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    • 专利摘要:
    Catalytic method for the synthesis of mesitylene from acetone. The present invention relates to a method for the production of mesitylene (1,3,5-trimethylbenzene) from acetone in a single stage by heterogeneous catalysis. The method comprises the use of a catalyst formed by a mixture of two solid materials with different catalytic functionality: the first one comprises a material with basic properties, while the second solid comprises a material with acidic properties. For application in the chemical, pharmaceutical and energy industries. More specifically in the field of catalysts for obtaining mesitylene. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2792176A1
    申请号:ES201900077
    申请日:2019-05-06
    公开日:2020-11-10
    发明作者:Garcia Salvador Ordonez；Fernandez Eva Diaz；Peon Laura Faba；Sanchez Jorge Quesada
    申请人:Universidad de Oviedo；
    IPC主号:
    专利说明:

    [0002] Catalytic method for the synthesis of mesitylene from acetone
    [0004] Technical sector
    [0006] The present invention relates to a method for the production of mesitylene (1,3,5-trimethylbenzene) from acetone in the vapor phase in a single stage by heterogeneous catalysis. The method comprises the use of a catalyst, which consists of a mixture of two solid materials with different catalytic functionality: the first of them comprises a solid material with basic properties, while the second solid comprises a material with acidic properties.
    [0008] The present invention belongs to the field of catalysts for obtaining mesitylene. Therefore, the invention would be applicable to the chemical, pharmaceutical and energy industries, since mesitylene is used as a chemical precursor in the synthesis of various chemical products.
    [0010] Background of the invention
    [0012] The interest in the production of mesitylene is due to its multiple applications in different industrial fields [H. W. Earhart and A. P. Komin, Polymethylbenzenes, in: Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley & Sons, Inc., 2000, pp. 2-13]. Its high reactivity in electrophilic reactions, with respect to the rest of polymethylbenzenes, makes it the most widely used as a chemical precursor for the synthesis of more complex compounds and other intermediate species through alkylation and acylation reactions using Friedel-Crafts catalysts. Thus, the formylation of mesitylene generates mesitaldehyde (2,4,6-trimethylbenzaldehyde), an intermediate in the production of plant growth regulators. The partial oxidation of mesitylene makes it possible to obtain trimesic acid (1,3,5-benzenetricarboxylic acid), as well as intermediate acids when the oxidation is carried out under more moderate conditions. It is also used as a starting material, by nitration, to obtain 2,4,6-trimethylaniline, used as a dye precursor. However, despite all the previously exposed industrial uses, its main application is as a chemical precursor for the production of colorless antioxidants and thermal stabilizers of plastics, gums, adhesives and waxes, due to its low oral toxicity. Likewise, mesitylene has an interesting application in the environmental field for the removal of nitric acid from gaseous effluents.
    [0014] Although mesitylene is one of the products that make up the mixture of chemical species with nine carbon atoms, obtained by super-fractionation of the reformate of petroleum naphtha, it cannot be separated with high purity. This is due to the presence of another compound in the mixture, 2-ethyltoluene, with a boiling point similar to that of mesitylene (165 ° C). Although pseudocumene (1,2,4-trimethylbenzene), isomer of mesitylene, does not present this problem. For this reason, at present, mesitylene is produced by the petrochemical route through isomerization of pseudocumene. However, the use of oil as a raw material is presented as the main drawback of this process, because it is a non-renewable carbon source. Furthermore, despite the fact that the isomerization of pseudocumene to mesitylene is a process implanted in the chemical industry, there are patents that seek to improve the catalysts used. Thus, for example, US patent 7157397 B2 proposes MFI zeolites modified by substituting the Si and Al atoms of their structure by Ti or Ge and Fe, Ga or B, respectively.
    [0015] It is also possible to obtain mesitylene from acetone through aldol condensation reactions and dehydration. In this way, it can be produced by dehydration-cyclization and dehydration of the intermediates phorone (4,6-dimethylhepta-3,5-dien-2-one) and α-isophorone (3,5,5-trimethylcidohex-2-en -1-one), respectively. The use of acetone for the synthesis of mesitylene is interesting due to the high volume of production as a by-product in the synthesis of phenol through the oxidation process of cumene. However, the main attraction of the use of acetone is when it is renewable (for example, obtained from fermentation processes or pyrolysis of biomass), allowing the substitution of the use of oil as raw material in the synthesis of mesitylene and its derivatives. This environmental incentive, together with the problems associated with the depletion of oil, makes the way of producing mesitylene from acetone of biological origin very interesting and promising.
    [0017] There are several patents that deal with the production of mesitylene from acetone. In them, different materials are considered to be used as catalysts in the reaction under consideration. In this way, catalysts have been developed for processes for producing mesitylene from acetone in the liquid phase. For example, US patent 2425096 A proposes the use, in the aqueous phase, of heteropolyacids of P or Si with W or Mo as metals, obtaining a mesitylene yield of 28%. Patent US 3267165 A considers the use of a mixture of sulfuric acid and polyphosphoric acid (1-50% by weight) as a catalyst, with a mesitylene yield of 17.5%. Patent u S 3946079 A indicates the use of metal phosphates (PO4 / Me; Me: Ti, Zr, Hf, Sn) to catalyze the reaction, reaching an acetone conversion of 41.9% with 50.4% of selectivity to mesitylene. In general, however, these processes have the usual drawbacks of homogeneous catalysis (eg high energy cost separation processes for catalyst recovery, corrosive operating conditions, environmental problems, use of complexes formed by metal elements uncommon or rare earths, etc.).
    [0019] Most of the patents for the production of mesitylene from acetone consider the contact process between acetone and the catalyst carried out with acetone in the vapor phase (heterogeneous catalysis). In patents US 2917561 A and GB 931893 A it is proposed to use catalysts of Ta and Nb, respectively, or any other stable compound formed by Ta and Nb supported on silica, alumina, silica-alumina, kieselguhr, pumice or carbons, with amounts of Ta or Nb comprised between 0.05 and 5% by weight. Patent US 5087781 A also considers the use of a Nb catalyst (0.5-3% by weight of Nb2O5) supported on silica, achieving an acetone conversion of 30% with selectivity towards mesitylene of 65%. In patent US 3201485 A, Cr2O3 and B2O3, supported on alumina, or Cr2O3 and ZnO supported on silica-alumina, with amounts of oxide not exceeding 20% by weight, reaching percentages by weight of mesitylene between reaction products of 24.2%. However, these catalysts have the disadvantage that they contain Cr, and their use can be dangerous for the environment and health. It has also been proposed, in US patent 3301912 A, the use of catalysts formed by Pd supported on a mixture of MoO3 and AhO3 (0.1-1% by weight of Pd), reaching a 42.5% conversion of acetone and 44.2% selectivity to mesitylene. However, these catalysts have a disadvantage based on the trend towards the design of catalysts free of precious metals and formed by abundant elements. The interest in the use of catalysts composed of abundant elements is based mainly on the possible scarcity of alternative elements (eg precious metals), as well as their geographical distribution (eg some of these elements are located in conflict regions, causing problems for their exploitation and significant fluctuations in prices).
    [0020] According to the self-condensation reaction mechanism of acetone, the aldolisation reaction of acetone with itself produces diacetone alcohol which is then dehydrated giving rise to the rest of C6 compounds (mesityl oxide and isomesityl oxide). These C6s can react with acetone through aldol condensation (aldolisation between C6 and acetone, followed by dehydration of the corresponding aldol adduct), generating the phorones. The latter can be transformed by dehydration-cyclization reactions into isophorones or mesitylene, depending on the starting phorone. On the other hand, mesitylene can be generated from isophorone by dehydration reaction. Both aldol condensation reactions and dehydration-cyclizations are catalyzed by active centers of the acid-base pair type. On the other hand, a high concentration of acidic active centers is detrimental, since they are mainly responsible for the stabilization of the intermediate chemical species adsorbed on the catalytic surface. This encourages the aldol condensation reactions to continue, giving rise to the phenomenon of oligomer formation, decreasing selectivity towards C9s and favoring catalytic deactivation [J. Quesada et a /., Role of surface intermediates in the deactivation of Mg-Zr mixed oxides in acetone self-condensation: A combined DRIFT and ex situ characterization approach, Journal of Catalysis 329, 1-9 (2015)]. For this reason, the catalysts used in the recovery of acetone by means of aldol condensation reactions are mainly oxides of a basic nature, since they present the most suitable distribution of active centers for this purpose. Thus, from the results obtained in the literature using basic oxides as a catalyst, it is observed that at high temperature the production of isophorones is favored among the cyclic C9 (constituted by isophorones and mesitylene) [L. Faba et al., Gas phase acetone self-condensation over unsupported and supported Mg-Zr mixed-oxides catalysts, Applied Catalysis B: Environmental 142-143, 387-395 (2013)]. This suggests: (i) that the forone that generates mesitylene is formed with less selectivity than the rest of the phorones, or that the dehydration-cyclization reaction towards isophorone is promoted to a greater extent than that corresponding to mesitylene; and (ii) that the dehydration reaction of isophorone to mesitylene practically does not occur.
    [0022] It has been observed that the use of aluminosilicates (eg, FER, MFI, BEA zeolites, etc.) in the aldol condensation reaction of acetone in the vapor phase produces mesitylene in low quantities, due to its acid function that allows dehydration of phorones and isophorones [S. Herrmann and E. Iglesia, Elementary steps in acetone condensation reactions catalyzed by aluminosilicates with diverse void structures, Journal of Catalysis 346, 134-153 (2017)]. However, an unwanted side reaction occurs from the six carbon atom compounds (C6: diacetone alcohol, mesityl oxide and isomesityl oxide) producing isobutene and acetic acid with high selectivity [S. Herrmann and E. Iglesia, Selective conversion of acetone to isobutene and acetic acid on aluminosilicates: Kinetic coupling between acid-catalyzed and radical-mediated pathways, Journal of Catalysis 360, 66 80 (2018)].
    [0024] Recently, a method has been studied, starting from acetone in the vapor phase, based on a process that uses two catalytic beds in series [J. Quesada (2018). Doctoral Thesis: Valorization of ethanol and acetone by catalytic processes. Oviedo University]. The materials used as catalysts in both beds were commercial. In the first bed, the use of TiO2, anatase phase, was considered, and in the second bed a mesoporous aluminosilicate with MCM-41 type structure or a BEA zeolite, with the aim of improving the dehydration stages. Although the desired synergistic effect between both materials was achieved when MCM-41 aluminosilicate was used as a second catalytic bed (improvement in mesitylene production), the results were not very satisfactory (acetone conversion: 12.0%; selectivity to mesitylene : 14.5%).
    [0025] Due to the high interest in obtaining mesitylene, new and better catalysts continue to be needed for its production from acetone.
    [0027] Explanation of the invention
    [0029] The present invention relates to a method for the production of mesitylene (1,3,5-trimethylbenzene) from acetone in the gas phase in a single stage by heterogeneous catalysis. The method comprises the use of a catalyst, which consists of a mixture of two solid materials with different catalytic functionality: the first of them comprises a solid material with basic properties, while the second solid comprises a material with acidic properties.
    [0031] An object of the present invention is, therefore, a method for the synthesis of mesitylene (1,3,5-trimethylbenzene) that comprises contacting acetone in the gas phase with a catalytically effective amount, for aldol condensation and dehydration-cyclization reactions, of a mixture of a basic solid material and an acidic solid material in a mass ratio between 1/4 and 3/4, at a temperature between 200 ° C and 500 ° C, and at a pressure between 0.05 bar and 200 bar.
    [0033] In a preferred embodiment, the acetone is conducted through a stream of inert carrier gas, selected from He, Ar and N2.
    [0035] In a more preferred embodiment, the acetone, in the liquid state, is injected into the carrier inert gas stream that is at a temperature equal to or higher than the vaporization temperature of the acetone, causing the injected acetone to vaporize. In this way, the acetone vaporization occurs in situ. This makes it possible to apply the invention when it is carried out in a reactor in which the proposed catalyst is located in a fixed-bed arrangement.
    [0037] In another preferred embodiment, the basic solid material is a single oxide or a mixed oxide. In a more preferred embodiment, the oxide is a selection from a Mg oxide, a Zr oxide, a Ti oxide, an Al oxide, or a Zn oxide, or a combination of the foregoing.
    [0039] In another preferred embodiment, the acidic solid material is a selection from aluminosilicates, silicoaluminophosphates, or aluminophosphates. In a more preferred embodiment, the acidic solid material is one or more mesoporous or microporous aluminosilicates.
    [0041] In this invention, the use of an oxide as the basic material component of the catalyst is considered due to the good results that basic oxides present in catalyzing the aldol condensation reactions. The basic oxide can be a single oxide or a mixed oxide, preferably selected from Mg, Zr, Ti, Al or Zn. The addition of a second component comprising an acidic solid material such as aluminosilicates, silicoaluminophosphates or aluminophosphates is proposed. The purpose of the addition of this second component is to increase the concentration of strong acid centers in the resulting mixing catalyst. In this sense, the use of mesoporous and microporous aluminosilicates (zeolites) is preferably proposed as acid component of the new material used as catalyst, for two reasons: (i) aluminosilicates have strong acid centers (Bronsted type); and (ii) aluminosilicates of different acidity can be obtained in a simple way by modifying the Si / AI ratio.
    [0043] The mass ratio of both solid materials that comprise the catalyst is proposed variable, preferably with an oxide / aluminosilicate mass ratio comprised between 1/4 In another preferred embodiment, the catalyst compound is a granular solid with a grain size on the order of microns to millimeters.
    [0044] In another preferred embodiment, the catalytic compound is a solid arranged in a fixed bed inside a reactor.
    [0045] In another specific embodiment, the temperature of the method is between 300 ° C and 450 ° C.
    [0046] In another specific embodiment, the pressure is atmospheric pressure.
    [0047] In another specific embodiment, the amount of acetone mass fed per catalyst mass, defined by the WHSV ( weight hourly space velocity), is between 1 and 20 h-1.
    [0048] In another specific embodiment, the method further comprises the following previous steps for the pretreatment of the catalyst:
    [0049] a) Activation / regeneration of the catalytic compound in the presence of an effective amount of pretreatment gas for the desorption of chemical substances adsorbed by the catalytic compound, before the reaction process (activation) or after each reaction cycle (regeneration).
    [0050] b) Carry-over of desorbed chemicals.
    [0051] In a more specific embodiment, catalyst pretreatment steps a) and b) are performed simultaneously in a continuous operation in which the pretreatment gas is introduced as a gas stream.
    [0052] In another more specific embodiment, the gas used in the pretreatment of the catalyst is selected from an inert gas (He, Ar or N2), air or oxygen.
    [0053] In another more specific embodiment, the activation / regeneration temperature of the catalytic compound is between 200 ° C and 500 ° C.
    [0054] In an even more specific embodiment, the temperature for activation is the same as that for the catalytic reaction.
    [0055] The catalyst pretreatment is carried out for a time that allows ensuring the efficiency of the process (activation / regeneration). In a preferred embodiment, the catalyst pretreatment is carried out for 1 h.
    [0056] The mode of operation of this invention has the following advantages compared to the known state of the art:
    [0057] (i) Eliminates the characteristic problems of processes based on homogeneous catalysis (p.
    [0058] (e.g., high energy cost separation processes for catalyst recovery, corrosive operating conditions, environmental problems, use of complexes formed by elements of rare metals or rare earths, etc.).
    [0059] (ii) It allows to work continuously, with respect to discontinuous processes carried out by heterogeneous catalysis in the liquid phase.
    [0061] Likewise, the oxide and aluminosilicate catalyst proposed in the present invention has the following main advantages:
    [0063] (i) Both materials (oxides and aluminosilicates) can be obtained in high volumes and are made up of common elements, unlike what is indicated in previous patents (among those that propose to operate in a similar way to the one proposed), which consider the use of catalysts containing rare metals (Ta or Nb) or precious metals (Pd).
    [0065] (ii) Compared with the catalysts formed solely by oxides, the transformation of the C9 compounds other than mesitylene (phorones and isophorones) to mesitylene is greatly increased by the presence of the acid component material in the catalyst. Thus, the relative selectivity of mesitylene with respect to the set of C9 compounds (phorones, isophorones and mesitylene) for different examples of catalysts proposed in this invention increases significantly with respect to using only the corresponding oxides, since it goes from values of around 5% at values between 75 and 90%.
    [0067] This is due to the incorporation of strong acidic active centers in the proposed catalyst, as a consequence of the presence of the acid component. These strong acid centers catalyze dehydration reactions favoring the production of mesitylene. In the invention the acidic component material is considered as the catalytically active phase for dehydration reactions. This proposal presents an important advantage over other possible proposals that consider the modification of the active surface of the catalysts formed by oxides, or new synthesis processes of these oxides, in order to increase their concentration of strong acidic active centers. In the catalyst proposed in this invention, the additional strong acid centers belong to a catalytic phase different from the basic oxide (acid component of the catalyst), so the stabilization capacity of the intermediate chemical species adsorbed on the oxide surface is not increased. . This makes it difficult for aldol condensation reactions to proceed, which would lead to the formation of oligomers and a consequent reduction in selectivity towards mesitylene.
    [0069] (iii) In the catalyst proposed in the present invention, most of the phorones and isophorones are produced on the surface of the basic component of the catalyst, while most of the active centers of the aluminosilicate catalyze dehydration-cyclization or dehydration ( starting from phorones or isophorones, respectively). Therefore, the generation of isobutene and acetic acid formed by the unwanted reaction of the C6s chemical species that catalyze the aluminosilicates is reduced.
    [0071] The present invention is applicable in the chemical, pharmaceutical and energy industries, since mesitylene is used as a chemical precursor in the synthesis of different chemical products of interest. In particular, this invention belongs to the field of catalysts for the production of mesitylene.
    [0073] Throughout the section describing the invention, as well as in the claims, the word "comprises" and its variants do not mean the exclusion of other technical characteristics. For those skilled in the art, the advantages and characteristics of this invention may be deduced in part of the description and practical use of the invention. Examples and figures are They add with the purpose of showing the invention, without pretending that they generate limitations of the same.
    [0075] Brief description of the drawings
    [0077] Fig. 1 corresponds to the scheme of the reaction mechanism for obtaining mesitylene from acetone by aldol condensation and dehydration reactions. Short names for chemical compounds: ADA, diacetone alcohol; OM, mesityl oxide; iso-OM, isomesityl oxide.
    [0079] Fig. 2 illustrates how the use of catalysts formed by a mechanical mixture of oxide and aluminosilicate favors the formation of mesitylene from acetone in the vapor phase. The figure shows the selectivity values towards mesitylene relative to the set of chemical species C9 (Sm / IS c9) versus the mass proportions of oxide and aluminosilicate (O and A, respectively) that make up the catalysts used in examples a contact temperature between acetone and catalyst 300 ° C (1, 3-5, 7-10). Likewise, the figure includes the S m / IS c 9 values obtained with catalysts composed only of the oxides used (100% of showing a higher activity of the catalysts proposed in this invention due to the presence of the aluminosilicate. List of symbols : ^ TiO2 H-AI-MCM-41; TiO2 BEA; or Mg-Zr H-AI- MCM-41; 0 Mg-Zr BEA; ▲ TiO2; A Mg-Zr.
    [0081] Preferred embodiment of the invention
    [0083] For a better understanding of the present invention, the following preferred embodiment examples are set forth, described in detail, which should be understood without limiting the scope of the invention.
    [0085] EXAMPLE 1
    [0087] A catalyst was prepared in which the basic solid component was TiO2 (anatase crystalline phase) and the acidic solid component was a mesoporous aluminosilicate with MCM-41 type structure, H-AI- m C m -41, with Si / AI = ratio 39.5. Amounts of both materials were mixed to obtain a TiO 2 / H-AI-MCM-41 = 1 mass ratio. The mixture was pressed at a pressure of 370 MPa for approximately 2 min. The resulting pellets were crushed and all the catalyst particles obtained were screened, selecting those with a size between 0.25 and 0.35 mm. 200 mg of these particles were used as a catalyst for the synthesis reaction of mesitylene from acetone in the vapor phase. The operating temperature was 300 ° C, and the pressure was close to atmospheric. The space velocity, defined by the WHSV, was 4 h -1 . Prior to the reaction test, the catalyst was pretreated in situ at the reaction temperature under an inert atmosphere (He) for 1 h. An acetone conversion of 8.6% was achieved, with 19.9% selectivity to mesitylene. The selectivity towards mesitylene relative to all of the C9 chemical species was 76.3%, much higher than the 6.0% achieved when only oxide (TiO2) was used as a catalyst. Therefore, the presence of the acidic solid material (H-AI-MCM-41) in the mixture comprising the catalyst notably improves the formation of mesitylene.
    [0089] EXAMPLE 2
    [0091] Experiment analogous to that of Example 1, with the difference that the operating temperature was 350 ° C. An acetone conversion of 12.8% was achieved, with 15.7% selectivity to mesitylene. The selectivity towards mesitylene relative to the set of C9 chemical species was 79.7%.
    [0093] EXAMPLE 3
    [0095] Experiment analogous to that of Example 1, with the difference that the mass ratio TiO2 / H-AI- m C m -41 of the catalyst used was 3/2. An acetone conversion of 8.1% was achieved, with 20.8% selectivity to mesitylene. The selectivity towards mesitylene relative to all the C9 chemical species was 77.1%, much higher than the 6.0% achieved when only oxide (TiO2) was used as a catalyst. Therefore, the presence of the acidic solid material (H-AI-MCM-41) in the mixture comprising the catalyst notably improves the formation of mesitylene.
    [0097] EXAMPLE 4
    [0099] Experiment analogous to that of Example 1, with the difference that the TiO2 / H-AI-m Cm-41 mass ratio of the catalyst used was 2/3. An acetone conversion of 8.4% was achieved, with 22.1% selectivity to mesitylene. The selectivity towards mesitylene relative to all the C9 chemical species was 84.8%, much higher than the 6.0% achieved when only oxide (TiO2) was used as a catalyst. Therefore, the presence of the acidic solid material (H-AI-MCM-41) in the mixture comprising the catalyst notably improves the formation of mesitylene.
    [0101] EXAMPLE 5
    [0103] A catalyst was prepared in which the basic solid component was TiO2 (anatase crystalline phase) and the acidic solid component was a microporous aluminosilicate, BEA zeolite, with Si / AI ratio = 12.5. Amounts of both materials were mixed to obtain a TiO2 / BEA = 1 mass ratio. The mixture was pressed at a pressure of 370 MPa for approximately 2 min. The resulting pellets were crushed and all the catalyst particles obtained were screened, selecting those with a size between 0.25 and 0.35 mm. 200 mg of these particles were used as a catalyst for the synthesis reaction of mesitylene from acetone in the vapor phase. The operating temperature was 300 ° C, and the pressure was close to atmospheric. The space velocity, defined by the WHSV, was 4 h -1 . Prior to the reaction test, the catalyst was pretreated in situ at the reaction temperature under an inert atmosphere (He) for 1 h. An acetone conversion of 13.8% was achieved, with 18.2% selectivity to mesitylene. The selectivity towards mesitylene relative to all the C9 chemical species was 88.3%, much higher than the 6.0% achieved when only oxide (TiO2) was used as a catalyst. Therefore, the presence of the acidic solid material (BEA) in the mixture comprising the catalyst greatly improves the formation of mesitylene.
    [0105] EXAMPLE 6
    [0107] Experiment analogous to that of Example 5, with the difference that the operating temperature was 350 ° C. An acetone conversion of 20.7% was achieved, with 14.0% selectivity to mesitylene. The selectivity towards mesitylene relative to all the C9 chemical species was 78.4%.
    [0108] EXAMPLE 7
    [0110] Experiment analogous to that of Example 5, with the difference that the TIO2 / BEA mass ratio of the catalyst used was 3/2. An acetone conversion of 11.2% was achieved, with 17.8% selectivity to mesitylene. The selectivity towards mesitylene relative to all the C9 chemical species was 84.5%, much higher than the 6.0% achieved when only oxide (TiO2) was used as a catalyst. Therefore, the presence of the acidic solid material (BEA) in the mixture comprising the catalyst remarkably improves the formation of mesitylene.
    [0112] EXAMPLE 8
    [0114] Experiment analogous to that of Example 5, with the difference that the TiO2 / BEA mass ratio of the catalyst used was 2/3. An acetone conversion of 14.8% was achieved, with 20.0% selectivity to mesitylene. The selectivity towards mesitylene relative to all the C9 chemical species was 83.1%, much higher than the 6.0% achieved when only oxide (TiO2) was used as a catalyst. Therefore, the presence of the acidic solid material (BEA) in the mixture comprising the catalyst greatly improves the formation of mesitylene.
    [0116] EXAMPLE 9
    [0118] A catalyst was prepared in which the basic solid component was a mixed oxide of Mg and Zr, Mg-Zr, with a Mg / Zr ratio = 4.5. The Mg-Zr was prepared using the sol-gel technique previously described in the literature [L. Faba et al., Performance of bifunctional Pd / MxNyO (M = Mg, Ca; N = Zr, Al) catalysts for aldolization-hydrogenation of furfural-acetone mixtures, Catalysis Today 164, 451-456 (2011); J. Quesada et al., Role of surface intermediates in the deactivation of Mg-Zr mixed oxides in acetone self-condensation: A combined DRIFT and ex situ characterization approach, Journal of Catalysis 329, 1-9 (2015)]. The solid acid component was a mesoporous aluminosilicate with MCM-41, H-AI-MCM-41 type structure, with Si / AI ratio = 39.5. Amounts of both materials were mixed to obtain a mass ratio Mg-Zr / H-AI-MCM-41 = 1. The mixture was pressed at a pressure of 370 MPa for approximately 2 min. The resulting pellets were crushed and all the catalyst particles obtained were screened, selecting those with a size between 0.25 and 0.35 mm. 200 mg of these particles were used as a catalyst for the synthesis reaction of mesitylene from acetone in the vapor phase. The operating temperature was 300 ° C, and the pressure was close to atmospheric. The space velocity, defined by the WHSV, was 4 h -1 . Prior to the reaction test, the catalyst was pretreated in situ at the reaction temperature under an inert atmosphere (He) for 1 h. An acetone conversion of 5.6% was achieved, with 22.9% selectivity to mesitylene. The selectivity towards mesitylene relative to all the C9 chemical species was 57.3%, much higher than the 3.4% achieved when only oxide (Mg-Zr) was used as a catalyst. Therefore, the presence of the acidic solid material (H-AI-MCM-41) in the mixture comprising the catalyst notably improves the formation of mesitylene.
    [0120] EXAMPLE 10
    [0122] Experiment analogous to that of Example 10, with the difference that the acidic solid component of the catalyst used was a microporous aluminosilicate, zeolite BEA, with a Si / AI ratio = 12.5. An acetone conversion of 5.2% was achieved, with 18.3% selectivity to mesitylene. The selectivity towards mesitylene relative to all the C9 chemical species was 64.0%, much higher than the 3.4% achieved when only oxide (Mg-Zr) was used as a catalyst. Therefore, the presence of the acidic solid material (BEA) in the mixture comprising the catalyst remarkably improves the formation of mesitylene.
    [0123] The following table summarizes the catalytic activity of the various catalysts mentioned in each previous example.
    [0125]
    [0127] Table 1. Catalytic activity of different catalysts of mechanical mixtures of oxides and aluminosilicates in the transformation of acetone to mesitylene in the vapor phase.
    [0128] aT (° C): temperature at which the acetone-catalyst contact occurs. bO / A: oxide / aluminosilicate mass ratio of the catalyst used.
    [0129] cConv. (%): acetone conversion.
    [0130] dSM (%): selectivity to mesitylene.
    权利要求:
    Claims (17)
    [1]
    1. Method for the synthesis of mesitylene (1,3,5-trimethylbenzene) that comprises contacting acetone in the gas phase with a catalytically effective amount, for aldol condensation and dehydration-cyclization reactions, of a mixture of a basic solid material and a solid acidic material in a mass ratio between 1/4 and 3/4, at a temperature between 200 ° C and 500 ° C, and at a pressure between 0.05 bar and 200 bar.
    [2]
    2. Method according to claim 1, characterized in that the acetone is conducted through a stream of inert carrier gas, selected from He, Ar and N2.
    [3]
    3. Method according to claim 2, characterized in that the acetone, in liquid state, is injected into the carrier inert gas stream that is at a temperature equal to or higher than that of the acetone vaporization, causing the vaporization of the injected acetone.
    [4]
    4. Method according to claim 1, characterized in that the basic solid material is a simple oxide or a mixed oxide.
    [5]
    Method according to claim 4, characterized in that the oxide is a selection between an oxide of Mg, an oxide of Zr, an oxide of Ti, an oxide of Al or an oxide of Zn, or a combination of the above.
    [6]
    6. Method according to claim 1, characterized in that the acidic solid material is a selection among aluminosilicates, silicoaluminophosphates or aluminophosphates.
    [7]
    7. Method according to claim 6, characterized in that the acidic solid material is one or more mesoporous or microporous aluminosilicates.
    [8]
    8. Method according to claim 1, characterized in that the catalytic compound is a granular solid with a grain size of the order of micrometers to millimeters.
    [9]
    9. Method according to claim 1, characterized in that the catalytic compound is a solid arranged in a fixed bed inside a reactor.
    [10]
    10. Method according to claim 1, characterized in that the temperature is between 300 ° C and 450 ° C.
    [11]
    Method according to claim 1, characterized in that the pressure is atmospheric pressure.
    [12]
    12. Method according to claim 1, characterized in that the amount of acetone mass per catalyst mass corresponds to a space velocity (WHSV) comprised between 1 and 20 h-1.
    [13]
    13. Method according to claim 1, characterized in that it also comprises the following previous stages for the pretreatment of the catalyst:
    a) activation / regeneration of the catalytic compound in the presence of an effective amount of gas for the desorption of chemicals adsorbed by the catalytic compound;
    b) carryover of desorbed chemicals.
    [14]
    Method according to claim 13, characterized in that steps a) and b) are performed simultaneously in a continuous operation in which the pretreatment gas is introduced as a gas stream.
    [15]
    15. Method according to claim 13, characterized in that the gas used in the pretreatment of the catalyst is selected from an inert gas (He, Ar or N2), air or oxygen.
    [16]
    16. Method according to claim 13, characterized in that the activation / regeneration temperature of the catalytic compound is between 200 ° C and 500 ° C.
    [17]
    17. Method according to claim 14, characterized in that for the activation of the catalyst the temperature is the same as that of the catalytic reaction.
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    同族专利:
    公开号 | 公开日
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB852674A|1958-02-17|1960-10-26|Exxon Research Engineering Co|Production of mesitylene|
    CN1243117A|1999-07-16|2000-02-02|王男|Production technology of high-purity mesitylene using acetone|
    US20040225170A1|2003-02-27|2004-11-11|Polimeri Europa S.P.A.|Process for the production of mesitylene|
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