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  _{I nternational Seminar on Sustainable Biomass Production and Utilization Challenges and Oppurtunities (I SOMASS) August, 3-4, 2009} Proceeding

  

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  _{I nternational Seminar on Sustainable Biomass Production and Utilization Challenges and Oppurtunities (I SOMASS) August, 3-4, 2009} Proceeding

  Preface

  Environmental issues and uncertainly in the future of fossil based energy sources have stimulated global interest in the development of alternative and renewable fuels. In this context, biomass has been identified as a promising resource because of it is abundantly available and convertible into different forms of bio-energy which suits various needs. In addition, bio-energy is acknowledged as environmental friendly because it produces less CO2. There is also a high potential benefits from C-sink for carbon trade in line with Kyoto protocol. However, during the past few years, several controversies have complicated bio-energy development. It has been implicated for exacerbating climate change rather than mitigating and also been cited as a major factor in rising food prices. Such different views reflect that in addition to technical issues, socio-economic issues should be taken into account in pursuing of bio-energy development.

  Recognizing the important roles of biomass, The University of Lampung placed biomass development as one of the priorities. In line with this commitment, currently The University of Lampung has established The Biomass Laboratory, under the management of Research Institution. This particular laboratory is devoted to biomass development in a board sense related to biomass utilization, including development of alternative energies. Further development is projected to up-grade this laboratory into A Centre of Excellent on Biomass Research in the next few years. As a part of development plan toward establishment of the centre, Lampung University and Yokohama National University are planning to collaboratively host international seminar on biomass utilization and management, in order to gain more insight on biomass utilization impacts on Green House Gas Emission (GHGE).

  The seminar is planned to be carried out to pursue the following three main goals (1) to improve knowledge and understanding of Indonesian scientists (participants) on the ongoing development of science and technology in the field of biomass, (2) to enhance the capacity of the participants in carrying out research on various aspects of biomass, and (3) to enhance understanding on the impacts of biomass utilizations and related issues of C-sink issues for carbon trade in line with Kyoto Protocol and Green House Effects due to CO2 emission.

  In this opportunity, on behalf of the Organizing Committee and The University of Lampung, I would like to thank all the participants for their presentation. I would like to extent our sincere thanks and highest appreciation to Yokohama National University for invaluable supports, including financial support for the seminar. Our appreciation also extent to the Government of the Province of Lampung, PT Gunung Madu Plantation, BNI 46, Directorate General of Higher Education Department of National Education, and many others for their supports.

  Proceeding _{I nternational Seminar on Sustainable Biomass Production and Utilization Challenges and Oppurtunities (I SOMASS) August, 3-4, 2009} Seminar Organization Organizing Committee:

• Chairman : Dr. Eng. Admi Syarif
• Vice Chairman : Ir. Zainal Abidin, M.Sc.
• Secretary : Wasinton Simanjuntak, Ph.D.
• Vice Secretary : Dr. Suripto Dwi Yuwono
• Treasurer : Dr. Irwan Ginting Suka, M.Sc.

  Scientific committee:

• Prof. Dr. Ir. Muhajir Utomo (Indonesia)
• Prof. Dr. Koichi Fujie (Japan)
• Prof. Dr. Nobuhiro Kaneko (Japan)
• Prof. Dr. Ryohei Kada (Japan)
• Prof. Dr. Michel Ritz (USA)*
• Prof. Dr. Ir. Jamalam Lumban Raja (Indonesia)
• Prof. Dr. Bustanul Arifin (Indonesia)
• Dr. John Hendri (Indonesia)
• Dr. Udin Hasanuddin (Indonesia)

  Seminar Committee:

• Dr. F.X. Susilo (Coordinator)
• Dr. Ainin Niswati
• Dr. Bartoven Vivit Nurdin

  Secretariat Committee:

• Yasir Wijaya, S.Si (Coordinator)
• Frensi Riastuti S.Sos
• Adiguna Setiawan

  _{I nternational Seminar on Sustainable Biomass Production and Utilization Challenges and Oppurtunities (I SOMASS) August, 3-4, 2009} Proceeding

  

PROCEEDING

International Seminar

  

ON SUSTAINABLE BIOMASS PRODUCTION AND UTILIZATION:

CHALLENGES AND OPPORTUNITIES

Editor:

  Prof. Muhajir Utomo (Indonesia) Prof. Jamalam Lumban Raja (Indonesia) Prof. Nobuhiro Kaneko (Japan) Prof. Ryohei Kada (Japan) Prof. Koichi Fujie (Japan) Prof. John Hendri (Indonesia) Dr. Udin Hasanuddin (Indonesia) Dr. Irwan Ginting Suka, M.Sc (Indonesia) Wasinton Simanjuntak, Ph.D (Indonesia) Dr. Darwin Pangaribuan (Indonesia) Dr. Suripto Dwi Yuwono (Indonesia) Ir. Zainal Abidin, M.Sc (Indonesia) Dr. Eng. Admi Syarif (Indonesia) Dr. F.X. Susilo (Indonesia)

Organizing Editor:

  Yasir Wijaya, S.Si

  

Proceeding of International Seminar :

August 2009 / Editor,

… [et al.].—Bandar

  John Hendri

  

Lampung : Lembaga Penelitian

Universitas Lampung, 2009.

viii +437 pg. ; 21 x 29,7 cm

ISBN 978-979-18755-7-8

  Published by :

LEMBAGA PENELITIAN UNIVERSITAS LAMPUNG

  Jl. Prof. Dr. Sumantri Brojonegoro no. 1 Gedungmeneng Bandarlampung 35145 Telp. (0721) 705173, 701609 ext. 136, 138,

  _{I nternational Seminar on Sustainable Biomass Production and Utilization Challenges and Oppurtunities (I SOMASS) August, 3-4, 2009} Proceeding

  Content: NO Name

  Title Page

  Sustainable Production of Tropical Biomass: Challenges and

Opportunities

  1 Muhajir Utomo _{1) 2)} 1-20

  Koichi FUJIE Naohiro GOTO Hirotsugu _{2) 3)} Materials and Energy Flow Analyses in Bio-Product Processing of Plantation

2 KAMAHARA Udin HASANUDIN

  21-27 Network Development of Research, Development and Application of National Innovation System of Science and Technology With Special Case on The Utilization of Oil Palm Biomass For Food, Feed, Fuel and

E. Gumbira-Sa’id Furniture Production

  3 29-39 Emerging Ecological Risks and Food Security Issues In Asia

  4 Ryohei KADA 40-48 Ecological Risk Management In Asian Viewpoints

  5 Hiroyuki Matsuda 49-56 Collaborative Program Among International Higher Education:

  Callenges and Opportunity of Student Mobility and Institutional Jamalam Lumbanraja Capacity Building

  6 57-70 _{1 2} Spectral Reflectance Characteristics of Forest Vegetation Using 7etm Landsat Satellite Data

  7 Syamsir Dewang , Samsu Arif 71-79

  Ainin Niswati, Dermiyati, Mas Achmad Succession of Soil Fauna During The Composting Process of Oil Palm

  Syamsul Arif and Sri Yusnaini Empty Fruit Bunch

  8 80-86 The Effects of Ethanol-Gasoline Blends on Performance of Modified

  Arya Wulung, Bambang Puguh , Slameto Four Stroke Si Engine

  9 87-94 Dual Fuel Engine Performance Using Biodiesel and Syn-Gas From

  Rice Husk Downdraft Gasification For Power Generation

  10 Bambang Sudarmanta 95-104 The Important Role of Asiatic Black Bear (Ursus Thibetanus) In The

  Seed Dispersal Process

  11 Bainah Sari Dewi 105-114

  v

  _{I nternational Seminar on Sustainable Biomass Production and Utilization Challenges and Oppurtunities (I SOMASS) August, 3-4, 2009} Proceeding

  1 ² Christine Wulandari , FX Susilo , Pitojo _{3 4} Status And Viability of Policy For Supporting Below Ground Biodiversity and Forest Biomass Sustainability In Indonesia

  12 Budiono and Sri Murwani 115-125 The Effect of Cultivar and Storage Temperature on Postharvest

  Characteristics of Tomato Fruits

  13 Donald Irving and Darwin H. Pangaribuan 126-134 Soil Fauna Succesion, Microbial Respiration and Microbial Biomass

  Dermiyati, Ainin Niswati, Sri Yusnaini and ₁ During The Composting Process of Bandar Lampung City Municipal Wastes

  14 M.A.Syamsul Arif 135-142 Chemical and Biological Treatments of Corn Cob To Improve The

  Erwanto, Muhtarudin, and Mucharomah Nutritional Content And In Vitro Digestibility As A Feed For Ruminant

  15 Prayuwidayati 143-149 Nutrient Content of Rice (Oryza Sativa L.) Herbage As Feed For

  Ruminants

  16 Farida Fathul 150-158 _{1 2} The Development Renewable Sugarcane Biomass Energy In Lampung

  17 Fitriani and Suripto Dwi Yuwono Province To Support The National Energy Sufficiency 159-169 Bba (Bagasse, Blotong, Ash) Affect The Diversity and Abundance Of Ita Fitriyana, Indriyati, F.X. Susilo Soil Arthropods In Sugarcane Plantation In Lampung, Indonesia

  18 170-177 Biomass and Carbon Sequestration Potential of Plantation Forest In

  West Kalimantan ( Case Study In Plantation Forest Pt. Finnantara Ganjar Oki Widhanarto Intiga)

  19 178-186

  Hendro Risdianto, Kevin Jonathan C., Yoke Evaluation of Crude Laccase Enzyme Performance At Pulp Bleaching Pre-Treatment Process

  20 Christine V.M., Tjandra Setiadi _{1 2 2} 187-196

  Komariah , Masateru SENGE , Kengo ITO , ₂ Soil Physical Properties Affected By Combinations of Soil Solarization

  21 John Tawiah ADOMAKO and Organic Amendment 197-209 Prospect of Canna (Canna Edulis Ker.) Rhizome as A Feedstock For Kumala Dewi Bioethanol Production

  22 ₁ 210-221

  Maria Transiska Mahvie Syahroh , Sri _{2 2 2} The Effect of Vermicompost Extract on The Growth and Nutrition Uptake of Caisim (Brassica Camprestris L-Spp.)

23 Yusnaini , Ainin Niswati , Dermiyati

  222-233

  vi

  _{I nternational Seminar on Sustainable Biomass Production and Utilization Challenges and Oppurtunities (I SOMASS) August, 3-4, 2009} Proceeding

  Effect of Amino Acid Restricted Supplementation In Rations Based on Sugarcane Forage Ammoniated on Production of Rumen Vollatil Muhtarudin, Liman, Ali Husni Fatty Acid, Rumen Ammonia, and Nutrient Digestibility on Cattle

  24 234-237 _{1) 1) 3),} Model Cdm of Mangrove Forest: an Estimation of Net

  Munandar , R.A.Suwignyo , Akihiro Nose _{2) 1} Co2 Fixation Capacity In Mangrove Forest By Using Sarno , and Sabaruddin

  25 Methods of Co2 Gas Exchange and Allometric Method 238-249 Production Surfactant Methyl Ester Sulfonate (Mes) of Jatropha Oil (Jatropha Curcas L.) With Temperature and Time Sulfonation,

  Rachmad Edison*, Sri Hidayati** Temperature Purification, and Concentration Methanol Settings

  26 250-263 _{1 2} Rice Husk Stove As An Effective Solution of Oil Crisis and Environmental

  27 Rahman , Azrul Sulaiman Karim Pohan Pollution Which Is Efficient and Economical 264-270 _{1,2* 1,3} An Alternative Utilization of Tropical Wood Sawdust As an Artificial Rizki Maharani , Yutaka Tamai , Yajima _{1,3 3} Soil Matrix: Effects of Different Mills on The Physical Properties of

  28 Takashi , Minoru Terazawa Sawdust 271-282

  Rudy Situmeang, R. Supryanto, Wasinton Nio/Lacro Catalyst For Converting Methane To Methanol

  29 Simanjuntak, and Joko Susilo _{1 2 2} ³ 283-292

  Rusdi Evizal , Tohari , Irfan D. Prijambada , _{2 2} Biomass Production of Shade-Grown Coffee Agroecosystems

  30 Jaka Widada , Donny Widianto 293-303 Changes in Organic – C, N, P And K in Vermicompost of

  31 Sri Yusnaini, Ainin Niswati, Dermiyati Biodegradable Organic Wastes 304-310 The Effects of Some Corn Purelines And Varieties on Rust (Puccinia

  32 S. Mujim and J. Prasetyo Polysora ) Severity and Yield of Corn (Zea Mays L.) 311-316 _{1 2} Production of Activated Carbon From Solid-Coffee Waste By Na2so4 Sutikno and Udin Hasanuddin Activation

  33 318-329 Utilization of Natural Solvent From Noni’s Fruit (Morinda Citrifolia)

  Sutrasno Kartohardjono and Andri Krestianto For Co2 Absorption Using Hollow Fiber Membrane Contactor

  34 330-338

  vii

• **Yulianto S. Nugroho; *Dwi Endah Lestari Characteristics of Biomass Pellet As Fuel

  Potential Utilization of Rice Husk Silica as an Alternative for Mineral- Derived Silica 396-403

  Potential of Coastal Region as a source Biomass in Lampung

Mangrove Center

447-454

  46 Yasir Wijaya, Asihing Kustanti, and Imam Akbar

  45 Wan Abbas Zakaria Economic Efficiency of Cassava (Manihot Esculenta) Farming In Terbanggi Besar Subdistrict of Central Lampung District 438-446

  The Effect of Salinity to The Growth and Yield of Tomatoes (Lycopersicon Esculentum Mill) on Hydrophonic System 429-437

  44 R.A. Bustomi Rosadi1), Diding Suhandy1), Ahmad Tusi1) and Teguh Wiyono2)

  Design of High Efficiency and Environmental Friendly Biomass Pellet Stove Using Heat Recovery Principle 415-428

  43 Dijan Supramono; *Widodo Wahyu Purwanto;

  404-414

  Electrochemical Pretreatment For Enhanced Production of Reducing Sugar From Fresh Cassava Starch to Improve Bioethanol Production Efficiency.

  42 Wasinton Simanjuntak, Irwan Ginting Suka, and Kamisah. D. Pandiangan.

  41 Irwan Ginting Suka, Wasinton Simanjuntak, and Kamisah D. Pandiangan

  40 Zainal Abidin Proftitability of Jatropha Farming to Support Desa Mandiri Energi (Village Self Reliance On Energy) In Lampung Province 387-395

  39 Yusuf Widodo and Arif Qisthon Optimalization of Utilizing Cassava Waste (Onggok) Through Biological Processing on Rumen Parameters by In Vitro Method 380-386

  38 Yusmiati ¹ , Udin Hasanudin ¹ Biogas Production From Tapioca Wastewater in Pilot Scale Bioreactor 370-379

  37 Yosef Manik Mass and Energy Balance of A Municipal Solid Waste Incinerator 363-369

  348-362

  36 Widodo Wahyu Purwanto; *Dijan Supramono;

  Contactor 339-347

  Utilization of Natural Solvent From Leaves of Noni (Morinda

Citrifolia ) in Co

₂ Absorption Through Hollow Fiber Membrane

  35 Sutrasno Kartohardjono and Muhammad Haikal Nur

  Proceeding _{I nternational Seminar on Sustainable Biomass Production and Utilization Challenges and Oppurtunities (I SOMASS) August, 3-4, 2009}

• **Yulianto S. Nugroho; *R. Febry Rizqiardihatno

  viii

  !" #$$% Horisawa, S., Sunagawa, M., Tamai, Y., Matsuoka, Y., Miura, T., Terazawa, M., 1999.

  Biodegradation of nonlignocellulosic substances II: physical and chemical properties of sawdust before and after use as artificial soil. Journal of Wood Science 45 (6), 492-497. Houghton, J.I., Burgess, J.E., Stephenson, T., 2002. Off-line particle size analysis of digested sludge. Water Resources 36, 4643-4647. Hwang, S.I., Lee, K.P., Lee, D.S., Powers, S.E., 2002. Models for estimating soil particle- size distributions. Soil Science Society of America Journal 66 (4), 1143-1150. Kitsui, T., Terazawa, M., 1999. Bio-Toilet environmentally-friendly toilets for the 21 century (dry closet using sawdust as an artificial soil matrix). In: Proceedings of international symposium of bio-recycling/composting. 6-8 september, Sapporo, Japan. Paulrud, S., Mattsson, J.E., Nillson, C., 2002. Particle and handling characteristics of wood fuel powder: effects of different mills. Fuel Processing Technology 76, 23-39. Rühlmann, J., Körschens, M., Graefe, J., 2006. A new approach to calculate the particle density of soils considering properties of the soil organic matter and the mineral matrix.

  Geoderma 130, 272-283. Terazawa, M., Horisawa, S., Tamai, Y., Yamashita, K., 1999. Biodegradation of

  Lignocellulosic substance I: System for complete degradation of garbage using sawdust and aerobic soil bacteria. Journal of Wood Science 45 (4), 354-358. Terazawa, M., 2003. Sawdust Saves Globe―Bioconversion of biomass wastes into multifunctional recyclates using sawdust as an artificial soil matrix―. In: Proceedings of the 1st International Symposium on Sustainable Sanitation, Nanjing, China (1), 9-12. The Ministry of Forestry Republic of Indonesia., 2007. Forestry Statistics of Indonesia year 2006. Jakarta, Indonesia. http://www.dephut.go.id/INFORMASI/STATISTIK/2006/IV24_06.pdf>. Zavala, M.A.L., Funamizu, N., Takakuwa, T., 2004. Modeling of aerobic biodegradation of feces using sawdust as a matrix. Water Resources 38 (5), 1327-1339

  

NiO/LaCrO Catalyst for converting methane to Methanol

3 Rudy Situmeang, R. Supryanto, Wasinton Simanjuntak, and Joko Susilo

  

Department of Chemistry, FMIPA University of Lampung, BandarLampung 35415

situmeangr@unila.ac.id

  !" #$$%

Abstract

  NiO/LaCrO ^{3 catalyst was prepared using citric acid method from its’ precursor of nitrates. The preparation}

steps consist of wet impregnation of varied percentages (b/b) NiO into LaCrO , evaporation and calcination.

₃ To examine its activity, the catalyst was used in CH ^{4 conversion experiment at different temperatures. The}

experimental results indicated the dependency of CH conversion on temperature, with the highest methanol

_{o -1}

₄

formation (176.05 L) was achieved at 100 C under Ar/CH (40/10, 50 mL min ) as a feed. Adding O gas

µ ^{4 2}

into feed increasing the methanol formation and the increment achieved 68%. X-ray diffraction examination

proved that its crystalline phases consist of NiO cubic structure in a bulk crystalline of LaCrO perovskite

₃

structure. Furthermore, increasing Ni content enlarging unit cell volume of catalyst. FTIR analysis appeared to

  _{Keywords : CH}

indicate that both the Lewis and Brønsted-Lowry acid sites were involved in the catalytic conversion of CH .

_{4 Conversion, NiO/LaCrO 3 activity, CH 3 OH formation, Lewis and Brønsted-Lowry acid properties 4}

1. Introduction

  Now days, air emission regulation has been applied a broadly across the nations, especially on activities resulting pollutant gases such as NO x , SO x , and CO x . In addition, source of fuel energy is limited for 20 – 30 years. Therefore, finding out the energy resource dealt with environment is really interesting and challenging (Bell et al., 2004, AtlanticBiomass@aol.com, www.acrion.com, and www.methanol.org ). One of alternative energy resources is biomass with its marvelous abundance. Biomass can be change simply to biogas by catalytic pyrolyse or microbial process. The main product of these processes is methane gas. Furthermore, methane gas is processed to methanol by these methods, first forming synthesis gas and then methanol or direct methane oxidation to oxygenates excluding the synthesis gas generating step. In the first method, including synthesis gas forming, unfortunately is a highly endothermic process, thus also expensive.

  In case of direct methane oxidation to oxygenates, many researchers are involved in over the world. For instances, HZSM-5 supported Fe and Na were considered to be active to methanol production both in intermediate and high temperatures (Michalkiewicz, 2004). In other research, one group reported that methane can be transformed into higher hydrocarbons or alcohol by using first row transitional metal oxides – containing ZSM-5

• catalyst . The reaction is happened via C

  5 ion formation (Han et al., 1994). Another group

  !" #$$%

  of research used water as a feed due to increase the methanol formation (Alptekin, et al., 2000).

  In this moment, we study the conversion of methane into methanol using LaCrO

  3 doped

  NiO. Here, we emphasize our study on how increasing Ni content into LaCrO can give a

  3

  synergic effect in directly partial oxidation of methane to methanol at low reaction temperature.

2. Experimental

  2.1. Catalysts Characterization o

  X-rays power diffraction pattern of NiO/LaCrO

  3 were recorded from 2 = 10 to 90 on a θ o

  Philips diffractometer Model PW 1710 using Cu K radiation at a step 0.02 . Electron

  α

  micrographs were obtained with Scanning Electron Microscope . To determine Lewis and BrØnsted – Lowry sites, catalysts were previously contacted to ammonia saturated vapor at ambient temperature, using FT-IR spectrophotometer.

  2.2. Catalysts Preparation

  Solid LaCrO

  3 was prepared by dissolving Cr(NO 3 ) 3 . 9 H

  2 O, and La(NO 3 ) 3 . 6 H

  2 O in citric

  solution. Then, these solutions (1:1) was mixed and evaporated until sol – gel solution

  o

  formed. Furthermore, this precursor was calcinated at 600 C for 6 hours (increased by 2

  o -1

  C min ). Solid formed was crushed into a fine grain. Catalyst LaCrO

  3 supported NiO were

  prepared by dissolving nickel nitrate solid in citric solution and then adding LaCrO

  3 solid

  with ratio 5 to 7% (NiO : LaCrO

  3 ). After solvent evaporated, sol – gel form was dried and calcinated as before. Solid NiO was also prepared as follow as mentioned above.

  2.3. Catalytic Measurements

  The reaction was carried out in the U – tube reactor containing catalyst. A schematic diagram of the experiment is shown in Fig. 1. Methane (1), oxygen (2), hydrogen (3), and Argon (4) were supplied from the gas cylinders equipped by micrometric valves (5). The

  !" #$$%

  mixing reagents were passed by valve (6) to the quartz reactor (7) of an inside diameter 12 mm. The catalyst bed was placed on quartz grains. The reactor was heated by furnace. The measurement and control of temperature was ensured by thermocouple and temperature regulator with a digital meter. The gas products are passed to dichloromethane solution as a

  

o

  trapper. The reaction was held at 100 – 250

  C. The contact time was carried out for 30 minutes. The composition of mixture products was analyzed chromatographically using a Varian apparatus equipped with mass spectrometer detector with argon as a carrier gas.

  1

  2

  4

  5

  3

  6

  7

  3 Figure 1. A schematic diagram of the experimental set up : Methane (1), oxygen or hydrogen (2), and

Argon (3) were supplied from the gas cylinders equipped by micrometric valves. The mixing

reagents were passed by valve to the quartz reactor (4) and catalyst is located on (5), furnace with

temperature program (6). The gas products was collected on trapper containing dichloromethane (7)

and gas plastic bag before analyzing.

3. Results and Discussion

3.1. Catalyst Characterizations

  In Figs. 2 and 3 XRD powder patterns of the prepared LaCrO

  3 , NiO and 6% NiO/LaCrO

  3

  catalysts are presented. All the patterns of prepared solids exhibit the typical lines for LaCrO

  3 , NiO and 6% NiO/LaCrO 3 solids respectively.

  !" #$$% o

  Figure 2. Diffractogram LaCrO

  3 and NiO calinated at 600 C and reduced by H 2 gas o

  In case of NiO/LaCrO solid, there are two lines at 2 = 44.5 and 62 which are the strong

  3 θ

  lines of Cubic NiO, JCPDF 47 – 1049. No evidence of any other phase besides LaCrO and

  3 NiO was found in all samples. For catalyst impregnated various NiO, the obtained line intensities and patterns are not depending on NiO content. _{800 b. u ni t) 500 600} 700 _{te ns In 300 as ( 400} ar _{it 200} 100 _{10 20 30 Sudut 2 / 40 50 o 60 70 80 90} θθθθ o

  Figure 3. Diffractogram 6% NiO/LaCrO

  3 calinated at 600 C and reduced by H 2 gas

  !" #$$%

  Further investigation using Rietveld program to 6%NiO/LaCrO solid, proved that its unit

  3

  cell change such as parameter a = 5,536Å , b=5,4794Å, dan c = 7,7941Å (goodness of

  2

  3

  fitting, χ = 1,306 and unit cell - volume = 236,426Å ) as shown on Figure 5 and Table 1 below. Increasing NiO content in LaCrO

  3 enlarging unit cell volume of NiO/LaCrO

  3 catalyst.

  Figure 5. XRD diffractogram 6% NiO/LaCrO

  3 calculated by Rietveld method

  Table 1. Unit cell Parameter of 5 – 7% NiO/LaCrO

  3 obtained by Rietveld method ₃ NiO/LaCrO ₃ ) a (Ǻ) b (Ǻ) c (Ǻ) Volum (Ǻ

  5% 5,5300 5,4867 7,7850 236,208 6% 5,5360 5,4794 7,7941 236,426 7% 5,5390 5,4800 7,7950 236,607

  Note: calculated cell volume, V = a x b x c because simple orthorhombic structure

  Fig. 6 shows the typical scanning electron microscopy (SEM) picture. The background homogeneity of LaCrO

  3 phase was covered partially distribution of NiO. Analysis of EDAX

  ZAF result showed that 6% NiO/LaCrO

  3 consists of 34.53% La atom, 34.05% Cr atom, and

  6,38% Ni atom. It implies that the solid of LaCrO3 doped 6% NiO has formed in an apropriate ratio.

  !" #$$%

  Figure 6. Electron micrograph 6% NiO/LaCrO

  3 those

  Gravimetric acidity of NiO/LaCrO

  3 increases if it is compared to of both NiO and

  LaCrO as shown on Figure 7 below. Quantitatively, acidity increment caused of NiO

  3

  addition to LaCrO

  3 is about 24%. Acidity distribution of brønsted-Lowry and Lewis sites respectively is further discussed.

  7 ) _-1

  6

  1

  5 t * ka

  4 g / ( ₃

  3 H N

  2 ol m

  1 m

  NiO LaCrO3 NiO/LaCrO3

  Figure 7. Gravimetric acidity of NiO, LaCrO

  3 , and 6% NiO/LaCrO 3 respectively

  !" #$$%

  Infra red spectra analysis of 6% NiO/LaCrO absorbed ammonia have done in order to

  

3

  knowing acid distribution on both brønsted-Lowry and Lewis sites . Vibration of –NH

  3 and

• –NH

  4 forms is referred BrØnsted-Lowry and Lewis acid sites respectively. This spectra is

• 1

  showed on Figure 8, scanned on the range 450 – 4000 cm . Wave number range of 3100 –

• 1
• 1

  3700 cm refers to stretching vibration and below 2500 cm is indicated to bending and rocking vibrations.

  Figure 8. FTIR spectra of 6% NiO/LaCrO

  3 treated ammonia for 24 hours

• Formation ammonium ion, –NH

  4 (BrØnsted-Lowry acid) is showed on wave number of

• 1

  1483,15 and 1409,12 cm , whereas coordinated species is referred to Lewis acid site and is

• 1
• 1

  showed on wave number of 1600 cm . Peak appeared at 606,66 dan 420,35 cm is referred respectively to O-Cr-O deformation and Cr-O stretching vibration (Zheng et al., 1999).

• 1

  However, peaks appeared on wave number 498; 488; dan 510 cm as a characteristic adsorption of NiO is not exist .

3.2. Methane oxidation

  In this experiment, the gas composition as a feed is Ar/CH

  4 (40/10) and temperature o

  reactions are 100, 150, 200, and 250

  C, respectively . As shown on Figure 9 below, the tendency of methanol formation is decreased as temperature increase. Since there was no oxygen supply from outside, the transformation is only occured by oxygen bulk involved.

  !" #$$%

  o

  o

  C, 2= 150

  o

  C, 3= 200

  

o

  C, 4= 250

  C) Furthermore, by adding O

  3

  2

  gas in the feed as Ar/CH

  4

  /O

  2

  (35/10/5), the methanol formation on the lowest reaction temperature, 100

  ( Label 1 = 100

  Figure 10. Methanol formation in various temperature reaction on 5 and 7% NiO/LaCrO

  20 ^{40 60 C 180 160 140 120 80 100 H H 3 O , m ic ro L} _{1 2 3 4 Temperature}

  C, 3= 200

  Figure 9. Methanol formation in various temperature reaction on 6% NiO/LaCrO

  3

  ( Label 1 = 100

  o

  C, 2= 150

  o

  o

  3 catalyst.

  C, 4= 250

  o

  C) The same pattern of tendency is also happened on LaCrO

  3 doped by 7% NiO as shown on

  Figure 10. However, the tendency on LaCrO

  3 doped by 5% NiO is the methanol formation

  increases as temperature reaction increases even though its quantity is lesser than that of 6% NiO/LaCrO

  o C is increased as shown in Figure 11 below.

  _250.00 !" #$$% _{-6 H , 1 L 150.00} 200.00 _{H C 3} O _{100.00 50.00}

  0.00 _{5%NiO 6%NiO 7%NiO LaC rO dope d 3} o

  Figure 11. Methanol formation under the feed of Ar/CH

  4 /O 2 (35/10/5) at 100 C

  In general, by adding O

  2 gas on the feed, the methanol formation is increased. In addition, as

  NiO quantity as dopant increases the methanol formation also increases. The biggest increment is happened on 7% NiO/LaCrO

  3 catalyst. The increment is almost achieved 68%.

  It means that oxygenous supply on transform CH

  4 gas into CH 3 OH is working.

  Conclusions

  Based on this experiment, we can conclude that the temperature reaction affect the formation of methanol from methane gas. In general, all catalyst of LaCrO

  3 doped NiO is

  active on this reaction. In the reaction under Ar/CH

  4 as a feed, the bulk oxygen of catalyst

  played a role on transforming methane gas into methanol. Increasing the Ni content in LaCrO

  

3 catalyst giving a negative effect to methane conversion. Furthermore, adding O

2 gas on the feed increasing methanol formation.

  Acknowledgements

  This research project was financially supported by The National Fundamental Research and Technology of Indonesia program under contract No. 030/RD/Intensif/PTK/II/2008. I

  !" #$$%

  would like to thank Andi Setiawan Ph.D for chromatography – mass spectroscopy data discussion.

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