Method of producing polymethylols

FIELD: chemistry.

SUBSTANCE: invention relates to a method of distilling an aqueous polymethylol mixture containing a polymethylol of formula

,

a tertiary amine, water, as well as an adduct of a tertiary amine and formic acid (amine formate). According to the disclosed method, distillation is carried out in a distillation column equipped with a condenser, the lower part of the column being connected to an evaporator, wherein temperature in the lower part of the column is higher than the evaporation temperature of the monoether of formic acid and polymethylol (polymethylol formate) formed during the distillation process. In formula (I), R in each case independently denotes another methylol group or an alkyl group with 1-22 carbon atoms or an aryl or aralkyl group with 6-22 carbon atoms.

EFFECT: method enables to obtain polymethylols with low content of polymethylol formate.

14 cl, 4 ex

 

The invention relates to a method of distilling water polymethylenes mixture, which is obtained during the synthesis of polietileno from alcanada and formaldehyde. In addition, the present invention relates also to a composition containing Polymetal and from 1 to 10000 wt. including million Polimetall-formate, as well as to its use.

Polimetall, such as neopentylglycol ("NPG") and trimethylolpropane ("TSR") are used in the field of synthetic polymers to obtain varnishes, coatings, polyurethanes and polyesters.

In industry Polimetall, basically, get the reaction of the Kan-Nazzaro. To obtain trimethylolpropane this way is subjected to the interaction of the n-Butyraldehyde with an excess of formaldehyde in the presence of inorganic bases. At the same time to form one equivalent of an inorganic formate as a by-product interaction. The separation of the salt of trimethylolpropane is complex and requires additional costs. In addition, if necessary, the useful life of an inorganic salt, it requires processing and purification. The formation of the product of the interaction leads to the loss used in the stoichiometric amount of sodium lye and formaldehyde. In addition, the yield of the reaction product in respect of the h-Butyraldehyde in this inorganic reactions Kahn is Azzaro is unsatisfactory, as in the reaction are formed of the high-boiling components, which cannot then be used. Same problems as described for trimethylolpropane, there are at getting other polietileno, such as trimethylated (derived from n-propanole and formaldehyde) or trimethylbutane (derived from n-pentanal and formaldehyde) or neopentylglycol (derived from Isobutyraldehyde and formaldehyde).

In order to avoid these defects in the international application WO 98/28253 published multi-stage method of producing polietileno, according to which the aldehydes containing from 2 to 4 carbon atoms, in the first stage (andolina reaction) condense with formaldehyde in the presence as catalyst of amines with the formation of the first relevant methylalanine, and then at another stage (hydrogenation) hydronaut with the formation of the corresponding polietileno. This multi-stage method is usually called by way of hydrogenation. In this way produces few side products of interaction. After the first stage of the method of hydrogenation of unreacted aldehyde and a part of the amine base is usually separated by distillation from the resulting methylalanine and return in the process.

In the product distillation in the lower part of the column in addition to the formed methylalanine is water, Addu what you are formic acid and used tertiary amines (amine-formate) itself formic acid.

As a rule, polymetallurgical according to this method are in the form of 20-70%aqueous solution.

An aqueous solution containing polymetallurgical, hydronaut in the second stage to convert polymethylenes in the appropriate Polimetall, such as trimethylolpropane ("TSR") and neopentylglycol ("NPG").

When the hydrogenation is commonly observed adverse reactions such as reverse splitting methylalanine free alkanal and formaldehyde and, in addition, the formation of a simple ester, complex ester and acetal.

These side reactions lead to low selectivity of the hydrogenation and low output polietileno.

These by-products can also degrade the quality of the formed polietileno and damage when used for certain purposes. So, contained in the final product the formate can decompose with the formation of formic acid. Formic acid may, for example, catalyze the hydrolysis of urethane or ester groups, which leads to accelerated aging of varnishes and plastics.

In the framework of the present invention has now been found that, in particular, complex monoether of formic acid and educated polietileno (Polimetall-formate) leads to the content in the final product formate.

Therefore, the present invention was to create the AI method to purify water polymetallic mixtures to obtain polietileno low Polimetall-formate.

The present invention is solved by the method of distillation of water polymethylenes mixtures containing Polimetall formula (I):

in which R, independently of one another, in each case, other means of methylol group or an alkyl group with 1-22 carbon atoms or aryl or aracelio group with 6-22 carbon atoms, and containing tertiary amine, water, and adduct of tertiary amine and formic acid (Amin-formate), characterized in that the distillation product of the hydrogenation is carried out in a distillation column, the bottom of which is connected to the evaporator, and the temperature in the lower part of the column exceeds the evaporation temperature generated in the process of distilling complex monoamino formic acid and Polymetal (Polymetal-formate).

Used in the way water polimetalla mixture preferably has the following composition:

from 20 to 90 wt.% Polymetal (I)

from 0 to 5 wt.% methanol,

from 0 to 5 wt.% tertiary amine,

from 0 to 5 wt.% organic side connections

from 0.01 to 5 wt.% adduct of tertiary amine and formic acid (Amin-formate),

the rest is water.

Particularly preferably, water polimetalla mixture has the following composition:

from 50 to 80 wt.% Polymetal (I)

from 0.1 to 3 wt.% methanol,

from 0.01 to 5 m is S.% tertiary amine,

from 0 to 5 wt.% organic side connections

from 0.01 to 5 wt.% adduct of tertiary amine and formic acid (Amin-formate),

the rest is water.

Such water polymethylene mixture, preferably, get a multistage interaction alcanada with formaldehyde. Preferably, water polietileno mixture obtained by way of hydrogenation.

However, it is also possible to carry out the method according to the invention for distillation of water polymethylenes mixture with polymethylenes mixture obtained by the organic cannizzaro reaction (strong organic base and formaldehyde).

As mentioned above, water polietileno mixture, preferably, get a multistage method of hydrogenation, and at the stage a) alkanal condense with formaldehyde by aldol reaction in the presence of tertiary amines as a catalyst with the formation of metrolina formula (II), and R, independently of one another in each case have the abovementioned meaning:

and then, in stage b) the reaction mixture obtained in stage a), divided by the distillation of the product exiting the bottom of column containing, primarily, the compounds of formula (II), and head (leaving the top of column) a stream containing low-boiling components, and in step c) the product exiting the bottom of column subjected to hydrogenation.

In the first stage of the method (a) (aldol reaction) is usually subjected to the interaction of alkanal with formaldehyde by aldol reaction in the presence as catalyst of tertiary amines.

Generally, the formaldehyde is used in the way in the form of its aqueous solution. Technical formaldehyde usually arrives on the market in the form of an aqueous solution with a concentration of 30, 37 and 49 wt.%. However, in the method according to the invention can also be used solutions of formaldehyde with a concentration of up to 60 wt.%.

Technical formaldehyde, typically contains formic acid, due to the conditions of its reception. Decomposition of formic acid may reduce the period of stability of the hydrogenation catalyst, at a subsequent stage of hydrogenation, which may lead to reduced output polietileno. In a particular embodiment, the method uses a formaldehyde containing 150 parts per million of formic acid. As described in the international application PCT/EP2008/052240, the formaldehyde can be obtained by treating formaldehyde or an aqueous solution of formaldehyde basic ion exchangers. As the anion-exchanger can be used strong, weakly basic or srednesrocnye gel-like or macroporous ion exchangers. For example, aminoalkenes with the structure of polystirol the second resin, crosslinked divinylbenzene, and tertiary amino groups as functional groups. Can also be used ion exchanger based on acrylic or methacrylic acid, crosslinked with divinylbenzene, or resins obtained by condensation of formaldehyde and phenol. In particular, using, for example, commercial products Ambersep® 900, Amberlyst® and Amberlite® company Rohm und Haas, Philadelphia, USA, and Lewatit® Lanxess, Leverkusen.

In the method according to the invention can be used, alkanal with a methylene group in α-position to a carbonyl group.

Preferably, the source material may be used aliphatic, alkanal with 2-24 carbon atoms, which may be remotemachine or branched or may contain an alicyclic group.

As the source material can be used also alkanal, analiticheskie, provided that they contain a methylene group in α-position to a carbonyl group. Usually as the source material used, aralkylamines with 8-24 carbon atoms, preferably from 8 to 12 carbon atoms, such as phenylacetaldehyde. It is preferable to use aliphatic, alkanal with 2-12 carbon atoms, such as 3-ethyl-, 3-n-propyl-, 3-isopropyl-, 3-n-butyl-, 3-isobutyl-, 3-vtoroj-, 3-tertbutyl-butanol, and also the corresponding-n-pentanal, ' n ' hexanal, -n-heptane is; 4-ethyl-, 4-n-propyl, 4-isopropyl-, 4-n-butyl-, 4-isobutyl-, 4-vtoroj-, 4-tertbutyl-pentanal, ' n ' hexanal, -n-heptanal; 5-ethyl-, 5-n-propyl-, 5-isopropyl-, 5-n-butyl-, 5-isobutyl-, 5-vtoroj-, 5-tertbutyl-n-hexanal, -n-heptanal; 3-methylhexane, 3-methylheptane, 4-methylpentanol, 4-methylheptane, 5-methylhexane, 5-methylheptane, 3,3,5-trimethyl-n-pentyl-, 3,3-diethylphenyl-, 4,4-diethylphenyl-, 3,3-dimethyl-n-butyl-, 3,3-dimethyl-n-pentyl-, 5,5-dimethyl-n-pentyl-, 5,5-dimethylheptyl-, 3,3-dimethylheptyl-, 3,3,4-trimethylpentyl-, 3,4-dimethylheptyl-, 3,5-dimethylheptyl-, 4,4-dimethylheptyl-, 3,3 is di-ethylhexyl-, 4,4-dimethylhex-, 4,5-diethylhexyl-, 3,4-dimethylhex-, 3,5-dimethylhex-, 3,3-diethylhexyl-, 3,4 is di-ethylhexyl-, 3-methyl-4-ethylphenyl-, 3-methyl-4-ethylhexyl-, 3,3,4-trimethylpentyl-, 3,4,4-trimethylpentyl-, 3,3,4-trimethylhexane-, 3,4,4-trimethylpentyl-, 3,3,4,4-tetramethylethylenediamine; especially, n-alkanal with 2-12 carbon atoms.

In addition to the preferably used to obtain neopentyl glycol of Isobutyraldehyde as a starting compound can be used, preferably, in addition, n-Butyraldehyde to obtain trimethylolpropane, acetaldehyde to obtain pentaerythritol, Propionaldehyde to obtain trimethyloctane and n-pental to obtain trimethylbutane.

As tertiary amines can be used amines described, for example, the R, in the German patent applications DE-A 28 13 201 and DE-A 2702582. Especially preferred are tri-n-alkylamines followed, especially tri-ethylamine, tri-n-Propylamine, tri-n-butylamine and trimethylamine. Especially preferred are the trimethylamine (TMA), triethylamine ("TEA") and tri-n-Propylamine ("TRA"), since these compounds generally have a lower boiling point than is preferably formed Polimetall and, therefore, easier to distillation to remove from the reaction mixture. Especially preferably, as the tertiary amine used trimethylamine ("TMA").

Aldorino reaction can be carried out with addition or without addition of organic solvents or tools to facilitate dissolution. The addition of solvents or contributing to the dissolution of the funds may be preferred, especially when using as starting materials long alcanada. Through the use of solvents, forming the corresponding low-boiling azeotropic mixtures with a low-boiling compounds, if necessary, distillation method according to the invention can be reduced energy consumption for distillation and/or distillation separation of boiling components from the high-boiling compounds.

As a suitable solvent, for example, cyclic and acyclic simple the e esters, such as tetrahydrofuran (THF), dioxane, methyl-trebuemuyu ether or alcohols such as methanol, ethanol or 2-ethylhexanol.

It is expedient, if the relation is added, in each case, fresh alkanes to add to the quantity of formaldehyde in the aldol reaction is between 1:1 and 1:5, preferably from 1:2 to 1:3,5.

The number used in the aldol reaction of the tertiary amine catalyst is usually from 0.001 to 0.2, preferably from 0.01 to 0.07 equivalent with respect to alkanal, that is, the amine is usually used in catalytic amounts.

Aldorino reaction is usually carried out at a temperature of from 5 to 100°C, preferably from 15 to 80°C, and the residence time is usually set from 0.25 to 12 hours depending on the temperature.

In the described conditions aldorino reaction can be conducted at a pressure of from 1 to 30 bar, preferably from 1 to 15 bar, particularly preferably from 1 to 5 bar, it is expedient, when the pressure in the particular reaction system.

Aldorino reaction can be continuous or periodic manner. Preferably, aldorino the reaction is carried out in a continuously operating boiler reactor with stirring or in a cascade boiler reactor with stirring. To regulate the residence time in the reactor part p is a promotional product, coming out of the reactor, return in the running of the boiler reactor with stirring.

Coming out of the reactor product of aldol reaction typically contains unreacted starting compound, such as formaldehyde, alcalali and also used a tertiary amine catalyst and, possibly, water.

In addition, emerging from the reactor product of aldol reaction contains methylallyl formula (II):

in which R in each case independently of one another, mean a different methylol group or an alkyl group with 1-22 carbon atoms or aryl or aracelio group with 6-22 carbon atoms. An example of methylalanine is hydroxypivalic aldehyde formed as educt when using Isobutyraldehyde, or dimethylaminoethanol formed as educt when using n-Butyraldehyde.

Usually coming out of the reactor product also contains impurities and by-products of aldol reactions such as formic acid, which may be formed from formaldehyde in the reaction Cannizzaro or Tishchenko, and formate salts used amine catalysts, such as trimethylammonium.

Coming out of the reactor product of aldol reaction is usually then subjected to distillation separation (stage b)).

Thus o is handled from the reactor product of aldol reaction is directed to a device for distillation, usually in the column, which is divided into more low-boiling and more high-boiling liquid components.

The conditions of distillation, usually chosen in such a way as to form a fraction of the low-boiling components, in which the main components contained unreacted alkanol, formaldehyde and, optionally, water and methanol. This so-called low-boiling fraction may be returned to the first stage of the method of hydrogenation - aldorino reaction, or sent to another stage of processing.

After separation of low-boiling fractions described distillation processing remains more high-boiling liquid product leaving the bottom of the distillation column, consisting mainly of methylalanine formula (II), for example hydroxypivalic aldehyde, water, formic acid, and amine-formate.

When using trimethylamine (TMA) as a tertiary amine of the conditions of distillation is chosen such that the TMA is partially contained in the low-boiling fraction and a small part was in the product from the bottom of the column. When using amines, more storable than TMA, the conditions of distillation is chosen such that the product from the bottom of the column was enriched tertiary products.

Distillation separation should implement a preference for the equipment, under moderate pressure, to methylalanine (II) is not decomposed at elevated temperatures. For example, hydroxypivalic aldehyde can turn into neopentylglycol ether hydroxypivalic acid (NRM). On the other hand, the pressure should not be too low to low-boiling alkanol, such as Isobutyraldehyde, and amine base, such as trialkylamine, such as trimethylamine, to condense even at the head of the column.

Therefore, the distillation should be carried out at not too low pressure, as a rule, below about 60°C the solubility of alkanes (II), such as hydroxypivalic aldehyde (NDA), in aqueous solution immediately falls to a value from about 1 to 3 wt.% depending on the content of alkanes and methanol.

In addition, separation of the product effluent from the reactor at aldol reaction, carried out so that the amount of methanol in the stream of low-boiling components were maintained as low as possible, so that the concentration of methanol in the aldol reaction is not increased. Typically, methanol is transferred through a solution of formaldehyde, which depending on the conditions of receipt contains from about 1 to 3 wt.% of methanol.

The boiling point of methanol, as a rule, is lower than that of unreacted alkanes, resulting in methanol accumulated is moved to the head of the column and maintaining the concentration of methanol in the process at a certain level.

To maintain a low concentration of methanol can be used a variety of techniques.

First, it is preferable to use as educt in the aldol reaction depleted methanol formaldehyde.

In addition, you can withdraw from the process methanol together with unreacted alkanals that leads to loss of alkanes.

However, in the preferred embodiment, the distillation is carried out in special conditions, resulting methanol in sufficient quantity is retained in the lower part of the column. This preferred option distillation separation of the product effluent from the reactor at aldol reaction described in international application PCT/EP2008/052240.

In this embodiment, the distillation separation of product at low-boiling fraction and the product from the bottom of the column is carried out in distillation column typically at a temperature of from 50 to 200°C, preferably from 90 to 160°C and a pressure of usually from 0.1 mbar to 10 bar, preferably from 0.5 to 5 bar, particularly at atmospheric pressure. Usually the distillation column operates at a pressure in the head part of from 0.5 to 1.5 bar.

In the head area is provided, preferably, the two-stage condensation, in which the secondary (juice) pairs of first guide in working at a temperature of from 50 to 80°C the partial condenser, the condensate to the showing, at least partially returned to the distillation column, and which is not condensed in the partial condenser secondary (juice) pairs sent to additionally attached at the temperature ranging from -40°C to +30°C, the condenser, the condensate from which at least partly down.

The condensate from the partial condenser, preferably more than 70 wt.%, particularly preferably, completely return to a distillation column. The condensate from the attached additional capacitor, preferably lower, at least 70 wt.%, especially, completely.

The partial condenser operates at a temperature in the range from 50 to 80°C, preferably between 55 and 60°C. Additionally attached to the condenser operates at a temperature range from -40°C to +30°C, preferably from -10°C to +10°C. the Pressure in the head of the column, particularly preferably ranges from 1 to 1.2 bar.

The lower part of the distillation column, preferably, connected to the evaporator with a short residence time, operating at a temperature in the range from 90 to 130°C, particularly preferably from 100 to 105°C. this can be particularly preferred to use film evaporator, falling film. In addition, it may be preferable to use the square the night evaporator (Wischfilmverdampfer) or molecular distillation evaporator (Kurzwegverdampfer). It is important to achieve short residence time and, consequently, a small thermal effect. The evaporator can be supplied with heat in the usual way, for example with steam pressure of 4 bar.

To improve the efficiency of separation distillation column preferably has a nozzle. When escaping from the reactor product of aldol reaction, preferably, is applied in the spatial domain between 1/4 and 3/4 of theoretical plates of the distillation column, particularly preferably, in the spatial region between 1/3 and 2/3 of theoretical plates of the distillation column. Preferably, the fluid supply may be a little above the middle of theoretical plates (ratio 3:4). Distillation nozzle may be, for example, in the form of ordered packages, such as tin packages, such as Mellapak 250 Y or Montz Pak, Tour B1-250. Can also be used a package with a reduced or increased specific surface or may use a tissue package or a package with a different geometry, such as Mellapak 252 Y. Advantage of these distillation nozzles compared to, for example, with the valve plates are small pressure loss and a small specific retention of fluids. In the partial condenser as condensate is formed, the advantage is significant, water, which, preferably, down in the column in the form of reverse flow. Upon receipt of neopentyl glycol ("NPG") as the condensate can be obtained, for example, a mixture containing in addition to water about 10 wt.% Isobutyraldehyde, about 5 wt.% amine bases, such as trimethylamine, about 1 wt.% hydroxypivalic aldehyde and about 5 wt.% methanol, if the educt used Isobutyraldehyde. In this case, the residual secondary pairs contains the vast number of Isobutyraldehyde and amine base, such as trimethylamine. Them, as much as possible, condense in addition attached condenser. At the same time as the cooling medium can be used as more cold water (for example, with a temperature of about 5°C) or cool the mixture (such as a glycol - water, for example, -20°C). The mixture enriched methylalkanes (II), for example hydroxypivalic aldehyde or dimethylaluminum, released from the bottom of the evaporator. It is also possible release from the circulating stream.

More high-boiling liquid product from the bottom of the column for the distillation separation of the product effluent from the reactor for the aldol reaction, before further processing can be cooled in the refrigerator with a cooling temperature in the range from 50 to 80°C, particularly preferably from 55 is about 60°C, to reduce thermal effects.

Thus obtained product leaving the bottom of the column at stage b), can then be subjected to subsequent hydrogenation in stage (c).

The product leaving the bottom of the column at the stage b) of the method, hydrogenation, contains methylallyl General formula (II) and stage c) of the method, the hydrogenation is subjected to hydrogenation (hydrogenation) with formation of corresponding polietileno.

For the hydrogenation, preferably using a catalyst containing at least one metal side groups 8 to 12 of the Periodic system of elements, such as Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, preferably Fe, Co, Ni, Cu, Ru, Pd, Pt, particularly preferably si, mainly on the media.

As a material medium, it is preferable to use material from oxides of titanium, zirconium, hafnium, silicon and/or aluminum.

Getting used catalysts can be known from the prior art method of obtaining such catalysts on the media. Preferably, can be used catalysts on a carrier containing copper on a carrier containing aluminum oxide or titanium dioxide, in the presence or absence of one or more elements such as magnesium, barium, zinc or chromium. Such catalysts and methods for their production are known from IU the international application WO 99/44974. In addition, for the hydrogenation of suitable copper-containing catalysts on a carrier, such as described, for example, in international application WO 95/32171, and the catalysts described in European patent application EP-A 44444 and in the German patent DE 1957591.

The hydrogenation may be periodic or continuous methods, for example, in a tube filled with filling the catalyst, when the reaction solution is passed through the catalytic poured, for example, irrigation or kubovy balance (Sumpffahrweise), as described in the German patent applications DE-A 1941633 or DE-A 2040501. It may be preferable to return back portion of the stream exiting the reactor, if necessary, with cooling, and again pass through the fixed catalyst bed. It may be also preferable to carry out the hydrogenation pass through several adjacent reactors, for example 2-4 reactor, and in a separate reactor before the last reactor, the hydrogenation reaction is conducted only to a partial degree of conversion, for example, from 50 to 98% and only in the last reactor hydrogenation complete fully. Thus, it may be desirable to cool the product of hydrogenation, emerging from the preceding reactor, before entering it into the subsequent reactor, for example, through the cooling unit or through the OHL is born nozzle flow of cold gas, such as hydrogen or nitrogen, or by direction of the flow in the cold reaction solution.

The temperature of hydrogenation is usually between 50 and 180°C, preferably between 90 and 140°C. the Pressure during the hydrogenation is usually varies from 10 to 250 bar, preferably from 20 to 120 bar.

Power supply solution for hydrogenation, as a rule, are mixed before entering the reactor for hydrogenation with a tertiary amine to the value of the pH coming out of the reactor for hydrogenation product from 7 to 9. You can also submit separately to the reactor feed solution for hydrogenation and tertiary amine and there to mix. As tertiary amines may be used the above-mentioned amines, especially trimethylamine (TMA).

Coming from the stage hydrogenation (stage c)) the product is a water polietileno mixture containing Polimetall formula (I):

in which R, independently of one another in each case denote different methylol group or an alkyl group with 1-22 carbon atoms or aryl or aracelio group with 6-22 carbon atoms and containing a tertiary amine, water and adduct of tertiary amine and formic acid (Amin-formate).

As mentioned above, water polimetalla mixture preferably has the following composition:

from 20 to 90 wt.% Polymetal (I)

from 0 to 5 mA is.% methanol,

from 0 to 5 wt.% tertiary amine,

from 0 to 5 wt.% organic side connections

from 0.01 to 5 wt.% adduct of tertiary amine and formic acid (Amin-formate),

the rest is water.

Particularly preferably, water polimetalla mixture has the following composition:

from 50 to 80 wt.% Polymetal (I)

from 0.1 to 3 wt.% methanol,

from 0.01 to 5 wt.% tertiary amine,

from 0 to 5 wt.% organic side connections

from 0.01 to 5 wt.% adduct of tertiary amine and formic acid (Amin-formate),

the rest is water.

As the organic side of the connection can contain, for example, gidrirovanny form used alkanes, namely alcohol of formula (III):

in which R, independently of one another in each case have the above-mentioned value.

Water polietileno mixture purified according to the invention the separation of low-boiling components from prematilleke connection. The separation of low-boiling compounds from water polymethylenes mixture is performed according to the invention by distillation.

The distillation is preferably carried out so that the low-boiling components such as water, alcohol of formula (III), methanol and tertiary amine is separated through the head of the column, especially if the amine has a lower temperature of the pile is Oia, than educated Polimetall, as, for example, in the case of trimethylamine (TMA), triethylamine (TEA) and tri-n-Propylamine (TPA).

If you use a tertiary amine having a higher boiling point than educated Polimetall, the tertiary amine is separated together with educated polietileno in the lower part of the column and at a later stage distillation concentrate in the lower part of the column, while Polymetal selected as the head product.

In the framework of the present invention discovered that part of the amine-formate reacts with polimetinovymi compounds in the distillation process in the lower part of the column or in a distant part of the column with the formation of free amines and formate polymetallic compounds. In this case, preferably, is formed of monoether formic acid and prematilleke compound called in the context of this application, Polimetall-formate. Released in the interesterification reaction amines, usually separated in the distillation process, along with other low-boiling components in the head of the column. Distillation adjust so that the concentration of the educated Polimetall-formate in coming out of the bottom of the column the product to maintain a low and get as clean as possible target product - Polymetal.

According to the invention this is implemented by choosing the Ohm temperature at the bottom of the distillation column at higher temperature evaporation Polimetall-formate, resulting in Polimetall-formate fully or almost fully translated by evaporation into the gas phase.

Due to the conditions of the invention increase the yield of the target product and improve its quality, probably due to the fact that Polimetall-formate usually have a higher boiling point than the other low-boiling components, and therefore Polimetall-formate, as a rule, is condensed in the strengthening of the column when the corresponding reflux. Condensed in the concentrating of column Polimetall-formate can be either hydrolyzed with water and the regeneration of formic acid and prematilleke connection. Formic acid is usually separated at the head of the column, while polymethylene connection, usually away from the bottom of the column.

In a preferred embodiment of the method, the distillation is carried out as follows, as described below.

In this preferred embodiment, the capacitor typically operates at a temperature at which the predominant part of the low-boiling components are condensed with a corresponding pressure in the head of the column.

Typically, the operating temperature of the condenser is in the range from 0 to 80°C, preferably from 20 to 50°C.

As the cooling medium may be used, the pre is respectfully, more cold water (for example, with a temperature of about 5°C) or cooling the mixture (such as a glycol - water, with a temperature of, for example, -20°C).

The pressure in the head of the column, particularly preferably, is from 0.001 to 0.9 bar, most preferably from 0.01 to 0.5 bar.

The industry usually create a vacuum by means of steam jet ejector. In the lower part of the column, preferably, keep the temperature above the evaporation temperature of Polymetal-formate, making Polimetall-formate completely or almost completely in the gas phase.

Particularly preferably, the support temperature exceeding the boiling temperature of Polymetal-formate in the amount of from 5% to 50% and, most preferably, on the order of 10% to 20%. For example, upon receipt of neopentyl glycol (NPG) using trimethylaluminum (TMA) as a tertiary amine, and at a pressure in the head of the column 175 mbar in the lower part of the column can be maintained at a temperature of, preferably, from 150 to 170°C, most preferably from 160 to 165°C.

Return the thread to the head of the column, as a rule, adjust so that the column remained predominant amount of Polymetal-formate.

Preferably condensed in the condenser, the condensate is returned to the distillation column in which Alceste more than 30 wt.%, preferably more than 60 wt.%. When the condensate return, preferably in the head of the column.

Necessary for the evaporation of energy usually get through the evaporator in the lower part of the column. Usually used as an evaporator evaporator with natural circulation or forced circulation. However, you can also use a vaporizer with a short residence time, a thin-film evaporator or tubular loop evaporator, washed film evaporator or molecular distillation evaporator. The evaporator can be heated in the usual manner, for example, vapor pressure of 16 bar or oil cooled.

To improve the efficiency of separation distillation column preferably has a nozzle. Distillation nozzle may be, for example, in the form of an ordered packing, such as tin packing, such as Mellapak 250 Y or Montz Pak, Tour B1-250. Can also be used the package with reduced or increased specific surface or can be used a package of tissue or packing with another geometric shape, such as Mellapak 252 Y. Advantage of such distillation nozzles are low pressure loss and low specific retention of fluids in comparison, for example, with the valve. Nozzle mo which should be located in one or more injections. The product leaving the reactor hydrogenation, preferably served in a spatial region between 1/4 and 3/4 of theoretical plates of the distillation column, particularly preferably, in the spatial region between 1/3 and 2/3 of theoretical plates of the distillation column. For example, fluid may be approximately above the middle of theoretical plates (ratio 3:4). The number of theoretical plates of the distillation column is typically in the range from 5 to 30, preferably from 10 to 20.

In the condenser as condensation condense the mixture of low-boiling components, most of which, as described above, return in the form of return flow in the column. The mixture of low-boiling components may include, for example, amine, water, and alcohols of the formula (III), such as Isobutanol from Isobutyraldehyde or n-butanol from n-Butyraldehyde and methanol from formaldehyde.

Neskondensirovannyh residual secondary pairs can be routed directly into a gaseous state for combustion, which is energetically favorable, or it can be sent to a distillation column operating at a pressure close to the atmospheric ambient pressure. This additional column is an additional distillation separation of the condensate.

The product emerging from the nether is it part of the evaporator, containing mainly polymethylene connection, preferably, spuskaetsja also the product of the circulation circuit of the evaporator.

The product leaving the bottom of the reactor, in the framework of the present invention are called "raw Polimetall".

Obtained according to the invention "raw Polimetall" compared with the prior art contains fewer Polimetall-formate. Contents Polimetall-formate, preferably less than 1500 parts by weight per million, particularly preferably less than 1200 parts by weight per million, most preferably, less than 800 parts by weight per million and more preferably less than 600 parts by weight per million

Crude Polimetall, in addition, contains Polimetall formula (I):

in which R in each case independently of one another, mean a different methylol group or an alkyl group with 1-22 carbon atoms or aryl or aracelio group with 6-22 carbon atoms, and gidrokshikislotu formula (IV):

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

Crude Polimetall preferably has the following composition:

from 90 to 99 wt.% Polimetall formula (I),

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

from 0 to 5 wt.% organic side joint is.

Particularly preferably, the crude Polymetal, has the following composition:

from 95 to 99 wt.% Polimetall formula (I),

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

from 0 to 3 wt.% organic side connections.

As described above, such crude Polimetall receive, preferably, the multistage interaction alcanada with formaldehyde. Preferably, the crude Polimetall get way with hydrogenation.

For the Department located in the lower part of the column more high-boiling acid components, especially hydroxyacids of formula (IV), low loss prematilleke connection when distillation is used as the evaporator for the product exiting the bottom of the column, in a particularly preferred embodiment, the method uses at least one evaporator with short residence time, such as film evaporator with a downward flow and return of final product, a thin-film evaporator or loop the tube.

In a special embodiment of the method the bottom of the column may be concave (als eingezogener Sumpf)to further reduce the residence time of the product in the lower part of the column.

Distillation of the crude Polimetall preferably conducted in the following conditions.

Condensed in the condenser condens is t, preferably, return to a distillation column (return or reverse flow) in an amount of more than 30 wt.%, especially preferably more than 50 wt.%.

The condenser operates at a temperature in the range from 50 to 180°C, preferably from 130 to 160°C.

As the cooling medium, it is preferable to use, whenever possible, the water that evaporates.

The pressure in the head part of the column is, particularly preferably, from 0.001 to 0.9 bar. The industry usually create a vacuum by means of steam jet ejector.

The temperature in the lower part of the column, usually choose to translate Polimetall in the gas phase, while hydroxycitrate formula (IV) remains in the lower part of the column. The temperature in the lower part of the column is adjusted, preferably, so that it ranged from 100 to 150% of the boiling point Polimetall, preferably from 105 to 140%, most preferably from 110 to 130%.

For example, neopentyl glycol (NPG) perform when used as the tertiary amine trimethylamine (TMA), and when the pressure in the head of column 150 mbar, the temperature in the lower part of the column, preferably set from 150 to 200°C, particularly preferably from 160 to 190°C.

The bottom of the distillation column, preferably, is connected, on ENISA least with one evaporator with a short time.

The bottom of the distillation column and evaporator with short time form according to the invention the General stage of evaporation.

Stay at the stage of evaporation, as detected, is calculated by dividing the volume of liquid retained in the hottest part of the column (VHold-up hold. fluidly.)) by the sum of the amount of back-flow amount flowing into the column flow (VHold-up/(inflow volume+volume-return)), i.e. VHold-up/(Vtributary+Vreturn), and the volume of liquid retained in the hottest part of the column (VHold-up) compute the sum of the volume of liquid held in the lower part of the column (VHold-up-sumpf), and volume of the liquid held in the evaporator (VHold-up-Verdampfer), ie (VHold-up=VHold-up-Sumpf+VHold-up-Verdampfer) or (Vuderground-Vuderground in the bottom. part of the column+Vhold the liquid in the evaporator).

The residence time of the liquid at the stage of evaporation, mainly, is less than 45 minutes, preferably less than 30 minutes, particularly preferably, less than 15 minutes, more preferably, less than 10 minutes and, most preferably, less than 5 minutes.

Typically, the residence time of the liquid at the stage of evaporation is preferably chosen so that at a higher temperature of the liquid in the lower part of the colon is s, respectively, to set a shorter time, at the stage of evaporation.

When the temperature in the lower part of the column component in the range from 130 to 150% of the boiling point Polimetall, the residence time of the liquid at the stage of evaporation, preferably, is 5 minutes or less, particularly preferably 4 minutes or less and most preferably 3 minutes or less.

When the temperature in the lower part of the column component in the range from 120 to 130% of the boiling point Polimetall, the residence time of the liquid at the stage of evaporation, preferably 30 minutes or less, especially preferably 15 minutes or less, even more preferably 10 minutes or less and most preferably 5 minutes or less.

When the temperature in the lower part of the column component in the range from 100 to 120% of the boiling point Polimetall, the residence time of the liquid at the stage of evaporation, preferably 45 minutes or less, especially preferably 30 minutes or less, even more preferably 15 minutes or less and most preferably 10 minutes or less.

In another particular embodiment, the method evaporator with short residence time therein is connected at least with the other evaporator with a short stay in it.

In this preferred embodiment of the method, the lower part of the distillation columns and the evaporator with a short time pre is ivania in it together form according to the General definition of the first stage of evaporation.

The evaporator or other evaporator with short residence time of fluid in it by definition constitute the second or (1+n)-th (n≥2)the stage of evaporation.

Evaporator with short residence time of fluid in it, preferably associated with a different evaporator with short residence time of fluid in it (two-stage implementation evaporation).

In this embodiment of the method the predominant part of the energy required for the evaporation of liquids, are typically supplied in the first stage of evaporation. Then in the second stage of evaporation can be achieved necessary for evaporating the higher the temperature the shorter the residence time of the liquid, resulting in a residence time in the evaporator the liquid in the second stage of evaporation is shorter.

The first stage of the apparatus is issued, mainly in the form of a film evaporator with a flowing stream of liquid or in the form of a loop of tubular evaporator.

The second stage of this special case for evaporation, preferably, the apparatus is arranged in the form of a film evaporator with the flowing liquid stream, loop tubular evaporator or thin-film evaporator.

The residence time of the liquid in the first stage of evaporation, as detected, is calculated by dividing the volume of the liquid, aderivative hottest part of the column (V uderground) the sum of the amount of reverse fluid flow (Vreturn liquidand volume of the tributaries of the liquid in column (Vthe flow of fluid), (Vuderground/(Vthe flow of fluid+Vreturn liquid)), and the volume of liquid retained in the hottest part of the column (Vuderground) compute the sum of the volume of liquid held in the lower part of the column (Vhold. fluid in the lower part of the column), and volume of the liquid held in the evaporator (Vuderground in the evaporator):

(Vuderground=Vuderground in the lower part of the column+Vuderground in the evaporator) or (VHold-up=VHold-up-Sumpf+VHold-up-Verdampfer)

The residence time of the liquid in the second stage of evaporation, as detected, is calculated by dividing the volume of liquid held in the second evaporator, the volume of liquid back-flow into the second evaporator.

The residence time of the liquid (1+n) stages of evaporation, respectively, is calculated by dividing the volume of liquid held on the (1+n) stages of evaporation, the amount of supply fluid flow in (1+n)-th evaporator.

In this preferred embodiment of the method, the temperature in the lower part of the column at the first stage of evaporation, preferably, higher than the evaporation temperature of Polymetal. The temperature in the bottom h is STI columns in the first stage of evaporation, preferably is in the range from 100 to 130%, particularly preferably from 110 to 125% of the boiling point Polimetall.

Usually the temperature in the second stage of evaporation is chosen in such a way that almost completely translate Polimetall in the gas phase.

The temperature in the second stage of evaporation, preferably, ranges from 105 to 150%, particularly preferably from 120 to 150%, most preferably from 130 to 140% of the boiling point Polimetall.

The residence time of the liquid in the first stage of evaporation, preferably, is less than 45 minutes, in particular less than 30 minutes, particularly preferably, less than 15 minutes, even more preferably, less than 10 minutes and, most preferably, less than 5 minutes.

The residence time of the liquid in the second stage of evaporation, preferably, is less than 30 minutes, in particular less than 15 minutes, especially preferably less than 5 minutes, even more preferably less than 2 minutes and, most preferably, less than 1 minute.

Typically, the residence time of the liquid in the apparatus for evaporating chosen so that at a higher temperature in the lower part of the column, respectively, were established in a shorter residence time in the evaporator. As mentioned above, the evaporator with a short residence time of fluid in it can be connected to more than one other COI is realem short residence time of fluid in it, for example, with 2 or 3 evaporators, and the last evaporator in the chain forms a so-called final stage of evaporation. The residence time of the fluid and the temperature at the last stage of evaporation corresponds to the residence time and temperature in the second stage of evaporation in the second variant implementation of the method.

Upon receipt of neopentyl glycol (NPG) using trimethylamine (TMA) as a tertiary amine in the first stage of the evaporation temperature in the lower part of the column, preferably, can be installed from 135 to 170°C, particularly preferably from 150 to 160°C with residence time of less than 45 minutes, in particular less than 30 minutes. In the second stage of evaporation, it is preferable to set the temperature from 160 to 220°C, particularly preferably from 180 to 200°C with residence time of less than 15 minutes, in particular less than 10 minutes and, most preferably, less than 5 minutes.

The distillation column preferably has a nozzle to increase the efficiency of the separation fluid. Distillation nozzle may represent, for example, an ordered packing, for example, tin packing, such as Mellpak 250 Y or Montz Pak Tour B1-250. Can also be used the package with reduced or increased specific surface or can be used a package of tissue or packing on the other by the geometry of the th, such as Mellpak 252Y. The advantage of using such distillation of the nozzles is to reduce the pressure loss and the reduction of specific water retention compared to, for example, with the valve. The nozzle can be in one or more injection (Schussen).

The products of hydrogenation, preferably served in a spatial region between 1/4 and 3/4 of theoretical plates of the distillation column, particularly preferably, in the spatial region between 1/3 and 2/3 of theoretical plates of the distillation column. For example, fluid may be approximately above the middle of theoretical plates of the column (the ratio 3:4). The number of theoretical plates of the distillation column is typically in the range from 5 to 30, preferably from 10 to 20.

Under these conditions, as a rule, preferred polietileno (neopentyl glycol, trimethylolpropane, trimethyloctane and trimethylbutane) more low-boiling Polimetall formula (I) is separated from the more high-boiling hydroxyacids of formula (IV). If the method is used other Polimetall, you may want to choose a different pressure and temperature conditions, so that it is possible to separate Polimetall from hydroxyacids.

In the condenser, preferably, is condensed purified Polimetall. The purity of Polymetal,preferably, is at least a 99.0%, especially preferably at least 99.2 percent.

Formed by condensation of the condensate, preferably, contains Polimetall formula (I) and from 1 to 10000 parts by weight per million of ester of Polymetal formula (I) and the hydroxy acid of formula (IV), preferably, from 5 to 5000 parts by weight per million and, particularly preferably, from 10 to 1000 parts by weight per million of ester of Polymetal formula (I) and the hydroxy acid of formula (IV).

Formed by condensation of the condensate typically contains, in addition, a small amount of Polymetal-formate.

Accordingly, the present invention relates also to a composition containing Polimetall formula (I) and from 1 to 10000 parts by weight per million Polimetall-formate, preferably, from 5 to 5000 parts by weight per million and, particularly preferably, from 10 to 1500 parts by weight per million Polimetall-formate.

Neskondensirovannyh residual secondary pairs, as a rule, contains in addition to the leaked air and traces of water, mainly neopentylglycol (NPG) and, preferably, directly in the gaseous state is returned to the distillation.

The product leaving the bottom of the evaporator, preferably lower. It contains, mainly, more high-boiling compounds, such as hydroxy acid of the formula (IV), for example hydroxypivalic acid (HPS).

O is handled from the bottom of the column, the product can either be used thermally combustion, or it may be sent to the additionally attached distillation column where it is subjected to decomposition into several fractions.

For example, coming out of the bottom of the column the product of neopentyl glycol (NPG) may be subjected to decomposition at low-boiling fraction primarily containing hydroxypivalic acid (HPS), v.a. HPN - containing (>97% HPN), the fraction with a moderate boiling point, and high-boiling fraction (v.a. ether HPS and HPN).

An advantage of the present invention is a receiving method according to the invention of polietileno low Polimetall-formate. Therefore, obtained by the method according to the invention Polimetall especially suitable for use in the polymers or to wetting, such as in varnishes and coatings, in which links can be broken down by acid catalysis, for example, in complex polyesters or polyurethanes. Obtained by the method according to the invention Polimetall when used for these purposes have a high stability.

Polimetall with contents Polimetall-formate less than 10,000 parts by weight per million, preferably less than 5000 parts by weight per million and, particularly preferably, less than 1500 parts per million, most preferably can be used to improve the resistance to hydrolysis of the polymer or as a mesh filter (Netzwerken). To improve stabil the abilities to hydrolysis or mesh filter is particularly preferably can also be used in polymers and grids formulations containing Polimetall formula (I) and from 1 to 10000 parts by weight per million Polimetall-formate, preferably, from 5 to 5000 parts by weight per million and most preferably from 10 to 1500 parts by weight per million Polimetall-formate.

Another advantage of the method according to the invention is the possibility of obtaining polietileno with a very high yield. This eventually leads to greater efficiency of the process of obtaining polietileno.

The efficiency of the method can be further improved by the division in accordance with the invention, the condensed by-product and the target product, as most components can be used in the form of solids, for example, by returning to the process. The number of connections that should be aimed at the elimination of the process is reduced, resulting according to the method according to the invention can be reduced, the cost of removing them from the process.

The invention is illustrated in the following examples.

Example 1

Receiving water polymethylenes mixture method by hydrogenation

Stage a) Andolina reaction

About 750 g/h Isobutyraldehyde (1 VA) (>99,5 GC-LPS % 1 VA) were subjected to interaction with about 700 g/h formaldehyde (about 49% formaldehyde, 1.5% methanol, the rest is water) and 80 g/h trimethylamine solution (TMA) (50% TMA in water) in dogsto what anatom cascade boilers with stirring.

Stage b) Distillation separation of the reaction mixture from stage a)

Then from the solution was removed low-boiling components by distillation in the column. The column was equipped with a 1.5 m fabric package (specific surface 500 m2/m3in concentrating part and 4 m tin packing (250 m2/m3). The product emerging from the stage of aldol reaction, carried out over a tin package, at the head of the column was used for condenser cooling water (about 10°C) and the optional phase separator. At the head of the distillate in the gaseous state was sent to the condenser. Got about 255 g/h of liquid condensate. In addition the attached phase separator separating the aqueous phase in the amount of 95 g/h and fully directed to the column. In addition, the phase separator was sent in the amount of 135 g/h in the first boiler with stirring. To maintain a regulated temperature in the column at the level of 85°C column additionally summed 25 g/h of organic phase. In addition attached to the condenser cooling collection (in der Kdhlfalle) was about 1 g/h of liquid (about 80% of Isobutyraldehyde, about 20% trimethylamine), which also returned to the column.

Department of Isobutyraldehyde (1 VA) was carried out at an absolute pressure in the head of the column of about 1 bar. In the operation of the evaporator used film evaporator with the flowing stream. The temperature in the lower part of the column was set at 102°C. the Amount of reverse flow (or the amount of the cooling water of the partial condenser) in the column was regulated by the temperature in the middle of the tissue package. Established the temperature of 85°C. From the bottom of the column by the pump was selected about 100 kg/h of liquid. This liquid is sent to a film evaporator with a flowing stream (consisting of heated oil pipe from stainless steel, 2.5 m long with an internal diameter of about 21 mm and a wall thickness of about 2 mm). From the bottom of the film evaporator with a flowing stream took about 1.5 kg/h of product concentration Isobutyraldehyde about 0.3%. Secondary vapor and excess liquid was sent to the bottom of the column. The descent from the lower part of the column, the product contained about 70 wt.% NRA, about 1.5 wt.% HPN, 0.3 wt.% IBA, the rest is water.

Stage c) Hydrogenation product leaving the bottom of the column with stage b)

The resulting product, vihodyashie from the bottom of the column was then subjected to hydrogenation in a fixed bed of catalyst. Activation of the catalyst was carried out as follows.

150 ml of catalyst Cu/Al2O3such as described in European patent EP 44444 or France FR 57216, activated in a tubular reactor at a temperature of 190°C. by passing a mixture of the C 5 vol.% hydrogen and 95 vol.% nitrogen (total volume of 50 nl/h) without the pressure within 24 hours.

The hydrogenation was carried out as follows. As initial solution was a mixture, previously described as a supply for the hydrogenation. To the mixture was added to about 10 wt.% in the calculation of the power in the hydrogenation of a 15%aqueous solution of trimethylamine. Thus obtained inlet stream was passed with irrigation at a pressure of 40 bar of hydrogen through heated to 120°C reactor. Loading was 0.4 kg NDA (Ikat*h). Part of the product coming from the stage hydrogenation, again mixed with the fresh air flow (circulation). The ratio of the circulation stream to the inlet stream was 10:1. The pH of samples of the product at the outlet of the reactor at room temperature during the measurement was 8.9.

The composition of the water polymethylenes mixture from step c):

neopentylglycol (NPG):69 wt.%
methanol:3.5 wt.%
trimethylamine (TMA):2 wt.%
organic side connection (hydroxypivalic acid (HPS), Isobutanol):<2 wt.%
trimethylamine-formate (TMA-formate):1 wt.%
water:23 wt.%

Example 2. Distillation water polymethylenes mixture from stage (c)

The product obtained by hydrogenation hydroxypivalic aldehyde, after exit from the stage hydrogenation was sent to the distillation separation. Used a column packing (DN 50 mm) with three sequences of structured packing, in each case, a length of 1 m and a specific surface of 500 m2/m3. The influx brought above the lowest of the sequences of the package. Pressure (absolute) in the head of the column was set to about 175 mbar. In the lower part of the column was set temperature of 164°C. the Temperature of 164°C corresponded to 110% of the boiling point neopentylglycol-formate at a pressure of 175 kPa.

The energy in the column was summed up by the evaporator with natural circulation. However, it can also be used the other evaporator, for example a film evaporator with the flowing stream. Received in the head of the column the secondary steam is sent to a condenser, in which the secondary vapor is almost completely condensed at a temperature of 30°C. By means of a simple commercial water-jet vacuum pump created a vacuum. From the obtained distillate of about 350 g/h down, about 250 g/h were dosed out on the upper portion of the packing in the form in which brachnogo flow. Used to create a vacuum water was sent for biological treatment of wastewater. In the lower part of the column was obtained crude neopentylglycol with the following structure:

97 wt.% neopentyl glycol (NPG) containing about 400 parts by weight per million neopentylglycol-formate.

Comparative example

Under the same conditions as in Example 2, the intensity of the boil in the bottom of the column was reduced by reducing return flow to 75 g/H. In the lower part of the column was set temperature of 145°C. In the lower part of the column was obtained crude neopentylglycol (Roh-NPG) of the following composition:

97 wt.% neopentyl glycol (NPG) with contents neopentylglycol-formate of about 5700 parts by weight per million

Example 3. Distillation water polymethylenes mixture from stage (c)

The product obtained by hydrogenation hydroxypivalic aldehyde, after exit from the stage hydrogenation was sent to the distillation separation. Used a column packing (DN 50 mm) with three sequences of structured packing, in each case, a length of 1 m and a specific surface of 500 m2/m3. The influx brought above the lowest of the sequences of the package. Pressure (absolute) in the head of the column was set to about 70 mbar. In the lower part of the column was set temperature of 148°C. the Temperature of 148°C corresponded to 120% of the t boiling point neopentylglycol-formate at a pressure of 70 mbar.

The energy in the column was summed up by the evaporator with natural circulation. However, it can also be used the other evaporator, for example a film evaporator with the flowing stream. Received in the head of the column the secondary steam is sent to a condenser, in which the secondary vapor is almost completely condensed at a temperature of 10°C. By means of a simple commercial water-jet vacuum pump created a vacuum. From the obtained distillate of about 350 g/h down, about 250 g/h were dosed out on the upper portion of the packing in the form of return flow. Used to create a vacuum water was sent for biological treatment of wastewater. In the lower part of the column was obtained crude neopentylglycol with the following structure:

97 wt.% neopentyl glycol (NPG) containing about 400 parts by weight per million neopentylglycol-formate.

Example distillate water polymethylenes mixture from stage (C)

The product obtained by hydrogenation hydroxypivalic aldehyde, after exit from the stage hydrogenation was sent to the distillation separation. Used a column packing (DN 50 mm) with three sequences of structured packing, in each case, a length of 1 m and a specific surface of 500 m2/m3. The influx brought above the lowest of the sequences of the package. Giving is giving (absolute) in the head of the column was set to about 500 mbar. In the lower part of the column was set temperature of 189°C. the Temperature of 189°C corresponded to 106% of the boiling point neopentylglycol-formate at a pressure of 500 mbar.

The energy in the column was summed up by the evaporator with natural circulation. However, it can also be used the other evaporator, for example a film evaporator with the flowing stream. Received in the head of the column the secondary steam is sent to a condenser, in which the secondary vapor is almost completely condensed at a temperature of 50°C. By means of a simple commercial water-jet vacuum pump created a vacuum. From the obtained distillate of about 350 g/h down, about 250 g/h were dosed out on the upper portion of the packing in the form of return flow. Used to create a vacuum water was sent for biological treatment of wastewater. In the lower part of the column was obtained crude neopentylglycol with the following structure:

97 wt.% neopentyl glycol (NPG) containing about 400 parts by weight per million neopentylglycol-formate.

1. The distillation of water polymethylenes mixtures containing Polimetall formula (I):
,
in which R in each case independently of each other means methylol group or an alkyl group with 1-22 carbon atoms or aryl or aracelio group with 6-22 ATO the AMI carbon and containing tertiary amine, water, and adduct of tertiary amine and formic acid (Amin-formate), characterized in that the distillation is carried out in equipped with a condenser distillation column, which lower part is connected to the evaporator, and the temperature in the lower part of the column exceeds the evaporation temperature generated in the distillation process of monoether formic acid and Polymetal (Polymetal-formate).

2. The method according to claim 1, characterized in that the water polimetalla mixture has the composition:
from 20 to 90 wt.% Polymetal (I),
from 0 to 5 wt.% methanol,
from 0 to 5 wt.% tertiary amine,
from 0 to 5 wt.% organic side connections,
from 0.01 to 5 wt.% adduct of tertiary amine and formic acid (Amin-formate),
the rest is water.

3. The method according to claim 1, characterized in that the water polietileno mixture get multistage reaction, and at the stage a) alkanal Alderney reaction condense with formaldehyde in the presence as catalyst of tertiary amines with the formation of metrolina formula (II), R in each case independently of one another have the value specified in claim 1,

and directly after that at the stage b) obtained in stage a), the reaction mixture is separated by distillation product of the lower part of the distillation Colo the us, containing a vast number of compounds of formula (II), and head stream containing low-boiling part, and at the stage (c) the product emerging from the lower part of the distillation column, with stage b) is subjected to hydrogenation.

4. The method according to claim 1, characterized in that polietileno is neopentylglycol, trimethylolpropane, pentaerythritol, trimethylated or trimethylbutane.

5. The method according to claim 4, characterized in that polietileno is neopentylglycol.

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

7. The method according to claim 6, characterized in that the tertiary amine is trimethylamine.

8. The method according to claim 1, characterized in that the pressure in the head part of the column is from 0.001 to 0.9 bar, and the temperature of the condenser is in the range from 0 to 80°C.

9. The method according to claim 1, characterized in that the lower part of the column set temperature exceeding the boiling temperature of Polymetal-formate by 10-50%.

10. The method according to claim 1, characterized in that the condensate obtained in the condenser, more than 30 wt.% return to a distillation column.

11. The method according to claim 1, characterized in that the distillation column contains from 5 to 30 theoretical plates.

12. The method according to claim 1, characterized in that the distillation number of the nna has a nozzle to increase the efficiency of separation, and water polietileno mixture down in a spatial region between 1/4 and 3/4 of theoretical plates of the distillation column.

13. The method according to claim 3, characterized in that the product emerging from the lower part of the distillation columns with stage b), add the tertiary amine.

14. The method, at least one of PP. 3-13, characterized in that the product emerging from the lower part of the distillation column, from the stage of distillation of water polymethylenes mixture is separated into the head stream containing Polimetall, and thread the bottom of the distillation column, containing more high-boiling organic components.



 

Same patents:

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

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: 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

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: 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

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