Integrated process for the production of tert-butyl ethers of glycerol or isooctene stream.

Abstract

INTEGRATED PROCESS FOR THE PRODUCTION OF GLYCEROL TERT-BUTYL ETHERS OR ISOOCTENE STREAM. The present invention relates to an integrated process that allows the production of glycerol tert-butyl ethers, used as a high-boiling-point solvent (SAPE) in paint formulations (water-based) and cleaning products, or of an isooctene stream to be used as an octane booster in the gasoline pool, in a simple manner, merely directing the flow through the areas necessary for the conversion and separation of the process streams and using the same equipment, aiming at process yield gains (maximization of glycerol and isobutene conversions) and minimization of investment and operating costs. Therefore, the unit has flexibility in the production of different high value-added products.

Description

1 / 14 “INTEGRATED PROCESS FOR THE PRODUCTION OF GLYCEROL TERC-BUTYL ETHERS OR ISOOCTENES STREAM” Field of Invention

[001] The present invention relates to an integrated process for producing glycerol tert-butyl ethers for use as a high-boiling-point solvent (SAPE) or an isooctene stream to be used as an octane booster in the gasoline pool, aiming at process yield gains (glycerol and isobutene conversion) and minimization of investment and operating costs. Description of the State of the Art

[002] Currently, there are few publications involving the synthesis of glycerol tert-butyl ethers (GTBE) in the literature. Existing processes have different configurations in terms of reactor type (mixed reactors) and product separation step (glycerol extraction), which result in lower yields. Figure 1 summarizes the chemical reactions involved in the synthesis process.

[003] One of the first and most important publications was US patent 5476971 (1995) “Glycerine di-Tertiary Butyl Ether Preparation (Arco Chemical Technology)” which addresses the production process of diGTBE, in which glycerol and isobutene are fed into a CSTR-type reactor with the homogeneous catalyst p-toluenesulfonic acid or methanesulfonic acid, receiving the recycle streams of unreacted isobutene from the rectifier column, and a stream of glycerol and monoGTBE from the decanter. The reactor effluent is sent to a decanter for separation of the dense phase, recycled to the reactor, and the light phase, directed to the rectifier column for isobutene recovery. The bottom stream from the rectifier column is directed to an extraction column for removal of glycerol and monoGTBE and obtaining the product composed basically of die triGTBE. Petition 870210092639, dated 06 / 10 / 2021, page 16 / 37 2 / 14

[004] In terms of advantages, it can be highlighted that this configuration eliminates the need for distillation of monoGTBE and glycerol from the product of interest. This is a difficult separation that requires a considerable number of theoretical stages and under vacuum to avoid degradation of the ethers present. However, there is a loss of glycerol, monoGTBE and the homogeneous acid catalyst in the washing water, which must be subsequently treated before being discarded.

[005] Furthermore, the tert-butyl alcohol formed (TBA), as well as any formation of isobutene dimers and trimers, will concentrate and contaminate the product stream.

[006] The work of BEHR, A.; OBENDORF, L. (2002) “Development of a process for the acid-catalyzed etherification of glycerine and isobutene forming glycerine tertiary butyl ether”, Engineering in Life Sciences, v.2, p. 185-189, which addresses an alternative process configuration to produce a diGTBE stream, aims to use the product as an octane booster. The described process involves 3 CSTR reactors in series in the reaction section, claiming that there is phase formation and agitation would increase mass transfer. It uses pure isobutene, and glycerol is added later in the LL extraction section, aiming at the extraction of the formed monoGTBE, which are recycled to the 1 reactor. The di- and triGTBE stream, along with the isobutene, is sent to a flash vessel, where the isobutene is removed in vapor phase, condensed, and recycled to the 1 reactor.A final rectification column removes the product from the top, and the monoGTBE and residual glycerin from the stream are removed by the bottom stream, which is also recycled to the reactor.

[007] Several catalysts were tested, but homogeneous catalysis with phosphorotungstic acid (H3PW12O4) and p-toluenesulfonic acid (pTS), both soluble in glycerol, showed the best performance. Thus, the entire kinetic study, carried out in a batch reactor in a bench-scale unit, was based on pTS, which had the highest yield of diethers. Petition 870210092639, dated 06 / 10 / 2021, page 17 / 37 3 / 14

[008] It claims that isobutene dimers and trimers were not formed and, therefore, there was no need for additional water or tert-butyl alcohol (TBA) feed to increase process selectivity. TBA was detected at levels below 1% w / w in the effluent, due to the water present in the medium. This TBA should be removed along with the product, resulting in its concentration. Isobutene dimers and trimers that may eventually be formed will also be collected with the product. However, the article does not mention whether there are losses of the catalyst in the product stream or even its deactivation.

[009] This process configuration adds advantages such as the recovery of the monoGTBE stream and residual glycerol in the product through distillation, increasing the final yield, and the addition of glycerol directly to the decanter to improve extraction performance.

[0010] KLEPÁCOVÁ, K. et al. (2007) “Etherification of glycerol and ethylene glycol by isobutylene”, Applied Catalysis A: General, v. 328, p.1-13 conducted a comparative study of glycerol etherification using ethylene glycol and isobutene with Amberlyst-15 and Amberlyst-35, pTS, and HY and H-Beta zeolites. The highest yield of di- and triGTBE was obtained with the resins, while the highest glycerol conversion was obtained with H-Beta zeolite. In this case, the formation of triGTBE was very low, allegedly due to the pore size of the catalyst. Furthermore, it was concluded that zeolites are more susceptible to deactivation and are not suitable for this type of reaction. The etherification of glycerol with ethylene glycol proved easy at a temperature of 60°C. For good pTS performance, various solvents were used, with the sulfonating agent being the most suitable.

[0011] The article by FRUSTERI, F. et al. (2009) “Catalytic etherification of glycerol by tert-butyl alcohol to produce oxygenated additives for diesel fuel”, Applied Catalysis A: General, v.367, p.77-83 addresses the synthesis of GTBE using glycerol and tert-butanol as reagents in a batch reactor. Several catalysts were tested and the highest glycerol conversion was achieved with the Petition 870210092639, dated 06 / 10 / 2021, page 18 / 37 4 / 14 Amberlyst-15 resin. The study continued with this catalyst to verify the influence of process variables. Furthermore, this article mentions the fact that it did not form isobutene dimers or trimers.

[0012] The article by Dl SERIO et al. (2010) “New process for the Production of Glycerol tert-Butyl Ethers”, Energy Fuels, v. 24, 4668-4672 addresses an integrated process configuration, starting from glycerol and isobutene, in a CSTR-type reactor, using Amberlyst-15 resin as a catalyst. The reactor effluent is directed to a flash vessel F1 (73°C, 0.1 bar) for vaporization of the hydrocarbons (isobutene and its dimers and trimers), maintaining the GTBE formed and the glycerol in the bottom liquid stream. The gas stream goes to a second flash vessel F2 (25°C, 0.1 bar), for condensation of the dimers and trimers (used as gasoline) and the isobutene obtained in the top gas stream is recycled to the reactor. The bottom stream from F1 is sent to a 6-stage extraction column where the solvent is biodiesel (FAME), obtaining a mixture of biodiesel, GTBE and glycerol above the permitted specification.The authors mention that this glycerol can be removed with aqueous washing, creating a complication and increasing the cost of the suggested configuration. The advantage of this process lies in the fact that it uses distillation columns to obtain GTBE (made by extraction with biodiesel); however, it cannot be inferred whether these lower CAPEX and OPEX are offset by the added equipment to specify the biodiesel in terms of glycerol.

[0013] VLAD, E. et al. (2011) “Design of Glycerol Etherification Process by Reactive Distillation”, Chemical Engineering Transactions, v.25, p.779-784, conducted a simulation of the GTBE production process based on data available in the literature using a reactive distillation column and its variations. The conversions obtained were 80% for glycerol and 55% for isobutene, which were fed at a molar ratio of isobutene / glycerol equal to 4. There was a large formation of monoGTBE which is recycled to the reaction system and the addition of glycerol in the settling vessel increases the Petition 870210092639, dated 06 / 10 / 2021, p. 19 / 37 5 / 14 extraction of monoGTBE. In another work by VLAD et al. (2012) “Design and Process Control of Glycerol-tert-Butyl Alcohol Etherification”, The Scientific World Journal, v. 2012, 1-11 describes different process configurations aiming to maximize yield.

[0014] Document WO2017 / 105246A2 “GTBE Composition, Methods and Installations for Enhanced Octane Boosting” does not show a specific process configuration for the production of GTBE, being used as an octane booster. It mentions unit operations to achieve certain component contents in the streams, but there are no drawings showing this configuration. The tests are conducted in a batch reactor, using sulfuric acid as a catalyst, but it mentions that heterogeneous catalysts can be used.

[0015] Other less important bibliographic references include the article by JAMRÓZ, ME et al. (2007) “Mono-, di-, and tri-tert-butyl ethers of glycerol: A molecular spectroscopic study”, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, v.67, p.980-988, which conducts a molecular spectroscopy study with GTBE, showing the most stable compounds among the mono and diGTBE families.

[0016] CAVALCANTE et al. (2014) “Qualitative and Quantitative Chromatographic Methods for Analysis of Glycerin Tert-butylation Products”, Virtual Chemistry Journal, v. 6 (2), 244-257 addresses the development of a methodology for chromatographic analysis of GTBE, presenting response factors, chromatographic conditions and retention time typical of the components.

[0017] The authors LIU et al. (2014) “Liquid-liquid equilibrium for system of glycerol and glycerol tert-butyl ethers”, Fluid Phase Equilibria, v. 365, 50-57, conducted a more detailed study on the thermodynamic LL equilibrium of glycerol and its ethers (GTBE), in ternary diagrams, using the NRTL model and 3 variations of the UNIFAC model. The solubility of GTBE in glycerol decreases with increasing degree of tert-butyl groups. Temperature influences Petition 870210092639, dated 06 / 10 / 2021, page 20 / 37 6 / 14 moderately to the solubilities of GTBE in glycerol. The activity coefficients of the NRTL model correlated well with the experimental data and the corresponding binary interaction parameters were resolved. However, for the original UNIFAC, UNIFAC-LLE and UNIFAC-Dortmund models, the prediction for this system failed.

[0018] In order to solve such problems, the present invention was developed, through the use of fixed bed reactors under optimized operating conditions and process configuration aimed at high product recovery and yields, in which the process allows the production of glycerol tert-butyl ethers to be used as a high boiling point solvent or an isooctene stream to be used as an octane booster in the gasoline pool.

[0019] The present invention offers advantages in the valorization of C4 cut from the FCC (Fluid Catalyst Cracking), Delayed Coking and / or Steam Pyrolysis (Steamcracking) processes as a high value-added solvent, producing a renewable alternative solvent for paints and cleaning products. Furthermore, the process allows for obtaining a product of higher purity. Brief Description of the Invention

[0020] The present invention relates to an integrated process comprising the sections of feed washing, reaction, product separation and product purification, enabling the production of glycerol tert-butyl ethers (GTBE) to be used as a high boiling point solvent (SAPE) with a minimum content of 95% w / w of di- and tri-substituted glycerol tert-butyl ethers to be used in paint formulations (water-based) and cleaning products or alternative production of an isooctene stream to be used as an octane booster in the gasoline pool.

[0021] The design and dimensioning of the process equipment of the present invention aim to enable the production of tert-butyl ethers or Petition 870210092639, dated 06 / 10 / 2021, page 21 / 37 7 / 14 isooctene streams in a simple way, just by directing the flow through the areas necessary for conversion and separation of the process streams. Brief Description of the Drawings

[0022] The present invention will be described in more detail below, with reference to the attached figures which, in a schematic and non-limiting way of the inventive scope, represent examples of its embodiment. The drawings show: Figure 1 illustrates the etherification reactions of isobutene and glycerol to produce mono- / di- / tri-tert-butyl ethers of glycerol (GTBE); Figure 2 illustrates dimerization and trimerization reactions of isobutene and the formation of TBA; Figure 3 illustrates a diagram of the SAPE and ISOOCTENOS production process. Detailed Description of the Invention

[0023] The integrated process, according to the present invention and illustrated in Figure 3, involves the production of a glycerol ether stream formed by the etherification of glycerol at 2 or 3 positions with isobutene present in the C4 olefinic section. The C4 olefinic section can originate from an FCC (Fluid Catalytic Cracking) unit, a delayed coking unit, or steam cracking. The process aims to produce a product stream with a minimum content of di- and trisubstituted ethers of 95% w / w, which can be used as a high-boiling-point solvent (SAPE). Due to the similarities between the ether stream production processes and the isobutene dimerization process for the production of an isooctene stream, the proposed configuration allows for simple switching between solvent production and isooctene production.Figure 1 presents a simplified process scheme proposed for a production unit that will be referred to as a hybrid unit. The glycerol tert-butyl ether stream is called SAPE (High Boiling Point Solvent). The tert-butyl ethers... Petition 870210092639, dated 06 / 10 / 2021, page 22 / 37 8 / 14 butyl groups of glycerol are called mono-, di-, and triGTBE (Glycerol Tert-Butyl Ethers) according to the number of tert-butyl groups present in the molecule.

[0024] The process can be divided into 4 distinct sections: (A) cargo washing section; (B) conversion section; (C) product separation section; (D) SAPE fractionation section. Description of the SAPE chain production process:

[0025] The olefinic C4 cut (1) is admitted from the bottom of the washing tower (T-01) of the feed washing section and undergoes countercurrent extraction with demineralized water (3) admitted from the top aiming at the removal of basic compounds (e.g. acetonitrile) and cations (e.g. Na+) present at levels below 1 mg / kg. The oily water (17) from the extraction is removed from the bottom of the washing tower (T-01) and sent to the organic effluent treatment, and the washed 04 cut (6) is obtained from the top and directed to the conversion reactor (R-01) in the conversion section, containing acid ion exchange resin. The washed C4 receives the recycle stream from the bottom (5) of the product separation tower (T-02), containing monoGTBE and unconverted glycerol, and water used as a reaction moderator, generating the feed stream (7) of the conversion reactor (R-01).Alternatively, the unreacted O4 stream (10) from the top of the product separation tower (T-02) can be recycled to the conversion reactor (R-01), generating the feed stream (9) of the conversion reactor (R-01). This practice aims at additional temperature control or an increase in the overall conversion of isobutene. Otherwise, the composition of streams (7) and (9) will be identical. It should be noted that this practice is mandatory and dependent on the isobutene content, aiming at reactor temperature control only when the unit operates in isooctene production mode.

[0026] In the conversion reactor (R-01) the etherification reactions of glycerol with isobutene occur, forming GTBE (mono-, di- and tri-tert-butyl ethers) and, Petition 870210092639, dated 06 / 10 / 2021, page 23 / 37 9 / 14 Concomitantly, in much smaller quantities, the formation of isobutene dimers (isooctenes) and trimers (isododecenes), in addition to tert-butanol (TBA - tert-butyl alcohol), as a moderating agent for the reaction, through the hydration reaction of isobutene. Alternatively, the unit can operate with more than one reactor in series, in order to maximize the conversion of glycerol and isobutene.

[0027] The effluent from the reactor (8) is sent to the product separation tower (T-02), which operates under pressure in the range of 2 to 8 bar, where a stream (11) containing the products formed is withdrawn from the bottom; this stream is sent to the gasoline splitter tower (T-03), still in the product separation section. The top stream (12) from the product separation tower (T-02) is composed of unreacted C4 hydrocarbons which are destined for storage in LPG spheres or, alternatively, recycled to the conversion reactor (R-01) for bed temperature control or to maximize the overall conversion of isobutene. From the top of the gasoline splitter tower (T-03) comes the stream (13) composed of isobutene dimers and trimers and TBA (isooctene stream), usually sent to the gasoline pool or marketed as octane booster or special gasoline.Alternatively, if SAPE does not require high purity (less than 95%), the gasoline splitter tower (T-03) can be taken out of operation and the isooctene stream will be recovered as a side stream (17) from the product separation tower (T-02). From the bottom of the gasoline splitter tower (T03), the stream (14), containing the product of interest, goes to the purification tower (T-04). This tower operates under vacuum in order to limit the maximum bottom temperature, preventing the decomposition of the formed ethers and the unreverted glycerol. The stream (16) withdrawn from the bottom of the purification tower (T04), containing the formed monoGTBE and the unreacted glycerol, is recycled to the conversion section. Along with this stream (16), process glycerol (2) and demineralized water (4) are fed in to produce TBA in the reactor and increase the selectivity of the reaction by inhibiting the reactions. Petition 870210092639, dated 06 / 10 / 2021, page 24 / 37 10 / 14 dimerization and trimerization of isobutene. Stream (5) results from mixing the recycle stream (16) from the bottom of the purification tower (T-04) with the glycerol (2) and water (4) streams. The resulting stream (5) joins stream (6), corresponding to the washed C4 cut obtained from the top of the washing tower (T-01), feeding the conversion reactor (R-01). Finally, stream (15) from the top of the purification tower (T-04), containing a minimum content of 95% w / w of di- and triGTBE, considered the product (SAPE), will be sent for storage in tanks before its commercialization.

[0028] The advantages of the process configuration of the present invention in relation to the processes in the literature are: the distillation tower condensers can operate with cooling water; greater flexibility for SAPE purification; higher conversion of glycerol (> 92%) and isobutene per pass (> 55%); higher overall conversion of isobutene with recycling of unreacted C4 cut; obtaining SAPE with di- and triGTBE content above 95% w / w; direct utilization of isobutene eliminating the need to separate it from the olefinic C4 cut. Description of the isooctene stream production process:

[0029] The operation of the hybrid unit for isooctene production is quite similar to the operation for SAPE production. A higher temperature is needed to achieve adequate isobutene conversions and, consequently, higher pressures for the conversion reactor (R01) to operate in the liquid phase. The space velocity is higher than that used in SAPE production, allowing for a higher feed flow rate of olefinic 04 cut (1) and, consequently, higher productivity. For the formation of the isooctene stream, the glycerol feed (2) is interrupted, there is no product recycling (5) to the reaction section, but the demineralized water (4), used in the formation of TBA, continues to be fed. In this mode of operation, the unreacted 04 cut (10) obtained from the top of the product separation tower (T-02) must necessarily be recycled to the reactor in order to control the temperature of the resin catalytic bed, due to exothermicity. Petition 870210092639, dated 06 / 10 / 2021, page 25 / 37 11 / 14 of the reactions. The reactor effluent is sent to the product separation tower (T-02), recovering the product containing isooctenes, isododecenes and TBA via the bottom stream (11). The splitter tower (T-03) and the purification tower (T-04) do not need to operate for the production of isooctenes. Similarly, unreacted C4 is sent to the sphere for its commercialization as LPG and the isooctene stream is sent to the gasoline pool or marketed as octane booster or special gasoline.

[0030] The operating conditions for the integrated process of the present invention are: Process variable ranges - SAPE mode • Inlet temperature in the 1st and / or 2nd reactors: T = 50 - 80°C; • Isobutene / glycerol molar ratio: RM(ISOZGLI) = 2-4:1 mol / mol; • Molar ratio of water / isobutene: RM(H2O / ISO) = 0.03 - 0.08:1 mol / mol; • Space velocity: LHSV (Liquid Hourly Space Velocity) = 0.2 - 2.0 tr1. Process variable ranges - ISOOCTENOS mode • Inlet temperature to the 1st and / or 2nd reactors: T = 70 - 100°C; • Molar ratio of water / isobutene: RM(H2O / ISO) = 0.03 - 0.08:1 mol / mol; • Space velocity: LHSV (Liquid Hourly Space Velocity) = 1.0 - 8.0 tr1. EXAMPLES:

[0031] The following examples are presented to illustrate more fully the nature of the present invention and the manner of practicing it, without, however, being considered as limiting its content. The results of the examples described below were obtained through experimental tests in a pilot unit, altering the operation for the production of SAPE and the ISOOCTENOS stream. The ranges explored for the operational variables, as well as the response variables such as conversions and selectivities, are summarized in Table I. With the effluent composition of the reactor for each test, the operating modes aimed at the production of SAPE and ISOOCTENOS were simulated. A Petition 870210092639, dated 06 / 10 / 2021, page 26 / 37 The 12 / 14 specification achieved for SAPE is shown in Table II. Table III presents the mass balances for the main process streams for each optimized operating mode.

[0032] Example 1: Case 1 - SAPE

[0033] The C4 cut from the FCC process, contained in a nitrogen-pressurized cylinder, is fed into the fixed-bed reactor containing Amberlyst-35 acid ion-exchange resin via a positive displacement pump. Simultaneously, a stream of glycerol (pharmaceutical grade, 99.5% w / w) containing a water content that provides an isobutene:water molar ratio in the range of 0.03-0.08 mol / mol is mixed with the C4 cut before entering the catalytic bed, which is at a temperature of 60°C and a pressure of 12 bar. The unit pressure is controlled by a PSV (Pressure Switch Valve) that discharges the effluent into a phase separator vessel. The light phase (containing unreacted C4 and di- and tri-butyl glycerol ethers) and the heavy phase (containing unreacted glycerol and tert-butyl glycerol monoethers) are separated and analyzed independently in order to obtain the conversions and selectivities of the process.The results obtained are presented in Table I (SAPE case).

[0034] Example 2: Case 1 - ISOOCTENES

[0035] Analogous to Example 1, the isooctene production test feeds the C4 cut into the reactor via a positive displacement pump. In this case, glycerol is not fed into the process, as the only interest lies in producing an isooctene stream to be used as an octane booster. To facilitate operation, instead of water, TBA (tert-butyl alcohol) is fed as a reaction moderator, previously mixed with the C4 cut, in order to obtain an equivalent isobutene:water ratio in the range of 0.03-0.08 mol / mol. The temperature used in this example is 80-90°C, maintaining a pressure of 15-18 bar. The catalyst used was also Amberlyst-36, and the space velocity is higher than in the SAPE mode, resulting in higher production for the same. Petition 870210092639, dated 06 / 10 / 2021, p. 27 / 37 13 / 14 volume of resin from the installed / used reactor. There was no need to recycle unreacted C4 to the reactor for temperature control of the bed, since it is a small-scale reactor (pilot scale), where the removal of heat generated in the reactions can be done more efficiently, without causing large temperature increases. Pressure control and effluent collection are performed similarly to Example 1. However, since the effluent is in a single phase, the composition analysis is simplified. The results obtained are presented in Table I (ISOCTENOS case).

[0036] It should be noted that, although the present invention has been described with respect to the accompanying drawings, it may undergo modifications and adaptations by those skilled in the art, depending on the specific situation, but provided that it is within the inventive scope defined herein.

[0037] It should be noted that for these experiments, there is no need to wash the feedstock to remove contaminants since the amount of contaminants received by the catalytic bed is not sufficient for significant resin deactivation.

[0038] In summary, the present invention utilizes the same unit, the same catalyst, and the same equipment, and only by varying the process conditions, it is possible to produce SAPE (used as a solvent in the formulation of cleaning products and paints) or ISOOCTENOS (used as gasoline and octane booster). The present invention offers advantages by obtaining a higher final yield in terms of products and flexibility in the specification of SAPE, reaching contents in the range of 95% w / w of di- and triGTBE. Petition 870210092639, dated 06 / 10 / 2021, pp. 28 / 37 14 / 14 Table I: Performance results of the SAPE and ISOOCTENOS production processes. Parameter Case SAPE Case ISOOCTENOS Glycerol conversion >92% - Selectivity of di- + triGTBE > 96% - Isobutene conversion 50-60% > 95% n-butene conversion <2% 3-5% Selectivity to C8 and C12 1.0 - 2.5% > 90% Mass ratio C8 / (C8+C12) 85 - 95% 80 - 90% Table II: High Boiling Point Solvent (SAPE) Specification Property Unit Value Di- + TriGTBE content (min.) m / m 95% Boiling point °C > 210 Vapor pressure kPa <7.0 Table III: Mass balance of the process - Example 1 (SAPE) and Example (ISOOCTENE) Current Discrimination Flow Rate (kg / h) SAPE Mode ISOOCTENE Mode (D Cut C4 11,200 27,000 (2) Glycerol 717 - (12) LPG 10,230 22,791 (13) Isooctene (gasoline) 154 4,241 (15) SAPE 1,493 - Petition 870210092639, dated 06 / 10 / 2021, pp. 29 / 37

Claims

1 / 4 Claims 1- INTEGRATED PROCESS FOR THE PRODUCTION OF TERBUTYL GLYCEROL ETHERS OR ISOOCTENES STREAM, characterized by comprising the following steps: (A) Feed washing section: i. The olefinic C4 cut (1) is admitted through the bottom of the washing tower (T-01) of the feed washing section in countercurrent with demineralized water (3) admitted through the top; ii. Through the bottom of the washing tower (T-01) the oily water (17) from the extraction is removed and sent to the organic effluent treatment and, through the top, the washed C4 cut (6) is directed to the conversion reactor (R-01) in the conversion section, containing acid ion exchange resin; iii. The washed C4 receives the recycle stream from the bottom (5) of the product separation tower (T-02) containing unconverted monoGTBE and glycerol and water used as a reaction moderator, generating the feed stream (7) of the conversion reactor (R-01); iv.Alternatively, the unreacted C4 stream (10), originating from the top of the product separation tower (T-02), is recycled to the conversion reactor (R-01), forming the feed stream (9) of the conversion reactor (R-01); (B) Conversion section-. i. In the conversion reactor (R-01), operating in liquid phase, the etherification reactions of glycerol with isobutene occur, forming GTBE (mono-, di- and tri-tert-butyl ethers), dimers (isooctenes) and trimers (isododecenes) of isobutene, and tert-butanol (TBA) as a reaction moderator, by the hydration reaction of isobutene; ii. The effluent from the reactor (8) is sent to the product separation tower (T-02), which operates pressurized in the range of 2 - 8 bar) where a stream (11) with the products formed is obtained from the bottom, forwarded to Petition 870210092639, dated 06 / 10 / 2021, page 30 / 37. 2 / 4 gasoline splitter tower (T-03), still in the product separation section; (C) Product separation section - i. The top stream (12) from the product separation tower (T-02) is composed of unreacted C4 hydrocarbons which are destined for storage in LPG spheres or, alternatively, recycled to the conversion reactor (R-01) for bed temperature control or to maximize the overall conversion of isobutene; ii. From the top of the gasoline splitter tower (T-03) is obtained the stream (13) composed of isobutene dimers and trimers and the TBA (isooctene stream); iii. Alternatively, if SAPE does not require high purity (less than 95%), the gasoline splitter tower (T-03) can be taken out of operation and the isooctene stream will be recovered as a side stream (17) from the product separation tower (T-02); iv.From the bottom of the gasoline splitter tower (T-03), stream (14) is destined for the purification tower (T-04), which operates under vacuum; (D) SAPE fractionation section: i. Stream (16) obtained from the bottom of the purification tower (T-04), containing the formed monoGTBE and unreacted glycerol, is recycled to the conversion section, along with this stream (16), process glycerol (2) and demineralized water (4) are fed; ii. Stream (5) results from the mixture of the recycle stream (16) from the bottom of the purification tower (T-04), together with the glycerol (2) and water (4) streams; this resulting stream (5) joins stream (6), corresponding to the washed cut 04 obtained from the top of the washing tower (T-01), feeding the conversion reactor (R-01); iii. The stream (15) from the top of the purification tower (T-04), containing a minimum content of 95% w / w of di- and triGTBE (SAPE), will be sent for storage in tanks. Petition 870210092639, dated 06 / 10 / 2021, p. 31 / 37. 3 / 4 2- PROCESS, according to claim 1, characterized in that the inlet temperature to the conversion reactor (R-01) is in the range of 50°C to 80°C. 3- PROCESS, according to claim 1, characterized in that the isobutene / glycerol molar ratio is in the range of 2 to 4:1 mol / mol. 4- PROCESS, according to claim 1, characterized in that the water / isobutene molar ratio is in the range of 0.03 to 0.08:1 mol / mol. 5- PROCESS, according to claim 1, characterized by the space velocity (LHSV) being in the range of 0.2 to 2.0 h'1. 6- PROCESS, according to claim 1, characterized by operating with more than one reactor in series to maximize the conversion of glycerol and isobutene. 7- PROCESS, according to claim 1, aiming at maximizing the production of the isooctene stream (composed of isooctenes and isododecenes), characterized by the glycerol feed (2) being interrupted, without recycling the stream (5) to the reaction section; the demineralized water (4) being continuously fed for the formation of TBA; the unreacted C4 cut (10) from the top of the product separation tower (T-02) being recycled to the conversion reactor (R-01), operating in liquid phase; the effluent from the reactor (8) being sent to the product separation tower (T02), recovering the product containing isooctenes, isododecenes and TBA by the bottom stream (11); the splitter tower (T-03) and the purification tower (T-04) not operating for the production of isooctenes; The unreacted C4 is sent to the sphere as LPG, and the isooctene stream is sent to the gasoline pool or marketed as octane booster or special gasoline. 8- PROCESS, according to claim 7, characterized in that the inlet temperature to the conversion reactor (R-01) is in the range of 70°C to 100°C. 9- PROCESS, according to claim 7, characterized by the water / isobutene molar ratio being in the range of 0.03 to 0.08:1 mol / mol. Petition 870210092639, dated 06 / 10 / 2021, page 32 / 37 4 / 4 10- PROCESS, according to claim 7, characterized by the space velocity (LHSV) being in the range of 1.0 to 8.0 h'1. 11- PROCESS, according to claim 7, characterized by alternatively operating with more than one reactor in series to maximize the conversion of isobutene to isooctenes and isododecenes. Petition 870210092639, dated 06 / 10 / 2021, pp. 33 / 37

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