INTEGRATED PROCESS FOR BIODIESEL PRODUCTION THROUGH THE APPLICATION OF SALINE DEMULSIFICATION, DISTILLATION AND ESTERIFICATION STAGES OF FATTY ACIDS AND DERIVATIVES

Abstract

The current invention refers to an integrated process for the production of biofuels, through the application of integrated saline demulsification, distillation and esterification stages for fatty acids and its derivatives in a process involving the breakdown of fatty acids stable emulsions and its derivatives through the isolated or joint utilization of physical processes, as well as saline demulsification of greasy residue denominated from aqueous emulsions, developed in such manner as to promote a suitable destination for such residue, such as the use for the production of biofuels, more specifically, biodiesel. The process proposed herein employs a raw-material purification methodology, which implies in better yields in the production of biodiesel through physical processes, such as sifting, filtration, and distillation of the extracted grease, followed by an esterification and transesterification process.

Claims

1. An integrated process for the production of biodiesel by applying the steps of salt demulsification, distillation and esterification of fatty acids and respective derivatives, characterized in that it comprises a first stage of demulsification for the emulsions separation phase containing water and fatty acids, followed by a purifying step of the fatty matter by a physical process and by an esterification step of the fatty acids.

2. A process in accordance to claim 1, characterized in that the fatty acid is produced from sewage slag, grease traps boxes, industrial processing waste, agricultural processing waste, urban processing waste, animal fat or refining lees of vegetable oils.

3. Process in accordance to claim 1, characterized in that it is the fatty acid obtained from the thermal, enzymatic hydrolysis or by chemical catalysis of mono-, di- and triglycerides from new or used, crude or refined vegetable oils.

4. Process in accordance to claim 3, characterized in that it is the vegetable oil of soybean, canola, rapeseed, palm, palm, peanut, sunflower, cotton, olive, coconut, babassu, canola, corn, mammoth, macauba or jatropha.

5. Process in accordance to claim 1, characterized in that it is the fatty acid obtained from the thermal, enzymatic hydrolysis or by chemical catalysis of mono-, di- and triglycerides derived from animal fat.

6. Process in accordance to claim 5, characterized for animal fat from bovine, porcine, caprine, ovine and equine tallow, fish oil and fat of chicken, duck or turkey.

7. Process in accordance to claim 1, characterized by a fatty acid with over 5 carbon atoms.

8. Process in accordance to claim 1, characterized by the de-emulsification carried out at temperatures ranging from 60 to 90 Celsius.

9. Process according to claim 8, characterized in that the de-emulsification is preferably carried out at a temperature of 70 C.

10. Process according to claim 1, characterized in that the de- emulsification is carried out with the addition of salt in an amount, which varies between 5% and 15%, by weight of the emulsion mass.

11. Process according to claim 10, characterized in that the de-emulsification is preferably carried out with the addition of salt for 10% by weight of the emulsion mass.

12. Process according to claims 10, characterized in that the salt is sodium chloride.

13. A process in accordance to claim 1, characterized in that the de-emulsification is conducted continuously.

14. A process in accordance to claim 13, characterized by the use of centrifuges coupled to sieves to accelerate the separation of the phases after the settling step.

15. Process according to claim 1, characterized in that the demulsification is carried out in batches.

16. A process in accordance to claim 15, characterized by the use of a spillway at the top of the vessel to promote separation of the phases after the settling step by increasing the internal pressure of the vessel.

17. A process in accordance to claim 14 or 16, characterized by the use of suction pumps to promote phase separation after the decantation step by transferring the grease material to the next purification step.

18. A process in accordance to claim 1, characterized by the purification of the grease material by a distillation process prior to the esterification process operating with a gradual rise in temperature between 100 C. and 350 C.

19. A process in accordance to claim 1, characterized by the purification of the grease material by a distillation process prior to the esterification process operating under vacuum between 350 mmHg and 700 mmHg.

20. A process in accordance to claim 19, characterized by the purification of the grease material by a distillation process prior to the esterification process, preferably with a vacuum operating between 500 mmHg and 600 mmHg.

21. A process in accordance to claim 1, characterized by the use in the esterification step of the fatty acids having an alcohol/fat ratio of between 0.5/1 and 2/1 with respect to the fat to be esterified.

22. A process in accordance to claim 1, characterized in that it preferably employs 0.5/1 in relation to the fat to be esterified.

23. Process according to claims 21, characterized in that the esterification is by acid catalysis followed by transesterification.

24. A process in accordance to claim 1, characterized in that it uses an amount of catalyst ranging from 0.5% to 10% of the mass of the material to be esterified.

25. Process according to claim 24, characterized in that it preferably uses an amount of catalyst ranging from 2% to 6% of the mass of the material to be esterified.

26. A process in accordance to claim 1, characterized in that it is carried out by homogeneous catalysis.

27. A process in accordance to claim 1, characterized by the use in the esterification of lower alcohol, preferably having from one to five carbon atoms.

28. A process in accordance to claim 1, characterized in that the reaction temperature in the esterification ranges from 60 C. to 90 C.

29. A process in accordance to claim 28, characterized in that the reaction temperature in the esterification is preferably between 70 C. and 80 C.

30. Process according to claim 1, characterized in that the time of the esterification reaction is from 1 hour to 7 hours.

31. A process in accordance to claim 30, wherein the time of the esterification reaction is preferably from 2 hours to 5 hours.

32. A process in accordance to claim 1, characterized in that after the completion of the esterification reaction the product is washed and conducted to the step of transesterification at the ratio of alcohol/ester between 0.2/1 and 1/1, in presence of alkaline catalyst to obtain the biofuel.

Description

DESCRIPTION OF THE INVENTION

[0017] The first step of the present invention consists in the separation of the grease matter from other contaminants with the intent of making it suitable for the esterification process. Some grease matter sources, such as those from household grease trap boxes or the primary decanters of sewage treatment plants, have an acid content of 30% to 90%; others as refining sludge from vegetable oils have typical contents in the order of 30% to 70%. The increase in the acid content is related to the natural degradation process of the glycerides in fatty acids. Thus, the more degraded the raw material, the higher the acidity content. Among the mechanisms that lead to this degradation can be mentioned oxidative rancidity, related to the reaction with oxygen in the air, and hydrolytic rancidity, related to enzymes that degrade glyceride in aqueous medium. The higher the acidity content, the higher the viscosity of the grease material and, therefore, the higher the propensity to compose stable emulsions with polar solvents, especially water. Thus, it is common to form water emulsions and grease with water content, varying between 40% and 80%, with a solid appearance and imprisoning in its interior other materials such as pieces of wood, paper, plastics, even objects of fairly high density as sand, small stones and metal. Under these conditions, the emulsion is not suitable for use in the esterification process and, therefore, it is indispensable to separate such contaminants grease matter.

[0018] The stability of these emulsions is mainly due to two factors. The first refers to the grease material high viscosity, which increases appreciably with the proportion of fatty acids present. The second factor relates to the occurrence of emulsifying substances that act at the water interface with the grease matter. These emulsifiers are naturally present in vegetable oils and even in petroleum, and in addition, are added on purpose in some cases, such as in kitchen sinks to facilitate the transport of grease matter. Basically, the emulsifiers have in their molecule a polar part, which presents affinity with water, and an apolar part, with affinity with the grease phase. With this, the emulsifiers form micelles by isolating the dispersed phase from the dispersing phase.

[0019] Thus, one way of breaking the stability of grease emulsions with water is to heat the emulsion in agitation until the grease material viscosity is reduced to allow movement of water particles which are combining to form new particles, and the phase separation may occur. However, heating alone is often not enough to break the emulsion, due to the presence of the emulsifying agents. A bond with an ionic character between a carbon atom and a strongly electropositive chemical element generally forms the polar part of the emulsifying agent. The action of the electrolyte on the demulsification is to reduce the thickness of the double layer. Its purpose is achieved every time the electrostatic colloidal protection is broken or reduced. With the reduction of this double layer, the particle becomes more susceptible to shocks by the action of Brownian motion, also favored by agitation, thus occurring coalescence and, consequently, the demulsification. The colloidal particle, upon movement within the fluid, undergoes a shear in relation to this fluid. This shear force is unable to pull off some layers of the fluid itself or the protective film, in this case, formed by the detergent, which covers the particle. A medium rich in salts reduces or eliminates the thickness of the double layer, so that simple aggregation by collision between the particles is easy. Even if there is a surface charge due to the protective film, it will not be sufficient to avoid the collision caused by the Brownian motion, also favored by mechanical agitation, causing particles to arrive very close to each other and, with the reduction of the double layer, the of van der Waals forces (forces of attraction) will overcome the coulombian forces (charges of the same sign), giving room for the demulsification to occur.

[0020] The result of this reaction is the formation of a generally soluble ionic salt layer and an insoluble nonpolar compound, both in the aqueous medium and incapable of forming micelles. Such conditions, i.e., high enough temperature to reduce the viscosity of the grease material and salt availability to break the double layer, are sufficient to depolarize the emulsifier and the phase separation may occur.

[0021] The temperature required to allow the coalescence of droplets depends on the specific composition of the grease matter at hand. However, the values are often in the range from 60 to 90 Celsius, preferably around 70 C. Likewise, the amount of salt (sodium chlorideNaCl) required to depolarize the demulsifying agents depends on the concentration thereof, often this value ranges between 5% and 15% by the emulsion weight, preferably around 10%.

[0022] Once the heating and addition of the salt are done, the coalescence of droplets of the dispersed phase and the consequent separation of the phases begins to occur. At this point, the emulsion should decant for a period ranging from one to twenty four hours, at a room temperature ranging between 60 to 90 Celsius, preferably about three hours. The settling time will depend on the viscosity, the average density of the grease material in separation and the utilization degree intended to be achieved in the decantation process. As a way to accelerate the separation of the phases, a centrifuge may be used. At this point, it is possible to sieve the impurities of the grease phase. The mesh of the sieve will depend on the average size of the impurities, since they vary greatly depending on the origin of the raw material used. However, it has been found that the uses of filters complicates the process in such manner, without leading to an improvement in the final yield, and are therefore totally expendable. Likewise, the use of crushers or mills in a step prior to the breaking of the emulsion did not lead to an improvement in the process. The demulsification can be performed continuously or in batch. In the first case, centrifuges attached to sieves with appropriate mesh sizes to the size of the contaminants present in the specific raw material should be used. In the batch process, the best way to promote the phase separation is by pouring the grease material through a spillway in the upper part of the vessel by increasing the internal pressure of the equipment. This can be achieved by injecting water under pressure, or by expanding a plunger or any other equipment that allows for or increases the volume of compressed air within the demulsifying vessel without, however, letting the air escape through the upper part, where it is desired to pour the demulsified grease. With this method, it is possible to increase the internal pressure of the vessel, thus expelling the raw material through the spillway, at the same time that it is sieved under pressure. Another way to separate grease material from the remaining impurities is to use suction pumps, transferring the grease material to the next purification step.

[0023] Acid demulsification usually releases unpleasant odors, a problem that can be mitigated by the use of tall chimneys, or the passage of gases exuded by deodorizing filters or by any other deodorization method available, in which cases the operating costs would be higher in comparison to the construction of high chimneys that require an increase in investment.

[0024] Saline demulsification, the core aspect of the present invention, does not require using resources such as chimneys or deodorizers, since such are used in the acid demulsification, for the dispersion of foul and undesirable gases, but are transferred to another vessel in the course of purification by a vacuum pump, suction pump or by any other methodology described in this invention.

[0025] Fatty acids are carboxylic acids with a long aliphatic chain. These are often classified by the absence or presence of unsaturation. Acids containing two or more unsaturation are called polyunsaturated and represented by numerical symbols such as, for example, C 18: 2, which represents linoleic acid, the first number juxtaposed to the symbol C indicates the number of carbon atoms and the second number, the amount of double bonds.

[0026] Distillation is a separation method based on the liquid-vapor equilibrium phenomenon between mixtures. In practical terms, when two or more substances form a homogeneous liquid mixture, distillation may be a method to separate these substances. These substances just have to have reasonably different volatilities (i.e., the respective boiling points are relatively far apart). It is also possible to separate a volatile liquid from a non-volatile solid. The use of distillation as a separation method is widely used by the modern chemical industry. It can be found in almost all industrial chemical processes in the liquid phase where purification is required.

[0027] Knowledge of the physical and chemical properties of fatty acids is one of the prerequisites for industrial production and technical applications. Thermodynamic and transport properties are required for the calculation of heat transfer, for separation processes by distillation and chemical reactions.

[0028] The fusion behavior is very specific for each fatty acid. The fatty acids fusion point depends on the number of carbons, the degree of saturation and the chain structure. In a linear chain, the fatty acids fusion point increases with the increase of the chain. For unsaturated fatty acids, the behavior is a little more complex.

[0029] The heat from vaporization and the properties related to the boiling point and vapor pressure are very important for fatty acids distillation and thermal separation by means of fractional distillation. To avoid decomposition, the thermal processes are performed at the lowest temperature possible under vacuum (ULLMAN, 2003). The distillation of the grease material starts at temperatures around 100 C., when the fatty acids from lower carbon chains are vaporized and extracted, up to temperatures of 350 C. for carbon chains considered large. The vacuum directly influences the distillation temperature. The higher the vacuum, the lower the temperature used, ranging from 300 mmHg to 700 mmHg, preferably using values between 500 mmHg and 600 mmHg.

[0030] Although studies and researches related to fatty acids distillation are well known, no prior state of the art document, especially patent or patent application, uses waste grease such as sewage slag, grease traps boxes, industrial processing, agricultural processing waste, urban processing waste, animal fat such as bovine tallow, swine, goat, sheep and equine, fish oil and chicken fat, duck and turkey and oil refining lees raw or refined, such as soybeans, canola, rapeseed, palm, palm oil, peanut, sunflower, cotton, olive, coconut, babassu, canola, corn, mammoth, macauba and jatropha, in order to purify the grease matter. Through the distillation process, all impurities contained in the grease material are eliminated, thus obtaining good quality raw material to be transformed into biofuel.

[0031] Since the fatty material is purified and separated from its contaminants, the esterification is carried out as demonstrated below. Once the fatty matter is distilled, it is basically composed of fatty acids and, consequently, the acidity is very high, around 100%, not requiring hydrolysis processes, which would serve for the transformation of mono-, di-, and triglycerides into fatty acids.

[0032] The concern about the quality of the raw material is reflected in the biodiesel production through esterification, as less quantities of reagents are needed. In order to improve the reactants conversion into the product, the use of excess alcohol, although in some prior state of the art patent applications, it reaches a ratio of up to 10/1, as is the case of patent application 0500333-4, or even more, as is the case of patent application PI 0301254-9, which advocates up to 15/1 as an efficient form to convert, whereas in the present invention, proportions range between 0.5/1 to 2/1 alcohol/fat, and are sufficient for the total conversion of fatty acids into biodiesel.

[0033] Esterification is reached by the reaction of fatty acids with short chain alcohol, preferably one to five carbons, such as methanol, ethanol, n-propanol, n-butanol, sec-butanol, iso-butanol among others in the presence of homogeneous acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, sulfonic acid, methanesulfonic acid and toluenesulfonic acid, among others, or heterogeneous substances that have the thermal stability and acidity of Bronsted and/or Lews in the conditions of such as calcium chloride, ferric chloride, zinc chloride, ferric sulfate, sulfated zirconia, nihobic acid and zeolites, provided they have hydrogen as the exchange cation, in the proportion of 0.5% to 10% %, preferably between 2% and 6%.

[0034] The reaction temperature is the boiling temperature of the mixture between reactants, between 60 C. and 90 Celsius, preferably at temperatures between 70 C. and 80 Celsius. The reaction time varies from one hour to seven hours, preferably from two hours to five hours.

[0035] At the end of the reaction the product is washed and transferred to transesterification in the proportions between 0.2/1 and 1/1 alcohol/ester and an alkaline catalyst, such as sodium hydroxide, potassium hydroxide, among others, and washed again with cold water in proportions between 5% and 30%, preferably in proportions between 10% and 20%. The biofuel is then washed and dried.