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"[ABSTRAKIndustri bahan bakar bio berkembang dengan cepat sebagai konsekuensi dari naiknya harga minya dan meningkatnya kepedulian terhadapa perubahan iklim global. Produksi biodiesel dari transesterifikasi minyak nabati saat ini merupakan rute yang utama untuk menghasilkan bahan bakar nabati (BBN) untuk mesin diesel. Namun, biodiesel memiliki viskositas tinggi, titik kabaut dan tuang yang tinggi, emisi nitrogen oksida (NOx) yang lebih tinggi, densitas energi rendah dan keausan injektor/mesin tinggi. Beberapa rute telah dicoba untuk mengurangi viskositas, seperti blending minyak nabati dengan bahan bakar diesel, mikroemulsi dengan alkohol, pirolisis dan hidrodeoksigenasi (HDO). Solar terbarukan melalui HDO dapat dihasilkan dari beragam bahan baku minyak nabati seperti minyak sawit dan minyak jarak pagar tanpa mengorbankan kualitas bahan bakar. Reaksi pembentukan solar terbarukan melalui HDO minyak nabati melibatkan katalis untuk menurunkan energi aktivasi reaksi dan meningkatkan selektifitasnya. Jenis katalis yang digunakan didalam studi ini adalah katalis berbasi Pd dan berbasis NiMo yang disanggakan pada ZAL atau C. Metode microwave polyol process (MP) cocok untuk preparasi katalis berbasis Pd sedangkan metode rapid cooling (RC) cocok untuk preparasi katalis berbasis NiMo. HDO asam oleat sebagai senyawa model, minyak sawit dan minyak jarak pagar dilakukan pada suhu 375°C dan 400°C dengan tekanan H2 15 bar didalam reaktor autoclave 250 ml semibatch berpengaduk. Didalam HDO, katalis Pd/ZAL-1 selektif terhadap jalur dekarboksilasi sedangakan katalis NiMo/ZAL selektif terhadap jalur dekarboksilasi dan dekarbonilasi katalitik. Soalr terbarukan yang dihasilkan dari HDO memiliki densitas dan viskositas yang sesuai sesuai dan indeks setana yang lebih tinggi disertai dengan kesetaraan dalam kualitasnya dengan solar komersial turunan minyak bumi namun sedikit lebih rendah daripada solar terbarukan komersial (NExBTL®).;

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ABSTRACTThe biofuels industry is growing rapidly as a result of high petroleum prices and increasing concerns about global climate change. Biodiesel production from trans-esterification of vegetable oils is currently the primary route for production of diesel engine biofuels from vegetable oils. However, biodiesel still has higher viscosity, higher cloud point and pour point, higher nitrogen oxides (NOx) emissions, lower energy density, and higher injector/engine wear. Several routes have been tried for reducing this viscosity, such as diluted vegetable oil with diesel fuel, microemulsification with alcohols, pyrolysis and hydrodeoxygenation (HDO). Renewable diesel through HDO can be produced from many kind of vegetable oil feeed stock such as palm oil (edible oil) and jatropha curcas (non-edible oil)without compromising fuel quality. Forming reaction of renewable diesel through HDO vegetable oil involves catalyst to decrease the activation energy of the reaction and increase its selectivity. The type of catalyst used in this study is Pd and NiMo supported on ZAL or C. Microwave polyol method (MP) is suitable for preparation of Pd-based catalyst while rapid cooling method (RC) is suitable for preparation of NiMo-based catalyst. The HDO of oleic acid as model compound, palm oil and jatropha curcas oil were carried out at temperature of 375°C and 400°C with H2 pressure of 15 bar in a 250 mL semibatch stirred autoclave reactor. In HDO, Pd/ZAL-1 catalyst was selective to decarboxylation route while NiMo/ZAL was selective to decarboxylation and catalytic decarbonilation. Renewable diesel synthesized through HDO have suitable density and viscosity and quite high cetane index with similar in their quality with comercial diesel derived from crude oil but slightly lower than comercial renewable diesel (NExBTL®).;The biofuels industry is growing rapidly as a result of high petroleum prices and increasing concerns about global climate change. Biodiesel production from trans-esterification of vegetable oils is currently the primary route for production of diesel engine biofuels from vegetable oils. However, biodiesel still has higher viscosity, higher cloud point and pour point, higher nitrogen oxides (NOx) emissions, lower energy density, and higher injector/engine wear. Several routes have been tried for reducing this viscosity, such as diluted vegetable oil with diesel fuel, microemulsification with alcohols, pyrolysis and hydrodeoxygenation (HDO). Renewable diesel through HDO can be produced from many kind of vegetable oil feeed stock such as palm oil (edible oil) and jatropha curcas (non-edible oil)without compromising fuel quality. Forming reaction of renewable diesel through HDO vegetable oil involves catalyst to decrease the activation energy of the reaction and increase its selectivity. The type of catalyst used in this study is Pd and NiMo supported on ZAL or C. Microwave polyol method (MP) is suitable for preparation of Pd-based catalyst while rapid cooling method (RC) is suitable for preparation of NiMo-based catalyst. The HDO of oleic acid as model compound, palm oil and jatropha curcas oil were carried out at temperature of 375°C and 400°C with H2 pressure of 15 bar in a 250 mL semibatch stirred autoclave reactor. In HDO, Pd/ZAL-1 catalyst was selective to decarboxylation route while NiMo/ZAL was selective to decarboxylation and catalytic decarbonilation. Renewable diesel synthesized through HDO have suitable density and viscosity and quite high cetane index with similar in their quality with comercial diesel derived from crude oil but slightly lower than comercial renewable diesel (NExBTL®)., The biofuels industry is growing rapidly as a result of high petroleum prices and increasing concerns about global climate change. Biodiesel production from trans-esterification of vegetable oils is currently the primary route for production of diesel engine biofuels from vegetable oils. However, biodiesel still has higher viscosity, higher cloud point and pour point, higher nitrogen oxides (NOx) emissions, lower energy density, and higher injector/engine wear. Several routes have been tried for reducing this viscosity, such as diluted vegetable oil with diesel fuel, microemulsification with alcohols, pyrolysis and hydrodeoxygenation (HDO). Renewable diesel through HDO can be produced from many kind of vegetable oil feeed stock such as palm oil (edible oil) and jatropha curcas (non-edible oil)without compromising fuel quality. Forming reaction of renewable diesel through HDO vegetable oil involves catalyst to decrease the activation energy of the reaction and increase its selectivity. The type of catalyst used in this study is Pd and NiMo supported on ZAL or C. Microwave polyol method (MP) is suitable for preparation of Pd-based catalyst while rapid cooling method (RC) is suitable for preparation of NiMo-based catalyst. The HDO of oleic acid as model compound, palm oil and jatropha curcas oil were carried out at temperature of 375°C and 400°C with H2 pressure of 15 bar in a 250 mL semibatch stirred autoclave reactor. In HDO, Pd/ZAL-1 catalyst was selective to decarboxylation route while NiMo/ZAL was selective to decarboxylation and catalytic decarbonilation. Renewable diesel synthesized through HDO have suitable density and viscosity and quite high cetane index with similar in their quality with comercial diesel derived from crude oil but slightly lower than comercial renewable diesel (NExBTL®).]"

"Pengembangan bahan bakar yang berbasis renewable diesel saat ini mulai banyak dikembangkan sebagai solusi permasalahan bahan bakar nasional. Renewable Diesel merupakan hidrokarbon turunan dari minyak nabati yaitu minyak nyamplung (Calophyllum Inophyllum Oil) yang mengalami proses hidrodeoksigenasi. Untuk mendapatkan renewable diesel yang diinginkan, diperlukan sebuah katalis yang memiliki selektivitas yang tinggi terhadap reaksi hidrodeoksigenasi tersebut. Salah satu penyangga katalis yang cocok yaitu karbon aktif dan zeolit. Kedua katalis tersebut memiliki banyak kelebihan dibandingkan penyangga katalis lain yaitu sifat kristalinitas dan luas permukaan yang tinggi, serta ketersediaannya yang melimpah di Indonesia. Inti aktif yang digunakan pada penelitian ini yaitu logam nikel molibdenum. Sintesis nanokristal logam dilakukan dengan menggunakan metode modifikasi simple heating dengan pemanasan serta pendinginan yang cepat. Metode ini mampu menghasilkan ukuran kristal dalam bentuk nano dalam waktu yang cepat dan energi yang rendah. Dengan menggunakan kedua penyangga tersebut, didapatkan katalis yang memiliki aktivitas, selektifitas, dan stabilitas yang tinggi. Setelah katalis diaktivasi, sintesis renewable diesel dilakukan dalam reaktor hidrogenasi pada kondisi operasi 375 oC, 12 bar, dan 800 rpm selama 2,5 jam. Dari sintesis tersbut dihasilkan konversi sebesar 81,99%, selektivitas sebesar 84,54%.

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Nowadays, development of diesel fuel based on renewable feedstock is started as a solution of national energy problems. Renewable diesel is hydrocarbon derivative from hydrodeoxygenation reaction of non-edible vegetable oil which uses nyamplung oil (Calophyllum Inophyllum Oil). It has many oleic acids and seed productivities for renewable diesel synthesis. To obtain desired renewable diesel product, use of catalyst that has high selectivity with hydrodeoxygenation reaction is important. One of suitable support catalysts are activated carbon and zeolite. These catalysts has many advantages which are high crystallization, high surface area, and has very abundant availability in Indonesia. Active site which supported in this research is nickel molybdenum. The synthesis of metal nanocrystal was conducted by modification preparation from simple heating method which heating and cooling process run rapidly. This method can produce catalyst crystal with nano size, short time, and low energy. By using these catalysts, obtained high activity, selectivity, and stability. After catalysts activated, synthesis of renewable diesel performed in hydrogenation reactor at 375 oC, 12 bar, and 800 rpm for 2.5 hours. The result of conversion was 81.99% and selectivity was 84.54 %."

"Diesel terbarukan merupakan salah satu komoditas energi terbarukan yang marak dikembangkan karena karakteristik yang sangat mirip dengan petro diesel dan memiliki bilangan setana yang tinggi. Penelitian ini bertemakan eksperimen produksi diesel terbarukan dalam reaktor trickle bed dari minyak nabati yang diwakilkan oleh triolein. Mekanisme yang terjadi adalah penjenuhan ikatan rangkap, dilanjutkan dengan deoksigenasi selektif. Deoksigenasi selektif yang terjadi mencakup hidrodeoksigenasi sebagai reaksi utama, serta dekarbonilasi dan dekarboksilasi. Katalis yang digunakan adalah NiMo/Al2O3 dengan komposisi Ni 6,13% w/w, Mo 12,49% w/w, dan Al2O3 81,33% w/w. Eksperimen menggunakan reaktor berdiameter 2,01 cm dengan tinggi unggun katalis 24 cm. Reaktan cair (triolein) dan gas hidrogen direaksikan dengan kondisi operasi temperatur 272°C-327,5°C, dan tekanan 5 dan 15 bar. Produk cair dianalisis dengan GC-MS, GC-FID, dan Karl Fischer, sementara produk gas dengan GC-TCD. Setelah reaksi berlangsung, triolein sebagai bahan baku terkonversi menjadi banyak senyawa meliputi asam lemak, lemak alkohol, ester, hidrokarbon C17, hidrokarbon C18, monoolein, dan diolein. Profil spesi-spesi ini menggambarkan mekanisme reaksi. Kondisi terbaik dalam penelitian ini adalah 15 bar dan 313°C, dengan konversi 99,53%, yield diesel terbarukan 78,95%, selektivitas diesel terbarukan 383,62%, dan kemurnian 79,40%. Tren yang didapatkan menunjukkan semakin tinggi tekanan dan temperatur semakin bagus dan selektif reaksi yang berjalan.

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Renewable diesel is a renewable resource that is currently developed rapidly because it has similar characteristics with petro diesel and has high cetane number. This research involves renewable diesel production in trickle bed reactor from vegetable oil, represented by triolein. Mechanisms include double bond saturation and selective deoxygenation. Selective deoxygenation includes hydrodeoxygenation as main mechanism, decarbonylation, and decarboxylation. Catalyst NiMo/Al2O3 is being used with Ni 6,13% w/w, Mo 12,49% w/w, dan Al2O3 81,33% w/w. Reactor used has diameter of 2.01 cm and 24 cm of catalyst height. Liquid reactant (triolein) and hydrogen gas are reacted with operating condition: temperature 272°C-327,5°C and pressure 5 bar and 15 bar. Liquid product is analyzed using GC-FID, GC-MS, and Karl Fischer, while the gaseous product is analyzed using GC-TCD. After the reaction occurs, triolein as feed is converted into many compounds such as fatty acid, fatty alcohol, ester, C17 hydrocarbon, C18 hydrocarbon, monoolein, and diolein. Each species profile describes the reaction mechanism. Best condition for producing renewable diesel is at 15 bar and 313°C, with triolein conversion of 99.53%, renewable diesel yield of 78,95%, renewable diesel selectivity of 383,62%, and 79,40% purity. The trend shows better production of renewable diesel with increasing pressure and temperature."

"ABSTRAK

Green diesel merupakan bahan bakar nabati generasi kedua yang memiliki potensi untuk menjawab kebutuhan energi baik dalam negeri maupun dunia. Proses yang digunakan untuk memproduksi green diesel adalah hidrolisis sebagai pre-treatment dan hidrodeoksigenasi menggunakan katalis NiMo/Al2O3. Hidrolisis akan mengubah trigliserida pada bahan baku, yaitu minyak jelantah menjadi free fatty acid FFA yang selanjutnya dikonversi menjadi green diesel melalui hidrodeoksigenasi. Hidrolisis minyak jelantah dilakukan pada suhu 200oC dan tekanan 16 bar dengan rasio volume air dan minyak sebesar 1:1. Waktu reaksi divariasikan dari 1 hingga 3 jam. Kondisi operasi optimum hidrolisis, yaitu pada waktu 3 jam mampu menghasilkan FFA sebanyak 73,89 . Untuk proses hidrodeoksigenasi dilakukan variasi kondisi operasi, yaitu pada suhu 375oC dan tekanan 12 bar yang dapat menghasilkan green diesel dengan konversi 80,24 , selektivitas 53,37 , dan yield 19,26 , serta pada suhu 400oC dan 15 bar yang dapat menghasilkan green diesel dengan konversi 82,15 selektivitas 69,58 , dan yield 68,87 .

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ABSTRACT

Green diesel is a second generation of biofuel that has a potential to answer the energy needs either in Indonesia or in the world. The process used to produce green diesel are hydrolysis as a pre treatment and hydrodeoxygenation by using NiMo Al2O3 catalyst. Hydrolysis will change the triglycerides in the raw material, which is waste cooking oil into free fatty acid FFA and then converted into green diesel through hydrodeoxygenation. Hydrolysis of waste cooking oil carried out at temperature of 200oC and pressure of 16 with water and oil volume ratio of 1 1. Time is varied from 1 to 3 hours. The optimum condition of hydrolysis, which is at 3 hours can produce FFA as much as 73.89 . For hydrodeoxygenation, variations in operating condition used are 375oC with pressure of 12 bar that can produce green diesel with conversion of 80.24 , selectivity of 53.37 , and yield of 19.26 , also 400oC with pressure of 15 bar that can produce green diesel with conversion of 82.15 , selectivity of 69.58 , and yield of 68.87 . "

"Semakin tingginya kebutuhan BBM, dan semakin menurunnya cadangan minyak bumi untuk memenuhi kebutuhan tersebut, maka para peneliti akan berusaha untuk mencari alternatif bahan bakar lain. Salah satu solusi tersebut yaitu bahan bakar yang diproses dari minyak nabati yang merupakan sumber daya alam yang dapat diperbaharui. Pada penelitian ini, akan dibuat bahan bakar dari minyak nabati yang disebut dengan renewable diesel. Renewable diesel merupakan generasi kedua dari biofuel yang menggunakan minyak nabati. Bahan baku yang dipilih dalam penelitian ini yaitu minyak sawit. Renewable diesel ini diharapkan memiliki komposisi yang menyamai petroleum diesel, dan juga memiliki spesifikasi yang minimal sama dari petroleum diesel, tetapi di sisi lain juga memiliki keunggulan yaitu seperti angka setana yang lebih tinggi dan kandungan impurities yang lebih rendah. Adapun metode yang digunakan untuk mensintesis renewable diesel yaitu metode hidrodeoksigenasi dengan menggunakan katalis Pd/Zeolit dengan bahan baku minyak sawit. Pada reaksi hidrodeoksigenasi ini, kondisi operasi yang diberlakukan yaitu tekanan 9 bar, 12 bar, dan 15 bar dan variasi suhu operasi yang digunakan yaitu 375oC dan 400oC. Harapan yang ingin dicapai dari proses ini yaitu konversi setinggi-tingginya, angka setana yang lebih tinggi dari solar komersial, dan kandungan impurities serendah-rendahnya.

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Time by time, the demand for fuel is getting higher, while petroleum reserves is decreasing significantly, then the researchers will try to look for other alternative fuels. One best solution is processed fuel from vegetable oil which is a natural resource that can be renewed. In this study, the solution will be made from vegetable oil fuel called renewable diesel. Renewable diesel is a second generation of biofuels that use vegetable oil. Raw materials that are selected in this study, namely palm oil. Renewable diesel is expected to have an equal composition of petroleum diesel, and also have the same minimum specifications of petroleum diesel, but on the other hand also has the advantage of such a higher cetane number and lower content of impurities. The method used to synthesize the renewable diesel is hydrodeoxygenation method using the Pd/Zeolite catalyst with palm oil feedstock. In this hydrodeoxygenation reaction, the operating conditions are pressure of 9 bar, 12 bar, and 15 bar and operating temperature variations used are 375oC and 400oC. Hopefully the ressult achieved from this process is the conversion as high as possible, higher cetane number than commercial diesel, and the content of impurities as low as possible."

"Persediaan minyak bumi sebagai salah satu sumber bahan bakar tak terbarukan semakin menipis. Solusi untuk masalah cadangan minyak bumi yang menipis adalah pencarian sumber energi terbarukan, salah satu di antaranya adalah renewable diesel. Penelitian ini melakukan studi penggunaan model prediktif Analytical Semi Empirical Model(ASEM) dalam menggambarkan produksi renewable dieseldari hidrodeoksigenasi minyak nabati.Penelitian ini bertujuan menentukan kondisi suhu optimum dalam aspek ekonomis dan kualitas melalui simulasi model ASEM. Data penelitiandisimulasikan dengan perangkat lunak komputasi numerik menggunakan metode curve fitting.Hasil dari simulasi untuk suhu optimum memproduksi produk renewable dieselberkisar antara 292,5 °C - 337,6 °C. Dengan akurasi nilai R2 yang mendekati 1, berkisar antara 0,913 - 0,999 dan SSE yang mendekati 0, berkisar antara 3,078 - 10^-15, bergantung padajenis yang diinginkan.

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Petroleum oil reserve asone of the largest source of unrenewable fuel is decreasing in quantity. The solution is the search for a renewable energy source, sch as renewable diesel. This researchstudiesthe implementationof the predictive Analytical Semi Empirical Model (ASEM)in representing renewable diesel productkrom hydrodeoxygenation of vegetable oil.

This research aims for optimum temperature condition of each products through simulationofproducing renewable diesel in higher economical and quality aspect by using ASEM model simulation. Experimental secondary are simulated using Numerical Computation Software with curve fitting method.

The simulation result ofoptimum temperature condition to produce renewable dieselis 292,5 oC.With accuracy R2value is 0,913–0,999and SSE value is 3,078–10-15, depend on desirable product."

"Ketersediaan minyak bumi yang semakin menipis, harganya yang tidak stabil, dan potensi kerusakan lingkungan akibat pemakaian bahan bakar fosil mendorong pengembangan bahan bakar alternatif yang dapat menggantikan bahan bakar fosil, termasuk avtur. Bioavtur merupakan bahan bakar terbarukan yang memiliki karakteristik serupa dengan avtur. Bahan baku potensial untuk produksi bioavtur di Indonesia adalah minyak kelapa. Komposisi asam lemak dalam minyak kelapa sesuai dengan kisaran rantai atom karbon avtur. Selain itu, Indonesia juga merupakan negara dengan pangsa ekspor minyak kelapa terbesar kedua di dunia yang menunjukkan bahwa pemanfaatan minyak kelapa di Indonesia masih sangat minim.Pada penelitian ini, bioavtur disintesis dari minyak kelapa melalui reaksi hidrodeoksigenasi untuk mengonversi asam lemak menjadi hidrokarbon dengan menghilangkan oksigen. Katalis yang digunakan dalam reaksi ini adalah katalis NiMoP/Al2O3. Reaksi hidrodeoksigenasi dilakukan dengan variasi tekanan dan suhu, yaitu pada tekanan 10, 15, dan 20 bar, dan suhu 375, 385, dan 400°C. Reaksi dihentikan apabila telah mencapai kesetimbangan berdasarkan analisis produk gas dengan GC-TCD. Reaksi hidrodeoksigenasi pada suhu 375°C dan tekanan 10 bar mampu menghasilkan konversi sebesar 92,16%, hydrocarbon content sebesar 87,18%, serta selektivitas dan yielad bioavtur sebesar 79,36% dan 55,56%. Produk cair didistilasi untuk memperoleh produk fraksi avtur. Dari hasil uji densitas, viskositas, bilangan asam, nilai kalor, dan titik beku pada distilat bioavtur diperoleh nilai yang cukup baik.

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The increasing of scarce of petroleum availability, unstable prices, and potential environmental damage due to the use of fossil fuel encourage the development of alternative fuels that can replace fossil fuels, including jet fuel. Bio-jet fuel is a renewable fuel that has similar characteristics to jet fuel. The potential raw material for bio-jet fuel production in Indonesia is coconut oil. The composition of fatty acids in coconut oil corresponds to the range of carbon atomic chain of jet fuel. In addition, Indonesia is also the country with the second largest share of coconut oil exports in the world which shows that the use of coconut oil in Indonesia is very less.

In this study, bio-jet fuel was synthesized from coconut oil through hydrodeoxygenation reaction to convert fatty acids to hydrocarbons by removing oxygen. The catalyst used in this reaction was NiMoP/Al2O3 catalyst. The hydrodeoxygenation reaction was carried out with variations of pressure and temperature, at pressures of 10, 15, and 20 bar, and temperatures of 375, 385, and 400°C. The reaction was stopped if it had reached equilibrium based on GC-TCD analysis of gas product. The hydrodeoxygenation reaction at 375°C and 10 bar was able to produce high conversion (92.16%), much hydrocarbon content (87.18%), high selectivity and also yield of bio-jet fuel (79.36% and 55.56%). Liquid products were distilled to obtain avtur fraction products. From the results of the density, viscosity, acid number, heating value, and freezing point analysis of the bio-jet fuel distillate, good values were obtained."

"Upaya intens dilakukan oleh pemerintah Indonesia dalam mengatasi persoalan defisit kebutuhan diesel domestik dengan mewajibkan pencampuran biodiesel pada solar hingga 20 pada tahun 2016. Namun, biodiesel yang ada memiliki beberapa kekurangan diantaranya penggunaan minyak nabati pangan sebagai bahan baku produksi. Simulasi sintesis renewable diesel berbasis minyak nabati non-pangan dengan rute produksi hidrodeoksigenasi trigliserida langsung dibuat dengan simulator Unisim Design R 390.1 pada penelitian ini. Dari simulasi didapatkan kondisi operasi optimal untuk sintesis renewable diesel yaitu pada tekanan 30 bar dan suhu 320?-380?C, dengan konversi 71.50 , yield 45.5 , dan selektivitas 38.3 . Selain itu, diperoleh pula tiga jenis minyak nabati non-pangan yang sesuai untuk menjadi alternatif bahan baku pembuatan renewable diesel di Indonesia, yaitu minyak kosambi, minyak nyamplung, dan minyak kemiri sunan.

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Intense efforts is exerted by the Indonesian government in solving the domestic diesel demand deficit problem by obligating the mixing of biodiesel in diesel up to 20 on 2016. However, biodiesel has some disadvantages such as the use of edible oils as raw materials for production. Synthesis simulation of non edible vegetable oil based renewable diesel with direct triglyceride hydrodeoxigenation production route was made with Unisim Design R 390.1 simulator in this research. From the simulation, the optimum operating conditions for renewable diesel synthesis reached are 30 bar and temperature 320 380 C, with 71.50 conversion, 45.5 yield and 38.3 selectivity. In addition, three types of non food vegetable oils are also suitable to be an alternative raw material for making renewable diesel in Indonesia, namely kosambi oil, nyamplung oil, and siri kemiri oil."