RO118287B1 - Process for sinthesizing simultaneously 115 pentadecane dicarboxylic acid and cyclopentadecanone - Google Patents

Abstract

The invention relates to a process and installation for synthesizing simultaneously 1.15 pentadecane dicarboxylic acid and cyclopentadecanone, starting from cyclohexanone. The process consists in converting the cyclohexanone into cyclohexanone triperoxide by a peroxidation reaction, the resulting triperoxide cyclohexanone being further subjected to a continuous thermal decomposition of air catalytic oxidation, when the cyclopentadecanone and the 1.15 pentadecanone dicarboxylic acid result simultaneously. The installation comprises a peroxidation reactor, having some structural members allowing the peroxidation reaction at the industrial scale, a coil-type tubular isothermal reactor for decomposition, a continuous reactor for the air catalytic oxidation and a dehydrogenating reactor in a heterogenous catalysis.

Description

The invention relates to a process and an installation for simultaneous acid synthesis

1,15 pentadecandicarboxylic and cidopentadecanone, products used in the synthetic chemical industry.

It is known that cyclopentadecanone is a cyclic aldehyde with odorant qualities valorized in the perfume industry, being demanded on the market in appreciable quantities.

The 1,15 pentadecandicarboxylic acid is used in the plasticizers industry, as well as as a starting material for the synthesis of cidopentadecanone, a variant of the musk perfume (US 2717266).

Data on the synthesis of 1,15-pentadecandicarboxylic acid (GB 753222) are known in the laboratory, which describes the synthesis starting from the esters of U-acid:

ch ₂ -oh H (j = a COOH | I HCOH (CH ₂ ) | 3 (Chi) L3 | (ch ₂ ) ₁₃ COOR COOH I COOR (I) (Π) (ΠΙ)

wherein: R is an alkyl group of up to 4 carbon atoms, for example, 15,16-dihydroxyhexadecanoic acid ester, which in the presence of an oxidizing agent, such as lead tetraacetate in acetic acid solution, leads to an aldehyde-pentadecanoate II .

This aldehyde is oxidized with an alkaline solution of oxygenated water, which results in an alkaline salt of 1,15 pentadecandicarboxylic acid.

The alkaline salt decomposition and the III acid are obtained with a strong acid (hydrochloric, sulfuric, nitric).

No data is known about the industrial synthesis of this product.

The disadvantage of the presented procedure lies in the difficulty, starting from the hard to find raw materials (esters of the uric acid), it is strongly corrosive, working with strong acids.

There is no data in the literature on the process, as a sequence of chemical and physical phases that synthesize simultaneously, industrial cyclopentadecanone and acid

1.15 pentadecandicarboxylic acid.

A known laboratory procedure for the preparation of trimeric and dimeric cyclohexane peroxide is described in US 3925417 by P. Story and P. Busch.

To obtain a mixture of the mentioned peroxides, the authors left from a wet mixture 50 ... 300% of l-hydroperoxy-Γ hydroxycyclohexyl peroxide and 1-r-dihydroperoxidicyclohexyl peroxide, dissolved in hexane, which they cooled to - 15 ° C, after which they added, under strong stirring, a strong acid. The oily product resulting after washing and neutralization contains trimeric and dimeric cyclohexane peroxide.

The intermediate peroxides used were synthesized separately by oxidation of cyclohexaneone with oxygenated water, in the presence of strong acid (hydrochloric or sulfuric).

In the aforementioned patent, in order to avoid the danger of explosion, the two-step reaction for the synthesis of cyclohexanone di- and triperoxide was used.

The disadvantage of the peroxidation reaction in one phase is that the reaction can become violent, difficult to control and dangerous on an industrial scale.

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It is known for the decomposition phase of cyclohexane di- and triperoxides (US 3528898) stages consisting of heating to temperatures above 100 ° C by radiation with 50 U.V. radii. of methanol solutions of cyclohexane di- and triperoxides. The application is for the laboratory phase. Depending on the reaction time, the ratio of peroxides in the alkanine solution subjected to decomposition yields different percentages of cyclopentadecane and dihydroambrettolide in the reaction mass.

The patent (US 3584067) complements the previous patent, specifying that decomposition 55 can also be done by heating at temperatures above 100 ° C, without making other specifications regarding temperature and pressure. He notes, however, that occasionally heated peroxides explode with considerable violence and recommends the use of a small amount of solvent, benzene or methanol, as a carrier of peroxides in the decomposition process, as a method of avoiding explosions. 60

The experiment is exemplified by the fact that a solution of 12 g of cyclohexanone triperoxide in 4.51 methanol was irradiated with ultraviolet rays for 3 hours, resulting in decomposition and removal of the solvent, 15% cyclopentadecane, 25% lactone. C16 (16-hexadecanolactone).

About 20% of the triperoxide reagent was recovered as cyclohexanonone. 65

If the working temperature at decomposition reaches 150 ° C, 16% cyclopentadecane and less than 1% 16-hexadecanolactone break down from the above solution. The amount of triperoxide recovered as cyclohexane decreased to 15%.

No data are known about the accomplishment of these processes on an industrial scale, the specialized literature refers exclusively to laboratory experiments.

Cidopentadecane obtained from the decomposition reaction of the peroxide mentioned is the intermediate in the synthesis of cyclopentadecanone and 1,15 pentadecandicarboxylic acid.

According to a process described in US 3584067, cyclopentadecane may be treated with chlorine or bromine in the presence of light. Cyclopentadecanil chloride or cidopenta bromide - 75 decays thus obtained are then hydrolyzed in the presence of weak alkali to cidopentadecanol, which then, after oxidation with chrome, produces cyclopentadecanone.

There are no literature data on the oxidation of cyclopentadecane with air in order to obtain oxygenated products of cyclopentadecane, such as cyclopentadecanone, cyclopentadecanol and 1,15 pentadecandicarboxylic acid. 80

A process for dehydrogenation of cyclododecanol to cyclododecanon in liquid phase is known in the presence of copper catalyst on adivate alumina at temperatures between 160 and 230 ° C (DE 1248650).

No data are known about the dehydrogenation of cyclopentadecanol to cyclopentadecanone on an industrial reactor. 85

These being the known data regarding the methods of obtaining the acid »»

1.15 pentadecandicarboxylic and cyclopentadecanone, products used in the perfume industry, the present invention aims to find a technical solution for the simultaneous synthesis of said products starting from cyclohexane as a starting material.

The technical problem, which is solved by the invention, consists in the simultaneous induction of 90-trial, pentadecandicarboxylic acid and cyclopentadecanone, taking into account the technical problems of each phase, respectively:

- performing the peroxidation operation of cyclohexanone to cyclohexane triperoxide in a single phase, in an industrial reactor, in safe conditions by accurately taking the heat of reaction correlated with a correct reaction time established by a careful dosing 95 a reactants;

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- performing the oxidation operation of cyclohexanone by adding acetic acid to the reaction medium in the reactor, the acid being at the same time a solvent for intermediate peroxides;

- the solvent used for the synthesis phase of cyclohexane di- and triperoxides at industrial level is a mixture of higher alkanes, the resulting alkane solution being safe to be decomposed in order to obtain cyclopentadecane, the intermediate in the synthesis of cyclopentadecanoneic and pentane 1,15;

- establishing the optimal parameters (temperature, pressure, reaction time) for the process at the industrial level, so that it proceeds in complete safety.

The process for the simultaneous synthesis of cyclopentadecanone and 1,15 pentadecandicarboxylic acid, according to the invention, consists of the following steps: the cyclohexanone is subjected to the peroxidation reaction with 50% oxygenated water in the presence of glacial acetic acid and concentrated hydrochloric acid, in the presence of an alkane solvent. from a mixture of dean, undecane, dodecane in equal parts, at a temperature between 10 ... 35 ° C resulting in cyclohexane triperoxide which is then subjected to a continuous thermal decomposition in alkaline solution of dean, undecane and dodecane, according to of 4: 1 ... 8: 1 relative to the peroxide, at a temperature of 220 ... 240 ° C and a pressure of 5 ... 5.5 bar, followed by the catalytic oxidation by air of the cyclopentadecane by partial oxidation in the presence of 5% boric acid, at a temperature of

165 ... 170 ° C where cyclopentadecanol and 1,15 pentadecandicarboxylic acid are simultaneously produced, separation after which cyclopentadecanol is subjected to catalytic dehydrogenation in heterogeneous catalysis with copper chromite, 2% from cyclopentadecanol, at a temperature of 210 ° C and pressure , under continuous stirring, for 8 hours.

The installation for applying the process for the simultaneous synthesis of cyclopentadecanone and 1,15 pentadecandicarboxylic acid is formed by a reactor 6 of 10 m ³ for the peroxidation reaction having a surface / volume ratio of 2/1 and a heat output capacity of 4 kcal / m ² .h for 11 reaction masses, with a heat transfer coefficient of 250 kcal / m ² . h ° C, a reactor 19, serpentine tubular isothermal for the decomposition of cyclohexane triperoxide, provided with static devices for creating turbulence at linear speeds of 0.16 ... 0.20 m / s and contact times of 20 ... 25 min, catalytic oxidation reactor 25 with air for oxidation of cyclopentadecane, with an air flow of

12.5 m ³ / h (mol cyclopentadecane, batch dehydrogenation reactor 35 of cyclopentadecanol in heterogeneous catalysis.

The advantages of the process, according to the invention, consist in carrying out on an industrial scale the process of peroxidation, of decomposition of peroxides in order to obtain pentadecane and other macrocycles. A process for industrially obtaining 1,15 pentadecandicarboxylic acid, starting from cyclopentadecane, is made according to the invention.

The proposed installation for the synthesis but also for the decomposition of peroxides, which present certain explosion hazards, eliminates these shortcomings and leads to obtaining valuable products.

The advantages of the process, according to the invention, consist in:

- performing for the first time an industrial process of simultaneous synthesis of cyclopentadecanone, an important semi-manufactured product in perfumery and of 1,15 pentadecandicarboxylic acid, semi-manufactured for the synthesis of cyclopentadecanone. This process is a logical succession of chemical and physical phases, the realization of each phase bringing original solutions to achieve the proposed purpose.

- thus, the process of obtaining the cyclohexanone triperoxide was carried out in a single phase compared to the known state of the art, in an industrial reactor, by a strict ordering of the chemicals, depending on the possibilities of heat transfer. A dilution was performed

R0118287 Β1 with a new solvent, in an appropriate ratio, which would allow advantages in the next phase of decomposition of peroxides, which avoids the danger of explosion at this phase.

- Regarding the decomposition of the cidohexanone triperoxide, the pilot experiments suggested optimum decomposition times, the shape of the industrial reactor, the necessary linear speeds, the solution found, the tubular reactor with the necessary annexes ensuring the safe decomposition of the triperoxide. 150

The shape of the reactor is crucial in avoiding the secondary reactions of forming resins and increasing in yields of useful products, cyclopentadecane and dihydroambrettolide.

- The oxidation of cyclopentadecane to cyclopentadecanol and 1,15 pentadecandicarboxylic acid with air, as a process, is not known at the present state of the art. The reaction conditions, namely temperature, pressure, air flow, stopping the reaction at a certain phase of 155 oxidation in order not to destroy cyclopentadecane in secondary reactions, were experimentally and industrially transposed.

- for the dehydrogenation of ddopentadecanol to ddopentadecanona, another chromium and copper catalyst was used, compared to the known state of the art, compared to the copper catalyst on activated aluminum support. The latter catalyst was also used for the dehydrogenation of cyclododecanol.

The process according to the invention consists in the peroxidation reaction of cidohexanone as a starting material and obtaining a cidohexanonone triperoxide, followed by its thermal decomposition and obtaining the cidopentadecane which is then oxidized with air, when the 1,15-pentadecandicarboxyl addad, of the acid mixture, and cyclopentadecanol is dehydrogenated to cyclopentadecanone.

The industrial realization of the reaction to obtain the cidohexanone triperoxide in a single phase requires a precise correlation of the reactant dosage, in the oxygen water tank, with the reaction heat taking over, so that the temperature inside the reactor in the nest at one point does not exceed 40 ° C. The peroxidation reaction of cidohexanone being strongly exo- 170 thermal, escaping under the control of the temperature can lead to explosion.

For the industrial reaction to be carried out safely, an appropriate volume reactor was chosen for the synthesis of a batch of cidohexane triperoxide from an acid-resistant material of 10 m ³ , with the surface / volume ratio of 2/1. , with shaker type propeller, with the mantle, which for a coefficient of thermal transfer of 250 kcal / m ² h ° C, assures the dosage in 175 for 6 ha of oxygenated water.

The heat output capacity under these conditions is 4kcal / l.h, a reaction mass that ensures that the working temperature is maintained at 20 ... 22 ° C (fig. 1).

The calculated amount of cidohexanonone is introduced into the reactor.

The introduction of a suitable solvent, a medium alkane solvent consisting of dean, 180-can and dodecane in equal parts, in an amount of 4: 1 to 8: 1 relative to the kidohexanone introduced into the reactor, will provide the necessary dilution of the formed triperoxide, facilitating the thermal decomposition phase of the triperoxide.

The introduction of glacial acetic acid at the beginning, prior to the dosing of oxygenated water, will provide better conditions for peroxidation, creating the peracetic adduct, which dissolves 185 in the excess of acetic acid introduced.

Under strong stirring (120 rpm), the calculated amount of 50% oxygenated water is introduced in 6 hours, the operation of the temperature control system in the reactor being monitored. After the introduction of a strong acid, hydrochloric acid 32% in relation to 10 ... 15% compared to the basic raw material, the reaction is continued for another 3 hours for finalization. 190

It is neutralized, the reaction mass is washed, the chemically impure water is drained, obtaining an alkaline solution of 14 ... 16% cyclohexane triperoxide and cyclohexane diperoxide.

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The alkanine solution of di- and triperoxide is stored, then drained of water, subjected to a phase following thermal decomposition.

Considering the extreme danger of this phase, experiments were conducted on decomposition machines of pilot size, establishing the optimal non-hazardous parameters when decomposing.

One can imagine heat exchanger type reactors for thermal decompression. These experienced, however, required high reaction times, with local overheating of the triperoxidic solution, thus with danger of explosion.

The yields on useful products were low, there were important deposits of polymers.

Much emphasis has been placed on reducing reaction times, on their more precise control, on reducing working temperature and pressure.

The use of film evaporator reactors has improved yields in macrocyclic products, reducing polyester resins obtained as residues.

The disadvantage of these machines is that they are expensive, they have moving elements, they are a little unreliable under difficult working conditions.

Working conditions such as temperature, pressure, type of solvent chosen, diluent / peroxide ratio, reaction time, are decisive for the safety of the decomposition process, for its economics.

The solvent chosen in the synthesis phase of the triperoxide, the mixture in equal parts of the decane, undecane, dodecane, in the mentioned ratio, ensures the optimal dilution of the peroxides formed in the order of 4: 1 to 8: 1, so that the decomposition can take place under conditions non-hazardous and economical in the proposed industrial reactor.

For the industrial realization of the decomposition phase of cyclohexane di- and triperoxide, the present invention proposes a serpentine tubular reactor, usable for reactions at moderate temperatures of 200 ... 300 ° C for liquid-liquid, liquid-gas reactions.

In such reactors, the reactions are conducted mainly isothermal, the heat transfer is made through the walls of the reaction pipe.

The thermal decomposition reaction of the peroxides being endothermic, the heat requirement is provided with heat oil heated in the reactor sheath with an electrical resistance.

On the pilot installation, the dynamic behavior of the reactor was studied, namely the conditions for initiating the reaction, for defusing the decomposition reaction.

This study allows the continuous operation of this synthesis phase.

Feeding of the cyclohexane triperoxide solution is done at the bottom of the coil, the reaction products coming out at the top.

Concomitant achievement of a low contact time to precede the formation of the resins, but at the same time and the time required for the thermal transfer required for the endothermic reaction, required numerous experiments to determine the optimum linear velocity at the apparent apparent volume velocity (considering and static devices used to create turbulence in pipes).

The best results were obtained at linear speeds between 0.16 and 0.20 m / s, corresponding to contact times of 25, respectively, 20 min.

For the achievement of the scope, the optimal combination of some constructive elements was sought, so that the reactor is equipped with a phase separator vessel, coolant for the decomposition products in the form of gases, a drop separator for the entrained products (fig. 2).

The working temperature is between 190 and 260 ° C and the pressure is between 4 and 6 bar.

Following the decomposition of di- and triperoxides an alkanine solution is obtained, mainly of cyclopentadecane of about 17% and dihydroambrettolid of 12.5%.

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After separation and recirculation of the alkane solvent, the above products are separated by distillation.

Dihydroambrettolide is used as such in the perfume industry, and cyclopentad-245 can is the semi-manufactured product for the synthesis of 1,15 penta-decandicarboxylic acid and cyclopentadecanone in the following phases.

The invention proposes the synthesis of 1,15 pentadecandicarboxylic acid starting from cyclopentadecane, by oxidation with air.

The required amount of 99% cyclopentadecane is introduced into the reactor. This 250 is obtained at this concentration from the crude semi-finished product obtained in the preceding phase after purification by recrystallizing cyclopentadecane dissolved in methanol at 50 ° C, cooled to 20 ° C and then filtered.

The oxidation reaction is catalytic, it is carried out in the presence of boric acid, introduced in an amount of 5% by weight. 255, depending on how the oxidation process is conducted, results in a significant amount of cyclopentadecanol. The reaction is carried out voluntarily with a higher air flow to obtain the mentioned acid, ie with 12 ... 15 m ³ air / kmol.h pentadecane.

The oxidation process of cyclopentadecane is carried out in a specially designed batch reactor, provided with heating, coil cooling, the blanket, optimally associated with the construction elements that allow the introduction of air, the emptying of the waste air and the products obtained.

The reaction is conducted at 165 ... 170 ° C, at a pressure slightly above the atmospheric pressure, for 8 hours under continuous stirring (fig. 3).

The reaction stops at a 40% conversion of cyclopentadecane, at which time 265 yield of 1.15 pentadecandicarboxylic acid is 11.65%. A significant percentage of cyclopentadecanol as well as untransformed cyclopentadecane is also found in the reaction mass.

The temperature inside the reactor is reduced to 80 ... 90 ° C, followed by hydrolysis of borate esters from the reactor with a solution of 20% NaOH. 270

From the reaction mass after washing, 1.15 pentadecandicarboxylic acid is separated by distillation, the non-transformed cyclopentadecane which is recycled to oxidation and the semi-manufactured cidopentadecanol for the next phase, that of obtaining cyclopentadecanone.

Cyclopentadecanol is introduced into an electrically heated mantle reactor, with stirring. The dehydrogenation reaction is endothermic, the heat of reaction being 75.4 kj / mol. In 275 the reactor introduces copper chromite as catalyst, quantitative 2% of the reaction mass.

The reaction occurs under stirring (see example), at atmospheric pressure and at a temperature of 230 ... 245 ° C.

The end of the reaction is determined analytically at the total conversion of cyclopentadecanol to cyclopentadecanone. 280

The reaction mass obtained is vacuum distilled at 3 ... 4 mm Hg, remaining at 170 ° C, when a cyclopentadecane of 98.5% is obtained.

The following is an example of an embodiment of the invention, in connection with FIGS.

- Fig. 1, reactor for the synthesis of cyclohexanone 285 dimeric and trimeric peroxides (phase 1);

- Fig. 2, a reactor for the decomposition of the dimeric and trimeric peroxides of cyclohexane (phase 2);

- Fig. 3, reactor for obtaining 1,15 pentadecandicarboxylic acid and cyclopentadecanone (phase 3). 290

Prepare the required quantities of chemicals in the dosing vessels.

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750 kg of cyclohexane (flow b) is dispensed from the vessel 2 into the enamelled reactor with shaking and cooling in the mantle.

Stirring is started and 2013 kg of glacial acetic acid is loaded from vessel 1 (flow a).

Adjust the reactor temperature to 20 ° C.

From vessel 5 (flow e) it is dosed for 6 h, the amount of 520 kg oxygenated water 50% under stirring and continuous cooling to maintain the temperature of 20 ° C. Add the alkane solvent (equal mixture of dean, undecane and dodecane) in a quantity of 2357 kg from vessel 3 (flow c).

The solvation proceeds without thermal effect.

Immediately from vessel 4, the amount of 107 kg of 32% hydrochloric acid (flow d) is introduced into the reactor.

The reaction mass is maintained under stirring for approximately 9 h, during which time the total conversion of cyclohexanone into cyclic peroxides is required.

Laboratory analysis should indicate the absence of cyclohexanone. at this point the agitation is stopped, the resulting acid waters decanted, which flows into vessel 9 (flow f) in the amount of 2518 kg. These waters are subsequently processed for acetic acid recovery.

The agitation of the reaction mass is resumed and an additional 1825 kg of alkane solvent (flow c) is introduced from vessel 3, then 1913 kg of softened water is introduced to wash for 10 minutes the reaction mass.

Stop stirring, decant and drain the washing water in vessel 7 (flow h) to send them to the chemical treatment plant.

Finally, the reaction mass is flowing from the reactor 6 into the semi-finished product tank 8 (flow I).

The resulting mass of reaction mass is 5081 kg.

The trimeric peroxide content of cyclohexane is 13.74% (Table 1) and the dimeric peroxide is 3.43%.

In this form the solution will be sent to the pyrolysis reactor 19, continuously, with a flow rate of about 450 l / min (for about 12.5 h) to achieve a linear speed of 0.17 m / s and a contact time of approximately 25 min.

Initially the necessary preparations are made. Start the feed dosing pump 15, fill the reactor coil 19 with alkane solvent from the vessel 12.

The level is also made in the phase separator (pulse damper) no. 21.

Fill the reactor shell with the thermal oil by means of the pump 14 in the vessel 10. Connect the resistors 25 and raise the reactor temperature to 200 ° C, which is the starting temperature of the thermal decomposition reaction.

At this point the feed of the triperoxide alkane solution from tank 8 with pump 15 (flow j) starts, with a flow rate of 357 kg / h.

The temperature in the reactor is gradually increased to 240 ° C with the help of heat resistors.

The working pressure of the reactor is set at 5.5 bar. In this way, the best conditions for the safe thermal decomposition of trimeric peroxide are obtained.

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Solvent 5.5 bar

A

II / ^c (CHi) is

II o

+ COI

335

340

345

Trimeric cyclohexanone peroxide

ChHîoOî

DilactonaCn

350

Solvent 5.5 bar

+ 2CCh

355

360

Trimeric cyclohexanone peroxide

CieH3oQj

Dihydroambrettolide $ 65

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Trimeric cyclohexanone peroxide

C17H30O2 Cyclopentadecan

240 ° C (CH ₂ ) i5 + nCOj Sterile polymers Solvent 5.5 bar

Trimeric cyclohexanone peroxide

Table 1

The quantities and concentrations of the flows that are part of fig. 1 (kg / sow)

Flow component of b c d e f 9 h 1 k (J /% kg /% kg /% KQ /% kg /% kg /% kg /% kg /% kg /% Qfacial acetic acid 2013/100 Cicohexanona 750/100 Alkane solvent 4209/100 4209 / 82.8 Hydrochloric acid 38% 107/100 Oxygenated water 50% 520/100 Acidic water for recovery 2518/100 Splashing water 1913/100 Exhausted washing water 1913/100 Trimeric peroxide 698 / 13.7 Dimeric peroxide 174 / 3.4 Total 2013/100 750/100 4209/100 107/100 520/100 2518/100 1913/100 1913/100 5081/100

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Table 2 415

The quantities and concentrations of the flows that are part of fig.2

Flow component and k 1 m n a KQ / h /% kg / h /% kg / h /% kq / h /% ¹ kg / h /% kg / h /% Alkane solvent 295.7 / 82.8 4.36 / 33.5 4.36 / 100 295.7 / 84.9 Trimeric peroxide 49 / 13.7 Dimeric peroxide 12.2 / 3.4 Cicopentadecan 8.1 / 2.28 8.1 / 2.34 Dihidroambrettolida 8.1 / 1.71 6.1 / 1.75 Carbon dioxide 8.6 / 2.42 8.6 / 66.4 8.6 / 100 Dilactone C17 2.32 / 0.65 2.32 / 0.66 Cicopentadecan 2 / 0.57 2 / 0.58 Dilactone C11 1.53 / 0.43 1.6 / 0.44 Polymer esters 32.4 / 9.1 32.4 / 9.33 Total 357/100 357/100 13/100 8.64 / 100 4.36 / 100 348.367100

Table 3

The quantities in kg / batch according to the flows in fig.3

Flow component P S t 8 f * u V 2 2* X V 0 , * 9- kg. kg. KFL · ko. kg. kg. ko. . ko. * 9 ko- KFL ko. Fresh cyclopentadecane 11S.B Recycled cicooentadacan 270.2 Acid bort 19.3 Air 236. " Cidopentadecanol 85 Waste air and alas 217.6 / 2.4 Used acidic acid 19.3 Acid oontadecandicarboxWc 45 Razidki dMNaro 2.4 Chromium from copper 1.8 Used copper chromite Cidopenladecanona 82.46 Hydrogen in the atmosphere 0.75 Razldlu to the burned 1.0 Total 386 19.3 236.8 85 220 19.3 45 2.4 1.8 1.8 82.45 0.75 1.8

435

440

445 in the undesirable case, when the dimeric peroxide (3.42% in feed), however, accompanies the trimeric one, by decomposition it gives rise to cyclododecane and undecanlactone.

The products resulting from the decomposition of the dimeric, trimeric peroxides, dissolved in 450 solvents (flow k), reach the phase separator 21, where an amount of 13 kg / h, consisting of a mixture of carbon dioxide and entrained solvent (flow I), is separated, it passes through the air cooler 20 and reaches the drop separator 18.

From here, the entrained solvent (flow n), condenses with a flow rate of 4.36 kg / h, is recovered in the phase separator 21, and the carbon dioxide (flow m) with a flow rate of 8.64 kg / h, 455 is released into the atmosphere by the flame arrestor 8.

The liquid product from the phase separator 21 (flow o), after cooling to 60 ° C in the refrigerator 22 with a flow rate of 348.36 kg / h, is continuously collected in the pyrolysis product solution tank 23.

After completion of the peroxide solution batch processing, reduce the reactor temperature to 460 and displace the reaction mass with solvent.

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Deposits of polymers inside the reactor coil 19 worsen the heat exchange, a phenomenon that is highlighted by the decrease of the yield in useful products (chromatographic analysis), as well as by the increase of the electricity consumption.

In this situation (increasing the electricity consumption by 25% and increasing the pressure difference on the reactor coil 19 by 15%), the reactor coil was washed with a 5% NaOH solution at 80 ° C. To this end, cool the solvent in the reactor coil to 80 ° C (by uncoupling the resistors 25 and recirculating the thermal oil from the reactor casing with the pump 14 through the cooler 16).

At 80 ° C the solvent is removed from the nitrogen coil and the serpentine is washed with 5% NaOH solution for 10 hours, with a flow rate of 0.5 m ³ / h by recirculation from the tank 24.

The waste water, at the end of the process, does not pose problems and is sent to the treatment plant chemically impure water.

The pyrolysis product in tank 23 is subjected to a process of separation by distillation, after which the reused alkane solvent is recovered.

Also useful products are obtained such as: dihydroambrettolide used in the perfume industry, as well as cyclopentadecane, the starting material for obtaining 1,15 pentadecandicarboxylic acid. This is obtained by the oxidation of cyclopentadecane.

From the reservoir 11, 25,115.8 kg of freshly decyclopentadecane is introduced into the oxidation reactor, and from the reservoir 28, 270.2 kg of recycled cyclopentadecane (flow p) are introduced and heating of the reactor 25 with steam introduced into the inner coil begins.

The condenser guard 26 and the phase separator 27. The 19.3 kg boric acid is stirred (flow r).

The temperature of the reaction mass is raised to 150 ° C and under stirring the air is introduced (flow s) with an initial flow rate of 10 ... 15 m ³ / h.

Increase the reactor temperature to 165 ° C, setting the air flow to 22 ... 25 m ³ / h. The oxidation is continued at the proscribed parameters, approximately 8 h, samples are taken from the reaction mass and the oxidation is stopped at h when the conversion of cyclopentadecane reaches 40% and the yield in 1,15 pentadecandicarboxylic acid reaches 11 ... 12%.

During this period, the waste air in the atmosphere is removed (flow and).

Stop the heating and proceed to cooling the reaction mass by inserting the cold agent into the reactor casing.

When the temperature reaches 95 ° C, the cooling is stopped and the neutralization is washed, the reaction mass washed with a 20% NaOH solution, respectively with softened water.

Neutralizing and washing waters are directed to the chemical treatment plant.

The reaction mass of the reactor 25 is hot transferred to the separation column 30, which has 20 real plates, in order to separate the products.

The column works in a residual vacuum of 5 ... 6 mm Hg, with a reflux of 3 / I, where at the top is collected in turn cyclopentadecane, cyclopentadecanol mixed with acid

1.15 pentadecandicarboxylic, which is subsequently separated into the two products.

The temperature at the top of the column increases from 144 to 180 ° C while in the blaze the temperature increases from 154 to 235 ° C.

Finally, 270.2 kg 98% recyclable cyclopentadecane (p flow), 85 kg 98% cyclopentadecanol is stored in the heated vessel 31 (t flow) and 45 kg of acid

1.15 98% pentadecandicarboxylic acid (flow u) which is stored in the heated vessel 29, from which it is packaged.

The residue from the column base, in the amount of 2.4 kg (flow v), is stored in the vessel 32 from where it is sent to burn.

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Cyclopentadecanol collected in vessel 31 is fed into the stirring reactor and 510 electric heater in casing 35, in which 1.8 kg of copper chromite (flux z) was previously introduced.

Turn on the heating and stirring and bring the temperature of the reaction mass to

230 ... 235 ° C. Adjust the temperature to this value.

The resulting hydrogen is released into the atmosphere after the gas passes through the condenser 515 on guard 33 and separates the liquid into the drop separator 34. The separated liquid is returned to the reactor 35.

After 2 hours of reaction the stirring stops, the sample is taken from the reaction mass. The reaction is considered complete when the product has 98 ... 98.5% cyclopentadecane.

The yield of cyclopentadecanone is 97%. 520

Reduce the temperature of the reaction mass to 170 ° C. Vacuum the reactor 35, through the vessel 37, through the cooler 36.

A 5 mm Hg vacuum is left on the system and the cyclopentadecanone is collected in vessel 37.

After the distillation is completed, cool the reactor by canceling the heating to 525 65 ... 70 ° C and drain the catalyst slurry into vessel 38 (flow q).

The product from vessel 37, cyclopentadecanone is passed on a solver for conversion into scales and packaged in bags.

The melting point of the product is 59 ... 61 ° C.

Claims (2)

530 Claims 1. The process for the simultaneous synthesis of cyclopentadecanone and 1,15 pentadecandicarboxylic acid, characterized in that the cyclohexanone is subjected to the peroxidation reaction with 50% oxygenated water in the presence of glacial acetic acid and concentrated hydrochloric acid, in the presence of 535 of alkane solvent consisting of a mixture of dean, undecane, dodecane in equal parts at a temperature between 10 and 35 ° C, resulting in cyclohexane triperoxide which is then subjected to a continuous thermal decomposition in alkaline solution of dean, undecane and dodecane, in a ratio of 4: 1 ... 8: 1 to the peroxide, at a temperature of 220 ... 240 ° C and a pressure of 5 ... 5,5 bar, followed by the catalytic oxidation by air of cyclopentadecane by 540 partial oxidation in the presence of 5% boric acid, at a temperature of 165 ... 170 ° C, where cyclopentadecanol and 1,15 pentadecandicarboxylic acid are simultaneously produced, after which cyclopentadecanol is subjected to dehydrogenation as tertiary in heterogeneous catalysis with copper chromite 2% compared to cyclopentadecanol, at a temperature of 210 ° C and pressure, under continuous stirring for 8 hours. 545 2. The plant for applying the process as defined in claim 1, characterized in that it is formed by a reactor (6) of 10 m ³ for the peroxidation reaction having a surface / volume ratio of 2/1 and a capacity of heat discharge. of 4 kcal / m ² .h for 11 reaction masses, with a heat transfer coefficient of 250 kcal / m ² . h ° C, a serpentine tubular isothermal reactor (19) for the decomposition of cyclohexane triperoxide, provided with 550 static devices for creating turbulence at linear speeds of 0.16 ... 0.20 m / s and contact times of 20. 25 min., Catalytic air oxidation reactor (25) for cyclopentadecane oxidation, with an air flow of 12.5 m ³ / h mol cyclopentadecane, discontinuous reactor (35) for dehydrogenation of cyclopentadecanol in heterogeneous catalysis.