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Rizki E. 1,2 , Evita Emaniatin P. R. 1 , Zarrah Duniani 1 & R. Sutontro 1 1 PT Pertamina (Persero), Research & Development - Refining Directorate Jl. Raya Bekasi KM20, Pulogadung, East Jakarta 13920 - Indonesia 2 [email protected] Introduction The use of alternative, sustainable resources of energy for the transportation sector has been increasing as a consequence of the concern over limited fossil fuel resources and global warming from CO 2 emissions. Nowadays the main biodiesel fuel product are FAME (Fatty Acid Methyl Ester) derived from palm oil. This type of fuel have some disadvantages which limit its use in an unmodified diesel engine. Indonesia is one of the biggest palm oil producer and exporter. Realizing this fact, Pertamina has started to develop a process to convert vegetable oil into biodiesel. The process function is to remove oxygen to transform renewable organic material into pure hydrocarbon (n-parafin), which is basically the same component as those present in fossil derived diesel fuel, eliminating all limitation related to FAME. Isomerization step is required to further enhance the cold properties of the fuel produced, which is critical in an engine cold start up in cold climate countries, by transforming some of the n-parafin into iso-parafin. This process has a promising future to be easily integrated into an existing refinery infrastructure. Methods Using two hydroprocessing pilot plant which incorporate hydroteating and hydroisomerization catalyst, we were able to produce biodiesel from crude palm oil. Liquid product are checked with capilary column gas chromatography with FID detector and confirmed that it consist of parafin molecules. Gas product are checked with packed column GC Refinery Gas Analyzer. Hydrotreating catalyst are Ni-Mo based with gamma alumina support which composition are checked using X-Ray Fluorescence. Surface area tested to be 207 m 2 /g, pore volume 0.38 cc/g, and Average pore diameter 73 Å. All testing are done according to ASTM D3663, D4222 and D4641 respectively. Hydroisomerization catalyst are Pt based catalyst. Hydrotreating is run at 330ºC, 30 Kg/cm 2 pressure, and LHSV of 1 H -1 and H 2 /HC 1000 nm 3 /m 3 , while hydroisomerization is run at 360ºC, 5 Kg/cm 2 , LHSV 2.6 H -1 , and H 2 /HC 11.54 nm 3 /m 3 . GREEN INNOVATIONS Biodiesel Production by Hydrotreating & Hydroisomerization RESEARCH & DEVELOPMENT GREEN INNOVATIONS Product & Fe eed Characteriza ation Crude Palm Oil Hydrotreating Product Isomerization Product Fossil Diesel Specification Lauric acid %wt 0.247 Miristic acid %wt 1.316 Palmitic acid %wt 23.115 Stearic acid %wt 1.56 Oleic acid %wt 65.335 Linoleic acid %wt 4.117 Sulfur content %wt 0.05 (max) Distillation T90 ºC 301.27* 297.67* 340 (max) Distillation T95 ºC 299.64* 295.74* 360 (max) Final Boiling Point ºC 324.68* 323.1* 370 (max) Pour Point ºC 18 -9 18 (max) Density kg/m 3 904 778 758 820-860 *calculated from simdis D2887 H 2 triglyceride hydrogenated triglyceride diglyceride monoa cylglycerol fa3y acid light alkane nparaffin isoparaffin isomeriza8on H 2 hydrogena8on dehydra8on H 2 O C 3 H 8 H 2 decarboxyla8on decarbonyla8on H 2 CO 2 CO polymeriza8on Wax cracking Chiller Chiller HPS HPS Flow control Flow control N 2 N 2 H 2 H 2 Booster Gas Chromatography WTM WTM Feed CPO HBD End Product Vent Vent Comp. Sulfiding line Sulfiding line Reactor 1 Reactor 2 Scrubber Scrubber Dryer Dryer LPS LPS Ope erating Condition Hydrotreating Hydroisomerization Temperature ºC 330 360 Pressure kg/cm 2 30 5 LHSV H -1 1 2.6 H 2 /HC nm 3 /m 3 1000 11.54 Loading Density g/L 750 680 Hydroprocessing Pilot Plant Reactions C Catalyst C Characterization n Catalyst Support Hydrotreating Catalyst Surface Area mm 2 /g 260.2 207 Pore Volume cc/g 0.56 0.38 Avg. Pore Diameter Å 85.68 73 Crushing Strength Kg Conf. Diameter mm 2.03 - 2.07 2.03 - 2.07 Attrition Loss %wt 0.0408 - 0.0422 Ni content %wt Conf. Mo content %wt Conf. Si content %wt Conf. P content %wt Conf. Yield Hydrotreating Isomerization Liquid product Hydrocarbon %wt 75.26 85.34 Water %wt 9.47 Gas C6+ %wt 0.08 Methane %wt 0.03 Ethane %wt 0.14 0.07 Propane %wt 2.52 7.73 n-Butane %wt 4.05 n-Pentane %wt 1.15 CO 2 %wt 2.27

Symposium Catalyst Poster

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Poster explaining hydrotreated biodiesel process.

Text of Symposium Catalyst Poster

  • Rizki E.1,2, Evita Emaniatin P. R.1, Zarrah Duniani1 & R. Sutontro1

    1PT Pertamina (Persero), Research & Development - Refining DirectorateJl. Raya Bekasi KM20, Pulogadung, East Jakarta13920 - [email protected]

    IntroductionThe use of alternative, sustainable resources of energy for the transportation sector has been increasing as a consequence of the concern over limited fossil fuel resources and global warming from CO2 emissions. Nowadays the main biodiesel fuel product are FAME (Fatty Acid Methyl Ester) derived from palm oil. This type of fuel have some disadvantages which limit its use in an unmodified diesel engine. Indonesia is one of the biggest palm oil producer and exporter. Realizing this fact, Pertamina has started to develop a process to convert vegetable oil into biodiesel. The process function is to remove oxygen to transform renewable organic material into pure hydrocarbon (n-parafin), which is basically the same component as those present in fossil derived diesel fuel, eliminating all limitation related to FAME. Isomerization step is required to further enhance the cold properties of the fuel produced, which is critical in an engine cold start up in cold climate countries, by transforming some of the n-parafin into iso-parafin. This process has a promising future to be easily integrated into an existing refinery infrastructure.

    MethodsUsing two hydroprocessing pilot plant which incorporate hydroteating and hydroisomerization catalyst, we were able to produce biodiesel from crude palm oil. Liquid product are checked with capilary column gas chromatography with FID detector and confirmed that it consist of parafin molecules. Gas product are checked with packed column GC Refinery Gas Analyzer.

    Hydrotreating catalyst are Ni-Mo based with gamma alumina support which composition are checked using X-Ray Fluorescence. Surface area tested to be 207 m2/g, pore volume 0.38 cc/g, and Average pore diameter 73 . All testing are done according to ASTM D3663, D4222 and D4641 respectively. Hydroisomerization catalyst are Pt based catalyst. Hydrotreating is run at 330C, 30 Kg/cm2 pressure, and LHSV of 1 H-1 and H2/HC 1000 nm3/m3, while hydroisomerization is run at 360C, 5 Kg/cm2, LHSV 2.6 H-1, and H2/HC 11.54 nm3/m3.

    GREEN INNOVATIONS

    Biodiesel Production by Hydrotreating & Hydroisomerization

    RESEARCH & DEVELOPMENT

    GREENINNOVATIONS

    Product & Feed CharacterizationProduct & Feed CharacterizationProduct & Feed CharacterizationProduct & Feed CharacterizationProduct & Feed CharacterizationProduct & Feed Characterization

    Crude Palm Oil

    Hydrotreating Product

    Isomerization Product

    Fossil Diesel Specification

    Lauric acid %wt 0.247

    Miristic acid %wt 1.316

    Palmitic acid %wt 23.115

    Stearic acid %wt 1.56

    Oleic acid %wt 65.335

    Linoleic acid %wt 4.117

    Sulfur content %wt 0.05 (max)

    Distillation T90 C 301.27* 297.67* 340 (max)

    Distillation T95 C 299.64* 295.74* 360 (max)

    Final Boiling Point C 324.68* 323.1* 370 (max)

    Pour Point C 18 -9 18 (max)

    Density kg/m3 904 778 758 820-860

    *calculated from simdis D2887*calculated from simdis D2887*calculated from simdis D2887*calculated from simdis D2887*calculated from simdis D2887*calculated from simdis D2887

    H2

    triglyceride hydrogenated triglyceride

    diglyceridemonoa-

    cylglycerolfa3y acid

    light alkane

    n-paraffin iso-paraffin

    isomeriza8on

    H2

    hydrogena8ondehydra8on

    H2OC3H8H2

    decarboxyla8ondecarbonyla8on

    H2

    CO2CO

    polymeriza8on

    Wax

    cracking

    ChillerChiller

    HPSHPS

    Flow control

    Flow control N2

    N2

    H2 H2

    Booster

    Gas Chromatography

    WTM

    WTM

    Feed CPO

    HBD

    End Product

    Vent

    Vent

    Comp.

    Sulfiding line

    Sulfiding line

    Rea

    ctor

    1

    Rea

    ctor

    2

    Scru

    bber

    Scru

    bber

    Dry

    er

    Dry

    er

    LPS

    LPS

    Operating ConditionOperating ConditionOperating ConditionOperating Condition

    Hydrotreating Hydroisomerization

    Temperature C 330 360

    Pressure kg/cm2 30 5

    LHSV H-1 1 2.6

    H2/HC nm3/m3 1000 11.54

    Loading Density g/L 750 680

    Hydroprocessing Pilot Plant

    Reactions

    Catalyst CharacterizationCatalyst CharacterizationCatalyst CharacterizationCatalyst Characterization

    Catalyst Support

    Hydrotreating Catalyst

    Surface Area mm2/g 260.2 207

    Pore Volume cc/g 0.56 0.38

    Avg. Pore Diameter 85.68 73

    Crushing Strength Kg Conf.

    Diameter mm 2.03 - 2.07 2.03 - 2.07

    Attrition Loss %wt 0.0408 - 0.0422

    Ni content %wt Conf.

    Mo content %wt Conf.

    Si content %wt Conf.

    P content %wt Conf.

    YieldYieldYieldYield

    Hydrotreating Isomerization

    Liquid product

    Hydrocarbon %wt 75.26 85.34

    Water %wt 9.47

    Gas

    C6+ %wt 0.08

    Methane %wt 0.03

    Ethane %wt 0.14 0.07

    Propane %wt 2.52 7.73

    n-Butane %wt 4.05

    n-Pentane %wt 1.15

    CO2 %wt 2.27

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