TW201026845A - Method for production of biofuel - Google Patents

Abstract

Alkyl esters boiling largely within the specification range for jet fuel may be made from triglycerides without a water-washing step, by centrifugation in a timely manner and at a sufficiently high time/G-force/distance product so as to bring about separation of a transitory second phase containing the residual catalyst. The esters or fractions thereof may be combined with jet or diesel fuels to lower the freezing and cloud points respectively.

Description

201026845 </ RTI> Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a biofuel. [Prior Art] The demand for renewable energy includes the need to improve the fuel burned by aviation engines. It would be advantageous if there were high volume continuous flow preparation processes that were not only suitable for the high volume requirements of this market and capable of producing materials in the boiling range of aviation fuels. As is known to those skilled in the art, the use of a water rinse process to produce emulsification is time consuming and difficult to break through. The residual water itself must be removed to minimize not only the corrosion and growth of harmful microorganisms, but also the possibility of ice crystal formation in the frozen fuel, and it is expected that the fuel will be produced in the absence of a process in contact with water. According to Noureddini, US Patent No. 6, 〇15 44 生, I have been used as fuel in South Africa before World War II. While oils such as peanut oil can be used as diesel fuels, it is speculated that at least some of the diesel fuel is made using transesterification of glycerol vinegar, a technique that dates back to the early preparation of soap technology. The transesterification of glycerides is the subject of many patents. Early patents such as Bradshaw et al., No. 2 36〇 844,

No. 2,383,58 and 2,383,581 to Arrowsmith et al., Re22751 to Ding, No. 2,383,614 to Percy, No. 2,494,366 to Spnjles et al. and No. 4,371,470 to Matsukura for the manufacture of soaps. Pure fatty acids to prepare esters. Other early patents such as 3 201026845

Goss et al., No. 2, 29G, 6() No. 9, Kuhn No. 2 634 279, -m No. 2 '875, 221, and Als〇p et al., No. 3, No. 83, 216, are related to the manufacture of glycerin. Stuffed with two vinegar. A number of processes have been developed for the manufacture of biodiesel from glycerides. This disclosure focuses on such processes using alkali catalysts. Although batch reaction batch separation, batch rinsing, and batch processing can be incorporated into other continuous processes, or can be continuously fed to a large reservoir and discharged, it also focuses on continuous processes and the entire process is called &quot; Continuous &quot;' implementers such as biodiesel technology. Strictly speaking, a continuous process has a continuous flow everywhere, whether it is laminar or turbulent. It can be compared to a line carrying a flowing liquid. A typical continuous process is described by Noureddini in No. 6,174,501. The triglyceride methanol and the catalyst are fed to a heated, stirred reactor. The upper layer is then fed to a separator. This upper layer is then passed through a deionization ("scouring" unit) to become a biodiesel product. "However, this exposes a portion of the monoglyceride and diglycerin Sa for the purpose of making monoglycerin and a low φ alkyl ether of diglyceride and glycerol itself. Therefore, it does not seek the integrity of the reaction or the purity of the ester product, as it is taught by the production of a racemic mixture or a raffinate containing a slit. Point reduction. A number of patents have been issued for the type of reactor in which a chemical reaction occurs. Triglycerides and methanol appear to be immiscible in excess of a limited solubility, and are added as in the patents of Boocock, No. 6,624,399. A co-solvent to achieve a homogenous solution. Several patents have been proposed to enhance the agitation of the reactor. The Reynolds Number of more than 2,300 is taught by Assmann et al., at 5,514,820. Hooker, U.S. Patent Application Serial No. 4 201026845. /0027137 teaches the acceleration of the ultrasonic wave of this reaction. There have been a lot of techniques to deal with the production of this reaction. Its preliminary separation and small amount of reaction by-products Fine separation of the desired material is accomplished by chemical means, physical means or a combination. Fatty acid alkyl esters are lighter than glycerol (unless a very large excess of alcohol is used, such as 20:1) and are separated by gravity. Wimmner The addition of 0.3% to 3.0% water promotes separation in No. 5, 399, 73. In contrast, McDonald, in No. 6,262,285, claims to be very effective by removing all of the water and using a continuous pour in the absence of an embodiment. Separation. McDonald removes all the water with a sorbent type molecular sieve. There is no evidence that the process is as effective as it is. Of course, using a centrifuge to separate two phases of different densities is a very old technique, such as the cream of the 1800s. As shown by the separators, in the past, many patents have referred to the use of centrifuges in the production of biodiesel. See, for example, Assmann at 5,514,820, column 2, lines 7 and 13, Granberg φ et al., No. 5,648,483, item 7. Column 51, Matsukura et al., No. 4, 371, 470, column 3, line 18, and 4, 668, 439, column 6, line 25, Hayafuji et al., No. 5, 972, 057, column 15, line 38, and N Oureddini, No. 6, 174, 501, col. 10, line 59. In the case of Barnhorst et al. 6, 489, 496, the essence of the use of a centrifuge is claimed.

McDonald, at 6,262,285, claims to obtain an acceptable product by pouring. Those skilled in the art have recognized that trace amounts of impurities are not only inferior to current biodiesel standards in the United States and Europe, but also very serious. 5 201026845 There are several ways to remove impurities, where the raw diesel is first rinsed with water and dried. The third embodiment of the water rinsing is No. 4,303,590 to Tanaka et al., No. 6,624,399 to Boocock, and U.S. Patent Application No. 2006/0224005 to Felly. No. 5,354,878 to Connemann et al., which is directed to flushing biodiesel with a buffer of aqueous pH 8 to 10. Conversely, Wimner No. 5,434,279 is rinsed with a dilute acid such as citric acid. No. 5,424,467 to Bam et al. proposes rinsing with glycerin. Hayafuji No. 5,972,057 proposes the use of a sorbent such as acid clay. U.S. Patent Application Serial No. 2005/0081536 to Bertram et al. discloses the use of an adsorbent such as magnesium ruthenate. Noureddini used an ion exchange resin to remove impurities at No. 6,174,501. Discussion The presence of any significant amount of a particular monoglyceride and diglyceride is due, at least in part, to insufficient reaction time/temperature/catalyst concentration. By means well known to those skilled in the art, a substantial complete reaction leading to negligible amounts of monoglycerides and diglycerides can be achieved. Therefore, the following discussion focuses primarily on the removal of specific impurities, but this removal is also taken into account. Removal of undesired materials from the biodiesel stream is known to be accomplished by rinsing or by sorbent. Although in principle any liquid which does not dissolve the product in significant amounts can be used, it is known to those skilled in the art that this flushing is usually accomplished with water or glycerin. The emulsion is typically formed by rinsing with water and can be formed with other rinsing liquids. These salts are formed by the presence of residual phytol, phospholipids, and by-products of biomass, and are used as emulsifying surfactants. During the manufacture of biodiesel batches from canola oil and 6 201026845 canola oil (rapeseed oil), it was observed that when attempting to rinse with water, compared to palm kernel oil, canola seeded diesel A stronger emulsion is formed which requires more effort to destroy and ultimately clean. Emulsification can be reduced by very slow water rinsing, as the water droplets drip from the rising liquid of the base. Very slow water rinsing is incompatible with the design of high volume continuous flow processes. The rinsing can also be carried out in a reversed manner, in which a suitable solvent does not dissolve the pure product but dissolves the desired ester product and separates the product from the material which is not expected to be present in the final product. An example of the reverse rinsing in the prior art is U.S. Patent No. 6,211,39 to Peter et al. The sorbent includes those that are very reactive, such as Magnes G1, which is an inert magnesium monosilicate (talc) material. The sorbent includes a molecular sieve. The sorbent can also be a more active one, such as an ion exchange resin in the form of a dehydrating acid.

This material can be adsorbed with even fatty acids by hydrating, hydroxy-functional materials such as water, alcohols, glycerol, monoglycerol and diglycerin. The metal catalyst can also be clamped by ion exchange. There are other possible types of sorbents, but in bed or suspended form, they all have the disadvantage of being a solid material that is removed from the process stream or from the filling reaction chamber of the filtration process stream. Become a waste. Although this process is generally compatible with the continuous flow preparation process, it is not an ideal structure for this process. In an ideal continuous flow process (4), at any point in the process, the material will be mixed and treated with the reaction zone. Where this is the continuous flow process, it will produce the most consistent product. The fuel required by the aero engine is a very small 16 drops that are broken into a large burning surface area when ejected through the hole under the high magic, and become a fog in the engine room 35. It has been proposed to define petroleum products with a range of physical and chemical properties that must be adhered to in current engine designs. The upper and lower limits of the Xianxin Buddha point specification are derived from the early control of the viscosity to try to obtain the atomization property of the filament. Generally, two kinds of natural triglycerides (Norraine oil and standard oil) have a large amount of fatty acids in the range of C8_C14. These fatty acids are converted to their methyl vinegar form, that is, the fatty acid methyl vinegar (fame), which is expected to boil in the boiling point range of the route material based on its molecular configuration and molecular weight. It is known to those skilled in the art that triglyceride can be directly fed to the pyrolysis process and the necessary fractionation and/or isomerization of the raffinate stream can be used to produce the material. For lighter and heavier sub-categories of fuel hot oil or petroleum, but some materials with boiling points in the aviation fuel range are available. The disadvantage is that the material preparation plant requires more than a few million dollars, and small-scale plants are not economically viable. Therefore, there is a need for a manufacturing process where the production plant costs are much lower, and it can be established on a large scale and on a small scale depending on the needs of the region. The natural triglyceride vinegar is esterified with methanol, ethanol, etc. into a process that is easy to establish in very small, medium and large scale. The low molecular weight alcohol generally used is decyl alcohol. Sterols are currently produced from natural gas, which is converted to synthesis gas by controlled partial combustion. It is a mixture of carbon monoxide and hydrogen, and is then mostly converted to the f-alcohol. Equipment that completes this process can only be built on a large scale. There are two ways to overcome this obstacle to achieve the basic objectives of this patent application, and the two are known per se. The conceptual integrity is disclosed herein to facilitate the disclosure of the present invention. One method is the use of an alcohol, especially ethanol, which can be obtained from a source of regeneration by a person known to those skilled in the art by known methods, and is currently acted upon by the enzymatic action of corn syrup. And mass production. The second party, the manufacture of methanol for renewable energy, such as the destructive steaming of fiber materials. It can be returned to methanol, also known as the initial name of methyl alcohol, which is named because of its early manufacturing method.

It is also noted that the aviation engine 揪M H 竽 钭 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 由 由 由 由 。 。 。 。 。 。 。 。 。 。 。 。 。 航空 航空 航空 航空 航空 航空 航空 航空 航空 航空 航空 航空 航空The right is made from a source of regeneration. This fuel production does not significantly increase global warming because it is made entirely of plants that take carbon from the atmosphere. Accordingly, the present invention is directed to the production of this fuel on an industrial scale by an efficient continuous industrial process in the context of describing the source of the alcohol component in the (4) structure. SUMMARY OF THE INVENTION It has been found that after a few minutes and hours of a specific reaction, when the reaction mixture is allowed to stand, the turbid phase of the turbid phase actually contains the -suspension phase, which is reduced to the extent of Re-dissolve after a few days. This material is alkaline and settles under the influence of gravity. The separation can then be accelerated by centrifugation, as is the use of a knife to separate liquids of different densities (or liquids with suspended solids). This &amp; Xu-improved benefit in the manufacture of s曰, "in the hope of a degree of purity, this purity is more than that obtained by the initial cleavage of glycerol by ester separation by means of conventional storage tank settling or cyclonic separation. Also provided is a simplified preparation process which removes the water rinse step for removing a homogeneous catalyst. An improved preparation process for the production of a methyl ester of a specific but non-limiting triglyceride will now be described which is incorporated into the process wherein the glycerol triacetate is obtainable from a plant source. Of course, other sources of animal, seawater or glycerin and other alcohol esters can be used in this technique. If the triglyceride vinegar of animal or plant source is purified by appropriate stalking to produce parsyl triglyceride, it is free of fatty acids, water and planting Φ 帛, dish fat f, antioxidants and other possible follow-up A minor component that is unfavorable in process or has non-major commercial value. In addition to the recovery of a suitable phytosterol for a particular oil, trace amounts of water and free fatty acids can be removed by a low pressure distillation in a stirred membrane evaporator, falling film evaporator or the like. An inert atmosphere is flushed through the system to help remove residual water and free fatty acid vapors, as well as prevent oxidation during the entire process. This purified triglyceride is combined with an alcohol solution of a basic catalyst. Although it is known that any basic catalyst known to those skilled in the art can be used in the process, a notable example of a suitable base catalyst is sodium decoxide, potassium hydroxide and the like. The alcohol solution of the catalyst is mixed with the triglyceride in a compact mixer such as an emulsification mill. This is generally used in the asphalt industry to make aqueous asphalt emulsions. It is known that any mixer can be used, the initial reaction rate being limited by the contact surface of the liquid, which is first dissolved in each other with p艮 and thus into a two-phase system. Although the prior art uses batch processes and agitation, and settling tanks, the preferred implementation of this technique is still a continuous flow type, which can be used to produce a mill from a mill through a plug flow system. 201026845 The output provides a retention time that is sufficient for the transacetalization to proceed substantially to completion. For specific oils and catalysts and alcohol concentrations can be known by skilled artisans. It has been found experimentally at a temperature (4) and changes to other temperatures to achieve the desired reaction time. Time-temperature product depending on catalyst type, concentration and mixing tightness ^ ° Journal 〇f 〇α Palm Research γ〇1 16 ? No. 2&gt; December 2004. f

The temperature will reduce the time required to complete. The factor is 10 degrees Celsius, and the range varies from 4 to 2. Therefore, at 7 (rc for 2 hours, 4 is equal to 8G C - hour, 纟i 〇 () () °c quarter-hour, etc. The process loop can be a single tube or many smaller parallels. The length of the tube is as visible in a larger heat exchanger. The pipe or tube may contain static mixing components or maintain a sufficient mixed state in the reactor for a residence time of the reactants. Filling material. Maintain a temperature suitable for the residence time from the mixer to the process loop. Separate the glycerol phase with the subsequent cooling and/or termination of the mixture. Depending on the alcohol = glycerin and in the form of special money or The phase solubility in the vinegar mixture and the excess alcohol are layered between the ester phase and the glycerin phase. Depending on how much excess alcohol is used and the difference in density between the alcohol and the ester, the less dense glycerol/alcohol phase will separate. And floating on a denser self-acting/alcoholic phase i, or a less dense alcohol phase floating on a denser glycerol/alcohol phase. In these examples and subsequent discussions, 'assumed to use more than stoichiometric reactions Approximately one to two moles of excess methanol is required, and thus the formation-density ratio The glycerol/alcohol phase settles to the bottom, but this choice is not intended to limit the process of the process. 201026845 The main part of the glycerol/alcohol phase can be easily graduated by gravity, a continuous flow basis, in different batches or half. Continuously arranged settling tank separation, or separation by a simple continuous flow apparatus such as a cyclone separation. Cyclone separators are known, not only for separating liquids of different densities, but also for separating particles of gas flow, for example Particle ash from a combustion process or wood chips from air rinsing through a wooden product preparation process. The second centrifugation process is not obvious at this point, such as φ, continuation of high G amount and durability after this patent. - not obvious, and this step is insoluble at least at a short time and will produce a surprising degree of material separation. The basic reasons for this centrifugation step will be described in detail. In the experiments described in the examples, it was observed The visible matter settles over time, and the visible settled material has different concentrations of certain alkali materials. By observing the sink with a suitable substance Performing centrifugation at a rate of deceleration to speed up the process can result in a significantly improved production process for biodiesel. • Sphere particles based on physical laws (assuming the particles are spherical to simplify calculations because their precise shape is unknown and may vary irregularly The spherical hypothesis has been found to give appropriate practical results in general physics. The sedimentation rate of a fluid with a special viscosity (empty fluorine or gas) varies with particle radius. From http://www.sciencebyjones .com/Viscosity.htm: Theory · Objects that fall through a viscous medium When the sum of buoyancy and cohesion equals gravity, the object can reach a terminal velocity [constant velocity, no acceleration] q versus density (p) In terms of the radius of the sphere in the fluid, 12 201026845 F foreign force + twist = Ft Λ F buoyancy = 4/3 7tr3pg F« «=6πη r vt F* force = mg where v is the terminal speed and η is the viscosity. g is 980.7 cjfi/s2 Cautious generation game 4· .· Viscosity (t])=2h g a2/9 ν

Where b = the difference in density between the sphere and the liquid, g = gravitational acceleration, ά = sphere radius, and ν = velocity (d/t)) so by solving the terminal velocity v, we can see that we have a velocity positive suspension A complete map of the effective radius map of the particle, which varies directly with the square of the particle radius. From the data observed in the following (10) 2, it is essential that the industrial centrifugation and the required range of force are used to separate the turbid substance containing the residual group f derived from methyl group 8 and residual glycerin and glycerin. Obtained from the observations—the settlement distance at ^9.mm/hr is the starting point of the centrifugal specification. If the (four) ring belt (four) rotates in the centrifuge, the average radial enthalpy

With a Π pitch of 90mm, it is clear that it takes 100 hours at i G. At 100 G, cloud i, and n ± 4 take 1 hour, while at 6000 g, it takes one minute to transfer the button M in the centrifuge, leaving time to separate the suspended alkaline substance. The horses and amps that need to drive this centrifuge need to have enough horsepower to accelerate the expected liquid output to a rotating technique with a minimum radial clearance of 90 mm at a distance of about 6000 G. Of course, the turbine at the -+ ^ end recovers a significant component of the rotational energy by slowing the speed of the rotating liquid and feeding back the energy to the wheel station. Thus, an industrial miscellaneous, tea centrifuge can be designed and applied by methods known to those skilled in the art. 13 201026845 Of course, if a design is made for 1 minute at 6000 G, you can use 6〇〇 G 1〇 minutes, or use the product of any time force that can achieve equal results. Because the size of the precipitated catalyst particles and/or glycerol/glyceride emulsion droplets depends on the type of oil droplets and the nature of the oil and its natural emulsifier (such as phospholipids), it varies over a wide range to obtain an emulsion. Or suspension, this tendency will also depend on the particular alcohol used, so the required centrifuge retention time will vary accordingly. The approximate range of centrifugation requirements can be any of the conditions observed in (4). According to the foregoing embodiment, the height of the final ester &quot;refining&quot; will not be completed by water rinsing, nor will it destroy the general emulsion, remove residual water or use ion exchange resin or other sorbent &quot;refining&quot; Inconvenience that comes with this. After this centrifugation step, the process can then provide an alcohol stripping step to remove the light ends, which consist essentially of excess alcohol still dissolved in the ester. It is expected to be so operated that the final steaming If the (4) step will not load an additional vapor load on the relatively low-boiling material, the low-boiling material will be recovered and returned to the ® 1 stream. Therefore, 'you can use a membrane evaporator or a falling film evaporator or Similarly, #, it can be operated or heated at the temperature of an input process & stream. This fugitive vapor, although preferred at atmospheric pressure, is designed to simplify design at a reduced pressure or a pressure higher than atmospheric. If the vapor is more desirable to be reused throughout the process, a condenser can be used to return the vapor to a liquid state. It is highly desirable to flush an inert gas to effectively carry away all of the alcohol as it is undesirable. In the final product, the European Biodiesel Standard (eni42i4) limits methanol to 0.2%. US ASTM D6751 requires a closed cup flash point of 13 ° C. It requires hundreds of parts per million of lower methanol. 201026845 The output of this light-end stripper can then be transferred to a distillation column for final purification of the process stream for the end use. Light distillate, for example at tenths of a ton at 100-15 ( The rc boiling can be in the range of aviation fuel or No. 2 diesel. The higher boiling point material is in the range of heavier fuel materials, such as heating/supply, while the bottom liquid stream can be used in applications that do not require special fuel standards, such as in the process. Burning in heated manufacturing equipment. Various steps require heating' and there is an economic trade-off between the quality, cost and heat exchange efficiency of the insulation structure. Therefore, the inevitable loss of some heat is one between manufacturing and economic feasibility. Actual compromise. This heat can be supplied by the less desirable product of the combustion preparation process, since these sources are derived from atmospheric photosynthetic carbon dioxide, followed by combustion and reduction. The storage of solar energy to carbon dioxide and extracted from recovered plants, the return of this carbon dioxide to the atmosphere does not substantially have a net effect on the earth's ecosystem. [Embodiment] The drawings of the present specification are illustrative of a preferred embodiment of the system of the present invention. Depicting Figures 1-A and 1-B, as an embodiment, element 1〇1 is a catalyst source which is combined with an alcohol. The catalyst, alcohol and purified triglyceride may of course be combined together in a mixer 106. Or mixing before entering the mixer; in order to illustrate the catalyst shown in the figure, the catalyst is pre-mixed with alcohol. These materials are managed by a strict process (4), so the specific proportion of the components is maintained. This ratio is based on the raw material-based diacid. The glyceride content. The triglyceride content can be determined by known procedures, such as in the tank or by sampling along the line. This information can be used to manage the proportion of 15 201026845 raw materials. This process control determines the appropriate amount of alcohol to catalyst based on the feed triglyceride content. Element 102 is a triglyceride source such as palm oil, palm kernel oil or rapeseed oil. This oil has substantially removed all of the water before it enters the process. No water is added during any subsequent steps during the process described herein. Element 103 is suitable for recovery of the particular triglyceride starting material. Examples of recovered compounds are phytosterols, phospholipids, and other trace compounds that may be beneficial or detrimental to subsequent esterification processes. The ringing element 104 is a vacuum distillation process for pretreating the unprocessed triglyceride, typically a stirred film evaporator, falling film evaporator or the like, which is as in Example 10 (M5 (rC example temperature and An example pressure is one tenth of the atmospheric pressure rating, typically flushed with an inert gas to specifically remove any water or free fatty acids that subsequently degrade the esterification catalyst and form an undesired soap. Element 105 is a condenser for steam Leaving from 1〇4. • Element ι〇6 is a physically compact (eg high shear) mixer that typically produces a heating of the process stream, which in this embodiment incorporates a triglyceride stream. And an alcohol/catalyst stream. An additional heater can be used, such as in the flow between elements 104 and 106. The temperature of the combined mixture rises to about 140. (: to a process temperature of 160 t and the pressure is maintained sufficient to prevent The pressure at which the liquid is converted to vapour, about 10 (four) to 3 〇 (iv). Therefore, the reaction occurs rapidly 'for example, in less than i minutes. Of course, this temperature and Lili can be adjusted according to the parameters of the system operation. Typical In the prior art process, the operating temperature is 60 ° C to 65 ° C and the pressure is atmospheric. " 16 201026845 107 107 is a suitable process circuit, maintained at the desired process The reactant-plug flow environment is provided during the transport from the inlet port to the outlet port, so that the material entering the component is maintained at the desired temperature for a desired period of time and then transported to the next process component. In its simplest form 'This component can be the length of the pipe or pipe, preferably with suitable filling material' to maintain the plugging environment for the material being transported. &quot;plug flow&quot; means that the material enters in one unit and is nominally The unit 108 is a heat exchanger which exchanges the reactant mixture at the previous element: the reaction temperature to a temperature suitable for the desired function of the next process element. Element 1〇9 is a Glycerin-acetic acid separation element. A suitable element is a cyclone: a mixture of glycerin and vinegar is injected near the circumference of the circular element, and the phase force of the large force k is shifted to the outer circumference and the phase of the lower density is moved. To the axis Direction: In a dense glycerol/alcohol phase and a less dense ester/alcohol phase, Taiguo a + β β Τ shows a cyclone in the figure and a vertical gravitational field (not shown in the figure) The glycerol/alcohol phase of the formula φ, Α α, a) 3⁄4 is moved downward and is drawn into a small space by the conical shape of the cyclone. This device is named after the 。. Described as a separate component is the glycerin sensor at the spin, which controls the removal of glycerol leaching when the glycerol is stacked but does not remove the lighter cool/alcohol phase. This auxiliary component is known to those skilled in the art. The element 110 is a cymbal:, a centrifuge, as described in the specification, the second embodiment, and the patent application. The element 111 is - y, ', heat exchanger' which exchanges the process flow to - It is suitable to use 17 201026845 for the temperature at which the process component is intended to function. Element 112 is a stirred film evaporator, component, hair dryer or other similarly stripped residual alcohol from a less volatile vinegar process stream. Preferably, it is inert, volatility, and volatility to facilitate the removal of the residual alcohol enthalpy which is not expected to be vaporized, and the enthalpy 114 is a certain distillation. The effluent from the top steaming hall is preferably the expected product of the material of the steamed pavilion. The element 113 is a vapor condenser amp that is required for condensing the vapor of the low point material of the self-contained liquid stream, which is preferred. The liquid condensate can be used in all processes. ❹ and: U4 is a distillation element of sufficient theoretical plate to separate the process liquid flow into roughly different points | two or more process liquid flows, such as the expected different flow of the 2 liquid flow . In the round mode, the process stream is the lowest boiling stream, which is shown as vapor at the top of the steam column; for example, another process stream, shown at a higher temperature, is discharged halfway down the column. 'Because this corresponds to how the ordinary steaming column is operated, it is traditionally connected to the bottom of the column to present a higher temperature and a lower temperature at the top, and the external gravity field draws a denser liquid to the bottom with a lower density. The vapor to the top. A third effluent is shown at the bottom where the material is a liquid which is preferably boiled at a high temperature to extract a low boiling point material. An optional volume sensor and liquid heart valve are displayed and can be used if needed. This process illustrated in element U4 is intended to include a continuous fractionation process. Different boiling fractions are separated during the fame distillation to remove unwanted components such as excess methanol, monoglycerides and diglycerides with any excess glycerol from FAme. Finally, FAME is cracked into individual boiling fractions, and each of them 18 201026845 can be used for different types of fuels, such as a cloud point or solidification 4 and diesel fuel. Part of the ... inhibitor. Lighter fractions (eg 刖20/〇) are suitable for blending with aviation fuels ^ ^ • freezing point. The remaining points are :: oil blended to reduce cloud point. Of course, the heavier denominator can be used as a diesel fuel itself, in addition to the blending component. 4 or HOW's smelt may be blended with diesel fuel, or all of the output may be used as diesel fuel under appropriate conditions. As pointed out in this article

The aerospace and diesel fuels are all petroleum, biofuel or a blend. - Member 115 is a vapor condenser' whose output is a condensing process stream having a boiling point within the specifications of aviation fuel. Element 116 is a vapor condenser whose output is a condensed process stream having a boiling point above the temperature range of the condensate of element 115. Element 117 is a higher boiling distillate, i.e., condensate from element 116. The condensate of 116 is intended to be the main steaming residue of the net of the palm fuel or the coconut oil in the range of the fuel fuel point of the aviation fuel (4), which has the higher boiling fraction of the triglyceride. Suitable for use as No. 2 diesel or a higher boiling point. Therefore, this distillate is presented as a recycle for the use of other uses other than aviation fuel. Referring to Figure 2, 70 piece 201 is a process for the preparation of an alkyl ester from a triglyceride stream which does not include a rinsing step or a sorbent step. Several pieces 202 are a centrifugation process with a force/detention time product comparable to or greater than the observed sinking rate of the suspended matter described in the examples. This example: nominally {at 90 mm The radius distance is 6000G X 1 minute}' and it has a discharge flow of a substance with a higher density 19 201026845 separated by a process flow 2 〇 1 . Element 203 is any post-centrifugation process, which does not include a rinse Step or a sorbent step. A description of a preferred embodiment of a process such as triglyceride available as an animal or plant source is purified by suitable means to produce substantially no fatty acids, water and phytosterol antioxidants Tri-flycidyl glycerides and other minor components which may have commercial value. In addition to the recovery of phytol which is suitable for specific oils, especially traces of water and free fatty acids are preferably used by agitated membrane evaporators. The falling film evaporator or similar element is removed by low pressure distillation. An inert gas flushing system helps to remove residual water and free fatty acid vapors and helps prevent oxidation during the entire process. The glyceride is mixed with the alcohol solution of the base catalyst. Sodium decoxide is easily obtained, and sodium methoxide is preferred if the catalyst circulates in the process loop. If ethyl vinegar is used instead of methyl vinegar, sodium ethoxide is preferred. Phase _ (10) ground ' can use A (four) or ethanol ★, and if the catalyst or its substantial part appears in the waste stream of the process, 'potassium is better than sodium, because potassium salt has been used as fertilizer, so it is not considered Unusable waste. A catalyst alcohol solution and triglyceride are measured in proportion to a sufficient amount of alcohol in the amount of alcohol per vinegar in the triglyceride, preferably f amount Reaction to - the desired degree of completion. Use as low as 10%: is rare. On the right there is an excess of _ etc., which promotes the reaction to a high degree of enthalpy ID. The alcohol dissolved in glycerol reduces the viscosity of glycerol. And help to reduce it; the viscosity of the reacted glycerol product. It can be used twice or three times 20 201026845 and the molar excess of about 1 to 2 times the stoichiometric amount is 1 molar excess compared with the comparison. If it is about 15', the glycerin phase change is less dense than the basic knowledge. And floating on top rather than sinking in the lower part is desirable in some implementations of this technique - the alcohol solution of the catalyst is mixed with the triglyceride s intended to be a tightly acting mixer, preferably an emulsion mill, Because it is already available. It is known that any &amp; combines, the initial reaction rate is limited by the contact surface of the liquid

The product is first dissolved in a limited amount and thus becomes a two-phase system. The preferred hold of this technique is continuous flow, where the mill's output continues to pass through a process loop to achieve a sufficient residence time for the - (iv) reaction. The process loop can be the length of a single tube or a plurality of smaller parallel tubes as seen in a larger heat exchanger. The pipe or fitting may contain a static mixing component or a packing material in the reactor that maintains a sufficiently mixed state during the residence time of the reactants. Maintain from the mixer to the process loop – temperature suitable for the time remaining. The glycerol/alcohol phase is separated by subsequent cooling and/or termination of the mixing and a complete or near complete reaction. The excess alcohol is determined by the relative solubility of the glycerol in the particular ester or ester mixture formed, between the ester phase and the glycerin phase. Depending on how much alcohol is used and the difference in density between the alcohol and the ester, the less dense ester/alcohol phase floats on a denser glycerol/alcohol phase or the male, less glycerol/alcohol phase floats in one Higher density ester/alcohol phase enthalpy In these examples and subsequent discussions, it is assumed that an excess of methanol of 1 to 2 moles is required for more than the stoichiometric reaction, and thus a higher density glycerol is formed / Alcohol phase and settled at the bottom, but this choice is not intended to limit the process of the invention of 2010 21845. The major portion of the glycerol/alcohol phase can be readily separated by gravity on a continuous flow basis, in different batch or semi-continuously disposed settling tanks, or by a simple continuous flow apparatus such as a cyclone. The next step is a high G force separation step. A set point at which i ^ is 〇 9 mm/hr is taken as the starting point of the centrifugal specification based on the observation of the sedimentation rate of the suspended matter. If the average radial ❹ distance of the liquid annulus is 9 〇 _, then clearly, at 1 G, 100 hours is required. At 1 〇〇 G, it will take 1 hour' and at _〇G, the retention time of the alkaline material in the centrifuge that needs to be separated and suspended is calculated to be one minute. Of course, if the 6000 G is 1 to 8 * _, and the 1 knives are not counted, any time-force product can be used to get equal results. Because of the catalysts of the sacred temples, and the "Gan, by / Gan, from the size of the milky droplets according to the size of the oil droplets" or even the specific m natural phytosterol m and so on The suspension is varied to obtain a suspension, so the required centrifuge retention time will vary accordingly. Centrifugal i seven Μ away. The general range of the absence can be achieved in any case by simple observation as described above. There are no subsequent water rinse steps or sorbent steps. This is followed by a step which may then include an alcohol stripping step to remove the light end which consists essentially of excess alcohol remaining in the ester. It is expected that the final steaming step will not be relatively low if used: the additional vapor/negative enthalpy of the material will be recovered and returned to the process stream. It is expected that an inert gas flush will effectively carry all of the low-flood component to prevent oxidation as the stripping of the light stripper 22 201026845 can then be transferred to a distillation column for end use. The final purification of the process stream. Example 1 1000 g of mustard seed oil, 24 g of methanol and 3.0% by weight of sodium decyl methoxide solution in a 4 liter Erlenmeyer flask at a temperature of 65 〇c on a hot plate with a pentoxide The stir-coated magnetic stirring was carried out for 2 hours, and the flask was attached with a reflux condenser. This reaction was considered complete at this time and the mixture was allowed to cool to about 50% and then poured into a separatory funnel. This glycerol phase was visualized after a few minutes and the 1 〇〇〇 ml turbid upper phase was placed in a graduated cylinder and allowed to stand at room temperature for about 30 hours. A clear area was observed at the top to form 'about 1 cm high. A sample having a volume of 4 cc was taken from a different depth by a syringe and a long needle. The samples were rinsed once with 16 cc of deionized water, allowed to stand for several hours, and the bottom 6 cc of water was removed and placed in a test tube. Take a picture of this, which clearly shows the difference in turbidity, which has different components at different depths. The pH of each layer was measured by using a pH meter using a solid-state FET electrode. The value from top to bottom is: 2 〇 mL ' from the top ' ρ Η = 7 · 5 - 7.9 ; from 750 mL layer [250 ° ], pH = 7 8 7 9 . From 500 mL layer, pH=8.3-8.4; from 250 mL layer, pH=8 〇_8 3 . About 20 mL layer on the thin layer of glycerol generated from the bottom, PH:=8 2_8 3 ; And for sampling the bottom glycerol layer itself 'pH = 11.2-11.3. The range of pH presents two consecutive measurements of the same material' which reflects some of the uncertainty in the measurement. Nonetheless, it is clear that there is a significant change in pH that can only be explained by the settlement of a certain velocity at the same rate. 23 201026845 2 It can be seen that there is a concentration gradient in the suspension test material, because the concentration is almost neutral, and the concentration is almost in the order of magnitude, and the glycerol layer is about 35 times higher than the alkali concentration of the top ester layer. - ° It is clear that if the material is centrifuged, the separation of the upper material from (at least temporarily) the insoluble material will occur rapidly, so the upper vinegar layer will be purified. Analysis by gas chromatography revealed that the reaction was essentially complete and contained a visibly monoglyceride or diglycerol. ~ The conditions required to reach a specific retention time can be calculated from experimental data. It was found at 65. (: The reaction time is 2 hours, in the hungry! Hours and in the order of 1/2 hours, it can be estimated by extrapolation that the reaction is available at a price of about 15 minutes - a similar degree of completion, at 1Q5t: about 8 Minutes, at 4 minutes. To perform this reaction on a continuous flow basis, select a process loop to provide the desired residence time. After the glycerol/alcohol phase cold section and centrifugation, further centrifugation steps remove the residue. Glycerin and catalyst, and the material can be stripped of methanol and distilled if necessary., Example 2 1440 g of brown thrown oil is placed in a 4 liter flask with magnetic induction, placed in a heat with a stirring motor On board, about 2 moles, molecular weight about 720. Add 18 moles or a total of 54 〇g of methanol with a molecular weight of "methanol" and 34 g of 30% sodium methoxide in methanol. This mixture is heated under mixing It was maintained at a temperature range of 6 G to 7 G ° C for 2 hours. It was then allowed to cool for about 0.5 hours under the transfer, to a temperature of about 45, and poured into a 4 liter separatory funnel. In a few seconds, it formed at the bottom. a glycerin layer, and in the next = clock 24 201026845 within the interface The broken layer &quot;disappears&quot; leaves an almost mirror-clear interface. Glycerol is discharged from the bottom and a turbid methyl vinegar layer of about 1020 rainbow is placed in a milliliter cylinder, and a 4 mL sample is taken to represent the average of suspended matter. The method described previously determined and obtained 9 3 - 9 4 . When allowed to stand at room temperature for another hour, the ester was further cooled and the volume was close to 1 〇〇〇 mi ^. The substantial size of the 1000 mL graduated cylinder was about 6 coffees on the inside. And the cylinder part is 35 cm in length. Therefore, after calculation, the 1 〇 scale is 〇35 (10) interval. The reference is observed at about I·5 hours (during about 2 〇. During the period of ', a clear volume of about 4 cc is observed. The clear layer is formed on top of the freshly processed palm kernel methyl vinegar l〇〇〇mL graduated cylinder. Within about 3 hours, a clearly clear layer of about 8 cc is formed on top of the 1000 mL graduated cylinder. At this point, in the graduated cylinder 4 &lt; 忒 samples were taken at different depths. The water extracts of these samples were measured from the top according to the depth: 20 mL from the top, pH = 92_94; from 75 〇 1 ^ layer [250 times] ' ph = 8.3 -8.5 [This amount is suspicious]; from 5〇〇mL layer, pH-9.5-9.6' from 250 mL layer, ρη=9 .9-10·0; a layer of about 20 mL on a thin layer of Φ generated from the bottom, ΡΗ = 9.5-9.8; and for sampling the bottom glycerol layer itself, ρ Η = 11.6-1-11.7. The remainder is allowed to stand overnight. A slightly clearer layer of a negative demarcation of about 150 cc to 300 cc in the upper 15 〇 3 〇〇" of the ester in the cylinder for 18 hours. The clarity decreased downwards to about one third of the downward It is not more turbid, just like the turbidity of the original I filling of the measuring cylinder. This property is consistent with the high-density particle size distribution of vinegar, which slowly settles under the influence of a force of gravity. At 20 hours, a second set of samples was taken from different depths as previously described, and 25 201026845 from the top 20 mL, ρ Η = 9.3; from 5 〇〇 mL layer, ρ Η = 9.6-9.7; a thin layer of glycerol generated at the bottom The pH of the glycerol layer itself was measured by the above method, and its pH was measured as described above. 750 mL layer [250], ρΗ=9·6; from 250 mL layer, ρΗ=9·7-9.8; from 20 mL layer, ρΗ=9.3-9·4; and ρΗ=11.4-11.7.

The initial sedimentation observation was about 14 cm at 15 hours and about 0.28 cm at about three hours, both of which were equal! G is about cm cm 9 cm / hour. Later sedimentation observations are approximately 5 to 1 〇cm at about 18 hours, or about 0.28-0.56 cm per hour at 1 (}. This is likely to be Brownian motion and sedimentation in later measurements. Competition and blurring effect. However, there is a re-dissolution phenomenon or a chemical reaction in about 21 hours, the whole amount is almost clear, only about the lower third is slightly blurred than the upper part. The room temperature does not change significantly during this period. Therefore, the temperature is not the cause. This clarity is not the same as the initial layer of the ester in the first few hours, the crystal is clear &quot;' but substantially clearer than the lower part of the first few hours. On the second day Previously 'except for a light orange glycerin layer of about 10 to 20 ml at the bottom, the entire cylinder became pale yellow and crystal clear. This change is consistent with the redissolution of something' and therefore the height may be simultaneous for several conditions. Approximately 70 hours after the initial reaction mixture was poured, the third set of samples was taken in the manner previously described. The pH was measured in the previous manner. From the top 2 〇 mL ' ρ Η = 9.4-9·6; from the 750 mL layer [250下],ρΗ=9·5 -9.7; from 500 mL layer, ρΗ=9·4-9·8; from 250 mL layer, ρΗ=9.6; about 20 mL layer on the thin layer of glycerol generated from the bottom, ρΗ=9.5-9.6; The bottom glycerol layer itself, ρΗ=11.5-11.6. 26 201026845 It is noted that the extraction and agitation of the water and the treatment of the pH sample must be kept within the best possible range, since a small amount of all-alkaline material is present and not covered. It is possible to obtain sufficient carbon dioxide from the air to reduce or even neutralize the alkali, thus masking this effect. The letter has occurred to some extent in the experimental process of the previous embodiment 'although it is not until very late. The standard palm oil, FAME &amp; steaming hall is a different branch. Then take the first 2G% of the building that constitutes the steaming hall and the freezing point of the branch is -16 ° C. Then the previous 2 %% of the objects Blending with petroleum aviation fuel with _4〇t: freezing point at a ratio of 8〇% aviation fuel to 2%% of the first 2% fraction. Occurs - Unexpected result, the freezing point of the fart drops _56Ό. Mixing in other percentages and ratios can also have advantages. Mixing less than 2% of the fraction before the distillate may have advantages because it also reduces the mixture of the ingredients and the proportions that the skilled person can determine. The similarity is that the process produces all of the material. Or the combination of smashed knife and diesel fuel can reduce the cloud point of diesel fuel. Discussion Therefore, one purpose of the process is to produce a biofuel material by esterification of triglyceride, such as via bio Life is produced and is therefore a source of regeneration. A further objective of the process is to produce a biofuel product with a range of swim points ranging from the boiling point defined by aviation fuel. A further objective of the process is the removal of scientific and technical barriers to continuous flow manufacturing processes. In all of the known techniques, it is seen that there are specific common elements that make the entire process difficult to handle and require a solution that is not seen. 27 201026845 Heterogeneous catalyst technology is known in principle but scientifically not well developed until it can be used on an industrial scale, so homogeneous catalysts are used, but this is accompanied by the removal of post-reactions, or the use of extreme reaction conditions A catalyst-free acetification reaction. In either case, there are unreacted starting materials, residual glycerin, catalyst residues, phytosterols, and the removal of contaminants commonly found in bio-derived oils, which are high quality esterified An obstacle to continuous flow production of fatty acid products. Φ Because most of the basic catalyst is dissolved in the glycerol/alcohol phase, even large-scale industrial production uses large settling tanks to allow the heavier glycerol phase to separate from the lighter oil phase in its usual slow manner. The removal of the residual test catalyst is particularly troublesome and most of it is separated upon standing. Since the alcohol prefers to dissolve in the more polar glycerin phase, only a small portion of the alcohol is dissolved in the oil phase. The salt catalyst is layered accordingly, and most of the test gas oxide or burnt oxygen is dissolved in the glycerol/alcohol phase and only a small portion is dissolved in the alcohol/vinegar phase. Without wishing to be bound by this theory, the glycerol from the solution sinks at the end of the reaction, which is a general temporary condition in which the residual catalyst is present in an emulsified phase with other materials, in which it has A certain solubility. At this time, it can be centrifuged because of its high density. Over time, this temporary emulsified phase is largely dissolved in the oil phase, indicating that the residual catalyst is commonly found in many unwashed biodiesel products. The temporary presence of a material-insoluble phase is clearly unnoticed because the opinion on the existence of the biodiesel manufacturer's patent has been clearly lost. The reason for the month t* is that no one observes the inside of the metal container or pipeline. The evidence that this situation has not been noticed is that all conventional centrifugation techniques 28 201026845 teach (if all) that the time G force product is only suitable for the initial separation of the denser glycerol phase from the less dense oil phase. Its continuous flow system is easily achieved by low-order techniques such as a cyclone. This temporary phase, which was gradually clarified at the same time as the initial 10 hours of small sedimentation and essentially the entire height of the 1 〇〇〇ml graduated cylinder, was found only when it was carried out in a transparent laboratory vessel, not in metal Production equipment. Moreover, this temporary situation has once again disappeared in the literature published by scientists.

Vincente (Bioresource Technology 92 (2004) 297 305), which discloses the results of small-scale experiments using laboratory glassware. This later heavy clarification may be mistaken for the sedimentation of the insoluble glycerin phase. This discovery opens the door of a continuous dynamic manufacturing process, the key component of which is the presence of a centrifugal process with a specific high range of time G force distances, and a waterless rinsing step or a sorbent treatment procedure. Therefore, the scope of the patent application is as follows. BRIEF DESCRIPTION OF THE DRAWINGS The first A-1 diagram is a preferred embodiment of the system of the present invention. Figure 2 is a view of a preferred embodiment of the process of the present invention. [Main component symbol description] 101 Catalyst source 102 Triglyceride source 103 Recycling component 29 201026845 104 Vacuum distillation process 105 Condenser 106 Mixer 107 Process circuit 108 Heat exchanger 109 Glycerol-ester separation element 110 Centrifuge

111 Heat exchanger 112 Evaporator 113 Vapor condenser 114 Distillation element 115 Vapor condenser 116 Vapor condenser 117 High-boiling distillate 201 Preparation of alkyl ester of triglyceride stream 202 Centrifuge 203 Post-centrifugation process 30

Claims (1)

201026845 VII, Shen Sqing patent range: 1 · In a homogenization or heterogeneous catalysis or a high temperature uncatalyzed acetification process 'after the esterification reaction, a centrifugation step in the centrifuge to facilitate fatty acid When the ester is separated at the end of the esterification reaction, the insoluble matter precipitated by the residual catalyst, the glycerin emulsion and/or the mono/diglycerol vinegar and other eutectics is separated from the ester product stream, and the centrifugation step is equivalent to every 90 mm. The radial separation distance is the product of a retention time / G force / distance on the order of 6000 G φ for about one minute. 2_ The method of claim 1, wherein neither the rinsing step nor the sorbent step is followed. 3. The method of claim 1, wherein the method comprises a continuous flow transesterification process of triglyceride, wherein the glycerol is separated from the fatty ester by any method suitable for the process. The ester phase is discharged as a product without a rinsing step or a sorbent step but in the centrifugal refining step of claim 1 of the patent application. 4. If you apply for a patent scope! The method of the method, in the -triglyceride-batch-to-Vinylation process, wherein the glycerol is separated from the fat vinegar when it is left standing, the brewing phase is not patented by a rinsing step or _.❹(4) The centrifugal refining step of the range i is discharged as a product. 5. The method of claim 1, wherein the centrifugation step of claim 1 is performed by a relatively low-G force separator such as gravity settling or a cyclone separator. Two or more of them 6. The method of the ninth aspect of the patent application is a parallel operation. 7 · If the patent application scope is 篦1 jg $古固固弟1, two or more of the centrifugation processes are operated in series. 8. An ester produced by the method of claim 1 of the patent application. 9. A acetification process using a catalyst comprising the steps of: mixing the catalyst with an alcohol and a purified triglyceride; adjusting the amount of the catalyst and the alcohol based on the triglyceride content of the raw material; The temperature is raised in the process so that the catalyst, the mixture of alcohol and triglyceride rises to about i 00. 〇; maintaining a sufficiently high positive pressure in the process to prevent liquid from being converted to vapor during the process; and residing the process product into two or more fractions. 1) The process of claim 9, wherein the temperature in the process is between about 14 ° C and 16 Torr. (U.S. Patent Application Serial No. 9), wherein the pressure in the process 32 201026845 is between about 10 psi and 30 psi. 12. As in the process of claim 9, one of the fractions contains Approximately the first 20% of the distillate. 13. The process of claim 12, wherein about 20% of the distillate is about 80% of the aviation fuel and about 20% of the distillate The first 20% of the mixture is mixed. 14. If the process of claim 9 is applied, one or more fractions are mixed with diesel fuel. 15. If the process of claim 9 is excluded, one water rinse is excluded. step 33