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    • 专利摘要:
    Continuous oxidative cleavage process of vegetable oils A continuous process for the oxidative cleavage of vegetable oils containing unsaturated carboxylic acid triglycerides to obtain saturated carboxylic acids is described, comprising the steps of: a) feeding into a continuous first reactor at least a vegetable oil, an oxidizing compound and a catalyst capable of catalyzing the oxidizing reaction of the olefinic double bond to obtain an intermediate compound containing vicinal diols; b) feeding a second continuous reactor said intermediate, an oxygen-containing compound and a catalyst, capable of catalyzing the oxidation reaction of the vicinal diols to carboxylic groups to obtain saturated monocarboxylic acids (i) and triglycerides containing saturated carboxylic acids with more than one acidic function (ii); c) separating saturated monocarboxylic acids (i) from triglycerides having more than one acidic function (ii); and d) hydrolyzing in a third reactor triglycerides having more than one acidic function (ii) to obtain glycerol and saturated carboxylic acids with more than one acidic function.
    公开号:BR112012016249B1
    申请号:R112012016249
    申请日:2010-12-29
    公开日:2019-10-22
    发明作者:Ferrari Adriano；Pirocco Alessandro；Bieser Arno；Digioia Francesca；Borsotti Giampietro
    申请人:Novamont Spa；
    IPC主号:
    专利说明:

    1/14
    CONTINUOUS PROCESS OF OXIDATIVE CLIVING OF VEGETABLE OILS
    DESCRIPTION [0001] The present invention relates to a continuous process for oxidative divination of vegetable oils containing triglycerides of unsaturated carboxylic acids, to obtain saturated carboxylic acids, comprising the steps of:
    a) feed in a first reactor at least one vegetable oil, an oxidation compound and a catalyst, capable of catalyzing the oxidation reaction of the olefinic double bond, to obtain an intermediate compound containing vicinal diols;
    b) feed in a second reactor the said intermediate compound, a compound containing oxygen and a catalyst, capable of catalyzing the oxidation reaction of vicinal diols to carboxylic groups, to obtain saturated monocarboxylic acids (i) and triglycerides containing saturated carboxylic acids with more an acidic function (ii);
    c) separating saturated monocarboxylic acids (i) from triglycerides having more than one acid function (ii); and
    d) hydrolyze triglycerides in a third reactor having more than one acid function (ii), to obtain glycerol and saturated carboxylic acids with more than one acid function.
    [0002] The processes for oxidative dividing of vegetable oils containing triglycerides from unsaturated carboxylic acids are already known in the technical literature.
    [0003] For example, patent application W02008 / 138892 describes a batch process for the oxidative dividing of vegetable oils, characterized by the fact that oxidation reactions are performed on unmodified oils, without the addition of organic solvents and in the presence limited amounts of water (water: diol <1: 1).
    [0004] The oxidation reactions described are significantly exothermic and require constant control, together with adequate removal of the developed heat, in order to avoid an excessive increase in temperature.
    [0005] The oxidation phase of unsaturated carbons to form vicinal diols, in particular, is subject to the risk of explosive decomposition of the peroxide used as an oxidizing agent, since the peroxide is very unstable under high temperature conditions.
    [0006] In addition, an additional limit of the entire process is related to the accidental accumulation of oxidizing agent, which can cause the sudden acceleration of the reaction, with the consequent uncontrolled increase in temperature. Such accumulation may depend on a slow reaction rate or on the difficulty of mixing the oxidizing agents with the reagents.
    Petition 870190057589, of 06/21/2019, p. 7/26
    2/14 [0007] In the oxidative dividing stage of glass diols, for example, significant difficulties are encountered in the mixture, since under the conditions used the reagents form a liquid phase characterized by high viscosity, while the oxidizing agent is in the phase gaseous.
    [0008] Furthermore, the mechanism of the oxidative dividing reaction of vicinal diols with oxygen proved to be of the radical type. Such a reaction has an induction time in which the proper concentration of radicals has to be reached before the reaction starts; after this time, the reaction begins to spread exponentially and in an uncontrolled manner, with the formation of by-products having different chain lengths, due to the lack of selectivity.
    [0009] To overcome the above mentioned drawbacks, the present continuous process for the production of carboxylic acids from vegetable oils was developed. In said process, each of the oxidation reactions is conducted continuously, and not in a batch process.
    [0010] The term “continuous” refers to a process in which the operations to feed the reagents and to remove the products occur simultaneously during the total duration of the process, in which, at each stage, the conditions of the process (ie , temperature, pressure, flow rate, etc.) remain substantially unchanged.
    [0011] The continuous process according to the present invention is more effectively controllable with respect to known processes, making it possible to feed high concentrations of oxidizing agent in safe conditions during step a) of the process. [0012] In addition, the continuous process according to the invention solves the difficulties of mixing the oxidizing agent during the oxidative dividing reaction of the diols, linked to the high viscosity of the reaction mixture. In fact, in the said process, during the total duration of step b), the reaction mixture contains a high percentage of reaction products which, because they are more fluid than the reagents, contribute to significantly reduce the viscosity of the system.
    [0013] In the continuous process according to the invention, it is also possible to keep the concentration of radicals low and constant during step b), thus limiting the formation of by-products and increasing the reaction yield.
    [0014] The process according to the invention will now be described in greater detail with reference to figures 1 and 2, where:
    - Fig. 1 is a flow diagram of the process according to the invention; and
    Petition 870190057589, of 06/21/2019, p. 8/26
    3/14
    - Fig. 2 is a diagram of the plant on which the process takes place.
    [0015] In particular, the present invention relates to a continuous process for the oxidative dividing of vegetable oils containing unsaturated carboxylic acid triglycerides, to obtain saturated carboxylic acids, comprising the steps of:
    a) feed in a first continuous reactor (1) at least one vegetable oil and an oxidation compound in the presence of a catalyst, capable of catalyzing the oxidation reaction of the olefinic double bond, to obtain an intermediate compound containing vicinal diols;
    b) feed in a second continuous reactor (2) the said intermediate compound, oxygen or an oxygen-containing compound, and a catalyst capable of catalyzing the oxidation reaction of the diols of carboxylic groups, to obtain saturated monocarboxylic acids (i) and triglycerides containing saturated monocarboxylic acids with more than one acid function (II);
    c) transferring the product from step b) to an apparatus (3) suitable for separating saturated monocarboxylic acids (i) from triglycerides having more than one acid function (ii); and
    d) hydrolyze in a third reactor (4) said triglycerides (ii), to obtain glycerol and saturated carboxylic acids with more than one acid function.
    [0016] The starting material for the process, according to the present invention, is a vegetable oil, or a mixture of vegetable oils, containing triglycerides of unsaturated carboxylic acids. These vegetable oils are intended to be both in the form of unmodified pressed products and in the form of an oil that has undergone chemical or physico-chemical modifications, such as purification treatments or enzymatic enrichment operations. Examples of vegetable oils are: soybean oil, olive oil, castor oil, sunflower oil, peanut oil, corn oil, palm oil, pine nut oil, Cuphea oil, Brassicaceae oils, such as Crambe abyssinica , Brassica carinata, Brassica napus (canola), Lesquerella, and other oils with a high content of monounsaturated acid. The use of sunflower seed oil and Brassicaceae oil is particularly preferred. The use of sunflower oil with a high oleic content and Brassicaceae oils with a high erucic content is even more preferred.
    [0017] Triglycerides can contain both monounsaturated and polyunsaturated carboxylic acids. Examples of unsaturated carboxylic acids are: 9-tetradecenoic acid (myristoleic acid), 9-hexadecenoic acid (palmitoleic acid), 9-octadecenoic acid
    Petition 870190057589, of 06/21/2019, p. 9/26
    4/14 (oleic acid), 12-hydroxy-9-octadecenoic acid (ricinoleic acid), 9-eicosenoic acid (gadoleic acid), 13-docosenoic acid (erucic acid), 15-tetracosenoic acid (nervic acid), 9 , 12-octadecadienic (linoleic acid), and 9,12,15-octadecatrienoic acid (linolenic acid).
    [0018] Monounsaturated carboxylic acids are particularly preferred. The use of oleic acid and erucic acid is particularly advantageous in the process according to the invention. In these cases, pelargonic acid with high yields is obtained as saturated monocarboxylic acid.
    [0019] In the process according to the invention, reactors 1 and 2 used to carry out steps a), b) are continuous reactors, preferably connected to each other by means of a gear pump. The use of these continuous reactors allows a reduction in reaction volumes, facilitating the exchange of heat.
    [0020] In a preferred form of incorporation of the process, reactors 1 and 2 are of the CSTR type (Continuous Stirred Tank Reactor). Each of the CSTRs 1 and 2 can be advantageously replaced by several reactors of the same type, arranged in series, determining an increase in the surface / volume ratio (consequently, facilitating even more the heat exchange during the reaction) and a reduction in the volume of total reaction.
    [0021] In step b) continuous gas / liquid type reactors are advantageously used. Preferably, jet return reactors (CSTR Loop) are used, which promote contact between the oxidizing agent in the gas phase and the reaction mixture in the liquid phase.
    [0022] Both steps a), b) are preferably carried out without the addition of organic solvents.
    [0023] The intermediate product obtained as a reactor outlet (1) is fed continuously, preferably by a gear pump, to the reactor (2), where it is allowed to react with oxygen or an oxygen-containing compound, without the need for any preliminary purification treatment.
    [0024] In a preferred embodiment of the process, according to the invention, at the end of step a) the catalyst is not removed.
    [0025] In a preferred embodiment of the process, step b) is carried out without adding more water, in addition to that in which the catalyst is dissolved. Advantageously, during said step b) the ratio between the aqueous / organic phases is kept below 1: 3 by weight.
    Petition 870190057589, of 06/21/2019, p. 10/26
    5/14 [0026] The oxidizing substance used to carry out step a) of the process, according to the invention, is preferably selected from osmium tetroxide, permanganates, hydrogen peroxide, alkyl hydroperoxides and percarboxylic acids, as per example perfromic acid, peracetic acid or perbenzoic acid. More preferably, said oxidizing substance is an aqueous solution of hydrogen peroxide in concentrations between 30 and 80%, preferably between 40 and 70%, and even more preferably between 49 and 65%.
    [0027] In the continuous process, according to the present invention, it is possible to use hydrogen peroxide solutions even in very high concentrations. In fact, the continuous nature of the process allows the peroxide concentration to be kept constant during the reaction, avoiding dangerous accumulation phenomena that, on the contrary, can occur during batch-type reactions. Surprisingly, the applicant found that the concentration of H2O2 during the continuous process, according to the invention, is even lower than that observed during a batch process carried out with a lower initial concentration of hydrogen peroxide.
    [0028] The use of hydrogen peroxide solutions in high concentrations has the advantage of introducing smaller amounts of dilution water in the reaction mixture. [0029] The diol resulting from step a) and coming from reactor 1 is fed to reactor 2, where it is allowed to react - in step b) - with oxygen or with an oxygen-containing compound. The use of air is particularly advantageous. Oxygen-enriched air can also be used.
    [0030] The catalyst in step a) belongs to the group of transition elements. Advantageously, Fe, Mn, Mo, Nb, Os, Re, Ti, V, W, Zr and their acids, alkaline and complex salts are used as catalysts in homogeneous or heterogeneous phase, optionally in a supported or nano-structured form. The use of tungstic acid or phosphotungstic acid is particularly preferred. Said catalyst is present in amounts between 0.03% and 3% by moles, preferably between 0.05% and 1.8% by moles, and even more preferably between 0.06% and 1.5% by moles, in relation to the total moles of unsaturation. In a preferred embodiment of the process, the catalyst can be fed as a solution in a non-organic solvent.
    [0031] As regards the catalyst of step b), it belongs to the group of transition elements. Advantageously, Ce, Cr, Co, Cu, Mn, Mo, Re, Os, V and W and their acids, alkaline and complex salts are used as catalysts in homogeneous phase or
    Petition 870190057589, of 06/21/2019, p. 11/26
    6/14 heterogeneous, optionally in a supported or nano-structured form. The use of cobalt salts, such as acetate, chloride, sulfate, bromide and nitrate, used in amounts between 0.05% and 3% by moles, preferably between 0.1% and 2% by moles, and even more preferably between 0.3% and 1.5 mole%, based on the diol produced in step a), is particularly preferred. The use of cobalt acetate and cobalt chloride is particularly preferred.
    [0032] An inorganic acid can be added to the catalyst in step b). Examples of inorganic acid are phosphoric acid, sulfuric acid, hydrochloric acid, perchloric acid and mixtures thereof.
    [0033] The initiation phase of the continuous process, according to the invention, can be performed by adding a small amount of the intermediate compound obtained with step a), since the diols contained in it promote the activation of the reaction. Said intermediate compound can be added in an amount <5%, preferably <3%, by weight, with respect to the starting oil.
    [0034] Advantageously, during step a) of the process according to the invention, nitrogen or air is made to flow to remove a part of the water produced in the process. In this way, an excessive dilution of H2O2 is avoided. An alternative to the flow of these gases is evaporation under vacuum.
    The reaction temperature of step a) and step b) of the present process is advantageously between 45 and 95 ° C, preferably between 50 and 90 ° C.
    [0036] The reaction temperature of step a) is advantageously between 55 and 80 ° C.
    [0037] The reaction temperature of step b) is advantageously between 55 and 90 ° C, and even more advantageously between 60 and 70 ° C.
    [0038] Advantageously, to carry out both step a) and step b) of the present process, the average retention time in the reactor is between 2 and 8 hours.
    [0039] In a preferred embodiment of the process, the intermediate product resulting from step a) is fed directly into the reactor in which step b) is carried out. In fact, surprisingly, it was found that due to the feeding of the intermediate product directly into the oxidative cleavage reactor, this reaction time is reduced in relation to the batch reaction, because of the greater reactivity of this intermediate product. This increase in reactivity also determines a significant increase in reaction yield.
    [0040] The process according to the invention can be advantageously carried out under pressure
    Petition 870190057589, of 06/21/2019, p. 12/26
    7/14 atmospheric or, in any case, at moderate partial oxygen pressures, which are particularly advantageous in terms of industrial production.
    [0041] Step a) is preferably carried out at atmospheric pressure or under a light vacuum. [0042] Step b) is preferably carried out with air at a pressure <50 χ 10 5 Pa, preferably <25 χ 10 5 Pa. Advantageously, the aqueous phase of the product obtained as an output from step b) is separated from the organic phase .
    [0043] The separation of the organic phase can advantageously be carried out by continuous centrifugation, by means of a separating disc or using other established separation techniques.
    [0044] Optionally, a small amount of organic solvent can be added to improve the separation of the two phases.
    [0045] The aqueous phase contains the catalysts from steps a) and b), which can optionally be recovered and recycled as catalysts from step b). The organic phase is a transparent oil that consists of a mixture that substantially comprises saturated monocarboxylic acids and triglycerides containing saturated carboxylic acids with more than one acid function, saturated monocarboxylic acids present in the initial mixture and vicinal diol, formed during step a).
    [0046] In a preferred embodiment of the process, in which oil with a high oleic content is used as the starting material, the organic phase is substantially composed of pelargonic acid and triglycerides of azelaic, palmitic, stearic and dihydroxy-stearic acid.
    [0047] In another preferred form of incorporation of the process, in which oils with a high content of erucic acid are used as starting material, the organic phase is substantially composed of pelargonic acid and triglycerides of azelaic, brassic, palmitic, stearic, di- hydroxy-stearic and dihydroxy-behenic.
    [0048] In step c) of the process according to the invention, the organic phase obtained as a product of oxidative divination is fed to an apparatus (3) suitable for separating saturated monocarboxylic acids from triglycerides containing saturated carboxylic acids having more than one function carboxylic. The separation is advantageously carried out by distillation processes.
    [0049] Distillation processes that do not subject the mixture obtained in step b) to a high thermal stress, such as steam distillation, thin film distillation, downward film distillation, molecular distillation, are preferred. Advantageously, the
    Petition 870190057589, of 06/21/2019, p. 13/26
    8/14 mixture of evaporated monocarboxylic acids can be subjected to additional fractional distillation to obtain monocarboxylic acids with a higher degree of purity.
    [0050] In a preferred embodiment of the process, monocarboxylic acids are separated from triglycerides by distillation using thin film evaporators.
    [0051] Triglycerides containing saturated carboxylic acids with more than one acid function, present in the residual organic phase, are in turn hydrolyzed to form glycerol and saturated carboxylic acids in step d) of the process (reactor 4). The hydrolysis reaction can be carried out using different techniques, such as only with water, with strong acid ion exchange resins, or by catalysis of the reaction with enzymes.
    [0052] In the case of hydrolysis with water, the reaction occurs at temperatures between 150 and 350 ° C, preferably between 180 and 320 ° C, at the corresponding equilibrium vapor pressure, with or without the addition of a catalyst and with a proportion of water / oil, preferably between 0.5: 1 and 5: 1.
    [0053] Hydrolysis with strong acid ion exchange resins is carried out at a temperature of 100 to 140 ° C. Examples of suitable resins are those of the Amberlyst® and Amberlite® type (both produced by the company Rohm and Haas Co.).
    [0054] In the case of the reaction catalyzed by enzymes (lipases), it is advantageous to use lipases selected from the group comprising: Candida cylindracea, Candida antarctica, Pseudomonas sp., Swine pancreatic lipases, Candida rugosa, Geotrichum candidum, Aspergillus niger, Mucor miehei, Rhizopus arrhizus, Rhizopus delamar, Rhizopus niveus, Chromobacterium viscosum, Thermomyces lanuginosus, Penicillium cyclopium.
    [0055] In a preferred embodiment of the process, according to the invention, the hydrolysis reaction is carried out continuously using only water at 260 - 300 ° C, in a constant flow tubular reactor, preferably with a reaction time between 1 minute and 1 hour, preferably between 3 minutes and 30 minutes. The ratio between the aqueous / organic phases is between 1: 1 and 3: 1.
    [0056] After hydrolysis, an organic phase and an aqueous phase containing glycerol are obtained. Advantageously, the aqueous phase is separated and concentrated to recover the glycerol, using well-established separation techniques.
    [0057] The organic phase contains mainly saturated carboxylic acids with more than one acid function. Monocarboxylic acids, released after the hydrolysis reaction, diol and a reaction residue consisting of oligomers are also contained in the organic phase. [0058] Carboxylic acids are advantageously separated from the diol and the residue by
    Petition 870190057589, of 06/21/2019, p. 14/26
    9/14 distillation on a thin film evaporator or by molecular distillation.
    [0059] The diol and the residue thus separated can be used, for example, as biofuel, or recycled in the oxidative dividing reactor 2 (step b).
    [0060] The evaporated carboxylic acids are then advantageously subjected to column distillation to separate the low molecular weight monocarboxylic acids, thus purifying the saturated carboxylic acids with more than one acid function.
    [0061] In a preferred embodiment of the process, according to the invention, these carboxylic acids are further purified, from monocarboxylic acids with high molecular weight, by means of extraction in water.
    [0062] In a preferred embodiment of the process, according to the invention, these carboxylic acids are further purified by fractional crystallization, by means of a washing column (melted crystallization).
    [0063] Depending on the type of vegetable oils used as starting material, different saturated carboxylic acids with more than one acid function can be obtained, such as: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pyelic acid , submeric acid, azelaic acid, sebacic acid, undecandicarboxylic acid, dodecandicarboxylic acid, brassylic acid, tetradecandicarboxylic acid, pentadecandicarboxylic acid. In a preferred embodiment of the process, according to the invention, azelaic acid is mainly obtained from the oxidative dividing reaction of oils with a high erucic content.
    [0064] The process according to the invention will now be described according to the following non-limiting examples and figures 3 to 5, in which:
    - Fig. 3 is a diagram showing the concentration of hydrogen peroxide in the reaction mixture during step a) of Example 1 (continuous process according to the invention, with an initial H2O2 concentration of 60%);
    - Fig. 4 is a diagram showing the concentration over time of hydrogen peroxide, during step a) of Comparative Example 2 (batch process with an initial H2O2 concentration of 60%).
    - Fig. 5 is a diagram showing the concentration over time of hydrogen peroxide, during step a) of Comparative Example 3 (batch process with an initial H2O2 concentration of 50%).
    [0065] The concentration (weight / weight) of hydrogen peroxide in the reaction mixture can be determined by techniques already well known in the art. The concentration of
    Petition 870190057589, of 06/21/2019, p. 15/26
    10/14 hydrogen peroxide of Examples 1 to 3 is determined according to the method described in patent application WO 02/063285.
    EXAMPLE 1
    Step a) [0066] The following substances were fed continuously in a CSTR, with a working capacity of 100 liters, equipped with an agitator and with an adequate temperature regulation system:
    [0067] - sunflower oil with high oleic acid content (82% oleic, 10% linoleic, 3.5% stearic; flow rate of 12.5 kg / h);
    [0068] - 60% aqueous hydrogen peroxide solution (flow rate of 2.9 kg / h);
    [0069] - tungstic acid (H2WO4) (flow rate 38 g / h; 0.35% in moles, in relation to the moles of unsaturation).
    [0070] The reaction was carried out at a constant temperature of 62 ° C, under vacuum (absolute pressure from 0.10 to 0.20 χ 10 5 Pa) to evaporate the water fed with the hydrogen peroxide; the evaporated gas was collected and condensed (about 1.25 kg / h of water).
    [0071] FIG. 3 shows the general concentration of hydrogen peroxide during step a). [0072] As can be seen in fig. 3, the general concentration of hydrogen peroxide in the reactor remained constant at about 2 g / kg.
    [0073] The intermediate product containing vicinal diols was continuously discharged from the reactor and fed to step b) by means of a gear pump, adjusted to maintain a constant level in the reactor, with a flow rate of around 14 kg / h .
    Step b) [0074] Step b) was carried out in a jet return reactor with a working capacity of 100 liters, equipped with a 4 m 3 / h recirculation pump and a heat exchanger. The intermediate product from step a) was fed continuously with a flow rate of 14 kg / h, together with:
    [0075] - cobalt acetate (Co (CH3COOH) 2 · 4H2O, dissolved in an aqueous stream (flow rate 4 kg / h) partially from the recycling of the catalytic solution (about 2 kg / h);
    [0076] - compressed air (20 χ 10 5 Pa; flow rate from 13 to 16 kg / h).
    [0077] The air flow rate was adjusted to maintain a constant O2 content (about 10 to 12%) at the reactor outlet.
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    11/14 [0078] The reaction was carried out at 72 ° C and a pressure of 20 χ 10 5 Pae, keeping the reaction volume constant for 60 liters.
    [0079] The viscosity of the intermediate product from step a) at 72 ° C was 300 cP. The viscosity of the reaction mixture during step b) was approximately 35 cP, constant. The reaction started instantly; the reaction time was about 3 h 30 min.
    [0080] The reaction mixture from step b) was continuously discharged from the jet return reactor and fed in a liquid / liquid centrifuge, to separate the oil phase from the aqueous phase. Approximately 16 kg / h of oily product was obtained.
    Step c) [0081] The separated oil phase was dried and degassed, and then transferred to a thin film evaporator. The vapor phase produced in the evaporator essentially contained monocarboxylic acids, and was fractionated within a rectification column, in order to separate the pelargonic acid from the lighter monocarboxylic acids. The main component of the fraction of lighter monocarboxylic acids (by-products of the oxidative divination reaction) was octanoic acid.
    [0082] Approximately 4.5 kg / h of the vapor phase containing monocarboxylic acids (crude pelargonic acid), of which 4.2 kg / h were pelargonic acid with a titre of more than 99%, were obtained. The currents 4.5 kg / h of crude pelargonic acid contained approximately 0.13 kg / h of octanoic acid.
    [0083] An organic stream of approximately 10.3 kg / h, containing triglycerides with more than one carboxyl function as the main component, was extracted from the bottom of the evaporator.
    Step d) [0084] The organic stream was pumped at high pressure to a tubular hydrolysis reactor of the constant flow type, where it was mixed with a stream of preheated water. The total flow rate of the water / oil mixture was approximately 33 kg / h.
    [0085] The reactor operates in conditions of 300 ° C and 105 χ 10 5 Pa, with a reaction time of 20 min.
    [0086] The hydrolyzed reaction mixture was cooled to 2 to 5 ° C. A solid / liquid sludge was obtained, from which the aqueous phase containing glycerol was separated by a continuous solid / liquid filtration centrifuge.
    [0087] After drying and degassing, the organic phase, rich in azelaic acid, was
    Petition 870190057589, of 06/21/2019, p. 17/26
    12/14 transferred to a thin film evaporator. A liquid stream of 2.8 kg / h, consisting of a mixture of saturated products, was extracted from the bottom of the evaporator.
    [0088] The steam phase was fed into a rectification column, through which a current of 0.8 kg / h, consisting of a mixture of light monocarboxylic acids with a content of pelargonic acid of about 70% by weight, has been distilled. Approximately 6.6 kg / h of a mixture of dicarboxylic acids (mainly azelaic acid) with a content of heavy monocarboxylic acids of 10% to 12% (essentially palmitic acid and stearic acid) was obtained from the bottom of the rectification column.
    COMPARATIVE EXAMPLE 2 [0089] Step a) was carried out in batches, compared to the continuous process, with 60% H2O2.
    [0090] A batch process was carried out by placing the following substances in a 100 liter reactor:
    - 80 kg of high oleic sunflower oil (same composition as in Example 1);
    - 400 g of tungstic acid (0.7 mole%, compared to unsaturated fatty acid);
    - 4 kg of crude hydroxylated oil (intermediate product obtained at the end of step (a) from a previous reaction, the so-called activation reaction).
    [0091] The temperature was raised to 60 - 65 ° C, and 18.5 liters of 60% H2O2 solution were added in 4 h. During the reaction, a nitrogen flow was applied to distill a part of the process water and to avoid excessive dilution of H2O2.
    [0092] Once the addition of H2O2 was completed, the reaction was continued at 65 ° C for 2 h to obtain the intermediate product containing vicinal diols.
    [0093] FIG. 4 shows the hydrogen peroxide concentration over time during step a) of Comparative Example 2. As can be seen in fig. 4, the concentration of hydrogen peroxide in the reaction mixture varied, reaching peaks also twice as high as in Example 1 (fig. 3).
    [0094] In the continuous process according to Example 1 (fig. 3), the H2O2 concentration remained constant and at a significantly lower level, providing a safer process.
    COMPARATIVE EXAMPLE 3 [0095] Effect of H2O2 concentration in step a) performed in batches.
    [0096] Step a) of a batch process was performed according to the Example
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    13/14
    Comparative 2 with the same total amount of H2O2, but with a lower initial concentration.
    [0097] 22.4 liters of a 50% H2O2 solution were added to the reactor in 6 h. After the addition of H2O2 was completed, the reaction was continued at 65 ° C for 4 h. Due to the lower initial concentration of hydrogen peroxide, a longer reaction time was required compared to Comparative Example 2.
    [0098] FIG. 5 shows the concentration over time of hydrogen peroxide during step a) of Comparative Example 3. It can be noted that the concentration of hydrogen peroxide was considerably higher than the concentration of H2O2 in Example 1 (fig. 3) , although the initial concentration of H2O2 is lower.
    COMPARATIVE EXAMPLE 4 [0099] Step b) was carried out in batches, compared to the continuous process.
    [0100] The mixture formed at the end of reaction step (a) of Comparative Example 2 was discharged. 70 kg of this intermediate product were transferred to a jet return reactor.
    [0101] 19 kg of 1% aqueous cobalt acetate solution were added (0.4 mol%, based on the diol produced in step (a)). The reactor was placed at 72 ° C and a pressure of 22 χ 10 5 Pa with air, to perform step (b). An air flow was provided continuously to provide a sufficient amount of oxygen. After an induction period of 1 h 30 min the reaction started. The start of the reaction was highlighted by the increase in the temperature of the mixture, due to the exotherm of the oxidative divage. The batch reaction lasted 5 h.
    [0102] At the end of step b) the hot separation of the aqueous phase from the organic phase was carried out. The organic phase was then distilled by steam distillation to separate 22.6 kg of crude pelargonic acid, containing pelargonic acid and short chain free monocarboxylic acids (by-products of the oxidative divination reaction), of which about 2 kg were octanoic acid. The distillation residue (49.7 kg) consisted mainly of triglycerides of azelaic acid. The corresponding yield for the oxidative divination reaction (step
    b)) was about 70% with respect to the moles that could be obtained theoretically.
    [0103] The conversion achieved after 3 h 30 min of reaction from step b), in the continuous process according to Example 1, was greater than the final yield reached after 5 h of reaction in the batch process (Comparative Example 4) , as can be seen in the Table
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    14/14
    1:
    Table 1
    yield of oxidative cleavage reaction(mole% of the theoretical amount) Example 1 Comparative Example 4 pelargonic acid 79.2 69.9 azelaic acid 80.1 72.8
    [0104] The selectivity of the oxidative cleavage reaction in the continuous process, according to Example 1, was also greater than in the batch process, as can be seen in Table 2, showing that the by-product / product ratio was lower.
    Table 2
    by-product / product (% by weight / weight) Example 1 Comparative Example 4 octanoic acid / crude pelargonic acid 2.9 8.8
    Petition 870190057589, of 06/21/2019, p. 20/26
    权利要求:
    Claims (16)
    [1]
    1. Continuous oxidative dividing process of vegetable oils, containing triglycerides of unsaturated carboxylic acids, to obtain saturated carboxylic acids, characterized by the fact that it comprises the steps of:
    a) feed in a first continuous reactor at least one vegetable oil and an oxidation compound in the presence of a catalyst, capable of catalyzing the oxidation reaction of the olefinic double bond, to obtain an intermediate compound containing vicinal diols;
    b) feed in a second continuous reactor the said intermediate compound, oxygen or an oxygen-containing compound, and a catalyst capable of catalyzing the oxidation reaction of said diols to carboxylic groups, to obtain saturated monocarboxylic acids (i) and triglycerides containing monocarboxylic acids saturated with more than one acidic function (ii);
    c) transferring the product from step b) to an apparatus suitable for separating saturated monocarboxylic acids (i) from triglycerides having more than one acid function (ii); and
    d) hydrolyze said triglycerides (ii) in a third reactor, to obtain glycerol and saturated carboxylic acids with more than one acid function;
    where operations to feed the reagents and to remove products occur simultaneously during the entire duration of the process and the conditions of the process remain substantially unchanged at each stage of the process.
    [2]
    2. Continuous oxidative dividing process of vegetable oils, according to claim 1, characterized by the fact that vegetable oils belong to the group of oils with a high content of monounsaturated acids, such as soybean oil, olive oil , castor oil, sunflower oil, peanut oil, corn oil, palm oil, pine nut oil, Cuphea oil, Brassicaceae oils, and mixtures thereof.
    [3]
    3. Continuous oxidative divination process of vegetable oils, according to claim 2, characterized by the fact that the oil having a high content of monounsaturated acids is sunflower oil, Brassicaceae oil, and mixtures thereof.
    [4]
    4. Continuous oxidative dividing process of vegetable oils, according to claim 2, characterized by the fact that the unsaturated carboxylic acids of the triglycerides contained in the vegetable oil belong to the group consisting of
    Petition 870190057589, of 06/21/2019, p. 21/26
    2/3 9-tetradecenoic acid (myristoleic acid), 9-hexadecenoic acid (palmitoleic acid), 9-octadecenoic acid (oleic acid), 12-hydroxy-9-octadecenoic acid (ricinoleic acid), 9-eicosenoic acid (gadoleic acid ), 13-docosenoic acid (erucic acid), 15tetracosenoic acid (nervous acid), 9,12-octadecadienic acid (linoleic acid), and 9,12,15-octadecatrienoic acid (linolenic acid).
    [5]
    5. Continuous oxidative dividing process of vegetable oils, according to claim 4, characterized by the fact that the unsaturated carboxylic acid is a mono-unsaturated carboxylic acid, preferably 9-octadecenoic acid (oleic acid) or 13-docosanoic acid (erucic acid).
    [6]
    6. Continuous oxidative dividing process of vegetable oils, according to claim 1, characterized by the fact that the catalyst from step a) is used in a homogeneous or heterogeneous phase, optionally in a supported or nano-structured form, belonging to the group of transition elements and their acids, salts and complexes.
    [7]
    7. Continuous oxidative dividing process of vegetable oils, according to claim 6, characterized by the fact that the catalyst of step a) is selected from the group of tungsten and molybdenum derivatives or their mixtures, with said catalyst being present in an amount between 0.03% and 3% in moles, in relation to the total moles of unsaturation.
    [8]
    8. Continuous process of oxidative divination of vegetable oils, according to claim 1, characterized by the fact that the catalyst of step b) is used in a homogeneous or heterogeneous phase, optionally in a supported or nano-structured form, belonging to the group of transition elements and their acids, salts and complexes.
    [9]
    9. Continuous oxidative dividing process of vegetable oils, according to claim 8, characterized by the fact that the catalyst of step b) is selected from the group of cobalt and manganese derivatives, including acetates, chlorides, sulfates, nitrates and bromides , said catalyst being present in an amount between 0.05% and 3 mole%, in relation to the diol.
    [10]
    10. Continuous oxidative dividing process of vegetable oils, according to claim 1, characterized by the fact that the oxidation compound of step (a) is hydrogen peroxide present in aqueous solution, in concentrations between 30 and 80%, with the oxidation compound of step (b) being air.
    Petition 870190057589, of 06/21/2019, p. 22/26
    3/3
    [11]
    11. Continuous oxidative dividing process of vegetable oils, according to claim 1, characterized by the fact that step (a) is carried out at a pressure equal to or slightly below atmospheric pressure, while step (b) is carried out higher than atmospheric pressure.
    [12]
    12. Continuous oxidative dividing process of vegetable oils, according to claim 1, characterized by the fact that the reaction temperature of step a) and step b) is between 45 and 95 ° C.
    [13]
    13. Continuous oxidative dividing process of vegetable oils, according to claim 1, characterized by the fact that step c) is carried out by distillation, preferably by thin layer distillation.
    [14]
    14. Continuous oxidative divination process of vegetable oils, according to claim 1, characterized by the fact that step d) is performed using only water, acid ion exchange resins, or lipases.
    [15]
    15. Continuous oxidative dividing process of vegetable oils, according to claim 1, characterized by the fact that step d) is carried out with water at 260 - 300 ° C in a tubular reactor with constant flow.
    [16]
    16. Continuous oxidative dividing process of vegetable oils according to claims 14 or 15, characterized by the fact that saturated carboxylic acid having more than one acid function is purified by thin layer distillation, followed by distillation and water extraction .
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    法律状态:
    2019-01-08| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-03-12| B15K| Others concerning applications: alteration of classification|Free format text: AS CLASSIFICACOES ANTERIORES ERAM: C07C 51/245 , C07C 53/126 , C07C 67/31 , C07C 67/333 , C07C 69/67 , C11C 3/00 Ipc: C07C 51/09 (1968.09), C07C 51/16 (1968.09), C07C 5 |
    2019-04-24| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-09-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-10-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/12/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    ITMI2009A002360A|IT1397378B1|2009-12-30|2009-12-30|CONTINUOUS PROCESS OF OXIDATIVE DISPOSAL OF VEGETABLE OILS|
    PCT/EP2010/070843|WO2011080296A1|2009-12-30|2010-12-29|Continuous process of oxidative cleavage of vegetable oils|
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