US20150184098A1 - Biomass Bio Oil Upgrade Method - Google Patents

Abstract

A bio oil pyrolysis and conditioning system produces a useful fuel oil. The pyrolysis system includes an auger carrying biomass feed material though an oxygen rare pyrolysis chamber. Vapor phase bio oil is collected at three locations along the length of the pyrolysis chamber and carried from the pyrolysis chamber to condensers and quenched by a water spray before release into the condensers. The water also serving as a solvent to reduce pH in the liquid phase raw bio oil. The raw bio oil is carried to a conditioning system where the raw bio oil resides in a separation tank where the water separates and is removed producing refined bio oil. Ethanol is mixed with the refined bio oil to provide the fuel oil.

Description

BACKGROUND OF THE INVENTION
• The present invention relates to biomass bio oil and in particular to a method for converting biomass feed material into a useful fuel oil.
• Biomass is comprised mainly of cellulose, hemi cellulose and lignin. A typical woody biomass may contain 40-50% cellulose, 25-35% hemi cellulose, and 15-18% lignin. Typical yields from a slow pyrolysis machine are 30% charcoal containing 70% plus carbon, 35% non-condensable gases containing hydrogen, methane, carbon mono oxide, carbon dioxide primarily, and 35% pyrolysis oil, also known as bio oil or bio crude, consisting tar, aldehydes, formic acid, acetic acid, water, esters, phenols, sugar derivatives, lignins. Such typical slow pyrolysis machine yields oil and charcoal in nearly equal portions. Slow pyrolysis involves heating of dried biomass (<8% moisture) in an oxygen free environment at 450-500 degrees centigrade in heated auger tubes. The process involves thermo chemical conversion of solid biomass to a liquid product, bio oil, and solid material, charcoal. Non condensable gases are utilized to heat the incoming wet biomass material, thus creating a closed loop system.
• Convention slow pyrolysis process yields bio oil that has the following properties:
• Chemical formula: CH_1.3O_0.47
• Flash point: 80 deg C.
• pH=2.5
• Sp Cr.=1.2
• Moisture content: 20-25%
• Heating value=7,522 btu/lb (17.5 mj/kg)
• Viscosity=60-100 cp and
• Elemental Analysis:
• C=55-60%
• H=5-8%
• O=28-40%
• N=0.06%
• Unfortunately, there are several issues with the use of such bio oil as a heating oil. The bio oil has a very low pH. Formation of acetic acid and formic acid during the pyrolysis process (derived mainly from the hemi cellulose portion of the wood) are the cause of low and highly acidic pH which makes it difficult to use this fuel with carbon steel, aluminum and natural rubber due to corrosion issues. To avoid corrosion issues, pH of the fuel should be close to neutral 7. The viscosity of bio oil can be as high as 100 cp and as a result can cause issues with the spray nozzles, fuel pumps, and other fuel handling equipment. Very heavy fuel oil such as Bunker C can have very high viscosity, however, upon heating; the viscosity of heavy petroleum fuels goes down to acceptable levels. Heating of bio oil leads to polymerization and hardening of fuel, thus making the problem worse. Additionally, the bio oil is immiscible with all petroleum fuels, so it cannot be mixed with other low viscosity fuel oils to lower its viscosity either. Over time, the bio oil starts to degrade due to the polymerization reactions. It becomes more viscous and water starts to separate out. This phenomenon can happen in as little as 30 days. Viscosity can increase tenfold at times. Heating value of bio oil is approximately 45% of that of fuel oil due to the presence of high levels of oxygen and water.
• Other attempted uses of bio oil include utilization as a substitute for road asphalt, also known as hot mix asphalt. Asphalt is currently derived from petroleum sources. Road asphalt may contain certain additives to prevent cracking, providing elasticity, and increased weather resistance. Raw bio oil, when heated, would indeed polymerize and harden; however, it still does not harden enough for use as road asphalt. Asphalt application for road requires that the asphalt harden within 24 hours to resume traffic, bio oil's utilization as asphalt does not contain this quick hardening property
BRIEF SUMMARY OF THE INVENTION
• The present invention addresses the above and other needs by providing a bio oil pyrolysis and conditioning system which produces a useful fuel oil. The pyrolysis system includes an auger carrying feed material though a oxygen rare pyrolysis chamber. Vapors are carried from the pyrolysis chamber to condensers and pH is reduced using a solvent and condensed raw bio oil is drained into storage tanks. The raw bio oil is provided to the conditioning system where further oil/water separation is performed to produce refined bio oil. Ethanol is mixed with the refined bio oil to provide the fuel oil.
• In accordance with one aspect of the invention, there is provided a pyrolysis system including quenching of bio oil in vapor phase. Longer residence times of vapors from a pyrolysis chamber in the presence of charcoal tend to increase tar formation. To reduce such tar formation, vapors coming from the pyrolysis chamber are quickly quenched by a spray of cooling water. Other oils, for example, bio diesel or the pyrolysis oil itself, may be used as a cooling medium, however, the use of water is beneficial for the following step explained below. Reduction in tar formation helps keep the viscosity of the bio oil lower and prevents clogging of the lines and equipment from tar formation.
• In accordance with another aspect of the invention, bio oil pH is reduced by removing water soluble formic and acetic acids from the bio oil using water as a solvent. Experiments with varying amounts of water found that water addition in the amount of 40-50 percent in the liquid phase bio oil by volume results in the formation of two district phases, an aqueous phase and an oil phase, with the aqueous phase floating to the top. Additionally, the aqueous phase pulls the water soluble acidic constituents of raw bio oil resulting in a refined bio oil. The aqueous phase is drained providing the refined bio oil for further processing. The pH of the aqueous phase is generally about 2.5, while the pH of the refined bio oil is generally about 6.2. The water added during the quenching process thus provides two advantages: a) better contact of water and oil and b) a cooling medium at the same time.
• In accordance with yet another aspect of the invention, the bio oil is mixed with at least 20% ethanol (i.e., one part bio oil and at least 0.2 parts ethanol) and preferably the bio oil is mixed with at about 20% ethanol. Bio oil is soluble in ethanol. Viscosity of bio oil obtained from mixing of ethanol is reduced to 4-5 cp which makes it very comparable to that of fuel oil. The bio oil can now be used as fuel without heating. Methanol may be used, but ethanol is renewable and has a higher heating value of compared to methanol. Additionally, stability of bio oil was enhanced with the addition of ethanol. Ethanol also has a higher flash point compared to methanol and is therefore easier and safer to handle. Due to the solvent nature of ethanol, no water separation has been observed and the bio oil remains in homogeneous phase with no increase in viscosity for the observation period of six months. Additional of ethanol also helps as an ignition improver. Ethanol also helps improve clogging in lines and keeps the storage and contact surfaces clean.
• In accordance with still another aspect of the invention, the heating value of the bio oil is increased from 17.5 kj/kg to 22.5-25 kj/kg, thus making the bio oil closer to petroleum fuel oils and a viable fuel.
• In accordance with another aspect of the invention, a combination of quench, water extraction, ethanol addition resulted in fuel that has higher pH, more stable, extremely low viscosity, stable and useable as a heating fuel (closer to #4 fuel oil) without needing any external heating. The heating value of bio oil unexpectedly increased about 25%, providing a commercial viability bio oil.
• In accordance with yet another aspect of the invention, there is provided a substitute for road asphalt, also known as hot mix asphalt. Currently, asphalt is derived from petroleum sources. Road asphalt may contain certain additives to prevent cracking, providing elasticity, and increased weather resistance. There are several issues with the use of Raw Bio Oil: Raw bio oil when heated would indeed polymerize and harden; however, it still does not harden enough for use as road asphalt. Asphalt application for road also require that the asphalt harden within 24 hours to resume traffic, bio oil's utilization as asphalt does not contain this quick hardening property. The substitute for road asphalt is obtained using refined bio oil, which is essentially devoid of acidic components to reduce pH, mixed with an equal or greater amount of petroleum asphalt. Such a mixture unexpectedly hardens and behaves like a standard asphalt. Greater amounts of petroleum asphalt may be used if desired. A secondary benefit is that using of raw bio oil as a road asphalt ingredient also imparted a shiny glow to the surface which improves appearance.
• In accordance with another aspect of the invention, there is provided a method for processing bio mass. The method includes feeding biomass material into an oxygen rare pyrolysis chamber, heating the biomass material to create vapor phase bio oil, carrying vapor phase bio oil from the pyrolysis chamber to a condenser, quenching the vapor phase bio oil before releasing into the condenser, cooling the vapor phase bio oil in the condenser, condensing the vapor phase bio oil into liquid phase raw bio oil in the condenser, separating water from the raw bio oil to produce refined bio oil, and mixing ethanol with the refined bio oil to produce a fuel oil.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
• The above and other aspects, features and advantages of the present invention will be more apparent from the following more particular description thereof, presented in conjunction with the following drawings wherein:
• FIG. 1 is a pyrolysis system for producing bio oil according to the present invention.
• FIG. 2 is a bio oil conditioning system according to the present invention.
• FIG. 3 is a method according to the present invention.
• Corresponding reference characters indicate corresponding components throughout the several views of the drawings.
DETAILED DESCRIPTION OF THE INVENTION
• The following description is of the best mode presently contemplated for carrying out the invention. This description is not to be taken in a limiting sense, but is made merely for the purpose of describing one or more preferred embodiments of the invention. The scope of the invention should be determined with reference to the claims.
• Apyrolysis system10 for producing bio oil according to the present invention is shown inFIG. 1. Thepyrolysis system10 primarily includes apyrolysis chamber12 andcondensers38a,38b, and38c. An auger16 residing in anauger housing14 extends through the length of thepyrolysis chamber12 and is rotated by amotor18.Biomass feed material20, for example dry sawdust, is fed through anentry21 into theauger housing14 at one end of thepyrolysis chamber12 andcharcoal material22 is released from theauger housing14 through achute23 at an opposite end of thepyrolysis chamber12. The interior of thepyrolysis chamber12 is substantially oxygen free and at a high temperature, causing thebiomass feed material20 to release vapors phase bio oil into the interior of thepyrolysis chamber12. Ahot air tube24 runs through thepyrolysis chamber12 above theauger housing14 carryingambient air28 heated and pumped byheater26 and released on the opposite end of thepyrolysis chamber12. Theexhaust30 from thehot air tube24 is directed to dryincoming biomass material20.
• The vapor phase bio oil generated in thepyrolysis chamber12 is collected in thecollectors38a,38b, and38cand vapor flows36a,36b, and36crespectively are carried to double wall condensers38. Thecollectors38a,38b, and38creceive the vapor phase bio oil from three zones of thepyrolysis chamber12. A first zone, zone Z1, is approximately the first third of thepyrolysis chamber12 length which will allow the collection of mostly moisture vaporized along with some very light ends. A second zone, zone Z2, is approximately the second third of thepyrolysis chamber12 length to collect light vapors and acid constituents vapors along with the reaction water. A third zone, zone Z3, is approximately the last third of thepyrolysis chamber12 length to collect heavier vapors, for example, vapor phase tar. Themultiple collectors38a,38b, and38callow product segregation from light to heavy ends in addition to keeping the water content of light and heavy liquid products low. Additionally, themultiple collectors38a,38b, and38callow for heavy liquid to have pH closer to 6 rather than 2.5. The light liquid will have pH of 2.5 but the absence of tar in that allows lowering of pH by conventional means, such as addition of alkali.
• Temperature indicators34 monitor the temperature of the vapor flows36. Quenchwater40 is introduced into the vapor phase bio oil flows36a,36b, and36cthrough valves V1 before the vapors enter thecondensers38a,38b, and38c, and coolingwater42 is provided between thedouble walls39 of thecondensers38a,38b, and38cto cool the vapor phase bio oil flows36a,36b, and36cpassing through the centers of thedouble wall condensers38a,38b, and38c, the coolingwater42 exits thecondensers38a,38b, and38cas flows32. The amounts of quenchwater40 is controlled to obtain desired properties of a liquidphase bio oil50aand50. Quenchwater40 also acts as solvent to extract acidic components from the liquidphase bio oil50aand50 which makes the bio oil more transportable and stable.
• The amounts of quenchwater40 provided is preferably determined by thebiomass feed material20 feed rate into thepyrolysis chamber12. The rate which thebiomass feed material20 is fed into thepyrolysis chamber12 is monitored and an expected production of refinedbio oil86 is calculated. Therefined bio oil86 production is generally about 35 percent by weight of thebiomass feed material20. The rate of providing the quenchwater40 is preferably controlled to result in amixture 40 to 50 percent by volume of the quenchwater40 and 50 to 60 percent by volume of bio oil in theraw bio oil50.
• Condensed bio oil50adrains from thecondensers38a,38b, and38cintostorage tanks48.Condensed water44 collected between thecondensers38a,38b, and38cand thestorage tanks48, andcondensed water44afromstorage tanks48, is carried to a water Knock Out (KO)drum46.Raw bio oil50ais released from thestorage tanks48 through second valves V2.
• FIG. 2 is a bio oilfuel conditioning system60 according to the present invention. The bio oilfuel conditioning system60 includes an oil/water separator62 which receives theraw bio oil50 from thestorage tanks48 and separates water from theraw bio oil50 to produce refinedbio oil86. Thewater66 is transferred to apH balance tank64 which also receives a pH control additive68 to produce pH balanced water. The pH balancedwater70. ThepH balance water70 is pumped by pump72 from thepH balance tank64 through afilter76 to produces filteredwater78, and through a cooler80 to produce cooledwater82, and to a cooled water supply. Optionally, additional water51 may be added to the oil/water separator62 if necessary as a solvent.
• Separatedrefined bio oil86 is carried to a mixing tank84 whereethanol88 is mixed with therefined bio oil86 to create a useful fuel oil90. An amount ofethanol88 equal to at least 20 percent by volume of the refinedbio oil86, is mixed with therefined bio oil86 to produce a useful fuel oil.
• A method for processing biomass according to the present invention is shown inFIG. 3. The method includes feeding biomass material into an oxygen rare pyrolysis chamber atstep100, heating the biomass material to create vapor phase bio oil atstep102, carrying vapor phase bio oil from the pyrolysis chamber to a condenser atstep104, quenching the vapor phase bio oil before releasing into the condenser atstep106, cooling the vapor phase bio oil in the condenser atstep108, condensing the vapor phase bio oil into liquid phase raw bio oil in the condenser at step110, separating water from the raw bio oil to produce refined bio oil atstep112, and mixing ethanol with the refined bio oil to produce a fuel oil atstep114.
• While the invention herein disclosed has been described by means of specific embodiments and applications thereof, numerous modifications and variations could be made thereto by those skilled in the art without departing from the scope of the invention set forth in the claims.

Claims (14)

I claim:

1. A method for producing a useful bio oil material, the method comprising:

feeding biomass into a pyrolysis chamber;

heating the biomass to create vapor phase bio oil;

carrying the vapor phase bio oil to a condenser;

condensing the bio oil vapor into liquid phase raw bio oil in the condenser;

separating water from the raw bio oil in a separator to produce refined bio oil; and

processing the refined bio oil into a useful material.

2. The method ofclaim 1, further including quenching the vapor phase bio oil before releasing the vapor phase bio oil into the condenser.

3. The method ofclaim 2, wherein quenching comprises spraying water into the vapor phase bio oil before releasing the vapor phase bio oil into the condenser.

4. The method ofclaim 3, wherein spraying the water into the vapor phase bio oil comprises spraying the water into the vapor phase bio oil, resulting in the raw bio oil including 40 to 50 percent of the water by volume and 50 to 60 percent liquid phase bio oil by volume.

5. The method ofclaim 1, wherein:

the condenser is a double wall condenser; and

further including providing a coolant flow between the double walls of the condenser to cool the vapor phase bio oil flowing through the center of the condenser.

6. The method ofclaim 5, wherein providing a coolant flow between the double walls of the condenser comprises providing a flow of cool water between the double walls of the condenser

7. The method ofclaim 1, wherein processing the refined bio oil into a useful material comprises mixing the refined bio oil with ethanol to produce a fuel oil.

8. The method ofclaim 7, wherein mixing the refined bio oil with ethanol to produce a fuel oil comprises mixing one part of the refined bio oil with at least 0.2 parts of the ethanol.

9. The method ofclaim 7, wherein mixing the refined bio oil with ethanol to produce a fuel oil comprises mixing one part refined bio oil with about 0.2 parts ethanol.

10. The method ofclaim 1, wherein feeding biomass comprises feeding dry sawdust.

11. The method ofclaim 1, wherein feeding biomass into a pyrolysis chamber comprises feeding biomass into an oxygen rare pyrolysis chamber.

13. The method ofclaim 1, wherein;

the pyrolysis chamber comprises at least three zones:

a first zone nearest to the entry of the biomass feed material;

a second zone in the middle; and

a third zone opposite to the first zone;

and the method further including:

collecting vapor phase bio oil in collectors residing in each zone; and

carrying the collected vapor phase bio oil independently from each collector to corresponding condensers.

14. A method for producing fuel oil from biomass material, the method comprising:

feeding biomass material into an oxygen rare pyrolysis chamber, the pyrolysis chamber comprises at least three zones:

a first zone nearest to the entry of the biomass feed material;

a second zone in the middle; and

a third zone opposite to the first zone;

heating the biomass material to create vapor phase bio oil;

collecting vapor phase bio oil in collectors residing in each zone; and

carrying the collected vapor phase bio oil independently from each collector to corresponding condensers;

quenching the vapor phase bio oil before releasing the vapor phase bio oil into the condensers;

condensing the vapor phase bio oil into liquid phase raw bio oil in the condensers;

releasing the liquid phase raw bio oil into a separation tank;

removing water from the liquid phase raw bio oil to produce refined bio oil;

carrying the refined bio oil into a mixing tank;

mixing an amount of ethanol of at least 20 percent by volume of the refined bio oil with the refined bio oil to produce fuel oil; and

releasing fuel oil from the mixing tank.

15. A method for producing fuel oil from biomass material, the method comprising:

feeding dry sawdust into an oxygen rare pyrolysis chamber;

heating the dry sawdust to create vapor phase bio oil;

carrying the vapor phase bio oil to a condenser;

quenching the vapor phase bio oil with water before releasing the vapor phase bio oil into the condenser;

condensing the bio oil vapor into liquid phase raw bio oil in the condenser;

carrying the liquid phase raw bio oil into a separation tank;

removing water from the liquid phase raw bio oil to produce refined bio oil in the separation tank;

carrying the refined bio oil from the separation tank into a mixing tank;

mixing one part of the refined bio oil with about 0.2 parts ethanol to produce fuel oil; and

releasing fuel oil from the mixing tank.

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