Laboratorium Produktion af biobrændstoffer og biokemikalier fra en Rapsolie gennem Catalytic Cracking Conversion
Summary
Denne artikel præsenterer en eksperimentel metode til at producere biobrændstoffer og biokemikalier fra raps olie blandet med en fossil-baseret foder i tilstedeværelse af en katalysator ved milde temperaturer. Gasformige, flydende og faste produkter fra en reaktion enhed kvantificeres og karakteriseres. Omstilling og individuel produkt udbytter beregnes og rapporteres.
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
Der er stærk global interesse i både den private og den offentlige sektor for at finde effektive og økonomiske midler til at producere transportbrændstof fra biomasse-afledte råmaterialer. Denne interesse er drevet af en generel bekymring over den betydelige bidrag af brændende olie fossile brændsler til drivhusgas (GHG) og dens tilhørende bidrag til den globale opvarmning. Også, der er en stærk politisk vilje i Nordamerika og Europa til at fortrænge udenlandsk produceret råolie med vedvarende indenlandske flydende brændstoffer. I 2008 biobrændstoffer forudsat 1,8% af verdens transportbrændstof 1. I mange udviklede lande, kræves det, at biobrændstoffer erstatte fra 6% til 10% af brændstoffer i den nærmeste fremtid 2. I Canada, regler kræver et gennemsnitligt indhold vedvarende brændstof på 5% i benzin start December 15, 2010 3. Direktivet om vedvarende energi (RED) i Europa har også mandat et mål for Den Europæiske Union trans 10% vedvarende energihavnesektoren i 2020 4.
Udfordringen har været at udvikle og demonstrere en levedygtig økonomisk vej til at producere ombyttelige transportbrændstof fra biomasse. Biologiske kilder omfatter triglycerid-baserede biomasse såsom vegetabilske olier og animalsk fedt samt affald madolie og cellulosebaseret biomasse som flis, skov affald og restprodukter landbrug. I de seneste to årtier har forskning fokuseret på evalueringen af biomasse-afledte olie behandling under anvendelse af konventionel flydende katalytisk krakning (FCC) 5 – 12, en teknologi ansvarlig for at producere de fleste af benzinen i et olieraffinaderi. Vores nye tilgang i denne undersøgelse er at co-proces rapsolie blandet med olie sand bitumen-afledte råmateriale. Normalt skal bitumen opgraderes før raffinering, der producerer raffinaderiråmaterialer såsom syntetisk råolie (SCO) -dette behandling rute er særligt energikrævende, der tegner sig for 68-78% af GHG emissions fra SCO produktion 13, og i 2011, udgør 2,6% af Canadas samlede drivhusgasemissioner 14. Udskiftning af en del af opgraderede HGO med biofeed ville reducere drivhusgasemissionerne, da produktionen af biobrændstoffer indebærer en meget mindre carbon footprint. Rapsolie er valgt i dette arbejde, fordi det er rigeligt i Canada og USA. Dette råmateriale har en densitet og viskositet svarende til dem i HGOs medens indholdet af svovl, nitrogen og metaller, der kan påvirke FCC ydeevne eller produktkvalitet er ubetydelige. Desuden dette samarbejde behandling option giver betydelige teknologiske og økonomiske fordele, da det ville tillade udnyttelse af den eksisterende raffinaderi infrastruktur og dermed ville kræve lidt ekstra hardware eller ændring af raffinaderiet. Derudover kan der være potentiel synergi, der kan resultere i produktkvalitet forbedring, når co-behandling en yderst aromatisk bitumen fodre med sin ligekædede biomasse modstykke. Imidlertid co-behandlingindebærer vigtige tekniske udfordringer. Disse omfatter de unikke fysiske og kemiske egenskaber bio-feeds: højt iltindhold, paraffin–rige sammensætning, kompatibilitet med jordolieråstoffer, begroning potentielle, osv
Denne undersøgelse giver en detaljeret protokol for produktion af biobrændstoffer i laboratorieskala fra raps olie gennem katalytisk krakning. En fuldautomatisk reaktionssystem – der henvises til i dette arbejde som laboratoriet test enhed (LTU) 15 – bruges til dette arbejde Figur 1 viser skematisk, hvordan denne enhed fungerer.. Denne LTU er blevet branchens standard for laboratorie FCC studier. Formålet med denne undersøgelse er at teste egnetheden af LTU til krakning raps olie til produktion af brændstoffer og kemikalier med det mål at mindske drivhusgasemissioner.
Figur 1: Conceptual illustration af reaktoren. Illustration viser flow linjer i katalysatoren, foder, produkter og fortynder. Klik her for at se en større version af dette tal.
Protocol
Representative Results
Discussion
Protokollen beskrevet her anvender cyklisk drift af en enkelt reaktor indeholdende et parti af fluidiserede katalysatorpartikler at simulere foder olie krakning og katalysatorregenerering. Den olie, der skal krakket forvarmes og føres fra toppen gennem en injektor rør med sin spids tæt på bunden af fluid bed. Dampen genereres efter katalytisk krakning kondenseres og opsamles i en modtager, og det flydende produkt opsamlet efterfølgende analyseret for simuleret destillation for at bestemme udbytterne af frakti…
Divulgations
The authors have nothing to disclose.
Acknowledgements
Forfatterne vil gerne takke den analytiske laboratorium CanmetENERGY Teknologi Center for sin tekniske support, og Suncor Energy Inc. for at levere den syntetiske råolie. Delvis finansiering til denne undersøgelse blev leveret af Natural Resources Canada og regering Canadas tværfaglig Program for Energy Research og udvikling (perd) med projekt-id A22.015. Yi Zhang vil gerne anerkende hans naturvidenskab og teknik Forskningsråd (NSERC) i Canada Visiting Fellowship fra januar 2015 til januar 2016.
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 |
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