Abstract:
A quantitative enrichment of volatile compounds from substances of the macro- to submicro field in a short time is realized by capillary distillation in a system which includes an evaporator vessel, on the bottom of which one or more filter plates are provided and which is connected to a condensing vessel by means of a capillary tube. The presence of filter plate(s) guarantees a uniform and constant boiling which facilitates the quantitative isolation of the volatile compounds.

Description:
BACKGROUND OF THE INVENTION 
     According to the EP 0248987 B 1, an upgrading method for volatile compounds has become known, according to which the enrichment of volatile compounds from liquid and solid substances containing said volatile compounds is possible in a closed system without using any auxiliary substances if it is carried through by heating the basic material at elevated temperatures and condensing the volatile substances at lower temperatures in a system which consists of an evaporator- and condensing vessel as well as a capillary tube connecting said vessels and having an inside diameter of less than 1 mm. The method according to the EP 0248987 B1 did allow an enrichment of the volatile substances in the condensate which had not been known before. For this purpose, however, a relatively high expenditure of time had been necessary. 
     SUMMARY OF THE INVENTION 
     There had been found out now that a quantitative enrichment of volatile compounds from liquid or suspended substances of the macro- to submicro field (ppm-ppb) containing said compounds is possible in a short time by capillary distillation of these substances and condensing or absorbing the volatile compounds if the enrichment is carried through in a system which consists of an evaporator vessel, on the bottom of which one or more filter plates are provided which guarantee a continuous and constant development of steam bubbles during boiling, a condensing vessel and a capillary tube connecting said vessels. 
     Filter plates may consist of the most different materials, such as glass, quartz, porcelain, clay, precious metal and synthetic material, such as teflon, PEEK (polyetheretherketone), etc. Preferably, purchasable filter plates of borosilicate glass are employed. 
     In the inventive systems, preferably, cylindrical evaporator vessels with flat bottom are used. The form of the evaporator vessel is not decisive for the effectiveness of the filter plates to form steam bubbles, they even are fully effective on an arched bottom. 
     As condensing vessels, preferably, small threaded bottles or beaded rim bottles with ranged cap are used. The size depends on the quantity of the condensate. 
     As a cover for the condensing vessels, in particular, silicone sepia are suited which are centrically slotted or provided with a bore. A capillary tube can be inserted therethrough very easily. Besides, these covers also guarantee a sufficient venting of the condensing vessel in order to be able to carry through the capillary distillation without problems. 
     Moreover, in the inventive system a capillary tube having an inside diameter of less than 1 mm proved to be very advantageous. 
     The suitable materials for the capillary tubes depend on the chemical properties of the volatile compounds to be enriched. Capillary tubes of fused amorphous silicon dioxide, so-called &#34;fused silica&#34; capillary tubes, are particularly advantageous but those of synthetic material, such as polyfluoroethylene (teflon) and polyetheretherketone (PEEK) are advantageous as well. 
     For the enrichment of basic volatile compounds, such as amines, a base basicity of the capillary tubes is necessary which for &#34;fused silica&#34; capillary tubes can be easily obtained by basic leaching. 
     The length of the capillary tubes and their inside diameter have a certain influence on the transport procedures. So, for the capillary distillation of unstable volatile compounds, which should not be exposed to elevated temperatures for an unnecessarily long time, a short capillary tube having an average inside diameter of 0.20 to 0.32 mm is convenient. Short capillary tubes are those having a length of 100 to 500 mm. 
     Surprisingly, however, capillary tubes having a length of 500 mm or many meters are suitable for fractionated capillary distillations, e.g. for the separation of organic solvents adapted to be mixed with water. The overpressure in the evaporator vessel occurring thereat at the beginning can be avoided by preheating the capillary tubes. For short capillary tubes a regulation of the substance transfer is possible by cooling the capillary tubes below room temperature. It comes true for all lengths of capillary tubes that heating increases the substance transfer through the capillary tubes while it is reduced by cooling. For single capillary distillations not fractionated lengths of capillary tubes of 100-500 mm, preferably those having a length of 150-230 mm, have well proven. 
     For an optimum function of the inventive system a continuous and constant development of steam bubbles in the boiling liquid is necessary. Boiling stones are useless for the inventive system as they often lose their effectiveness or are not effective at all. Surprisingly, porous filter plates proved to be very suitable. In consequence of the use of these filter plates so many uniformly distributed steam bubbles are formed in the boiling liquid or suspension that even submicroquantities of volatile substances are expelled and quantitatively transported into the condensing vessel through the capillary tubes. This is more detailedly explained with the aid of examples 1 to 12. Compared to this, the cyanide determination according to DIN 38405 e.g. involves quite some expense: a relatively large sample quantity of 100 ml is required and needs to be heated to boiling point for one hour in a complicated apparatus by, at the same time, passing therethrough 20 l/h of air for quantitatively enriching the hydrocyanic acid. According to the inventive system, maximally 1/10 of the sample quantity and only half the time of experimentation are required for the same procedure. The inventive system can be operated individually or in groups. If there is an arrangement of 6 units, for example, the sample throughput per unit of time is increased by factor 6. Consequently, in the inventive system any additional measures, such as the generation of vibrations, see W. Dunges, Prachromatographische Mikromethoden, publisher: Dr. A. Huthig, pages 86-87, can be renounced. 
     Even in aqueous suspensions, e.g. suspensions of samples of the soil, a filter plate including pores Within the range of 160 . . . 250 μm still forms sufficient steam bubbles in order to guarantee a uniform boiling. 
     Instead of one filter plate, several correspondingly smaller filter plates can be used for the inventive system as well. The total surface of a single or several filter plates, preferably, should cover 25% of the bottom surface of the evaporator vessel. 
     As appears from Table 1, a different overpressure is generated inside the evaporator vessel according to the inside diameters of the capillary tubes. Under such conditions, it was not to be expected that filter plates would be capable of forming steam bubbles at all. In any case, boiling stones are very problematic under such conditions. See also Ullmann vol. 2/1, page 71, 1961, second complete paragraph. 
     Table 1 
     Pressure ratios for the boiling point of water in closed 20 ml beaded rim bottles for headspace analytics being provided with a capillary tube and manometer, wall 0.95 mm, volume 10 ml of water. 
     
         ______________________________________Capillary tube,inside diameter          Overpressuremm             mbar______________________________________0.20           2100.25           1600.32           1400.53            80______________________________________ 
    
     Table 2 provides a survey of the distillation characteristics of water and ethanol in the presence of filter plates of different porosity in closed 20 ml beaded rim bottles as they are used for the headspace analytics. Through the septum of the sealing cap fused silica capillary tubes with different inside diameters had been inserted and the content of 10 ml had been heated to boiling point. It appears from the table that filter plates comprising pores within the range of 160 . . . 250 and 100 . . . 160 μm are most convenient for water as well as for ethanol, that is for all inside diameters of capillary tubes from 0.20 to 0.53 mm. If there are concerned filter plates including pores within the range of 40 . . . 100 μm the steam bubbles formed are no longer capable of passing through the pores of the filter plate, however, the steam bubbles uniformly rising from the edge of the filter plate are advantageous for many applications since the boiling procedure takes place slightly damped as a result. 
     Table 2 
     Distillation characteristics of water and ethanol in the presence of filter plates of different porosity in closed 20 ml beaded rim bottles being provided with a capillary tube. Volume 10 ml. 
     
         ______________________________________Glass filter plate   Capillary tube,max. pore width        Volume  inside diameter                             Distillationμm        10 ml   mm           characteristics______________________________________160 . . . 250        water   0.20         A                0.25         A                0.32         A                0.53         A        ethanol 0.20         A                0.25         A                0.32         A                0.53         A100 . . . 160        water   0.20         B                0.25         B                0.32         B                0.53         B        ethanol 0.20         B                0.25         B                0.32         B                0.53         B 40 . . . 100        water   0.20         C                0.25         C                0.32         C                0.53         C        ethanol 0.20         C                0.25         C                0.32         C                0.53         Cboiling stones        water   0.20         D-E                0.25         D-E                0.32         D-E                0.53         D-E        ethanol 0.20         D-E                0.25         D-E                0.32         D-E                0.53         D-Ewithout auxiliary agents        water   0.20         E                0.25         E                0.32         E                0.53         E        ethanol 0.20         E                0.25         E                0.32         E                0.53         E______________________________________ 
    
     Explanations of: 
     A: Rising of midsize steam bubbles through the filter plate. Good distribution in all the liquid. 
     B: Rising of small steam bubbles through the filter plate. Good distribution in all the liquid. 
     C: Rising of steam bubbles around the edge of the filter plate. Average distribution in the liquid, damped boiling. 
     D: Formation of steam bubbles considerably depending on the kind and structure of the boiling stone. Steam bubbles rise, if at all, from a certain point of the boiling stone only, often in an abrupt manner. Altogether very unreliable since there often is a loss of efficiency after a short time. 
     E: There are no steam bubbles formed. 
     As a result of the inventive method, a reliable quantitative collection of volatile compounds from the substances containing said volatile compounds is possible, that is without gaseous auxiliary agents as well as without special additional arrangements. It is suitable for the isolation of volatile substances as they are required for the perfume industry, aroma research, cosmetics industry, for example, as well as for the isolation of volatile contaminants from waste water, samples of the soil, from pharmaceutical products, products of the food industry, from plant extracts, pesticides and for analytical purposes. 
     The inventive method is particularly suitable for the quantitative isolation of contaminants damaging the environment, such as free hydrocyanic acid and hydrocyanic acid set free from cyanides or complex cyanide ions as well as for the quantitative isolation of free hydrogen sulfide and hydrogen sulfide from waters and soils of any type, such as industrial waste waters, infiltration waters, soil samples and sludges, said hydrogen sulfide being set free from sulfides. Besides, it is most suitable for the quantitative isolation of ingredients from infiltration waters, such as chlorinated hydrocarbons, aromatic hydrocarbons, chlorinated aromatic and hydroaromatic hydrocarbons from infiltration waters containing said ingredients. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     The objects and feature of the present invention will now be explained on examples with reference to the accompanying drawings, wherein: 
     FIG. 1 shows a schematic view of a system for quantitative enrichment of volatile compounds by capillary distillation according to the present invention; 
     FIGS. 2-10 shows on ion chromatograms of materials separated in accordance with the inventive method, as described with reference to examples 1-10 below; 
     FIG. 11 shows gas chromatograms of different materials separated in accordance with the inventive method, as described in example 11 below. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The system for the capillary destillation is schematically shown in FIG. 1: The evaporator vessel 2 including the glass filter plate lis provided within a heatable block 3; the condensing vessel 4 is surrounded by a cooling block 5; the capillary tube 6 leads the gas transport from vessel 2 to the condensing vessel 4. The invention is more detailedly explained with the aid of the following examples, wherein the system according to FIG. 1 was used. 
     EXAMPLE 1 
     Quantitative isolation of hydrocyanic acid from a 10 ppb standard cyanide solution. 
     10 ml of a 10 ppb standard cyanide solution (pH 12) are pipetted into a 20 ml pressure resistant borosilicate glass with rolled flange, a filter plate of borosilicate glass, porosity range 100 to 160 μm, is inserted and flanged. Thereafter, there is inserted through the flanged cap a &#34;fused silica&#34; capillary tube having a length of 200 mm and an inside diameter of 0.32 mm and the evaporator vessel is positioned within the heating block still being cold. As condensing vessel a borosilicate glass with rolled flange, volume 10 ml, is used as well and 1 ml of a molar sodium hydroxide solution is used as an absorbent for the hydrocyanic acid. In the cooling block the condensing vessel is cooled to -2°C. The flanged cap of the condensing vessel contains a septum which in its center is provided with a bore of 1/16 inch through which the capillary tube of the evaporator vessel can be easily introduced. The capillary tube is submerged in the sodium hydroxide solution. By means of injecting 1 ml of a mixture of citrate buffer and phosphoric acid/hydrophosphoric acid (2+1) hydrocyanic acid is liberated from the solution to be analyzed and is driven over by heating to the recipient vessel for boiling. The boiling procedure is discontinued after 20 minutes. The contents of the recipient vessel is filled up with distilled water to exactly 10 ml and is analyzed by means of ionic chromatography with an anionic exchange column and an electrochemical detector. 
     
         ______________________________________Result:   Desired value                =     10.0 ppb     Effective value                =     10.1 ppb (compare FIG. 2)______________________________________ 
    
     In the following examples the evaporator vessel, filter plate, capillary tube, condensing vessel, acid mixture for liberating hydrocyanic acid or hydrogen sulfide, absorbent and analytics have not been changed unless mentioned to the contrary. 
     EXAMPLE 2 
     Quantitative isolation of hydrocyanic acid from a 10 ppb standard cyanide solution. 
     According to example 1, the hydrocyanic acid is quantitatively isolated from 10 ml of a 10 ppb standard cyanide solution (pH 12) within 20 minutes. 
     
         ______________________________________Result:   Desired value                =     10.0 ppb     Effective value                =      9.9 ppb (compare FIG. 3)______________________________________ 
    
     EXAMPLE 3 
     Quantitative isolation of hydrocyanic acid from a 2 ppb standard cyanide solution. 
     According to example 1, the hydrocyanic acid is quantitatively isolated from 10 ml of a 2 ppb standard cyanide solution (pH 12) within 20 minutes. 
     
         ______________________________________Result:   Desired value                =      2.0 ppb     Effective value                =     1.95 ppb (compare FIG. 4)______________________________________ 
    
     EXAMPLE 4 
     Quantitative isolation of hydrocyanic acid from a 10 ppb standard cyanide solution. 
     According to example 1, the hydrocyanic acid is quantitatively isolated from 10 ml of a 10 ppb standard cyanide solution (pH 12) after 10 minutes already. 
     
         ______________________________________Result:        Desired value                     =     10.0 ppb          Effective value                     =     10.2 ppb______________________________________ 
    
     EXAMPLE 5 
     Quantitative isolation of hydrocyanic acid from complex cyanide ions (potassium ferrocyanide, K 4  [Fe(CN) 6  ]. 
     According to example 1, 10 ml of a 11.1 ppb cyanide solution of potassium ferrocyanide K 4  [Fe(CN) 6  ] are used. The mineralization of the complex is complete after a capillary distillation of 30 minutes. 
     
         ______________________________________Result:   Desired value                =     11.1 ppb     Effective value                =     10.6 ppb (compare FIG. 5)______________________________________ 
    
     EXAMPLE 6 
     Quantitative isolation of hydrocyanic acid from complex cyanide ions (potassium ferrocyanide, K 4  [Fe(CN) 6  ]. 
     According to example 1, 10 ml of a 22.2 ppb cyanide solution of potassium ferrocyanide K 4  [Fe(CN 6  ] are used. The mineralization of the complex is complete after a capillary distillation of 30 minutes. 
     
         ______________________________________Result:   Desired value                =     22.2 ppb     Effective value                =     21.6 ppb (compare FIG. 6)______________________________________ 
    
     EXAMPLE 7 
     Quantitative isolation of hydrocyanic acid in the presence of thiocyanate ions (SCN 31 ). 
     According to example 1, 5 ml of a 10 ppb standard cyanide solution, 5 ml of distilled water and 100 μm of a 1000 ppm potassium thiocyanate standard solution (pH 12), according to 10 ppm thiocyanate ions (1000-fold excess), are used and subjected to a capillary distillation for 30 minutes. 
     
         ______________________________________Result:   Desired value                =     5.0 ppb     Effective value                =     5.3 ppb (compare FIG. 7)______________________________________ 
    
     The high peak in the chromatogram at a retention time of 7.02 min. shows sulfide ions (40 ppb approx.) which have caused a contamination of the potassium thiocyanate per analysis. 
     EXAMPLE 8 
     Simultaneous isolation of hydrocyanic acid and hydrogen sulfide, 10 ppb in each case, from corresponding standard solutions. 
     According to example 1, 10 ml of a 10 ppb standard cyanide solution (pH 12) and 0.1 ml of a 1 ppm standard sodium sulfide solution (pH 12) are used and subjected to a capillary distillation for 20 minutes. 
     
         __________________________________________________________________________Result:    Desired value cyanide         =  10 ppb               Desired value sulfide                         =  10 ppb    Effect. value cyanide         = 9.8 ppb               Effect. value sulfide                         = 9.9 ppb (compare FIG. 8)__________________________________________________________________________ 
    
     EXAMPLE 9 
     Quantitative isolation of hydrocyanic acid and hydrogen sulfide from an industrial waste water. 
     According to example 1, 10 ml of an original industrial waste water are used and subjected to the capillary distillation for 30 minutes. During this time, complexed cyanide and cyanide which can be easily liberated as well as hydrogen sulfide are isolated from sulfides. 
     
         ______________________________________Result:     Cyanide =     13.3 ppb       Sulfide =      9.9 ppb (compare FIG. 9)______________________________________ 
    
     EXAMPLE 10 
     Quantitative isolation of hydrocyanic acid and hydrogen sulfide from an industrial waste water. 
     According to example 1, 10 ml of an original industrial waste water are used and subjected to the capillary distillation for 30 minutes. During this time, complexed cyanide and cyanide which can be easily liberated as well as hydrogen sulfide are quantitatively isolated from sulfides. 
     
         ______________________________________Result:     Cyanide =     13.5 ppb       Sulfide =      3.1 ppb (compare FIG. 10)______________________________________ 
    
     EXAMPLE 11 
     Quantitative isolation of volatile substances from an infiltration water. 
     According to example 1, 2 ml of an original infiltration water are diluted with 5 ml of distilled water and subjected to the capillary distillation for 30 minutes without adding the acid mixture used in example 1. The volatile substances are condensed in n-pentane which is precooled to -5° C. 
     Evaporator vessel: beaded rim borosilicate glass with flanged cap 
     Filter plate: borosilicate glass, porosity range 40 to 100 μm 
     Capillary tube: &#34;fused silica&#34; inside diameter 0.32 mm 
     Condensing vessel: 10 ml beaded rim borosilicate glass with flanged cap 
     Absorbent: 2 ml of n-pentane, cooled to -5° C. 
     Analytics: gaschromatography (compare FIG. 11) 
     In FIG. 11 are: 
     1. cis-1.2-dichloroethylene, 
     2. 1.1.1-trichloroethane, 
     3. benzene, 
     4. trichloroethylene, 
     5. toluene, 
     6. chlorobenzene, 
     7. tetrachloroethylene, 
     8. ethyl benzene, 
     9. m-, p-xylene, 
     10. o-xylene, 
     11. propylbenzene, 
     12. 1.3.5-trimethylbenzene, 
     13. 1.2.4-trimethylbenzene, 
     14. 1.2.3-trimethylbenzene, 
     15. p-dichlorobenzene, 
     16. o-dichlorobenzene, 
     17. 1.3.5-trichlorobenzene, 
     18. 1.2.4-trichlorobenzene, 
     19. 1.2.3-trichlorobenzene, 
     20. 1.2.3.5-tetrachlorobenzene, 
     21. 1.2.3.4-tetrachlorobenzene, 
     22. pentachlorophenol 
     Range of concentration: ppb-ppm 
     
         __________________________________________________________________________Data of FIG. 11__________________________________________________________________________DATE     : 11.04.94           / INJ (grd)                   : 250                        / LSG-DERI V.GC       : Dani 6500           / DET (grd)                   : 300                        / PRM (mg)GRAPHER  : BD 8 / OFEN A (grd)                   : 50 / LMVORSCH. (cm/m/n)    : 1.0  / OFEN E (grd)                   : 230                        / LM.M.(m)ATTENUATION     / INIT (m/n)                   : 5.0                        / DMDET - SCHR.    : 1 × 16           / FINAL (m/n)                   : 20.0                        / DM.M.(m)EINSPR. M. (mel)    : 1.00 /RATE grd/m/n)                   : 10.0                        / TEMP (grd)INJECTION    : H 7001            / TIME (m/n)GAS      : HELIUM           /COLUMN    : DB 5PRESSURE (bar)    : .4   /LENGTH   (m)                      : 30.0FLOW     :      /CARRIER   : ID-32 mm/FD-1 mu 6DIGITAL  :      /No. + MATERIAL                      : FS 32100966SPLIT (m/mn)    : 1:15SAMPLE DESCRIPTION       :NOTES       :__________________________________________________________________________ 
    
     EXAMPLE 12 
     Quantitative isolation of ethanol from a water-ethanol mixture by means of fractionated capillary distillation. 
     According to example 1, a mixture of 9 ml of water and 1 ml of abs. ethanol (0.789 g) is used and distilled for 30 minutes by making use of a fused silica capillary tube of 1200 mm length. 
     Evaporator vessel: beaded rim borosilicate glass with flanged cap 
     Filter plate: borosilicate glass, porosity range 160 to 250 μm 
     Capillary tube: &#34;fused silica&#34; inside diameter 0.32 mm, length 1200 mm, room temperature 
     Condensing vessel: 10 ml beaded rim borosilicate glass with flanged cap 
     Absorbent: none 
     Analytics: gaschromatography 
     Result: 1.12 g condensate consisting of the whole amount of ethanol (96 per cent), rest=water. In the distillation residue only traces of ethanol could be detected gaschromatographically.