A couple of industrial sized, fast pyrolysis oil plants have been constructed, see Table below.
|Host Organisation||Country||Technology||Capacity kg feed/h||Capacity kg bio-oil/h||Applications||Status||Year|
|BTG-BTL EMPYRO||Netherlands||Rotating cone||5000||Fuel||Commissioning||2014|
|Fortum - VALMET||Finland||Fluid bed / riser||10,000||Fuel||Operational||2013|
|Red Arrows - Ensyn||Canada||Fluid bed / riser||1,667||Fuel||Operational||1996|
|Ensyn||Canada||Fluid bed / riser||3,500||Fuel||Operational||20xx|
|KiOR||USA||Catalytic fast pyrolysis||21,000||Transportation fuel||dormant||2014|
The commercial pyrolysis plants are discussed further below.
Fortum commercialised the fast pyrolysis technology by building a pyrolysis-oil plant connected to the Joensuu power plant in Finland. The integrated bio-oil plant, based on fast pyrolysis technology, is one of the first of its kind in the world on an industrial scale. The pyrolysis plant commensed in 2013. The pyrolysis plant, which will be integrated with the combined heat and power production plant (CHP) in Joensuu, will produce electricity and district heat and 50,000 tonnes of bio-oil per year. The bio-oil raw materials will include forest residues and other wood based biomass. Trade name of Fortum's pyrolysis oil is Fortum Otso.The first patent was granted to VTT 2006 on the integrated fast pyrolysis, which employs hot sand from a fluidized-bed boiler for heating the pyrolysis feedstock.
The concept allows also integration of fast pyrolysis to existing industrial or district heating CHP plants. The heat needed for the pyrolysis is provided by the CHP plant fluidized-bed boiler by feeding hot sand to the CFB pyrolysis unit (800oC). Cold sand together with the char (at around 500oC) is send back to the fluidized-bed boiler, in which also the non-condensables are fired. The combination allows lower investment costs when integrating into existing boilers. In addition to integrating to existing boilers, also green-field integrate enables excellent control and smooth operation for fast pyrolysis. A 7 t/d pyrolysis liquids production unit was constructed at Metso’s premises in Tampere (Finland) in 2008 and since 2009 more than 140 tons of liquid have been produced. A first commercial scale demonstration unit was commissioned in 2013. The plant is located in Joensuu (Finland) with a capacity to produce 50 kton/y pyrolysis liquids. The product is used as a substitute for heavy fuel oil, and as raw material in the chemical industry or for biodiesel production in the future.
At the start of 2014, Metso’s Pulp, Paper and Power business formed a new independent company under the name Valmet. In the same year Fortum, UPM and Valmet joined forces to develop technology to produce advanced high value lignocellulosic fuels, such as transportation fuels or higher-value bio liquids by catalytic pyrolysis. The five-year project is called LignoCat (lignocellulosic fuels by catalytic pyrolysis).
Biomass particles at room temperature and hot sand particles are introduced near the bottom of the cone where the solids are mixed and transported upwards by the rotating action of the cone. In this type of reactor, rapid heating and a short gas phase residence time can be realized. Since no “inert” carrier gas is needed (unlike fluidized bed pyrolysis), the pyrolysis products are undiluted. This undiluted and hence small vapour flow results in downstream equipment of minimum size. Consequently, the capital costs of the complete unit are minimal.
The rotating cone reactor for fast pyrolysis was originally developed by the University of Twente. The initial work of the University of Twente has been the starting point in 1993 for BTG Biomass Technology Group to further develop the pyrolysis reactor and the overall process. Rapid removal of the pyrolysis vapours from the hot reactor enclosure ensures that less than 10 wt.% bio-oil is lost due to cracking reactions. A batch-wise 50 kg/hr was supplied to a Chinese University in 1995, but -as far as known- hardly been operated by the researchers. In 1998, BTG has built its own 5 t/d pilot plant and this unit is still in operation in Enschede, the Netherlands. A first full scale unit was delivered to Malaysian company Genting aiming to convert Empty Fruit Bunches. Late 2007, the daughter company BTG Bioliquids (BTG-BTL) was established with the objective to commercialize BTG's fast pyrolysis process. BTG-BTL was one of the founders of the company Empyro.
completed at the AkzoNobel site in Hengelo (The Netherlands), and is being commissioned in 2015. Wood is converted into pyrolysis oil, process steam for AKZO and electricity. The production capacity will then be gradually increased to its maximum of over 20 million litres of pyrolysis oil per year. This amount of renewable oil will replace 12 million cubic meters of natural gas.
Being a private company incorporated in Delaware, USA, Ensyn has over 100 shareholders, including institutional entities and private individuals. Its leading institutional and strategic shareholders include Chevron Technology Ventures (a division of Chevron USA), the financial company Credit Suisse, Impax Asset Management Group PLC (a London-based investment group), Felda Palm Industries (Malaysian palm oil and plantation operator), Investeco Capital Corp. (an environmental investment company) and Fibria Celulose (Brazilian company in wood pulp). Ensyn has a proven track record for continuous commercial operations for > 25 years, its majority of production dedicated to chemicals, viz. for the production of food ingredients such as liquid smoke. Ensyn Corporation claims to be a producer of advanced, drop-in cellulosic biofuels that can replace petroleum products.
Ensyn's core technology, the Rapid Thermal Processing or RTP™, converts non-food biomass from the forest and agricultural sectors to liquids through fast pyrolysis. The residence time in this unit operating at 520 °C is 1-2 s, where after the product vapors are condensed using cold pyrolysis liquid.
The origin of Ensyn is in 1984, when Robert Graham and Barry Freel established the company to produce liquids by fast pyrolysis. The cooperation between Graham and Freel started while working in the group of Bergougnou in 1982 at the University of Western Ontario. One of the first patents was applied for in 1991 (see for example US5961786 and US5792340).
Further commercialization of Ensyn’s technology took place in the period 1985-1989. Since 1989 together with Red Arrow Products Company LLC, a Wisconsin-based food products company, to produce Liquid smoke (derived products) for the food industry. US4876108 and US5952029 describe ways to produce such wood flavors. Several RTP facilities have been delivered to Red Arrow since then – six of which are still operating. From 1990 onwards the technology was scaled up, with a facility scaled up to 45 t/d (dry) biomass unit. A 20 kg/h Process Development Unit (PDU) was delivered to VTT in 1995, subsequently modified by VTT. Also in 1995, Ensyn shipped a 625 kg/h unit to Bastardo (Perugia in Italy), to be operated by ENEL. The last 15 years the plant is stated ‘running on demand’, but in practice this is never or hardly ever.
In 1998 Ensyn adapted the 45 t/d unit to upgrade heavy oil (approx. 20 barrel-per-day petroleum pilot facility). In the period from 2000 to 2005 focus was on this petroleum application, resulting in construction of a 1,000 bpd heavy oil RTP facility built in the Belridge oil field in California in 2004. Ivanhoe Energy purchased 100% of the petroleum RTP technology rights in 2005, licensed under the name of HTL. As of 2014 a Test Facility is operational in Saint Antonia in Texas. From 2005 onwards, focus was again on renewable fuels, and a 75 t/d unit was commissioned in Renfrew Ontario in 2007. In 2008 Ensyn and UOP established a joint venture Envergent Technologies LLC., providing engineering services and supplies to projects. A series of announcements appeared in the period 2009 – 2012 on all types of activities (of which the status is unclear):
- In 2009 Envergent announced that the Italian power company Industria e Innovazione selected the Envergent for the development of a 150 BDT/d facility to convert biomass into pyrolysis oil for renewable power generation.
- In 2010 Tolko and Ensyn formed a partnership (High North BioResources Limited Partnership) to build the world’s largest commercial fast pyrolysis plant in High Level, Alberta, to process 400 bone dry tonnes of biomass per day into 85 million l/yr pyrolysis liquids annually to be used as heat carrier in Tolko’s sawmill.
- Also in 2011 a MoU was signed with Finland’s Green Fuel Nordic Oy to collaborate on projects to convert biomass to renewable fuel for use in district heating systems in Finland.
- In 2011 UOP (with Envergent and Ensyn) started to break ground at Kapolei to transform biomass into transportation fuels. The plant is built at an existing Tesoro refinery, funded through a $25 million grant from the DOE. The plant supposedly was operational by the end of 2012, and running at full capacity in no later than 2014.
- In 2012 Ensyn established a 50/50 Joint venture with Fibria Celulose (Brazil) to develop in Brazil. The first project of the joint venture is being developed at Fibria’s Aracruz mill in Espirito Santo.
- In 2012 Ensyn established a joint venture with Premium Renewable Energy, a Malaysian renewable energy development company established in 2007. The joint venture aims at the conversion of palm and bagasse residues to RFO, the oil to be used for power generation, heating and for upgrading to transport fuels. The first project is to be located in Felda Sahabat, Sabah.
Ensyn’s alliance with UOP was expanded in early 2014 to include cooperation between UOP and Ensyn in developing and commercializing in an application referred to as Refinery Coprocessing to facilitate integration of RFO into refineries. Over the last 25 years Ensyn designed and commissioned 16 facilities (from pilot to commercial scale) for the production of chemicals and heating fuels and for testing and product development, from which six are in operation. The RTP facilities with commercial scale operations are:
- Renfrew (Ontario) is Ensyn’s demo unit for fuels production, producing renewable fuels for testing, for market development and for existing customers. The Renfrew plant has been in operation since 2006, focused primarily on production of liquids and heating fuels for the speciality chemicals industry, and was used to produce liquids for biofuels. The Renfrew facility is now being converted to a dedicated RFO™ biofuels facility. Ensyn produces a renewable fuel oil, called RFO™, a petroleum-replacement to be used for heating purposes. In 2014, up to CAD 4 million was reportedly invested in the facility in Renfrew to convert it to a dedicated biofuels facility with production capacity of three million gallons/year.
- Red Arrow RTP Facilities (Rhinelander, Wisconsin). Red Arrow, Ensyn’s partner in the food chemicals business, owns and operates five commercial RTP plants in Wisconsin. Ensyn provides RTP operations supervision, maintenance and technical support. In addition, two Red Arrow commercial RTP plants were decommissioned after more than 15 years each of continuous operation and their capacity replaced with production from next-generation, larger RTP facilities.
Dynamotive Technologies Corporation (DMTF) is established in 1991, and is Canadian company that acquired the patent from Resource Transforms Ltd. (RTI) in 2000. Under the agreement with RTI, DMTF gained the rights to new products derived from BioOil including blended fuels, in addition to the right to produce air emissions control additives like BioLimeR. The claims of the patent of Radlein et al. include the use of a fluidized bed for the fast pyrolysis of biomass, in which the char produced is elutriated from the bed, and the bed is heated indirectly.
Dynamotive’s concept applies a Bubbling Fluidized Bed technique, in which the biomass is rapidly heated by introducing the particles in a fluid bed of hot (usually) sand particles. Locally, high sand-to-biomass heat transfer rates can indeed be achieved, as the bed usually contains small sand particles, generally about 250 m. The heat required to keep the sand at the required temperature is generated by the use of heating coils, in which hot gases are introduced obtained from the combustion of (part of) the non-condensables from the process.
In 2001 DMTF commissioned a 10 t/d unit plant, in 2003 a 100 t/d commercial unit was commissioned in West Lorne, Ontario (Canada), in which the bio-oil was to be combusted in an Orenda 2.5 MWe gas turbine. This West Lorne BioOil cogeneration project was partially funded with a CAN$5 million contribution from Sustainable Development Technology Canada, a foundation created by the Canadian Government. The feed stock for the plant is derived from wood residues from Erie Flooring and Wood Products, at which premises the unit was located. The demonstration plant design was an almost 80 scale-up of a previous 10 to 15 t/d pilot plant. It encountered some technical issues resulting from scale-up issues (feeding system, reactor heating and problems with fines in the feed). The bio-oil contained a decade more char than that obtained from pilot plant experiments, which affected the operation of the Orenda gas turbine. Eventually partners withdrew from the consortium, nevertheless it was decided to upgrade the plant. The upgrades were completed in 2008.
In 2005 a full 200 t/d commercial unit was launched (Guelph, Ontario). The total investment in the plant was about $18.5 million. The Guelph plant began producing bio-oil in 2007 under the name Evolution Biofuels Inc in which DMTF had a minority ownership. In May 2007 Dynamotive announced that it had completed the initial production run and so-called Intermediate grade bio-oil - BioOil Plus - containing higher quantities of char was produced. In 2007 offices were opened in the United States and Argentina. The Guelph plant was a fully commercial modular design that was reportedly commissioned successfully in 2008. Feed supply was biomass from demolition construction wood (MSW) recycling operations and bio-oil clients supposedly two large cement companies in Ontario as well as other industries in Quebec. However, by 2008 the cement plants started to slow down while in the same year the West Lorne plant went into receivership. West Lorns is still dormant (2015), while the Guelph plant became uneconomic, was shut-down, abandoned and finally dismantled.
In 2009, Dynamotive released results of a year-long test applying the produced biochar in commercial farming test plots while at the same time gasoline and diesel were produced from biomass, through a two-stage high pressure catalytic upgrading process - Biomass INto GasOil (BINGO). The process involves a hydroreforming of the oil to a liquid that can either be directly utilized in blends with hydrocarbon fuel for power and heating or be further upgraded to transportation grade liquid hydrocarbon fuels in a further hydrotreating process. In June 2010, Dynamotive announced that they had signed a memorandum of understanding to cooperate in the field of bio-oil upgrading with IFP, a French R&D center. A patent application is published in 2012 (WO 2012/035410).
From 2012 onwards -despite some public announcements- it is silent around Dynamotive.
The KiOR process can be classified as a Catalytic Fast Pyrolysis process. In November 2007 KiOR was founded as a joint venture of Khosla Ventures (KV) and BIOeCON, where BIOeCON contributed Intellectual property, and technology know-how in the field of Biomass Catalytic Cracking. The founder BIOeCON officially started operations beginning 2006 but already in May of 2006 BIOeCON's 5 patents were filed and R&D activities were ongoing in Valencia (UPV), Twente University, Delft University, Greece CPERI and research groups in the USA. The claims in these patents generally relates to (i) a the fluid catalytic cracking of oxygenated hydrocarbon compounds (including pyrolysis liquids) with or without a crude oil derived feedstocks in standard or modified FCC processes (for example US 8207385(B2)) and (ii) the use of additives to the biomass to make it more susceptible for conversion prior to a subsequent conversion process (for example US 8022260(B2) and EP 1852491(A1)). In the latter case examples provided include clays, metal oxides and alkaline earth metals. A first commercial plant was constructed an operated in 2012, operated in 2013 and shutdown in 2014. KiOR has ‘substantial doubts about the ability to continue as a going concern’, and is the subject of some lawsuits from investors.
ProcesAt KiOR’s BFCC refinery in Columbus wood chips are first "processed and conditioned" for conversion into oil. The processing and conditioning probably refers to seizing and drying.
Yields of renewable fuel products of approximately 67 gallons per bone dry ton of biomass are reported in 2011 and potentially to be increased to approximately 92 gallons per BDT. In 2012 next generation catalysts were implemented at the full scale commercial facility, herewith reducing the amount of coke made in the process by up to 25 percent. However, 2014 figures indicate actual yields of only 30 gallons per bone dry tons.
By 2006 the process of "Biomass Catalytic Cracking" (BCC) was introduced as a technology to convert lignocellulosic biomass (such as grass, wood, and various agricultural and forestry wastes) into a liquid product that can be further upgraded to transportation fuels, which was believed to be at a status close to commercialization for which financial funding was required. The early process claims by BIOeCON were to lower the degradation temperature of the holocellulose by catalysis. Biomass impregnated by salts indeed showed reduced decomposition temperatures, but clear beneficial effects on yields and liquid quality have not been demonstrated. Aiming to move into the market with the BCC technology before the end of 2010, offices and an R&D center were set up in Houston Texas with the construction of a state-of-the-art BCC pilot plant. The pilot plant was an opportunity for KiOR’s proof of concept to convert cellulosic feedstock into renewable crude oil through a scalable catalytic process. However the technology appeared far from ready as the initial technology approach failed. By the time the pilot came online, the team had innovated an entirely new process, one that yielded ‘better product, economics and ease of scalability’. Whereas one of the BIOeCON’s original ideas was to use additives upfront to make the biomass more susceptible for conversion prior to a subsequent conversion (to lower the decomposition temperature), it might be that in the new path this a priori pretreatment of the biomass has been abandoned, and temperatures similar to pyrolysis were to be applied.
KiOR began work on a demonstration unit, referring to Biomass Fluid Catalytic Cracking (BFCC) On New Year's Day, 2010, the demonstration unit was installed, representing a 400 times scale up from the pilot. Having demonstrated the technical feasibility and scale of its process in 2011, KiOR moved on to commercial production. KiOR's "drop in" advantages intrigued potential customers, including oil companies. In the summer of 2013 it was clear that KiOR wasn’t reaching the volumes at the factory that it forecasted.In January 2014, KiOR shut down its Columbus production facility since it was having difficulty with its production. In 2014 KIOR files for bankruptcy, and it is unclear what will happen with the Columbus plant.