) ay ay (3) as) as) (16) ayn (®) method of preventing entry of oil/vapours into the engine room Dangers of and precautions against oil leakage ‘Use and control of Inert Gas Precautions against electrostatic hazards Personnel requirements (training and qualifications) Methods of communication during COW List of Crude Oils unsuitable for Crude Oil Washing Crude Oil Washing Checklists Approved methods and programmes for crude oil washing Typical crude oil wash programmes ‘The method of draining cargo tanks ‘The method and procedures for draining cargo pumps and lines, Typical procedures for ballasting and method of preventing hydrocarbon ~ vapour emissions Compliance procedures for regulation 9 of annex 1 of MARPOL 73/78 Inspections and maintenance of equipment Although this manual contains all the necessary information regarding the technical operation for the crude oil washing equipment and associated onboard systems, the information regarding the washing medium, namely the crude oil, is limited to that contained in section 9 of the manual. Typically this section will contain the following information: . "This section contains a list of crude oils unsuitable for crude oil washing.” The appropriate following sub-section is thereafler inserted depending upon the type of heating facility or its availability on board the specific vessel (2) — Fora Tanker not fitted with heating coils ‘This tanker is not fitted with heating coils in the cargo tanks and should not carry cargoes which will require to be heated for pumpability. 2@) Fora Tanker fitted with heating coils This tanker is fitted with heating coils in the cargo tanks and, subject to the limitations of the cargo heating system, can carry cargoes which require to be heated for pumpability. Attention is drawn to the difficulties which may be encountered with certain crude oils. During discharge of a heated cargo the crude oil washing of each tank scheduled for such operation should be carried out concurrently with the discharging of the particular tank in order to minimise the cooling down of the tank surfaces. Asa general guide to the suitability of an oil for crude oil washing on board this tanker, the following criteria should be used: (@) The viscosity of the oil at the discharging temperature should never exceed 600 cSt.; (b) The cargo should be discharged at a temperature which exceeds its Pour Point (temperature) by at least 10°C; and © All necessary precautions should be taken to prevent the washing oil from solidifying in the COW piping system. These criteria are for general guidance and should be used when other information is not available. ‘The following is an informative list of potentially difficult crude oils due to their high Pour Points or viscosity (the list should not be regarded as exhaustive): Amna Lagunillas Argjuna Lucina Boscan Maya Bu Attifel ‘Minas (Sumatra Heavy) Cabinda ‘Minas (Sumatra Light) Cinta Sarir Dui Shengli Gamba Tapis Jatibarang Tia Juana Pesado Labuan Tila Laguna Note: It should be clearly understood that crude oils found to be unsuitable for crude oil washing should not be carried in this tanker‘The foregoing information, as inserted in Crude Oil Wash Manuals, was developed in the early 1980s and remains currently unaltered. However, with time the many crude cils carried by sea have altered with respect to their behaviour and “new”, crude oils have entered the production and transportation market. Together with the foregoing greater and wider practical experience has been gained by tanker officers over the interim fifteen years for the handling, transportation and use of crude oils as a washing medium. It is therefore necessary to investigate and discuss the suitability of the current and limited advice as contained within a standard COW manual for application to standard or modified COW programmes for crude oils as currently transported. Central to all COW programmes is the cargo as the washing medium, namely crude oil, but crude oil is a generic name for a broad selection of varying liquids. Crude oils can range from the wax rich high Pour Point temperature to the aromatic high viscosity types. It can range in its Density from about 700 kg/m* to 980 kg/m’. Some crude oils contain large amounts of geseous/volatile components which may contain hydrogen sulphide whereas others contain little or no gaseous component. Therefore it is essential to understand the nature and behaviour of a crude oil prior to its use as a washing medium to adequately clean the tanks in which it was contained, VETTING INSPECTIONS An INTERTANKO Publication Provides a brief but comprehensive description of some of the present vetting systems, including information on companies’ vetting department addresses, telephone and fax numbers, contact persons, inspection particularities. Our information has been verified as correct by the vetting departments of the oil companies listed. . Price: USD 50 to Members and Association Members, USD 100 to all others.2 WHAT IS CRUDE OL? Crude Oil is @ naturally formed liquid/substance which is probably the most complex liquid carried by sea, The term “Crude Oil* loosely describes a vast number of varying types of liquids which form the basis of supply of all hydrocarbons required by society. ‘To the general population this substance is perceived to be the black sticky material found washed up on beaches or seen in media coverage of pollution incidents covering sea birds and mammals, In fact, such a perception is wrong as crude oil is a heterogeneous mixture of hundreds of differing hydrocarbon species, all in differing proportions depending upon the specific type of erude oil and even perhaps the unique shipment of the oil, In nature it is far from the black sticky substance (save for certain types of crude oil) as generally perceived and is normally a brown/black liquid whose viscosity is similar to that of water. ‘The Marine Pollution regulations (MARPOL) which include the requirements for crude oil washing of crude oil carriers define crude oil for the purposes of crude oil washing as:- “Crude oil means any liquid hydrocarbon mixture occurring naturally in the earth whether or not treated to render it suitable for transportation and includes, (@ __cnide oil from which certain distillate factions may have been removed; and (2) crude oil to which certain distillate fractions may have been added." In the primary definition the word "treated" is presumed to mean whether the crude oil has been prepared for transportation by stabilisation (the reduction of the dissolved gas content within the crude oil including the toxic hydrogen sulphide B05). Part (a) of the definition expands the number of liquids capable of being used for crude oil washing to those of "topped crude oils" (Le. partially refined crude oil) and, in the absolute extreme case, to a fuel oil (atmospheric residue from a crude oll distillation). The number of liquids is further expanded by the-explanation in Part (©) of the definition. This includes the possibility of spiked crude oils and, again in the extreme case reconstituted crude oils (RECON crude oil) as being termed crude oil for the purposes of crude oil washing. Crude Oil The basis of crude oil is a molecule of hydrocarbon. This general term is derived from the atoms within the numerous types of molecules within crude oil which are of hydrogen and carbon, Thus hydrocarbon. The basic molecular structure of hydrocarbon species within crude oil fall into two fypes, namely a chain like molecule and a ring like molecule, although there are 5variants to these structures. In Figure 1 the basic structures are shown but the main three types of structure are those of the Paraffins (sometimes referred to particularly by scientists’ as Alkanes), Aromatics (or Arenes) and the Naphthenes (or cyclo-paraffin), “ Fig. 1 Poratfins Olefins Nophthenes Aromatics Ay ow c c= go ¢ td [ coc c-ene oH AN, c Ye c-c-c-c c~c-cae if LA 5 ac c cbc c-cac-c oN ¢. TF ¢ c=c-c=c AN Qe Ne c-¢-c FFs Sev é SAS © AN | J ANA Fog %& SAAKA | SARAA| OARS ow Now COE | CLE | Nooo 1 bocd. ete ete An examination of Figure 1 shows how the basic molecules are "built upon" to create the numerous and varied hydrocarbon molecules that finally make up the mixture called crude oil, The final crude oil mixture with all of its individual molecules may be represented by the trace shown in Figure 2. Figure 2 shows a series of vertical lines or peaks in a trace obtained from an analytical instrument called a Gas Chromatograph. Each vertical line or peak Tepreserits an individual type of molecule and the comparative amount of the individual hydrocarbon is roughly represented by the height of the individual vertical lines or peaks, At the top of each major vertical line it is identified with a “C" and associated number. This signifies the number of carbon atoms within the specific molecule (see Figure 1). As the size of the molecule increases so does the molecule’s boiling point as signified in Figure 2. This point is particularly relevant when considering the preparation of the crude oil wash medium for use in the designed programme. Finally, it can be seen from Figure 2 that the individual hydrocarbon types may be grouped together to form well known products used in every day life such as “Gasoline” and "Yet FueV/Kerosene". The species ofhydrocarbons within the respective groups and their extent will be considered farther below when examining the suitability and action of a specific crude oil with its properties as a washing medium. Fig.2 gases Lp¢ | Nophtho & Gasoline Kerosene Diesel C-Cs Cr Ce Co Increasing boiling point ——> As stated above and within a typical crude oil wash manual there are some crude oils that have been identified as apparently not being suitable for carriage on certain tankers that are not equipped with heating coils in their cargo tanks or possibly as a medium for crude oil washing if the prescribed criteria can not be fullfilled (e. the temperature of the wash medium is not above the Pour Point Temperature plus the required 10°C). As the list of crude oil types quoted in Section 9 of your COW manual is stated not to be "exhaustive", thereby implying that other unidentified crude oils exist that could create a problem both for discharge and their use 2s a COW medium, it is necessary, given the foregoing knowledge of the basic structure of a crude oil, to investigate the physical behaviour of crude oils during their handling and transportation.3. THE PHYSICAL BEHAVIOUR OF CRUDE OIL As with all substances their physical state varies with the temperature of the substance which reflects the heat energy imparted into the substance or retained by it, The physical states ofa substance fall into three prime categories namely, Solid, Liquid and Gaseous/Vapour, In the case of crude cil as a heterogenous mixture its normal visual state is that of a liquid. However as explained above, crude oil as a mixture, contains numerous species of hydrocarbons which also will, if separated from the mixture, exhibit the same three phases with varying temperature. If a pure individual hydrocarbon specie were to be studied, then precise temperatures may be ascertained for the formation of each of the relevant phases. However, by mixing the numerous hydrocarbon types together to generate such a complex micture as to be found in a crude oil, the determination of the behaviour of the overall mixture and the interaction of the various hydrocarbon species upon each other becomes very ‘complicated and beyond the primary objectives of this publication. Therefore, this publication will not attempt to describe such behaviour in detail but will concentrate upon that behaviour that would affect their transportation criteria and subsequent use as a crude oil washing medium. Before exploring the relevant behaviour of crude oil it is worthwhile defining the broad types of crude oils that are carried by sea Classification of crude oil allows three broad categories to be defined namely, paraffinic, aromatic and intermediate. By defining the paraffinic and aromatic types, the intermediate type can be placed in a category between these two "extreme" categories, A paraffinic crude oil is a crude whose sub-species show a greater preponderance of paraffins. In practical terms these crude oils are those with higher Pour Point temperatures, such as for example Bu Attifel and Sarir as quoted in Section 9 of the COW manual. The higher Pour Point temperatures for these crude oils is caused by the abundance of paraffinic wax contained within the crude oil. These types of crude oils are therefore temperature sensitive in order to prevent "solidification" during transportation and for pumpability which accounts for the stipulated criteria within Section 9 of the crude oil Wash Manual for the Pour Point Temperature plus 10°C to prevent such occurrences. Aromatic Crude oils are those with the higher kinematic viscosity characteristics, for example Boscan and Tia Juana Pesado crude oils as quoted in Section 9 of the” COW Manual. Given the pumpability/nandling criteria of 600 oSt as quoted in Section 9 of the COW Manual these crude oils are also temperature sensitive such that upon discharge the kinematic viscosity of the crude oil should not exceed the viscosity criterion as quoted. Indeed for optimum pumping, given the operational criteria for a typical centrifugal pump, the temperature of the crude oil cargo should be such that its viscosity is preferably lower than 250 cSt. These types of crude oils do not exhibit the same scope of difficulties for transportation and handling/COW 8as do the parafiinic types due to the phase separation characteristics of a paraffinic: crude oil. (A) The Physical Behaviour of Aromatic Crude Oils ‘An aromatic crude oil contains the relevant hydrocarbon species that would create all the three phases referred to above. The gascous and liquid phases are readily detectable within a cargo but its partially solidified phase is less noticeable. An aromatic crude oil's true Pour Point temperature (the near "solidification" temperature) is difficult to accurately ascertain but given that such oils contain litle or no paraffinic wax species, such a marked temperature determination is normally Jow and may vary significantly depending upon the analyst. Why should this be so? As stated above, an aromatic crude oil is temperature dependant due to its larger kinematic viscosity parameter when compared with 2 paraffinic crude oil. As viscosity varies with temperature (log linear variation) with the cooling of this species of crude oil the viscosity of the oil increases. The Pour Point temperature determination is made when the oil is observed to cease to move within the testing apparatus. Such a determination for an aromatic crude oil will be observed when its kinematic viscosity slowly becomes so large that movement within the test sample is not detected. This scenario is very different to that for the ascertainment of the Pour Point temperature of a paralinic oil due to the crystallisation of its waxes. At an aromatic crude oil's Pour Point temperature the oil still remains as a fairly homogenous heterogeneous mixture with no observable phase separation. This phase separation factor distinguishes the two species of oil for their transportation and heating criteria and subsequent uses for crude oil washing together with associated difficulties. This factor will be discussed further below when other physical properties of erude oils are considered. However, there is one thesis that suggests that an aromatic crude oil will always have a suspended solidified phase at all normal transportation temperatures. This phase is constructed from the high melting point temperature poly-cyclic aromatic species within the liquid such as the asphaltenes. Evidence of the existence of this phase is rarely seen when transporting aromatic crude oils but can readily be seen when the phenomena of incompatibility occurs. This phenomena is more closely associated with blended fuel oils and creates a significant deposition of highly viscous sludge in the bottom of the storage tank. (B) ‘The Physical Behaviour of Paraffinic Crude Oils Phase Separation and their Temperature Criterion The phase that creates the greatest difficulty for crude oil washing is that of paraffinic sludge (sometimes erroneously referred to as "sediments" when they are 9not but do resemble foreign matter). Sludge is the partially solidified hydrocarbon deposits from a crude oil which also has entrapped within its complex structure a variety of hydrocarbon species fiom the crude oil as a liquid phase. Predominantly, the structure of sludge is a selection of the various wax species as contained within a paraffinic crude oil cargo and once occurred it is nearly impossible, given the normal facilities on board a tanker, to retum the phase separated material to its original homogenous phase within the oil's liquid phase, Asa result of the examination of the behaviour of numerous paraffinic crude oils it ‘was noted that, given certain circumstances, extensive sludge/residues separated from the crude oil which would, under normal circumstances, remain onboard tankers after a discharge and the mandatory (or charter party specified) crude oil washing of the vessel's tanks. Some of these crude oils, for example Gulf of Suez” mix, Flotta, Iranian Heavy, Iranian Light, Kuwait Export Blend (on occasions and subject to the blend), were not traditionally expected to behave in such a manner. Samples of the residues from actual circumstances/discharges were obtained for physical examination and analysis together with numerous samples of a wider selection of crude oils. This enabled a preliminary investigation to be undertaken to gain a greater understanding of the behaviour/effectiveness of the crude oil as a medium for a crude oil washing programme to meet the primary and mandatory objective of obtaining clean tanks for ballast and sludge control of cargo spaces (especially for Segregated Ballast Tankers). It also had a consequence for cargo Joss control and the maximising of the discharge of the relevant crude oil cargo for the benefit of the cargo owner, ‘The quest of this enquiry was essentially to identify the critical temperature at which a specific crude oil will begin to precipitate these sludge forming hydrocarbon species as noted onboard the various vessels; to determine/model the extent of the likely deposition for comparison with the observed/measured volumes onboard the various vessels and, as a result of understanding the behaviour of the sludge, to determine the likely effectiveness of crude oil washing and develop suitable methods for the removal of the sludge by crude oil washing, : The deposits/sludges were examined to determine their flow/pumpability properties under differing conditions and dilutions so that the effectiveness of COW could be established for their removal. The relevant temperature as ideritified for the phase separation/sludge deposition phenomena has been termed as the Cloud Point temperature but alternatively referred to as the Wax Appearance temperature. (©) The Cloud Point Determination ‘The Cloud Point temperature may be defined as the temperature at which an oil's waxes change fiom their liquid phase and become a suspended quasi solid particle, associated with its oils, within the bulk of the remaining liquid thereby creating a phase separation within the cargo. This temperature has traditionally been obtained for transparent oils (Gas oil) by visual examination of samples subjected to a 10cooling programme and the identification of the cloud or haze of precipitated wax crystals at the critical sample temperature. It is to be noted that this “new” and higher temperature critetion is the start of the phase separation, whereas the traditional Pour Point temperature criterion is the “completion” temperature for the phase separation ~ Clearly, as a policy decision it is more important to determine the temperature for the start of such a phase separation than consider the temperature for the “completion” of the separation. This is particularly important due to the statement above that once phase separation has occurred on a tanker the vessel will not normally have the facilities or heating capacity to reliquify the partially solidified phase. ‘The visual technique as stated above could not be utilised for crude oils due to their opalescence, Therefore, two alternative methods were tested for their accuracy for the determination of the critical temperature at which the phase separation was observed to occur. Due to the impact of this phenomena for the sludging of vessel's tanks and the associated difficulties for crude oil washing, it was also important to be able to find or develop a technique that could easily be undertaken onboard a tanker by vessel's officers without the supply of expensive and specialist equipment, The first method investigated utilised the physical behaviour of an oil during a controlled cooling programme. The first of the methods relies upon the detection Of the oil's stable temperature transition through its latent heat loss to partial "solidification" Fig. 3 BONDI TEST PLOT =e (erie deg} Timeie Minutes LlAn examination of Figure 3 shows a plot of temperature (drop) of a sample of oil against time. At two positions along the temperature gradient no apparent temperature loss is observed. However, heat loss (energy) will be occurring at these positions which is termed “Latent Heat". It is these positions that determine the phase transition from liquid to solid for the wax species within the oil sample. The highest temperature “plateau is the Cloud Point Temperature of the sample, {approximately 59°C ) with the lowest being the Pour Point Temperature (approximately 43°C). Although this method was seen to supply reasonable indications of the critical Cloud Point temperature for high Pour Point temperature/wax content opaque hydrocarbons, the overall results for all of the crude oils tested did not meet the accuracy criterion of the investigation (4 3°C of the equivalent observed Cloud Point temperature). However for high wax content/Pour Point temperature crude cil, which would show distinct/clear phase separation temperature criterion as in the example shown for Figure 3, the test may be suitable and certainly useable on board tankers. For advice as to the specific test procedure that could be undertaken on board a tanker please refer to Appendix 1 herewith, ‘The second method, <4 subsequently the sciected technique, relies upon the potential non linear (logarithmic) increase in the kinematic viscosity of the crude oil with decreased temperature caused by the precipitation of the wax/sludge phase. This method sounds very complicated but in fact relies upon a basic dynamic. physical parameter of a liquid which is well known to most vessels’ Chief Engineers. However, before this procedure could be relied upon to supply accurate and reliable temperature results (within the investigation criterion as stated above), correlated results had to be obtained utilising the traditional visual test procedure for a series of transparent oils with varying paraffinic wax contents, This was deemed necessary due to the unknown affects and induced inaccuracies of the physical behaviour of the oils for Kinematic viscosity determinations obtained at or below the wax precipitation (Cloud Point) temperatures, The guiding test method used, namely the standard kinematic viscosity test method used in all oil laboratories, states that the method “includes the determination of Kinematic viscosity of fire oils which often exhibit" non linear physical behaviour. The log (Kinematic viscosity) plots for the series of transparent liquids is shown as Figure 4. 12