WO2004099115A1 - Process for extraction and catalytic esterification of fatty acids found in sewage scum - Google Patents
Process for extraction and catalytic esterification of fatty acids found in sewage scum Download PDFInfo
- Publication number
- WO2004099115A1 WO2004099115A1 PCT/BR2004/000058 BR2004000058W WO2004099115A1 WO 2004099115 A1 WO2004099115 A1 WO 2004099115A1 BR 2004000058 W BR2004000058 W BR 2004000058W WO 2004099115 A1 WO2004099115 A1 WO 2004099115A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- esterification
- fatty
- fatty acids
- scum
- 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.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Definitions
- Field of the Invention is related to the esterification process of the fatty acids found in the "sewage scum", namely the surface phase of sewage rich in fatty matter. By dry weight, this oily phase consists of over 80% carboxy acids with 2 - 24 carbon atoms deriving from the decomposition process of different triglycerides and soaps in sewage. Through this invention, these fatty acids are extracted from the scum and esterified with methanol or ethanol through the use of acid catalysts in this process.
- Background of the Invention Sewage may be defined as a dilute aqueous solution formed by organic and inorganic substances, either dissolved or in suspension.
- the total fats potential contained in Brazilian sewage may reach some 2.10 6 tons/year, on the basis that each person generates about 250 liters of sewage a day containing 30 - 80 grams of fat.
- bio- diesel consisting of fatty acid esters, which is an alternative fuel obtained from renewable biological sources such as vegetable oils and animal fats.
- fatty acid esters which is an alternative fuel obtained from renewable biological sources such as vegetable oils and animal fats.
- biodiesel is an environmentally clean fuel as it reduces emissions of atmospheric pollutants and particulate matter, in addition to being bio-degradable and atoxic. With physical and chemical properties similar to those of petro-diesel, biodiesel may be used directly in engines with no major mechanical modifications or outlays on maintenance.
- the pre-esterification of free fatty acids using homogenous acid catalysis has the disadvantage that it is difficult to remove the catalyst residues from the pre- esterified matter.
- the catalyst is normally removed through washing the mixture with methanol, which is separated from the oil phase through extraction by a solvent that does not blend with the oil, normally glycerin.
- methanol a solvent that does not blend with the oil, normally glycerin.
- bio-catalysts enzyme
- Foglia et al . US patent 5,713,965
- This invention covers the process of extracting fatty acids from sewage scum, using a catalytic esterification process and presenting the optimum reaction condition ranges in terms of temperature, pressure, space- time and reagent concentrations for the efficient transformation of the fatty acids in the sewage scum into methyl or ethyl esters.
- This invention also covers the use of solid acid site-based catalysts in the alcohols esterification process for free fatty acids in sewage scum.
- Figure 1 presents a flow sheet for the bio-diesel production process based on fatty acids extracted from scum. This sequence involves the following items of equipment: 1-pump, 2-centrifuge, 3-press-filter, 4-extractor, 5-esterification reactor, and 6-distillation column to recycle surplus alcohol and solvents.
- Figures 2 and 4 give the conversion graphs (%) x reaction time ( in) for the esterification reaction of the fatty acids extracted from scum.
- Table 5 presents some physical and chemical properties of the methyl ester obtained through the procedure described in Example 1. The trials were carried out according to the ASTM standards described in the table .
- the purposes of this invention include a process for extraction followed by the esterification of free fatty acids in sewage scum and the use of solid acid catalysts in this process.
- the scum collected at sewage treatment stations has a high water content level.
- the water dilutes the reagents, slowing the reaction speed.
- the water is a product of the esterification reaction, with thermodynamic effects on the chemical balance lowering the process yield.
- Another negative aspect of the water is its interaction with the catalyst acid sites, minimizing this effect. Consequently, as much water as possible should be removed before the reaction.
- Conventional filtering ⁇ equipment such as a press filter may be used for this purpose.
- a centrifuge is also recommended to remove the water.
- apolar solvent either organic or not.
- organic apolar solvents may be used, such as pentane, hexane or heptane, or even solvents in super-critical conditions such as C0 2 , ethane or propane.
- polar solvents with the esters is not advisable, due to simultaneous interaction with the remaining water content.
- an upper phase is attained, containing the fatty matter.
- the lower phase contains the waste waters.
- the surplus solvent should be recycled through a flash in a distillation unity. A certain amount of solvent is kept for carrying the solubilized fatty matter to the esterification reactor, boosting the reaction yield.
- the esterification reaction may occur in the presence of a homogeneous or heterogeneous catalyst.
- acid catalysts are used for esterifying blends of fatty scum acids. These fatty acids may be esterified with methyl or ethyl alcohol.
- alcohol/fatty acid mol ratios of 3 to 15 should be used, preferably working between 6 and 12.
- a catalyst is required that triggers the esterification reaction of the fatty acids at the lowest possible temperatures, in order to ensure that the reaction is economically feasible with no heat breakdown of the reagents.
- This process involves temperatures in a range of 40°C - 200°C, preferably using a range of 60°C - 170°C.
- High pressure promotes the reaction, although it is not vital.
- the reaction temperature range described above means that in some cases the process pressure is necessarily larger than atmospheric pressure.
- the reactions involve liquid phase components and possibly active sites located inside the solid catalyst particles and consequently subject to mass-transfer constraints.
- High-speed stirring is required at levels sufficient to minimize this problem. Stirring speeds ranging between 400 and 1,500 RPM are appropriate for this purpose.
- any catalyst with heat stability and Br ⁇ nsted and/or Lewis acidity under the reaction conditions may be used.
- the catalysts listed below are used: Sulfated zirconia (sulfur content of 3% - 6%) with a surface area of 30 - 200 m 2 /g, pre-calcined between 300°C and 800°C;
- Zirconia promoted with tungsten (tungsten level of 5% - 15%) , with a surface area of 70 - 200 m 2 /g, pre-calcined at 300°C - 800"C;
- the fatty acid esterification process using heterogeneous catalysts may be run on a batch basis, in a continuous reactor, as well as in fixed bed reactors.
- the spatial time in terms of the fatty acids is 1 - 30 minutes, preferably limited to 3 - 20 minutes.
- the catalysts When using heterogeneous catalysts, the catalysts are removed after the reaction through simple filtering, or maintained through a fixed bed.
- neutralization of the medium is required after the reaction. This neutralization produces a salt that should be removed by washing.
- calcium carbonate and sodium carbonate solutions are used, with the possibility of also using controlled amounts of sodium hydroxide or potassium hydroxide, or even ammonia bubbled directly into the solution.
- the solvent used for extraction in the reaction medium is recovered, in addition to retrieving surplus alcohol.
- the sequence depends on the solvent vapor pressures and the alcohols used. Vacuum evaporation is recommended, in order to minimize heat decomposition or parallel reactions.
- esters formed should be dried through heating (vacuum or not) . Esters with high purity levels may then be obtained through vacuum distillation. This stage may be skipped, depending on the bio-diesel specifications .
- Figure 1 gives a schematic process flow sheet. The items of equipment listed are: 1-pump, 2-extractor, 3-press filter, 4-flash vessel, 5-reactor, 6-distillation column.
- Figure 2 presents a chromatogram of the methyl esters obtained through the esterification of fatty acids contained in sewage scum.
- C ⁇ 6 refers to the palmitic acid ester
- C ⁇ refers to the heptadecanoic acid ester
- Ci ⁇ refers to the stearic, oleic, linoleic and linolenic acid esters
- C n -OH refers to the hydroxy fattyesters.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The innovation proposed herein describes the process of a fatty acids esterification presents in the sewage scum namely the surface phase of sewage rich in fatty matter, being that this fatty acids are extracted from the scum and esterified by acid catalysts and reagents like as methanol or ethanol.
Description
Description of the Patent of Invention for "PROCESS FOR EXTRACTION AND CATALYTIC ESTERIFICATION OF FATTY ACIDS FOUND IN SEWAGE SCUM". Field of the Invention This invention is related to the esterification process of the fatty acids found in the "sewage scum", namely the surface phase of sewage rich in fatty matter. By dry weight, this oily phase consists of over 80% carboxy acids with 2 - 24 carbon atoms deriving from the decomposition process of different triglycerides and soaps in sewage. Through this invention, these fatty acids are extracted from the scum and esterified with methanol or ethanol through the use of acid catalysts in this process. Background of the Invention Sewage may be defined as a dilute aqueous solution formed by organic and inorganic substances, either dissolved or in suspension. When reaching the sewage treatment stations, the formation of at least three important phases becomes quite clear: a) A lower level called sludge results from the decantation of the solid, dense matter in the sewage; b) An aqueous phase with high BOD and COD values that requires physical and chemical treatment before being discharged into rivers and seas;
c) A surface phase known as scum, consisting basically of organic matter that is not soluble in water, mainly greasy matter .
The total fats potential contained in Brazilian sewage may reach some 2.106 tons/year, on the basis that each person generates about 250 liters of sewage a day containing 30 - 80 grams of fat.
Although representing a relatively low percentage of sewage, the disposal of this scum is extremely harmful to the environment. As it covers the surface, the scum layer hampers the diffusion of oxygen into the water, with disastrous consequences for submerged eco-syste s . It should be noted that sewage treatment stations are stepping up their capacities - in the Greater Rio de Janeiro area, for instance, through the Guanabara Bay Clean-up Program
(PDBG) . This means that the amount of scum is increasing more significantly in absolute terms. Even in regions or countries already endowed with ample sewage treatment infrastructure, the usual disposal facilities for this scum consist of sanitary landfills, also with limited capacities.
Another problem caused by this scu is associated with its transportation, as it is a thick paste which is hard to pump.
An important by-product of fatty matter is bio- diesel, consisting of fatty acid esters, which is an alternative fuel obtained from renewable biological sources such as vegetable oils and animal fats. Compared to oil- based diesel (petro-diesel, biodiesel is an environmentally clean fuel as it reduces emissions of atmospheric pollutants and particulate matter, in addition to being bio-degradable and atoxic. With physical and chemical properties similar to those of petro-diesel, biodiesel may be used directly in engines with no major mechanical modifications or outlays on maintenance.
The pre-esterification of free fatty acids using homogenous acid catalysis has the disadvantage that it is difficult to remove the catalyst residues from the pre- esterified matter. The catalyst is normally removed through washing the mixture with methanol, which is separated from the oil phase through extraction by a solvent that does not blend with the oil, normally glycerin. However, this means that part of the esterified fatty acids is lost, lowering the yield from this process. In order to deal with this problem, bio-catalysts (enzymes) may be used or even solid acid catalysts. Foglia et al . (US patent 5,713,965) proposed the use of upases for esterifying the free fatty acids with normal or secondary alcohols. The reaction takes place at low temperatures (between 30°C and 60°C) with high
ester yield levels, but it is necessary to separate and recycle the solvent. Jeromin et al . (US patent 4,698,186) proposed the use of cation exchange resins as esterification catalysts. These resins contain sulfonic or carboxy acid groups linked to a polymer matrix, normally polystyrene. This reaction also takes place at low temperatures (55°C - 65°C) at a methanol : fatty acid mol ratio of 10:1 to 50:1, with the catalyst being hard to separate from the reaction products. HOOC-R + R'OH <> R-COO -R' + H20
Fatty acid alcohol ester water
Scheme 1 - Esterification Reaction Heterogeneous acid catalysts were used by Bradin (US patent 5,578,090) to esterify free fatty acids with alcohols or olefins. When esterification takes place with alcohols, water is formed as a by-product, which may dilute or destroy the acid catalyst. When using olefins, there is no water formation, but strict temperature control is required (under 70°C) in order to prevent excessive polymerization of the olefins. Lewis acids were used as catalysts, including aluminum chloride and iron chloride, with the latter being preferable for esterification with olefins, as it minimizes parallel dimerization and polymerization reactions.
Efforts to transform free fatty acids are justified because their presence is generally associated with fatty raw materials with low commercial value, such as sewage scum, allowing fatty acid esters to be produced at costs competitive with those of petro-diesel and other feedstock used by the petrochemical industry. Moreover, the use of heterogeneous catalysts minimizes the separation and purification costs, making this process even more attractive. Sumary of the Invention
This invention covers the process of extracting fatty acids from sewage scum, using a catalytic esterification process and presenting the optimum reaction condition ranges in terms of temperature, pressure, space- time and reagent concentrations for the efficient transformation of the fatty acids in the sewage scum into methyl or ethyl esters.
This invention also covers the use of solid acid site-based catalysts in the alcohols esterification process for free fatty acids in sewage scum.
Brief Description of the Drawings
As an example, Figure 1 presents a flow sheet for the bio-diesel production process based on fatty acids extracted from scum. This sequence involves the following
items of equipment: 1-pump, 2-centrifuge, 3-press-filter, 4-extractor, 5-esterification reactor, and 6-distillation column to recycle surplus alcohol and solvents.
Figures 2 and 4 give the conversion graphs (%) x reaction time ( in) for the esterification reaction of the fatty acids extracted from scum.
Tables 1 through 4 give detailed descriptions of the reaction conditions used respectively in Examples 1 through 4.
As an example, Table 5 presents some physical and chemical properties of the methyl ester obtained through the procedure described in Example 1. The trials were carried out according to the ASTM standards described in the table .
Detailed Description of the Invention
The purposes of this invention include a process for extraction followed by the esterification of free fatty acids in sewage scum and the use of solid acid catalysts in this process. The scum collected at sewage treatment stations has a high water content level. The water dilutes the reagents, slowing the reaction speed. Moreover the water is a product of the esterification reaction, with thermodynamic effects on the chemical balance lowering the
process yield. Another negative aspect of the water is its interaction with the catalyst acid sites, minimizing this effect. Consequently, as much water as possible should be removed before the reaction. Conventional filtering ■ equipment such as a press filter may be used for this purpose. A centrifuge is also recommended to remove the water.
The fatty matter is then removed from the scum through extraction by an apolar solvent, either organic or not. In this case, organic apolar solvents may be used, such as pentane, hexane or heptane, or even solvents in super-critical conditions such as C02, ethane or propane. The use of polar solvents with the esters is not advisable, due to simultaneous interaction with the remaining water content.
Should organic solvents be used, an upper phase is attained, containing the fatty matter. The lower phase contains the waste waters. The surplus solvent should be recycled through a flash in a distillation unity. A certain amount of solvent is kept for carrying the solubilized fatty matter to the esterification reactor, boosting the reaction yield.
The esterification reaction may occur in the presence of a homogeneous or heterogeneous catalyst.
In this invention, acid catalysts are used for esterifying blends of fatty scum acids. These fatty acids may be esterified with methyl or ethyl alcohol.
The use of solid acid catalysts in this process to esterify the fatty acids requires the existence of acid sites that can promote the reaction.
In this invention, it is shown that the addition of alcohol in stoichiometric excess is of the utmost importance. At the current international ratification stage of bio-diesel, methanol and ethanol are the main alcohols used. However, other products may also be used for the formation of biodiesel, as well as additives to enhance its lubricity and ketone rating, or even as tenso-actives for blends of polar and apolar fuels (for instance, alcohol- diesel blends) . The esters formed in this manner may also be used as solvents, tenso-actives, intermediate tenso- actives or detergents .
In order to obtain high conversion and selectivity rates for the esters, alcohol/fatty acid mol ratios of 3 to 15 should be used, preferably working between 6 and 12.
Within this reaction environment, a catalyst is required that triggers the esterification reaction of the fatty acids at the lowest possible temperatures, in order to ensure that the reaction is economically feasible with
no heat breakdown of the reagents. This process involves temperatures in a range of 40°C - 200°C, preferably using a range of 60°C - 170°C.
High pressure promotes the reaction, although it is not vital. For more volatile alcohols such as methanol and ethanol, the reaction temperature range described above means that in some cases the process pressure is necessarily larger than atmospheric pressure.
The reactions involve liquid phase components and possibly active sites located inside the solid catalyst particles and consequently subject to mass-transfer constraints. High-speed stirring is required at levels sufficient to minimize this problem. Stirring speeds ranging between 400 and 1,500 RPM are appropriate for this purpose.
Whether solid or not, any catalyst with heat stability and Brδnsted and/or Lewis acidity under the reaction conditions may be used. Preferably, the catalysts listed below are used: Sulfated zirconia (sulfur content of 3% - 6%) with a surface area of 30 - 200 m2/g, pre-calcined between 300°C and 800°C;
Zirconia promoted with tungsten (tungsten level of 5% - 15%) , with a surface area of 70 - 200 m2/g, pre-calcined at 300°C - 800"C;
H-Zeolites, with a silica/alumina mol ratio of 4 - 75 and a surface area of 200 - 800 m2/g;
Aluminum chloride, super-anhydrous or chemically supported; Concentrated sulfuric acid; Methane-sulphonic acid; Toluenesulfonic acid; Concentrated hydrochloric acid; Concentrated phosphoric acid. The fatty acid esterification process using heterogeneous catalysts may be run on a batch basis, in a continuous reactor, as well as in fixed bed reactors. For the continuous systems, in order to reach balance conversions, the spatial time in terms of the fatty acids is 1 - 30 minutes, preferably limited to 3 - 20 minutes.
For both the batch and continuous processes, new reaction steps may be required in order to ensure better global yield. Ideally, the water produced during the initial esterification stage should be removed in order to promote the shift in the chemical balance in the right direction.
When using heterogeneous catalysts, the catalysts are removed after the reaction through simple filtering, or maintained through a fixed bed. When using homogeneous catalysts, neutralization of the medium is required after
the reaction. This neutralization produces a salt that should be removed by washing. Preferably, calcium carbonate and sodium carbonate solutions are used, with the possibility of also using controlled amounts of sodium hydroxide or potassium hydroxide, or even ammonia bubbled directly into the solution.
After neutralization followed by filtering, the solvent used for extraction in the reaction medium is recovered, in addition to retrieving surplus alcohol. The sequence depends on the solvent vapor pressures and the alcohols used. Vacuum evaporation is recommended, in order to minimize heat decomposition or parallel reactions.
Finally, the esters formed should be dried through heating (vacuum or not) . Esters with high purity levels may then be obtained through vacuum distillation. This stage may be skipped, depending on the bio-diesel specifications . As an example, Figure 1 gives a schematic process flow sheet. The items of equipment listed are: 1-pump, 2-extractor, 3-press filter, 4-flash vessel, 5-reactor, 6-distillation column.
Figure 1 - Flow Sheet giving an Example of the Process.
As an example, Figure 2 presents a chromatogram of the methyl esters obtained through the esterification of fatty acids contained in sewage scum. Cχ6 refers to the
palmitic acid ester, Cι refers to the heptadecanoic acid ester, Ciβ refers to the stearic, oleic, linoleic and linolenic acid esters, Cn-OH refers to the hydroxy fattyesters. This chromatogram was obtained as described in Example 1 and the Figure 2 - Typical Chromatogram - Chromatographic Method: Column: Carbowax, Length: 25 m, internal diameter: 0.32 mm, oven temperature: 200°C (isotherm), FID temperature: 250°C, injection temperature: 250°C, flow gas (He): 1.9 mL/min, Split: 1:20. Example 1
* Mol Ratio SiO2/Al2O3.
Example 2
Claims
1- "PROCESS FOR EXTRACTION AND CATALYTIC ESTERIFICATION OF FATTY ACIDS FOUND IN SEWAGE SCUM" characterized by consisting of the following stages: - centrifuging;
- extraction of the fatty matter by organic or non-organic apolar solvents;
- esterification of the fatty matter using a homogeneous or heterogeneous catalyst, at temperatures ranging from 40°C to 200°C and pressures varying from 1 to 25 atm;
- drying and distillation of the esters obtained thereby.
2- "PROCESS" according to claim 1, characterized by the use of solvents such as pentane, hexane or heptane to extract the fatty matter or C02, ethane or propane under supercritical conditions.
3- "PROCESS" according to claim 1, characterized by the use of esterification of the fatty matter preferably at temperatures varying from 60°C to 180°C.
4- "PROCESS" according to claim 1, characterized by the use of an acid catalyst and reagents in the esterification process, such as methyl or ethyl at an alcohol/fatty acid molar ratio of 2 to 15.
5- "PROCESS" according to claim 4, characterized by the preferential use of reagents at an alcohol/fatty acid molar ratio of 6 to 12.
6- "PROCESS" according to claim 1, characterized by the use of heterogeneous catalysts such as sulfated zirconium, tungsten-doped zirconium and zeolites or homogeneous catalysts such as aluminum chloride, concentrated sulfuric acid, methane sulfonic acid, toluene sulfonic acid, concentrated hydrochloric acid and concentrated phosphoric acid.
7- "PROCESS" according to claim 6, characterized by the sulfonated zirconium having a sulfur content of 3% to 6%, with a surface area of 30 m2/g to 200m2/g, precalcined at 300°C to 800°C. 8- "PROCESS" according to claim 6, characterized by the tungsten-doped zirconium having a tungsten content of 5% to 15%, with a surface area of 70 m2/g to 200m2/g, precalcined at 300°C to 800°C.
9- "PROCESS" according to claim 6, characterized by the zeolites having hydrogen as the compensation cation with a silica/aluminum ratio of 4 to 75 and a surface area of 200 m2/g to 800m2/g.
10- "PROCESS" according to claim 1, characterized by the use of stirring speeds of 400rpm to 1500rpm, to facilitate mass transfers when using heterogeneous catalysts.
11- "PROCESS" according to claim 1, characterized by the inclusion of a reaction media neutralization stage, washing away the formed salt with calcium carbonate, sodium carbonate, sodium hydroxide or potassium hydroxide solutions, or ammonia bubbled directly into the solution when using homogeneous catalysts.
12- "PROCESS" according to claim 1, characterized by inclusion of a product purification stage with a vacuum distilation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BRPI0301254-9 | 2003-05-06 | ||
| BR0301254A BR0301254B1 (en) | 2003-05-06 | 2003-05-06 | "process for extraction and catalytic esterification of fatty acids present in sewage scum". |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004099115A1 true WO2004099115A1 (en) | 2004-11-18 |
Family
ID=33426142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/BR2004/000058 Ceased WO2004099115A1 (en) | 2003-05-06 | 2004-04-29 | Process for extraction and catalytic esterification of fatty acids found in sewage scum |
Country Status (2)
| Country | Link |
|---|---|
| BR (1) | BR0301254B1 (en) |
| WO (1) | WO2004099115A1 (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010010118A1 (en) * | 2008-07-22 | 2010-01-28 | Yellow Diesel B.V. | Sulfated zirconia catalyst; its production by melting the precursors and its use for esterification of fatty acids with alcohols |
| DE102008060902A1 (en) | 2008-12-09 | 2010-06-10 | Grace Gmbh & Co. Kg | Preparing fatty acid alkyl ester from feed stock containing e.g. free fatty acids and fatty acid triglycerides, comprises esterifying feedstock with alkyl alcohol in presence of catalyst and transesterifying the free fatty acid feedstock |
| US7790044B2 (en) * | 2006-04-04 | 2010-09-07 | Nowa Technology, Inc. | Method and apparatus for separation of chemical materials from feces |
| JP2011507695A (en) * | 2007-12-27 | 2011-03-10 | エルジー・ケム・リミテッド | Esterification catalyst composition containing zirconium compound and method for producing ester compound using the same |
| US7915474B2 (en) | 2009-04-01 | 2011-03-29 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
| US7951988B2 (en) | 2009-04-01 | 2011-05-31 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
| WO2011085461A1 (en) * | 2010-01-18 | 2011-07-21 | Marcos Vinicios Marques Fagundes | Process for integrated demulsification and esterification of fatty acids and derivatives thereof using residual reagents and simultaneous alcohol recovery and water removal |
| CN101358138B (en) * | 2008-09-23 | 2011-08-24 | 浙江大学 | Method for improving quality of biomass oil |
| US8115047B2 (en) | 2009-04-01 | 2012-02-14 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
| US8168847B2 (en) | 2009-04-01 | 2012-05-01 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
| EP2481733A1 (en) * | 2011-01-28 | 2012-08-01 | Süd-Chemie AG | Process for manufacturing esters of 2,5-furandicarboxylic acid |
| US8481800B2 (en) | 2009-04-01 | 2013-07-09 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
| CN103923685A (en) * | 2014-05-09 | 2014-07-16 | 北京师范大学 | Method for preparing biodiesel through activated sludge |
| CN103936091A (en) * | 2013-12-26 | 2014-07-23 | 重庆宜化化工有限公司 | Weak liquid distillation method |
| US9611158B2 (en) | 2009-04-01 | 2017-04-04 | Earth Renewal Group, Llc | Waste treatment process |
| CN106867566A (en) * | 2017-03-15 | 2017-06-20 | 北京师范大学 | It is a kind of to improve the method that excess sludge prepares yield of biodiesel |
| RU2813102C1 (en) * | 2022-12-06 | 2024-02-06 | Общество с ограниченной ответственностью "Центр разработки низкоуглеродных технологий" (ООО "ЦРНТ") | Method of producing esters of carboxylic acids |
| WO2024123205A1 (en) * | 2022-12-06 | 2024-06-13 | Общество С Ограниченной Ответственностью "Центр Разработки Низкоуглеродных Технологий" | Process for producing carboxylic acid esters |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990008127A1 (en) * | 1989-01-17 | 1990-07-26 | Davy Mckee (London) Limited | Process and apparatus |
| US6399800B1 (en) * | 1999-09-22 | 2002-06-04 | The United States Of America As Represented By The Secretary Of Agriculture | Process for the production of fatty acid alkyl esters |
-
2003
- 2003-05-06 BR BR0301254A patent/BR0301254B1/en not_active IP Right Cessation
-
2004
- 2004-04-29 WO PCT/BR2004/000058 patent/WO2004099115A1/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990008127A1 (en) * | 1989-01-17 | 1990-07-26 | Davy Mckee (London) Limited | Process and apparatus |
| US6399800B1 (en) * | 1999-09-22 | 2002-06-04 | The United States Of America As Represented By The Secretary Of Agriculture | Process for the production of fatty acid alkyl esters |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7790044B2 (en) * | 2006-04-04 | 2010-09-07 | Nowa Technology, Inc. | Method and apparatus for separation of chemical materials from feces |
| EP2231327A4 (en) * | 2007-12-27 | 2011-09-28 | Lg Chemical Ltd | CATALYSING COMPOSITION COMPRISING ZIRCONIUM COMPOUNDS FOR CREATING AN ESTERIFICATION REACTION, AND METHOD FOR PREPARING ESTER COMPOUNDS |
| JP2011507695A (en) * | 2007-12-27 | 2011-03-10 | エルジー・ケム・リミテッド | Esterification catalyst composition containing zirconium compound and method for producing ester compound using the same |
| EP2153893A1 (en) * | 2008-07-22 | 2010-02-17 | Yellow Diesel B.V. | Sulfated zirconia catalyst; its production by melting the precursors and its use for esterification of fatty acids with alcohols. |
| WO2010010118A1 (en) * | 2008-07-22 | 2010-01-28 | Yellow Diesel B.V. | Sulfated zirconia catalyst; its production by melting the precursors and its use for esterification of fatty acids with alcohols |
| CN101358138B (en) * | 2008-09-23 | 2011-08-24 | 浙江大学 | Method for improving quality of biomass oil |
| DE102008060902A1 (en) | 2008-12-09 | 2010-06-10 | Grace Gmbh & Co. Kg | Preparing fatty acid alkyl ester from feed stock containing e.g. free fatty acids and fatty acid triglycerides, comprises esterifying feedstock with alkyl alcohol in presence of catalyst and transesterifying the free fatty acid feedstock |
| US7915474B2 (en) | 2009-04-01 | 2011-03-29 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
| US9611158B2 (en) | 2009-04-01 | 2017-04-04 | Earth Renewal Group, Llc | Waste treatment process |
| US8115047B2 (en) | 2009-04-01 | 2012-02-14 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
| US8168847B2 (en) | 2009-04-01 | 2012-05-01 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
| US7951988B2 (en) | 2009-04-01 | 2011-05-31 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
| US9902632B2 (en) | 2009-04-01 | 2018-02-27 | Earth Renewal Group, Llc | Waste treatment method |
| US8481800B2 (en) | 2009-04-01 | 2013-07-09 | Earth Renewal Group, Llc | Aqueous phase oxidation process |
| WO2011085461A1 (en) * | 2010-01-18 | 2011-07-21 | Marcos Vinicios Marques Fagundes | Process for integrated demulsification and esterification of fatty acids and derivatives thereof using residual reagents and simultaneous alcohol recovery and water removal |
| EP2481733A1 (en) * | 2011-01-28 | 2012-08-01 | Süd-Chemie AG | Process for manufacturing esters of 2,5-furandicarboxylic acid |
| WO2012101015A1 (en) * | 2011-01-28 | 2012-08-02 | Süd-Chemie AG | Process for manufacturing esters of 2,5-furandicarboxylic acid |
| CN103936091A (en) * | 2013-12-26 | 2014-07-23 | 重庆宜化化工有限公司 | Weak liquid distillation method |
| CN103936091B (en) * | 2013-12-26 | 2015-09-02 | 重庆宜化化工有限公司 | A kind of light liquid distil process method |
| CN103923685B (en) * | 2014-05-09 | 2016-03-16 | 北京师范大学 | A kind of method utilizing active sludge to prepare biofuel |
| CN103923685A (en) * | 2014-05-09 | 2014-07-16 | 北京师范大学 | Method for preparing biodiesel through activated sludge |
| CN106867566A (en) * | 2017-03-15 | 2017-06-20 | 北京师范大学 | It is a kind of to improve the method that excess sludge prepares yield of biodiesel |
| RU2813102C1 (en) * | 2022-12-06 | 2024-02-06 | Общество с ограниченной ответственностью "Центр разработки низкоуглеродных технологий" (ООО "ЦРНТ") | Method of producing esters of carboxylic acids |
| WO2024123205A1 (en) * | 2022-12-06 | 2024-06-13 | Общество С Ограниченной Ответственностью "Центр Разработки Низкоуглеродных Технологий" | Process for producing carboxylic acid esters |
Also Published As
| Publication number | Publication date |
|---|---|
| BR0301254A (en) | 2005-10-04 |
| BR0301254B1 (en) | 2012-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2004099115A1 (en) | Process for extraction and catalytic esterification of fatty acids found in sewage scum | |
| Gomes et al. | Biodiesel production from degummed soybean oil and glycerol removal using ceramic membrane | |
| JP5484903B2 (en) | Novel process for producing biodiesel using immobilized catalyst | |
| JP5419713B2 (en) | Use of fuels or fuel additives based on modified structure triglycerides and processes for their preparation | |
| JP5470382B2 (en) | Production method of fatty acid alkyl ester | |
| US7851643B2 (en) | Method of manufacturing fatty acid ethyl esters from triglycerides and alcohols | |
| JP2008231345A (en) | Method for producing biodiesel fuel | |
| US7872149B2 (en) | Biodiesel processes in the presence of free fatty acids and biodiesel producer compositions | |
| ITMI971837A1 (en) | FOREIGN MANUFACTURING PROCESS FROM VEGETABLE OR ANIMAL OILS AND ALCOHOLS | |
| CZ20014388A3 (en) | Process for preparing fatty acid esters and monovalent alkyl alcohols and their use | |
| US20100305346A1 (en) | Method for producing fatty acid monoesterified product using solid acid catalyst | |
| AU2017246581B2 (en) | Process for recovery of glycerol from biodiesel production streams | |
| US20100242346A1 (en) | Processes for the esterification of free fatty acids and the production of biodiesel | |
| CN101282921B (en) | Production method of alkyl carboxylate | |
| Cukalovic et al. | Development, optimization and scale-up of biodiesel production from crude palm oil and effective use in developing countries | |
| JP4078383B1 (en) | Method for producing biodiesel fuel | |
| Hillion et al. | Biodiesel production by a continuous process using a heterogeneous catalyst | |
| WO2006081644A2 (en) | Catalytic process for the esterification of fatty acids | |
| US20100058652A1 (en) | Method for Obtaining Fuels from Vegetal and Animal Fat Waste and Installation for Carrying out Said Method | |
| EP2028260A1 (en) | Esterification process | |
| JP7252588B2 (en) | Method for producing biodiesel fuel | |
| EP2154226A1 (en) | Process for manufacturing acid esters through reactive distillation | |
| Piloto‐Rodríguez et al. | Downstream Strategies for Separation, Washing, Purification, and Alcohol Recovery in Biodiesel Production | |
| JPWO2006016492A1 (en) | Method for producing composition for biodiesel fuel and apparatus for producing biodiesel fuel | |
| WO2008091944A2 (en) | Biodiesel production with reduced water emissions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
| DPEN | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101) | ||
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| 122 | Ep: pct application non-entry in european phase |