US20050081435A1 - Continuous flow method and apparatus for making biodiesel fuel - Google Patents

Continuous flow method and apparatus for making biodiesel fuel Download PDF

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Publication number
US20050081435A1
US20050081435A1 US10/235,065 US23506502A US2005081435A1 US 20050081435 A1 US20050081435 A1 US 20050081435A1 US 23506502 A US23506502 A US 23506502A US 2005081435 A1 US2005081435 A1 US 2005081435A1
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tank
plant
tanks
methanol
oil
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Joseph Lastella
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BIO-CLEAN FUELS Inc
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BIO-CLEAN FUELS Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1862—Stationary reactors having moving elements inside placed in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • B01F27/90—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms 
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • B01F27/90—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms 
    • B01F27/906—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms  with fixed axis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80—Mixing plants; Combinations of mixers
    • B01F33/81—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80—Mixing plants; Combinations of mixers
    • B01F33/81—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles
    • B01F33/811—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles in two or more consecutive, i.e. successive, mixing receptacles or being consecutively arranged
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00189—Controlling or regulating processes controlling the stirring velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761—Details of the reactor
    • B01J2219/00763—Baffles
    • B01J2219/00779—Baffles attached to the stirring means
    • 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

Definitions

  • the present invention is directed to a process and apparatus for producing “biofuel” from oil or waste oil such as “yellow grease” (also known as tallow or used oil from food).
  • the method involves obtaining a fatty acid alkyl ester by transesterification of monoglycerides, diglycerides and triglycerides with alkyl alcohol.
  • the yellow grease may be heated and then mixed with sulfuric acid and methanol in a large tank or reaction vessel.
  • the acid and methanol break down long chain molecules (“fatty acid reduction”). That is, the methanol reacts with the fatty acid in the oil and produces a methyl ester material.
  • the mixture is pumped into a large settling tank. The methanol and sulfuric acid settle to the bottom, and the treated yellow grease is at the top. The bottom material is recycled.
  • the oil is then pumped to an unloading tank, reheated, and then mixed with potassium hydroxide and more methanol in a second reaction vessel.
  • the material is mixed for a period of time, e.g., one hour and undergoes “esterification.” A slight excess of caustic alcohol may be added.
  • the mixture is then pumped into a second settling tank. Again, the treated oil, now “ester,” is separated from the top, and glycerol and more fatty acid soap are settled at the bottom of the tank.
  • This process uses extremely large tanks, e.g., thousands of gallons. It takes a very long time, e.g., ten (10) to twelve (12) hours or more to empty a 10,000 to 12,000 gallon tank.
  • the footprint of a plant that is sized for a million gallons of biodiesel fuel per year is about one to one and a half acres (40,000 to 60,000 sq ft) to accommodate large reactors and multiple settling tanks, collectively totaling 60,000 to 100,000 gallons in capacity.
  • the plant runs twenty four (24) hours and requires a lot of labor, pumps and heating equipment.
  • Because of the need for settlement in the multiple settlement tanks the industry does not consider a continuous flow process. Due to such large tanks and handling time, it is difficult to control the temperature of the tank's contents. The tank's contents cool during lengthy unloading and settling processes, and the temperature of the contents vary in such large tanks. A number of approaches have thus been taken to optimize the reaction and process.
  • U.S. Pat. No. 5,972,057 incorporates an initial pre-mixing step wherein the alkaline catalyst is completely dissolved in the alcohol before adding the alcohol and catalyst to the oil rather than mixing the catalyst, alcohol and oil together in the same tank simultaneously.
  • the pre-mixing step accelerates the reaction such that the oil reaches an equilibrium conversion rate of 99% in 1.0 minute or less at a reaction temperature of 60° C., and at a stirring speed of 300 rpm.
  • conventional methods would produce an equilibrium conversion rate of 96% in thirty minutes or more under the same conditions.
  • the method disclosed in the '057 patent requires that the heat of dissociation generated at the time of dissolving the catalyst in the alcohol be removed by heat exchange between cooling water and the catalyst-containing alcohol solution. This is accomplished by placing a cooling water jacket on the outside of the dissolving and stirring tank. Further, the supply speed of the catalyst to the dissolving and stirring tank is controlled so that the temperature of the catalyst solution does not exceed 64° C. If the supply speed of the catalyst is too high, the generated heat of dissolution is not removed in time and creates a hazard.
  • U.S. Pat. No. 5,424,467 discloses a method for producing purified alcohol esters and a method for recovering the by-products of transesterification.
  • the process involves reacting an alcohol and a triglyceride in the presence of a catalyst and separating out a first phase, which includes the alcohol ester, unreacted alcohol and catalyst, from a second heavier phase comprising a by-product such as glycerin, un-reacted alcohol and catalyst.
  • the second heavier phase is then treated to separate glycerin from un-reacted alcohol and catalyst, and the first phase is treated to separate out glycerin and catalyst from the alcohol ester.
  • the transesterification reaction is catalyzed by bases such as sodium hydroxide, or by acids such as sulfuric acid, which are mixed with the alcohol prior to reaching the reaction vessel.
  • an excess of alcohol in the transesterification reaction is used to effect separation of the resulting ester phase from the alcohol phase without further treatment of the reaction mixture.
  • the alcohol is introduced in a ratio ranging from 7% to 40% by weight based upon the amount of oil used.
  • the catalyst is added in an amount ranging from about 0. 1% to 2.0% by weight based upon the amount of oil used. If sufficient excess alcohol is not employed, it may be necessary to add more alcohol to initiate the phase separation, which would result in larger equipment sizes being required to handle the increased volume.
  • U.S. Pat. No. 6,015,440 recognizes that the use of biodiesel fuel is limited in practice due to adverse cold temperature properties such as viscosity, ‘pour point’ and ‘cloud point’, and discloses a method for producing a biodiesel fuel with reduced viscosity and a cloud point below 32° F.
  • the process utilizes potassium hydroxide and methanol to transesterify triglycerides from animal or vegetable origin. Once transesterification occurs, the mixture of crude glycerol and biodiesel fuel esters are subjected to an etherification process, which produces a mixture of ethers of glycerol and biodiesel esters. This mixture is then recombined with pure biodiesel fuel to form an ‘oxygenated’ biodiesel fuel with a cloud point reduced to approximately 20° F.
  • the present invention achieves continuous flow through all the reaction vessels and separation tanks without the need for additional pumps.
  • the invention preferably employs preferably closed tanks (though preferably not sealed) to provide for methanol recovery, and may include vertical rotating feed tubes having separators and inlet and outlet openings. These features permit production of a larger quantity of biodiesel fuel while employing reaction and mixing tanks having a limited size, which in turn permits a dramatically smaller plant layout or “footprint”. Further, the process preferably pre-mixes the catalyst and methanol, but does not require pre-mixing prior to adding the catalyst to the oil or a means for actively removing heat from the system.
  • the process comprises the steps of providing waste oil at a starting temperature of about 50° F. to 150° F., mixing it with a catalyst and alcohol, such as sulfuric acid and methanol, and passing the mixture through a heating means to promote the reaction of methanol and sulfuric acid with the oil to produce methyl ester material.
  • a catalyst and alcohol such as sulfuric acid and methanol
  • the methanol and sulfuric acid may be fed back to the pump for re-use.
  • the oil or “yellow grease” is preferably provided to the system using a means for controlling the flow rate of the grease.
  • a chemical mixing pump may be employed to pump at a desired flow rate, e.g. 2 gpm, through a heat exchanger to reach a temperature of about 160° F.
  • the mixture is then directed to a first reaction vessel (“RV 1 ”), preferably through a rotating central pipe.
  • the pipe may be rotated by a motor, chain and sprocket configuration and comprises blades and upper and lower perforations that permit the reaction mixture to flow into and out of separate chambers within RV 1 . It is desireable to maintain a temperature of 140 to 155° F. homogeniously. This is very difficult to do in large tanks without incorporating very expensive heating and cooling units.
  • the reaction mixture flows next to a first separation tank (“ST 1 ”).
  • ST 1 a first separation tank
  • Flow through the tanks and reaction vessels is preferably set up to be continuous due to level differentials, thus the flow coming to ST 1 from RV 1 is relatively hot (e.g. 140° F.), and RV 1 and ST 1 may be insulated to help maintain the heat.
  • Sulfuric acid and methanol are heavier than the oil and flow out of the bottom of ST 1 , while the oil flows out near the top of ST 1 and to a second reaction vessel (“RV 2 ”).
  • the oil may be passed through a heating means after it exits ST 1 so that it is close to 150° F. to 180° F. when it enters RV 2 .
  • RV 2 may be identical to RV 1 , but is preferably shorter to maintain static pressure continuous flow and since the reaction time in reactor RV 2 is approximately half of the reaction time required for RV 1 , the plant design lends itself to a smaller RV 2 which may thus be shorter in height than RV 1 to perfectly accommodate the difference in height needed for static flow through-processing.
  • ST 2 may be identical to ST 1 , but is preferably shorter and has an input level lower than the liquid level in RV 2 .
  • oil and glycerol separate, and the ester is sent to a means for removing additional methanol and glycerol, such a water centrifuge.
  • the present invention is to provide an economical process and apparatus for obtaining biofuel from waste oil or oil byproducts.
  • the present invention produces biofuel using as continuous flow process.
  • the present invention may also provide an efficient method and apparatus for producing biofuel in large quantities while simultaneously permitting reduced tank size and plant footprint in comparison to prior plants for producing the same quantity.
  • static pressure is used to move the flow from one tank or vessel to successive tanks or vessels in a continuous flow manner.
  • a novel mixing tank is formed by a housing, multiple vertical chambers, mixing blades and a rotating input pipe passing through all of the chambers.
  • a novel input pipe has inlet and outlet openings, mixing blades and structure to rotate the blades.
  • a plant for the production of biofuel has a first and a second reaction vessel and a first and a second separation tank located in a two by two layout.
  • a method and an apparatus are provided for the production of biofuel wherein the apparatus and method produce about one million or more gallons per year from four tanks, with the largest tank having a capacity of about 360 gallons.
  • FIG. 1 is a flowchart of the steps, using schematic views of a preferred plant structure, for producing biofuel according to a preferred embodiment.
  • FIG. 2 is a cross sectional view of a tank RV 1 and its input pipe used in a plant and process of FIG. 1 .
  • FIG. 3 is a cross sectional view of a tank ST 1 used in a plant and process of FIG. 1 .
  • FIG. 4 is a side view schematic of the height differentials and configuration of the tanks and vessels used in a plant and process of FIG. 1 .
  • FIG. 5 is a cross sectional view of the input pipe for RV 1 or RV 2 of FIG. 1 .
  • FIG. 6 is a top view of the plant layout and flow direction used in a plant and process of FIG. 1 .
  • FIG. 7 is a plane view of an exemplary biofuel plant of a first floor of a two story plant in accordance with a second embodiment of the invention.
  • FIG. 8 is a plane view of a second floor in the exemplary biofuel plant of FIG. 7 .
  • FIG. 9 is a sectional view taken along a line A-A of the first and second stories of the plant of FIG. 7 .
  • FIG. 10 is a sectional view taken along a line B-B of the first and second stories of the plant of FIG. 7 .
  • FIG. 11 is a schematic flow diagram of a biodiesel plant in accordance with a third embodiment of the invention.
  • FIG. 12 is a schematic side elevation view of a stage A mixing vessel.
  • FIG. 13 is a schematic partial top view of the mixing vessel of FIG. 12 showing a cover thereof.
  • FIG. 14 is a schematic top view and sectional view of the mixing vessel of FIG. 12 showing a stand and details of a water jacket for the mixing vessel.
  • FIG. 15 is a schematic side elevation view of a stage A settling tank.
  • FIG. 16 is a schematic partial top view of the settling tank of FIG. 15 showing a cover thereof.
  • FIG. 17 is a schematic top view and sectional view of the settling tank of FIG. 16 showing a stand and details of a water jacket for the mixing vessel.
  • FIG. 18 is a schematic side elevation view of a stage B mixing vessel.
  • FIG. 19 is a schematic partial top view of the mixing vessel of FIG. 18 showing a cover thereof.
  • FIG. 20 is a schematic top view and sectional view of the mixing vessel of FIG. 18 showing a stand and details of a water jacket for the mixing vessel.
  • FIG. 21 is a schematic side elevation view of a stage B settling tank.
  • FIG. 22 is a schematic partial top view of the settling tank of FIG. 21 showing a cover thereof.
  • FIG. 23 is a schematic top view and sectional view of the settling tank of FIG. 21 showing a stand and details of a water jacket for the mixing vessel.
  • FIG. 24 is a schematic view of a variation of a separator in the reaction vessel RV 1 (or RV 2 ) of FIG. 2 .
  • FIG. 25 is a schematic view of another embodiment of a reaction vessel and settling tank, with a hot water jacket and a pressure maintaining apparatus.
  • FIG. 26 is a schematic view of another embodiment of a reaction vessel.
  • the invention comprises a continuous flow process for extracting oil from yellow grease, e.g., for making biodiesel fuel, and an apparatus for such process.
  • the invention may be described, with reference to FIGS. 1-5 , as follows:
  • Yellow grease preferably at a starting temperature of about 50° F. to 150° F., is mixed with an alcohol and catalyst, such as sulfuric acid and methanol.
  • the yellow grease is preferably provided to the system using a means for controlling the flow rate of the grease.
  • a chemical mixing pump may be employed to pump at a desired flow rate, e.g. 2 gpm, through a heat exchanger to reach a temperature of about 160° F., which promotes the reaction of the H 2 S and methanol with the yellow grease to produce the methyl ester material.
  • the sulfuric acid and methanol may be fed back and reused at the pump.
  • RV 1 In the first reaction vessel, RV 1 , the H 2 S and methanol enter through a centrally located pipe.
  • the pipe is preferably rotated, e.g. by a motor using a chain and sprocket, and has blades on it, e.g., two or more. Where there are two blades, e.g., the pipe may be turned at approximately 120 RPMs, while four blades would preferably be turned slower.
  • the blades may be flat or curved. It is preferable to keep the liquid in the tank as long as possible, so a blade tending to send liquid out and/or up is preferable.
  • the blade may have a scoop on the end to help lift liquid away from the wall.
  • the pipe is preferably 21 ⁇ 2′′ to 3′′ in diameter and has perforations, as shown in FIG. 2 .
  • the upper perforation in each chamber (shown with a dot inside in FIG. 2 ) is an inlet of liquid into the chamber, preferably above the blades.
  • the pipe is blocked off at or just above the blade.
  • these holes are on opposite sides of the pipe.
  • the pipe in tanks RV 1 and RV 2 may be formed by tack welding four 21 ⁇ 2′′ pipe sections, each with one closed end inside the larger 3′′ pipe. The holes for inlet and outlet may then be drilled in the two pipes where needed.
  • RV 1 is divided into chambers, e.g., four chambers using separators.
  • the separators preferably attach to the central pipe in a liquid tight manner, and are angled slightly up.
  • the separators preferably meet a rubber ring to help prevent fluid flow downward between the tank wall and the separators.
  • the mixture eventually flows out the lower hole (with the “x” as shown in FIG. 2 ), into the pipe, then out the upper hole in the next lower chamber (chamber 2 ), and so on. Flow reaching the bottom of RV 1 and the bottom of the pipe flows through an elbow and up to the inlet at the top of the first separating tank ST 1 .
  • the flow is continuous due to the pump continuously sending liquid at the flow rate into RV 1 , and the static pressure from the liquid level of RV 1 being sufficiently higher than the highest level of the input to ST 1 , by a distance A. See FIG. 4 .
  • Flow through remaining tanks ST 1 , RV 2 and ST 2 is also set up to be continuous due to level differentials B, C and D, respectively, as shown in FIG. 4 .
  • the liquid must pass from one chamber to the other in equal amounts depending on the feed rate at the top. Liquid can not pass from one chamber to the next and commingle. In other words, new liquid entering a tank will not mix with liquid that has been in the tank for a long time thus ensuring a reaction time of at least two hours for at least 90 to 95% of all liquid. The balance of the liquid with less than two hours reaction time will still be partially reacted. Therefore, there is only a small amount of unreacted liquid that will pass through the system. Any such unreacted biofuel is liquid will end up in the glycerin, which may also be sold. This is a relatively small loss, and is insignificant compared to the many benefits of the continuous flow process.
  • the reaction mixture next flows to a first settling tank, ST 1 .
  • Sulfuric acid and methanol which are heavier than oil, eventually separate from the oil and flow out the bottom of ST 1 .
  • ST 1 preferably includes a deflector located just below the outlet hole of the inlet pipe to help the liquid disperse and also to help prevent liquid from flowing out of the tank before the sulfuric acid and methanol and oil separate.
  • RV 1 and ST 1 may be insulated tanks, to help maintain the heat. At temperatures of about 110° F. and up, the oil and sulfuric acid and methanol in tank 1 and glycerol in tank ST 2 separation will occur almost immediately.
  • the first tank may also have a hot water jacket, preferably of about 11 ⁇ 2′′ to 2′′, and a hot water heater may supply the water jacket.
  • a hot water heater may supply the water jacket. This however, is generally not necessary, since at about 140° F., the input is sufficiently above 110° F. such that the separation is fast.
  • the water out from the bottom of the jacket may be returned to the heater and then back to the top of the jacket at about 160° F.
  • a conventional standard water heater may be used, such as a 50-gallon water heater with a recovery rate of about 75 gallons per hour.
  • the tanks may be insulated instead of or in addition to the use of the heater, and insulating may also be provided around a water jacket.
  • the oil flows out near the top of ST 1 and goes to RV 2 . It may be returned to the heat exchanger (or the flow may be directed through a second heat exchanger) before entering tank RV 2 so that it is preferably at or close to 160° F., or is preferably at least about 150° F. This is a good temperature for the reactions in RV 1 and RV 2 .
  • RV 2 potassium hydroxide and additional methanol is added to the oil.
  • RV 2 may be identical to RV 1 , but is preferably shorter to maintain the static pressure continuous flow (See FIG. 4 .)
  • ST 2 may be identical to ST 1 , but is preferably shorter and has its input level disposed at a position lower than the liquid level in RV 2 .
  • a sufficient drop between the liquid level of one tank and the input level of the next tank is expected to be about two feet. (A, B, C and D equal two feet in FIG. 4 .)
  • the flow is next directed to a second separation tank, ST 2 .
  • Glycerol and oil (ester) separation in ST 2 is fast at over 110° F., especially since glycerol has an sg of about 1.05 and biofuel has an sg of about 0.85.
  • the oil (ester) is sent to a water centrifuge, as is conventional in the art, to remove more methanol and glycerol.
  • the continuous flow settling tank for stage B can be significantly increased by simply increasing the diameter of the tank only a relatively small amount. For example, a diameter increase of six (6) inches from twenty four (24) inches to thirty (30) inches increases settling time by over fifty percent (50%) and has little or no impact on the plant's overall design.
  • the glycerin may be centrifuged as is well known in the art. Or, an additional settling tank or additional settling tanks may be added, preferably in parallel. In addition, a coalescing agent may be used as is well known in the art.
  • All four tanks RV 1 , ST 1 , RV 2 , ST 2 may be about 2′ in diameter, and may comprise a 11 ⁇ 2′′ to 2′′ water jacket and 11 ⁇ 2′′ to 2′′ of insulation. Each of the four tanks may be supported on a four foot by four foot stand, four feet high, to provide a footprint of 8′ ⁇ 8′ (See FIG. 6 ). If desired or necessary, an additional reaction vessel may be plumbed in series with RV 1 and/or RV 2 to ensure complete reactions, especially if the flow rate is increased.
  • the tanks preferably are not sealed, and are preferably vented. All of the tanks preferably have level indicators. It is expected that at 2 gpm, over one million gallons a year can be produced from a set of four tanks, with the largest tank being about 360 gallons instead of 17,000 gallons.
  • FIGS. 7-10 An example of a plant designed for a two story building is shown in FIGS. 7-10 . It uses the process and apparatus described with reference to FIGS. 1-6 , or it may use the process as shown in FIG. 11 , or as shown and described with respect to FIGS. 12 et seq.
  • Three sets of four tanks are provided in FIG. 7 .
  • the first set of four tanks is shown in a two by two arrangement plumbed in series going clockwise, starting from the top left of the rectangle, i.e., A 1 mixer, A 2 settlor, B 1 mixer, B 2 settlor.
  • the next group of four tanks is also plumbed in series clockwise, but is split somewhat due to the existing building structure, i.e., C 1 mixer, C 2 settlor, D 1 mixer, D 2 settlor.
  • the last group of four tanks is shown as the four tanks in a two by two array at the right side of the second rectangle, i.e., E 1 mixer, E 2 settlor, F 1 mixer, and F 2 settlor.
  • E 1 mixer, E 2 settlor, F 1 mixer, and F 2 settlor In the plant, it is envisioned that preferably the methanol and sulfuric acid will be pumped from separate sources into mixing tanks (in the explosion proof rooms), and the contents of the mixing tanks will simultaneously be pumped into the A stage reactors (A 1 , C 1 and E 1 , respectively), achieving continuous flow of the methanol and acid mixture too. This is distinct from the concept of batch mixing of the catalyst.
  • the plant of FIG. 7 has three sets of four tanks. Using just one set of tanks, with the 2 gpm flow rate and the tank corresponding to the first reaction vessel RV 1 , i.e., tank A 1 , having a 360 gallon capacity, the annual output of biofuel is expected to be about 1.3 million gallons. If two sets of tanks are used, the output is expected to be about 2.6 million gallons. If three sets of tanks are used, the output is expected to be about 3.9 million gallons.
  • the plant is divided into the following areas:
  • Crude oils typically vegetable oils or grease, specifically yellow grease
  • an esterification/transesterification reaction to produce methyl and ethyl esters suitable for combustion in a diesel engine.
  • This product is generically referred to as biodiesel, having similar boiling points and density as conventional diesel.
  • the National Biodiesel Board currently defines specifications for this product.
  • the primary reaction for biodiesel is the conversion of triglycerides into an ester having the desired characteristics as mentioned above. This is accomplished via a transesterification reaction where the raw oils are reacted with a C 1 to C 4 alcohol, e.g. methanol, in the presence of a basic catalyst, e.g. potassium or sodium hydroxide.
  • a basic catalyst e.g. potassium or sodium hydroxide.
  • the base catalyst and the alcohol produce a sodium or potassium methoxide, which in turn is reacted with the raw oils and allowed to settle.
  • Glycerin forms on the bottom, while the methyl esters float to the top.
  • This reaction is generally carried out with an amount of alcohol in excess of stochiometric conditions so that the bias of the reaction is directed towards the production of esters and glycerin.
  • FFA free fatty acids
  • esters After the production of glycerin and methyl esters, the esters must be washed to separate them from any residual glycerin not separated, the catalyst, any water, particulates, etc. prior to the esters being suitable for a certified biodiesel product.
  • the size of the plant described is for an 5.5-gpm throughput, resulting in approximately 2.8 million gallons per year throughput.
  • Crude Oil The capacity of crude oil on hand at any given time should be of sufficient volume so as not to impede production, should delays in delivery be incurred. For a 5.5 gpm throughput, a desired tank size would be 25,000 gallons, thereby providing a three day supply of feedstock. A suitable alternative would be to feed the oil or grease directly from its production to the plant, thereby capturing for use any residual temperature as a result of initial processing. The tradeoff for this energy saving approach would be that a loss of production of the oils or grease would halt the production of biodiesel.
  • the crude oil tank would also consist of the following peripheral equipment:
  • Methanol In the esterification reaction (Stage A), the methanol content is typically 15% of the volume of the raw oil or grease feedstock. As a result, approximately 5% of the total volume is defined as bottoms and is removed from the processing sequence. Therefore, approximately 95% of the initial feedstock, including catalyst and surplus alcohol is available for the transesterification reaction (Stage B). For this reaction, approximately 20% by volume of methanol is added to the feed material of Stage B, or approximately 19% by volume additional alcohol is required (95% ⁇ 20%). This necessitates that the methanol demand is 34% of the volume of raw oil feedstock, the bulk of which will be consumed as part of the reaction. A three-day supply of the methanol would require that the tank have the capacity for storage of at least 8500 gallons (34% ⁇ 25,000 gallons). The methanol tank would also consist of the following peripheral equipment:
  • Sulfuric Acid For Stage A, the amount of sulfuric acid is 4.62 v % of the amount of methanol or 0.693 v % the volume of the raw oil or grease. For a three-day supply, the size of the sulfuric acid holding tank would need to be a minimum of 175 gallons (25,000 gal ⁇ 0.693 v %).
  • the sulfuric acid tank would also consist of the following peripheral equipment:
  • the feed pump from the feed oil to the Stage A reactor will be shut down, as will downstream agitators and pumps. Either an HH or LL alarm will force a full plant shutdown.
  • the mixing tank size must be of sufficient capacity to allow the operator time to make corrections.
  • the reaction vessel is relatively low capacity in comparison with the conventional plant designs, the catalyst may be mixed relatively slowly and thus relatively safely.
  • Safety Protocol The design capacity allows 45 minutes for the extreme condition of a downstream blockage. The same would be true if the methanol and sulfuric acid feed tanks went empty. A loss of flow from either the methanol or the sulfuric acid would also constitute a likewise potential shutdown.
  • a temperature gauge would monitor the temperature inside the vessel. The mixing of sulfuric acid and methanol is exothermic and therefore releases heat as the two are mixed. If the ratio of acid to methanol is reduced, the temperature will decrease. If the ratio of acid to methanol is increased, then the temperature will increase. Should either of the flow meters become stuck, the operator would not know that a potential alarm condition existed. The temperature monitoring would give an independent alarm status monitoring as a redundant safety backup.
  • Temperature monitoring also consists of 4 alarm states: HH, HL, LH, and LL.
  • the triggering of HL or LH would alert the operator that the reaction has exceeded nominal conditions, allowing for the capability of correcting the problem without disrupting production.
  • the output could be limited iteratively until the condition is rectified.
  • a HL alarm would shut down or decrease the speed of the pump supplying the acid (P 05 ) to limit the exothermic reaction.
  • a LH alarm would shut down or decrease the output of the methanol pump (P 04 ) until the temperature is brought back into tolerance. In the case of a pump shut down, the pump could restart once the HL or LH alarm had been deactivated below 10% of the triggering event.
  • the MeOH/H 2 SO 4 mixing tank will also consist of the following peripheral equipment:
  • the MeOH/KOH solution is transferred to a feed tank, which is now ready for use in the operation.
  • a level indicator in the MeOH/KOH feed tank alerts the operator when the volume is sufficiently low enough to require a new batch of MeOH/KOH to be mixed.
  • a predetermined amount of the alcohol/basic catalyst is added to the feed stream from Stage A Settler to the Stage B Reactor.
  • Design Capacity 95 v % of the initial raw oil is transferred over for processing from the Stage A settler, with the remaining 5 v % settling out of the bottom. Therefore, the quantity of raw oil is 5.225 gpm (5.5 gpm ⁇ 95%).
  • An alternative method to sizing the feed tank is to examine the practical nature of a manual mix.
  • the interval between mixes is 6 hours or the requisite volume of the feed tank is 2000 gallons.
  • the mixing tank is designed to mix 80% of the volume of the feed tank, therefore the volume of the mixing tank is 800 gallons, or 1600 gallons for a plant turn up of 100 percent.
  • Pump 08 will require a positive flow signal from the flow meter from Stage A settler in order to initiate flow.
  • the MeOH/KOH mixing tank and feed tank will also consist of the following peripheral equipment:
  • the crude oil, having been mixed with the appropriate amounts of sulfuric acid and methanol are heated via Heat Exchanger HE 01 to a nominal temperature of 140 to 145° F., where it is then introduced into the Stage A reactor from the top.
  • Agitators of a proprietary design maintain the solution as a homogenous mixture with a relative residence time of between one to two hours before exiting from the bottom.
  • the Stage A reactor is stainless steel and jacketed, with the jacket containing 145 to 150° F. water. The purpose is to maintain the optimal temperature profile across the reactor. Once the product leaves the Stage A reactor, it is directed to the center of the Stage A Settler from the top. The Stage A Settler is also jacketed to maintain a nominal temperature profile.
  • the oil is directed to the Stage B Reactor for further treatment.
  • the acid catalyst and any salts are dropped to the bottom of the Stage B Settler, where they are periodically drained off of the tank.
  • the salt is separated from the acid and the acid is returned to the sulfuric acid holding tank for reuse.
  • the Stage A reactor is a vertical cylinder with a tapered bottom and a ratio of an internal diameter to height of 1:6.15.
  • the exact dimensions and ratio of the reactor is not critical, however in general terms a slender cylinder has a smaller footprint than one with a lower diameter to height ratio.
  • the Stage B Settler is also of a slender vertical cylinder, with the intent not only to have a smaller footprint for compactness of design, but also provides for better separation of the reacted oil from the acid and salts.
  • the premise is that a greater height to diameter ratio allows for better separation of the oil, which tends to rise to the top versus the heavier acid and salts, which tend to settle to the bottom.
  • the reduction of FFA's is a time sensitive reaction, meaning that too little of a residency time and low yields are obtained, while too long of a residency time results in an unusable product without additional treatment. For this reason, the maximum capacity design should not deviate significantly from the target residency.
  • the reactor utilizes a proprietary staged design integral to the agitators.
  • a temperature gauge at both the entrance and the exit of the reactor keep the operator informed of the temperature inside the reactor. Should the temperature exceed 150° F., an excessive amount of alcohol may evaporate. Allowing for this contingency, the reactor is covered with a removable stainless steel top with a 11 ⁇ 2′′ vent pipe. The vent pipe is connected to a collection tank where evaporating methanol is captured for reuse. The collection tank also serves as an overflow secondary protection device. A level indicator on the reactor with alarms notifies the operator if the reactor becomes too full or too low.
  • the Stage A Settler has an isolation valve at the bottom which normally remains closed. The valve is periodically opened and drained of excess salts and acid. The opening of the bottom of the Stage A Settler is noted in the operators log.
  • the agitators in the Stage A reactor are not engaged until the level is sufficient to cover the agitators.
  • a bottom drain valve is not opened for downstream treatment until the level is within a nominal operating range. This valve is manually opened and is part of the start up and shut down procedures.
  • the Stage A Settler bottom valve is checked to make sure it is closed, where it remains during the processing until manually drained by the operator.
  • An alternative is to have an automatic dump, based on the volume of bottoms accumulating. For the size of the 5.5 gpm unit described, the additional cost of automation for an automatic dump does not appear warranted.
  • Stage B the product is directed towards the Stage B Reactor.
  • the appropriate quantities of KOH and methanol are injected into the stream.
  • the mixture passes through the trimmer heat exchanger HE 02 to maintain 140 to 145° F.
  • the feed stream is introduced into the top of the Stage B Reactor and is kept as a homogenous mixture through the use of agitators.
  • Stage B is also jacketed and hot water is passed through the jacket to maintain a consistent temperature profile.
  • the use of the water through the jacket is to maintain the appropriate temperature profile.
  • any heat transfer medium may be used, e.g. steam, thermoil, heater coils, etc.
  • the reaction time of the esterification stage is one hour, being one half that of the first stage to remove FFA's. This reaction is not time sensitive specifically however. Therefore, the dimensions of the Stage B reactor is smaller than Stage A reactor. For consistency, the internal diameter may be kept the same as the Stage A reactor, reducing only the height, although this is not a requisite. As in Stage A, the Stage B Settler is of a slender cylindrical design, allowing for greater separation of the biodiesel from the crude glycerin.
  • the amount of KOH added in the transesterification is greater than the acid added at Stage A, therefore any residual acid that is carried across to Stage B is neutralized.
  • the bottom is protected by an isolation valve which maintains fluid in the reactor until the height is of a level sufficient to cover the agitators. So as not to entrain air in the mixture, the agitators are not engaged until they are completely covered. Notification to the operator is via a level indicator in the reactor.
  • the top of the Stage B Reactor has a removable stainless steel cover with a 11 ⁇ 2′′ vent pipe which serves a dual role of collecting any methanol vapors and condensing them into a collection tank and also as an overflow secondary safety device. Any excess methanol is returned to the methanol storage tank for reuse.
  • HE 01 the purpose is to raise the temperature of the crude, raw oil to the nominal operating temperature.
  • HE 02 and the water jackets the purpose is to trim, or maintain the desired temperature profile.
  • HE 02 trims the temperature back up to the desired temperature range, being 140 to 145° F., making up the losses from the pipe from the Stage A Settler to the Stage B Reactor.
  • the water jackets of both Stage A and B Reactors, as well as Stage A and B Settlers maintains an even temperature profile. Given that the reaction in both of the reactors is mildly exothermic, the jacket serves to carry any excess heat, if any, away from the reactors.
  • Design Capacity The size of HE 01 is dependent upon the application. For example, if the raw, crude oil is coming directly off of a production stream, in all likelihood the oil is already at an elevated temperature, therefore the size of HE 01 need not be excessively large. If, on the other hand, the oil is stored outdoors in a storage tank where it is allowed to cool, HE 01 will need to have a greater heating capacity.
  • the product must be washed with water to remove any excess glycerin and KOH not separated in the Stage B Settler.
  • the water is removed from the biodiesel in a commercial dryer. Depending upon the application and size of the plant, this may be accomplished by any of the standard industrial methods, e.g. centrifuge, molecular sieves, etc.
  • the number of wash and dry sequences is dependent upon the initial feedstock and the resistance of separation of the final product.
  • the glycerin is separated from the wash water in the conventional method, with the glycerin directed to the glycerin storage tank and the recovered water recycled for the next wash sequence.
  • Industrial wash and drying stages are available from various manufacturers and are incorporated into the plant design, based upon the recommendations of the manufacturer.
  • biodiesel In the completion of the process, there are essentially four products produced: biodiesel, crude glycerin, wash water, and recovered alcohol.
  • the biodiesel is typically stored in a rundown tank, where the lab on location can verify basic properties prior to its being released into the final biodiesel storage tank.
  • the biodiesel can be either stored in a biodiesel storage tank, or loaded directly from the rundown tank into tankers or rail cars.
  • the primary purposes of the systems controller is to maintain the appropriate nominal operating conditions, i.e. temperature, throughput, blend ratios, etc., and to serve as an alarm and safety device, should any condition arise that forces a shutdown of the plant.
  • the systems controller serves as a diagnostic tool to aid the operators in producing a consistent product safely.
  • the task is performed by either a PLC (programmable logic controller) or a PC-based system, which integrates the information supplied by the I/O devices monitoring temperature, flow, pump speeds, and tank levels. Depending upon the size of the plant, bottom valves may be closed or opened in a similar fashion.
  • PLC programmable logic controller
  • PC-based system which integrates the information supplied by the I/O devices monitoring temperature, flow, pump speeds, and tank levels.
  • bottom valves may be closed or opened in a similar fashion.
  • Such PLC or PC based systems are readily available by various manufacturers and can be programmed for each of the specific demands as described above.
  • Safety Protocol As with all good operating practices, the systems controller is backed up with standard gauges for the operator to monitor periodically. Servicing the plant requires that the operator manually lock out any valves or controls that might adversely affect the safety of the system or the operator during any shut down. This entails standard “tag and lock” safety protocols.
  • two settling tanks may be used for one mixing tank. Therefore, instead of doubling the size of the settling tank, a second tank is provided to yield about twice as much settlement time without reducing the throughput of the system.
  • the settlement tanks would be identical, other than the second tank preferably having a lower liquid level than the first settlement tank in order to facilitate the use of static pressure, where static pressure is used.
  • the central pipe may simple be a rotatable axis, but not have pipe sections and inlets and outlets for the liquid being mixed.
  • the separators can have an upward slanted shape having a small pipe section, e.g., one and a half inches (11 ⁇ 2′′) in diameter and two to two and a half inches (2 to 21 ⁇ 2′′) tall at a predetermined distance on the separator from the central axis, extending upward from the separator, and communicating with a hole in the separator leading to the chamber below. The liquid will drip through due to the pressure.
  • the height and diameter of the through pipe and its radial position on the separator may be selected to help ensure sufficient mixing of the liquid in the chamber.
  • multiple pipes could be used too.
  • FIG. 24 This variation of the separators is shown in FIG. 24 .
  • the edges of the separators may sit on or against bearings, formed e.g., by polyurethane riveted to the tank walls. In this embodiment, there may be no need for a bearing at the bottom center of the vessel.
  • Another variation of the invention may involve use of a semi-continuous flow process.
  • a 360 gallon first reaction vessel can be filled in about 9 minutes using a 40 gpm pumping rate. After 2 hours, the reaction vessel is unloaded at 40 gpm into the settling tank.
  • This settling tank may be made 360 gallons also, or may be split into two tanks totalling 360 gallons. For the stage A settling, separation occurs quickly, i.e., typically in about ten minutes with the lighter or thinner sources of biofuel. Even for heavier biofuel sources, settling in stage A should be well within the two hour reaction time of the mixing tank.
  • the remainder of the tanks could also be semi-continuous flow, i.e., using a high speed, e.g., 40 gpm pump for the B stage mixing tank and for the B stage settling tank(s). Because the tanks are small and because the reactions and/or settling are accelerated by heating, the through put of the system is still quite fast.
  • the filling and unloading time of the first tank totals 18 minutes, which only adds about 15% to the processing time of the system with continuous flow (2 hours). Therefore, the plant throughput will be as much as the continuous flow will 15% more time.
  • such higher speed pumping was thought to mix up the separator tanks to much and be adverse to the settlement process.
  • the B stage can be conducted over a longer time than two hours by using larger tanks or preferably multiple tanks filled in parallel.
  • reactor and settlor tanks may be built to be interchangeable, by removing the separators and spinning mechanisms from the reactor, if plant output needs or operational parameters change necessitating modifications to the number and/or placement of tanks.
  • FIG. 25 shows a variation of a reaction vessel RVx and settlor tank STx combination, and shows additional aspects of the invention, to form a hot water control system.
  • a head tank HT is connected by a pipe line HTx to a line Lx between the hot water jacket on the reaction vessel RVx and settlor tank STx.
  • the head tank maintains a constant pressure, e.g., 6 psi, on the reaction vessel and/or settlor tank from the water in the water jacket.
  • This structure enables the tank and vessel walls to be made of a strength less than otherwise needed to avoid implosion, buckling or the like if no head tank or other constant tank pressure mechanism were used.
  • the tank well may be made of sixteen (16) gauge stainless steel, rather than a heavier gauge, thereby reducing the cost of construction materials and construction in general.
  • Head tank HT may be a fifty five (55) gallon drum. If pressure drops in line Lx, e.g., due to head loss, water will tend to flow down in line HTx to make up for lost pressure.
  • a water pump, WPx is preferably a high volume, low pressure pump. Preferably, a constant low pressure such as six (6) psi is desireable.
  • the pumped water enters heat exchanger HEx which it is heated, as previously explained, e.g., to at or about 155° F.
  • the hot water passes along pipe line Lxi, enters a hot water jacket on reaction vessel RVx, and exists the vessel via line Lx, e.g., at about 152° F.
  • Hot water then enters a water jacket around settlor tank STx, and exits at about 149° F. through a pipe line Lxo.
  • High volume flow is preferred for better control of tank temperatures, especially since the boiling point of methanol is 160° F. The control helps avoid boiling the methanol.
  • FIG. 26 shows a variation of a reaction vessel RVy generally similar to that of FIG. 2 , using a center shaft, separators, and mixing blades (not shown) as in FIG. 2 .
  • a vessel also has a vacuum vent V, a pipe coupling, e.g., a standard 2′′ pipe coupling PC, a shaft S connected to a chain, gear and motor (e.g., as in FIG. 2 ), a hot water jacket having an inlet and outlet, as may be provided for all vessels and tanks, and an inlet and outlet for reaction fluid.
  • a pipe coupling e.g., a standard 2′′ pipe coupling PC
  • a shaft S connected to a chain e.g., as in FIG. 2
  • gear and motor e.g., as in FIG. 2
  • a hot water jacket having an inlet and outlet, as may be provided for all vessels and tanks, and an inlet and outlet for reaction fluid.
  • the outlet is located at the bottom of the tank, where the lower end of the center shaft fits into a standard pipe coupling PC′, such as a 2′′ coupling, preferably with a threaded surface and a machined surface, for fitting into a plug PG such as a 4′′ plug with bearings for the machined surface of the pipe coupling PC′.
  • the pipe coupling PC′ and bottom of the center shaft CS are located in a T-fitting, such as a 4′′ tee.

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