CA2633632C - Production of biodiesel from triglycerides by using thermal cracking - Google Patents
Production of biodiesel from triglycerides by using thermal cracking Download PDFInfo
- Publication number
- CA2633632C CA2633632C CA2633632A CA2633632A CA2633632C CA 2633632 C CA2633632 C CA 2633632C CA 2633632 A CA2633632 A CA 2633632A CA 2633632 A CA2633632 A CA 2633632A CA 2633632 C CA2633632 C CA 2633632C
- Authority
- CA
- Canada
- Prior art keywords
- biodiesel
- stream
- middle distillate
- thermal cracking
- distillate fraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/40—Thermal non-catalytic treatment
-
- 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
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
-
- 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
- C10G2300/1014—Biomass of vegetal origin
-
- 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
- C10G2300/1018—Biomass of animal origin
-
- 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
- C10G2300/80—Additives
- C10G2300/805—Water
- C10G2300/807—Steam
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method is presented for producing biodiesel from a triglyceride feedstock. The feedstock is pretreated by thermal cracking or rapid pyrolysis to convert triglycerides to form a middle distillate fraction rich in fatty acids. The middle distillate fraction is then esterified the in the presence of an alcohol and a catalyst to produce a biodiesel stream. The biodiesel stream can be treated with a basic solution to convert unesterified free fatty acids to non-foaming metallic soaps, which can be removed by known means. A method is also provided for producing a biodiesel/naphtha mixture, in which a triglyceride feedstock is pretreated by thermal cracking or rapid pyrolysis to produce a middle distillate fraction, a naphtha stream and a gas stream. The naphtha stream and the middle distillate fraction are then esterified to produce a mixed biodiesel/naphtha stream, which can be treated with a basic solution to convert unesterified free fatty acids to non-foaming metallic soaps, which are then removed by known means.
Description
Production of Biodiesel from Triglycerides by Using Thermal Cracking Technical Field The present invention relates to a method of producing biodiesel from triglycerides using thermal cracking. The present invention specifically relates to the production of biodiesel from waste triglycerides.
Background Art In recent years, the area of biodiesels has drawn a great deal of attention.
Biodiesels are plant and animal based fuels produced from the esterification of biomass-derived oils with alcohol. Biodiesel can be produced from such sources as canola, corn, soybean etc. Biodiesels are generally considered less environmentally damaging than traditional fossil fuels.
Another potential source for biodiesels is the waste triglycerides of animal rendering facilities and waste cooking oils, such as those found as restaurant trap greases. However, this potential is presently still under-explored and waste triglycerides are most commonly dumped into landfills (`Biodiesel Production Technology, August 2002 - January 2004"; Van Gerpen, J. et al., July 2004, NREL/SR-510-36244). Waste triglycerides often have a high contaminants content that must effectively be removed before processing. Furthermore, waste triglycerides tend to have a high content of free fatty acid (FFA), anywhere in the range of from 50% to 100%. Mixtures of free fatty acids and triglycerides have been found to be very difficult to convert to useful fuels by any traditional methods.
Traditional methods of producing biodiesels include transesterification and esterification with alcohol using either an acid or base catalyst. However, the high FFA content in waste triglycerides causes undesirable soap formation in base catalyzed esterification processes, rendering this process inoperable.
Waste triglycerides are also often heavily contaminated by contaminants, such as bacteria, detergents, silts and pesticides. These contaminants must be removed before esterification can take place, without adding significant additional cost to the overall processes.
One known method of processing high FFA feedstocks involves adding glycerol to the feedstock to convert FFA's to mono- and diglycerides, followed by conventional alkali-catalyzed esterification. This method addresses the high FFA content of waste triglycerides, but does not treat or remove contaminants.
A second method involves performing both esterification and transesterification of triglycerides using a strong acid such as H2SO4.
However, water formation by FFA esterification prevents this process from going to completion. A third method involves pre-treating an FFA-rich triglyceride feedstock with an acid catalyst to convert FFA to alkyl-esters and reduce FFA concentrations to less than about 0.5%, followed by traditional base-catalyzed esterification. This method again, only deals with the FFA
content of waste triglycerides, and not the high contaminant levels.
Thermal cracking of clean triglycerides under typical cracking conditions with and without catalyst has been attempted, but this process was found to yield mainly naphtha, not diesel fuels. Furthermore, in typical thermal cracking of clean or waste triglycerides in the presence of a catalyst, there is a tendency for coke formation to occur on the catalyst, resulting in rapid deactivation.
It is therefore greatly desirable to find a method of converting waste triglycerides feedstocks to biodiesel that is both efficient and economical.
It is also desirable to find ways of dealing with contaminants and high FFA content in waste triglyceride feedstocks so that they can be converted into usable fuels.
Disclosure of Invention The present invention provides a method of producing biodiesel from a waste triglyceride feedstock. The method first involves pretreating a waste triglyceride feedstock by a thermal cracking reaction at a temperature in a range of 390-460 C and a pressure in a range of 0 to 60 psig to remove contaminants and convert triglycerides to form a middle distillate fraction rich in free fatty acids. A middle distillate fraction having a boiling point range from 150 to 360 C is separated from a remainder of a reaction product of the thermal cracking. The middle distillate fraction is esterified in the presence of an alcohol and a catalyst to produce a biodiesel stream, and then the biodiesel stream is treated with a basic solution to convert unesterified free fatty acids to non-foaming metallic soaps. Finally, the non-foaming metallic soaps are removed by centrifugation, filtering or a combination thereof.
The present invention also provides a method of producing a biodiesel/naphtha mixture from a triglyceride feedstock. The method involves first pretreating a waste triglyceride feedstock by thermal cracking at a temperature in a range of 390-460 C and a pressure in a range of 0 to 60 psig to remove contaminants and convert triglycerides to produce a middle distillate fraction rich in free fatty acids, a naphtha stream and a gas stream. A middle distillate fraction having a boiling point range from 150 to 360 C, a naphtha stream and a gas stream are separated from a remainder of a reaction product of the thermal cracking. The naphtha stream and middle distillate fraction are esterified in the presence of an alcohol and a catalyst to produce a mixed biodiesel/naphtha stream, and the mixed biodiesel/naphtha stream is then treated with a basic solution to convert unesterified free fatty acids to non-foaming metallic soap;. Finally, the non-foaming metallic soaps are separated by centrifugation, filtering or a combination thereof.
Brief Description of the Drawings The present invention will now be described in further detail with reference to the following drawing, in which:
Fig. 1 is a flow sheet of a first preferred process for carrying out the present invention.
Background Art In recent years, the area of biodiesels has drawn a great deal of attention.
Biodiesels are plant and animal based fuels produced from the esterification of biomass-derived oils with alcohol. Biodiesel can be produced from such sources as canola, corn, soybean etc. Biodiesels are generally considered less environmentally damaging than traditional fossil fuels.
Another potential source for biodiesels is the waste triglycerides of animal rendering facilities and waste cooking oils, such as those found as restaurant trap greases. However, this potential is presently still under-explored and waste triglycerides are most commonly dumped into landfills (`Biodiesel Production Technology, August 2002 - January 2004"; Van Gerpen, J. et al., July 2004, NREL/SR-510-36244). Waste triglycerides often have a high contaminants content that must effectively be removed before processing. Furthermore, waste triglycerides tend to have a high content of free fatty acid (FFA), anywhere in the range of from 50% to 100%. Mixtures of free fatty acids and triglycerides have been found to be very difficult to convert to useful fuels by any traditional methods.
Traditional methods of producing biodiesels include transesterification and esterification with alcohol using either an acid or base catalyst. However, the high FFA content in waste triglycerides causes undesirable soap formation in base catalyzed esterification processes, rendering this process inoperable.
Waste triglycerides are also often heavily contaminated by contaminants, such as bacteria, detergents, silts and pesticides. These contaminants must be removed before esterification can take place, without adding significant additional cost to the overall processes.
One known method of processing high FFA feedstocks involves adding glycerol to the feedstock to convert FFA's to mono- and diglycerides, followed by conventional alkali-catalyzed esterification. This method addresses the high FFA content of waste triglycerides, but does not treat or remove contaminants.
A second method involves performing both esterification and transesterification of triglycerides using a strong acid such as H2SO4.
However, water formation by FFA esterification prevents this process from going to completion. A third method involves pre-treating an FFA-rich triglyceride feedstock with an acid catalyst to convert FFA to alkyl-esters and reduce FFA concentrations to less than about 0.5%, followed by traditional base-catalyzed esterification. This method again, only deals with the FFA
content of waste triglycerides, and not the high contaminant levels.
Thermal cracking of clean triglycerides under typical cracking conditions with and without catalyst has been attempted, but this process was found to yield mainly naphtha, not diesel fuels. Furthermore, in typical thermal cracking of clean or waste triglycerides in the presence of a catalyst, there is a tendency for coke formation to occur on the catalyst, resulting in rapid deactivation.
It is therefore greatly desirable to find a method of converting waste triglycerides feedstocks to biodiesel that is both efficient and economical.
It is also desirable to find ways of dealing with contaminants and high FFA content in waste triglyceride feedstocks so that they can be converted into usable fuels.
Disclosure of Invention The present invention provides a method of producing biodiesel from a waste triglyceride feedstock. The method first involves pretreating a waste triglyceride feedstock by a thermal cracking reaction at a temperature in a range of 390-460 C and a pressure in a range of 0 to 60 psig to remove contaminants and convert triglycerides to form a middle distillate fraction rich in free fatty acids. A middle distillate fraction having a boiling point range from 150 to 360 C is separated from a remainder of a reaction product of the thermal cracking. The middle distillate fraction is esterified in the presence of an alcohol and a catalyst to produce a biodiesel stream, and then the biodiesel stream is treated with a basic solution to convert unesterified free fatty acids to non-foaming metallic soaps. Finally, the non-foaming metallic soaps are removed by centrifugation, filtering or a combination thereof.
The present invention also provides a method of producing a biodiesel/naphtha mixture from a triglyceride feedstock. The method involves first pretreating a waste triglyceride feedstock by thermal cracking at a temperature in a range of 390-460 C and a pressure in a range of 0 to 60 psig to remove contaminants and convert triglycerides to produce a middle distillate fraction rich in free fatty acids, a naphtha stream and a gas stream. A middle distillate fraction having a boiling point range from 150 to 360 C, a naphtha stream and a gas stream are separated from a remainder of a reaction product of the thermal cracking. The naphtha stream and middle distillate fraction are esterified in the presence of an alcohol and a catalyst to produce a mixed biodiesel/naphtha stream, and the mixed biodiesel/naphtha stream is then treated with a basic solution to convert unesterified free fatty acids to non-foaming metallic soap;. Finally, the non-foaming metallic soaps are separated by centrifugation, filtering or a combination thereof.
Brief Description of the Drawings The present invention will now be described in further detail with reference to the following drawing, in which:
Fig. 1 is a flow sheet of a first preferred process for carrying out the present invention.
Fig. I is a flow sheet of a first preferred process for carrying out the present invention.
Best Modes for Carrying Out the Invention The present process employs a novel combination of thermal cracking followed by esterification to convert low quality triglycerides feedstock into usable biodiesel. In the present process, thermal cracking is used as a pre-treatment step to break down the triglycerides into a broad range of free fatty acids and lower molecular weight components. Thermal cracking also serves to remove contaminants found in waste triglycerides, which can cause problems downstream. The resulting product from the cracking step can then be esterified to convert fatty acids into alkyl esters (biodiesel).
For the purposes of the present invention, thermal cracking is considered to loosely cover the process of breaking down large molecules into smaller molecules at a predetermined temperature and pressure.
A flow diagram of the process steps and streams of one embodiment of the present invention is shown in Fig. 1. A feedstock 12 of low quality or waste triglycerides is fed to a thermal cracking unit 10. The feedstock 12 can be any variety of waste triglyceride, including restaurant trap greases, waste greases from animal rendering facilities and other forms of waste oils and greases and low-quality vegetable oils. The feedstock stream 12 can be heterogeneous in nature and can contain water and other contaminants. Waste triglycerides used as the feedstock stream 12 can also have free fatty acid (FFA) content as high as 50 to 100 wt.%. In an optional embodiment (not shown), the triglyceride feedstock 12 may be filtered to remove any macroscopic contaminant particles prior to thermal cracking.
In the thermal cracking unit 10, triglycerides in the feedstock stream 12 are significantly reduced since they are converted into free fatty acids, thus forming a mixture of free fatty acids and conventional hydrocarbons, such as paraffins, olefins and aromatics. Thermal cracking is preferably carried out at 4a mild cracking conditions which, for the purposes of the present invention, are described as an operating temperature preferably in the range of from 390 to 460 C, more preferably from 410 to 430 C, and preferably at an operating pressure of from 0 to 60 psig (6.9 to 515 kPa), more preferably from 30 to 40 psig (308 to 377 kPa). Thermal cracking produces various fractions including gases 14, naphtha 16, middle distillate 22, and residue 18.
Contaminants from the feedstock 12 end up in the residue stream 18.
It was noted that the mild thermal cracking conditions used in the present invention to crack waste triglycerides produces mainly diesel, having a boiling range of between 165 C and 345 C, rather than naphtha (IBP to 165 C), as was produced from thermal cracking of triglycerides at higher temperatures and pressures.
The middle distillate fraction 22 makes up more than half of the thermally cracked product and has been found to have suitable characteristics for further treatment by esterification. The middle distillate fraction 22 comprises free fatty acids formed from thermal cracking of triglycerides, the original free fatty acids 5 present in the feedstock and conventional hydrocarbons. Middle distillates typically encompass a range of petroleum equivalent fractions from kerosene to lubricating oil and include light fuel oils and diesel fuel. In one embodiment of the present invention the middle distillate fraction 22 was found to have a boiling point range of from 150 to 360 C, and more preferably from 165 to 345 T. The middle distillate fraction 22 still has some fuel quality issues such as high viscosity, high acid number, high cloud point and high concentrations of nitrogen and/or sulphur.
The middle distillate fraction 22 is next fed to an esterification unit 20, where it is reacted with an alcohol stream 24 in the presence of a catalyst to produce alkyl esters (biodiesel). The esterification process is carried out at a temperature preferably ranging from 70 to 120 C, more preferably in the range of from 90 to 110 C, and preferably at atmospheric pressure. The alcohol stream can be any suitable alcohol known in the art, or mixtures thereof. The alcohol stream 24 is preferably methanol.
It is surprisingly noted that esterification could be carried out well above the boiling temperature of the reacting alcohol, despite low alcohol concentration in the liquid phase of the reaction mixture. The ability to conduct the esterification at higher temperatures is advantageous since this allows continuous water stripping by the flashing alcohol stream. Since water is a co-product of acid esterification, it can detrimentally quench the esterification reaction if not removed continuously.
The catalyst can be either an acidic solid or liquid catalyst. Preferably, the acid catalyst is chosen from sulphuric acid (H2SO4(1)), sulphamic acid (H2NSO3H(j)), formic acid (HCO2H(q), acetic acid (CH3CO2H(1)), propionic acid (CH3CH2CO2H(p), hydrochloric acid (HCl(,)), phosphoric acid (H3PO4(l)), sulphated metal oxides such as sulphated zirconia, and styrene divinylbenzene copolymers having SO3H functional groups, such as Amberlyst 36TM. Amberlyst 36 is most preferred for the esterification reaction, as this does not leave any trace in the esterification product, and further washing of the esterification product is thus not required.
Free fatty acids can be acid esterified by the following reaction, here shown with the alcohol optionally being methanol:
H+
RCOOH + CH3OH RCOOCH3 +H20 The water byproduct can inhibit the reaction, and may prevent esterification from going to completion. As mentioned above, esterification at temperatures above the boiling temperature of the alcohol has been surprisingly found to alleviate this problem in the present invention.
Esterification produces a raw diesel stream 26 of approximately 50% alkyl esters (biodiesel) and 50% hydrocarbons. These hydrocarbons can include tetradecane, pentadecane, 1-hexadecene, hexadecane, heptadecane, 1-octadecene, octadecane, nonadecane, 1-eicosene, eicosane, heneicosane, 1-docosene, docosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, untriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, heptatriacontane, and octatriacontane.
It should be noted that, in addition to esterifying only the middle distillates fraction 22 from thermal cracking, it is also possible to esterify both the naphtha stream 16 and middle distillates fraction 22 from the thermal cracking step.
This optional method circumvents an extra step of separating naphtha 16 from the middle distillates 22.
Depending on the type of catalyst used and the degree of esterification achieved, the raw diesel stream 26 may exceed acidity limits allowed by ASTM
specifications for biodiesel, namely 0.8 mg KOH/g. To reduce acidity, the raw diesel stream 26 can optionally be fed to a base treatment unit 30, together with a basic solution 28. The basic solution 28 reacts with any unreacted fatty acids in the raw diesel stream 26 to produce non-foaming metallic soaps with low solubility in biodiesel. These non-foaming metallic soaps can then be removed by either centrifugation or filtering or a combination thereof. Base treatment is preferably carried out at temperatures of from 30 to 60 C, and more preferably at temperatures of from 40 to 50 C and preferably at atmospheric pressure. The basic solution is preferably chosen from lithium hydroxide (LiOH), magnesium hydroxide (Mg(OH)2), and calcium hydroxide (Ca(OH)2). Most preferred are LiOH and Ca(OH)2-The base treatment step results in a mixed biodiesel/diesel product 32 that has been found to have excellent fuel properties. The boiling point of the resultant biodiesel/diesel product 32 is found to be lighter and the boiling point distribution broader than that of biodiesel produced by conventional transesterification alone. The mixed biodiesel/diesel product 32 can be used both neat or can optionally be further blended with regular diesel.
The naphtha stream 16 from the thermal cracking unit 10 contains oxygenates and can optionally be sold as a valuable by-product such as octane improver. The residue stream 18 can be discarded by well known means in the art.
The following examples serve to better illustrate the process of the present invention, without limiting the scope thereof:
Example 1: Conversion of restaurant trap grease into mixed biodiesel/diesel product Restaurant trap grease having an average density of 0.925 g/mL was fed to a thermal cracking unit where it was cracked at a temperature of 418.5 C
and a pressure of 29 psig (301 kPa) for 40 minutes. Thermal cracking produced a gas stream, a naphtha stream, a middle distillate stream with a maximum boiling point of approximately 343 C, as well as water and residue. The middle distillates stream made up 63.0 wt.% of the total cracked product and had an acid number of 83.93 mg KOH/g.
Best Modes for Carrying Out the Invention The present process employs a novel combination of thermal cracking followed by esterification to convert low quality triglycerides feedstock into usable biodiesel. In the present process, thermal cracking is used as a pre-treatment step to break down the triglycerides into a broad range of free fatty acids and lower molecular weight components. Thermal cracking also serves to remove contaminants found in waste triglycerides, which can cause problems downstream. The resulting product from the cracking step can then be esterified to convert fatty acids into alkyl esters (biodiesel).
For the purposes of the present invention, thermal cracking is considered to loosely cover the process of breaking down large molecules into smaller molecules at a predetermined temperature and pressure.
A flow diagram of the process steps and streams of one embodiment of the present invention is shown in Fig. 1. A feedstock 12 of low quality or waste triglycerides is fed to a thermal cracking unit 10. The feedstock 12 can be any variety of waste triglyceride, including restaurant trap greases, waste greases from animal rendering facilities and other forms of waste oils and greases and low-quality vegetable oils. The feedstock stream 12 can be heterogeneous in nature and can contain water and other contaminants. Waste triglycerides used as the feedstock stream 12 can also have free fatty acid (FFA) content as high as 50 to 100 wt.%. In an optional embodiment (not shown), the triglyceride feedstock 12 may be filtered to remove any macroscopic contaminant particles prior to thermal cracking.
In the thermal cracking unit 10, triglycerides in the feedstock stream 12 are significantly reduced since they are converted into free fatty acids, thus forming a mixture of free fatty acids and conventional hydrocarbons, such as paraffins, olefins and aromatics. Thermal cracking is preferably carried out at 4a mild cracking conditions which, for the purposes of the present invention, are described as an operating temperature preferably in the range of from 390 to 460 C, more preferably from 410 to 430 C, and preferably at an operating pressure of from 0 to 60 psig (6.9 to 515 kPa), more preferably from 30 to 40 psig (308 to 377 kPa). Thermal cracking produces various fractions including gases 14, naphtha 16, middle distillate 22, and residue 18.
Contaminants from the feedstock 12 end up in the residue stream 18.
It was noted that the mild thermal cracking conditions used in the present invention to crack waste triglycerides produces mainly diesel, having a boiling range of between 165 C and 345 C, rather than naphtha (IBP to 165 C), as was produced from thermal cracking of triglycerides at higher temperatures and pressures.
The middle distillate fraction 22 makes up more than half of the thermally cracked product and has been found to have suitable characteristics for further treatment by esterification. The middle distillate fraction 22 comprises free fatty acids formed from thermal cracking of triglycerides, the original free fatty acids 5 present in the feedstock and conventional hydrocarbons. Middle distillates typically encompass a range of petroleum equivalent fractions from kerosene to lubricating oil and include light fuel oils and diesel fuel. In one embodiment of the present invention the middle distillate fraction 22 was found to have a boiling point range of from 150 to 360 C, and more preferably from 165 to 345 T. The middle distillate fraction 22 still has some fuel quality issues such as high viscosity, high acid number, high cloud point and high concentrations of nitrogen and/or sulphur.
The middle distillate fraction 22 is next fed to an esterification unit 20, where it is reacted with an alcohol stream 24 in the presence of a catalyst to produce alkyl esters (biodiesel). The esterification process is carried out at a temperature preferably ranging from 70 to 120 C, more preferably in the range of from 90 to 110 C, and preferably at atmospheric pressure. The alcohol stream can be any suitable alcohol known in the art, or mixtures thereof. The alcohol stream 24 is preferably methanol.
It is surprisingly noted that esterification could be carried out well above the boiling temperature of the reacting alcohol, despite low alcohol concentration in the liquid phase of the reaction mixture. The ability to conduct the esterification at higher temperatures is advantageous since this allows continuous water stripping by the flashing alcohol stream. Since water is a co-product of acid esterification, it can detrimentally quench the esterification reaction if not removed continuously.
The catalyst can be either an acidic solid or liquid catalyst. Preferably, the acid catalyst is chosen from sulphuric acid (H2SO4(1)), sulphamic acid (H2NSO3H(j)), formic acid (HCO2H(q), acetic acid (CH3CO2H(1)), propionic acid (CH3CH2CO2H(p), hydrochloric acid (HCl(,)), phosphoric acid (H3PO4(l)), sulphated metal oxides such as sulphated zirconia, and styrene divinylbenzene copolymers having SO3H functional groups, such as Amberlyst 36TM. Amberlyst 36 is most preferred for the esterification reaction, as this does not leave any trace in the esterification product, and further washing of the esterification product is thus not required.
Free fatty acids can be acid esterified by the following reaction, here shown with the alcohol optionally being methanol:
H+
RCOOH + CH3OH RCOOCH3 +H20 The water byproduct can inhibit the reaction, and may prevent esterification from going to completion. As mentioned above, esterification at temperatures above the boiling temperature of the alcohol has been surprisingly found to alleviate this problem in the present invention.
Esterification produces a raw diesel stream 26 of approximately 50% alkyl esters (biodiesel) and 50% hydrocarbons. These hydrocarbons can include tetradecane, pentadecane, 1-hexadecene, hexadecane, heptadecane, 1-octadecene, octadecane, nonadecane, 1-eicosene, eicosane, heneicosane, 1-docosene, docosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, untriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, heptatriacontane, and octatriacontane.
It should be noted that, in addition to esterifying only the middle distillates fraction 22 from thermal cracking, it is also possible to esterify both the naphtha stream 16 and middle distillates fraction 22 from the thermal cracking step.
This optional method circumvents an extra step of separating naphtha 16 from the middle distillates 22.
Depending on the type of catalyst used and the degree of esterification achieved, the raw diesel stream 26 may exceed acidity limits allowed by ASTM
specifications for biodiesel, namely 0.8 mg KOH/g. To reduce acidity, the raw diesel stream 26 can optionally be fed to a base treatment unit 30, together with a basic solution 28. The basic solution 28 reacts with any unreacted fatty acids in the raw diesel stream 26 to produce non-foaming metallic soaps with low solubility in biodiesel. These non-foaming metallic soaps can then be removed by either centrifugation or filtering or a combination thereof. Base treatment is preferably carried out at temperatures of from 30 to 60 C, and more preferably at temperatures of from 40 to 50 C and preferably at atmospheric pressure. The basic solution is preferably chosen from lithium hydroxide (LiOH), magnesium hydroxide (Mg(OH)2), and calcium hydroxide (Ca(OH)2). Most preferred are LiOH and Ca(OH)2-The base treatment step results in a mixed biodiesel/diesel product 32 that has been found to have excellent fuel properties. The boiling point of the resultant biodiesel/diesel product 32 is found to be lighter and the boiling point distribution broader than that of biodiesel produced by conventional transesterification alone. The mixed biodiesel/diesel product 32 can be used both neat or can optionally be further blended with regular diesel.
The naphtha stream 16 from the thermal cracking unit 10 contains oxygenates and can optionally be sold as a valuable by-product such as octane improver. The residue stream 18 can be discarded by well known means in the art.
The following examples serve to better illustrate the process of the present invention, without limiting the scope thereof:
Example 1: Conversion of restaurant trap grease into mixed biodiesel/diesel product Restaurant trap grease having an average density of 0.925 g/mL was fed to a thermal cracking unit where it was cracked at a temperature of 418.5 C
and a pressure of 29 psig (301 kPa) for 40 minutes. Thermal cracking produced a gas stream, a naphtha stream, a middle distillate stream with a maximum boiling point of approximately 343 C, as well as water and residue. The middle distillates stream made up 63.0 wt.% of the total cracked product and had an acid number of 83.93 mg KOH/g.
The middle distillate stream was then fed to an acid esterification unit, where it was contacted with methanol in the presence of an Amberlyst 36 catalyst.
Esterification was conducted at a temperature of 90 C and at atmospheric pressure for 20 hours.
Esterification produced a raw diesel stream which was then treated with a calcium hydroxide solution, Ca(OH)2(aq), to produce a final mixed biodiesel/diesel product having an acid number of 0.45 mg KOH/g. The final product was found to have 0.22 wt.% nitrogen, 136 ppm sulphur and a viscosity of 5.02 cSt; the sulphur content and viscosity being well within ASTM 6751 standards for biodiesel Example 2: Conversion of rendered animal fat into mixed biodiesel/diesel product Rendered animal fat, having an average density of 0.918 g/mL was fed to a thermal cracking unit in which it was cracked at 411 C and atmospheric pressure for 40 minutes. The thermally cracked product contained 68.6 wt% middle distillates having a maximum boiling point of 345 C, naphtha and the remainder gas, water and residues.
The middle distillate stream, having a viscosity of 8.50 cSt, and an acid number of 146.96 mg KOH/g, was then fed to an acid esterification unit, where it was contacted with methanol in the presence of an Amberlyst 36 catalyst.
Esterification was conducted at a temperature of 90 C and at atmospheric pressure for 20 hours.
The resultant raw diesel stream was then treated with a calcium hydroxide solution, Ca(OH)2(,q), to produce a final mixed biodiesel/diesel product having an acid number of 0.75 mg KOH/g. The final product was found to have 18 ppm sulphur and 158 ppm nitrogen, and a viscosity of 4.84 cSt.
This detailed description of the process and methods is used to illustrate certain embodiments of the present invention. It will be apparent to those skilled in the art that various modifications can be made in the present process and methods and that various alternative embodiments can be utilized.
Esterification was conducted at a temperature of 90 C and at atmospheric pressure for 20 hours.
Esterification produced a raw diesel stream which was then treated with a calcium hydroxide solution, Ca(OH)2(aq), to produce a final mixed biodiesel/diesel product having an acid number of 0.45 mg KOH/g. The final product was found to have 0.22 wt.% nitrogen, 136 ppm sulphur and a viscosity of 5.02 cSt; the sulphur content and viscosity being well within ASTM 6751 standards for biodiesel Example 2: Conversion of rendered animal fat into mixed biodiesel/diesel product Rendered animal fat, having an average density of 0.918 g/mL was fed to a thermal cracking unit in which it was cracked at 411 C and atmospheric pressure for 40 minutes. The thermally cracked product contained 68.6 wt% middle distillates having a maximum boiling point of 345 C, naphtha and the remainder gas, water and residues.
The middle distillate stream, having a viscosity of 8.50 cSt, and an acid number of 146.96 mg KOH/g, was then fed to an acid esterification unit, where it was contacted with methanol in the presence of an Amberlyst 36 catalyst.
Esterification was conducted at a temperature of 90 C and at atmospheric pressure for 20 hours.
The resultant raw diesel stream was then treated with a calcium hydroxide solution, Ca(OH)2(,q), to produce a final mixed biodiesel/diesel product having an acid number of 0.75 mg KOH/g. The final product was found to have 18 ppm sulphur and 158 ppm nitrogen, and a viscosity of 4.84 cSt.
This detailed description of the process and methods is used to illustrate certain embodiments of the present invention. It will be apparent to those skilled in the art that various modifications can be made in the present process and methods and that various alternative embodiments can be utilized.
Claims (14)
1. A method of producing biodiesel from a waste triglyceride feedstock, the method comprising:
a. pretreating a waste triglyceride feedstock by thermal cracking at a temperature in a range of 390-460°C and a pressure in a range of 0 to 60 psig to remove contaminants and convert triglycerides to form a middle distillate fraction rich in free fatty acids;
b. separating a middle distillate fraction having a boiling point range from 150 to 360°C from a remainder of a reaction product of the thermal cracking;
c. esterifying the middle distillate fraction in the presence of an alcohol and a catalyst to produce a biodiesel stream;
d. then treating the biodiesel stream with a basic solution to convert unesterified free fatty acids to non-foaming metallic soaps; and e. removing the non-foaming metallic soaps by centrifugation, filtering or a combination thereof.
a. pretreating a waste triglyceride feedstock by thermal cracking at a temperature in a range of 390-460°C and a pressure in a range of 0 to 60 psig to remove contaminants and convert triglycerides to form a middle distillate fraction rich in free fatty acids;
b. separating a middle distillate fraction having a boiling point range from 150 to 360°C from a remainder of a reaction product of the thermal cracking;
c. esterifying the middle distillate fraction in the presence of an alcohol and a catalyst to produce a biodiesel stream;
d. then treating the biodiesel stream with a basic solution to convert unesterified free fatty acids to non-foaming metallic soaps; and e. removing the non-foaming metallic soaps by centrifugation, filtering or a combination thereof.
2. The method of claim 1 wherein the basic solution is an aqueous solution of a compound selected from the group consisting of lithium hydroxide (LiOH), potassium hydroxide (KOH), magnesium hydroxide (Mg(OH)2), and calcium hydroxide (Ca(OH)2).
3. The method of claim 2 wherein the basic solution is an aqueous solution of calcium hydroxide or lithium hydroxide.
4. The method of claim 1 wherein the triglyceride feedstock is selected from the group consisting of restaurant trap grease, rendered animal fats, waste greases, low-quality vegetable oils and combinations thereof.
5. The method of claim 1 wherein thermal cracking is conducted at a temperature of from 410°C to 430°C.
6. The method of claim 1 wherein the middle distillate fraction is esterified in the presence of methanol as the alcohol.
7. The method of claim 6 wherein esterifying is conducted at a temperature of from 70°C to 120°C.
8. The method of claim 7 wherein esterifying is conducted at a temperature of from 85°C to 110°C.
9. The method of claim 1, wherein the middle distillate fraction is esterified in the presence of an acid catalyst.
10. The method of claim 9 wherein the acid catalyst is selected from the group consisting of sulphuric acid (H2SO4) in liquid form, sulphamic acid (H2NSO3H) in liquid form, formic acid (HCO2H) in liquid form, acetic acid (CH3CO2H) in liquid form, propionic acid (CH3CH2CO2H) in liquid form, hydrochloric acid (HCl) in liquid form, phosphoric acid (H3PO4) in liquid form, and styrene divinylbenzne copolymers having SO3H functional groups.
11. The method of claim 10 wherein the acid catalyst is a styrene divinylbenzene copolymer having an SO3H functional group.
12. The method of claim 1, further comprising filtering the triglyceride feedstock before thermal cracking to remove macroscopic contaminant particles.
13. A method of producing a biodiesel/naphtha mixture from a triglyceride feedstock, the method comprising:
a. pretreating a waste triglyceride feedstock by thermal cracking at a temperature in a range of 390-460°C and a pressure in a range of 0 to 60 psig to remove contaminants and convert triglycerides to produce a middle distillate fraction rich in free fatty acids, a naphtha stream and a gas stream;
b. separating a middle distillate fraction having a boiling point range from 150 to 360°C, a naphtha stream and a gas stream from a remainder of a reaction product of the thermal cracking;
c. esterifying the naphtha stream and middle distillate fraction in the presence of an alcohol and a catalyst to produce a mixed biodiesel/naphtha stream;
d. then treating the mixed biodiesel/naphtha stream with a basic solution to convert unesterified free fatty acids to non-foaming metallic soaps; and e. removing the non-foaming metallic soaps by centrifugation, filtering or a combination thereof.
a. pretreating a waste triglyceride feedstock by thermal cracking at a temperature in a range of 390-460°C and a pressure in a range of 0 to 60 psig to remove contaminants and convert triglycerides to produce a middle distillate fraction rich in free fatty acids, a naphtha stream and a gas stream;
b. separating a middle distillate fraction having a boiling point range from 150 to 360°C, a naphtha stream and a gas stream from a remainder of a reaction product of the thermal cracking;
c. esterifying the naphtha stream and middle distillate fraction in the presence of an alcohol and a catalyst to produce a mixed biodiesel/naphtha stream;
d. then treating the mixed biodiesel/naphtha stream with a basic solution to convert unesterified free fatty acids to non-foaming metallic soaps; and e. removing the non-foaming metallic soaps by centrifugation, filtering or a combination thereof.
14. The method of any one of claims 1 to 13, wherein the waste triglyceride feedstock has a free fatty acid content of 50 to 100%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/304,658 | 2005-12-16 | ||
| US11/304,658 US20070137097A1 (en) | 2005-12-16 | 2005-12-16 | Production of biodiesel from triglycerides via a thermal route |
| PCT/CA2006/002015 WO2007068097A1 (en) | 2005-12-16 | 2006-12-12 | Production of biodiesel from triglycerides by using thermal cracking |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2633632A1 CA2633632A1 (en) | 2007-06-21 |
| CA2633632C true CA2633632C (en) | 2012-02-14 |
Family
ID=38162512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2633632A Expired - Fee Related CA2633632C (en) | 2005-12-16 | 2006-12-12 | Production of biodiesel from triglycerides by using thermal cracking |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US20070137097A1 (en) |
| EP (1) | EP1976959A4 (en) |
| CA (1) | CA2633632C (en) |
| WO (1) | WO2007068097A1 (en) |
Families Citing this family (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7754931B2 (en) * | 2005-09-26 | 2010-07-13 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources | Production of high-cetane diesel fuel from low-quality biomass-derived feedstocks |
| US7563915B2 (en) * | 2006-05-30 | 2009-07-21 | The Penn State Research Foundation | Green biodiesel |
| WO2008105798A2 (en) * | 2006-06-30 | 2008-09-04 | University Of North Dakota | Method for cold stable biojet fuel |
| US7897798B2 (en) * | 2006-08-04 | 2011-03-01 | Mcneff Research Consultants, Inc. | Methods and apparatus for producing alkyl esters from lipid feed stocks and systems including same |
| US7691159B2 (en) * | 2006-09-19 | 2010-04-06 | Applied Research Associates, Inc. | Method of converting triglycerides to biofuels |
| CN103540412A (en) | 2007-03-14 | 2014-01-29 | 恩迪科特生物燃料Ii有限责任公司 | Production of biodiesel fuels which are low in glycerin and sulfur |
| CA2680174C (en) * | 2007-03-14 | 2016-07-26 | Endicott Biofuels Ii, Llc | Production of biodiesel fuels which are low in glycerin and sulfur |
| US20090049739A1 (en) * | 2007-07-31 | 2009-02-26 | Endicott Biiofuels Ii, Llc | Production of Fuels with Superior Low Temperature Properties from Tall Oil or Fractionated Fatty Acids |
| WO2009017957A1 (en) * | 2007-07-31 | 2009-02-05 | Endicott Biofuels Ii, Llc | Production of alkyl esters from high fatty acid feedstocks |
| WO2009018390A1 (en) * | 2007-07-31 | 2009-02-05 | Endicott Biofuels Ii, Llc | Vacuum distillation process |
| WO2009017958A1 (en) * | 2007-07-31 | 2009-02-05 | Endicott Biofuels Ii, Llc | Production of renewable diesel by pyrolysis and esterification |
| US8545581B2 (en) * | 2007-08-01 | 2013-10-01 | Virginia Tech Intellectual Properties, Inc. | Production of stable biomass pyrolysis oils using fractional catalytic pyrolysis |
| WO2009029344A1 (en) * | 2007-08-27 | 2009-03-05 | Endicott Biofuels Ii, Llc | Production of ester-based fuels such as biodiesel from renewable starting materials |
| WO2009038865A1 (en) * | 2007-09-19 | 2009-03-26 | Endicott Biofuels Ii, Llc | Method for obtaining biodiesel, alternative fuels and renewable fuels tax credits and treatment |
| US20090076985A1 (en) * | 2007-09-19 | 2009-03-19 | Endicott Biofuels Ii, Llc | Method for Obtaining Biodiesel, Alternative Fuels and Renewable Fuels Tax Credits and Treatment |
| US7943791B2 (en) * | 2007-09-28 | 2011-05-17 | Mcneff Research Consultants, Inc. | Methods and compositions for refining lipid feed stocks |
| WO2009067779A1 (en) * | 2007-11-30 | 2009-06-04 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Canada | Vapour phase esterification of free fatty acids |
| BRPI0821663A2 (en) * | 2007-12-31 | 2015-06-16 | Univ North Dakota | Method for the production of esters and short chain carboxylic acids from biomass and its product |
| US8076504B2 (en) * | 2007-12-31 | 2011-12-13 | The University Of North Dakota | Method for production of short chain carboxylic acids and esters from biomass and product of same |
| JP5462258B2 (en) * | 2008-07-16 | 2014-04-02 | ハー・マジェスティ・ザ・クイーン・イン・ライト・オブ・カナダ・アズ・リプリゼンテッド・バイ・ザ・ミニスター・オブ・ナチュラル・リソーシーズ・カナダ | Conversion of glycerol to oxygenates in the naphtha range |
| US9102877B2 (en) * | 2008-11-12 | 2015-08-11 | Sartec Corporation | Systems and methods for producing fuels from biomass |
| US8450541B2 (en) * | 2008-11-26 | 2013-05-28 | The University Of North Dakota | Method for producing cyclic organic compounds from crop oils |
| WO2010077685A1 (en) * | 2008-12-08 | 2010-07-08 | Onestep Llc | Single step transesterification of feedstock using a gaseous catalyst |
| US20150267145A1 (en) * | 2008-12-08 | 2015-09-24 | Initio Fuels, Llc | Single step transesterification of biodiesel feedstock using a gaseous catalyst |
| CA2746879C (en) * | 2008-12-16 | 2014-07-22 | Cetane Energy, Llc | Systems and methods of generating renewable diesel |
| WO2010099058A2 (en) * | 2009-02-24 | 2010-09-02 | University Of Georgia Research Foundation, Inc. | Production of higher quality bio-oils by in-line esterification of pyrolysis vapor |
| US8333949B2 (en) * | 2009-05-14 | 2012-12-18 | University Of North Dakota | Method for creating high carbon content products from biomass oil |
| CN101805671A (en) * | 2010-04-09 | 2010-08-18 | 上海中器环保科技有限公司 | Method for using waste oil for carrying out one-step method acid catalysis to prepare biodiesel |
| WO2011156662A2 (en) * | 2010-06-09 | 2011-12-15 | Pa Llc | Method of ash removal from a biomass |
| WO2012027820A1 (en) | 2010-09-03 | 2012-03-08 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Canada | Production of high-cetane diesel product |
| MX2013012222A (en) * | 2011-04-22 | 2013-11-01 | Univ North Dakota | Production of aromatics from noncatalytically cracked fatty acid based oils. |
| CN102631911B (en) * | 2012-03-30 | 2013-05-15 | 北方民族大学 | Hydrophobic solid base catalyst and method for synthesizing biodiesel from grease containing water and free fatty acids |
| US9388345B2 (en) | 2012-07-03 | 2016-07-12 | Sartec Corporation | Hydrocarbon synthesis methods, apparatus, and systems |
| US9382491B2 (en) | 2012-07-03 | 2016-07-05 | Sartec Corporation | Hydrocarbon synthesis methods, apparatus, and systems |
| CN102994235B (en) * | 2012-11-12 | 2014-07-16 | 江苏高科石化股份有限公司 | Method for preparing printing ink solvent and co-producing biodiesel by utilizing waste animal and plant oil |
| US9162938B2 (en) * | 2012-12-11 | 2015-10-20 | Chevron Lummus Global, Llc | Conversion of triacylglycerides-containing oils to hydrocarbons |
| US9024096B2 (en) * | 2012-12-11 | 2015-05-05 | Lummus Technology Inc. | Conversion of triacylglycerides-containing oils |
| FI128441B (en) * | 2015-02-09 | 2020-05-15 | Neste Oil Oyj | Fatty acid composition |
| CN105964298B (en) * | 2016-05-18 | 2019-04-16 | 淮南泉润环保科技有限公司 | A kind of production method of biodiesel catalyst |
| US10239812B2 (en) | 2017-04-27 | 2019-03-26 | Sartec Corporation | Systems and methods for synthesis of phenolics and ketones |
| US10544381B2 (en) | 2018-02-07 | 2020-01-28 | Sartec Corporation | Methods and apparatus for producing alkyl esters from a reaction mixture containing acidified soap stock, alcohol feedstock, and acid |
| US10696923B2 (en) | 2018-02-07 | 2020-06-30 | Sartec Corporation | Methods and apparatus for producing alkyl esters from lipid feed stocks, alcohol feedstocks, and acids |
| NO346959B1 (en) * | 2018-07-20 | 2023-03-20 | Prototech As | Microwave assisted pyrolysis and gasification reactor and method |
Family Cites Families (45)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2211524A (en) * | 1937-10-30 | 1940-08-13 | Stanley Herbert Muggleton | Production of divinylated aromatic hydrocarbons |
| US2240764A (en) * | 1939-03-01 | 1941-05-06 | Dow Chemical Co | Distillation of vinyl aromatic compounds |
| US2385696A (en) * | 1941-09-10 | 1945-09-25 | Dow Chemical Co | Manufacture of divinyl-benzene compounds from corresponding ethylated benzene compounds |
| US2445941A (en) * | 1943-12-27 | 1948-07-27 | Dow Chemical Co | Purification of readily polymerizable vinyl aromatic compounds by distillation |
| US2659761A (en) * | 1948-08-23 | 1953-11-17 | Dow Chemical Co | Fractional crystallization method |
| US3109436A (en) * | 1961-11-02 | 1963-11-05 | Bavley Abraham | Tobacco products |
| IT1075695B (en) * | 1977-04-13 | 1985-04-22 | Sir Soc Italiana Resine Spa | FORMALDEHYDE PURIFICATION PROCEDURE |
| US4344770A (en) | 1977-11-04 | 1982-08-17 | Wilwardco, Inc. | Method and apparatus for converting solid organic material to fuel oil and gas |
| US4235702A (en) * | 1977-12-20 | 1980-11-25 | Imperial Chemical Industries Limited | Hydrocarbon processing |
| US4242526A (en) * | 1978-03-08 | 1980-12-30 | Magyar Asvanyolaj Es Foldgaz Kiserleti Intezet | Process for the direct separation of isobutylene from mixtures of hydrocarbons |
| US4192815A (en) * | 1978-06-22 | 1980-03-11 | Glushakov Sergei N | Method of preparing isocyanates |
| DE3124294A1 (en) * | 1981-06-19 | 1983-01-05 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING PURE TERT.-OLEFINS |
| DE3124293A1 (en) * | 1981-06-19 | 1983-01-05 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF PURE ALKYL-TERT.-ALKYLETHERS AND MOST OF THE HYDROCARBON REFINATES LEAVED BY ISOOLEFIN AND ALKANOL |
| DE3127751A1 (en) * | 1981-07-14 | 1983-02-03 | EC Erdölchemie GmbH, 5000 Köln | METHOD FOR HYDROGENATING HYDROCARBONS |
| DE3148109A1 (en) * | 1981-12-04 | 1983-06-09 | EC Erdölchemie GmbH, 5000 Köln | METHOD FOR THE PRODUCTION OF METHYL-TERT.-BUTYL ETHER (MTBE) AND MOSTLY OF I-BUTEN AND METHANOL-FREE HYDROCARBON REFINATES |
| IT1194350B (en) * | 1983-07-28 | 1988-09-14 | Snam Progetti | PROCEDURE FOR THE PRODUCTION OF HIGH-PURITY BUTENE-1 WITH LOW ENERGY CONSUMPTION |
| DE3412536A1 (en) * | 1984-04-04 | 1985-10-31 | Fried. Krupp Gmbh, 4300 Essen | METHOD FOR PRODUCING HYDROCARBONS FROM CLEANING SLUDGE |
| DE3538564A1 (en) * | 1985-03-23 | 1986-10-02 | EC Erdölchemie GmbH, 5000 Köln | ALKYL-TERT.-ALKYL-ETHER CONTAINING GUM-FREE FUEL COMPONENTS |
| US5171331A (en) * | 1986-01-29 | 1992-12-15 | Fina Research, S.A. | Process for producing gasoline |
| US4973764A (en) * | 1986-10-24 | 1990-11-27 | Exxon Research And Engineering Company | Alkylphenols and derivatives thereof via phenol alkylation by cracked petroleum distillates |
| US4914246A (en) * | 1986-10-24 | 1990-04-03 | Exxon Research & Engineering Company | Alkylphenols and derivatives thereof via phenol alkylation by cracked petroleum distillates |
| ES2032291T5 (en) * | 1987-12-11 | 1997-01-16 | Dsm Nv | PROCEDURE TO ELIMINATE MERCURY FROM ORGANIC MEDIA. |
| DE3812683A1 (en) * | 1988-04-16 | 1989-11-02 | Erdoelchemie Gmbh | PROCESS FOR ISOMERIZING ALKENES WITH ENDSTANDING DOUBLE BINDING TO ALKENES WITH INTERMEDIATE DOUBLE BINDING |
| DE4013711A1 (en) * | 1990-04-28 | 1991-10-31 | Erdoelchemie Gmbh | METHOD FOR THE PRODUCTION OF HIGH-OCTANE, LOW-OILFINE FUELS AND FUEL COMPONENTS |
| US5527449A (en) * | 1993-03-25 | 1996-06-18 | Stanton D. Brown | Conversion of waste oils, animal fats and vegetable oils |
| DE4343453A1 (en) * | 1993-12-20 | 1995-06-22 | Bayer Ag | Process for the preparation of alkyl-tert.-alkyl-ether-containing hydrocarbon mixtures |
| US5578090A (en) * | 1995-06-07 | 1996-11-26 | Bri | Biodiesel fuel |
| US5972057A (en) * | 1997-11-11 | 1999-10-26 | Lonford Development Limited | Method and apparatus for producing diesel fuel oil from waste edible oil |
| DE19752593C5 (en) * | 1997-11-27 | 2005-02-17 | Helsa-Werke Helmut Sandler Gmbh & Co. Kg | Process for the preparation of activated carbon from polymers with aromatic nuclei |
| US6117812A (en) * | 1998-10-06 | 2000-09-12 | China Petro-Chemical Corporation | Dual functional catalyst of packing type and the catalytic distillation equipment |
| DE19912153B4 (en) * | 1999-03-18 | 2004-08-19 | Carbotex Produktions-Und Veredelungsbetriebe Gmbh | Process for the production of shaped high-performance adsorbents |
| US6329563B1 (en) * | 1999-07-16 | 2001-12-11 | Westinghouse Savannah River Company | Vitrification of ion exchange resins |
| JP3777123B2 (en) * | 2000-04-28 | 2006-05-24 | ブリュッヒャー ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for producing spherical activated carbon |
| WO2001083655A1 (en) * | 2000-05-02 | 2001-11-08 | Prolab Technologies Inc. | Production of high grade and high concentration of free fatty acids from residual oils, fats and greases |
| WO2001094498A1 (en) | 2000-06-08 | 2001-12-13 | Valtion Teknillinen Tutkimuskeskus | Method and apparatus for producing pyrolysis oil |
| GB0019417D0 (en) * | 2000-08-09 | 2000-09-27 | Mat & Separations Tech Int Ltd | Mesoporous carbons |
| DE60237727D1 (en) * | 2001-03-30 | 2010-10-28 | Revo Internat Inc | Process for the preparation of fatty acid alkyl esters using a composite metal oxide catalyst |
| CA2360986A1 (en) * | 2001-11-01 | 2003-05-01 | Nicole Cadoret | Method for fractionating grease trap waste and uses of fractions therefrom |
| DE10155241C1 (en) * | 2001-11-09 | 2003-07-03 | Gmk Ges Fuer Motoren Und Kraft | Process for the production of fuels from acidic fats and plant for carrying them out |
| US20040074760A1 (en) * | 2002-10-17 | 2004-04-22 | Carnegie Mellon University | Production of biofuels |
| US7806945B2 (en) * | 2003-01-27 | 2010-10-05 | Seneca Landlord, Llc | Production of biodiesel and glycerin from high free fatty acid feedstocks |
| US20040267070A1 (en) * | 2003-06-30 | 2004-12-30 | Chevron U.S.A. Inc. | Hydrotreating of Fischer-Tropsch derived feeds prior to oligomerization using an ionic liquid catalyst |
| WO2005028597A1 (en) * | 2003-09-15 | 2005-03-31 | The Lubrizol Corporation | Low temperature operable fatty acid ester fuel composition and method thereof |
| US7579492B2 (en) * | 2003-09-30 | 2009-08-25 | Carolina Soy Products Llc | Two-stage extraction of soybean oil |
| US7345211B2 (en) * | 2004-07-08 | 2008-03-18 | Conocophillips Company | Synthetic hydrocarbon products |
-
2005
- 2005-12-16 US US11/304,658 patent/US20070137097A1/en not_active Abandoned
-
2006
- 2006-12-12 CA CA2633632A patent/CA2633632C/en not_active Expired - Fee Related
- 2006-12-12 WO PCT/CA2006/002015 patent/WO2007068097A1/en active Application Filing
- 2006-12-12 EP EP06840446A patent/EP1976959A4/en not_active Withdrawn
- 2006-12-14 US US11/638,348 patent/US20070144060A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007068097A1 (en) | 2007-06-21 |
| EP1976959A1 (en) | 2008-10-08 |
| CA2633632A1 (en) | 2007-06-21 |
| EP1976959A4 (en) | 2012-12-05 |
| US20070137097A1 (en) | 2007-06-21 |
| US20070144060A1 (en) | 2007-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2633632C (en) | Production of biodiesel from triglycerides by using thermal cracking | |
| CA2701136C (en) | Vapour phase esterification of free fatty acids | |
| US7754931B2 (en) | Production of high-cetane diesel fuel from low-quality biomass-derived feedstocks | |
| Kralova et al. | Biofuels–renewable energy sources: a review | |
| Sarin | Biodiesel: production and properties | |
| Demirbaş | Biodiesel fuels from vegetable oils via catalytic and non-catalytic supercritical alcohol transesterifications and other methods: a survey | |
| Banga et al. | Effect of impurities on performance of biodiesel: A review | |
| Elgharbawy et al. | Glycerolysis treatment to enhance biodiesel production from low-quality feedstocks | |
| WO2010059694A1 (en) | Bio-fuel and process for making bio-fuel | |
| Kato et al. | Evaluation of ozone treated fish waste oil as a fuel for transportation | |
| Ayoola et al. | Biodiesel fuel production processes: a short review | |
| WO2008093990A1 (en) | Method of making biodiesel with good low-temperature performance from palm oil | |
| Udeh | Biodiesel production from waste vegetable oil (Sunflower) obtained from fried chicken and plantain | |
| Sarma et al. | Recent inventions in biodiesel production and processing-A review | |
| Saputro et al. | A Biodiesel Production Technology From Used Cooking Oil: A Review | |
| Buasri et al. | Biodiesel production from crude palm oil with a high content of free fatty acids and fuel properties | |
| Van Gerpen | Biodiesel from vegetable oils | |
| Choudhary et al. | Performance Characteristics of Diesel Engine Using Biodiesel and their Esters as Fuel | |
| Jurac et al. | Impact of residual glycerides on viscosity of biodiesel (waste and rapeseed oil blends) | |
| Ikura et al. | Production of biodiesel from waste fat and grease | |
| Bertouchea et al. | Optimization of biofuel synthesis from used food oil by transesterification | |
| Pratt et al. | Food Waste as a Source of Biofuels | |
| KR20120130532A (en) | bio fuel for heating and its manufacture method | |
| JP2009203346A (en) | Easy oil decomposition reaction method | |
| Guo et al. | A clean biodiesel fuel produced from recycled oils and grease trap oils (BAQ 2002) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20211213 |