Pour Point Depressants

Crude and Fuel Handling Today

In today’s competitive environment, with crudes and fuels moving quickly around the globe, the oil industry is forced to run processes more efficiently. Advances in oil and fuel handling, such as lowering the Pour Point, can help keep this products liquid during transportation and storage. This is especially valid for crude oil, diesel, heavy fuel oil, marine hybrid-fuels and biodiesel, although the characteristics of those oils require different and specialized products. New Marine Fuels come up with Pour Point limits and have to be brought into specification.

Clariant Refinery Services offers a broad range of Pour Point Depressants designed to meet the customer’s specifications in a variety of streams and applications like transport of crudes, heavy Oils, waxy components, heating oils and biodiesel or like Marine Diesel Blends. Through constant innovation and the use of the latest technologies, we can offer individual solutions which:

  • Bring products to specification
  • Improve transport and pumpability of products
  • Help to design new products out of single components
  • Help to optimize existing products

Clariant’s global presence and local expertise allows us to provide customer-specific solutions to overcome oil treatment challenges.

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  • Application Range

    • Crude and Heavy Fuel Oil

      Crudes and heavy fuel oils are complex mixtures of various hydrocarbons ranging from paraffins, aromatics, naphthenes, and resins to asphaltenes. Long chained paraffins tend to crystallize when cooled down, which leads to severe sedimentation. In pipelines this leads to a reduction in transported material, reduction of production and in worst case to a completely blocked pipeline with high costs for cleaning and wax removal.

      There are only three ways to prevent wax precipitation:

      1. Diluting the waxy material with light components, such as cutter stocks or condensates. In this case the profitability of the waxy crude is diluted in the same ratio at increasing operative complexity.
      2. Heating to temperatures above Wax Appearance Temperature. Operating and installation costs will be significant higher.
      3. Adding a PPD before the material has cooled down. This will improve the cold flow behavior including lower Pour Points and prevents operational problems. No sedimentation takes place, pipeline and storage specifications can be met. Calculations show that this is the cheapest way to ensure steady flow.

      Typical products used here are DODIFLOW 5236 or DODIFLOW 5723-1C.

      PPDs, which are liquid at ambient temperature, can be used in areas, where handling at lower temperatures gives advantages or where heating is problematic. Examples are ex-protected zones, terminals or areas with limited access to steam and electricity.

      Product here would be DODIFLOW 8029.

    • Opportunity Crudes / Challenging Crudes

      Crudes are called Opportunity Crudes or Challenging Crudes if they combine some properties, which make them challenging for a refinery. They show a high Pour Point, high wax content, are mainly sweet and in most cases bought and sold on the spot market. Their lower costs and higher profitability in a refining process makes them more and more interesting.

      Before refining Opportunity Crudes they have to be treated to bring the Pour Points in pipeline and storage specifications. Clariant has developed Pour Point Depressant, which work very well at different places of the world since years. Dosages for opportunity crudes are between 100 and 200 ppm, additivation normally takes place directly when the warm crude is unloaded.

      Examples of some Opportunity Crudes used in different refineries are:

      Name Owner, Region PP (blank) PP (treated) WAT API
      Escravos Chevron, Nigeria -3 -12 24 33,7
      Okwori Addex, Nigeria 12 -6 18 38,0
      Skarv Blend BP, North Sea -12 -27 30 39,6
      Okono Eni, Nigeria 15 -12 21 40,6
      Yoho Exxon, Nigeria 15 -16 26 40,1
      Qua Iboe Exxon, Nigeria 10 -25 21 36,8
      Brent BP Exxon, North Sea 0 -24 -14 37,6
      Amenam Exxon, Elf, Nigeria 8 -30 23 39,0
      Norne Statoil; Norway 21 6 39 29,6
      Triton Exxon, UK -3 -18 -8 36,9

      Picture1: Properties of selected Opportunity Crudes

      Other crudes are probably already tested in one of our labs. Details can be given on request.

    • Fuels for Marine Applications, Marine Diesel, Hybrid-Fuels

      Recent limits for sulfur emissions have lead to Sulfur Emission Controlled Areas (SECA-zones), which are causing refiners and shipping industry to look at alternative fuels to comply with the new regulations.

      Marine fuels differ in many aspects from automotive fuels. In most cases the quality is much lower, ship engines are designed to accept different fuel grades with viscosities between 5 and 700 cSt and different pretreatment methods. In general these sulfur-rich residues or intermediates fuels are all less expensive than pure low sulfur distillates of DMA, DMB or DMC quality. Price reductions become the most pressing issues for shipping operators and refineries.

      To avoid a significant rise in fuel prices refineries are promoting or developing new blends combining heavy and light streams, which brings these Hybrid fuels into the focus of ship owners, who do not want or are not able to install expensive exhaust treatment equipment.

      These new marine diesel types have to be brought to Pour Point specification with PPDs. Clariant has followed this global emission reduction trend very early and developed a number of tailored additives for new types of ship diesel. Accordingly refiners can get help from experts and laboratories to combine their production streams to stable and marketable products meeting the new regulations.

      Typical products to treat Marine Fuels are DODIFLOW 6098 or DODIFLOW 6099. After reducing the Pour Point in these ship fuels it remains at the reduced position and does not show any reversion.

    • Crudes and Fuel Oils in Pipelines

      20% of all produced crudes today have high Pour Points and high wax levels. Most of them have to be transported by pipeline from bore hole to process plant, port storage or refinery. To overcome transportation problems different technologies are used:

      • Dilution with condensate or light components
      • Maintaining the crude oil temperature above its Pour point
      • Selection and use of suitable Pour Point Depressants

      For pipeline transport Clariant`s Pour Point Depressants are far more economical than other technologies. A selection of PPDs can be made in our laboraties and depends on the properties/behavior of the crude, the pipeline specification and individual/regional targets. Popular products are DODIFLOW 5236, DODIFLOW 8029 or DODIFLOW 4138X .

    • Diesel Fuels and Heating Oils

      Diesel fuels and heating oils contain lower molecular weight paraffins with carbon numbers up to approximately C30. Fuels within this range can differ significantly in cold flow properties. Diesel cuts coming from Coal to Liquid or Gas to Liquid procedures show higher Pour Points than diesel coming from raw oil distillation. Some Opportunity crudes lead to diesel cuts with high Pour Points. Specifications, like pipeline specifications and local requirements can make the use of PPDs necessary.

    • Biodiesel

      In the meanwhile there are different types of biodiesel on the market. Some contain fatty acid methyl esters made by trans-esterification of vegetable oils, cooking oils or animal fats with an alcohol producing fatty acid esters others contain hydrogenated systems out of biomass or Fischer-Tropsch similar Biomass to Liquid procedures.

      Biodiesel is used in standard diesel engines, as heating oil or as blend with petrodiesel. Blends of biodiesel and conventional hydrocarbon-based diesel are labeled with a B-factor in most part of the case. B20 means 20 % Biodiesel in petrodiesel. The higher this value is, the higher is the temperature, when waxes drop out. Pour Point Depressants are used for higher B-contents or when handling the pure substances, e.g. before blending or when transporting or storing pure biodiesel. B100 is also used in some engines but needs Pour Point and Cloud Point modifications.

      Clariant has developed specially designed biodiesel PPD’s, such as DODIFLOW 5603, to counteract these issues.


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  • Definitions, Measurements and Mechanism

    • Background

      Due to economic reasons, most refineries tend to use crude oils from a variety of sources. Depending on the origin of the crude and the conversion capabilities of the refinery that processed them, these fuels can differ significantly in their characteristics. Examples are wax and asphaltene content as well as API gravity. All of these have a significant impact on the physical properties and cold temperature behavior of the fuel.

    • Pour Point

      Cooling down a sample of crude or residual fuel causes the formation of wax crystals, which in turn causes the oil to gel. Pour point is the lowest temperature at which a fluid is can be pumped before solidifying.

      Standard test methods applied include ASTM D 97 / DIN ISO 3016 or ASTM D 5985.

    • API Gravity

      This is the American Petroleum Institute’s (API) inverted scale for denoting the “lightness” or “heaviness” of crude oils and other liquid hydrocarbons.

      Calibrated in API degrees (or degrees API) it is used universally to express the relative density of the oil.

      Crude oils with:

      • API° > 30 are termed light;
      • between 22° and 30°, medium;
      • below 22° as heavy and at
      • API°< 10, as extra heavy.

      Using the equation below, API° can be easily converted to specific gravity:

      Specific Gravity = 141.5 / (131.5 + API)

    • Wax Appearance Temperature (WAT)

      WAT is defined as the temperature at which the first wax crystals begin to form in heavy fuel oils and crudes. The WAT can be determined by various methods including DSC, cross- polarized light microscopy and viscosity.

    • Pour Point Depressants – Mode of Action

      Linear paraffins can form needle- or plate-like crystals which can agglomerate and create a three dimensional network solidifying the fuel. Pour Point Depressants act as a wax crystal modifier. Modification is achieved by nucleation, co-crystallization and anti-agglomeration, which results in reduction of the size and shape of wax crystals. Wax-crystals are not inhibited but modified in a way that they do not precipitate.

      RefineryServices_Pour_Point_Depressants_Brochure_PRINTER4 

      Picture 2: Crystal Modification of a wax by Pour Point Depressants

      In general PPDs consist of:

      1. Linear alkyl chains which can co-crystallize with the long chain paraffins in the oil
      2. A polar component which retards further wax crystal growth
      3. Very large polymer molecules which inhibit the formation of large wax crystals

      The performance of a Pour Point Depressant does not only depend on the concentration and distribution of linear n-paraffins, but is also influenced by Asphaltenes and other components.

      Clariant’s DODIFLOW® micro-dispersions as well as the liquid DODIFLOW®s feature excellent temperature handling characteristics for terminal applications, cold regions or EX-protected zones. DODIFLOW® additives also reduce the need to use expensive cutter stocks.

    • International Standards for Pour Point Determination

      ASTM D97

      Standard Test Method for Pour Point of Petroleum Products

      ISO 3016

      Petroleum products, Determination of pour point (EU)

      IP 15

      Petroleum products - Determination of pour point (US)

      GOST 20287

      Petroleum products, methods of test for flow point and pour point (GUS)

      ASTM D5853

      Standard Test Method for Pour Point of Crude Oils

      IP 441

      Determination of the pour point of crude petroleum

      ASTM D5949

      Standard Test Method for Pour Point of Petroleum Products (Automatic Pressure Pulsing Method) [Phase Tech 70Xi]

      ASTM D5950

      Standard Test Method for Pour Point of Petroleum Products (Automatic Tilt Method) [PAC CPP 5Gs]

      ASTM D5985

      Standard Test Method for Pour Point of Petroleum Products (Automatic Rotational Method) [PSL PPT 45150]

      ASTM D6892

      Standard Test Method for Pour Point of Petroleum Products (Robotic Tilt Method) [PAC HCP 852]

      ASTM D7346

      Standard Test Method for Pour Point of Petroleum Products (Automatic Pressure Differential Method) [PAC MPP 5 G2]


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  • Products

    • Clariant`s Pour Point Depressants

      We have developed a variety of DODIFLOW® Pour Point Depressant customized for specific applications. Please use the selection chart below to find the DODIFLOW® product which best suits your needs. Additional PPDs are available on request or after individual testwork in one of our laboratories.

      DODIFLOW®

      Medium/High API, Waxy

      Low API, Highly Waxy

      Low API, Highly Asphalthenic

      Heavy/Extreme Heavy Refinery Fuel Oils (PP > + 30˚C)

      Low Product PP

      Marine Diesel, Hybrid Fuel, Biofuel

      5603



       

       

       

      X

      4138 X

      X

      X

       

       

       

       

      5200

      X

      X

      X

       

       

       

      5200 MD

      X

      X

      X

       

      X

       

      5236

       

      X

      X

       

       

       

      5723-1c

       

       

      X

      X

       

       

      5773

      X

      X

       

       

       

       

      6087

       

       

       

       

       

      X

      6088

       

       

       

       

       

      XX

      8029

      X

       

      X

       

      XX

      X

      X = good

      XX = extraordinary

      Picture 3: Areas of application for Clariant`s Pour Point Depressants

      Clariant Pour Point Depressants enable customers to:

      • Treat discounted, high paraffin crudes & residual fluids
      • Reduce costs,associated with blending cutter stock with high paraffinic oils
      • Improve pipeline flexibility by allowing transportation of highly paraffinic oils without heating
      • Win flexibility by increasing No. of crude slates.
      • Reduce heating in fuel distribution system
      • Avoid removal costs of solidified paraffin waxes
      • Reduce pumping costs
      • Upgrade value of refinery residues / heavy fuels
      • Bring Marine Diesel, especially DMA and DMB to Pour-Point-specification
      • Use Biodiesel of all generations, even in higher concentration or pure.
    • Pour Point Depressants with improved handling properties

      Most Pour Point Depressants are solid or waxy at room temperature and have to be warmed up before used. The time effort and complexity to use a PPD increases. It is difficult to use heatable systems in special areas, like EX-zones or on board. Fluid PPDs at ambient temperature can solve the problem. The table below shows an example of a highly effective PPD, the DODIFLOW 8029, which will not be solid before -6 °C and remains pumpable down to this temperature region. Other system you can get on request.

      dodiflow 

      Picture 4 shows the DODIFLOW 8029 a

      To ensure that our customers are obtaining the most benefit from the additive, our service team offers a comprehensive analysis and characterization of the oil / oil blends. These include - but are not limited to - S.A.R.A., yield stress, rheological measurements etc. Based on the data received from these analyses, Clariant will select and recommend the best performing PPD for your needs.


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Disclaimer:
This information corresponds to the present state of our knowledge and is intended as a general description of our products and their possible applications. Clariant makes no warranties, express or implied, as to the information’s accuracy, adequacy, sufficiency or freedom from defect and assumes no liability in connection with any use of this information. Any user of this product is responsible for determining the suitability of Clariant’s products for its particular application. 


* Nothing included in this information waives any of Clariant’s General Terms and Conditions of Sale, which control unless it agrees otherwise in writing. Any existing intellectual/industrial property rights must be observed. Due to possible changes in our products and applicable national and international regulations and laws, the status of our products could change. Material Safety Data Sheets providing safety precautions, that should be observed when handling or storing Clariant products, are available upon request and are provided in compliance with applicable law. You should obtain and review the applicable Material Safety Data Sheet information before handling any of these products. For additional information, please contact Clariant.

* For sales to customers located within the United States and Canada the following applies in addition: No express or implied warranty is made of the merchantability, suitability, fitness for a particular purpose or otherwise of any product or service.

© Trademark of Clariant registered in many countries.
® 2013 Clariant International Ltd

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