Method of producing polymethylols

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of purifying raw polymethylol, which contains polymethylol of formula (I), as well as a hydroxy acid of formula (IV). According to the present method, raw polymethylol is obtained in a multistep process, wherein at step (a) alkanals react via aldol condensation with formaldehyde in the presence of tertiary amines as catalyst to form methylol alkanals of formula (II). Further, at step (b), the reaction mixture obtained at step (a) is divided by distillation into a still residue primarily containing compounds of formula (II) and a head stream containing low-boiling components. The stream coming from the bottom from step (b) is hydrogenated at step (c). The stream coming from step (c) is then distilled at step (d). Low-boiling components from the stream coming from step (c) are separated, and purification is carried out in a distillation column, wherein the bottom of the distillation column is connected to at least one evaporator with a short dwell time. In formulae , , R in each separate case independently denotes a methylol group or an alkyl group with 1-22 carbon atoms or an aryl group or an arylalkyl group with 6-22 carbon atoms.

EFFECT: method reduces losses in output of polymethylol.

12 cl, 5 ex

 

The invention relates to a method of distillation of crude Polimetall generated when receiving polietileno from alcanada and formaldehyde. In addition, the present invention relates to a composition containing Polymetal and from 1 to 10000 parts by weight per million complex polietilenovogo ether hydroxyacids, and to its use.

Polimetall, such as neopentylglycol and trimethylolpropane, find application in the field of polymers to obtain varnishes, coatings, polyurethanes and polyesters. In industrial scale Polimetall is mainly obtained by the method Cannizzaro. To obtain trimethylolpropane this way spend the interaction of n-butyric aldehyde with an excess of formaldehyde in the presence of inorganic bases. This produces simultaneously an equivalent amount of inorganic formate as a by-product. A branch of this salt from trimethylolpropane is a complex task, which requires additional effort. In addition, it is necessary to carry out the separation and purification of inorganic salts, if it must be disposed of. Otherwise, the formation of this side product leads to the loss of stoichiometric quantities of used sodium hydroxide and formaldehyde. In addition, when carrying out this is th inorganic cannizzaro reaction outputs based on n-butyric aldehyde is not satisfactory, because in the process of reaction formed high-boiling compounds which are not implemented.

Issues that were identified for the case of receipt of trimethylolpropane, arise and upon receipt of such other polietileno as trimethylated (n-propanole and formaldehyde), or trimethylbutane (n-pentanal and formaldehyde), or neopentylglycol (samalanga aldehyde and formaldehyde).

To overcome these shortcomings in WO 98/28253 proposed multi-stage method of producing polietileno, in accordance with which the aldehydes with the number of carbon atoms from two to twenty-four in the first stage (reaction of aldol condensation in the presence of tertiary amines as catalysts are condensed with formaldehyde, forming a first corresponding methylalanine, and then at the next stage (hydrogenation) they are reduced with the formation of the corresponding polietileno. This multistage process is usually called method by hydrogenation. When implementing this method produces a small amount of by-products.

After the first stage of the method, the hydrogenation of unreacted aldehyde and the amine part of the Foundation in the General case is separated from the formed methylalanine using distillation and returned to the process.

To receive the reception after distillation VAT residue along with the formed methylolacrylamide remain water, adducts of formic acid and used tertiary amines (amine formate), and formic acid.

As a rule, polymetallurgical obtained in this way in the form of an aqueous solution with a concentration of from 20 to 70 wt.%. Containing polymetallurgical solution is directed to the hydrogenation in the second stage, in order to transform polymethylsilane in such relevant Polimetall as trimethylolpropane or neopentylglycol.

Reaction mass from the stage hydrogenation is usually a water polietileno mixture, which contains Polimetall, tertiary amine, water and organic side components, for example the adduct of tertiary amine and formic acid (formate Amin). In accordance with this water polietileno the mixture is usually subjected to cleaning, separating the distillation from prematilleke compounds boiling components. The distillation residue is selected from the cube evaporator or from the circuit evaporator, contains mainly polymethylene connection. This is taken from cube product in accordance with this description is called "raw Polimetall".

In the framework of the present invention, it was found that the crude Polimetall along with primacialny connection contains a noticeable amount of oxidation products di is etalalalala, formed in the aldol condensation, for example, it hydroxypivalic acid from hydroxypivalic aldehyde. In addition, it was found that these acidic compounds by distillation of crude Polimetall can respond in Cuba columns with polimetinovymi compounds into esters. This leads generally to a decrease in the output prematilleke connection. Furthermore, in this reaction water is formed. Unexpectedly it was found that the formed reaction water interferes with the process of condensation of such polietileno as neopentylglycol. This can be explained by the fact that neopentylglycol. for example, hardens at a temperature of about 139°C and in accordance with this temperature in the head of the column cannot be set to any value. In accordance with this, when receiving neopentyl glycol condensation is conducted usually at temperatures above 139°C. under these conditions, the water acts as a virtually inert compounds and makes neopentylglycol of the capacitor, resulting in an additional reduction of output.

In accordance with the foregoing objective of the present invention consisted in the development of distillation of crude Polimetall, the implementation of which should be reduced loss of output Polimetall due to leakage of unwanted reactions of these is eficacia and ablation of Polymetal from the condenser, and this should lead to improved economic performance and efficiency of the process.

In accordance with the invention the task is solved by the method of purification of crude Polimetall containing Polimetall formula (I)

where

R in each case independently from one another mean one methylol group or an alkyl group with the number of carbon atoms of from one to twenty-two or aryl group or arylalkyl group with the number of carbon atoms from six to twenty-two

and gidrokshikislotu formula (IV)

where

R in each case independently of one another have the above meaning,

wherein the cleaning is performed in a distillation column, while the cube distillation column connected to at least one evaporator with a short time.

Used in accordance with the invention method crude Polimetall in the preferred case, get in a multistage process, in which stage (a) is the reaction of aldol condensation of alcanada and formaldehyde in the presence of tertiary amines as catalysts in the formation of metrolina formula (II):

where

R in each case independently from each other is and accept the above value,

and then at the stage b) obtained in stage a), the reaction mixture was separated using distillation to VAT residue, containing predominantly the compounds of formula (II), and leaving the head of the column head flow containing boiling components, then on stage) coming from the cube stage b) head flow hydronaut and then on stage g) conduct the distillation coming from the stage) brain flow with the Department of boiling components of the downstream flow from the stage).

In the first stage of process (a) (reaction of aldol condensation) in the General case about the reaction of alcanada with formaldehyde according to the scheme of aldol condensation in the presence of tertiary amines as a catalyst.

In this way the formaldehyde used, usually in the form of an aqueous solution of formaldehyde. Formaldehyde technical quality usually comes in the form of an aqueous solution with concentrations of 30, 37 and 49 wt.%. However, when implementing this method, you can use the solutions of formaldehyde with a concentration of up to 60 wt.%.

Technical formaldehyde contains, as a rule, formic acid, which is associated with the conditions of its reception. Decomposition of formic acid can reduce the operating time of the catalyst in the hydrogenation next next stage of hydrogenation that is may lead to reduced output polietileno. In a special variant of the method used, the formaldehyde content of formic acid which is 150 parts per million or even less. Such formaldehyde according to PCT/EP 2008/052240 can be obtained by treatment of a solution of formaldehyde or an aqueous solution of formaldehyde basic ion exchange resins. The role of anion-exchange resins suitable well-known strongly basic, weakly basic or basic medium gel-like or macroporous ion-exchange resin. They represent, for example, anion exchange resin with the structure of a polystyrene resin with a mesh formed by divinylbenzene, and amino groups as functional groups.

It can also go on ion-exchange resins based on acrylic acid or methacrylic acid with a mesh formed by divinylbenzene, or resins obtained by condensation of formaldehyde with phenol. In particular, suitable, for example, such brands as Ambersep® 900, Amberlyst® and Amberlite® Robin und Haas. Philadelphia. The U.S., as well as Lewatit® company Lanxess, Leverkusen.

In accordance with the invention method can be used alkanal with a methylene group in α-position to a carbonyl group. In the preferred case as original products can be used as efficiencies alkanal with the number of carbon atoms from two to twenty-four, which may be linear or branched structure or which may also contain alicyclic group.

As starting compounds can also be used analiticheskie alkanal provided that they contain a methylene group in α-position to a carbonyl group. In the General case as starting compounds used Arakelova alkanal with the number of carbon atoms from eight to twenty-four, in the preferred case from eight to twelve carbon atoms, for example phenylacetic aldehyde. In the preferred case, the use of aliphatic, alkanal with the number of carbon atoms from two to twelve, such as 3-ethyl-, 3-n-propyl-, 3-isopropyl-, 3-n-butyl-, 3-isobutyl-, 3-sec-butyl-, 3-tert-butyl-butanol, and also the corresponding-n-pentanal, ' n ' hexanal, -n-heptanal; 4-ethyl-, 4-n-propyl-, 4-isopropyl-, 4-n-butyl-, 4-isobutyl-, 4-sec-butyl-, 4-tert-butyl-pentanal, ' n ' hexanal, -n-heptanal; 5-ethyl-, 5-n-propyl-, 5-isopropyl-, 5-n-butyl-, 5-isobutyl-, 5-sec-butyl-, 5-tert-butyl-n-hexanal corresponding-n-heptanal; 3-methyl-hexanal, 3-methylheptane; 4-methylpentanol, 4-methyl-heptanol, 5-methylhexane, 5-methylheptane; 3,3,5-trimethyl-n-pentalogy, 3,3-detinitely, 4,4-detinitely, 3,3-dimethyl-n-butyl, 3,3-dimethyl-n-pentalogy, 5,5-dimethylheptane, 3,3-dimethylheptane. 3,3,4-trimethylantimony, 3,4-dimethylheptane. 3,5-dimethylheptane, 4,4-dimethylheptane, 3,3-diethylhexyl, 4,4-dimethylhexanoic. 4,5-dimethylhexanoic, 3,4-dimethyl-hexyl, 3,5-dimethylhexane, 3,3-dimethylhexane, 3,4-diethylhexyl, 3-methyl-4-ethylpentane, 3-methyl-4-ethylhexyloxy, 3,3,4-trimethylantimony, 3,4,4-trimethylpentyl. 3,3,4-trimethylhexane. 3,4,4-trimethylhexanoyl. 3,3,4,4-tetramethylpentane aldehyde; in particular, use of alcalali normal structure with the number of carbon atoms from two to twelve.

Along with used in the preferred case somaclonal aldehyde, representing the original product to get neopentyl glycol, preferably also used as starting compounds n-butyric aldehyde to obtain trimethylolpropane, acetaldehyde to obtain pentaerythritol, propionic aldehyde to obtain trimethyloctane and n-pentanal to obtain trimethylbutane.

As tertiary amines can be used amines represented, for example, in patent applications FRG No. And 2813201 and No. And 2702582. Particular preference is given to tri-n-alkylamines followed, in particular triethylamine, tri-n-Propylamine, tri-n-butylamine and trimethylamine. Most preferred trimethylamine, triethylamine and tri-n-Propylamine, since these compounds have, as a rule, the lower the second boiling point, than formed in the preferred case, Polimetall, which facilitates their separation from the reaction mixture using distillation. In a particularly preferred case, as the tertiary amine in the reaction using trimethylamine.

The reaction of aldol condensation can be conducted with the addition of organic solvents or without solvents. Adding solvent or solubilization may be appropriate, particularly when used as initial products of long chain alcanada. The use of solvents, which form a suitable low-boiling azeotropic mixtures with volatile compounds during each distillation with the implementation of the invention method, it is possible, accordingly, to reduce the consumption of energy in such distillations and/or to facilitate the separation by distillation of low-boiling compounds from high-boiling compounds. The role of solvents are suitable, for example, cyclic and acyclic ethers, such as tetrahydrofuran, dioxane, methyl tert-butyl ether, or alcohols such as methanol, ethanol or 2-ethylhexanol.

Appropriate, when carrying out the aldol condensation molar ratio are added in each case of alkanes to the added quantity of formaldehyde is about the 1:1 to 1:5, in the preferred case from 1:2 to 1:3,5.

The number added in the reaction of aldol condensation catalyst in the form of tertiary amine is based on the added alkanol, usually from 0.001 to 0.2, in the preferred case from 0.01 to 0.07 equivalents, that is, Amin usually use in catalytic amounts.

The reaction of aldol condensation in General carried out at a temperature from 5 to 100°C, in the preferred case from 15 to 80°C., and the residence time depends on the temperature and in the General case, it is set in the range of from 0.25 to 12 hours.

Described for the aldol condensation conditions of the reaction in General involve the use of pressure from 1 to 30 bar, in the preferred case from 1 to 15 bar, more preferred from 1 to 5 bar; it is expedient, when the reaction is under pressure, which itself is set in the corresponding reaction system.

The reaction of aldol condensation can be conducted on a periodic and continuous circuit, In the preferred case, the reaction of aldol condensation is carried out in a reactor with a stirrer, operating in continuous mode, or in a cascade of reactors with agitators, which operates in continuous mode. To regulate the residence time can be returned to the process part of the effluent from the reactor mesh is the LCA of the reaction mass back into the same reactor with a stirrer.

The reaction mass obtained in the aldol condensation, usually contains neprevyshenie parent compound, such as formaldehyde, alkanal, and also used as a catalyst, tertiary amine and, if appropriate, water.

In addition, the reaction mass is the aldol condensation contains methylallyl formula (II)

where

R in each case independently from one another mean one methylol group or an alkyl group with the number of carbon atoms of from one to twenty-two or aryl group or arylalkyl group with the number of carbon atoms from six to twenty-two.

Examples of metrolina serve hydroxypivalic aldehyde formed by using as starting product samalanga aldehyde, or dimethylaminoethanol (dimethylaluminum)formed by using as the initial product of n-butyric aldehyde.

Usually the reaction mass also contains impurities and by-products of the aldol condensation, for example formic acid, which could be formed from formaldehyde reaction Cannizzaro or Tishchenko, and formatnya salts used as catalysts amines, for example formate, trimethylammonium.

The reaction mass, the reaction is AI aldol condensation at the final stage separated typically by distillation (stage b). For this reaction the mass of the aldol condensation is usually served in a device for distillation, representing mostly the column in which it is split into components with higher and lower volatility.

The conditions of distillation choose, as a rule, so that there was a formation fraction boiling compounds, in which the main components are neprevyshenie alkanal, formaldehyde and, if appropriate, water and methanol. This so-called fraction boiling may be returned to the first stage of the hydrogenation process, i.e. the reaction of aldol condensation, or it can send the next stage of processing.

In the described method of separation after separation of the fractions boiling compounds by distillation still bottoms distillation residue with more high-boiling products, consisting mainly of methylalanine (II), for example hydroxypivalic aldehyde, water, formic acid and formate Amin.

When using trimethylamine as a tertiary amine of the distillation conditions are chosen so that the portion of trimethylamine was contained in the fraction boiling and to a smaller part of it remained in the bottom product. When using amines with higher than trimethylamine, temperature is th boiling in the distillation conditions are chosen so that to tertiary amines and accumulated in the bottom product.

Separation using distillation in the preferred case should be carried out under moderate pressure to high temperature did not lead to the decomposition of metrolina (II). For example, hydroxypivalic aldehyde can turn into neopentylglycol esters hydroxypivalic acid. On the other hand, the pressure should not be too low in order to the head of the column could go condensation of such low-boiling alcanada as somaclonal aldehyde, and amine bases, such trialkylamines as trimethylamine.

The distillation can be carried out at too low pressure because, as a rule, at temperatures below 60°C there is a sharp decrease in solubility in an aqueous solution such alkanes (II), as hydroxypivalic aldehyde, up to values of about 1 to 3 wt.% depending on the content of alkanes and methanol.

In addition, the separation of the reaction mixture of aldol condensation should occur so that the amount of methanol in low-boiling fractions were kept to a minimum to ensure that it did not lead to a permanent increase in the concentration of methanol in the aldol condensation. Typically, methanol is brought together with the aqueous solution of the formal is of Egida, depending on the conditions of obtaining it contains about 1 to 3 wt.% of methanol.

The boiling point of methanol is, as a rule, below the boiling point neprevyshenie of alkanes, resulting in the accumulation of methanol in the head of the column and an increasing concentration of methanol in the course of the current process. To maintain a low concentration of methanol can be used a variety of techniques.

On the one hand, it is advisable to use as a starting product in the aldol condensation of formaldehyde with low methanol content. You can also withdraw from the process methanol together with neprevzaidennymi alkanals, but it leads to loss of alkanes.

However, in the preferred embodiment of the method for the distillation is carried out under specific conditions so that the methanol is sufficiently accumulated in the bottom part of column. These preferred variants of the method distillative separation of the reaction mixture of aldol condensation presented in the application PCT/ER/052240.

Separation of low-boiling fraction and CBM product in accordance with this variant of the method is carried out with the help of distillation in General at a temperature of from 50 to 200°C, in the preferred case from 90 to 160°C and at a pressure in the distillation column in General from 0.1 mbar to 10 bar. predpochtitelno case from 0.5 to 5 bar, in particular at atmospheric pressure. Distillation column in the General case operates at a pressure in the head part in the range from 0.5 to 1.5 bar. In the preferred case, in the head part provides a two-stage condensation, in which saturated steam is first sent to the heat exchanger partial condensation of operating at temperatures in the range from 50 to 80°C., the condensate which is at least partially returned to the distillation column, while neskondensirovannyh in the heat exchanger partial condensation of the saturated steam is sent to the connected condenser operating at a temperature in the range from -40 to +30°C, the condensate which is at least partially withdrawn from the process.

In the preferred case, the condensate heat exchanger partial condensation of more than 70 wt.%, in a particularly preferred case is fully returned to the distillation column. In this case, preferably, when the condensate is returned to the head of the column. Condensed in the following capacitor product in the preferred case, not less than 70 wt.%, in particular completely removed from the process.

The heat exchanger partial condensation operates at a temperature in the range from 50 to 80°C, in the preferred case from 55 to 60°C. Next D. the more the condenser operates at a temperature in the range from -40 to +30°C, in the preferred case, -10 to +10°C. the Pressure in the head of the column in a particularly preferred case is from 1 to 1.2 bar.

Cube distillation clones in your preferred case is connected to the evaporator with short duration of stay, which operates at a temperature in the range from 90 to 130°C., in a particularly preferred case from 100 to 105°C. the evaporator in a particularly preferred case is an evaporator falling film, in addition, in the preferred case, you can use thin-film evaporator with a dispenser or the evaporator molecular acceleration. It is important, that this was achieved in a short time and the associated minor thermal effect. Heating of the evaporator can be provided in an appropriate way, for example, using steam with a pressure of 4 bar.

Preferably, when the distillation column includes built-in items intended to improve the effect of separation. In this reaction the mass of the aldol condensation in the preferred case, is introduced into the volume space between1/4and3/4theoretical plates of the distillation column, in a particularly preferred case, the volumetric space between 1/3 and 2/3 of theoretical plates of the distillation columns is s. For example, the filing can be done a little above the middle of theoretical plates (ratio 3:4).

Built-in distillation column elements may represent, for example, in an orderly and located the nozzle, for example, such nozzle of sheet metal, as Mellapak 250 Y or Montz Pak, type In 1-250. We can talk about the nozzle with a small or increased specific surface, or may be used for attachment of tissue-like material or a nozzle with a different geometry, as Mellapak 252 Y. Preferably, when using these built-in elements for distillation pressure loss is small and unlike valve trays in the column is delayed less liquid.

The condensate in the heat exchanger partial condensation is a predominantly water, which in the preferred case will be returned to the column as reflux liquid. Upon receipt of neopentyl glycol using as starting product samalanga aldehyde, for example, be obtained as condensate mixture along with water to about 10 wt.% samalanga aldehyde, about 5 wt.% such amine base, as trimethylamine, about 1 wt.% hydroxypivalic aldehyde and about 5 wt.% methanol together with water. In this case, the residual saturated p is p contains the main amount samalanga aldehyde and amine such basis as trimethylamine. These substances must be precipitated as fully as possible in the following capacitor. As the cooling medium in the preferred case, use cold water (for example, with a temperature of about 5°C) or cool the mixture (for example, glycol water with a temperature of, for example, -20°C). In the preferred case, an appropriate mixture enriched methylalanine (II), for example hydroxypivalic aldehyde or dimethylaluminum, derive from a bottom part of the evaporator. You can also derive it from the circulating stream.

CBM product with lower volatility when the separation of the reaction mixture of aldol condensation is possible to reduce thermal load to be cooled before further processing in the refrigerator with a cooling temperature in the range from 50 to 80°C. in a particularly preferred case from 55 to 60°C.

Obtained in this way, the VAT residue from step b) may be further gidrirovanny on stage).

VAT residue from step b) the method by hydrogenation containing methylallyl General formula (II), is fed to the hydrogenation in stage C) of the method, hydrogenation, which is relevant to polietileno ("hydrogenation").

When the hydrogenation in the preferred case of using the catalysts that contain at least one IU is all side groups 8 to 12 of the Periodic system of elements, for example, iron, ruthenium, osmium, cobalt, rhodium, iridium, Nickel, palladium, platinum, copper, silver, zinc, cadmium, mercury, in the preferred case of iron, cobalt, Nickel, copper, ruthenium, palladium, platinum, in a particularly preferred case, the copper, in the preferred case in the media. As the material of the carrier in the preferred case uses material from oxides of titanium, zirconium, hafnium, silicon and/or aluminum.

Getting used catalysts can be carried out in accordance with the prior art methods of making such catalysts on the media. In the preferred case can be used catalysts on a carrier on the basis of copper-containing aluminum oxide or titanium oxide bearing material in the presence or in the absence in their structure one or more elements such as magnesium, barium, zinc or chromium. Such catalysts and their getting well-known materials of WO 99/44974.

For the hydrogenation are also suitable such copper-containing catalysts on a carrier, e.g., catalysts, presented in WO 95/32171 and applications at the European patent No. 44444 and the Federal Republic of Germany patent No. 1957591.

The hydrogenation can be conducted in batch or in continuous mode, for example, in a tubular reactor with a nozzle of the catalyst, when the reaction solution is passed through the nozzle of the catalysate is RA, for example, in the irrigation mode or in a continuous stream, as disclosed in patent applications FRG No. And 1941633 or No. And 2040501. It may be appropriate abstraction part of the flow of the reaction mixture, if necessary with its cooling, and returning it for re-transmission through the layer of catalyst. Similarly, it may be expedient to carry out the hydrogenation in several reactors connected in series, such as two, three or four reactors, while in a separate reactor prior to the last reactor, the hydrogenation reaction is carried out at a partial degrees of transformation, components, for example, from 50 to 98%, with complete metamorphosis is achieved only in the last reactor. It may also be useful cooling coming from the previous reactor head flow hydrogenation before his entrance into the next reactor, for example, using cooling devices or by filing a cold gases such as hydrogen or nitrogen, or by introducing the cooled part of the flow of reaction solution.

The temperature of the hydrogenation is in General from 50 to 180°C, in the preferred case from 90 to 140°C. the Applied pressure is in General from 10 to 250 bar, in the preferred case from 20 to 120 bar.

As a rule, the stream supply device for hydrogenation before entry into the reactor hydrogenation add the tertiary amine in such numbers, so coming out of the reactor hydrogenation reaction mass had a pH value of from 7 to 9. You can also submit to the reactor feed device for hydrogenation stream and tertiary amine separately and to mix them already in the reactor. As tertiary amines may be used the above mentioned tertiary amines, in particular trimethylamine.

Reaction mass from the stage hydrogenation (stage C)) is usually water polietileno mixture containing Polimetall formula (I)

where

R in each case independently from one another mean one methylol group or an alkyl group with the number of carbon atoms of from one to twenty-two or aryl group or arylalkyl group with the number of carbon atoms from six to twenty-two

tertiary amine, water, and the product of the merger of tertiary amine to formic acid (amine formate).

Water polimetalla mixture in the preferred case has the following composition:

from 20 to 90 wt.% Polimetall formula (I),

from 0 to 5 wt.% methanol,

from 0 to 5 wt.% tertiary amine,

from 0 to 5 wt.% organic by-products,

from 0.01 to 5 wt.% the product of the merger of tertiary amine to formic acid (amine formate),

the rest is water.

In a particularly preferred case in which DNA polimetalla mixture has the following composition:

from 50 to 80 wt.% Polimetall formula (I),

from 0.1 to 3 wt.% methanol,

from 0.01 to 5 wt.% tertiary amine,

from 0 to 5 wt.% organic by-products,

from 0.01 to 5 wt.% the product of the merger of tertiary amine to formic acid (amine formate),

the rest is water.

As an organic by-product may be present, for example, the hydrogenation product used alkanes, namely the alcohol of formula (III)

where R in each case independently of one another have the above value.

In the preferred case, the cleaning water polymethylenes mixture is carried out by distillation of low-boiling components from prematilleke connection. The separation of low-boiling components from the water polymethylenes mixture in a particularly preferred case is carried out with the help of distillation.

The distillation in the preferred case carried out so that such low-boiling compounds, such as water, an alcohol of formula (III), methanol and a tertiary amine, was given in a vacuum through the head of the column, in particular, when used amine has a lower boiling point than the resulting Polimetall, for example, in the case of trimethylamine, triethylamine and Tripropylamine. If use of the tertiary amine, temperaturepanel which exceeds the boiling point of the formed Polimetall, the tertiary amine together with the formed polietileno is separated in the form of VAT residue and the next next stage distillation it accumulates in a bottom part of the column, while Polymetal is discharged through the head of the column.

Usually during the distillation part of the amine formate reacts with polimetinovymi compounds with formation of free amines and formate polymetallic compounds in Cuba columns or exhaustive of the column. In the preferred case is formed of monoether formic acid and prematilleke connection, which in the framework of the present invention is indicated as primacialny formate. Emitted from the esterification of free amines are discharged, usually by distillation together with other low-boiling compounds through the head of the column.

In accordance with these conditions of distillation must be installed so that the concentration of the formed polymetallic formate in leaving Cuba column head flow was quite low and that the target product Polymetal was as clean as possible. To achieve this, the temperature in Cuba during the distillation in the preferred case, the support above the evaporation temperature prematilleke formate, resulting in complete or near p is lnoe remove prematilleke formate by his transition into the gas phase. Due to this way increase the yield and improve the quality of the product can probably be explained by the fact that polymethylene the formate usually have a higher boiling point than the other low-boiling components and therefore, as a rule, with a corresponding value of the reflux ratio they are condensed in the strengthening of columns. Condensed in the strengthening of column polymethylene the formate can be either hydrolyzed with water, turning again in formic acid and polymethylene connection. Formic acid is usually removed through the head of the column, whereas polymethylene connection, generally output from the cube column.

In accordance with this preferred embodiment, the implementation of the distillation is carried out is presented below.

Typically, the condenser operates at a temperature that provides a condensation of the main part of the low-boiling compounds at the appropriate pressure in the head of the column. The operating temperature of the capacitor is usually from 0 to 80°C, in the preferred case from 20 to 50°C.

In the preferred case, as the cooling medium use cold water (for example, about 5°C) or cool the mixture (for example, a mixture of glycol with water with a temperature of, for example, -20°C). The pressure in gotovnosti columns in a particularly preferred case is from 0.001 to 0.9 bar, in even more preferred from 0.01 to 0.5 bar.

In industrial conditions, the vacuum created with the help projectional pump. In Cuba columns in a preferred case, the set temperature, which lies above the temperature of evaporation prematilleke formate and primacialny formate completely or almost completely in the gas phase. In a particularly preferred case, set the temperature to a value from 5% to 50% higher than the boiling point prematilleke formate, and in the most preferred case, it is on the order of 10% to 20% higher than the boiling point prematilleke formate. So, for example, preferably, when receiving neopentyl glycol using as a tertiary amine trimethylamine and when the pressure in the column 175 mbar temperature in the cube columns set in the range from 150 to 170°C., in a particularly preferred case from 160 to 165°C.

Reflux the number at the head of the column, usually set so that the main number prematilleke formate remained in the column. In the preferred case, deposited in the condenser, the condensate has more than 30%, more preferred case, more than 60% return in the distillation column. While it is preferable that the condensate is returned to holovnuyu part of the column. In the preferred case, the required evaporation energy served through the evaporator in a bottom part of the column. The evaporator is a usually evaporator with natural circulation or evaporator with forced circulation. However, you may be used and the evaporator with short duration of stay, an evaporator falling film evaporator with a spiral tube evaporator with switchgear or evaporator molecular acceleration. The heat at the evaporator can be carried out in an appropriate way, for example by means of steam with a pressure of 4 to 16 bar or by using organic heat carrier.

In the preferred case, the column has a built-in elements to improve separation efficiency. Built-in items for distillation can represent, for example, the ordering button nozzle, for example, such nozzle of sheet metal, as Mellapak 250 Y or Montz-Pak type 1-250. We can talk about the nozzle with a small or increased specific surface, or may be used for attachment of tissue-like material or such nozzle with a different geometry, as Mellapak 252 Y. it is Advisable, when using these built-in elements for distillation pressure loss is negligible and in contrast to, for example, from the valve plates in the colon is e delayed less liquid. Inline elements can be grouped in one block or several blocks.

Coming from the stage hydrogenation of the parent thread in the preferred case, is served in the open space between1/4and3/4theoretical plates of the distillation column, in a particularly preferred case, the flow is carried out in a volume of space between 1/3 and 2/3 of theoretical plates of the distillation column. For example, the filing can be done a little above the middle of theoretical plates (ratio 3:4). The number of theoretical plates in the range of from 5 to 30, in the preferred case from 10 to 20.

In the capacitor is deposited condensate in the form of a mixture of low-boiling substances, and the main part of it, as it was presented above, return in the form of phlegmy. So, for example, a mixture of low-boiling compounds may contain amine, water and such alcohols of the formula (III), as Isobutanol from samalanga aldehyde or n-butanol from n-Butyraldehyde and methanol from formaldehyde.

Neskondensirovannyh residual pairs can energetically feasible way to directly send in the form of gas for combustion, or they are sent to a distillation column operating at a pressure close to atmospheric. This serially connected column serves to separate the con is SATA distillative way.

In the preferred case of the cube evaporator divert the reaction mass consisting predominantly of prematilleke connection. The outlet can also be made from the circuit of the evaporator. Exhaust from the cube head flow in the framework of the present invention is designated as "crude Polimetall".

Obtained in accordance with the invention, the crude Polimetall contains a small amount prematilleke formate. In the preferred case, the content prematilleke formate is less than 1500 parts by weight per million, in the preferred case less than 1200 parts by weight per million, in a particularly preferred case is less than 800 parts by weight per million, in particular less than 600 parts by weight per million.

Crude Polymetal also contains polymethyl formula (I)

where

R in each case independently from one another mean one methylol group or an alkyl group with the number of carbon atoms of from one to twenty-two or aryl group or arylalkyl group with the number of carbon atoms from six to twenty-two

and gidrokshikislotu formula

where

R in each case has the above value.

Preferably, when crude Polymetal has this structure:

from 90 to 99 mA is from.% Polymetal (I)

from 0.01 to 5 wt.% hydroxyacids of formula (IV)

from 0 to 5 wt.% organic by-products.

Particularly preferably, when crude Polymetal has this structure:

from 95 to 99 wt.% Polymetal (I)

from 0.1 to 2 wt.% hydroxyacids of formula (IV)

from 0 to 3 wt.% organic by-products.

Such crude Polimetall in the preferred case, get as presented above, by multistage interaction alcanada with formaldehyde. Preferably, when crude Polimetall get way with hydrogenation.

For the Department present as residue acidic components with a higher boiling point, in particular hydroxyacids of formula (IV), with small losses prematilleke compounds by distillation in accordance with the invention is used as the cubic evaporator at least one evaporator with short residence time, such as an evaporator falling film and device for removal of residue, thin-layer evaporator or evaporators with spiral tubes. In a special variant of realization of the column has a built-in cube in order to further reduce the time spent in Cuba columns.

In a preferred embodiment, the implementation of the distillation of crude premartial conduct the following conditions.

Useful is brasno, when formed in the condenser, the condensate is more than 30 wt.%, in the preferred case, more than 50 wt.% is returned to the distillation column (flegma). While it is preferable that the condensate is returned to the head of the column.

The condenser operates at a temperature in the range from 50 to 180°C, in the preferred case from 130 to 160°C. In this case, preferably, when the cooling medium you can use the water when it evaporates.

The pressure in the head of the column in a particularly preferred case is from 0.001 to 0.9 bar. In industrial conditions, the vacuum is usually created with the help projectional pump.

In Cuba columns in the preferred case, set the temperature, which provides translation of Polymetal in the gas phase, while hydroxycitrate formula (IV) remains in the cube column. In the preferred case in Cuba, set the temperature, which ranges from 100 to 150%, more preferred case from 105 to 140%, in a particularly preferred case from 110 to 130% of the boiling point Polimetall. So, for example, upon receipt of neopentyl glycol using as a tertiary amine trimethylamine and when the pressure in the head of column 150 mbar may be appropriate when the temperature in the cube column is from 150 to 200°C. is particularly preferred case from 160 to 190°C.

In accordance with the invention, the cube distillation column connected to at least one evaporator with a short time.

In accordance with the invention, the cube distillation columns and the evaporator with short time together comprise the stage of evaporation.

Stay at the stage of evaporation calculated in accordance with the invention, for this purpose, the volume of liquid held in the hottest part of the column (Vhold) divided by the sum of the volume rate of return phlegmy and space velocity in the column head flow (Vhold/(volumetric rate of return phlegmy+volumetric feed rate to the column head stream)), while the amount held in the hottest part of the column of liquid (Vhold) is calculated from the amount held in the cube of the column of liquid (Vuderzoin sum, with the amount of liquid held in the evaporator (Vuderzo), by the formula:

(Vhold)=(Vuderzo)+(Vuderzo).

Advisable when the time on the stage of evaporation is less than 45 minutes, in the preferred case less than 30 minutes, in a particularly preferred case, less than 15 minutes, even more preferred, less than 10 minutes and in the most preferred case, less than 5 minutes. In the General case it is advisable to choose the time on stage evaporated the Oia so, so at higher temperatures in the cube, respectively, were established more than a short time.

When the temperature in the cube, which is in the range from 130 to 150% of the boiling point Polimetall, stay at the stage of evaporation is in the preferred case, 5 minutes or even less, in a particularly preferred case, it is 4 minutes or less and in the most preferred case, 3 minutes or even less.

When the temperature in the cube. which is in the range from 120 to 130% of the boiling point Polimetall, stay at the stage of evaporation is in the preferred case, 30 minutes or even less, in a particularly preferred case, it is 15 minutes or less and in the most preferred case, 10 minutes or even less, in particular, preferably, when it is 5 minutes or even less.

When the temperature in the cube, which is in the range from 100 to 120% of the boiling point Polimetall, stay at the stage of evaporation is in the preferred case, 45 minutes or even less, in a particularly preferred case, it is 30 minutes or less and in the most preferred case, 15 minutes or even less, in particular preferably, when it is 10 minutes or even less.

Another special variant of realization of the evaporator with short the m stay connected with at least one evaporator with a short time.

Cube distillation column together with the evaporator with a short time to form in this preferred embodiment, implemented in accordance with the above definition the first stage of evaporation.

Then the next evaporator or, respectively, the following evaporators form in accordance with the above definition of the second or, respectively, (1+n)-th, where n≥2, the stage of evaporation. In the preferred case, the evaporator with a short time connected with another evaporator with short residence time (dual-stage version).

Usually in this implementation the main part required for the evaporation energy is served on the first stage of evaporation. At the second stage of evaporation can then be set to a higher temperature required for evaporation, and get a shorter time, thus shortening the time spent on the second stage. In the preferred case, the first stage includes an evaporator falling film or the evaporator spiral tubes.

Preferably, when the second stage of this special version of the implementation is the evaporator falling film evaporator with spiral tubes or thin-film evaporator.

Stay at the first stage of evaporation calculated as the fit is accordance with the invention, for this purpose, the amount held in the hottest part of the column of liquid (Vhold) divided by the sum of the volume rate of return phlegmy and space velocity in the column head flow (Vhold/(volumetric rate of return phlegmy+volumetric feed rate to the column head stream)), while the amount held in the hottest part of the column of liquid (Vhold) is calculated from the amount held in the cube of the column of liquid (Vuderzoin sum, with the amount of liquid held in the evaporator (Vuderzo), by the formula:

(Vhold)=(Vuderzo)+(Vuderzo).

The residence time in the second stage of evaporation calculated in accordance with the invention by dividing held in the second evaporator liquid space velocity head of the flow fed to the second evaporator.

In accordance with the invention, time (1+n)-th stage of evaporation calculated respectively by dividing held in (1+n)-th evaporator liquid on the head of the stream fed to (1+n)-th evaporator.

Advisable when, in this preferred embodiment, the temperature in the cube at the first stage of evaporation exceeds the evaporation temperature of Polymetal.

In the preferred case, the temperature in the cube first stage evaporation ranges from 100 to 130%, more preferred case from 10 to 125% of the boiling point Polimetall.

The temperature in the second stage of evaporation in the General case are chosen so that Polimetall almost totally released into the gas phase. In the preferred case, the temperature at the second stage evaporation ranges from 105 to 150%, more preferred case from 120 to 150%, in a particularly preferred case from 130 to 140% of the boiling point Polimetall.

Advisable when the time on the first stage of evaporation is less than 45 minutes, in the preferred case less than 30 minutes, in a particularly preferred case, less than 15 minutes, even more preferred, less than 10 minutes and in the most preferred case, less than 5 minutes.

It is advisable, when the residence time in the second stage of evaporation is less than 30 minutes, in the preferred case, less than 15 minutes, in a particularly preferred case, less than 5 minutes, even more preferred, less than 2 minutes and in the most preferred case, less than 1 minute.

In the General case it is advisable to choose the time at the particular level of evaporation so that at higher temperatures in the cube, respectively, were established more than a short time.

As mentioned above, the evaporator with a short residence time can be connected with several evaporators short time, for example with two or three evaporators, when the last of the evaporators in the chain forms a so-called last stage of the evaporation. The time and temperature at the last stage of evaporation correspond to the residence time and temperature for the second stage of evaporation in two versions.

In the preferred case, upon receipt of neopentyl glycol using trimethylamine as a tertiary amine at the first stage of evaporation, you can set the temperature in the cube from 135 to 170°C., in a particularly preferred case from 150 to 160°C at a residence time of less than 45 minutes, in a particularly preferred case less than 30 minutes. At the second stage of evaporation in the preferred case, set the temperature from 160 to 220°C. in a more preferred case from 180 to 200°C at a residence time less than 15 minutes, in a particularly preferred case, less than 10 minutes and in the most preferred case, less than 5 minutes.

In the preferred case, the distillation column has a built-in elements to improve separation efficiency. Built-in items for distillation can represent, for example, in an orderly and located the nozzle, for example such nozzle of sheet metal, as Mellapak 250 Y or Montz-Pak type 1-250. We can talk about the nozzle with a small or increased specific surface, or can be used on adca of tissue-like material or such nozzle with a different geometry, as Mellapak 252 Y. it is Advisable, when using these built-in elements for distillation pressure loss is negligible and in contrast to, for example, valve trays in the column is delayed less liquid. Inline elements can be grouped in one block or several blocks.

Coming from the stage hydrogenation of the parent thread in the preferred case, is served in the open space between1/4and3/4theoretical plates of the distillation column, in a particularly preferred case, the flow is carried out in a volume of space between 1/3 and 2/3 of theoretical plates of the distillation column. For example, the filing can be done a little above the middle of theoretical plates (ratio 3:4). The number of theoretical plates in the range of from 5 to 30, in the preferred case from 10 to 20.

In these circumstances, as a rule, for the case of the preferred polietileno (neopentylglycol, trimethylolpropane, trimethylated and trimethylbutane) hold office Polimetall formula (I) with a lower boiling point of the hydroxy acid of formula (IV) with a higher boiling point. If in the process get other Polimetall, it may be necessary to select other conditions related to pressure or temperature, for stabitlity Polimetall from hydroxyacids.

In the preferred case, as the condensate is precipitated purified Polimetall. Preferably, when the purity of Polymetal is not less than 99,0 wt.%, in a particularly preferred case, not less than 99.2 wt.%.

In accordance with this present invention relates to received as condensate composition, the composition contains Polimetall formula (I) and from 1 to 10000 parts by weight per million of ester from Polymetal formula (I) and the hydroxy acid of formula (IV), in the preferred case from 5 to 5000 parts by weight per million, in a particularly preferred case from 10 to 1000 parts by weight per million of ester from Polymetal formula (I) and the hydroxy acid of formula (IV).

As a rule, formed as condensate composition also contains a small amount prematilleke formate. In the preferred case, the composition contains Polimetall formula (I) and from 1 to 10000 parts by weight per million prematilleke formate, in the preferred case from 5 to 5000 parts by weight per million prematilleke formate and in the particularly preferred case from 10 to 1500 parts by weight per million prematilleke formate.

In the preferred case of the cube evaporator assign the parent thread, which contains mainly such high-boiling compound, as hydroxycitrate formula (IV), for example, it hydroc Ievleva acid.

VAT residue can be processed by thermal or direct combustion, or send in a downstream distillation column to separate it into several factions. So, for example, upon receipt of neopentyl glycol VAT residue can be divided into low-boiling fraction containing predominantly hydroxypivalic acid, on average fraction containing primarily neopentylglycol ether hydroxypivalic acid (>97% neopentylglycol ether hydroxypivalic acid) and high-boiling fraction (primarily esters hydroxypivalic acid and neopentylglycol ether hydroxypivalic acid).

Neskondensirovannyh residual vapors, which contain, as a rule, along with the drawn in air and traces of water, mainly this Polimetall as neopentylglycol. in the preferred case, directly return to the stage distillation g) in the form of a gas.

The advantages of the present invention consist in the fact that the relevant invention method are Polimetall with high yield and with low content of esters formed by hydroxyacids of formula (IV) and polymethylene formula (I). When relevant to the invention of the distillation of crude Polimetall it is possible to reduce the loss of Polymetal arising from the CSOs, that formed during the esterification reaction, the water carries away from condensation of such Polimetall as neopentylglycol.

The advantage of corresponding to the invention of the method is that Polimetall can be obtained with very high yields, and this leads, eventually, to improve the economic performance of the process of obtaining polietileno.

Economic performance can be further improved by separation of the resulting products and target products, as main components can be used as appropriate substances, for example, by returning to the process. Reduces the content of compounds, which should be aimed at neutralization, resulting in reduced costs for disposal by implementing the invention method.

The invention is illustrated in the following examples.

Example 1

Raw Polimetall way hydrogenation

Stage a). The reaction of aldol condensation

In a two-stage cascade of reactors with agitators spend the interaction between about 750 g/h samalanga aldehyde (purity more than 99.5% of the area of the peaks on the gas chromatogram) and about 700 g/h of aqueous formaldehyde (about 49 wt.% formaldehyde, 1.5 wt.% methanol, and the rest water) and 80 g/h is of astora trimethylamine (50 wt.% trimethylamine in water).

Stage b). Separation of the reaction mixture from stage a) with the help of distillation

Then the solution is freed from low-boiling constituents using distillation in the column. In the strengthening part of the column at 1.5 m filled by the nozzle on the basis of the tissue (500 m2/m3specific surface) and 4 m nozzle sheet metal (250 m2/m3). The product from the stage of aldol condensation serves on the level above the nozzle sheet metal in the head of the column using a condenser, water cooled (10°C), and connected therewith apparatus for phase separation. At the head of the column distillate in the form of steam is sent to the condenser. Get about 255 g/h of liquid condensate. The following is the apparatus for phase separation to separate the aqueous phase in the amount of 95 g/h and fully return it to the column. In addition from the apparatus for phase separation are selected 135 g/h of the other phase and return it in the first reactor with a stirrer cascade of reactors. To maintain the column temperature of 85°C column additionally serves 25 g/h of organic phase. Connected to the condenser cooled trap is going to about 1 g/h of liquid (about 80 wt.% samalanga aldehyde and about 20 wt.% trimethylamine), which also returns in the process.

Department samalanga aldehyde is carried out at an absolute davlenie head of the column of about 1 bar. As the evaporator using an evaporator falling film. In Cuba columns set the temperature of the VAT residue 102°C. the Number returned in the column of condensate (or, respectively, the amount of the cooling water in the partial condenser) is determined by the temperature in the middle of the nozzles on a fabric basis set temperature is 85°C. From the cube of the column using a pump selected about 100 kg/h of liquid. This liquid is sent to an evaporator falling film (he is a heated oil to a stainless steel tube, length 2.5 m, an internal diameter of about 21 mm, wall thickness about 2 mm). From the cube evaporator falling film taken about 1.5 kg/h of product with a concentration of about 0.3 wt.% samalanga aldehyde. Couples and excess fluid is directed to the cube of the column. Derived from a cube, the product contains about 70 wt.% hydroxypivalic aldehyde, about 1.5 wt.% neopentylglycol ether hydroxypivalic acid, 0.3 wt.% samalanga aldehyde and water as the rest of the composition.

Stage b). Hydrogenation of VAT residue, obtained in stage b)

Received VAT residue then is directed to the hydrogenation in a fixed bed of the catalyst.

Activation of the catalyst is conducted are presented below. As described in the European is the first patent No. 44444 or accordingly, in French patent No. 57216, 150 ml of the copper catalyst on aluminum oxide activated in a tube reactor at 190°With the transmission at normal pressure for 24 hours a mixture of about 5. % hydrogen and about 95. % nitrogen (total volume of 50 normal liters per hour).

The hydrogenation is conducted are presented below. As the initial solution using the above-described mixture of the starting products for the hydrogenation. To the mixture add about 10 wt.% based on entering the hydrogenation of the flow of a 15%aqueous solution of trimethylamine. Thus obtained composition for hydrogenation under hydrogen pressure of 40 bar serves the irrigation regime in a heated up to 120°C reactor. The load on the catalyst is 0.4 kg hydroxypivalic aldehyde per liter of catalyst per hour. Part of the exhaust of the reaction mixture of the hydrogenation process again returns to the reactor (with circulation). The ratio of the flow of circulation to the stream recharge is 10:1. The pH value in taken from the reaction product samples, determined at room temperature is 8.9.

Water polimetalla mixture from stage b) has the following structure:

69 wt.% neopentyl glycol,

3.5 wt.% methanol,

2 wt.% trimethylamine,

less than 2 wt.% organic by-products (hydroxypivalic acid, n-butanol and Isobutanol),

1 wt.% of trimethylammonium formate,

23 wt.% water.

Stage g). Distillation water polymethylenes mixture from stage b)

The resulting reaction mass (about 1.5 kg/h) is directed to the separation using distillation. Use the Packed column (inner diameter 50 mm) with three zones ordering situated nozzle sheet metal length 1 m with a specific surface area of 500 m2/m3. The feed to the column carry over the bottom area of the nozzle. At the head of the column set an absolute pressure of about 175 mbar. In Cuba columns set the temperature from 160 to 165°C, the energy in the string is fed through the evaporator with natural circulation, but can be used and another evaporator, such as an evaporator of the falling film. Obtained at the head of saturated vapors are directed to a condenser in which at 30°C is almost complete precipitation of the obtained vapors. The vacuum created with the help of the usual purchased by commercial water-jet vacuum pump. From the obtained distillate is taken about 350 g/h and about 250 g/h return as phlegmy on the upper area of the nozzle. Used in water jet pump water is directed to the bioremediation of waste waters.

Get raw methylol the following composition:

97 wt.% neopentyl glycol,

1 the ACC.% ether hydroxypivalic acid and neopentyl glycol,

2 wt.% organic by-products.

Example 2 the Distillation of crude Polimetall

Selected from Cuba distilling water polymethylenes a mixture of the product from step g) is directed to the separation using distillation (feed rate of about 1.15 kg/h). Use a column with a nozzle (inner diameter 50 mm) with two zones of the nozzle, the upper area of 1 m length filled the nozzle on the basis of the tissue with a specific surface area of 750 m2/m3lower zone length 1 m - cap of sheet metal with a specific surface area of 500 m2/m3. Supply perform above the lower zone. At the head of the column set pressure 150 mbar. In Cuba set temperature of 180°C. From the cube of the column using a pump selected about 100 kg of fluid per hour. This liquid is sent to an evaporator falling film (he is a heated oil to a stainless steel tube 2.5 m long with an internal diameter of about 21 mm and a wall thickness of about 2 mm). His warm steam with a pressure of 16 bar. Vapors and liquid from the evaporator again served in the cube column. From circulating in the evaporator with a falling liquid film taken about 50 g/h of rest (with a concentration of about 15 wt.% neopentyl glycol, about 40 wt.% neopentylglycol ether hydroxypivalic acid, about 10 mass % hydroxypivalic acid, the rest of the OE - high-boiling esters hydroxypivalic acid and neopentylglycol ether hydroxypivalic acid). Formed in the head part of the column saturated pair is sent to the condenser, which is at a temperature of about 135°With precipitates corresponding specifications net neopentylglycol. From the head of column output of about 1.1 kg/h neopentyl glycol, about 1000 g/h return as phlegmy on the upper area of the nozzle (the rate at which the return flow of about 1000 g/h). The vacuum created with the help of conventional marketed water-jet vacuum pump. Used to produce the vacuum, the water is directed to the bioremediation of waste water. In the hottest part of the column is always about 1 liter of liquid. The residence time in the evaporator associated with the cube of the column, is in accordance with this 30 minute (1 l/(1.15 l/h + 1,0 l/h)).

The output of neopentyl glycol based on the content of neopentyl glycol in the original product is about 98 wt.%.

The purity of purified Polymetal is 99.3 wt.%.

Content as hydroxypivalic acid and neopentylglycol ether hydroxypivalic acid is less than 100 parts by weight per million.

Example 3 the Distillation of crude Polimetall

In the same conditions as described in example 2, with the installation of columns in the cube so the temperature of 160°C from the cube of the column using a pump selected about 100 kg of fluid per hour feed rate feed mixture is about 1.15 kg/h). This liquid is sent to an evaporator falling film (he is a heated oil to a stainless steel tube 2.5 m long with an internal diameter of about 21 mm and a wall thickness of about 2 mm his warm steam with a pressure of 16 bar). From circulating in the evaporator with a falling liquid film taken about 0.1 kg/h of product with a concentration of about 50 wt.% neopentyl glycol and send it to the connected thin-film evaporator. Residual neopentylglycol evaporated in the evaporator at 190°C and in the form of steam is directed into the column. The thin film evaporator output of about 40 g/h of residue, which contains about 10 wt.% neopentyl glycol, about 35 wt.% neopentylglycol ether hydroxypivalic acid, about 15 mass. % hydroxypivalic acid, the rest of the high-boiling esters hydroxypivalic acid and neopentylglycol ether hydroxypivalic acid. Coming to the head of column pairs are routed to the condenser, which is at a temperature of about 135°condensed With the appropriate specifications net neopentylglycol. From the head of column output of about 1.1 kg/h neopentyl glycol, about 1000 g/h return as phlegmy on the upper area of the nozzle (the rate at which the return flow of about 1000 g/h). The vacuum created with the help of ordinary postupayushih is on sale water-jet vacuum pump. Used to produce the vacuum, the water is directed to the bioremediation of waste water. In the hottest part of the column is always about 1 liter of liquid. The residence time in the evaporator (evaporator falling film), which is directly connected with the cube of the column, is in accordance with this 30 minute (1 l/(1,15 l/h+1,0 l/h)). The residence time in the hot zone connected to the evaporator, thin film evaporator, the temperature of which is maintained at 190°C for approximately 3 minutes (calculated as the ratio of the number held in the thin-film evaporator fluid to the speed of its receipt in the thin-film evaporator).

The output of neopentyl glycol based on the content of neopentyl glycol in the original product is about 99.5 wt.%.

The purity of purified Polymetal is 99.3 wt.%.

Content as hydroxypivalic acid and neopentylglycol ether hydroxypivalic acid is less than 100 parts by weight per million.

Example 4

Distillation of the crude Polimetall

VAT residue from step d) distillation of water polymethylenes mixture is directed to the separation using distillation (feed rate feed mixture is about 1.15 kg/h). Use a column with a nozzle (inner diameter 50 mm) with two zones of the nozzle, the upper zone of length 1 is filled with the nozzle on the basis of the tissue with a specific surface area of 750 m 2/m3lower zone length 1 m - cap of sheet metal with a specific surface area of 500 m2/m3. Supply perform above the lower zone. Set the pressure at the head of the column of about 90 mbar. In Cuba set the temperature of 176°C, from the cube of the column using a pump selected about 100 kg of fluid per hour. This liquid is sent to an evaporator falling film (he is a heated oil to a stainless steel tube 2.5 m long with an internal diameter of about 21 mm and a wall thickness of about 2 mm). His warm steam with a pressure of 16 bar. Vapors and liquid from the evaporator again served in the cube column. From circulating in the evaporator with a falling liquid film taken about 50 g/h of rest (with a concentration of about 15 wt.% neopentyl glycol, about 40 wt.% neopentylglycol ether hydroxypivalic acid, about 10 wt.% hydroxypivalic acid, the rest of the high-boiling esters hydroxypivalic acid and neopentylglycol ether hydroxypivalic acid). Formed in the head part of the column saturated pair is sent to the condenser, which is at a temperature of about 135°C precipitates corresponding specifications net neopentylglycol. From the head of column output of about 1.1 kg/h neopentyl glycol, about 1000 g/h return as phlegmy on the upper zone of NASA is Ki the rate of return flow of about 1000 g/h). The vacuum created with the help of conventional marketed water-jet vacuum pump. Used to produce the vacuum, the water is directed to the bioremediation of waste water. In the hottest part of the column is always about 1 liter of liquid.

The residence time in the evaporator associated with the cube of the column, is in accordance with this 30 minute (1 l/(1,15 l/h+1,0 l/h)).

The output of neopentyl glycol based on the content of neopentyl glycol in the original product is about 98 wt.%.

The purity of purified Polymetal is 99.3 wt.%.

Content as hydroxypivalic acid and neopentylglycol ether hydroxypivalic acid is less than 100 parts by weight per million.

Example 5

Distillation of the crude Polimetall

VAT residue from step d) distillation of water polymethylenes mixture is directed to the separation using distillation (feed rate feed mixture is about 1.15 kg/h). Use a column with a nozzle (inner diameter 50 mm) with two zones of the nozzle, the upper area of 1 m length filled the nozzle on the basis of the tissue with a specific surface area of 750 m2/m3lower zone length 1 m - cap of sheet metal with a specific surface area of 500 m2/m3. Supply perform above the lower zone. Set the pressure at the head of the column OK is about 300 mbar. In Cuba, set the temperature to 185°C, from the cube of the column using a pump selected about 100 kg of fluid per hour. This liquid is sent to an evaporator falling film (he is a heated oil to a stainless steel tube 2.5 m long with an internal diameter of about 21 mm and a wall thickness of about 2 mm). His warm steam with a pressure of 16 bar. Vapors and liquid from the evaporator again served in the cube column. From circulating in the evaporator with a falling liquid film taken about 50 g/h of rest (with a concentration of about 15 wt.% neopentyl glycol, about 40 wt.% neopentylglycol ether hydroxypivalic acid, about 10 wt.% hydroxypivalic acid, the rest of the high-boiling esters hydroxypivalic acid and neopentylglycol ether hydroxypivalic acid). Formed in the head part of the column saturated pair is sent to the condenser, which is at a temperature of about 135°C precipitates corresponding specifications net neopentylglycol. From the head of column output of about 1.1 kg/h neopentyl glycol, about 1000 g/h return as phlegmy on the upper area of the nozzle (the rate at which the return flow of about 1000 g/h). The vacuum created with the help of conventional marketed water-jet vacuum pump. Used to produce the vacuum, the water is directed to bi is the waste water treatment. In the hottest part of the column is always about 1 liter of liquid. The residence time in the evaporator associated with the cube of the column, is in accordance with this 30 minute (1 l/(1,15 l/h+1,0 l/h)).

The output of neopentyl glycol based on the content of neopentyl glycol in the original product is about 98 wt.%.

The purity of purified Polymetal is 99.3 wt.%.

Content as hydroxypivalic acid and neopentylglycol ether hydroxypivalic acid is less than 100 parts by weight per million.

1. The method of purification of crude Polimetall containing Polimetall formula (I)

where
R in each case independently of one another denote methyl group or alkyl group with carbon atoms of from one to twenty-two or aryl group or arylalkyl group with the number of carbon atoms from six to twenty-two,
and gidrokshikislotu formula (IV)

where
R in each case independently of one another have the above meaning,
characterized in that
crude Polimetall get in a multi-stage process, with stage and alkanal by the aldol condensation interact with formaldehyde in the presence of tertiary amines as catalysts education METI is olakunle formula (II)

where
R in each case independently of one another take the above value,
and then at the stage b) obtained in stage a), the reaction mixture was separated using distillation to VAT residue, containing predominantly the compounds of formula (II), and head stream containing boiling components, then on stage) coming from the cube stage b) stream hydronaut and then on stage g) conduct the distillation coming from the stage) flow while separating the boiling components from the flow coming from the stage), and cleaning is performed in a distillation column, while the cube distillation column connected to at least one evaporator with a short time.

2. The method according to claim 1, characterized in that the crude Polimetall contains
from 90 to 99 wt.% Polymetal (I),
from 0.01 to 5 wt.% hydroxyacids of formula (IV),
from 0 to 5 wt.% organic by-products.

3. The method according to claim 1, characterized in that polymethylene connection is neopentylglycol, trimethylolpropane, pentaerythritol, trimethylated or trimethylbutane.

4. The method according to claim 1, characterized in that polymethylene connection is neopentylglycol.

5. The method according to claim 1, wherein the tertiary amine is a triethylamine, tri-<> n-Propylamine, tri-n-butylamine or trimethylamine.

6. The method according to claim 5, wherein the tertiary amine is a trimethylamine.

7. The method according to claim 1, characterized in that the temperature in the cube set so that it ranged from 105 to 140% of the boiling point Polimetall.

8. The method according to claim 1, wherein the distillation column has from 5 to 30 theoretical plates, and the fact that crude Polimetall enters its volumetric space between1/4and3/4theoretical plates of the distillation column.

9. The method according to claim 1, characterized in that coming from the cube stage b) stream add the tertiary amine.

10. The method according to claim 1, characterized in that the purity of the obtained Polymetal (I) is more than 99 wt.%.

11. The method according to claim 10, characterized in that the content of the hydroxy acid (IV) in distilled polymethylene (I) is less than 500 parts per million.

12. The method according to one of claims 1 to 11, characterized in that the evaporator with a short time connected with at least one additional evaporator with short residence time.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing pentaerythritol which is used in production of lacquer, plastic and explosives. The method involves condensation of formaldehyde with acetaldehyde in the presence of sodium hydroxide, crystallisation, filtration and drying the pentaerythritol. The formaldehyde source used is paraformaldehyde in form of granules, into which water is added at temperature 40±2°C and stirred for 4.5-5.5 minutes. Paraformaldehyde then undergoes preliminary dissolution in an alkaline sodium hydroxide solution, said paraformaldehyde being taken in amount of 30% of the total weight of sodium hydroxide, for 15-16.5 minutes at temperature 40-45°C. Further, acetaldehyde cooled to -10±0.1°C and a residual amount of sodium hydroxide are added under cooling conditions, and pulled out for 15 minutes while gradually raising temperature of the condensed solution to 60°C. Formic acid is added to the condensed solution until pH 6.5 is achieved.

EFFECT: high effectiveness of the process while ensuring the required quality of the product.

1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing pentaerythritol, involving condensation of formaldehyde with acetyldehyde in the presence of sodium hydroxide, rectification and evaporation of the condensed solution, vacuum crystallisation, filtration, washing the obtained technical pentaerythritol, recrystallisation, filtration and drying the pentaerythritol. The formaldehyde is used in form of a mixture of formalin and paraformaldehyde, where the paraformaldehyde constitutes up to 1/5 of the total amount of formaldehyde in the reaction mixture, the components being in the following molar ratio: acetaldehyde 1; formaldehyde 8.4-8.5; sodium hydroxide 1.15-1.20; water 70-72.

EFFECT: method increases efficiency of the process while ensuring high quality of the ready product.

1 ex

FIELD: process engineering.

SUBSTANCE: invention relates to organic synthesis, particularly, to method of processing commercial sodium pentaerythritol and formiate and may be used in chemical industry, paint-and-varnish industry, etc. Method of processing commercial sodium pentaerythritol and formiate mother solution consists in extracting pentaerythritol and liquid phase separation. Mother solution is diluted by water to content of sodium formiate of 30-32%. Then produced solution is heated to at least 60°C and mixed at said temperature for at least 4 hours at the rate of 900-1100 rpm. Then, produced suspension is filtered in vacuum filter to precipitate pentaerythritol and separate filtrate containing sodium formiate to extract the latter therefrom.

EFFECT: separate crystallisation of sodium pentaerythritol and formiate.

2 cl, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of processing filtrate wastes from production of pentaerythritol, containing (wt %): 32-37.81 sodium formate, 22-27 pentaerythritol, 10-11 cyclic monoformals, 2-3 dipentaerythritol, as well as pentaerythritol derivative impurities, to obtain technical pentaerythritol and sodium formate. The method involves treatment of the filtrate with an extraction agent, followed by separation and recycling of the obtained liquid and solid phases. Treatment is carried with water in water/filtrate ration equal to (0.5-1.0)/1 and temperature 15-25°C, followed by taking the washed off residue to the evaporation and crystallisation step to obtain technical pentaerythritol and the filtrate solution for evaporation and crystallisation to obtain sodium formate.

EFFECT: efficient method of processing waste filtrate from production of pentaerythritol.

2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method for synthesis of pentaerythritol and dipentaerythritol, involving reaction of acetaldehyde with formaldehyde in the presence of sodium hydroxide, purification of the reaction solution through distillation of excess formaldehyde, evaporation and crystallisation of technical pentaerythritol, washing the residue, recrystallisation of technical pentaerythritol, separation of the residue from the solution and drying commercial-grade pentaerythritol and treatment of the product after drying. After drying the product is treated through separation, thereby extracting the pentaerythritol fractions most contaminated with non-volatile impurities of dipentaerythritol and cyclic formalin, and the extracted fractions are processed by leaching pentaerythritol with demineralised water at 10-80°C and ratio of liquid phase to solid phase equal to (5.5-8)/1, and subsequent separation of the formed pentaerythritol solution and dipentaerythritol precipitate and taking the pentaerythritol solution to the technical pentaerythritol recrystallisation step.

EFFECT: method enables to obtain pentaerythritol with low content of dipentaerythritol and cyclic formalin impurities, as well as recycling of dipentaerythritol.

6 cl, 1 tbl, 7 ex

FIELD: concentration of pentaerythrite formate mother liquors in the multi-case evaporation plant with vertical heat exchange tubes for production of high-quality lacquers, additives for oils and other products.

SUBSTANCE: proposed method includes concentration of pentaerythrite formate mother liquors at the first stage by evaporation to saturation state by pentaerythrite and crystallization of pentaerythrite from saturated solution; concentration at the first stage is performed at film flow solution; crystallization is carried out at two stages at forced circulation of suspension thus formed. Secondary vapor is divided into two flows after first stage of evaporation: one flow is delivered to the first stage of crystallization and second flow is delivered to the second stage of crystallization. At the second stage of crystallization boiling point of suspension is maintained at temperature of 45-53°C which is below that at the first stage by 7-20°C. Evaporation plant for processing the pentaerythrite formate mother liquors has two stages of evaporators connected in succession in way of flow of vapor and solution and provided with vertical tubes. Second stage of evaporation plant is just crystallizer provided with circulating loop with pump and vapor separator connected with final condenser by means of vapor pipe line. First stage consists of film liquid flow evaporator; second stage is provided with additional crystallizer with circulating loop and pump and additional condenser connected with vapor separator of additional crystallizer; it is also provided with non-condensable gas discharge unit. Last evaporator of the first stage is provided with additional pipe line for discharge of secondary vapor which is communicated with heating chamber of additional crystallizer. Solution volume of additional crystallizer exceeds that of the first one by 1.5- 2.5 times.

EFFECT: improved quality of crystalline products; increased degree of extraction of pentaerythrite from solution; increased rate of processing the solutions.

6 cl, 1 dwg, 1 tbl

The invention relates to an improved process for the preparation of pentaerythritol with a basic substance content of more than 98 wt.% and pentaerythritol, enriched dipentaerythritol in the amount of 5-20 wt.%, used in paint and other industries

The invention relates to a method for the simultaneous receipt of pentaerythritol and sodium formate used in the chemical, leather and paint and other industries

The invention relates to a method for pentaerythritol by the interaction of acetaldehyde with an excess of formaldehyde in the presence of sodium hydroxide

FIELD: chemistry.

SUBSTANCE: method of obtaining diphenylcarbonate includes a reaction of carbon dioxide and epoxide in the first reaction zone with the formation of the first reaction product, which includes cyclic carbonate; reetherification of cyclic carbonate with ethanol in the presence of a catalyst of the first reetherification in the second reaction zone with the formation of the second reaction product, which includes diethylcarbonate and glycol; separation of the second reaction product with the extraction of the first fraction of diethylcarbonate and the first fraction of glycol; reetherification of, at least, a part of the first fraction of diethylcarbonate with arylhydroxycompound in the presence of a catalyst of the second reetherification in the third reaction zone with the formation of the third reaction product, which includes ethylarylcarbonate and ethanol; separation of the third reaction product with the extraction of ethylarylcarbonate fraction and the first fraction of ethanol; disproportioning of, at least, a part of ethylarylcarbonate fraction in the presence of a catalyst of disproportioning in the fourth reaction zone with the formation of the fourth reaction product, which includes diarylcarbonate and diethylcarbonate; separation of the fourth reaction product with the extraction of diarylcarbonate fraction and the second diethylcarbonate fraction; recirculation of, at least, a part of the first ethanol fraction into the second reaction zone and recirculation of, at least, a part of the second diethylcarbonate fraction into the third reaction zone. Or a method of diarylcarbonate obtaining includes a reaction of ammonia and carbon dioxide in the first reaction zone with the formation of the first reaction product, which includes urea; reetherification of urea with ethanol in the presence of a catalyst of the first reetherification in the second reaction zone with the formation of the second reaction product, which includes diethylcarbonate and ammonia; separation of the second reaction product with the extraction of the first fraction of diethylcarbonate and the first fraction of ammonia; reethrification of, at least, a part of the first fraction of diethylcarbonate with arylhydroxycompound in the presence of a catalyst of the second reetherification in the third reaction zone with the formation of the third reaction product, which includes ethylarylcarbonate and ethanol; separation of the third reaction product with the extraction of the ethylarylcarbonate fraction and ethanol fraction; disproportioning of, at least, part of the ethylarylcarbonate fraction in the presence of a catalyst of disproportioning in the fourth reaction zone with the formation of the fourth reaction product, which includes diarylcarbonate and diethylcarbonate; separation of the fourth reaction product with the extraction of the diarylcarbonate fraction and the second fraction of diethylcarbonate; recirculation of, at least, a part of the ethanol fraction into the second reaction zone and recirculation of, at least, a part of the second diethylcarbonate fraction into the third reaction zone. Disclosed methods efficiently combine into one the whole production of diethylcarbonate and diarylcarbonate, eliminating the necessity of extraction distillation with a solvent, which is usually applied in the production of diarylcarbonates from dimethylcabonate, providing a combination of reaction and separation equipment and best use of the raw material and reducing production costs and capital investments for such methods. In some versions of realisation the methods disclosed in the invention can be realised, for instance, with a practically closed cycle for ethanol.

EFFECT: invention relates to the methods of obtaining diarylcarbonates, which make it possible to obtain diarylcarbonates from gases, causing the greenhouse effect, such as carbon dioxide.

29 cl, 24 dwg, 9 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: described are methods of producing propylene glycol, ethylene glycol and other polyatomic alcohols, diatomic alcohols, ketones, aldehydes, carboxylic acids and alcohols from biomass using hydrogen obtained from the biomass. Methods involve reaction of a portion of an aqueous stream of the crude solution of the biomass in the presence of a catalyst under aqueous phase reforming conditions to obtain hydrogen, and then reaction of hydrogen and the crude aqueous solution in the presence of a catalyst to obtain propylene glycol, ethylene glycol and other polyatomic alcohols, diatomic alcohols, ketones, aldehydes, carboxylic acids and alcohols.

EFFECT: described methods can be realised at lower temperature and pressure, and enable to obtain oxygen-containing hydrocarbons without the need for supplying hydrogen from an external source.

62 cl, 16 ex, 11 dwg

FIELD: improved method for transalcoholysis of trimethylolpropahe monocyclic formal or trimethylolethane monocyclic formal.

SUBSTANCE: claimed method includes transalcoholysis reaction of trimethylolpropahe monocyclic formal or trimethylolethane monocyclic formal with excess of mono- or dibasic alcohol at elevated temperature in presence of acid catalyst to obtain trimethylolpropahe or trimethylolethane, respectively, used as synthesis intermediate of vide variety of products and acetales as by-product. Further provided by the present invention is method for interaction of composition containing at least 10 mass % of trimethylolpropahe bis(monolinear) formal or trimethylolethane bis(monolinear) formal, not more than 5 mass % of water, and mono- or dibasic alcohol in stoichiometric excess with strong acid catalyst at 30-3000C, for such period of time as to convert sufficient amount of said trimethylolpropahe bis(monolinear) formal or trimethylolethane bis(monolinear) formal to trimethylolpropahe or trimethylolethane, respectively, and acetales as by-product.

EFFECT: method for production of target products with improved yield.

27 cl, 10 ex, 11 tbl

The invention relates to an improved method of separation of polyols, such as neopentyl glycol or atrial, and sodium formate or calcium, comprising adding to the mixture of the partial organic solvent, in which the polyhydric alcohol is dissolved, the crystallization of sodium formate or calcium, Department of formate sodium or calcium from the solution of a polyhydric alcohol in an organic solvent, for example, by filtration, recycling of organic solvent, cooling the solution and crystallization of a polyhydric alcohol, and as the organic solvent used solvent aromatic series such as toluene, after adding to the mixture of the partial substances organic solvent, the resulting mixture is heated to boiling point and produce at this temperature simultaneously: dehydration of the mixture by distillation with water recirculation separated from water, organic solvent, crystallization dissolved in an organic solvent, sodium formate or calcium and dissolution in an organic solvent, a polyhydric alcohol

The invention relates to the oil industry, namely to the production of distilled glycerol

The invention relates to a method for crude glycerol, which consists in resistive hydrolysis of fats and oils with subsequent separation of fatty acids and glycerin water

The invention relates to the processing of glycerin produced during the breakdown of fats or synthetic method, and can be used in cosmetic, chemical and medical industry for the preparation of drugs, physiologically compatible with human skin

The invention relates to the field of chemical technology and can be used in the distillation of organic compounds in the chemical, food, petrochemical and other industries

The invention relates to the field of chemical technology and can be used in the distillation of technical glycerol in the chemical processing, food and other industries

FIELD: chemistry.

SUBSTANCE: invention relates to a mesoporous carbon supported tungsten-carbide catalyst for direct catalytic conversion of cellulose to ethylene glycol, wherein the support is mesoporous carbon. The tungsten-carbide catalysts are dispersed on the surface or in channels in the carbon support. The metal component W ranges from 1 to 80 wt % of the catalyst and particularly from 30 to 42 wt %. The invention also relates to a method of producing a catalyst by impregnating a mesoporous carbon support with a tungsten and nickel or tungsten salt solution and use of the catalyst.

EFFECT: obtaining a catalyst for converting cellulose to ethylene glycol with high output and selectivity.

10 cl, 3 dwg, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: method of obtaining diphenylcarbonate includes a reaction of carbon dioxide and epoxide in the first reaction zone with the formation of the first reaction product, which includes cyclic carbonate; reetherification of cyclic carbonate with ethanol in the presence of a catalyst of the first reetherification in the second reaction zone with the formation of the second reaction product, which includes diethylcarbonate and glycol; separation of the second reaction product with the extraction of the first fraction of diethylcarbonate and the first fraction of glycol; reetherification of, at least, a part of the first fraction of diethylcarbonate with arylhydroxycompound in the presence of a catalyst of the second reetherification in the third reaction zone with the formation of the third reaction product, which includes ethylarylcarbonate and ethanol; separation of the third reaction product with the extraction of ethylarylcarbonate fraction and the first fraction of ethanol; disproportioning of, at least, a part of ethylarylcarbonate fraction in the presence of a catalyst of disproportioning in the fourth reaction zone with the formation of the fourth reaction product, which includes diarylcarbonate and diethylcarbonate; separation of the fourth reaction product with the extraction of diarylcarbonate fraction and the second diethylcarbonate fraction; recirculation of, at least, a part of the first ethanol fraction into the second reaction zone and recirculation of, at least, a part of the second diethylcarbonate fraction into the third reaction zone. Or a method of diarylcarbonate obtaining includes a reaction of ammonia and carbon dioxide in the first reaction zone with the formation of the first reaction product, which includes urea; reetherification of urea with ethanol in the presence of a catalyst of the first reetherification in the second reaction zone with the formation of the second reaction product, which includes diethylcarbonate and ammonia; separation of the second reaction product with the extraction of the first fraction of diethylcarbonate and the first fraction of ammonia; reethrification of, at least, a part of the first fraction of diethylcarbonate with arylhydroxycompound in the presence of a catalyst of the second reetherification in the third reaction zone with the formation of the third reaction product, which includes ethylarylcarbonate and ethanol; separation of the third reaction product with the extraction of the ethylarylcarbonate fraction and ethanol fraction; disproportioning of, at least, part of the ethylarylcarbonate fraction in the presence of a catalyst of disproportioning in the fourth reaction zone with the formation of the fourth reaction product, which includes diarylcarbonate and diethylcarbonate; separation of the fourth reaction product with the extraction of the diarylcarbonate fraction and the second fraction of diethylcarbonate; recirculation of, at least, a part of the ethanol fraction into the second reaction zone and recirculation of, at least, a part of the second diethylcarbonate fraction into the third reaction zone. Disclosed methods efficiently combine into one the whole production of diethylcarbonate and diarylcarbonate, eliminating the necessity of extraction distillation with a solvent, which is usually applied in the production of diarylcarbonates from dimethylcabonate, providing a combination of reaction and separation equipment and best use of the raw material and reducing production costs and capital investments for such methods. In some versions of realisation the methods disclosed in the invention can be realised, for instance, with a practically closed cycle for ethanol.

EFFECT: invention relates to the methods of obtaining diarylcarbonates, which make it possible to obtain diarylcarbonates from gases, causing the greenhouse effect, such as carbon dioxide.

29 cl, 24 dwg, 9 tbl, 18 ex

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