CS199154B1 - Alcohol cleaning method - Google Patents

Description

The invention relates to a process for the purification of alcohols of the formula I

R-CH (I) wherein R is alkyl and 1 to 4 carbon atoms, hydroocylethyl to hydroxyhexyl groups or a radical of formula II

HO - (R ₁ R ₂ ) _x - (II), wherein R 1 and R ₂ are the same or different chains and e is 2 to 6 carbon atoms and x is an integer from 1 to 3,

As is known, it is used in technological processes to obtain biologically active substances from animal organs, body fluids or plant material to isolate effective principles and further purify and separate them from ballasts, for example by extraction, precipitation, crystallization and the like. , a suitable water-miscible alcohol, most often ethanol, further propanel, isopropyl alcohol or methanol, and yeast or produced synthetically, very often anhydrous, rarely glycols or their ethers, which correspond to the general formula I, hereinafter for the sake of brevity only alcohol. Significant volumes of dilute, more or less contaminated alcohol or alcohol are eliminated from the above production processes

199 154 a mixture of alcohols that need to be regenerated for economic reasons.

The biologically active principles of the formulations produced are usually highly sensitive, and the more sensitive they are, the cleaner they are to the negative factors present in alcohols and in trace amounts. These factors can strongly influence not only the yield of the manufacturing process, but especially the quality and efficiency of the product produced. Therefore, the alcohol used must be as clean as possible; if it is not, the result of laborious and costly production process is affected by substantial reduction of yield, decrease or even total loss of activity of the preparation, etc. By usual distillation and rectification the waste alcohol is concentrated but not necessary purification, which, together with other ballasts, pass into waste alcohol cannot be separated by distillation. Especially in the case of volatile substances capable of producing both ions and complex azeotropic systems during distillation, their removal from waste alcohol is not successful even by repeated distillation, a process which is quite expensive and time consuming. On the contrary, the circulation of these undesirable impurities often increases after the re-use of the recovered alcohol and its further distillation.

The described adverse effects of the biologically active formulations during the manufacturing process often occur even in the case when used in the manufacturing process, the extraction or precipitation of the fermented or synthetic alcohol of the quality and purity in which it is supplied. In addition, even such pure alcohol cannot be freed from such undesirable impurities by distillation or rectification, which in turn will adversely affect the outcome of the isolation or purification process.

The above mentioned disadvantages and drawbacks of the prior art purification methods are eliminated by the method of purification of the alcohols of the formula I according to the invention.

The process according to the invention consists in contacting an alcohol of formula I or a mixture of alcohols of formula I with fcatex in an H-cycle and / or an anion exchange in an OH-cycle, in a volume ratio of 11: 1 to 1: 1000, at a temperature of -15 to + 50 ° C, preferably 10 to 25 ° C.

When applying the purification of the alcohols of formula (I) by the method of the invention, it is possible to use regenerated or commercially available alcohol of formula (I) obtained by fermentation or synthetically, without fear of adversely affecting the yields or quality of the biologically active formulations.

As is well known, ion exchange masses, cation exchangers and anion exchangers are commonly used to treat and separate ionic bonded compounds dissolved in water. After the cation exchanger is saturated with cations or anion exchanger, the ion exchanger activity is restored simply by letting the necessary volume of regeneration solution, either aqueous solution of strong mineral acid (usually hydrochloric acid) in case of cation exchanger or base in case of anion exchanger (usually sodium hydroxide solution). concentration. Today's ion-exchanged materials are absolutely stable in the aqueous environment, their swelling, expansion and smelling in aqueous solutions are satisfactory, they can be deactivated many times, i.e., saturate the ions, and regenerate, i.e. restore the ability to bind ions.

On the other hand, there has been a lack of data on the above mentioned ion exchange properties, their ion exchange activity and, in particular, their stability in the environment of alcohols of the general formula I, in particular contertraol above 90% by volume. they are also not adversely affected in the bexhydric alcohol environment and remain equally the same in the aquatic environment; it does not reduce the possibility of multiple regeneration.

Furthermore, it has been found that recovered alcohol, obtained by distillation of a dilute and heavily contaminated solvent resulting from the manufacture of biologically active agents, which, even after repeated certification and re-use in this manufacture for the reasons mentioned above, can be reliably disposed of. According to the invention, it is contacted with β by a suitable ion exchanger. If the purified regenerated alcohol is also used in the production of biologically active preparations, there will be no slightest detriment to the active principle or a reduction in yield. Whether the production or product character and the nature of the concomitant impurities in the recovered alcohol are decisive as to whether kstex and / or anion exchanger is used for purification.

It has also been shown experimentally that a salable alcohol, fermentable or synthetic, whether diluted or absolutely purified, can be purified by the process of the invention so that it is then reliably usable in the manufacture of said compositions without adverse consequences.

The process according to the invention solves, by simple technical means, the serious economic and technological problem of the regenerated, resp. Waste alcohols in many manufacturing sectors, especially in the demanding manufacture of organo-preparations, hormones and other active substances from natural euro coins.

The following examples illustrate the process according to the invention, but do not limit it in any way.

Example 1

75 g of a strongly acidic cation exchanger based on a sulfone-containing styrene-dlvinylbenzene blend polymer which had been dewatered by washing with 500 ml of pure ethanol were mixed in a volume of 7500 ml of regenerated ethanol having a pH of 8.80 and a conductivity of 78.0 gS. After 20 minutes of vigorous stirring at 20 ° C, the cation exchanger was filtered off. The purified ethand had a pH of 5.60 and a conductivity of 4.2 µS,

Example 2

Two 50 x 400 mm glass columns, connected one after the other so that the liquid flowing from the first flows through the second, and while being able to take samples from both, the first 450 g of cation exchanger of Example 1, the second 450 g of strongly basic anion exchanger to pH = 5.30, conductivity 3.0 µs, anion exchange pH 6 6.2, conductivity based on copolyaeraethyreadiviaylbenaeaebospheen quaternary groups. At the temperature of 24 ° C, the distillery absolute etaeal (99.7 # vol., Deneturated 1% vol. Of chloroferm, pH 5.75, conductivity 4.2 < S) was introduced on the first knees, and the partially purified ethanol flowing therethrough knees. The flow rate was maintained between 150 and 2000 ml / h. The course of the purification operation, i.e. the step of purifying the ethanol flowing out of both the cation exchange and anion exchange knees, was monitored by measuring pB and water even after diluting with the distilled sciences. The pe passage through the cation exchanger was pB 5 5.30, the conductivity was 3.2 µm, and the pe pass through αχχ &φφ ftχ ft X X X X Xααα. VRglveeti 2 ^ 3I ^ RS ·

Example 3

Two-column columns, unconverted as shown in Example 2, and at least 350 g of catox and 350 g of anion exchanger, flowed at 26 ° C at a flow rate of 1500 ml / h synthetic ethanol (95% by volume, 5.85, conductivity 3.9 µm). ). The purification Xfect is indicated by the measured values i ps cation exchanger 2.0 µS.

Example 4

Synthetic ethanol purified by hydrogenation and factory-produced (Contents «

99.9% v / v, pH (5.75), conductivity 3.0 µs) flowed through the apparatus of Example 2 with 450 g ion exchange charges at 3000 ml / h at 28 ° C. The final properties of the purified ethanol are pH &lt; 6.20, conductivity 1.2 µS *.

Example 5

The flow through the apparatus of Example 2 with the same amount of cation exchanger and anion exchanger was purified by ethanol regenerated by distillation and rectification (content 93 ebj., PH »7.45, conductivity 19.5 µS) at a rate of 1000 ml / h at 25 ° C. The purified ethanol was pH 6.45, and was 3.9%.

Examples

Glass demineralizing stanol for the treatment of Veda · 300 mm diameter, containing 75 kg. cation exchange resin, overflowed at a temperature of 15 to 17 ° C, a rate of 200 ltr / h, regenerated ethanol (content 94 # vol, pB 8 8.45, conductivity 52.0 µ / s). The measured values of the outgoing ethanol: pB 5.50 to 5.85, conductivity 2.45 and 3.2 ffS, the latex was standardized to purify 22,500 liters of recovered ethanol.

The recovered ethanol purified according to the invention was used in the production of the trivalent iron polyeaoharide complex. The yield was almost theoretical and the prepared injectable solution of the complex, administered intramuscularly, had excellent physiological properties: it was notoxic and absorbed in a short time from the pulverized ground.

In contrast to the test using ethanol recovered by pathogenesis, the yield of the complex decreased substantially (except for 6.8 6.8 and the properties of the prepared solution for injection were not nearly as good. <->

A similar adverse effect of aa activity is that the use of ethanol, purified according to the invention, in the manufacture of a protease inhibitor and some hermoaes has been named and yielded.

When using ethanol purified according to the invention, in the preparation of the enzyme pepsin, a preparation with an activity of greater than 100 g / g was always obtained in high yield. When using distilled alcohol, the yield was low and the preparation efficiency decreased to aa 2000 j / g. The effect of the purity of the ethanol used and the activity of the produced pepsin is shown in the table:

Alcohol used Activity of produced pepsin. __ «Μ / g recovered distillation 2000 sales absolut. untreated 8000 regenerated, purified katoxoa 10000 regonerevuuý or absolut. Clear cation exchanger i 16000

Example 7 <

A 25 µm 270 nm glass column filled with 65 g of cation exchanger, a 500 m / h marketed nethanel (pH 6 6.10, conductivity 9.7 µS) and a temperature of 10 ^to C was flowing through. £ 3.4 iS. In 5 liters of the partially purified mothanol, 50 .mu.l wet anion exchange resin was cut in an OH-cycle. After 15 minutes of chanleys. stirring was pH 6.40, conductivity 2.2 µS. These values did not change even after repeating the operation with an additional 50 [deg.] C. fresh anion exchange resin.

Example 8

The aparsAure flow of Example 2 was used to clean 9 parts by volume of abs. ethanol, 1 part by volume of iseprepylalkehel and 1 part by volume of distilled water having a pH value of 6.40 and a conductivity of 5.3. The flow rate was 1500 nl / h at 22 ° C. Liquid leaking! The cation exchange knees had a pH of »5.45, a conductivity of 8.4 pS, and after subsequent column flow, the aaoxone was pS» 6.80 and a conductivity of 3.2 <mS.

Example 9

A mixture of 4 parts by volume of methanol, 5 parts by volume of propylene glycol and 1 part by volume of distilled water was 8 Utina in the apparatus of Example 2 as it first flowed through an anion exchange resin and 145 (4iS). conductivity then katexcwým column at a rate 1200 ml / h at 20 ° C. The starting mixture had a pH «3.50 and a conductivity of 40.0 S ^. after passing through the anion exchange resin was pH 9.15, conductivity 7.0 gS _t after passing by the cation the final pH values were < 6.60 and the conductivity was 4.6 &lt; 1S.

Example 10

At a rate of 1000 ml / h at 25 ° C, the mixture flowed through the apparatus as in Example 2

X · absolute ethanol, triethylene glycol and distilled water (60 + 20 + 20 parts by volume, pH »5.90, conductivity 87.0 µS) · pH values» 3.50, water5.2 µS were measured after cation exchange .

Claims (1)

SUBJECT A LIKE A process for the purification of alcohols of the general formula I R = OH, (I) wherein R is alkyl and 1 to 4 carbon atoms, hydroxyethyl to hydroxyhexyl or a radical of formula II (II), wherein R 1 and R ₂ are the same or different chains and are 2 to 6 carbon atoms and x is a number from 1 to 3, characterized in that the alcohol of formula I or a mixture of alcohols of formula I is contacted with a cation exchanger in the H -ocycle and / or an anion exchanger in the QH cycle, in a volume ratio of 1: 1 to 1: 1000, at a temperature of -15 to +50 ° C, and preferably 10 to 25 ° C.