接触分解変換により菜種油からバイオ燃料および生化学の研究室の生産
Summary
本稿では、穏やかな温度で触媒の存在下で化石ベースのフィードと混合したキャノーラ油からのバイオ燃料とバイオケミカルを製造するための実験的な方法を提示します。反応器からの気体、液体、および固体の生成物を定量し、特徴付けられます。変換および個々の製品の収率が計算され、報告されています。
Abstract
The work is based on a reported study which investigates the processability of canola oil (bio-feed) in the presence of bitumen-derived heavy gas oil (HGO) for production of transportation fuels through a fluid catalytic cracking (FCC) route. Cracking experiments are performed with a fully automated reaction unit at a fixed weight hourly space velocity (WHSV) of 8 hr-1, 490-530 °C, and catalyst/oil ratios of 4-12 g/g. When a feed is in contact with catalyst in the fluid-bed reactor, cracking takes place generating gaseous, liquid, and solid products. The vapor produced is condensed and collected in a liquid receiver at -15 °C. The non-condensable effluent is first directed to a vessel and is sent, after homogenization, to an on-line gas chromatograph (GC) for refinery gas analysis. The coke deposited on the catalyst is determined in situ by burning the spent catalyst in air at high temperatures. Levels of CO2 are measured quantitatively via an infrared (IR) cell, and are converted to coke yield. Liquid samples in the receivers are analyzed by GC for simulated distillation to determine the amounts in different boiling ranges, i.e., IBP-221 °C (gasoline), 221-343 °C (light cycle oil), and 343 °C+ (heavy cycle oil). Cracking of a feed containing canola oil generates water, which appears at the bottom of a liquid receiver and on its inner wall. Recovery of water on the wall is achieved through washing with methanol followed by Karl Fischer titration for water content. Basic results reported include conversion (the portion of the feed converted to gas and liquid product with a boiling point below 221 °C, coke, and water, if present) and yields of dry gas (H2-C2‘s, CO, and CO2), liquefied petroleum gas (C3-C4), gasoline, light cycle oil, heavy cycle oil, coke, and water, if present.
Introduction
バイオマス由来の原料から輸送燃料を製造するための効率的かつ経済的な手段を見つけるために、民間部門と公共部門の両方で強力なグローバル関心があります。この関心は温室効果ガス（GHG）の排出と地球温暖化への関連寄与石油化石燃料の燃焼の実質的な貢献を超える一般的な懸念によって駆動されます。また、再生可能な国内の液体燃料と外国産石油を置換する北米やヨーロッパで強い政治的意志があります。 2008年には、バイオ燃料が世界の輸送燃料1の1.8％を提供しました。多くの先進国では、バイオ燃料が近い将来2に石油燃料の10％6％から置換することが必要です。カナダでは、規制が3。欧州における再生可能エネルギー指令（RED）は、欧州連合（EU）トランスのための10％の再生可能エネルギー目標を義務付けた2010年12月15日出発ガソリン中の5％の平均再生可能燃料のコンテンツを必要とします2020年4による港湾セクター。
課題は、バイオマスから代替可能な輸送燃料を製造するための実行可能な経済的な経路を開発し、実証することでした。生物学的供給源は、木材チップ、森林廃棄物、農業残渣などのトリグリセリドベースのような植物油や動物性脂肪などのバイオマスだけでなく、廃食用油とセルロース系バイオマスを含みます。過去20年間にわたり、研究を用いて、バイオマス由来の油処理の評価に焦点を当ててきた従来の（FCC）5流動接触分解– 12、石油精製所でガソリンのほとんどを生産する責任技術を。本研究で我々の新しいアプローチは、オイルサンドビチューメン由来の原料と混合する同時プロセスのキャノーラ油です。通常、ビチューメンは、合成原油（SCO）はGHG emissiの68から78パーセントを占め、処理ルートは、特にエネルギー集約的である – これとして精油所原料を生産、前精錬にアップグレードする必要がありますカナダの総温室効果ガス排出量14の2.6％を構成し、SCOの生産13と、2011年からアドオン。バイオ燃料の生産がはるかに小さいカーボンフットプリントを含むのでbiofeedでアップグレードHGOの一部を置き換えることは、温室効果ガスの排出量を減少させるであろう。それはカナダと米国で豊富であるため、キャノーラ油は、この作品に選ばれています。この原料は、FCC性能や製品の品質に影響を与える可能性が硫黄、窒素、および金属の内容は無視され、一方HGOsと同様の密度および粘度を有しています。また、この共同処理オプションは、それは少し追加のハードウェアや製油所の修正を必要とするであろう、したがって、既存の製油所のインフラストラクチャの利用を可能にし、同じよう重要な技術的および経済的な利点を提供しています。加えて、共処理高い芳香ビチューメンが直鎖状バイオマス対応して供給するとき、製品の品質向上につながる可能性が潜在的な相乗効果が存在してもよいです。しかし、同時処理重要な技術的課題を伴います。高酸素含有量、パラフィンリッチな組成、石油供給原料との相溶性、汚染電位、 等 ：これらは、バイオフィードのユニークな物理的及び化学的特性を含みます
本研究では、接触分解を通じてキャノーラ油から実験室規模でのバイオ燃料の生産のための詳細なプロトコルを提供します。完全に自動化された反応系-臨床検査ユニット（LTU）15としてこの仕事に呼ば-この仕事のために使用されている。図1は、本機の動作を模式的方法を示しています。このLTUは、実験室FCC研究のための業界標準となっています。本研究の目的は、温室効果ガス排出量を軽減することを目標に燃料や化学物質を生成するためにキャノーラ油をクラッキングするためのLTUの適合性をテストすることです。
図1：概念illustratio原子炉。触媒の流線を示すイラスト、飼料、製品、および希釈剤のn個。 この図の拡大版をご覧になるにはこちらをクリックしてください。
Protocol
Representative Results
Discussion
ここで説明するプロトコルは、クラッキング原料油と触媒再生をシミュレートするために、流動触媒粒子のバッチを含む単一反応器のサイクル動作を利用します。油は流動床の底部に近いその先端と注入管を通って予熱し、上部から供給され、ひび割れします。接触分解を凝縮して回収受信機において、液生成物が収集された後に発生した蒸気は、その後、異なる沸点範囲の留分の収率を決?…
Divulgaciones
The authors have nothing to disclose.
Acknowledgements
著者らは、合成原油を供給するため、その技術サポートのためのCanmetENERGY技術センター、およびSuncor社エナジー社の分析実験室に感謝したいです。この研究のための部分的な資金はカナダ天然資源省とプロジェクトIDのA22.015とエネルギー研究開発（PERD）のカナダの部門間のプログラムの政府によって提供されました。李チャンは、彼の自然科学と2016年1月から2015年1月からカナダ客員フェローシップの工学研究評議会（NSERC）を感謝したいです。
Materials
| Advanced Cracking Evaluation (ACE) Unit | Kayser Technology Inc. | ACE R+ 46 | Assembled by Zeton Inc. SN:505-46; consisting of (1) a reactor; (2) catalyst addition system; (3) feed delivery system; (4) liquid collection system; (5) gas collection system; (6) gas analyzing system; (7) catalyst regeneration system; (8) CO catalytic convertor; (9) coke analyzing system |
| Reactor (ACE) | Kayser Technology Inc. | V-105 | A 1.6 cm ID stainless steel tube having a tapered conical bottom and with a diluent (nitrogen) flowing from the bottom to fluidize the catalyst and also serve as the stripping gas at the end of the run |
| Catalyst Addition System (ACE) | Kayser Technology Inc. | Six hoppers (V-120F, with respective valves) for addition of catalyst for up to 6 runs | |
| Feed Delivery System (ACE) | Kayser Technology Inc. | Consisting of feed bottle (V-100), syringe (FS-115), pump (P-100), and injector (with 1.125 inch injector height, i.e., the distance from the lowest point of the conical reactor bottom to the bottom end of the feed injector) | |
| Liquid Collection System (ACE) | Kayser Technology Inc. | Six liquid receivers (V-110F) immersed in a common coolant bath (Ethylene glycol/water mixture in 50:50 mass ratio) at about –15 °C in a large tank (V-145) | |
| Gas Collection System (ACE) | Kayser Technology Inc. | Based on water displacement principle; consisting of gas collection vessel (V-150) with a motor-driven stirrer (MTR-100), and a weight scale (WT-100) for weighing the displaced water collected in a beaker (V100) | |
| Gas Analyzing System (ACE) | Kayser Technology Inc. | Key element being Agilent micro GC (model 3000A) with four capillary columns equipped with respective thermal conductivity detectors (TCDs) | |
| Catalyst Regeneration System (ACE) | Kayser Technology Inc. | V-105 | Spent catalyst in reactor being burned in situ in air at +700 °C to ensure complete removal of carbon deposited on the catalyst |
| CO Catalytic Convertor (ACE) | Kayser Technology Inc. | A reactor (V-140) with CuO as catalyst to oxidize any CO and hydrocarbons in exhausted flue gas to CO2 (to be analyzed by IR gas analyzer) and H2O (to be absorbed by a dryer) | |
| Coke Analyzing System (ACE) | Kayser Technology Inc. | Servomex (Model 1440C) IR analyzer for measuring CO2 in exhausted flue gas | |
| R+MM Software Suite | Kayser Technology Inc. | Including iFIX 3.5 | |
| Agilent Micro GC | Agilent Technologies | 3000A | For gas analysis after cracking |
| Cerity Networked Data System | Agilent Technologies | Software for Agilent Micro GC | |
| CO2 Gas Analyser | Servomex Inc. | 1440C | SN: 01440C1C02/2900 |
| NESLAB Refrigerated Bath | Themo Electron Corporation | RTE 740 | SN: 104300061 |
| Orion Sage Syringe Pump | Themo Electron Corporation | M362 | For delivering feed oil to injector tube |
| Synthetic Crude Oil (SCO) | Suncor Energy Inc. | Identified as Suncor OSA 10-4.1 | |
| Catalyst P | Petro-Canada Refinery | Equilibrium catalyst | |
| Balance | Mettler Toledo | AB304-S | For weighing liquid product receivers |
| Balance | Mettler Toledo | XS8001S | For weighing water displaced by gas product |
| Ethylene Glycol | Fisher Scientifc Inc. | CAS 107-21-1 | Mixed with distilled water as coolant (50 v% ) |
| Drierite | W.A. Hammond Drierite Co. Ltd. | 24001 | For water absorption after CO catalytic converter |
| Copper Oxide | LECO Corporation | 501-170 | Catalyst for conversion of CO to CO2 |
| Toluene | Fisher Scientific Co. | CAS 108-88-3 | For cleaning liquid receivers |
| Acetone | Fisher Scientific Co. | CAS 67-64-1 | For cleaning liquid receivers |
| Micro GC Calibration Gas | Air Liquid Canada Inc. | SPG-25MX0015306 | Multicomponent standard gas |
| 19.8% CO2 Standard Gas | BOC Canada Ltd. | 24069890 | For calibration of IR analyzer |
| Argon Gas | Linde Canada ltd. | 24001306 | Grade 5.0 Purity |
| Helium Gas | Linde Canada ltd. | 24001333 | Grade 5.0 Purity |
| Gas analyzer GC Module | Inficon | GCMOD-15 | Channel A |
| Gas analyzer GC Module | Inficon | GCMOD-03 | Channel B |
| Gas analyzer GC Module | Inficon | GCMOD-04 | Channel C |
| Gas analyzer GC Module | Inficon | GCMOD-73 | Channel D |
| HP 6890 GC | Hewlett-Packard Co. | G1530A | For simulated distillation |
| ASTM 2887 Standard Sample | PAC L.P. | 26650.150 | For quality control in simulated distillation |
| ASTM 2887 Standard Sample | PAC L.P. | 25950.200 | For calibration in simulated distillation |
| Column for GC 6890 (simulated distillation) | Agilent Technologies | CP7562 | 10m x 0.53mm x 1.2µm, HP 6890 GC column |
| Liquid Nitrogen | Air Liquid Canada Inc. | SPG-NIT1AC240LC | For use in simulated distillation |
| Nitrogen | Air Liquid Canada Inc. | Bulk (building N2) | For use in ACE unit operation |
| Isotemp Programmable Furnace | Thermo Fisher Scientifc Inc. | 10-750-126 | For calcination of catalyst |
| GC Vials, Crimp Top | Chromatograghic Specialties Inc | C223682C | 2ml, for liquid product |
| Seals, Crimp Top | Chromatograghic Specialties Inc | C221150 | 11 mm, for use with GC vials |
| 4 oz clear Boston round bottles | Fisher Scientific Co. | 02-911-784 | With PE cone lined caps, for use in feed system |
| Sieve | Endecotts Ltd. | 6140269 | Aperture 38 micron |
| Sieve | Endecotts Ltd. | 6146265 | Aperture 250 micron |
| Shaker | Endecotts Ltd. | MIN 2737-11 | Minor-Meinzer 2 Sieve Shaker for catalyst screening |
| V20 Volumetric KF Titrator | Mettler Toledo | 5131025056 | For water content analysis of the liquid product |
| Hydranal Composite 5 | Sigma-Aldrich | 34805-1L-R | Reagent for Karl Fischer titration |
| Methanol (extremely low water grade) | Fisher Scientific Co. | A413-4 | Mixed with toluene (40:60 w/w) for KF titration: also used to recover water in receiver |
| Glass Wool | Fisher Scientific Co. | 11-388 | Placed inside the top of receiver outlet arm |
Referencias
- Bringezu, S., et al. Towards Sustainable Production and Use of Resources – Assessing Biofuels. United Nations Environment Programme. , (2009).
- Sheehan, J., Camobresco, V., Duffield, J., Graboski, M., Shapouri, H. Life cycle inventory for biodiesel and petroleum diesel for use in an urban bus. National Renewable Energy Laboratory Report. , (1998).
- . Renewable Fuels Regulations. Canada Gazette Part II. 144 (18), 1614-1740 (2010).
- . Directive 2009/28/EC of the European Parliament and of the Council of 23 April 2009 on the promotion of the use of energy from renewable sources and amending and subsequently repealing Directives 2001/77/EC and 2003/30/EC (Text with EEA relevance). Official Journal of the European Union. 140, 16-62 (2009).
- Al-Sabawi, M., Chen, J., Ng, S. Fluid catalytic cracking of biomass-derived oils and their blends with petroleum feedstocks: A Review. Energy Fuels. 26 (9), 5355-5372 (2012).
- Dupain, X., Costa, D. J., Schaverien, C. J., Makkee, M., Moulijn, J. A. Cracking of a rapeseed vegetable oil under realistic FCC conditions. Appl. Catal. B: Environ. 72 (1-2), 44-61 (2007).
- Tian, H., Li, C., Yang, C., Shan, H. Alternative processing technology for converting vegetable oils and animal fats to clean fuels and light olefins. Chin J Chem Eng. 16 (3), 394-400 (2008).
- Melero, J. A., Clavero, M. M., Calleja, G., Garcia, A., Miravalles, R., Galindo, T. Production of bio-fuels via the catalytic cracking of mixtures of crude vegetable oils and nonedible animal fats with vacuum gas oil. Energy Fuels. 24 (1), 707-717 (2010).
- Bielansky, P., Reichhold, A., Schönberger, C. Catalytic cracking of rapeseed oil to high octane gasoline and olefins. Chem Eng Process. 49 (8), 873-880 (2010).
- Ng, S. H., Shi, Y., Ding, L., Chen, S. Catalytic cracking of a rapeseed oil for production of transportation fuels and chemicals: Yield structure. 2010 AIChE Annual Meeting. , (2010).
- Bielansky, P., Weinert, A., Schönberger, C., Reichhold, A. Catalytic conversion of vegetable oils in a continuous FCC pilot plant. Fuel Process Technol. 92 (12), 2305-2311 (2011).
- Ng, S. H., Lay, C., Bhatt, S., Freel, B., Graham, R. Upgrading of biomass-derived liquid to clean fuels. 2012 AIChE Annual Meeting. , (2012).
- Ordorica-Garcia, G., Croiset, E., Douglas, P., Elkamel, A., Gupta, M. Modeling the energy demands and greenhouse gas emissions of the Canadian oil sands industry. Energy Fuels. 21 (4), 2098-2111 (2007).
- . . Canada’s Emission Trends. , (2013).
- Kayser, J. C. Versatile fluidized bed reactor. US Patent. , (2000).
- . . ACE Operating Manual: PID Drawing No. R+ 101 and 102. , (2007).
- . . System Manual: ACE – Model R+. , (2007).
- . . ASTM D2887-15 Standard test method for boiling range distribution of petroleum fractions by gas chromatography. , (2015).
- . . AASTM D4377-00 Standard test method for water in crude oils by potentiometric Karl Fischer titration. , (2015).
- Ng, S. H., et al. FCC coprocessing oil sands heavy gas oil and canola oil. 1. Yield structure. Fuel. 156, 163-176 (2015).
- Cox, J. D., Wagman, D. D., Medvedev, V. A. . CODATA Key values for thermodynamics. , (1984).
- Ng, S. H., et al. FCC study of Canadian oil-sands derived vacuum gas oils. 1. Feed and catalyst effects on yield structure. Energy Fuels. 16 (5), 1196-1208 (2002).
- Ng, S. H., Dabros, T., Humphries, A. Fluid catalytic cracking quality improvement of bitumen after paraffinic froth treatment. Energy Fuels. 21 (3), 1432-1441 (2007).
- Scherzer, J., Magee, J. S., Mitchell, M. M. Chapter 5, Correlation between catalyst formulation and catalytic properties. Fluid Catalytic Cracking: Science and Technology. , 145-182 (1993).
- Fisher, I. P. Effect of feedstock variability on catalytic cracking yields. Appl. Catal. 65 (2), 189-210 (1990).
- Ng, S. H., et al. Study of Canadian FCC feeds from various origins and treatments. 1. Ranking of feedstocks based on feed quality and product distribution. Energy Fuels. 18 (1), 160-171 (2004).
- Ng, S. H., et al. Study of Canadian FCC feeds from various origins and treatments. 2. Some specific cracking characteristics and comparisons of product yields and qualities between a riser reactor and a MAT unit. Energy Fuels. 18 (1), 172-187 (2004).
- Ng, S. H., et al. Key observations from a comprehensive FCC study on Canadian heavy gas oils from various origins. 1. Yield profiles in batch reactors. Fuel Process Technol. 87 (6), 475-485 (2006).
- Scherzer, J. Octane-enhancing zeolitic FCC catalysts: Scientific and technical aspects. Catalysis Reviews: Science and Engineering. 31 (3), 215-354 (1989).
- . . ASTM D7964/D7964M-14 Standard test method for determining activity of fluid catalytic cracking (FCC) catalysts in a fluidized bed. , (2014).
- . . ASTM D5154-10 Standard test method for determining activity and selectivity of fluid catalytic cracking (FCC) catalysts by Microactivity test. , (2010).
- Moorehead, E. L., McLean, J. B., Cronkright, W. A., Magee, J. S., Mitchell, M. M. Chapter 7, Microactivity evaluation of FCC catalysts in the laboratory: Principles, approaches and applications. Fluid Catalytic Cracking: Science and Technology. , 223-255 (1993).
- Rawlence, D. J., Gosling, K. FCC catalyst performance evaluation. Appl. Catal. 43 (2), 213-237 (1988).
