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“Advanced Chemicals to Solve Petroleum Crude Oil Production and Transportation Problems” Professor Ayman M. Atta Chemistry department, college of science, king saud university [email protected]

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  • “Advanced Chemicals to Solve Petroleum Crude Oil Production and Transportation

    Problems”

    Professor Ayman M. Atta Chemistry department, college of science, king saud

    university [email protected]

  • 2015نهاية عام –( دوالر للبرميل)معدل تكلفة إنتاج برميل من النفط

    تكلفة اإلنتاج التشغيلية الدولةالتكاليف

    الرأسمالية

    إجمالي تكلفة إنتاج

    البرميل الواحد

    8.5 4.8 3.7 الكويت

    9.9 5.4 4.5 السعودية

    10.7 5.9 4.8 العراق

    11.3 6.0 5.3 عمان

    12.3 5.7 6.6 اإلمارات

    12.6 5.8 6.8 قطر

    12.6 5.7 6.9 إيران

    17.3 8.4 8.9 روسيا

    20.4 7.2 13.2 الجزائر

    23.5 13.9 9.6 فنزويال

    23.8 7.2 16.6 ليبيا

    27.8 11.5 16.3 كازاخستان

    29.0 10.7 18.3 المكسيك

    29.9 14.3 15.6 الصين

    31.5 15.3 16.2 نيجيريا

    35.3 19.8 15.5 كولومبيا

    35.4 16.6 18.8 أنجوال

    36.1 12.10 24.0 النرويج

    36.3 14.8 21.5 الواليات المتحدة األمريكية

    41.1 22.4 18.7 كندا

    48.8 31.5 17.3 البرازيل

    52.5 30.7 21.8 بريطانيا

    Rystad energy :المصدر

    2015نهاية عام –( دوالر للبرميل)معدل تكلفة إنتاج برميل من النفط

  • •Size of associative polymers compared with the permeability of the reservoir . •Association with oil •Absorption on the oil wetted parts •Very high variation viscosity against the salinity of the reservoir with possibility of plugging with salinity increment. •Very quick loss of viscosity by dilution. •Sensitivity to Calcium, Magnesium and precipitation . •Thermal stability. •Mechanical stability . •Dissolution problems . •Very high viscosities before dilution.

  • Exhibit high viscosities even at low polymer concentrations (0.2 wt%), which is an interesting feature in connection with enhanced oil recovery.

    The increased viscosity of the polymer solution will reduce the mobility ratio, and hence allow a greater volumetric swept efficiency.

    The role of the polymer in most IOR field applications is to increase the viscosity of the aqueous phase. This increase in viscosity can improve sweep efficiency during enhanced oil recovery processes.

  • Several different polymer systems have been suggested to be utilized in polymer flooding, such as:

    1.Polyacrylamides ,

    2.hydrophobically modified poly(vinyl alcohol),

    3. guar gums ,

    4.Xanthans,

    5.poly(acrylamide-styrene) copolymers ,

    6.polyacrylamide-sodium carboxymethyl cellulose graft polymer, as well as more complex polymers and mixtures of different polymers .

  • 1. Thermostable polymers which increase the stability of the polyacrylamides from 75°C to 90°C with new monomers .

    2. Associative polymers with a main polyacrylamide chain and statistic repartition of hydrophobic groups. There is an association of these hydrophobic groups in a specific brine to give a high viscosity

    3. Star polymers with 3 or more branches on a central polymer group. These polymers are normally associative to have a high viscosity

    4. Comb and T shape polymers with a main hydrophobic chain and end hydrophobic chain .

    5. Block associative polymers with multiple hydrophobic groups inside an hydrophylic chain.

    6. Structured polymers with hydrophilic branches in a main hydrophilic chain.

    7. Soft or Movable gels are totally insoluble yet injectable gels mainly used in profile modification but with high potential in EOR

  • Easy separation

    Very low vapor pressure

    Non-flammable substance

    High thermally stable

    High mechanically stable

    Electrochemically stable

    Low toxicity

    Non-volatility

    Ionic Liquids Advantage

    N

    R

    N NR1 R2

    * [PF6]- for moisture stable, water immiscible IL

    * [BF4]- for moisture stable, but water miscible IL

  • Synthesis and Assessment of Novel Water Soluble Poly (Ionic Liquids) Based on Quaternary AmmoniumAcrylamidomethyl Propane Sulfonate for Enhanced Oil

    Recovery Ayman M. Atta1,2* Abdulrahman A. AlQuraishi3, Hamad A. Allohedan 1 Mahmood M. S. Abdullah1 and Abdullah O. AlMansour3

    Journal of Molecular Liquids, Volume 233, May 2017, Pages 508-516

    Figure 9: Contact angle measurements between different aqueous

    seawater PIL concentrations and Berea rock.

    IFT measurements indicate that all PILs solutions promotes low IFT drop. The drop is not enough to mobilize trapped oil as drastic drop is needed to sufficiently decrease the capillary number.

    AMPSA/MAA provided the lowest contact angle. Zeta potential data confirm the wettability alteration towards more water wet condition.

    https://www.sciencedirect.com/science/journal/01677322

  • 0

    10

    20

    30

    40

    50

    60

    70

    80

    90

    0 10 20 30

    Re

    cob

    ery

    , %

    OO

    IP

    Pore volume injected

    Oil Recovery for Secondary

    Seawater and Tertiary

    PAMPSA/MAA flooding

    0

    20

    40

    60

    80

    100

    0 10 20 30

    Re

    cov

    ery

    , %

    OO

    IP

    Pore volume injection

    0.4 Slug PIL

    Contineous PIL

    ____ Secondary sea-Tertiary PIL

    ____Secondary continuous PIL

    ____ Secondary 0.4 PV PIL slug

    Pressure drop profile

    recorded during the

    runs conducted with

    PAMPSA/MAA.

    All measurements conducted indicate PIL solution adsorption to rock grain surfaces promoting wettability alteration as the main recovery mechanism .

    Multiple flooding runs in secondary and tertiary modes were conducted with AMPSA/MAA PIL solution. Clearly, recovery was improved with PIL solution and close recoveries were obtained in all flooding scenarios, however secondary flooding of 0.4 pore volume of PIL followed by continuous seawater was the most feasible since limited quantity is needed for the obtained ultimate recovery.

  • Nanomaterials

    First: The hydrophobic pore walls will be changed into hydrophilic due to nanoparticle adsorption, and consequently, The relative permeability of the oil phase increases, decreasing the resistance to oil flow, while at the same time, the relative permeability of the water phase decreases significantly.

  • Schematic injection concept

    Second, oil in the small pores will be displaced due to nanoparticle adsorption and wettability changes, and the effective pore diameters for oil flow in the porous medium may, in turn, be enlarged.

    if water is injected into a water-wet core sample, then water invades the rock and displaces the oil with a flat fluid front and is expected to arrive everywhere along the exit surface.

    Depending on the surface wettability, the arriving fluid (water) might then either emerge as a thin film and quickly spread over the grains of the wetting (waterwet) surface figure a. or emerge as individual droplets from the pores, repelled by the nonwetting (oil-wet) surface (Fig. 1b).

    a-b wetting fluid injection

    Non-wetting fluid Drainage

    C-d

  • Finally, the adsorption of nanoparticle on the porous surface and blocking of the small pore throats may lead to reduction in porosity and absolute permeability of the porous media.

    The first and second effects are favorable for improving oil recovery, but the last effect has an unfavorable effect on oil production due to decrease in absolute permeability.

  • Composition and method for enhanced oil recovery US patent 9850420(2017) Ayman Mohamamdy Atta, Mahmood Mohammed Abdullah, Hamad Abdulla Al-Lohedan

    (a)

    (b)

    Figure 3: TEM and DLS micrographs of a) CaCO3

    capped with 1g of AMPSA/VP and b) CaCO3 capped

    with 2 g of AMPSA/MAA PILs.

    https://patents.justia.com/patent/9850420https://patents.justia.com/patent/9850420

  • PIL Reactants Ratio

    PIL:nan

    oparticl

    es

    Nanopart

    icle

    Size

    (nm)

    PDI Zeta

    potent

    ial

    (mV)

    AMPSA/VP TiO2 2:1 43.0 0.326 -16.4

    AMPSA/VP ZrO2 2:1 98.1 0.349 -35.65

    AMPSA/VP CaCO3 2:1 151.1 0.415 -13.99

    AMPSA/VP Cu2O.Fe3O

    4

    2:1 239.0 1.289 -18.4

    AMPSA/M

    AA

    TiO2 2:1 58.9 0.248 -43.18

    AMPSA/M

    AA

    CaCO3 2:1 272.3 0.986 -22.72

    AMPSA/VP TiO2 1:1 30.7 0.203 -50.73

    AMPSA/VP CaCO3 1:1 64.2 0.323 -21.16

    Particle size and zeta potential results of

    nanoparticles

    Contact angles of oil droplet

    at limestone surface in the

    presence of sea water and

    5000 ppm of PILs.

  • Formation of Emulsions

  • Oil

    Water

    Oil

    W/O

    Water

    O/W

    Water

    Oil

    Water

    W/O/W

    Types of the crude oil water emulsions

  • Synthesis and Application of Poly (ionic liquid) Based on Cardanol as Demulsifier for Heavy Crude Oil Water Emulsions

    particle sizes of asphaltenes a) absence of PILs, b) QTECA and c) QDECA (asphaltene : PIL; 1:1 )in toluene/heptane solvent.

  • Synthesis of Dipoles Poly(ionic liquids)

    Based on 2-Acrylamido-2-Methylpropane

    Sulfonic Acid-co-Hydroxyethyl Methacrylate

    for Demulsification of Crude Oil Water

    Emulsions CH

    2=CH

    CONH

    CH3

    CH3

    CH2SO

    3H

    + CH2=C

    CH3

    COOCH2CH

    2OH

    + N

    (CH2)17

    CH3

    CH2CH

    2O-[CH

    2CH

    2O]

    5H

    CH2CH

    2O-[CH

    2CH

    2O]

    5H

    AIBN

    COOCH2CH

    2OH

    CONH

    n

    -CH2CH-CH

    2C-

    CH3

    CH3

    CH3

    CH2SO

    3 HN

    (CH2)17

    CH3

    CH2CH

    2O-[CH

    2CH

    2O]

    5H

    CH2CH

    2O-[CH

    2CH

    2O]

    5H

    +-

    COOCH2CH

    2OOCH

    2 PPh

    3 Br

    CONH

    n

    -CH2CH-CH

    2C-

    CH3

    CH3

    CH3

    CH2SO

    3 HN

    (CH2)17

    CH3

    CH2CH

    2O-[CH

    2CH

    2O]

    5H

    CH2CH

    2O-[CH

    2CH

    2O]

    5H

    +-

    + -

    AMPS-EOA / HEMA

    AMPS-EOA / HEMAP

    a)

    AMPSHEMA

    EOA

    CH2=C

    CH3

    COOCH2CH

    2OH

    b)BrCH

    2COCl

    (C2H

    5)3N

    CH2=C

    CH3

    COOCH2CH

    2OCOCH

    2Br

    AMPS

    ABINPh

    3P

    : Single-droplet protocol apparatus.

  • Synthesis and Application of

    Amphiphilic Ionic Liquid Based on

    Ethoxylated Octadecylammonium

    Tosylate As Demulsifier and Petroleum

    Crude Oil Spill Dispersant

    CH3(CH

    2)17

    NH2

    + ClCH2CH

    2OCH

    2CH

    2Cl + HO-[CH

    2CH

    2O-]

    4-H

    ODA DCDE TEG

    NaOH

    CH3(CH

    2)17

    N

    [CH2-CH

    2O-]

    6-H

    [CH2-CH

    2O-]

    6-H

    SO3H

    CH3

    PTSA

    [CH2-CH

    2O-]

    6-H

    [CH2-CH

    2O-]

    6-H

    +

    SO3CH3N(CH

    2)17

    CH3

    - Polarized optical microscope of dispersed oil

    droplet using HEOD-TS at different SOR a) 1:1,

    b)1:10, c) 1:25 and d) 1:100.

    Concentration

    s

    (ppm)

    Designation IFT (mN/m)

    90/10 70/30 50/50

    0 0 28 25 22

    100

    HEOD 18 17 10

    HEOD-TS 10 8 3

    250

    HEOD 15 13 8

    HEOD-TS 5 2 1.8

    500

    HEOD 10 8 5

    HEOD-TS 1.3 0.3 0.1

  • Synthesis and Application of New Poly

    (ionic liquids) Based on 1,3-

    Dialkylimidazolium as Demulsifiers for

    Heavy Petroleum Crude Oil Emulsions

    compounds

    Concentrations (mg/L)

    10/90 20/80 30/70

    %DE

    (%)

    Time (minute)

    %DE

    (%)

    Time

    (minute)

    %DE

    (%)

    Time (minute)

    EDHI

    50 0 - 30 120 35 120 100 12 120 60 120 50 120 250 35 120 70 120 65 120

    EPHIB

    50 10 120 35 120 50 120 100 25 120 50 120 60 120 250 40 120 85 120 70 120

    EDDI

    50 75 120 90 120 70 120 100 100 80 100 85 85 120 250 100 60 100 60 100 120

    EPDIB

    50 85 75 100 120 90 120 100 100 45 100 65 100 70 250 100 30 100 45 100 30

    RNH22 +

    OH

    CHO

    + HCO-COHCH

    3COOH

    WATER

    R = C7H

    15

    C12

    H25or

    N-R N-R

    OH

    +CH

    3COO

    -

    N-R N-R

    OH

    OH OHn

    +CH

    3COO

    -

    N

    NN

    N

    HMTA

    B(OH)2

    F3C O

    DCDE

    TEG

    N-R N-R

    O[CH2CH

    2O]

    5H

    OH OHn

    +CH

    3COO

    -

    HCHO

    NaOH

    N-R N-R

    OH

    *NH

    2 *n

    +

    -CH

    3COO

    +

    F3CPhBOH-O

    -

    N-R N-R

    O[CH2CH

    2O]

    5H

    *NH

    2 *n

    +

    -CH

    3COO

    +

    F3CPhBOH-O

    -

    DCDE

    TEG

    HBA

    GA

    Fluorescent

    optical

    microscope

    photo of crude

    oil/water

    emulsions in

    the presence of

    EPDIB.

  • Synthesis and Application of

    Amphiphilic Poly (Ionic Liquid) Dendron

    from Cashew Nut Shell Oil As Green

    Oilfield Chemicals for Heavy Petroleum

    Crude oil Emulsion OH

    OH

    H2SO4 conc.

    100 oCOH

    OH

    OH

    O

    +Cl

    ECH

    NaOH

    O

    O

    O

    CH2

    O CH2

    O

    CH2

    O

    H2NCH2CH2OH

    O

    O

    O

    CH2

    OH CH2

    OH

    CH2

    OH

    NHCH2CH2OH NHCH2CH2OH

    NHCH2CH2OH

    9 ClCH2CH20CH2CH2Cl

    9 HO

    OH

    418NaOH

    O

    O

    O

    CH2

    CH2

    O

    CH2

    ON

    O

    O

    H

    5

    O

    O H

    5

    H5

    O H

    6

    O H7

    NO H

    6

    O H

    7

    NO H

    6

    O H7

    TEG

    O

    O

    O

    CH2

    CH2

    O

    CH2

    ON

    O

    O

    H

    5

    O

    O H

    5

    H5

    O H

    6

    O H

    7

    NO H

    6

    O H

    7

    NO H

    6

    O H

    7

    H

    HH

    R R

    R

    +

    +

    R =

    NH

    SO3

    O

    PAMPS

  • Application of Hydrophobic Ionic

    Liquids as Asphaltene Dispersants for

    Heavy Crude Oil

    Ayman M. Atta1,2,* Abdelrhman O.

    Ezzat1 Mahmood M. Abdullah 1and

    Ahmed I. Hashem3

    N

    N

    CH3

    Cl

    +-

    AMC

    + KOHN

    N

    CH3+

    -OH

    COOH

    AbA

    N

    N

    CH3+

    OOC-

    AMA

    OH

    Cardanol

    OK

    KOH

    O-

    N

    N

    CH3

    Cl

    +-

    N

    N

    CH3+

    a)

    b)

    AMCO

  • Synthesis and Application of

    Amphiphilic Ionic Liquid Based on

    Acrylate Copolymers As Demulsifier

    and Oil Spill Dispersant CH

    3(CH

    2)17

    NH2 + ClCH2CH2OCH2CH2Cl + HO[-CH2CH2O-]4H

    NaOH

    CH3(CH

    2)17

    N

    CH2CH

    2O[-CH

    2CH

    2O]

    5H

    CH2CH

    2O[-CH

    2CH

    2O]

    5H

    CH2=CHCOOH

    CH2=CHCONH(CH

    3)2CCH

    2SO

    3H

    ODA DCDE TEG

    ODTE

    (AA)

    (AMPS

    AIBN

    Xyleene

    CH2 -CH - CH

    2-CH

    CONH(CH3)2CCH

    2SO

    3-COO-

    n

    NHH

    5[OCH

    2CH

    2]OCH

    2CH

    2

    CH3(CH

    2)17

    CH2CH

    2O[CH

    2CH

    2O]

    5H

    HN

    CH2CH

    2O[CH

    2CH

    2O]

    5H

    CH2CH

    2O[CH

    2CH

    2O]

    5H

    + +

    CH3(CH

    2)17

    AMPS/AA-TE

  • Superhydrophobic sand capped with silica/asphaltene nanoparticles for oil-spill cleanup and collector

  • Synthesis and Application of Monodisperse Hydrophobic Magnetite Nanoparticles Using

    Ionic Liquid as Oil Spill Collector Ayman M. Atta1,2,* Abdelrhman O. Ezzat1 and

    Ahmed I. Hashem, RSC Adv., 2017,7, 16524-16530

    F

    Oil

    collecti

    on

    sample

    CE % at different MOR

    1:10 1: 20 1:25 1:50

    Cycle 1 100 98 95 90

    Cycle 2 100 96 93 88

    Cycle 3 98 95 92 86

    Cycle 4 96 93 90 80

    Cycle 5 96 93 90 80

    Table 1: CE % of magnetite capped with AMO at

    different MOR.

    147.1◦