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    • 专利摘要:
    High efficiency process for the production of alkyl esters of fatty acids by acid catalysis, which is produced in an isothermal tubular reactor (5) preferably arranged vertically, with liquid methanol and a fatty material from 50% to 100% of free fatty acids and less than 1% moisture, residence time between 15 and 120 minutes and with a molar excess of methanol/fat over the stoichiometric in reactions in a stage of 12-18: 1 or in two-stage reactions first of 4-6: 1 (up to 5% of FFA), and the second stage of 30-80: 1. It also relates to the process of treating the products of the reaction by homogeneous acid catalysis comprising separating them into a light phase and a heavy phase, and reducing the methanol content of the light phase to a concentration between 33-50% by weight , preferably between 33-45% prior to neutralization of the catalyst remnant. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2660207A1
    申请号:ES201600775
    申请日:2016-09-21
    公开日:2018-03-21
    发明作者:María CONDE LIMÓN；Virginia OBREGÓN SÁNCHEZ；Luis J. ALEMANY ARREBOLA
    申请人:Bio Oils Huelva S L；Bio-Oils Huelva SL；Universidad de Malaga；
    IPC主号:
    专利说明:

     5 DESCRIPTION Highly efficient process for the production of alkyl esters of fatty acids by acid catalysis and treatment process FIELD OF THE INVENTION The present invention relates to a method of producing alkyl esters, with high efficiency, which is carried out in Acid medium in subcritical conditions of methanol starting from various types of low quality raw materials and with the possibility of processing both in homogeneous and heterogeneous catalysis. BACKGROUND Conventional trans-esterification and esterification processes, commercially available at this time, are indicated below: 15-Trans-esterification process for obtaining methyl esters from vegetable oils with maximum acidity of 0.1% in reactors agitated in series to obtain biodiesel within specification with homogeneous basic catalysis (Desmet-Ballestra process). - Process of esterification at room temperature using sulfuric acid as a catalyst in homogeneous phase, performed in stirred tanks, with 3-4: 1 excess of methanol, with esterification times of between 4 and 5 h on very high acidity raw materials. -Sterification process at 80ºC, with reflux and continuous supply of methanol, with sulfuric acid as a catalyst, in 2 stages, 2-3 h reaction and methanol excesses of 3-4: 1. -Sterification process at 120ºC and 3-5 bar in an autoclave (stirred tank) using methanesulfonic acid as catalyst and with reaction times of 3 h. - Process of simultaneous esterification and trans-esterification under supercritical conditions of methanol and without catalyst, of 120 atm and 200ºC. In addition, there are other patents related to the production of biodiesel: DE19908978 indicates the desirability of performing the two reactions in parallel using an acid catalyst. A temperature not exceeding 85 ° C, atmospheric pressure and a residence time of 3 hours are indicated. US2003032826 performs the reaction over a wide range of temperatures, but setting the conditions in the Reynolds number with which the reagents are mixed.US2010298586 describes a biodiesel production process by means of a previous stage of acid esterification and a later stage of basic trans-esterification, with a stage of water withdrawal between means. The applicant does not know a procedure similar to that of the present invention that allows the esterification and trans-esterification steps to be carried out simultaneously to achieve sufficiently acceptable yields for industrial implantation under subcritical methanol conditions and in the presence of catalyst. BRIEF EXPLANATION OF THE INVENTION The invention consists of a biodiesel production process according to the claims. The new acid esterification process allows alkyl esters to be obtained by esterification and simultaneous transesterification, reaching very high conversion levels under sub-critical conditions for methanol and in a continuous reactor with separation and recovery of the output streams and adaptable to heterogeneous catalysis The transesterification has a very slow kinetics, limited by the transfer of matter, so the reaction takes place at a temperature and pressure that ensures that the fat and methanol are dissolved and in the liquid phase. In this way, a very rapid acid transesterification is achieved. This pressure and temperature will be sufficient to keep the methanol in a liquid state, so it can be easily determined with a phase diagram of the methanol available in the scientific literature. On the other hand, esterifications have rapid kinetics, but are limited by equilibrium, so to achieve high conversions, <1% FFA (free fatty acids), even at one stage, are used High excess methanol, between 12 and 15: 1 of molar excess over the stoichiometric when performed in one stage, and 4 and 6: 1 followed by 30-80: 1 when working in two stages. It is understood as 12: 1 molar excess over the stoichiometric when the amount present is 12 times the stoichiometric amount. The process of the invention allows the transformation into alkyl esters of short chain alcohols from various types of high acid fatty material including low quality raw materials, with high heterogeneity and with high triglyceride and impurity contents. In this specification, straight or branched alkyl esters with non-cyclic alkyl esters with chains of ten to twenty-four carbon atoms will be considered "short chain alkyl ester."The system used in the invention is a continuous tubular system in both vertical and horizontal configuration, isothermal, which allows the process to be adapted to heterogeneous or homogeneous catalysis and initial mixers. The vertical configuration has certain advantages over the horizontal configuration, so this configuration is preferred. The invention also allows the use of two reactors in series, to carry out a two-stage process, with which similar conversions are achieved, with a reduction of up to 50% in the total amount of methanol since the excess High molar occurs when the amount of free fatty acids is already very small. The alkyl-10 esters produced are of sufficient quality to be marketed (alone or in mixtures) to obtain a product that meets the European specifications set in each case. The process of the invention achieves a product suitable for use as biodiesel with practically complete conversions. Depending on the raw material used, the reagent dosage and reaction times that allow conversions of the two very high reactions are established. This high conversion prevents the neutralization of the resulting product from being necessary, avoiding the cost and management of the losses involved. Likewise, the process conditions result in a minimum sulfonation of the carbonated chains, except in the case of oleins in which the double bonds if partially sulfonated. The free acidity range of the starting raw materials is very wide, with its main competitive advantage in raw materials with high contents, between 50-100% free acidity expressed as oleic acid. The reaction times with homogeneous catalysis are short, generally less than 1 h, which prevents degradation of the raw materials by catalyst action, under conditions of reactor inlet temperature lower than 132 2C. Although the reaction is accelerated at a higher temperature, undesirable side reactions are also favored, such as production of dimethyl ether by dehydration of methanol and sulfonation of double bonds, so that the optimal conditions will be selected based on the raw material. The preferred pressure 30 is less than 13 bar (g) and molar excesses of methanol are proposed between 12-18: 1 of molar excess over the stoichiometric in one stage, preferably between 12-15: 1 and, when carried out in two stages , between 4-6: 1 in the first stage, followed by 30-80: 1 in the second, preferably 30-40: 1. 35 It is possible to use homogeneous catalysts of acidic type, both mineral and organic, from hydrochloric acid or sulfuric acid to alkyl sulfonated acids withlow water content, thus avoiding secondary reactions to the process such as hydrolysis of the final product. In addition to the transformation reaction, the process described in the invention includes the management in successive stages of the currents generated in the process, 5 including the almost total recovery of the excess methanol from the reaction and the separation for use of the aqueous phases with glycerol. . The high-efficiency process for the production of fatty acid alkyl esters by acid catalysis, which is sought to be protected, is produced in a vertically arranged isothermal tubular reactor, with liquid methanol and a fatty material with up to 10 100% free fatty acids and less than 1% humidity, residence time between 15 and 120 m inutes and with a molar excess methanol / fatty matter over the stoichiometric in reactions at a stage of 12-18: 1, preferably 12-15: 1, or in reactions in two stages the first of 4-6: 1, and the second stage of 30-80: 1, preferably 30-40.1. The separation between the stages, when so produced, will preferably occur when the percentage of free fatty acids is approximately 5%. The temperature at the inlet of the reactor will be between 90-1322C, preferably about 1252C, the preferred pressure being less than 13 bar (g). The fat can be selected from among raw vegetable oils 20 or free fatty acids from oil refining or oily raw materials of low quality, with impurities and high variability. If the catalyst is homogeneous, it will preferably be present in a weight percentage of between 1 and 5% by weight with respect to the fat. If the process is performed in two stages, preferably the catalyst weight percentage is 1% in the first stage. In the proposed production process, and also as a treatment procedure in other similar procedures of homogeneous acid catalysis with excess methanol, it is proposed to separate the reaction product in a light phase with water, glycerin and the methanol surplus (more than 50% by weight) and a heavy phase, and subjecting the light phase to a partial recovery of methanol to a concentration between 33-50% by weight, preferably between 33-45%. After this partial recovery of methanol, the catalyst present in the light phase can be neutralized before recovering the remaining remaining methanol. In the same way, a previous recovery of methanol can be carried out in a decompression phase of the reactor outlet products.In the present invention, all methanol introduced into the process is recovered and reintroduced, with the consequent competitive advantage from the environmental point of view for generating less waste, as well as economically. DESCRIPTION OF THE SCHEMES For a better understanding of the invention, it is included: Figure 1, with a schematic example of the process in which the invention will be implemented. EMBODIMENTS OF THE INVENTION Next, an embodiment of the invention applied to the production of biodiesel is briefly described, as an illustrative and non-limiting example thereof. As can be seen in Figure 1, both the fat and methanol are stored in separate lung tanks (1,2), from where they are pumped to the plant to start the biodiesel production process of the invention. This begins with a first stage in a drying equipment (3) of the fatty substances, to reduce its humidity. In this way a better performance in the esterification reaction is achieved. 20 Next, a preheating stage is performed in a heat exchanger (4), preferably recovering heat from other process phases. If necessary, it will be completed with other equipment that provides steam to the heat exchange. The reaction mixture enters the isothermal reactor (5) which will be of the tubular type and preferably configured in an upright position. The preferred reactor will be designed in two tubular fragments that can work in series or in parallel, opening up multiple possibilities of operation that are included in the present invention. If the catalyst is heterogeneous, it will be in the form of pellets or the like at the inlet of the reactor (5), for example in a basket. If it is homogeneous, it will be added to the mixture just before entering the reactor (5), from its own tank (6). The residence time in the reactor (5) may vary by increasing the flow rate or by lateral outlets (not shown). In this way it can be treated from raw materials with practically 100% free acidity, with very short residence times, to raw materials with a content of around 50% free acidity with longer residence times. You can even perform the esterification reaction 35 in two stages which will allow the optimization of the amount of methanol used in the overall process. The concrete configuration of the flow in each moment will comedetermined by the characteristics of the item of fat used and the catalyst used. If the reaction is to be carried out in two stages, a first stage will be carried out with less molar excess of methanol, the medium being derived to react to the second reactor when it has less than 5% FFA. The residence time of the first reaction stage will be determined experimentally based on the molar excess of methanol. The percentage of glycerides, sulfur content or fatty acid methyl esters (FAME) in the mixture has not been found limiting. The final reacted product will be decompressed in an atmospheric pressure reactor 10 or flash reactor (7) that will allow recovering about 10-20% of the remaining methanol. The reaction product is separated into two phases in one or more first separators (8), for example decanters: Alkyl esters, which are washed and dried to be stored. Acidic waters, which are mostly methanol, with the water and glycerin produced in the reaction, the acid catalyst in case of homogeneous catalysis, and part of the fat that remains dissolved. In the existing procedures, the acidic water that accompanies the alkyl esters at the exit of the reaction is neutralized with a base and introduced directly into the methanol recovery column. The fatty matter present in acidic waters 20 makes the recovery processes very difficult, as it can cause problems of oxidation or soap formation. However, it has been found that by removing methanol, for example by evaporation, to a concentration between 33-50% by weight, with a preferred range of 35-45%, all dissolved fat can be separated by decantation or separation centrifuge thus avoiding the entire problem of oxidation and subsequent soaps formation. Therefore, another innovation of the present invention is that the acidic water can be directly subjected to a partial evaporation of methanol in an evaporator (9) until the necessary methanol concentration is reached, which allows all dissolved fat material to be insolubilized. Typically, 20-30% of the remaining methanol will be recovered in this evaporator (9). Thus, after a second separation in a second separator (8 '), a heavy phase of alkyl esters is recovered which can be returned to the process in the first separator (8) and also preventing the formation of soaps and solids from fatty type that greatly hinders the operation and reduces the yield of the methanol recovery column (10) that recovers the rest of methanol (generally more than 99.5% of the excess). In the embodiment shown, prior to entering the methanol recovery column (10) acidic waters without fat are neutralized with sodium hydroxidein a small reactor (11), generating a precipitate of sodium sulfate, which is separated by means of a decanter or a filter. If the intended application of glycerine waters allows the presence of sodium sulfate, the process of separating the precipitated salt can be skipped, since in the absence of methanol the sulfate is soluble in the water-glycerin mixture. This stage transforms what could result in a waste of the process, into a raw material that can be reused in wastewater treatment with high efficiency. The phase containing the alkyl ester is subjected in parallel to a purification process that includes a first stage of washing and centrifugation in a conventional plate centrifuge (12). As a wash stream, a small percentage of the water obtained from the bottom of the methanol recovery column (10) and a supply of clean water can be recycled. To finalize the procedure, a final drying equipment (13) is included to reduce the amount of water present in the final product. 15 Depending on the raw material used, the reagent dosage and reaction times that allow conversions of the two very high reactions are established. The possible intervals in the main process parameters are specified below under the conditions that will be covered with the present invention, the invention not being restricted only to these conditions: 20 -The reactor inlet temperature (5) will be in a range of 90 to 132 ° C, the environment of 125 ° C being preferred. -The pressure will depend on the temperature, being generally less than 13 bar (g). In any case, the limiting factor of temperature and pressure is that the methanol is in the liquid phase. 25 - When a homogeneous catalyst (sulfuric acid generally) is introduced, between 1 and 5% are preferred in one-stage reactions, 2.5% by weight being preferred with respect to the fat. For reactions in two stages, the first is set at 1% and the second maintains a range between 1 and 2%. It is also possible to use other homogeneous acidic catalysts of mineral type such as hydrochloric acid or organic acids such as alkyl sulphonates. -The residence time ranges between 7.5 min and 120 min -Molar excess of methanol / fat over the stoichiometric is variable, being in reactions at a stage in 12-18: 1 and preferred between 12-15 :one. In contrast, in two stages the first will have a molar excess of methanol between 4-6: 1, followed by 30-35 80: 1 in the second, preferably 30-40.15 It is essential that the tubular esterification reactor (5) has efficient exchangers at the inlet and good insulation to ensure that the temperature conditions are maintained throughout its length to ensure the necessary high conversions. Example 1 A constant flow rate of 0.56 I / h of fatty acids is introduced into a vertical tubular reactor, with an amount of free fatty acids between 83.31-85% and 15.04% of triglycerides and a humidity of 0.05%, a flow rate of methanol corresponding to a 10 molar excess with respect to the stoichiometric of 15: 1, and a percentage of H2S04 at 98% of 2.5% by weight with respect to the fat introduced, which is heated from previous form up to 1272C and at a pressure of 10.5 bar (g). After 60 min of reaction, and after a decantation, the product is washed with excess water at 802C and dried for 30 min at 1052C. The remaining free fatty acids of the heavy phase are analyzed by volumetry with soda solution, method EN 14104 And it is observed that the free fatty acids present in the mixture have been reduced to 0.77% and the triglycerides to 0.083% , using high temperature gas chromatography (EN 14105 standard). Example 2 20 A constant flow of 0.573 kg / h of a mixture of fatty acids with used frying oil is introduced into a vertical tubular reactor, the feed being fed to the reactor with a quantity of free fatty acids of 50% and 48.4% of triglycerides and a humidity of 0.1%, a flow rate of methanol corresponding to a molar excess with respect to the stoichiometric of 12: 1, and a percentage of H2S04 at 98% of 2.5% by weight with respect to 25 the fat introduced , which is preheated in a tubular reactor to 124.92C and at a pressure of 10.5 bar (g). After 70 min of reaction, and after a 3 h gravity decantation, the product is washed with excess water at 802C and dried for 30 min at 1052C. The remaining fatty acids of the heavy phase are analyzed by volumetry with soda solution, method EN 14104 And it is observed that the 30 free fatty acids present in the mixture have been reduced to 0.83% on average and the triglycerides to 0.746 %, using high temperature gas chromatography, EN 14105. Example 3 35 A constant flow of 2,249 kg / h of fatty acids is introduced into a vertical tubular reactor, with an amount of free fatty acids greater than 93.3% and 4 , 44% oftriglycerides and a humidity of 0.18%, a flow rate of methanol that corresponds to a molar excess with respect to the stoichiometric of 15: 1, and 3.5% of H2S04 at 98% by weight with respect to the fat introduced, preheat to 130 ° C and at a pressure of 10.5 bar (g). After 15 min of reaction, and after a stage of decantation, the product is washed with excess water at 80 ° C and dried for 30 min at 105 ° C. The remaining fatty acids of the heavy phase are analyzed by volumetry with sodium hydroxide solution, method EN 14104 And it is observed that the free fatty acids present in the mixture have been reduced to 0.79% on average and triglycerides to 0, 6745%, using high temperature gas chromatography, EN 14105. 10 Example 4 A constant flow rate of 0.94 kg / h of fatty acids is introduced into a vertical tubular reactor, with an amount of free fatty acids greater than 93.3% and 4.44% triglycerides and a humidity of 0.18%. In a first stage, a flow rate of 15 methanol is fed, corresponding to a molar excess with respect to the stoichiometric 6: 1, and a percentage of H2S04 at 98% of 1.5% by weight with respect to the fat introduced, which is heated previously up to 126.4 ° C and at a pressure of 10.5 bar (g). After approximately one hour of reaction, and after a decanting step, the product is washed with excess water at 80 ° C and dried for 30 min at 105 ° C. The remaining free fatty acids of the heavy phase are analyzed by volumetry with soda solution, method EN 14104 And it is observed that the free fatty acids present in the mixture have been reduced to 2.5% on average and the triglycerides to 0.4975%, using high temperature gas chromatography, EN 14105. This fatty material is reintroduced into the tubular reactor at a flow rate of 1,416 kg / h, for a second reaction stage, with a flow rate of methanol corresponding to a molar excess with respect to the stoichiometric of 30: 1, considering only the free acidity not converted in the first stage. A flow rate corresponding to 1% by weight of the reintroduced fat material of 98% sulfuric H2S04 is also added. The reactor feed temperature is 127.9 ° C for the second stage and the final result is 0.81% free acidity and 0.085% total triglycerides. 
    权利要求:
    Claims (1)
    [1]
    CLAIMS 1-High efficiency procedure for the production of fatty acid alkyl esters by acid catalysis, characterized in that it is produced in an isothermal tubular reactor (5) preferably arranged vertically, with liquid methanol and a fatty matter from the 50% and up to 100% free fatty acids and less than 1% moisture, residence time between 15 and 120 minutes and with a methanol / fat molar excess over stoichiometric in reactions in a 12-18: 1 stage, preferably 12-15: 1, or in two-stage reactions the first of 4-6: 1, and the second stage of 30-80: 1, preferably 30-40: 1. 2-Process according to claim 1, in which the reaction occurs in two stages, the first ending when the percentage of free fatty acids is approximately 5%. 3-Process, according to claim 1, wherein the temperature at the inlet of the reactor (5) is between 90-1322C, preferably around 1252C. 4-Process, according to claim 1, wherein the fat is selected from crude vegetable oils or free fatty acids from oil refining to very low quality oily raw materials. 5-Process according to claim 1, in which the reaction occurs in one stage and the catalyst is homogeneous and is present in a percentage by weight of between 1 and 5% by weight with respect to the fat. 6-Process according to claim 1, in which the reaction occurs in two stages, and the percentage by weight of homogeneous catalyst is 1% by weight with respect to the fat in the first stage and between 1-2% in the second stage. 7 -Procedure according to claim 1, where the fat has more than 50% free fatty acids. 8-Process according to claim 1, in which the reaction product is separated into a light phase with water, glycerin and the excess of methanol and a heavy phase, and wherethe light phase is subjected to a partial recovery of methanol to a concentration between 33-50% by weight, preferably between 33-45%. 9-Process according to claim 8, in which the reaction occurs with a homogeneous catalyst, and after partial recovery of the methanol the light phase is neutralized with a base before recovering the remaining excess methanol. 10-Process according to claim 8, in which a previous recovery of methanol occurs in a decompression phase of the output products of the reactor 10 (5). 11-Process for treating the reaction products of the formation of fatty acid alkyl esters by homogeneous acid catalysis, obtained according to claim 1, which comprises separating them into a light phase with more than 50% by weight of methanol and a phase heavy, characterized in that it comprises reducing the methanol content of the light phase to a concentration between 33-50% by weight, preferably between 33-45% prior to the neutralization of the remainder of the catalyst in the light phase. twenty
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    同族专利:
    公开号 | 公开日
    ES2660207B1|2018-12-07|
    ES2660207B8|2019-01-10|
    EP3299444A1|2018-03-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2008024716A2|2006-08-24|2008-02-28|Philadelphia Fry-O-Diesel, Llc.|Process of making alkyl esters of free fatty acids|
    US20080282606A1|2007-04-16|2008-11-20|Plaza John P|System and process for producing biodiesel|
    CN101362957A|2007-08-10|2009-02-11|张荣兴|Method for producing biodiesel by means of multistage ester conversion|
    CN101508904A|2009-03-24|2009-08-19|河南华泰粮油机械工程有限公司|Method for producing biodiesel|
    WO2013116342A2|2012-02-02|2013-08-08|Revolution Fuels, Inc.|Mobile processing systems and methods for producing biodiesel fuel from waste oils|
    DE3444893A1|1984-12-08|1986-06-12|Henkel KGaA, 4000 Düsseldorf|METHOD FOR PRODUCING FATTY ACID METHYL ESTERS|
    US5525126A|1994-10-31|1996-06-11|Agricultural Utilization Research Institute|Process for production of esters for use as a diesel fuel substitute using a non-alkaline catalyst|
    BRPI0818795A2|2007-10-30|2015-04-22|Bayer Technology Services Gmbh|Process for heterogenically catalyzed fatty acid esterification|
    WO2011033346A1|2009-09-15|2011-03-24|Council Of Scientific & Industrial Research|A process for conversion of low cost and high ffa oils to biodiesel|
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    EP17001568.9A| EP3299444A1|2016-09-21|2017-09-21|High efficiency method and catalyst for the production of alkyl esters from fatty acids with acid catalysis|
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