EP0885252A2

EP0885252A2 - Method of reprocessing residues containing dihydroxy compounds

Info

Publication number: EP0885252A2
Application number: EP97906160A
Authority: EP
Inventors: Peter Braune
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1996-03-06
Filing date: 1997-03-04
Publication date: 1998-12-23
Also published as: WO1997032915A2; DE19608614A1; US6174970B1; WO1997032915A3; KR19990087569A; CN1140561C; AU2095197A; CN1212712A; JP2000506203A

Abstract

The invention concerns a method of reprocessing residues which contain dihydroxy compounds and are obtained during the production of polyesters. According to this method: (1) in a first step, a dicarboxylic acid or its esters or ester-forming derivatives with a molar excess of dihydroxy compound are esterified or transesterified; (2) in at least one second step, the esterification product obtained according to (1) is polycondensed; and (3) the vapours (a) and (b) produced according to (1) and (2) are subjected to a treatment for recovering the starting substances. This method is characterized in that the treatment for recovering the starting substances is carried out in the presence of an alkali or alkaline earth compound in an amount of between 0.5 and 10 wt.% calculated as alkali metal or alkaline earth metal relative to the solids content of the vapours.

Description

Process for working up residues containing dihydroxy compounds

description

The present invention relates to a process for working up residues containing dihydroxy compounds which are obtained in the production of polyesters, wherein

(1) in a first stage, a dicarboxylic acid or its ester or ester-forming derivative is esterified or transesterified with a molar excess of a dihydroxy compound,

(2) polycondensing the esterification product obtained in (a) in at least a second stage,

(3) the vapors (a) and (b) obtained in the reactions according to (1) and (2) are subjected to a treatment for the recovery of the starting materials.

For the preparation of polyesters, in particular polyalkylene be terephthalates executed so-called large-scale transesterification / lykondensationsverfahren Po, wherein in a first stage of a esterification or transesterification, and in at least one white ^¬ more advanced stage, the actual polycondensation is carried out (see FIG. Man-made fibers ( Textilindustrie 40 (1992), 1058-1062 and Ulimann's Encyclopedia of Industrial Chemistry, 4th ed. Volume 19, pp. 61-88).

This process will be briefly explained using the example of the production of polybutylene terephthalate from terephthalic acid and butanediol-1,4.

In a first reaction space, terephthalic acid is esterified with a mo ^¬ stellar excess, preferably 50-120 mol%, in particular 70-100 mol%, 1,4-butanediol, wherein the esterified Ver¬ bond is subjected to further steps in the actual polycondensation . Products resulting from the esterification vapors advertising the transferred to a column in which the low-boiling constituents ^¬ parts THF / water removed via the top and a bottom product, which contains excess butanediol-1, 4 small amounts of oligomers, polymers and terephthalic acid obtained become. The esterification product is then polycondensed, the polycondensation in continuous processes advantageously being carried out in at least two stages, a so-called precondensation and postcondensation.

For economic reasons, it is desirable that as many of the resulting reaction products and excess dihydroxy compounds as possible are further treated, e.g. to recover the butanediol-1, 4 and to produce as little waste as possible.

In the unpublished DE-A 19509957.5 a method for the preparation of the vapors from the polycondensation is proposed.

DE-A 43 33 929 discloses a process for recovering the starting materials, a distillation residue from dihydroxy-containing compounds (so-called "hex") being metered into the column for easier handling of the usually very highly viscous bottom products.

A disadvantage of this process is that this residue mostly comes from butanediol or hexanediol distillation and is therefore not available everywhere.

Since the vapors also contain oligomeric and polymeric polyesters in addition to the starting materials and by-products, the pH of the vapors is below 7 owing to the content of carboxyl end groups. In addition, when they are recovered, they are fragmented again, which means that new carboxyl end groups are present

Carboxyl end groups arise. For these reasons, processing the vapors is very costly since corrosion-resistant stainless steel containers have to be used.

During the preparation and production of the polyester, for example, THF forms to a considerable extent as a by-product (with 1,4-butanediol as a starting material). Since these side reaction is catalyzed by acids, is also in the Destillationsrückge ^¬ winnung 1.4 butanediol to a considerable extent by THF formation be lost.

The present invention was therefore based on the object of improving the disadvantages described above and improving the work-up of the vapors in such a way that the largest proportion of the dihydroxy compounds contained therein is as economical as possible. lent can be recovered. At the same time, the product quality of the polyester should be maintained.

Surprisingly, it was found that this object can be achieved by treating the treatment for recovering the starting materials in the presence of an alkali or alkaline earth compound in an amount of 0.5 to 10% by weight, calculated as alkali metal or alkaline earth metal based on the solids content of the vapors.

As a result of the addition of alkali or alkaline earth compounds in the vapor preparation according to the invention, so-called basic buffering of the vapors takes place, so that corrosion of the containers is no longer possible. As a result, much cheaper normal steel containers can be used for these purposes. Furthermore, the by-product formation e.g. significantly reduced by THF.

At a pH of the vapors of 7 or higher there are also shorter fragments e.g. of the polymeric residues so that, on the one hand, they are more easily dispersible in the dihydroxy compound, i.e. the resulting distillation residue is easier to handle because it has a lower viscosity. On the other hand, the columns can be operated considerably longer without cleaning work (so-called longer service life) and the solid residues during cleaning can be removed more easily from the column e.g. be removed with water.

In a special embodiment of the invention, the evaporation device following the distillative preparation can further e.g. Butanediol can be recovered, this workup being independent of the availability of the residue containing dihydroxy compounds (HEX).

In the process according to the invention, 0.5 to 10, preferably 1 to 8 and in particular 2.5 to 6% by weight, preferably calculated as alkali metal or alkaline earth metal, is preferably in the bottom of columns A, B or C during the preparation of the vapors based on the solids content of the vapors added.

In principle, inorganic and organic compounds of the alkali metals, preferably of Li, Na, K, particularly preferably Na compounds, are suitable. Examples of suitable inorganic compounds of the (earth) alkali metals, preferably sodium, are the corresponding silicates, phosphates, phosphites, sulfates or preferably carbonates, hydrogen carbonates and hydroxides.

The organic compounds of the (earth) alkali metals, preferably sodium, include the corresponding salts of (cyclo) aliphatic, araliphatic or aromatic carboxylic acids with preferably up to 30 carbon atoms and preferably 1 to 4 carboxyl groups. Examples include: alkali metal salts of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, caprylic acid, stearic acid, cyclohexane carboxylic acid, succinic acid, adipic acid, suberic acid, 1,10-decanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, 1,2, 3-propane tricarboxylic acid, 1,3,5-cyclohexane tricarboxylic acid, trimellitic acid, 1,2,3,4-cyclopentantetracarboxylic acid, pyromellitic acid, benzoic acid, substituted benzoic acids, dimer acid and trimer acid, and neutral or partially neutralized montan wax salts or montan wax ester salts (montanates). Also salts with different types of acid residues, e.g. Alkali-paraffin, alkali-olefin and

Alkali aryl sulfonates or also phenolates and alcoholates, such as e.g. Methanolates, ethanolates, glycolates can be used according to the invention. Sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium salts of mono- and polycarboxylic acids, in particular the aliphatic mono- and polycarboxylic acids, preferably those having 2 to 18 carbon atoms, in particular having 2 to 6 carbon atoms and up to four, preferably up to two carboxyl groups, and sodium alcoholates with preferably 2 to 15, in particular 2 to 8, carbon atoms are used. Examples of particularly preferred representatives are sodium acetate, sodium propionate, sodium butyrate, sodium oxalate, sodium malonate, sodium succinate, sodium methoxide, sodium ethanolate, sodium glycolate. Sodium methoxide is very particularly preferred, which is used particularly advantageously in an amount of 2.5 to 6% by weight, calculated as Na, based on the solids content of the vapors. Mixtures of different (earth) alkali metal compounds can also be used.

The (earth) alkali metal or the (earth) alkali metal compound can, depending on the work-up method, be added to at least one column A, B or C. Of course, the addition can also be distributed over all columns, preference being given to metering the same amounts into each column.

The process according to the invention is again explained below using the example of the production of polybutylene terephthalate with reference to the figures; however, it should be emphasized again that it is accordingly also suitable for the production of other polyesters known to the person skilled in the art.

First, terephthalic acid and 1,4-butanediol (the latter in 5 150 to 220 mol%, preferably 70 to 100 mol% excess) in a manner known per se at temperatures in the range from 150 to 220 ° C., and pressures in the range from 0.7 to 2.0 bar for a period of from 150 to 300, preferably from 200 to 280 minutes, reacted with one another, an esterification taking place and ent

10 standing THF (tetrahydrofuran) together with excess butanediol (BD) and small amounts of oligomeric and polymeric compounds as well as residual amounts of terephthalic acid are transferred into a column A with the vapors (a). The place of addition is preferably in the middle or in the lower part of the column.

15

Step (1) of the process is shown in the figures as a process step. Step (1) is preferably divided into at least four process steps, these consisting of a mixing reactor for solvent, catalyst, etc. and at least

20 at least three stirred reactors are built.

The esterification product of stage (1) of the process is polycondensed in at least one second stage (2). This polycondensation is carried out in a manner known per se at temperatures of

25 240 ° C to 270 ° C and reduced pressure of 0.3 to 200 mbar over a period of 60 to 200, preferably 70 to 180 minutes. A particularly preferred embodiment of stage (2) is divided into two process steps, firstly a so-called precondensation and then one

30 post-condensation is carried out.

Fig. 1 shows a preferred embodiment for recovering the starting materials, the vapors (a) obtained in stage (1) being transferred to at least one column A and the

35 low-boiling components of the vapors (a) are removed overhead and the bottom product is returned to stage (1) and the vapors (b) obtained in stage (2) are transferred to at least one column B and the low-boiling components are removed overhead separates and discharges the bottom product from column B and this

40 is then subjected to a further treatment for recovering the dihydroxy compound in at least one column C.

Fig.2 shows a further preferred process for working up the vapors, the vapors (a) 45 and part of the vapors (bi) from stage (2) of the process obtained in stage (1) being combined in at least one column A and the low-boiling components of the vapors in column A are removed overhead and the bottom product, which predominantly contains the excess dihydroxy compounds and oligomeric and polymeric reaction products, is returned to stage (1) and the other part of the vapors (b ₂ ) of stage (2) of the process is passed into at least one column B. transferred and the low-boiling constituents of the vapors removed overhead and the bottom product discharged from column B and then subjected to at least one column C for a further treatment to recover the dihydroxy compound.

By dividing the vapors from the polycondensation, the vapors (bi) preferably originating from the precondensation and the vapors (b ₂ ) originating from the post-condensation, the excess diol can be recycled in a technically simple manner the esterification take place. As a result, the process is more economical and less expensive, while the product quality of the polyester is retained.

Fig. 3 shows a further preferred embodiment of the process, the vapors (a) and (b) obtained in stages (1) and (2) being transferred to at least one column A and the low-boiling constituents being removed overhead and then discharging the bottom product from column A and subjecting it in at least one column C to a further treatment for the recovery of the dihydroxy compound.

In column A or B of the process according to the invention, the low-boiling THF / water is removed overhead and these low-boiling constituents are then subjected to recovery of the starting materials (separation of THF from water).

In the case of the production of polyethylene terephthalate, the low-boiling components consist essentially of water or methanol with acetaldehyde; in the production of PBT based on methyl terephthalate from methanol and THF. Then the bottom product, which predominantly contains the excess dihydroxy compounds, is returned to stage (1). Depending on the size of the plant, columns A to C can be divided into several columns Ai, A ₂ to A _n or B _{1 (} B ₂ to B _n and Ci, C ₂ to C _n .

In the preferred embodiments according to FIGS. 2 and 3, the vapors are worked up in such a way that the vapors of stage (2), which are predominantly THF, water, excess butanediol and somewhat larger amounts than in the vapors from Stu¬ fe (1) of oligomeric and polymeric compounds and residual amounts of terephthalic acid are either proportionally A and B or all of them are transferred to a column A, the vapors from stage (1) of the process already being present in column A.

In the preferred embodiment in FIG. 1, the workup is carried out separately and the vapors (b) are transferred to a column B.

The place of addition is preferably in the middle or in the lower part of the columns. How to divide these proportions goes without saying, since the division depends on the filling quantity of the columns and the quality of the required starting materials in the esterification.

The low-boiling constituents of the vapors are separated off overhead and the bottom product is removed from column A and / or B depending on the procedure. Subsequently, the bottom product is subjected to a further treatment for the recovery of the dihydroxy compound. For this purpose, the bottom product from column A or B is discharged into a column C, depending on the procedure, if appropriate with removal of the solids.

A liquid residue containing dihydroxy compounds (“hex”), such as is obtained, for example, from the distillation of 1,4-butanediol or 1,6-hexanediol, is preferably introduced in column C in parallel. The composition of the residue is not subject to any particular restriction as long as the liquid form is present and there are no compounds which interfere with the separation in the column. This is usually the case with residues from butanediol or hexanediol distillation.

The point of addition is preferably in the middle or in the lower part of the column, and the amount added is generally 0.03 to 5 kg per kg of bottom products transferred into the column, preferably from 0.04 to 0, 1 kg / kg.

By adding this residue containing dihydroxy compounds, the bottom product remains liquid or conveyable in column C, and the dihydroxy compound can therefore be obtained at the bottom of this column in a process-technically simple manner overhead and in turn a liquid or conveyable bottom product which can be easily incinerated.

The dihydroxy compound is then returned from column C to the esterification (stage 1). In a particularly preferred embodiment of the process according to the invention, the bottom product is discharged from column C into an evaporation device D and the dihydroxy compound is separated off and returned to column C and the remaining residue is discharged from D.

This preferred embodiment further e.g. 1,4-butanediol is recovered and the residue can be worked up in a simple and economical way without adding a distillation residue. Another advantage of this procedure is that the removal of the dihydroxy compound does not have to be carried out completely in column C, the residue is not as viscous and thus remains manageable.

The place where the recovered butanediol is added is preferably in the lower part of column C, in particular above the vapor space of the column bottom of column C.

Suitable evaporation devices D are, for example, special columns, stirred evaporators, extruders, self-cleaning evaporators or disk evaporators.

The temperature of the evaporation device is preferably above the melting point of the remaining residue. This depends on the solids content and the type of residue. For the residue from the production of polybutylene terephthalate, the temperature is usually 180 to 250 ° C., preferably 190 to 230 ° C., for residues from the production of polyethylene terephthalate generally from 180 to 280 ° C., preferably 190 to 265 ° C.

If the bottom product in the device D is only concentrated to a solids content of 30 to 70%, based on the bottom discharge, lower temperatures of 150 to 220 ° C. in the device D are also suitable.

The starting materials such as butanediol can be recovered to a considerable extent simply and inexpensively by the process according to the invention. At the same time, the proportion of by-products such as THF is drastically reduced.

Example 1 (Fig. 2)

step 1

35.2 mol of terephthalic acid (TPA) and 82.7 mol of 1,4-butanediol (BD) were reacted in a 3-stage esterification cascade at temperatures of 210-220 ° C and 2 bar _abs pressure. As a catalyst 30 ppm Ti based on polybutylene terephthalate (PBT) as tetrabutyl orthotitanate (TBOT) were added (dwell time τ = 205-260 min in total).

The reaction product was transferred to stage 2 with at least 95% conversion. At the start of the precondensation, 50 ppm of Ti were added. added on PBT as TBOT:

τ = 30-40 min, T = 240-290 ° C,

P = 0.8 bar starting at 25 mbar.

After the precondensation in stage 2, the product was converted into the post-condensation of stage 2 with at least 98.5% conversion. At the beginning of the post-condensation 30 ppm Ti were. added on PBT as TBOT.

τ = 90-140 min, T = 245-265 ° C, P = 0.5 to 2.0 mbar.

The product PBT with a viscosity η (intrinsic) of 0.9-1.3 was then melted out and granulated.

The excess molar BD was worked up in accordance with the basic representation in accordance with FIG. 2 and the variation of the conditions in accordance with the table.

How BD Recovery Works:

The vapors from stage (1) were transferred to column A in vapor form as stream (a) (see table for Fig. 2) at 210-220 ° C and 2 bar _abs . Water and THF were separated off at the top. The butanediol was returned to stage (1). The butanediol contained in the vapors of stage (2) (stream b + b ₂ ) was fed into the columns A and B in liquid form with the entire vapors of this stage. The streams of the precondensation and postcondensation were divided up such that the vapors of the postcondensation of stage (2) and part of the vapors of the precondensation of stage (2) were added to column B while the other part of the vapors was added the precondensation of stage (2) was added to column A.

Column A was operated under the same pressure as the esterification of stage (1). The columns / apparatus B, C, D were operated under a pressure of <1 bar ^ _s . THF and water were drawn off at the top of column B, and the butanediol contained in the bottom of column B was fed to column C. At the head of the Line C was separated from butanediol. The bottom of column C was fed to apparatus D. There, the butanediol was quantitatively separated off in vapor form and returned to the vapor space via the bottom of column C.

In the procedure according to Example 1, 0.1 mol of PBT per 35.2 mol of TPA were discharged from apparatus D. Without apparatus D, the same amount of solids was discharged from the bottom of column C.

Table 1 for Fig. 2 shows the BD losses for the various processing variants according to Example 1.

The processing variants are 1.1. until 1.5. was carried out as follows:

1.1. The distillation residue "Hex" was added to column B in a total amount of 3.4 kg / kg of solids contained in the vapors b ₂ (for comparison according to De-A 43 33 929).

1.2. Sodium methoxide (30% in methanol) was added to column B in an amount of 0.05 kg Na / kg solid which was contained in the vapors b ₂ .

In addition, as under 1.1. "Hex" added.

1.3. Na-methanolate was added as under 1.2., But without the addition of "hex". The bottom of column C was fed to the evaporator D. The BD was returned in vapor form to the vapor space above the bottom of column C. The solid was discharged from D in a molten state at 235 ° C.

1.4. Neither "hex" nor sodium methoxide was added (for comparison).

1.5. As under 4, only without apparatus D (for comparison). I - IX all data in mol O

IX: a building block of the PBT polymer from diol and acid counts as mol (molecular weight: 220 g) H

I: THF formation in stages 1 u. 2 ^

II: THF formation during processing <*

III: BD in the bottom discharge from C or D

IV: b ₂ (on): BD in the brothers b ₂ b ₂ (back): BD recovered from b ₂

V: bi (one + back): BD in the brothers bi (fully recovered)

VI: a: BD in the brothers a (fully recovered)

VII: Entire BD processed

VIII Total loss of BD on reprocessing

IX: Solids discharge from C or D (0.1 mol PBT based on 35.2 mol TPA used)

* ) for comparison

»-» to

O

3 β 00

Example 2 (Fig. 1)

step 1

35.2 mol of dimethyl terephthalate (DMT) and 54.0 mol of BD were reacted in a 3-stage transesterification cascade at temperatures of 180-205 ° C. and 1.16 bar _abs pressure. At the start of the reaction, 115 ppm of Ti or on PBT as TBOT and 0.7 mmol of sodium methoxide per kg of PBT were added as catalyst (residence time τ = 205-260 min in total).

The reaction product was transferred to stage 2 with at least 95% conversion. In the first part of stage 2, the precondensation was carried out:

τ = 30-40 min, T = 240-290 ° C,

P = 0.8 bar starting at 25 mbar.

After the precondensation in stage 2, the product was transferred to the post-condensation in stage 2:

τ = 90-140 min, T = 245-265 ° C,

P = 0.5 to 2.0 mbar.

The product was then melted out with a viscosity η (intrinsic) of 0.9-1.3 and granulated.

The vapors were worked up in accordance with the basic illustration according to Fig. 1 and the variation of the conditions according to Table 2.

The processing variants listed in the table 2.1. until 2.5. were analogous to those under 1.1 until 1.5. conditions listed performed.

In a departure from the work-up in Example 1, the entire vapors from stage 2 were added to column B. In contrast to Example 1, MeOH and THF are separated off at the tops of columns A and B.

The conditions with regard to pressure, temperature, "hex", Na and solids content corresponded to Examples 1.1 to 1.5. CN

Q)

QJ XI approx I-VIII all data in mol O

VIII: As a mole, a building block counts as a PBT polymer made from diol and ester (molecular weight: 220 g) ^

I: THF formation in stages 1 u. 2 g

II: THF formation during processing w »

III: BD in the bottom discharge from C or D

IV: b (on): BD in the brothers b b (back): the portion of BD recovered from b:

V: a: BD fully recovered in vapors a

VI: All BD processed in the reprocessing

VII: Total loss of BD during processing

VIII: Solids discharge from C or D (based on 35.2 mol of DMT used, 0.1 mol of PBT resulted)

*) for comparison

in

O v β

©

00

Example 3 (Fig. 3)

The reaction was carried out analogously to Example 2, with the difference that the entire vapors of stages 1 and 2 are added to column A. MeOH and THF were separated off at the top of this column. The bottom was transferred to column C. Further processing was carried out analogously to Example 2. The explanations regarding "Hex", Na, D apply analogously. "Hex" and / or sodium methoxide was added in column A.

As in Examples 1 and 2, 3.4 kg of "hex" per kg of solids and 0.05 kg of Na / kg of solids were added (based on solids in vapors a and b).

The results are shown in Table 3.

ro Φ

Φ X) around EH IX: all data in mol Q

X: a building block of the PBT polymer from diol and ester counts as mol (molecular weight: 220 g) ^

I: THF formation in stages 1 u. 2 w

II: THF formation during processing

III: BD in the bottom discharge from C or D

IV: recovered BD from brothers a and b

V: BD in the brothers b

VII: BD in the brothers a

VIII: BD processed

IX: Total loss of BD during processing

X: solids discharge from C or D (0.1 mol PBT based on 35.2 mol DMT used)

*) for comparison

O a ©

∞

Claims

claims

1. Process for working up residues containing dihydroxy compounds, which are obtained in the production of polyesters, whereby

(3) subjecting the vapors (a) and (b) obtained in the reactions according to (1) and (2) to a treatment for the recovery of the starting materials,

characterized in that the treatment for the recovery of the starting materials in the presence of an alkali or alkaline earth compound in an amount of 0.5 to 10% by weight, calculated as alkali metal or alkaline earth metal based on the solids content of the vapors , makes.

2. The method according to claim 1, characterized in that an alkoxide is used as the alkali compound.

3. The method according to claims 1 or 2, characterized gekennzeich¬ net that sodium or potassium methoxide or mixtures thereof is used as the alkali compound.

4. Process according to claims 1 to 3, characterized gekennzeich¬ net that the vapors obtained in stage (1) (a) and part of the vapors (bi) of stage (2) of the process are combined in at least one column A and the slightly Her¬ Denden components of the vapors in the column A overhead from ^¬ separating and recycling the bottom product which, as well as oligomeric predominantly the über¬ schüssigen dihydroxy compounds and contains polymeric reaction products in step (1) and the other part of the vapors (b ₂₎ the step (2) converting the process into at least one column B and the slightly sieden¬ the components of the vapors is separated overhead and discharging the bottom product from the column B, and this subsequently ^¬ ßend at least one column C to a further treatment for recovering subject to the dihydroxy compound.

5. Process according to Claims 1 to 3, characterized in that the vapors (a) obtained in stage (1) are converted into at least one column A and the low-boiling constituents of the vapors (a) are overhead is separated off and the bottom product is returned to stage (1) and the vapors (b) obtained in stage (2) are transferred to at least one column B and the low-boiling constituents are removed overhead and the bottom product is removed from column B and is removed then subjected in at least one column C to a further treatment for the recovery of the dihydroxy compound.

6. Process according to Claims 1 to 3, characterized in that the vapors (a) and (b) obtained in stages (1) and (2) are converted into at least one column A and the low-boiling constituents separated off overhead and then discharging the bottom product from column A and subjecting it to at least one column C for further treatment to recover the dihydroxy compound.

Process according to Claims 1 to 6, characterized in that the low-boiling constituents of the vapors essentially consist of a mixture of water or methanol with tetrahydrofuran or acetaldehyde.

8. The method according to claims 1 to 7, characterized gekennzeich¬ net that a liquid residue containing dihydroxy compounds is added to the bottom product of column C in the further treatment for the recovery of the dihydroxy compound.

9. The method according to claims 1 to 7, characterized gekennzeich¬ net that the bottom product of column C is discharged into an evaporation device D, the dihydroxy compound is separated and returned to column C and the remaining residue is discharged.

10. The method according to claim 9, characterized in that the temperature of the device D is above the melting point deε remaining residue.

11. The method according to claims 1 to 10, characterized in ^¬ net that the recovered dihydroxy compound from the Ko¬ lonne C in the step (1) of the process is recycled.