Lattice Wax Structure

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    Pour-Point Depressant (Crystal Modifiers)PPDs are designed to be cost-effective method to improve cold-flow properties of crude and other fuel

    oils to remain primarily as a fluid (Wang et al. 1999).PPDs accomplish this task by modifying the size and

    shape of wax crystals and inhibit the formation of large wax crystal lattices (Wang et al. 1999).PPDs

    typically have three characteristics:

    1. A wax-like paraffinic part, typical mixture of linear alkyl chains of 14 to 25 carbon atoms long,

    which co-crystallizes with the oils wax-forming components (Wang et al. 1999)

    2. A polar component, to limit the degree of co-crystallization (Wang et al. 1999)

    3. Primarily consist of polymers, when attached to the wax crystal will sterically hinder growth of

    large crystals (Wang et al. 1999)

    Figure 1 PPD Chemical Structure (Hemant et al. 2008)

    Generally the polar component of the additive creates the barrier to the formation of the interlocking

    crystal wax network (Wang et al. 1999).As a result, the altered shape and smaller size of the wax crystals

    reduce the formation of the interlocking networks and reduces the pour point (Hemant et al. 2008).

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    Mechanism:

    The mechanism of prevention of agglomeration primarily involves the structure of the PPDs to disrupt

    the crystal habit of wax crystals (Hemant et al. 2008).The structure of PPDs primarily involved in this

    process are; the pendant chains to co-crystallize with the wax and the polar end groups which are

    responsible for disrupting the orthorhombic crystal structure into a compact pyramidal form (Hemant et

    al. 2008).This process is responsible to prevent the crystals from agglomerating and forming a gel-like

    structure to deposit on the pipeline surface (Hemant et al. 2008).

    Figure 2 PPD Inhibition mechanism of wax modification 2a) Chemical structure of wax 2b) Crystal shape

    of wax structure 2c) Crystal structure of growing wax lattice 2d) Polymeric Additive with wax-like

    components 2e) Co-crystallization of wax and PPD 2f) sterically hindered wax structure(Wang et al.

    1999)

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    Figure 3 Prevention Mechanism of Interlocking of Wax Crystals by polymer Additives through a)

    nucleating sites(brown) interaction to asphaltene and wax molecules (blue) b) Polar component of

    additive (green) hinder co-crystallization of asphaltenes and wax(Hemant et al. 2008)

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    Figure 4 Pictomicrographs of Waxes of KS and ND crude oils. A) KS crude without additive, B) KS crude

    with additive , C) ND crude without additive D) ND crude with additive (Hemant et al. 2008)

    The efficacy of the additive generally depends on the rheological properties on the crude oil(Hemant et

    al. 2008).As such crude containing comparable amount of asphaltenes may not react in the same

    manner as paraffin predominate crudes (Hemant et al. 2008). Asphaltenes in crude behaves as a natural

    PPD, and can hinder the growth the growth of wax crystals by attaching to the surface of the wax crystals

    (Herman et al. 2008). And as a result, by incorporating an additive into the crude can diminish the

    interaction between the additive and the wax crystals resulting in a poor performance of the PPD

    (Hermant et al. 2008). By the experimental data collected by hermant et al., a single PPD cannot

    effectively depress the pour point of all types of crudes (Hermant et al. 2008) (Wang et al. 1999).And as

    such, specifically tailored PPDs must be designed to match the crudes paraffin chain length and

    composition of the crude, to participate efficiently in the crystallization of wax crystals to depress the

    pour point (Wang et al. 1999).

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    Trichloroethylene -Xylene binary system :

    Xylene-based PPDs forms structures with segments which interact with the developing wax crystals to

    inhibit crystal formation (Bello et al. 2005).A specific xylene based PPD which exhibits a substantial

    effect as a pour-point depressant is trichloroethylene-xylene (TEX) binary system (Bello et al .2006).This

    additive utilizes one or more several postulated mechanisms, nucleation, adsorption, co-crystallization ()

    and improved wax solubility in the reduction of large wax crystals (Bello et al .2006).Trichloroethylene

    compound contains an ionic pair of electrons which facilitates greater adsorption of the inhibitor

    molecules onto the wax crystal networks and preventing the interlocking of the wax network (Bello et al.

    2005).

    TEX binary system has the ability to form a stable suspension in the crude oil which results in the

    inhibition of wax crystal formation in the parts per million ranges in comparison to the concentration of

    wax crystals (Bello et al. 2005).As a result this TEX additive has a greater application on various different

    crudes and a tremendous economic benefit in the inhibition of wax-crystal formation (Bello et al. 2006).

    Hemant PS, Kiranbala, Bharambe DP.2008.Performance Based Designing of Wax Crystal Growth

    Inhibitors. Energy & Fuels 22 (6):39303938.

    Wang SL, Flamberg A, Kikabhai T.1999.Select the Optimum Pour Point Depressant. Hydrocarbon

    Processing 78:2

    Bello OO, Fasesan SO,Teodoriu C, Reinicke KM.2006. An Evaluation of the Performance of Selected

    Wax Inhibitors on Paraffin Deposition of Nigerian Crude Oils. Petroleum Science and Technology 24:195-

    206.

    Bello OO, Ademodi BT, Akinyemi PO.2005. Xylene-based inhibitor solves crude oil wax problems in Niger

    Delta pipeline. Oil & Gas Journal.103:10-56.