WO2009018230A1 - Installation de production de biodiesel d'algue continue - Google Patents

Installation de production de biodiesel d'algue continue Download PDF

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Publication number
WO2009018230A1
WO2009018230A1 PCT/US2008/071385 US2008071385W WO2009018230A1 WO 2009018230 A1 WO2009018230 A1 WO 2009018230A1 US 2008071385 W US2008071385 W US 2008071385W WO 2009018230 A1 WO2009018230 A1 WO 2009018230A1
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Prior art keywords
biodiesel
methanol
present
acid
algae
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PCT/US2008/071385
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English (en)
Inventor
Mark Machacek
Thomas Smith
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Solix Biofuels, Inc.
Colorado State University Research Foundation
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Publication of WO2009018230A1 publication Critical patent/WO2009018230A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/08—Refining
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • Embodiments of the present invention concern methods, compositions and apparatus for continuous algal biodiesel production.
  • methods are provided for continuous biodiesel production from algal biomass, without the need for extraction or separation of algal lipids for esterification into biodiesel.
  • Such embodiments concern an in-situ hydrolysis and esterification process for production of fatty acid methyl esters (FAME), commonly referred to as biodiesel.
  • FAME fatty acid methyl esters
  • Embodiments of the present invention include methods, compositions and apparatus for continuous production of FAME from algae, without the need for purification and/or extraction of lipids from algal cells. Certain embodiments concern methods involving a novel in-situ hydro lysis-esterification reaction process. Lipids, or triglycerides, are first hydrolyzed to create fatty acids at a 99 percent conversion rate. These are then esterified to fatty acid methyl esters (FAME), commonly referred to as biodiesel.
  • FAME fatty acid methyl esters
  • a multiplicity of continuously stirred tank reactors are used and are split into three parallel streams.
  • continuous centrifuge and decanter units may be used to separate the solid, liquid and oil phases.
  • methanol is non-renewable and somewhat expensive, about 98 percent of the feed methanol may be recycled. Additional washing and reaction steps may be used to create FAME with 99 percent purity.
  • Various embodiments concern use of one or more closed system bioreactors for algal culture, to provide starting material for the methods of continuous biodiesel production. Additional details of such closed system bioreactors for algal culture are disclosed in U.S. Patent Application Serial Nos. 11/510,148 and 11/510,442; PCT Patent Application Serial No. PCT/US2006/033252; and provisional U.S. Patent Application Serial Nos. 60/894,082, filed March 9, 2007; 60/877,907, filed December 20, 1996, and 60/878,506, filed January 3, 2007; the text of each of which is incorporated herein by reference.
  • Certain embodiments may concern methods, compositions and apparatus for fermentation of glycerin or glycerol into ethanol.
  • the fermentation may be accomplished using bacterial fermenters, such as E. coli.
  • FIG. 1 illustrates a mechanism for acid-catalyzed ester hydrolysis, according to embodiments of the present invention.
  • FIG. 2 illustrates a process flow diagram for a reaction and separation process for converting algae into biodiesel, according to embodiments of the present invention.
  • FIG. 3 illustrates a reaction flow diagram, according to embodiments of the present invention.
  • FIG. 4 illustrates a separation flow diagram, according to embodiments of the present invention.
  • FIG. 5 illustrates a methanol purification flow diagram, according to embodiments of the present invention.
  • FIG. 6 illustrates a biodiesel purification flow diagram, according to embodiments of the present invention.
  • FIG. 7 illustrates an upper-left quadrant of an overall flow process diagram, according to embodiments of the present invention.
  • FIG. 8 illustrates an upper-right quadrant of an overall flow process diagram, according to embodiments of the present invention.
  • FIG. 9 illustrates an lower-left quadrant of an overall flow process diagram, according to embodiments of the present invention.
  • FIG. 10 illustrates an lower-right quadrant of an overall flow process diagram, according to embodiments of the present invention.
  • FIG. 11 illustrates a sample specification sheet for a hydrolysis reactor that may be used according to embodiments of the present invention.
  • FIG. 12 illustrates a sample specification sheet for an esterification reactor that may be used according to embodiments of the present invention.
  • FIG. 13 illustrates a sample specification sheet for a final esterification reactor that may be used according to embodiments of the present invention.
  • FIG. 14 illustrates a sample specification sheet for a heat exchanger that may be used according to embodiments of the present invention.
  • FIG. 15 illustrates a sample specification sheet for another heat exchanger that may be used according to embodiments of the present invention.
  • FIG. 16 illustrates a sample specification sheet for yet another heat exchanger that may be used according to embodiments of the present invention.
  • FIG. 17 illustrates a sample specification sheet for a decanter that may be used according to embodiments of the present invention.
  • FIG. 18 illustrates a sample specification sheet for another decanter that may be used according to embodiments of the present invention.
  • FIG. 19 illustrates a sample specification sheet for a distillation tower that may be used according to embodiments of the present invention.
  • FIG. 20 illustrates a sample specification sheet for a centrifuge that may be used according to embodiments of the present invention.
  • FIG. 21 illustrates a sample specification sheet for a flash drum that may be used according to embodiments of the present invention.
  • FIG. 22 illustrates a sample specification sheet for parallel pumps that may be used according to embodiments of the present invention.
  • FIG. 23 illustrates a sample specification sheet for a pump that may be used according to embodiments of the present invention.
  • FIG. 24 illustrates a sample specification sheet for another pump that may be used according to embodiments of the present invention.
  • FIG. 25 illustrates a sample energy balance chart for a methanol mixer, according to embodiments of the present invention.
  • FIG. 26 illustrates a sample energy balance chart for methanol purification, according to embodiments of the present invention.
  • FIG. 27 illustrates a sample energy balance chart for parallel heaters, according to embodiments of the present invention.
  • FIG. 28 illustrates a sample energy balance chart for a methanol pre-heater, according to embodiments of the present invention.
  • FIG. 29 illustrates a sample energy balance chart for a product pre-heater, according to embodiments of the present invention.
  • FIG. 30 illustrates a sample energy balance chart for parallel pumps, according to embodiments of the present invention.
  • FIG. 31 illustrates a sample energy balance chart for a supplemental reactant pump, according to embodiments of the present invention.
  • FIG. 32 illustrates a sample energy balance chart for a methanol pump, according to embodiments of the present invention.
  • FIG. 33 illustrates a sample energy balance chart for a supplemental reactor, according to embodiments of the present invention.
  • FIG. 34 illustrates a sample energy balance chart for a parallel reaction branch, according to embodiments of the present invention.
  • Algae are a very diverse and simple group of aquatic plant that are widespread across the world. Algae can vary in form from Eukaryote to Bacteria, and are spread across the kingdoms Plantae, Protista, and Protozoa. All forms contain biomass, which can be converted to various renewable fuels.
  • the types used for culture are photosynthetic Plantae algae, although the skilled artisan will realize that alternative algal types may be utilized in the practice of the disclosed methods. The algae are selected for their high lipid content and efficient growth under a variety of conditions.
  • Algae is a beneficial feed stock because it has the potential to provide over one hundred twenty times the fuel output (per acre) of soybeans, the primary crop used for present biodiesel production. Even palm oil, which has gained popularity recently, has a lower order of magnitude for production per acre. Algae farms are also advantageous in their ability to provide growth within a contained environment, drastically reducing water usage compared to conventional agriculture. Furthermore, livestock feed and general food supply (a current concern for corn based ethanol, soybean oil, and other biofuels ) will not be impacted by such a system.
  • An optimal location to grow algae quickly is next to a coal or natural gas fired power plant, where large amounts of CO 2 are released through combustion of fuel.
  • the carbon dioxide a greenhouse gas, can be sequestered by the algae and some of it can be converted into the carbon-containing lipids. Additional biomass may be created, resulting in a reduction of atmospheric carbon dioxide, even after the biodiesel is burned in a combustion engine.
  • the CO 2 enrichment provides for enhanced algal growth.
  • Certain embodiments of the present invention concern a continuous process for converting algae to biodiesel (fatty acid methyl esters-FAME).
  • Current methods for production of biodiesel from oil primarily utilize batch processes using a base catalyzed reaction in a dry environment.
  • Harvested algae contain a relatively high percentage of water which obviates use of the current technology in either the batch or continuous mode (soap, not biodiesel, would be produced).
  • a process utilizes a two step water based acid catalyzed reaction system to convert the algae lipids to biodiesel.
  • At least one novel feature of such a process is that the conversion of the lipids (embedded in the algae) to fatty acids in the first stage reactors proceeds without the prior extraction of the lipids. Extraction of lipids from algae can be problematic and inevitably introduces at least one additional chemical component which requires subsequent separation from the product, by-products, and other feed chemicals.
  • Another novel feature is the use of a water-based two stage reaction system to produce biodiesel.
  • the residual cell matter from the algae is energy-rich and is burned to generate most of the steam and electricity needed for the overall process (the carbon dioxide from this combustion can be captured and used to grow additional algae), according to embodiments of the present invention.
  • the overall energy balance for the process is exceptionally favorable, estimated at about 6 units of energy produced for every unit consumed, according to embodiments of the present invention.
  • ethanol plants are at an overall energy balance of approximately 1.2.
  • the first step in the transformation of these lipids to FAME proceeds by means of their acid catalyzed hydrolysis to free fatty acids.
  • the triolein the major oil component occurring in many plants, as a model lipid, the triolein would be converted to oleic acid as follows:
  • this reaction system not only allows for the subsequent production of FAME in a water based acid catalyzed medium (see equation 3 below) but eliminates the potentially severe reversibility of the first reaction (equation 2), while at the same time avoiding the extraneous extraction of the lipids themselves. This is accomplished all in the first reactor, according to embodiments of the present invention.
  • a difference in this synthesis is that a combination of in-vitro hydrolysis and esterification reactions are utilized.
  • the use of a hydrolysis reaction which converts the triglycerides to free fatty acids, increases the overall rate of conversion to the product.
  • Free fatty acids produced from the hydrolysis readily undergo acid catalyzed esterification with a residence time of about one hour with ninety-nine percent conversion, according to embodiments of the present invention. This can be contrasted with a direct acid catalyzed transesterification of triglycerides, which requires about thirty-six hours to achieve 80 percent conversion.
  • Certain embodiments concern design of commercial scale plants that will allow continuous production of 100 million gallons per year of biodiesel from algae. As discussed above, in-situ acid-catalyzed hydrolysis followed by esterification is used as the reaction for the conversion of algae biomass to biodiesel. The design focuses on the downstream processes that will convert an algae stream into biodiesel, according to embodiments of the present invention.
  • the incoming algae contain 40 percent lipid content by dry weight.
  • the incoming algae slurry is 25 percent water by weight.
  • the algae growth facility is located close to the plant.
  • the acid-methanol solution will be 4 percent sulfuric acid by volume.
  • FIG. 2 A basic block flow diagram for the process is shown in FIG. 2.
  • the full process flow diagram (FIGS. 7-10) encompasses the many different parts of the design, according to embodiments of the present invention. For simplification, it can be broken down into several sections: one for the main reaction, another for the separation of the byproducts, and the final two for the purification of the biodiesel product and the methanol recycle stream. These sections may be broken down further into their specific parts and analyzed individually.
  • the first is the algae feed. Its composition is 25 percent water, 30 percent triglycerides (as triolene), and the cell matter which accounts for the other 45 percent.
  • the cell matter contains carbohydrates (as energy storage or as cell wall material), proteins, and other cell mass. Additionally the phospholipids that make up each cell membrane are potential feed stocks for the reaction, but in the treatment below are assumed to be accounted for as part of the lipid content.
  • This algae slurry enters the system at approximately 27°C and 1 atmosphere. Prior to entering the first reactor sequence, it is combined with the second stream, sulfuric acid at 18 M. This second stream arrives at the same temperature and pressure. These streams are mixed before being split and sent to the three individual reaction chains.
  • a methanol feed stream for the Fisher Esterif ⁇ cation section of the reaction scheme is an additional inlet and is fed at 27 0 C and 1 arm.
  • the reaction scheme is run in parallel to reduce reactor size and individual flow rates, while maintaining the overall flow rates.
  • the streams Prior to reaction, the streams are pressurized by pump P-101 (P -201 and P-301 in the parallel chains) up to 2 atm. This keeps the methanol liquid at the reaction temperature.
  • the pressurized stream is then heated by H-101 (H-201, H-301) to 100 0 C, the preferred hydrolysis temperature.
  • the first section of the reaction scheme focuses on the triglyceride hydrolysis. Under appropriate conditions, three water molecules will combine with each triglyceride to form three stable fatty acids and glycerol.
  • Reactors R-101 and R- 102 combine to provide the one hour residence time required for ninety-nine percent hydrolysis. They are operated at 100 0 C and 2 atm. The output of the reactors reflects the ninety-nine percent conversion of triglycerides to free fatty acids.
  • the second section of the reaction scheme converts the free fatty acids to form the biodiesel end product.
  • a methanol stream is added, fed at two times the required stoichiometric amount to drive the reaction further to completion. Part of this stream consists of the methanol recycle stream.
  • the combined stream will be around 65°C, but only makes up about six percent of the total mass flow. Therefore, no additional heater is included, as the reactors are jacketed, and the reactions themselves are exothermic.
  • Reactors R- 103 and R- 104 combine to allow for a one hour residence time at 100 0 C and 2 atm, resulting in an 85 percent conversion of the free fatty acids to methyl esters (biodiesel).
  • the stream leaving the reaction section is then sent to the separation section. It is first centrifuged in C-101 to remove the algae cell matter. The supernatant includes all liquid components that left the reaction section. The solids are removed at a rate such that the mass flow rate downstream is reduced by almost 50 percent.
  • the liquid stream enters a decanter, which allows for a phase separation with a residence time of two hours. Water, glycerol, acid, and methanol leave in the heavy phase and are sent to the methanol purification section of the plant. The light phase, consisting of fatty acid methyl esters and free fatty acids, is sent to the secondary reaction section of the plant.
  • the heavy streams from the decanters are combined and preheated for flashing by H- 401. This stream is then flashed, resulting in a separation of the glycerol and acid from the water and methanol. Glycerol and acid leave the flash drum as a liquid bottoms stream, which is then sent on for further processing.
  • the vapor overhead stream is combined with the aqueous phase from the secondary esterif ⁇ cation reaction, for a total flow into tower T- 101.
  • the distillate leaving the tower consists of 99.1 percent methanol, which leaves a bottoms product of mainly water and trace sulfuric acid and glycerol.
  • the methanol distillate stream is recycled back to the esterif ⁇ cation portion of the reaction sequence, allowing for a significant reduction in the required methanol input.
  • the energy consumption of the plant can be a concern during the development of an overall process flow diagram, according to embodiments of the present invention.
  • it may be beneficial to recycle as much of the feed stocks as possible, including methanol and water.
  • it may be advantageous to utilize as many byproducts as possible in order to offset the costs of production.
  • a method used to separate the product biodiesel from the byproducts may be chosen with lower energy requirements.
  • Byproducts may be used in a manner that benefits the overall energy balance and cost of the process.
  • the glycerol produced in the esterif ⁇ cation reaction may be processed downstream to produce ethanol, which can either be sold or used as fuel.
  • Methodologies according to embodiments of the present invention can be shown to produce significantly more energy in the form of biodiesel than was required by the process to produce the biodiesel.
  • a flash drum is situated in front of the distillation column.
  • the product stream is heated to 125°C before entering the flash drum.
  • This heat exchanger has a heat duty of 77 MBtu/hr.
  • the flash drum has a heat duty of 6.5 MBtu/hr in order to keep it at 125°C.
  • the distillation column used to purify methanol has a heat duty of 198 MBtu/hr.
  • the reactors and smaller heat exchangers make up the balance of the total heat duty.
  • the heat for this process is mainly supplied by steam at 100 psi, which makes up most of the annual utility cost.
  • the 100 psi steam may be used for the feed heat exchangers, distillation column, and the reactors.
  • 450 psi steam may be utilized.
  • cooling water may be used in a number of applications. It may be used to condense the methanol leaving the distillation column. More cooling water may be necessary for the reactors as mentioned before, as well as cooling any product streams that may require further processing on site.
  • Table 1 shows the costs and amount of each utility that may be used, according to embodiments of the present invention. Electricity is used to power the pumps and centrifuges. Process water is calculated as the overall requirement, and could be potentially supplemented by a recycle later on in the system, but the full requirement is only 0.1 percent of the total annual cost and would not impact the pricing in any significant way, according to embodiments of the present invention.
  • a gravity separator may be used instead of a distillation column or other energy consuming unit, to conserve energy.
  • the biodiesel and water exist in different phases and will separate if given enough time, according to embodiments of the present invention. Decanters help to not only separate the water from the biodiesel, but since the acid, methanol, and glycerol are miscible in water they are also removed from the product stream. This leaves only biodiesel and unreacted free fatty acids in the product stream, and allows for continuous plant operation.
  • biodiesel and unreacted free fatty acids may be run through another reactor which converts almost all the free fatty acids to biodiesel.
  • a decanter is once again used to remove the added methanol and sulfuric acid.
  • Table 2 shows that the disclosed process has a positive energy balance, according to embodiments of the present invention.
  • the amount of sun used to make algae grow was not included in the energy balance.
  • the positive energy balance is an important consideration in the design and construction of a plant, in comparison to alternative methods. Concerns have been expressed about the net energy produced in the production of ethanol and rapeseed derived bio fuels.
  • the energy balance for the disclosed plant shows that 5.6 units of energy are produced for every one unit input into the system.
  • Embodiments of the present invention employ many different types of equipment, including reactors, centrifuges, decanters, a distillation column and many pumps and heat exchangers. Units discussed in this section have specification sheets that may be found at FIGS. 11-24.
  • reactors there are three different types of reactors used.
  • the first is the reactor used for the hydrolysis of the triglyceride into free fatty acids. These reactors are listed as R-101 and R- 102, R-201 and R-202, and R-301 and R-302 in the process flow sheet.
  • the algae and acid are fed at a pressure of 2 atm and a temperature of 100 0 C.
  • the conditions in the reactors are the same as the feed conditions, so no heating or pressurization needs to be done in the reactors, just the maintenance of these conditions.
  • the reactors are glass-lined continuous stirred tank reactors (CSTR) and are agitated and jacketed.
  • CSTR glass-lined continuous stirred tank reactors
  • the glass lined reactors may assist with the acidic nature of the feed.
  • the volumetric flow rates into each reactor are 8,585 gal/hr, according to embodiments of the present invention.
  • the residence time for each reactor is half an hour, according to embodiments of the present invention. A half hour residence time may be chosen to reduce the size of each reactor and help in achieving the 99 percent hydrolysis of triglycerides into free fatty acids in a smaller volume.
  • the size of each reactor may be calculated; according to some embodiments of the present invention, each reactor is calculated to be 4,293 gal.
  • An oversize factor of 1.16 may be used, leading to the choice of a a 5,000 gallon reactor. Such a rector size may allow for head space and help minimize overfilling.
  • Challenges in designing the reactors include selecting a residence time and operating conditions, according to embodiments of the present invention.
  • Each reactor may be jacketed to help maintain a selected temperature, for example 100 0 C. Cooling water and 100 psi steam may be used to heat and cool the reactor as necessary.
  • the reactors have very little heat duty overall compared to other units in the process, as the inlets are already at operating conditions, according to embodiments of the present invention.
  • the overall operating costs of the reactor are minimal due to low utility usage and maintenance cost, according to embodiments of the present invention. If one hydrolysis reactor must stop production for maintenance, then there are two other chains that can still produce biodiesel, according to embodiments of the present invention. The overall production of the plant will decrease but will not have to stop if one reactor needs maintenance, according to embodiments of the present invention.
  • the second type of reactor that may be used is for the esterif ⁇ cation of the free fatty acids into the fatty acid methyl esters or biodiesel, according to embodiments of the present invention.
  • These reactors are listed as R-103 and R-104, R-203 and R-204, and R-303 and R- 304 in the overall process flow diagram.
  • the feed to these reactors contains the components leaving the hydrolysis reactors which, according to embodiments of the present invention, may include: cell matter, water, glycerol, acid, and free fatty acids.
  • Another feed stream to the reactor is the methanol for the esterif ⁇ cation reaction.
  • the total volumetric flow rate of both streams is 9,472 gal/hr, according to embodiments of the present invention.
  • the conditions in these reactors are the same as the hydrolysis reactors with a temperature of 100 0 C and a pressure of 2 atm, according to embodiments of the present invention.
  • the esterif ⁇ cation reactors may be glass-lined due to the corrosive nature of the feed. Glass-lined may be preferred in some cases over stainless steel due to the high cost of stainless steel. All of these reactors are CSTRs and are jacketed and agitated as well, according to embodiments of the present invention.
  • the residence time of these reactors is also half an hour, according to embodiments of the present invention.
  • the total residence time may be selected to be 30 minutes, according to embodiments of the present invention.
  • a total residence time may be selected to be one hour between the two reactors, according to embodiments of the present invention.
  • the one hour may be divided across two reactors to help reduce the size of each reactor and help in achieving the desired conversion, according to embodiments of the present invention.
  • the calculated volume for each reactor is 9,023 gallons, according to embodiments of the present invention.
  • the esterif ⁇ cation reaction is an exothermic reaction that may result in a need to cool the reactors.
  • the reactors may be cooled with cooling water through their jackets.
  • the overall usage of cooling water to maintain the desired temperature in the reactors may be minimal, which leads to low operating cost due to utilities. Another operating cost is maintenance. If, for some reason, a reactor needs stop production due to maintenance, the other two branches may still be able to continue making biodiesel, according to embodiments of the present invention.
  • the final reactor is used to complete the esterif ⁇ cation of free fatty acids to biodiesel, according to embodiments of the present invention.
  • This reactor is listed as R-401 on the process flow diagram.
  • the product stream is separated from the byproducts (glycerol, water, etc)
  • the biodiesel product stream is fourteen percent free fatty acids.
  • the final reactor may be added to convert the remaining free fatty acids to biodiesel.
  • the reactor feed may be an acid and methanol mixture, along with the biodiesel product containing fourteen percent free fatty acids.
  • the conditions in the reactor are 100 0 C and 2 atm, according to embodiments of the present invention.
  • the volumetric flow rate through the reactor is 11,923 gal/hr, according to embodiments of the present invention.
  • This reactor may also be a jacketed and agitated glass-lined CSTR.
  • the residence time may be chosen to be one hour for reasons stated for the other esterification reactors.
  • the size for the reactor is 11,923 gal, according to embodiments of the present invention.
  • This reactor houses a low concentration of free fatty acids that need to react, according to embodiments of the present invention.
  • the temperature may be maintained using cooling water. Also, the amount of cooling water required is a minimal expense and so the overall yearly maintenance and cost is minimal, according to embodiments of the present invention.
  • this reactor if for some reason this reactor has to be shut down for maintenance, the whole plant would have to either stop production or the biodiesel product would have to be stored until the maintenance is completed. Therefore, two intermediate storage tanks may be included to allow for twenty-four hours of storage. Alternatively, a backup reactor may be provided to allow for maintenance during continuous production.
  • a process according to embodiments of the present invention utilizes three centrifuges to separate the cell matter from the liquid after the hydrolysis and esterification reactor sequence. After the triglycerides in the algae cells have been extracted and reacted, they may need to be separated out.
  • the centrifuges are listed as C-IOl, C-201 and C-301 in the process flow diagram. 316 stainless steel may be used for the material due to the acidity of the solution.
  • the centrifuges may be designed based upon the number of tons of solid per hour they were required to separate. The amount of cell matter removed is estimated at 23.85 tons/hr for each centrifuge, according to embodiments of the present invention.
  • decanters separate the heavy byproducts from the biodiesel product. Decanters are referred to as D-IOl, D-201, D-301 and D-401, according to embodiments of the present invention.
  • the decanters are designed to allow a sufficient time for the aqueous phase (water, glycerol, acid, and methanol) to separate from the oil phase (biodiesel, free fatty acids). This is accomplished by a gravity separation due to the significant difference in density of the phases, according to embodiments of the present invention.
  • the time taken for a separation is given by Equation 4:
  • ⁇ is the viscosity of the light phase
  • P H is the density of the heavy phase
  • P L is the density of the light phase.
  • a calculation time for separation of two hours may be used as the residence time of the liquid in the decanter.
  • the volumetric flow rate through D- 101, D-201 and D-301 is 7,112 gal/hr, according to embodiments of the present invention.
  • the volume of these decanters may be 14,107 gal, according to embodiments of the present invention.
  • the decanters may be horizontal vessels.
  • the length to diameter ratio may be selected as 6, to allow for proper settling of the heavy phase from the light phase. With such volume, the length of each decanter may be 60 ft. with a diameter of 10 ft., according to embodiments of the present invention.
  • the decanters may be constructed out of 316 SS due to the acidity of the feed, according to embodiments of the present invention.
  • D-401 has a different size, due to a volumetric flow rate of 16,791 gal/hr, according to embodiments of the present invention. With this flow rate the decanter size may be 33,305 gal, according to embodiments of the present invention.
  • This volume with a length to diameter ratio of 6 yields a length of 58.9 ft and a diameter of 9.8 ft.
  • 100 percent the aqueous phase is removed from the oil phase in the decanters.
  • the decanters require very little utilities to ensure proper operating conditions, resulting in a minimal yearly operating cost.
  • decanters after the initial reaction scheme have to be repaired there may be others that can function while maintenance is completed. If the decanter after the final reactor were to need maintenance, then the flow from that reactor could be stopped or moved to a storage tank elsewhere, according to embodiments of the present invention. However, decanters are unlikely to require maintenance due to their simple design.
  • a flash drum reduce the volume of liquid sent to the distillation column by flashing off about half the water and almost all the methanol, leaving glycerol, acid and some water in the liquid phase, according to embodiments of the present invention.
  • the flash drum is referred to as F-101 on the process flow diagram.
  • the inlet flow is the combination of the three aqueous streams from the decanters, and the total volumetric flow rate is 10,100 gal/hr, according to embodiments of the present invention.
  • Heuristics may be used to determine a residence time in the flash drum of 10 minutes, and that the volume of the flash drum may be twice the value of the volumetric flow rate times the residence time, according to embodiments of the present invention.
  • the volume of the flash drum may be calculated to be 3,972 gal.
  • the conditions inside the column are 125 0 C and 1 arm., according to embodiments of the present invention. At this temperature and pressure there is a 95 percent vapor fraction in the column.
  • Flash drums may be vertical columns with a length to diameter ratio of five; such value may also be calculated with heuristics, according to embodiments of the present invention.
  • the height of the flash drum may be 39.8 ft with a diameter of 8 ft, according to embodiments of the present invention.
  • the unit identification for the distillation column is T-101 on the process flow diagram.
  • a distillation column separates the water and any residual glycerol and acid from the methanol, according to embodiments of the present invention.
  • the purified methanol may then be recycled to become part of the reactor feed. This recycle process greatly reduces chemical costs.
  • the water that leaves the bottoms of the column may be further processed.
  • a software simulation engine for example ASPEN, may be used to determine the number of trays required for the column, the reflux ratio and the flow rates of liquid and vapor through the column, according to embodiments of the present invention.
  • the total number of trays for the column is 17 and the reflux ratio is 18.9, according to embodiments of the present invention.
  • the methanol product leaving the top of the column may be 99 percent pure.
  • the height of the column may be determined by the number of trays with 2 foot spacing, which would make the column 34 feet tall.
  • the tray type may be selected to be sieve trays, and the tray material may be determined to be 316 SS due to the possibility of acidic conditions in the column.
  • the flow rates for the liquid and vapor may be used to calculate the column diameter, which is 5.45 ft in some embodiments.
  • the overall weight of the column is 8,421 lbs., according to embodiments of the present invention.
  • the column material may be selected to be 316 SS as well due to the acidity of the solution.
  • the column pressure is 2 atm to make for a smaller diameter and a higher temperature of vapor leaving the column, according to embodiments of the present invention.
  • the main operating cost of the distillation column consists of utilities for the reboiler and the condenser.
  • the reboiler may be supplied with 100 psi steam and the condenser may be supplied with cooling water, according to embodiments of the present invention.
  • Pumps in the system may operate to raise the pressure in the feed streams from one atmosphere to a pressure of two atmospheres, according to embodiments of the present invention.
  • the pumps are designated as P-101, P-201, P-301, P-401 and P-501.
  • the pumps may be constructed of 316 SS. The sizes of the individual pumps are described in FIGS. 23- 24.
  • Heat exchangers H-101, H-201, H-301, and H-501 heat feed streams from their initial temperature to the production temperature of 100 0 C, according to embodiments of the present invention.
  • H-401 may be used to heat the aqueous solution from the decanters to 125°C to prepare it for the flash drum, according to embodiments of the present invention.
  • Heat exchangers may be made of 316 SS due to the acidity in the solution.
  • the surface area in the heat exchanger and overall heat transfer coefficients may be calculated using a facility design software program, for example ASPEN, according to embodiments of the present invention.
  • Heat exchangers are not duplicated according to embodiments of the present invention, and due to the fact that three parallel streams exist, if H-IOl, H-201, or H-301 need maintenance only one of the three branches needs to stop production.

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Abstract

L'invention concerne des procédés, des compositions et un appareil pour la conversion continue de lipides d'algues en biodiesel. Dans certains modes de réalisation, le biodiesel est formé selon une séquence à plusieurs étapes, les premières étapes survenant en présence d'eau et d'un acide fort, les lipides étant libérés des algues par l'intermédiaire d'une action mécanique et chimique, et étant ensuite hydrolysés en acides gras libres. Dans une étape consécutive, ce mélange d'acides gras libres est mis à réagir avec du méthanol pour générer des esters de méthyle d'acide gras (également connus en tant que biodiesel). De tels procédés produisent du biodiesel à partir de lipides d'algues sans l'exigence d'une lyse cellulaire d'algues séparée ou d'une extraction ou purification de lipide avant la séquence de catalyse acide. Dans d'autres modes de réalisation, la séquence de catalyse acide à plusieurs étapes survient à 100°C à deux atmosphères de pression.
PCT/US2008/071385 2007-07-27 2008-07-28 Installation de production de biodiesel d'algue continue WO2009018230A1 (fr)

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