DE1619826A1 - Separation processes in gas / solid chromatography - Google Patents

Description

Separation methods in gas / solid chromatography are known I separate gas mixtures into their components by putting them together with a iridescent carrier gas such as relium flows through a column, which is filled with an inert, solid carrier on which a liquid, selectively active adsorbent is applied is stuffed.

The carrier gas is sent through the column under pressure and takes with the gas mixture to be separated. The adsorbent adsorbs the individual Components of the mixture and holds them differently strong rest, so that they are different quickly released back into the carrier gas flowing at constant b speed will. The various components have been in this way for different lengths of time held back by the column, i.e. they leave the Pillar to different Times. Such a method in which a ptliquid is used as the adsorbent is called gas / liquid chromatography.

The use of gas / solid chromatography, in which this is selective An effective adsorbent is a solid, despite a number of procedural requirements Advantages over gas / liquid chromatography are not yet widespread Found application because no effective solid adsorbents are available state. Activated carbon as an adsorbent is unsuitable for many purposes, especially not for the separation of gas mixtures, their constituents at increased Temperature react with the activated carbon. Columns of coal can also be difficult to get through Heat can be regenerated when it is more or less permanently adsorbed Materials were clogged because the temperatures necessary for this, for example 500 ° C or above, destroy the surface of the coal particles, especially if Air or other oxidizing agents are present, object of the present invention is therefore a separation method of gas / solid chromatography, which is used for separation of mixtures of various oases and vapors, including reactive ones Gases, suitable and in which the regeneration of the adsorbent through Heat can be carried out without damaging the adsorbent. subject of The invention is a process for separating gaseous mixtures into their components by passing the oasis mixture together with an inert gas such as Helium through a long column containing an adsorbent, with at least one of the connections of the gas chamber at temperatures between 0 and 500 of the remaining components is separated. The procedure is characterized by the a synthetic diamond-containing material is used as adsorbent, that of polycrystalline aggregates formed by individual diamond particles a mean diameter of not more than 0.51 p and a surface area of between 40 and 400 m2 / g. Of course, the term used above means Ajus "Gaseous mixture", a mixture of which all components are used for the Separation applied temperature are gaseous or vaporous, and not that all. or some components may be gases or vapors at normal temperature of around 25 ° C had to.

The invention is described below with reference to the accompanying figures be clarified »where Figure 1 is a schematic representation of a implementation of The apparatus used according to the invention, FIGS. 2 to 7 in the The chromatograms obtained for carrying out the process according to the invention are shown in FIG 8 is a photomicrograph of a calcium fluoride crystal obtained at 140 magnifications is, which carries much smaller diamond crystals, which make up about 10% of the total amount are present on the crystal, and Figure 9 is one obtained at 150 times magnification Photomicrograph of a calcium fluoride crystal with about 1% adhered diamond particles represents.

The apparatus according to FIG. 1 consists of a chromatography column 1, which is stuffed with diamond-containing adsorbent 2 'A carrier gas storage container 3 is via a branching line 4 on the one hand by line 4a with the Reference detector 5, on the other hand connected to the head of the coil 1 by line 4t. To inject a sample of the gas mixture to be separated is at the top of the column An injection site 6 is provided in line 7. The outlet 8 at the bottom of the spool is' connected by line 9 to the sample detector 10, which in turn is connected to the Comparison detector 5 by a Wheatsone bridge, not shown is connected, the ends of which are connected to the registration device 11.

The inert carrier gas, such as helium, is taken from the storage tank 3 passed through connecting line 4, where it is divided into two partial flows with the same pressure and equal flow velocity is divided. One partial flow is through Connecting line 4a passed to the reference detector 5, the other partial flow through Lines 4b and 7 through the chromatography column 1. With uninterrupted, even, A gaseous or vaporizable sample is sent to the heated stream of the carrier gas Introductory part 6 injected, where necessary. Vaporized and with the carrier gas in the Column 1-carried. The components of the injected sample have added adsorbent different affinities in the column; the mixture therefore becomes continuous at The flowing carrier gas is separated into zones moving at different speeds. After this Leaving the column at outlet 8, each of these zones is flushed into the detector 10, which measures the thermal conductivity and in connection with one between him and the reference detector 5 located Wheatstone bridge an electrical signal generated which is proportional to the amount of the respective component contained in the carrier gas 1st. This signal is sent to a potentlometric recorder 11 where it causes the chromatogram pen to move.

The column can be used in a known manner, for example vertically, be arranged horizontally or inclined; they can also be in the form of a snake or be arranged in another space-saving form.

The column leaving the column can be used to analyze or separate mixtures Gas that contains the separated individual components> continuously through a Detector directed to a certain property of the component such as their thermal conductivity responds and any deviation from this property indicates the same property of the carrier gas. The separate appearance of one or more of the mixture components in the detector depending on the concentration of the component is shown as a longer or shorter deflection on a measurement diagram.

If desired, the individual components can be extracted from gas liquid chromatography known manner are collected separately, and one or more of the eluted Components can be used for further analysis, e.g. for infrared spectroscopy, subtracted from. On the other hand, the retention times and the Areas under the registered maxim sufficient conclusions on identity and proportion of the components are drawn on the overall mixture. in general can be the amount of each individual component as defined by the area under which it is to be assigned Maximum reproduced, provided one, as is the case with the interpretation Such chromatograms are usually corrections for the various thermal Conductivities of the individual components and other factors than synthetic Diamond-containing material is preferably that in patent application A 53 442 IVa / 12i used by the same applicant. It consists of finely divided, individual Diamond particles, which have a hydrophilic surface with acidic properties, and can be made by using shock wave treated graphite, i.

Graphite, the impact pressures and temperatures within the stability range of diamond and therefore contains fine diamond particles, at least approximately. 280 and preferably above 300 ° C and atmospheric pressure with nitric acid oxidized. The finely divided diamond-containing material produced in this way consists of polycrystalline aggregates with a mean particle diameter not exceeding about 0.15 @ (1500 i) and a surface area of between about 40 and 400 m2 / g, usually from 160 to 200 m2 / g.

The aggregates consist of individual diamond crystallites with a mean diameter of between about 50 Å and about 300 Å. After its manufacture contain the diamond particles, as described above, functional on the surface Groups. such as hydroxyl, carboxyl, and carbonyl groups that make up at least about 10% of the surface area cover.

The diamond-containing material that contains these functional groups is useful in the method of the present invention. However If desired, most of the surface area's sn can be functional Oruppen for example by heating to 600 to 1000 ° C in an inert or reducing atmosphere. 80 that a product is created that in fact no functional groups or in any case a greatly reduced concentration of solitary groups on its surface and that also chromatographically is as effective as the original oxidized product. This fact is because of it significant. because it enables the column to be regenerated by heating, if the column is poisoned by such adsorbed material that cannot can be easily eluted at low temperature.

It has been found that the diamond-containing materials described above the most varied of gases and vapors including a large number of different reactive and / or toxic gases and vapors, their separation and analysis have so far caused great difficulties, for example gaseous and vaporous Fluorine compounds, adsorb selectively, The diamond-containing material can be used as the only adsorbent. However, it will preferably be with one Inert, solid carrier material mixed or deposited on it, with at least about% by weight of the column charge consists of the diamond-containing material. Will If it is used without a backing then you need the DrUoke that is used to propel it through of the inert carrier gas and the gases or vapors to be separated by themselves relatively short columns are required because of the extremely small particle size of the diamond-containing Materials can be quite a bit higher than usual.

For this reason and to the relatively expensive diamond-containing To save material, this is preferably done with varying amounts of an inert, solid diluent consisting of slightly larger particles, for example between about 0.590 mm (30 mesh) and about 0.074 mm (200 US mesh) - and preferably 0.590 to 0.177 mm (30 to 80 US mesh) particles, mixed together, thereby not only the cost of the column is reduced, but also a faster gas flow through the column at lower pressures and without significant loss of adsorption properties or selectivity of the adsorbent will allow. In general, pillars used, the about 10 to 50% diamond-containing material and about 90 to 50% inert, contain solid diluent.

As a carrier for the diamond-containing adsorbent suitable inert, solid thinners are diatomaceous earth, fireclay, silicon dioxide, aluminum. oxide, polytetrafluoroethylene, calcium fluoride, etc. When using a column with Diamond-containing material as the only adsorbent is the carrier gas with a Pressure of about 5.6 to 6.3 atmospheres-pushed through the column. -When using only 90% or less diamond-containing material and the remainder inert diluent particle size from about 0.177 to about 0.149 mm (about 80 to 100US mesh) considerably lower pressures, the level of which is somewhat dependent on the diluent used varies, the Jedoeh for most separations be about 2.1 to 4.9 atii. In the cases. in which the proportion of diamond-containing material does not exceed about 20%, In general, pressures of about 2.1 to 2.5 atmospheres are sufficient.

A material that is particularly suitable as a filling material for the columns is that of crystalline calcium fluoride with a particle size between 210 and 590μ as well as diamond-containing material deposited thereon and firmly adhering to it and in which the diamond-containing material is between 1 and 20% of the total weight matters. The calcium fluoride carrier can be obtained from fluorine and is preferred by heating to, for example, 900 ° C Eereinlgt and in a suitable manner on the Destroy the said small size. Such particles generally have a Surface area of about 0.15 m2 / g. If you add such Calcium fluoride particles, as described here, add diamond-containing material by, for example, under gently stirring the diamond particles into a large amount of calcium fluoride particles, in this way the calcium fluoride particles are evenly covered by the diamond particles. With advantage will. after stirring the diamond particles into the calcium fluoride particles shake the resulting mixture gently to ensure an even distribution of the diamond particles without causing further comminution of the calcium fluoride particles. A diamond share in the column packing material of only about 1% by weight already results in effective adsorbents. and the diamond particles still adhere to the surface of the calcium fluoride particles firm if. they make up a weight fraction of about 20% of the column filling material. One can also use larger relative amounts of diamond-containing material, however Then some of the diamond particles easily fall off after some time of the carrier material.

Xikrofotografi.n of column filling material of the type mentioned are in Figures 8 and 9 of the barking figures shown.

Any gas that opposes each other can be used as the carrier gas behaves inertly to the gas mixture to be separated, in-game the noble gases such as helium and argon, as well as nitrogen The method of the present invention can be used to separate a wide variety of inorganic and organic mixtures if at least one of the components of the mixture is in the temperature range the column is selectively adsorbed by the diamond-containing material and it -s itself betindet at these temperatures in the gaseous state. Such temperature ranges may for example be between about 0 and 50 and preferably extend from about 20 to about 350 ° C. The flow rate of the carrier gas through the Column and the temperature of the gas can be regulated so that within a workable range of separations into more distant or Zones that are closer to one another are carried out, as is customary in gas chromatography is. For example, in a column with a diameter of 3.2 mm, useful Flow rates are about 10 to about 50 mlSsea.

To get a good separation of a mixture into all of its Components must have the retention times of the various components in the column differ considerably from one another, for example by at least about 30 seconds and preferably by about 1 to 2 minutes under the operating conditions of the column. In this way, zones of the individual components can be easily separated from one another elute and thus ssubsr separate maxima on the chromatograms for analysis to win.

BeiNplele for gaseous and steam-shaped mixtures which are based on the described Ways that can be separated are: gaseous elements such as fluorine, chlorine, etc .; Air; aliphatic and aromatic organic compounds such as alkanes, cycloalkanes, Alkenes, cycloalkenes, fluoroalkanes, including tetrafluorocarbon, and fluoroalkenes, Luminous kerosene and motor gasoline as well as inorganic compounds, such as heavy heafluoride, Carbon oxides, nitrogen oxides, hydrofluoric acid, tungsten hexafluoride and chlorine trifluoride.

The method according to the invention is particularly suitable for separation of mixtures containing at least one reactive fluorine-containing substance, for example for mixtures. the fluorine itself, hydrogen fluoride, difluoromonoxide or contain chlorofluorides and fluorinating agents such as chlorine trifluoride. With the according to the invention - method is also an excellent separation of fluoroalkane and fluoroalkene mixtures into their components possible. Another important area of application of the process according to the invention is the separation of impurities from reactive ones Gas mixtures, especially the separation of components such as F2, C1F, ClF2, HF. ° P2 and air, which occur as impurities in Chlortrifluorld ', the through Conversion of chlorine and fluorine in a reactor made from a catalytically active metal. for example a nickel reactor at an elevated temperature, for example at 280 ° C, will be produced The separations according to the method of the invention can either be complete, i.e. the mixture can be divided into all components or they can be partial, i.e. complicated mixtures can be broken down into mixtures with a smaller number of components.

The retention times in the column do not only vary depending on of the individual components to be separated by also depending on the Temperature of the column, the pressure of the carrier gas and the ratio of -diamond Material to inert, solid diluent in the column packing material, generally higher pressures and temperatures lead to shorter retention times; a higher one On the other hand, the proportion of diamond-containing material increases the retention times. These variables can easily be coordinated to create the best conditions for implementation a specific separation task can be achieved 1 The following examples serve to further explanation of the invention. Parts are by weight, provided not stated otherwise.

Example 1 Separation of Fluorine and Hydrogen Fluoride: A 4.88 m long Nickel chromatography column with an outer diameter from 3.2 m "n was loaded with material containing diamonds on a calcium fluoride carrier. The column filling material consisted of 90 «CaF2 with a particle size of 210 to 590μ and 10% diamond powder of one particle size deposited on the calcium fluoride between 50 and 300 Å and a surface area of about 200 m2t g. The column was in a normal chromatographic analyzer. The carrier gas was used Helium, part of which through the reference detector, the other part - through the column and passed through the sample detector. The flow velocity of the helium was kept at 80 mm, min in each of the substreams. the pressure used was 2.1 to 2.5 auü.

A sample of a gaseous mixture of 30 parts by volume of fluorine and one volume of hydrogen fluoride was injected into the helium stream before this got into the column.

The components of the mixture were with different retention times kept on the sow, then passed the sample detector one after the other and gave Separate maxima on the registration curve, the position of which corresponds to the following retention times corresponded to: component retention time, sec p2 30 210 The associated chromatogram is shown in FIG.

Example 2 Separation of hydrogen chloride and hydrogen fluoride: A.

Mixture of 30 parts by volume of hydrogen fluoride and 1 part of gaseous Hydrogen chloride was obtained as described in Example 1. in those made of helium Carrier gas flow at a rate of 40 ml / min at a pressure of 2.1 to 2.5 atmospheres, injected and with this through a column of 10% diamond particles added to 90% calcium fluoride, and the retention times of the components were determined: component retention time, sec HC1 120 HF 420 Example 3 Separation of Hydrogen fluoride. Hydrogen chloride and fluorine: a sample of 30 parts hydrogen fluoride, 1 part hydrogen chloride and a trace (less than 1 part) fluorine was used of the chromatography apparatus described in Example 1 into the helium stream, the a flow rate of 40 ml / min at 2.5 to 2.8 atmospheric pressure was injected. After eluting the components, the following retention times were found: Component retention time, sec F2 70 HC1 120 HF 400 The corresponding The chromatogram is shown in FIG.

Example 4 A sample of chlorine trifluoride. the reaction of chlorine and fluorine had been produced, was used to determine the nature and extent of therein Contaminants contained in the chromatography apparatus described in Example 1 into a carrier stream consisting of helium, which has a flow velocity of 30 ml / min at a pressure of 2.1 to 2.5 atmospheres, injected.

The chromatogram obtained is shown in FIG. 4 and leaves components with the following retention times and the following likely composition detect: connection retention time, sec F2 or ClF 90 HF.ClF3 190 ClF3 330 Die Areas under the different maxima of the chromatogram were 1.0%, 4.1% and 94.8%; they suggested a content of about 5% impurities, of which The main amount consisted of the complex ClF3.HF.

Example 5 A 61 cm long copper column with an outer diameter from 3.2 mm was made with an 85% calcium fluoride and 15% diamond Filling material of the same type as described in Example 1 is charged. The pillar was "calmed down" ~ by mixing through them for 120 minutes at 25 ° C Chlorine trifluoride and fluorine headed. After that, helium was at a speed of 60 mlsmin and passed through the column under a pressure of 2.1 to 2.5 ntU. A gaseous mixture of fluorine and tungsten hexafluoride was introduced into the helium stream injected, then eluted and analyzed. The chromatogram obtained eats shown in FIG. It gave the following retention times: compound retention time, sec F2 30 WF6 240 Example 6 A 3.05 m long copper column with an outer diameter of 3.2 mm was filled with 15% diamond powder and 85% calcium fluoride a part size of 210 to 590µ. The components of the filler material were the same as described in Example 1. The column was in a normal. Gas Chromatograph (F & M 500) - used and kept at a temperature of 25 ° C. Helium was used as the carrier gas at a rate of 35 ml / m @ and passed through the column under a pressure of 2.1 to 2.5 atü. Into the helium stream was a mixture of equal parts by volume of tetrafluoroethylene and vinyl fluoride, the was contaminated with a small amount of air, injected and flow through the column left. The chromatogram obtained is shown in FIG. It became the following retention times and approximate areas under the maxima of the individual. nen IZomponenten, (expressed in% of the total area under all maxima), get: Retention time component, area under the sec sec maxima,% air 50 CF2 = CF2 120 32.3 CH2 = CHF 245 67.7 Example 7 Example 6 was repeated with the difference that that the flow rate of helium is 20 ml / min and the column temperature 70 ° C and a mixture of equal parts by volume of dichlorodifluoromethane and perfluorocyclobutane, which was polluted with small amounts of air, in don He. lium current injected and passed through the column.

The chromatogram obtained showed the following retention times and areas below the associated maximum Component retention time. sec area under the maxima ..

Air 60 CCl2F2 180 54.1 C4F8 300 45.9 Example 8 A copper pipe according to Example 6 was made with a filler material of 99% calcium fluoride with a particle size charged from 210 to 590p and 1% diamond powder of the type described in Example 1, The column was used in a normal gas chromatograph (F&M 500). Through the column was at a rate of 35 ml / mln and under pressure from 2.1 to 2.5 atmospheres of helium, with the column at room temperature (about 25t) was held. A mixture of approximately equal parts by volume of dichlorodifluoromethane and perfluorocyclobutane was injected into the helium stream and adsorbed sequentially eluted and passed through the detector.

The chromatogram obtained, which is shown in Fig. 7, shows the following retention times and areas under the individual components' associated maxima: component retention time, seo area under the maxima,% air 35 CC12FS 45 45.9 9 C4F8 70 54.1 As from the values obtained the areas below the maxima caused by CCl2F2 and C4F8 can be seen practically the same, whereby the known composition of the sample was confirmed.

Example 9 A 9.14 m long stainless steel column with an outer Diameters of 3> 2 mm were made with a filling material made of 15% diamond and 85% calcium fluoride of the kind described in Example 1 and placed in a normal gas chromatograph used. The carrier gas used was helium with a flow velocity of 35 ml / min and under a pressure of 2 »1 to 2.5 atmospheres and a temperature of about 25 ° C, into which a small sample of difluoromonoxide was injected. One observed a retention time of 6 minutes for this compound.

Examples 10-12 Three gaseous mixtures of the approximate shown below Compositions were among those described in Example 6 with helium as the carrier gas Conditions by the also described there, with 15% diamond and 85% calcium fluoride charged column passed. The retention times obtained were as follows: example Nr component% retention times. sec 10 NO2 50 60 CO2 50 135 ii CO 10 60 CO2 90 120 12 NO2 50 60 NO 50 90 Example 13 A 2.40 m long copper column with an outer Diameter of 6.4 mm was made with synthetic diamond powder with an average Particle diameter of 50 to 300 Å and a surface area of about 200 m2 / g without Use a carrier material and loaded in a normal gas chromatograph of the type shown in the drawing (F @ 6 M 500) is used. As a carrier gas Used helium. The coil was held at a temperature of about 40 ° C during a stream of helium was passed through them at a rate of 30 mi / min became. Shortly before the helium gas flow entered the column, samples of injected six different fluorocarbons. The different fluorocarbons had different retention times and became different due to the flow of helium Times after their introduction into the system. The eluate was by the thexinic conductivity-responsive detector, which nilts a recorder was connected. on he was aware of the presence of a fluorocarbon recorded in the gas stream as a maximum. A pressure of 5.6 to was required 6.3 atmospheres, in order to achieve a flow velocity of the helium through the diamond column of to maintain jO ml / min.

The widely differing retention times, as shown in the following Table I, column A, show that there is excellent separation which allows fluorocarbons to be obtained from each other.

After these determinations, the diamond column was on for 3 hours Heated to 350 ° C while maintaining the flow of helium. Then were further samples of the same fluorohydrocarbons in the helium stream injected and their retention times determined while the temperature per minute around 7.9T was increased from 50 ° C to 350 ° C. The results obtained are in the table I. Column B together, - put together.

T a b e ll e I Retention times of fluorocarbons in one 2.4 m long column filled with synthetic diamond using with a speed of 30 ml / min flowing helium as carrier gas substance retention times, min A) Before heating column B) After heated column air 7.7. 3.4 CF4 8.4 4.4 CF2 = CF2 10.6 8.5 CH2 = CF2 12.4 13.0 CF2H2 18.0 18.2 CHClF2 33.2 CF3CF2CF3 41.5 21.5 Note: The temperature in test series A) was 40 ° C., in test series B) it rose the temperature by 7.9 ° C per minute from 50 ° C to 350 ° C, so that # the two rows are not strictly comparable. However, the values obtained show that the diamond material is an effective adsorbent even after heating to 350 ° C.

Example 14 A 1.2 m long chromatography column with an outer Diameter of 6.4 mm was made with a mixture of 80% diamond powder that in example 13 used type and 20% diatomaceous earth (Chromosorb W) with a particle size loaded from 0.147 to 0.175 mm; another, same column became loaded with a mixture of 50% diamond powder and 50% diatomaceous earth @ over both Columns were 5 fluorocarbons in helium as the carrier gas, which with a speed of 30 ml per minute and under a pressure of 4.2 to 4.9 a, tU the column flowed through, given, for comparison purposes the procedures were repeated with the deviation, that columns were used which were 100% activated carbon (29 to 65 Tylor mesh, approx 0.21 to 0.57 mm particle size), 100% with diatomaceous earth and mixtures 50% activated carbon and 50% diatomaceous earth and also made of ultra-fine graphite and 50% Diatomaceous earth were charged.

The eluate was in each case by a change in the thermal Conductivity responsive detector headed; and the occurrence of the test compounds Maxima indicating in the detector were recorded.

The retention times obtained for the various columns are summarized in Table II.

T a b e ll e II Retention times (in minutes) of fluorocarbons in 1.2 m long chromatography columns filled with various adsorbents 80% diamond- 50% diamond- 100% 50% active- 50% graphite- 100% 20% diatoms- 50% diatoms- Activated charcoal - 50% diatoms diatom substance earth earth charcoal 50% diatom earth earth earth air 3.4 1.5 2.5 4.8 1.3 0.7 CF4 4.4 1.8 7.6 6.7 1.3 0.7 CF2 = CF2 8.5 5.0 21.5 22.0 1.3 0.7 CH2 = CF2 13.0 20.3 22.4 1.3 0.7 C2F2H2 18.2 8.5 11.9 15.5 1.3 0.7 CHClF2 20.6 12.0 23.0 29.0 1.3 0.7 From the data received it can be seen that neither the graphite nor the diatomaceous earth alone are the components adsorb the test mixture selectively. Activated carbon, a well-known adsorbent, adsorbs differently than diamond powder and brings no significant separation between Tetrafluoroethylene (CF2 = CF2) and difluoroethylene (CH2 = cF2) - accessible. eli diamond powder the type described in Example 13 was with balls made of polytetrafluoroethylene with an average diameter of 30 to 60 US mesh (0.25 to 0.59 mm) in ratio 25:75 mixed and the mixture was put on a 1.2 m long chromatography column loaded with 6.4 mm outer diameter. With a column tempo, ur from 50 to At 200 ° C., helium was passed through as the carrier gas at a rate of 30 ccm / min sent the column.

Samples of various fluorocarbons were placed in the helium stream introduced and chromatographed. ' The retention times of the individual components are summarized in Table III: T a b e 11 e IIIt retention times of fluorocarbons on one with 50% diamond and 50% polytetrafluoroethylene filled column compound retention time en, min CHF3 4.9 CHC1F2 13, o CCl2FCClF2 17.0 CHCl2F 18.0 Example 16 A 1.2 m long chromatography column with 6.4 mm outer The diameter was that described in Example 13 with a mixture of 80% diamond Type and 20% diatomaceous earth with a particle size of 0.177 to 0.149 mm. as Carrier gas was helium through the column at a rate of 8.26 ml / min and passed under a 'pressure of 2.1 atti.

Thereafter, a sample of 98% by volume sulfur hexafluoride, 1% carbon tetrafluoride and a gas mixture containing 1% air is injected into the helium stream. After eluting The retention times of the components were measured by means of a, on thermal conductivity appropriate detector and compiled in Table IV: T a b e 11 e IV Retention times of carbon tetrafluoride and sulfur hexafluoride on a column of 80% diamond and 20% diatomaceous earth substance retention times minutes Seconds Air 5 '59 ° CF4 9' 01 "5F6 31 '46" Example 17 In through a with a Mixture of 10% diamond powder of the type described in Example 13 and 90% diatomaceous earth (Chromosorb W) charged chromatography column flowing helium became a sample injected from 0.01 ml kerosene.

The carrier gas flow of 50 ml per minute was at a pressure of 2.1 held up to 2.5 atmospheres. The column temperature was 154-155 ° C. After eluting the retention times of the various components of the luminous petroleum resulted, as stated in 'Taboll'e V.

T a b e 11 e ar Retention times of the components of luminescent kerosene (0.01 ml) on a 1.2 m long filled with 105 diamond and 90% diatomaceous earth Column at a column temperature of 154-155 ° C retention time en component no. Minutes Seconds 1 34 "2 1 '05" 3 1' 31 "4 1 '50" 5 2' 37 "6 2 '50" 7 3' 31 "8 4 ' 10 "9 4 '45" 10 5' 18 "11 6 '09" 12 7' 33 "13 8 '20" 14 9' 42 "15 - 11 '10" 16 16' 17 20 35 "18 24" 55 "19 29 '15" 20 33' Example 18 A 0.01 ml sample of motor gasoline was injected into a holium stream, the one with 50% diamond powder and 50%.

Diatomaceous earth charged chromatography column flowed through.

The temperature was kept at 99 ° C. The retention times of the separate components are compiled in the following table VI.

T a b e ll e VI Retention times of petrol components on a 1.2 m long, filled with 50% diamond and 50% diatomaceous earth, heated to 99 ° C Column Component No. Retention Times Minutes Seconds 1 4 '40 "51 3 11' 2" 4 11 ' 5 27 '6 32' 7 43 'Example 19 0.01 ml samples of a range of polar and non-polar organic Compounds were separately injected into flowing helium fed through a with a mixture of 50% diamond powder of the type described in Example 13 and 50% Diatomaceous earth with a larger particle size of 0.149 to 0.177 mm charged to 101 to 156 ° C heated column was passed. The retention times of the individual compounds were determined by passing the gas flow through a detector which was sensitive to changes in the thermal Conductivity responds, averages and is summarized in Table VII.

T a b e ll e VII Retention times of polar and non-polar compounds on a column filled with 50% diamond and 50% diatomaceous earth at 150 to 156 ° C Compound retention times minutes seconds CS2 1 t 4011 CCl4 2 '30 "amyl alcohol 3 '34 "chloroform 3' 45" formaldehyde 5 '12 "isoamyl alcohol 7' 45" from Table VII It is clear that both polar and non-polar organic compounds are after the process according to the invention can be separated. Polar connections become more strongly adsorbed than non-polar compounds.

Example 20 Example 19 was repeated with the difference that the chromatography column with a mixture of 10% diamond powder and 90% diatomaceous earth charged and heated to 150 to 170 ° C, while samples of organic compounds, en sent across the pillar. The retention tents obtained are shown in Table VIIt.

T a b e 11 e VIII Retention times of organic compounds on a with 10% diamond and 90% diatomaceous earth filled column heated to 150-170 ° C retention times Substance mins seconds air 0 '37 "benzaldehyde 1' 5" n-butanol 2 33 "isoamyl alcohol 2 t9ft aniline 15 '7 "The values obtained show that both aromatic such as polar aliphatic compounds by the method of the present invention can be separated.

Example 21 Diamond powder of the type described in Example 13 was made Heated to 800 ° C. in hydrogen for 4 hours. That. obtained reduced diamond; powder was made with diatomaceous earth (Chromosorb W) with a Telichen size of 0.149 mixed up to 0.177 mm, the mixture 10% reduced diamond powder and 90f Diatom ends contained. With the Germisch became one 1., 2 m long Chromatography column filled with 6.4 mm outer diameter, through which as carrier gas Helium was passed at a rate of 30 cc / min. Into the helium stream a sample was made from methane, butane, butene, hexane and trifluorotrichloroethane injected existing gas mixture and with it over the heated to 350 ° C column from reduced diamond and diatomaceous earth and then by a detector, that responds to changes in thermal conductivity. The received Retention times for the individual components are listed in Table IX.

T a b e 11 e IX Retention times of various mixture components on a 1.2 m long filled with 10% reduced DSiammant and 90% diatomaceous earth Compound retention times, min methane 0.6 butane 2.3 butene 2.5 CFCl2CF2Cl 4.4 hexane Example 22 A 1.2 m long chromatography column 6.4 mm on the outside diameter was with a mixture of 50% reduced diamond, which as described in Example 21, and 50% diatomaceous earth having a particle size of 0.149 Filled to Oß177 mm and flushed with helium. The column temperature was between 25 and 350 ° C held.

A sample of a mixture of fluoroalkanes was placed in the helium stream injected and passed over the column and then through the detector. The received Retention times for the various components of the mixture are given in the table X compiled.

T a b e 11 e X Retention times of fluorocarbons one filled with 50% reduced diamond and 50% diatomaceous earth, 1.2 m long Column substance retention times, mxn air 2.3 CF4 2.6 CF2 = CF2 4.2 CH2 = CF2 6.7 CF2C12 1i, 7 CH2F2 16, o CHC1F2 20.0

Claims (13)

P a t e n t a n s p r ü c h e 1. Procedure for separating a gaseous mixture into components by passing the gaseous through together Mix with an inert gas such as helium for a long time, with an adsorbent filled column, wherein at least one of the components of the gaseous mixture separated from the remaining components at temperatures between 0 and 500XC is characterized in that a synthetic diamond content is used as the adsorbent. ige material made of polycrystalline aggregates of individual diamond particles is used being, the agate having a mean diameter not exceeding 0.154 and a Have a surface area between 40 and 400 m2 / g. 2. The method according to claim 1, characterized in that units from individual diamond particles with an average particle diameter between 50 and 300 Å can be sent. 3. The method according to claim 1 or 2, characterized in that diamond-containing Material is used whose surface is at least 10% mis hydroxy, carboxy and Carbonyl groups covered; is. 4. The method according to claim 1 to 3, characterized in that, that as a diamond-containing material, a homogeneous mixture with a content of up to 99 used on an inert material with a particle size between 0.074 and 0.590 mm will. 5. The method according to claim 1 or 2, characterized in that the diamond-containing material adhering to the surface of crystalline calcium fluoride a part size of between 210 and 590μ is used, the weight fraction of the diamond-containing material is between 19 and 20% of the total amount. 6. The method according to any one of the preceding claims, characterized in, that the components of a gaseous, fluorine or at least one reactive fluorine-containing compound-containing mixture are separated. 7. The method according to claim 6, characterized in that the components a gaseous mixture containing chlorine trifluoride are separated. 8. The method according to claim 6, characterized in that the components a gaseous mixture are separated, the one or more fluoroalkanes and contains one or more fluoroalkenes with 1 to 3 carbon atoms each. 9. The method according to claim 6, characterized in that the components a gaseous mixture are separated, which in. essential from a main set Sulfur hexafluoride and a small amount of impurities including tetrafluorocarbon consists. 10. The method according to claim 6, characterized in that the components a gaseous mixture are separated, which essentially consists of a main amount Tetrafluoroethyls and a small proportion of impurities including tetrafluorocarbon consists. 11. The method according to any one of the preceding claims, characterized in, that the mixture to be separated contains at least one component that is associated with the diamond-containing Material has a retention time that is different from that of each of the remaining components of the mixture differs by at least 30 seconds. 12. Material suitable for use in accordance with the method of claim 5 and from a mixture of firmly adhering particles from A) 80 to 99 Parts by weight calcium fluoride with a particle size between 210 and 590μ and J) 20 to 1 parts by weight of a synthetic diamond-containing material made of polycrystalline Aggregates of individual diamond particles consists, with the aggregates a middle one diameter of not more than 1500 R and a surface between 40 and 400 m2 / g. 13. Material according to claim 12, characterized in that the individual Particles that make up the aggregates have an average diameter of 50 to Own 300 R.