WO2013038029A1 - Procédé de production d'additifs oxygénés à partir de glycérol brut - Google Patents
Procédé de production d'additifs oxygénés à partir de glycérol brut Download PDFInfo
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- WO2013038029A1 WO2013038029A1 PCT/ES2011/070637 ES2011070637W WO2013038029A1 WO 2013038029 A1 WO2013038029 A1 WO 2013038029A1 ES 2011070637 W ES2011070637 W ES 2011070637W WO 2013038029 A1 WO2013038029 A1 WO 2013038029A1
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- Prior art keywords
- glycerin
- tert
- butanol
- obtaining
- glycerol
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
- C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
- C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
- C10L2200/0446—Diesel
Definitions
- the present invention relates to a process for obtaining oxygenated additives derived from crude glycerin, by catalytic etherification thereof with tert-butanol in a discontinuous and hermetic reactor.
- the present invention focuses on obtaining the two isomers of di-tert-butyl glycerol (DTBG) and tri-tert-butyl glycerol (TTBG).
- DTBG di-tert-butyl glycerol
- TTBG tri-tert-butyl glycerol
- crude glycerin In the biodiesel manufacturing process, a large quantity of low quality glycerin that is called crude glycerin is generated as the final product of the reaction.
- the amount of crude glycerin that is generated is approximately 10% by weight of the amount of biofuel produced.
- This crude glycerin has a very low economic value, due to the high concentration of impurities it presents.
- the complete refining of crude glycerin is conditioned by the economy of scale, as well as by the existence of simple purification processes.
- Morgan presents a continuous glycerin etherification process by means of a reactive distillation process, in which glycerin reacts with an alcohol to obtain glycerin ether in the presence of a catalyst located in the reaction zone of said distillation column.
- the reaction temperature is set in the range between 120 and 140 ° C.
- the present invention relates to a process for obtaining oxygenated additives derived from crude glycerin, adapted for the selective obtaining of glycerol ethers.
- the present invention focuses on obtaining the two isomers of di-tert-butyl glycerol (DTBG) and tri-tert-butyl glycerol (TTBG), from crude glycerin and tert-butanol in the presence of a suitable catalyst, which has efficiency and performance advantages superior to those described in the state of the art.
- DTBG di-tert-butyl glycerol
- TTBG tri-tert-butyl glycerol
- the process of the present invention comprises three essential stages defined as: a first stage of purification or pretreatment of the crude glycerin, a subsequent reaction stage, of the purified glycerin obtained in the previous stage with tert-butanol in the presence of a catalyst and a final stage of separation or extraction of the glycerol ethers obtained as final reaction products.
- the technical problem solved in the present invention is the provision of a process for obtaining certain glycerol ethers that using raw glycerin as a starting material has important advantages in relation to the efficiency and performance of the process.
- crude glycerin is understood as the glycerin obtained as a byproduct of industrial biodiesel production processes. It is therefore an unpurified glycerol by-product that has a glycerol content greater than 75% and also contains water in an amount not exceeding 10%, ashes in an amount less than 10% and dissolved ions in concentrations between 5,000 and 30,000 ppm of Na + and K + in addition to particles of oily substance not miscible in suspension.
- purified glycerin refers to the product of purified glycerin through the first stage of purification of the crude glycerin according to the present invention, which has a glycerin content of between 80 and 95% with a concentration in Na + and K + ions of less than 3000 ppm, and a moisture content of less than 6% and which does not have oily matter in perceptible suspension.
- the term “hermetic discontinuous reactor” refers to a reactor in which an amount of feed is charged and allowed to react during the reaction time. Once that time has elapsed, another amount of power is reloaded. This operation is repeated successively. It also includes an impermeable closure or any system (such as a cooling column) that prevents the leakage of reagents in the liquid phase or in the vapor phase inside.
- An example of this reactor would be a cylindrical container with conical bottom that facilitates its emptying, with top lid with airtight seal which prevents losses of etherifying agent and reaction intermediates and a stirrer.
- Another example would be a reactor with the same geometric characteristics and with an agitator with a cooling column located on top of it through which a coolant circulates (for example water) at a temperature that prevents leakage by evaporation of the agent etherifier and reaction intermediates.
- a coolant for example water
- acid catalyst refers to a homogeneous or heterogeneous catalyst whose active sites have a protic acid nature.
- it refers to an "ion exchange resin”.
- examples include, among others, Zeolite BEA-CP814E, Amberlyst 15, Amberlyst 35, Sulfuric acid, Zeolite ZSM-5, Zeolite CBV-2314, Montmorillonite KSF and Montmorillonite KP10.
- It is therefore an object of the present invention a process for obtaining ethers of glycerol di-tert-butyl glycerol (DTBG) and tri-tert-butyl glycerol (TTBG) from crude glycerin and tert-butanol comprising a step of purification of glycerin, followed by reaction between glycerin and tert-butanol in the presence of a catalyst and separation and recovery of glycerol ethers.
- An object of the present invention is also a process for obtaining, in particular, ethers of glycerol di-tert-butyl glycerol (DTBG) and tri-tert-butyl glycerol (TTBG) from crude glycerin and tert-butanol whose Purification stage comprises a centrifugation stage of the crude glycerin to separate non-miscible impurities (composed mainly of non-glycerinic organic matter or MONG) and a second stage of treatment with an ion exchange resin to remove the alkaline ions from the glycerin.
- DTBG di-tert-butyl glycerol
- TTBG tri-tert-butyl glycerol
- DTBG glycerol di-tert-butyl glycerol
- TTBG tri-tert-butyl glycerol
- a further object of the present invention is also a process for obtaining in particular ethers of glycerol di-tert-butyl glycerol (DTBG) and tri-tert-butyl glycerol (TTBG) from crude glycerin and tert-butanol in which the ion exchange resin used is regenerated by washing with, preferably, hydrochloric acid after the purification step.
- DTBG glycerol di-tert-butyl glycerol
- TTBG tri-tert-butyl glycerol
- a further object of the present invention is also a process for obtaining in particular ethers of glycerol di-tert-butyl glycerol (DTBG) and tri-tert-butyl glycerol (TTBG) from crude glycerin and tert-butanol whose separation stage It comprises a first vacuum distillation followed by a first extraction with pentane or heptane solvent, followed by a second liquid-liquid extraction with water and a second distillation that allows the final reaction products, DTBG and TTBG, to be recovered and reused.
- DTBG glycerol di-tert-butyl glycerol
- TTBG tri-tert-butyl glycerol
- a further object of the present invention is also a process for obtaining in particular ethers of glycerol di-tert-butyl glycerol (DTBG) and tri-tert-butyl glycerol (TTBG) from crude glycerin and tert-butanol which additionally allows the catalyst to be recovered through a stage of filtering, washing and drying.
- DTBG glycerol di-tert-butyl glycerol
- TTBG tri-tert-butyl glycerol
- a further object of the present invention is also a process for obtaining in particular ethers of glycerol di-tert-butyl glycerol (DTBG) and tri-tert-butyl glycerol (TTBG) from crude glycerin and tert-butanol which allows recovering the tert-butanol for later use in the process of the invention through the addition of preferably calcium oxide (CaO) to the tert-butanol-water solution and subsequent distillation.
- DTBG glycerol di-tert-butyl glycerol
- TTBG tri-tert-butyl glycerol
- a further object of the present invention is also a process for obtaining in particular ethers of glycerol di-tert-butyl glycerol (DTBG) and tri-tert-butyl glycerol (TTBG) from crude glycerin and tert-butanol in which the yield of obtaining DTBG is between 1 1 and 13%.
- DTBG glycerol di-tert-butyl glycerol
- TTBG tri-tert-butyl glycerol
- glycerol ethers obtained from glycerin and tert-butanol obtained from glycerin and tert-butanol according to the process of the present invention as oxygenated additives for diesel fuels.
- the present invention relates to a process for obtaining oxygenated additives derived from crude glycerin, adapted for the selective obtaining of glycerol ethers selected from the group consisting of the two isomers of di-tert-butyl glycerol (DTBG) and tri-tert-butyl glycerol (TTBG), ( Figure 1), from crude glycerin and tert-butanol.
- DTBG di-tert-butyl glycerol
- TTBG tri-tert-butyl glycerol
- the process of the present invention is divided into three main stages: pretreatment or purification phase, reaction phase and separation phase.
- a schematic of the process of the present invention is illustrated in Figure 3.
- This glycerin comes directly from the biodiesel manufacturing process (transesterification). It contains moisture, non-glycerinic organic matter (MONG), oily matter of lower density than glycerin and dissolved ions (mainly Na + and K + from the previous transesterification process). These impurities must be removed as they directly and negatively affect the etherification reaction of the glycerin that will take place.
- MONG non-glycerinic organic matter
- dissolved ions mainly Na + and K + from the previous transesterification process
- the etherification reaction develops.
- glycerin in the presence of a catalyst, such as, for example, Amberlyst 15, reacts with the etherifying agent, tert-butanol to give, in serial reactions, mono-ethers, di-ethers and glycerine tri- ethers, preferably di-ethers, in particular, DTBG.
- the objective products of the process di-ethers and tri-ethers of glycerol
- di-ethers and tri-ethers of glycerol are isolated by successive processes of distillation and liquid-liquid extraction.
- the streams composed of unreacted raw material (tert-butanol, glycerin) and by-products (MTBG isomers) can be recovered successively for later reuse in the reaction stage.
- a centrifugation of the crude glycerin is carried out in which the less dense oily substance particles are removed from the glycerin.
- This centrifugation is carried out in a centrifuge (eg Digicen model of the Orto Alresa commercial house) at a glycerin temperature of between 45 and 75 ° C, preferably between 50 and 70 ° C to facilitate the separation of the phases by viscosity reduction of glycerin.
- adsorption of the alkaline ions takes place through the use of an ion exchange resin through which the clean centrifuged glycerin stream is passed.
- the resin used that has provided better results is Amberlyst 15 (Rohm and Haas), although other options have been tested, such as: Zeolite BEA (H-Form), commercial molecular sieve, hydrotalcite, sepiolite 60/120, sepiolite 15/30 , alumina, cobalt oxalate and combinations of several of them.
- the contact between the glycerin and the resin can be carried out in filler columns or in a stirred tank with subsequent filtration.
- the optimum ratio between the amount of glycerin and resin for exchange is 1: 3 to 1: 12
- Amberlyst 15: Glycerin preferably, 1: 3 by weight (1 kg of resin for every 3 kg of glycerin to be treated).
- the stirring time should be 60 minutes to 120 minutes, preferably 90 minutes.
- the agitation tank can be a cylindrical tank with a lower drain valve with an agitator inside.
- the filling column can be cylindrical with upper or lower feed and with product outlet on the opposite side that should consist of a filter to avoid losses of ion exchange resin.
- the filter For filtering the mixture (either after stirring or at the bottom of the filler column), the filter should have a mesh light of less than 600 microns, preferably 500 microns (0.5 mm). Any mesh or commercial filter with mesh light less than indicated can serve this purpose.
- the mixture has been filtered on a laboratory glass funnel on which metallic mesh of 500 microns of mesh light has been placed. It has been proven that this initial purification of crude glycerin improves the results obtained in the subsequent reaction in several aspects:
- the ion exchange resin used in this stage must be activated prior to use and regenerated after use in order to be reused. This reuse is possible as many times as necessary whenever the process of reactivation of the active sites of the resin is carried out.
- the activation of the resin consists in washing it with methanol or ethanol for a time of approximately 5 to 30 minutes, preferably 15 minutes (with stirring or recirculation through the filler column) and subsequent drying of the same at a temperature of between 100 and 130 ° C, preferably 100 ° C, for a period of time between 6 and 48 hours, preferably, 12 hours (in an oven or by circulating hot air current through the filler column ).
- the reactivation of the active sites of the resin is carried out by washing it with 1-6M HCI, preferably 4M, for a period of 2 to 4 hours, preferably 2 hours (under stirring or by recirculation in the column of filling). This reactivation of the active sites must be followed by the washing (activation) process described, prior to its use as an ion exchange resin.
- HCI any other acid capable of reactivating the active sites of the catalyst can be used, that is to say that it gives protons to the exchange resin and captures the alkaline ions retained therein, such as: HN0 3 , H 2 S0 4 , HCI0 4 , HCI0 3 .
- purified glycerin Once the glycerin has undergone this purification process it is called purified glycerin, and is apt to be introduced into the reaction phase.
- the characteristics of this purified glycerin are as follows: it has a glycerin content of between 80 and 95% with a concentration of Na + / K + ions of less than 3000 ppm, and a moisture content of less than 6% and not it presents oily matter in perceptible suspension
- the purified glycerin is fed to the reactor. It is a hermetic agitated discontinuous reactor or with a cooling column, as described above.
- the objective is to prevent the leakage of etherifying agent and reaction intermediates (eg isobutene) that favor the development and selectivity of the reaction towards the target products (therefore any type of reactor that serves this purpose could be used).
- the etherifying agent tert-butanol
- the catalyst Amberlyst 15
- the reaction conditions are a reaction temperature between 50 and 120 ° C, preferably 80 ° C and a reaction time between 30 minutes and 8 hours, preferably 120 minutes, which maximize glycerin conversion and yield in obtaining DTBG and TTBG.
- the resulting mixture is filtered through two successive grid filters, the first one with a mesh light of less than 600 microns, preferably 500 microns and the second one with a mesh light. less than 100 microns, preferably 50 microns.
- the filtering systems set forth above may be used for this purpose.
- the synthesis mixture is stored to pass the separation or isolation phase of the target reaction products.
- the catalyst used in the reaction must be previously activated by washing it with methanol or ethanol, during a stirring period of between 5 and 30 minutes, preferably 15 minutes and subsequent drying at a temperature between 100 and 130 ° C, preferably 100 ° C for a period of between 6 and 48 hours, preferably 12 hours.
- the catalyst collected in the first grid filter thanks to the initial purification of the glycerin made, can be reused in the reaction. It is necessary to apply a catalyst wash with methanol or ethanol and a drying under the same conditions as in the initial activation. In this way, the catalyst can be reused in up to ten reactions without decreasing the conversion of glycerin obtained or the yield of obtaining DTBG and TTBG.
- the filtered synthesis mixture is introduced in the separation phase to isolate the target additive (DTBG and TTBG) from the rest of the components of the reactor output current to recover and recirculate the unreacted raw material.
- target additive DTBG and TTBG
- a first vacuum distillation is performed (60 ° C and the absolute pressure OOmbar) in which the unreacted tert-butanol (mixed with water) is recovered.
- the present invention has carried out the distillation in vacuum systems composed as main equipment by a column, a heated vessel into which the fresh feed is introduced, a refrigeration system for the condensate collection of the most volatile compound and a commercial vacuum pump capable of reach up to 100 mbar of absolute pressure.
- the product stream passes to the first liquid-liquid extraction.
- a solvent penentane or heptane
- the mixture is stirred for a period of 10 to 120 minutes, preferably 30 minutes and allowed to stand.
- Two phases are formed.
- the densest phase is formed by unreacted glycerin and MTBG mainly, in addition to traces of DTBG.
- This current is recirculated to the reactor. The recirculation of this current improves the results obtained in the reaction.
- the less dense phase is formed by DTBG, TTBG and solvent and is fed to a second decanter in which a new liquid-liquid extraction is carried out.
- the solvent used in this case is water.
- the mixture is also stirred for a period of 10 to 120 minutes, preferably 30 minutes and allowed to decant.
- the densest phase of this extraction consists mainly of water and contains some traces of MTBG and glycerin.
- the objective of this extraction is to eliminate these traces of glycerin and MTBG that would contaminate the product additive stream (DTBG and TTBG). This denser stream is stored waiting to be reused again in the extraction, since it is mostly water.
- the less dense phase, formed by the solvent of the first extraction (pentane or heptane) and DTBG and TTBG, is introduced into a second distillation column (which operates under the same conditions as the first). In this distillation, the solvent is separated from the additives (DTBG and TTBG) targeted by the process.
- Extractions with chloroform, pentane, octane, heptane or ethyl ether have been tested in order to assess the suitability of each solvent in the separation process.
- the compositions of the exit streams are presented after successive extractions with the indicated solvents in the tables and the proportions (ratios) indicated.
- the separated solvent can be reused in the first liquid-liquid extraction, since the separation is practically total.
- the tert-butanol that has not reacted and that was separated in the first distillation can also be reused in the reaction. For this it is necessary to separate the water it contains (which forms azeotrope with tert-butanol) from the alcohol. This is achieved by mixing said stream with a drying agent, selected from the group consisting of: sodium sulfate heptahydrate, magnesium sulfate heptahydrate, hydrated calcium carbonate, potassium acetate and CaO, preferably CaO, in a proportion of between 5 and 30%, preferably 22% by weight compared to the water-alcohol mixture fed.
- a drying agent selected from the group consisting of: sodium sulfate heptahydrate, magnesium sulfate heptahydrate, hydrated calcium carbonate, potassium acetate and CaO, preferably CaO, in a proportion of between 5 and 30%, preferably 22% by weight compared to the water-alcohol mixture fed.
- the DTBG yields and conversion of the purified glycerin according to the process of the present invention are illustrated in Table 3. It can be concluded that according to the process described above, the catalyst can be reused for up to 10 cycles while maintaining the conversion and obtaining yields of DTBG obtained in the first cycle.
- the contact between the glycerin and the resin is carried out in an agitated tank consisting of a cylindrical vessel with a lower emptying system and an agitator inside with subsequent filtration.
- the ratio between the amount of glycerin and resin for exchange is 1: 3 by weight, and the stirring time 90 minutes.
- the filter For filtering the mixture, after stirring, the filter has a mesh light of less than 600 microns (0.6 mm). For filtering, a 500 micron mesh metal grid is placed on the glass funnel and the mixture from the previous stirred tank is passed through it.
- the ion exchange resin used in this stage is activated prior to use and regenerated after use to be reused. This reuse is possible as many times as necessary whenever the process of reactivation of the active sites of the resin is carried out.
- the resin is activated by washing it with methanol for 15 minutes while stirring and drying it at a temperature of 100 ° C, for 12 hours in an oven with forced air convection Binder brand model FD1 15 Reactivation of the active sites of the resin is carried out by washing it with 4M HCI for 2 hours with stirring. This reactivation of the active sites is followed by the washing (activation) process described above.
- This purified glycerin contains 1.4% moisture and an alkali ion concentration of 1,600 ppm K + ions and 90 ppm Na + ions.
- the etherifying agent (tert-butanol) is introduced in a ratio of 1: 4 molar to glycerin (4 moles of tert-butanol for each mole of glycerin fed, equivalent to 32.1 grams of tert-butanol) and the catalyst (Amberlyst 15) in an amount of 8% by weight against the fed glycerin (800 milligrams).
- the reaction conditions are a reaction temperature 80 ° C and a reaction time of 120 minutes, which maximize glycerin conversion and yield in obtaining DTBG.
- the synthesis mixture is filtered through two successive grid filters, the first one with a 500 micron mesh light and the second one with a 50 micron mesh light. This filtration is carried out as in the previous stage on glass funnels as previously mentioned.
- the synthesis mixture is stored to pass the separation or isolation phase of the target reaction products.
- the catalyst used in the reaction is previously activated by washing it with methanol, during a stirring period of 15 minutes and then drying at a temperature of 100 ° C for a period of 12 hours.
- the catalyst collected in the first grid filter is reused in the reaction.
- a catalyst wash with methanol and drying under the same conditions as in the initial activation is applied.
- the catalyst can be reused in up to ten reactions without decreasing the conversion of glycerin obtained or the yield of obtaining DTBG and TTBG.
- TTBG tri-tert-butyl glycerol
- a first vacuum distillation is carried out on the type equipment described above at 60 ° C and 100mbar of absolute pressure and the unreacted tert-butanol is recovered (mixed with water). The product stream passes to the first liquid-liquid extraction.
- the less dense phase is formed by DTBG, TTBG and solvent and is fed to a second decanter in which a new liquid-liquid extraction is carried out.
- the solvent used in this case is also water in a 2: 1 ratio to the fed mixture.
- the mixture is also stirred for 30 minutes and allowed to decant.
- the densest current is stored waiting to be reused again in the extraction, since it is mostly water.
- the separated solvent is reused in the first liquid-liquid extraction, since the separation is practically total.
- the tert-butanol that has not reacted and separated in the first distillation is also reused in the reaction. For this it is necessary to separate the water it contains (which forms azeotrope with tert-butanol) from the alcohol. This is achieved by mixing said stream with CaO 22% by weight versus the water-alcohol mixture fed. It is kept under stirring for a period of 7 hours and subsequently distilled at 120-150 ° C, preferably at 135 ° C the resulting paste. The vapor formed is condensed and collected as tert-butanol without water content. The remaining paste formed by hydroxide of Calcium can be distilled again to recover the CaO and reuse it in the process. This distillation takes place at between 80 and 100 ° C, 100 mbar of absolute pressure and a time of 1 hour.
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Abstract
La présente invention concerne un procédé destiné à obtenir des additifs oxygénés dérivés de glycérol brut, tels que les deux isomères du di-tert-butylglycérol (DTBG) et le tri-tert-butylglycérol (TTBG), à partir de glycérol brut et de tert-butanol. Le procédé comprend trois étapes essentielles définies ci-après : une première étape de purification ou de prétraitement du glycérol brut, une étape postérieure de réaction dans un réacteur discontinu et hermétique du glycérol obtenu à l'étape antérieure et du tert-butanol en présence d'un catalyseur, et une dernière étape de séparation des éthers de glycérol obtenus comme produits finaux de la réaction. Les éthers ainsi obtenus sont utilisés dans l'industrie en tant qu'additifs oxygénés de combustibles.
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PCT/ES2011/070637 WO2013038029A1 (fr) | 2011-09-12 | 2011-09-12 | Procédé de production d'additifs oxygénés à partir de glycérol brut |
ES201490020A ES2459865B1 (es) | 2011-09-12 | 2011-09-12 | Procedimiento de producción de aditivos oxigenados a partir de glicerina cruda |
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PCT/ES2011/070637 WO2013038029A1 (fr) | 2011-09-12 | 2011-09-12 | Procédé de production d'additifs oxygénés à partir de glycérol brut |
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WO2013038029A1 true WO2013038029A1 (fr) | 2013-03-21 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020006069A1 (fr) * | 2018-06-29 | 2020-01-02 | Lyondell Chemical Technology, L.P. | Procédé et catalyseurs permettant de produire des additifs pour diesel et essence à partir de glycérol |
WO2020120832A1 (fr) * | 2018-12-14 | 2020-06-18 | Neste Oyj | Composition de carburant diesel |
US11560525B2 (en) | 2018-12-14 | 2023-01-24 | Neste Oyj | Diesel fuel composition |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5308365A (en) * | 1993-08-31 | 1994-05-03 | Arco Chemical Technology, L.P. | Diesel fuel |
US5476971A (en) * | 1995-01-13 | 1995-12-19 | Arco Chemical Technology, L.P. | Glycerine ditertiary butyl ether preparation |
WO2007113776A2 (fr) * | 2006-04-05 | 2007-10-11 | The Procter & Gamble Company | Processus de conversion de glycérol en éthers de glycérol |
-
2011
- 2011-09-12 ES ES201490020A patent/ES2459865B1/es active Active
- 2011-09-12 WO PCT/ES2011/070637 patent/WO2013038029A1/fr active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5308365A (en) * | 1993-08-31 | 1994-05-03 | Arco Chemical Technology, L.P. | Diesel fuel |
US5476971A (en) * | 1995-01-13 | 1995-12-19 | Arco Chemical Technology, L.P. | Glycerine ditertiary butyl ether preparation |
WO2007113776A2 (fr) * | 2006-04-05 | 2007-10-11 | The Procter & Gamble Company | Processus de conversion de glycérol en éthers de glycérol |
Non-Patent Citations (4)
Title |
---|
FRUSTERI, F. ET AL.: "Catalytic etherification of glycerol by tert-butyl alcohol to produce oxygenated additives for diesel fuel.", APPLIED CATALYSIS A: GENERAL, vol. 367, 2009, pages 77 - 83 * |
KLEPACOVA, K. ET AL.: "Etherification of Glycerol with tert-Butyl Alcohol Catalysed by Ion-Exchange Resins.", CHEMICAL PAPERS, vol. 60, no. 3, 2006, pages 224 - 230 * |
SUSTOIL.: "Developing advanced Biorefinery schemes for integration into existing oil production/transesterification plants.", June 2008 (2008-06-01), Retrieved from the Internet <URL:http://www.york.ac.uk/res/sustoil/Pages/Deliverable%202-5.pdf> [retrieved on 20120312] * |
ZHOU, C.H. ET AL.: "Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals.", CHEMICAL SOCIETY REVIEWS, vol. 37, 2008, pages 527 - 549 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020006069A1 (fr) * | 2018-06-29 | 2020-01-02 | Lyondell Chemical Technology, L.P. | Procédé et catalyseurs permettant de produire des additifs pour diesel et essence à partir de glycérol |
US10774023B2 (en) | 2018-06-29 | 2020-09-15 | Lyondell Chemical Technology, L.P. | Process and catalysts for the production of diesel and gasoline additives from glycerol |
CN112334438A (zh) * | 2018-06-29 | 2021-02-05 | 利安德化学技术有限公司 | 用于由甘油生产柴油和汽油添加剂的方法和催化剂 |
WO2020120832A1 (fr) * | 2018-12-14 | 2020-06-18 | Neste Oyj | Composition de carburant diesel |
US11560525B2 (en) | 2018-12-14 | 2023-01-24 | Neste Oyj | Diesel fuel composition |
Also Published As
Publication number | Publication date |
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ES2459865B1 (es) | 2015-03-16 |
ES2459865A1 (es) | 2014-05-12 |
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