FI100859B - Method and apparatus for extracting extractable components directly from a stream - Google Patents

Description

100859

PROCEDURE AND DEVICE FOR PERFORMING ON-LINE FLOW EXTRACTION OF EXTRACTABLE COMPONENTS IN LIQUIDS MENETELMÄ JA LAITE UUTETTAVIEN COMPONENTTIEN UUTTAMISEKSI SUORAN VIRTAUKSESTA

This invention relates to a process for extracting extractable components, such as dissolved substances, colloidal and / or suspended particles, in liquids. In particular, the invention relates to an on-line flow extraction process comprising the following successive steps: feeding a first fluid stream containing the extractable components; feeding a second liquid which is substantially immiscible with the first liquid stream, in the first liquid stream, for extracting at least a portion of the extractable components from the first liquid into the second liquid, and - separating the second liquid, containing at least one; Part of the extractable components, from the combined flow of the first and second liquids.

This invention also relates to an apparatus for on-line flow extraction of extractable components, such as ···· dissolved substances, colloidal and / or suspended particles, in a liquid. Such apparatus comprises: - a first tube or channel through which · ·· * ... a first fluid containing extractable components, • * * * · * * and -: - a second tube, or a nozzle connected to it ·; the first tube, for feeding a second liquid, which is essentially immiscible with the first liquid, into the first tube.

• · 1 2 100859

A central need in the analytical core is to be able to work out and concentrate different material samples in order to be able to perform kinetic analysis. Secondary or interfering matrix components must then be able to be removed, whereas, on the other hand, the substances to be analyzed are often transferred to a medium compatible with a subsequent method of analysis. This step also usually leads to a concentration of the substances.

It is, for example, it is possible to transfer dissolved hydrophobic substances in water-based samples, such as in industrial or municipal wastewater, from the water to various organic solvents, e.g. hexane, by extracting the aqueous sample with a small amount of the solvent. Thereby, a concentrate of the hydrophobic substance is obtained in an almost anhydrous hexane phase. It is important that the liquids in a liquid-liquid extraction are not miscible, since the liquids after the extraction should be separable into two different phases.

A liquid-liquid extraction commonly used today comprises a manual / mechanical shaking or stirring of the sample with an extraction medium or solvent. However, it is also known to utilize flow extraction systems with continuous liquid-liquid extraction. These systems include a continuous and controllable solvent input into the sample stream to be analyzed.

In these flow injection analysis systems, Flow Injection Analysis (FIA), discrete segments of samples are formed and of • · * * ... 30 extraction medium. A gradual extraction rises in a # · · *. Extraction coil or in a tube, the time being ·,; f is required to achieve equilibrium depends on the extraction kinetics.

• «. In FIA systems, a tube with a T-piece is usually used to inject solvent into the sample stream. This system has * · e.g. used to analyze wastewater or to analyze drugs in aqueous solutions. Coaxially arranged tubes can be used in place of said tubes with T-piece.

However, a problem arises when extracting colloidal substances such as fat droplets in water or very fine particles suspended in water. Such colloidal or very finely dispersed substances may e.g. have a negative surface charge which stabilizes the colloidal condition. Often, the colloidal or suspended state is further stabilized by other mechanisms, such as by steric stabilization, whereby a protective polymer layer is formed on the finely dispersed droplets. This condition has been found to arise e.g. dk fat / resin 15 drops in the process water from paper mills are covered by a thin layer of hemicellulose.

in attempting to carry out a continuous transfer of said colloidal fat / resin drops into an organic solvent, it has been found that the aforementioned flow injection assay, FIA, provides an extremely poor; extraction yield. This is believed to be due to a minimal contact between organic solvent and colloidal particles at the phase interfaces between the segments of the organic solvent and the segments of the sample. Repulsive electrostatic forces formed at the phase interfaces prevent the colloidal substances from coming into sufficient contact with the organic solvent phase. Almost no extraction occurs even if there is a relatively good contact between the two main phases, the organic phase and the water phase. The situation is another for different in water solved; * · *. substances. A clean two-phase system soon leads to an extraction equilibrium. However, the fat / resin drops dissolve * * poorly in water.

* • 35

It is known that the above problems can be solved by vigorously stirring the liquids, e.g. by shaking them manually. The extraction medium, the solvent, is then atomized and a forced contact between the colloidal particles and the extraction medium is obtained.

5

The applicability of the manual shaking method has been demonstrated in laboratory experiments in extracting colloidal substances from the process water of the paper industry. A vigorous shaking of these water samples together with methyl tertiary butyl ether over a period of 2 minutes gave a satisfactory extraction of the colloidal substances. However, manual liquid-liquid extraction processes are often time consuming and require large amounts of solvents. It is also difficult to apply the mechanical shaking method to continuous or on-line analysis systems, especially when working with small samples.

Miniaturization of the systems and the dimensions of the samples have become increasingly important aspects in analytical applications, e.g. in order to minimize the consumption of chemicals and the costs and pk due to environmental considerations. Especially in such situations where only minimal sample quantities are offered, as in many analyzes in medicine, it is important to be able to minimize the analysis systems.

25

The purpose of this invention is to provide an improved method and device for on-line solder extraction especially of colloidal and / or suspending agents: substances in liquids. This invention, therefore, has as its object to provide a method which provides an efficient; . and fast on-line flow extraction of as well as solved as ···. colloidal particles, suspended particles or extractable components absorbed on particulate matter.

In addition, this invention aims to provide an improved on-line flow extraction method and a device which can be used in chemical analysis as well as in the production of substances from extractable matrices.

This invention has yet further objects to provide an on-line flow extraction system requiring only minimal quantities of samples and extraction solvents.

The above-mentioned objects of the invention are achieved by methods and devices characterized by the following claims.

It has now been unexpectedly discovered that an on-line flow extraction of both colloidal and suspended material in liquid can be effectively accomplished by injecting the solvent or extraction agent as a high velocity jet stream into the sample stream into an extraction tube. To achieve this high-speed jet stream, a small inlet passage or nozzle is required between the extraction tube and the solvent inlet combined with high pressure at the solvent inlet, usually around 25-400 bar.

It is important that the jet stream formed has sufficient kinetic energy for the solvent to be immediately atomized into fine droplets which may affect the particulate or suspended particles in the sample stream.

• The solvent is preferably atomized into fine droplets. , with a diameter of about 0.1 - ίο μη. The kinetic energy of the resulting jet stream should preferably be so large that the jet stream can pass through the sample stream and hit the opposing inner wall in the extraction tube. Advantageously, the kinetic energy of the jet stream, when it hits, the opposing wall's wall, should still be so large that the current; at least partially reflected back from this wall into the sample stream.

6 100859

The term "extraction tube" is used herein for widely separated tubes or channels in which an extraction medium such as an organic solvent is involved in a sample stream. The extraction tube may be a tube or extraction channel formed between two plates or any other suitable structure.

The term "narrow inlet passage" is used herein for a variety of nozzles or small apertures, such as for capillary nozzles, small orifice tubes or derived with a small orifice insert, simple small orifices, which in their form are circular or non-circular , and which can be used to inject solvent into the extraction tube.

The term "colloidal or suspended particles" as used herein refers to both liquid and solid particles in a more or less stable colloidal or suspended form.

In an extraction process of this invention, the flow of sample liquid containing soluble, colloidal and / or suspended material is pumped or sucked through an extraction tube or test tube. A second liquid, the extraction medium of the solvent, is fed into the extraction tube via a solvent inlet tube. The second fluid is fed through one or a plurality of narrow inlet passages under high pressure, giving the liquid a high velocity.

The solvent inlet tube may be directly or indirectly connected to the extraction tube. The outlet end of a solvent inlet tube itself may be sufficiently narrow to form the narrow inlet passage or the: , which is needed to feed the solvent, where the inlet tube is directly connected to an opening in the side wall of the extraction tube. Alternatively, to obtain a narrow inlet passage, a capillary tube with a small opening can be inserted in the 5.5 outlet end. In yet another alternative application, in which an ordinary size inlet pipe is directly connected to the extraction tube, the inlet passage between the tubes is formed by a very small opening or a very small h & l made in the side wall of the extraction tube.

Even in such applications, where the solvent inlet tube is connected indirectly to the extraction tube, a small heel or some other suitable narrow opening can be made in the side wall of the extraction tube, which heel or opening forms the narrow inlet passage needed to inject solvent.

In the extraction process, relatively narrow extraction tubes are advantageously used. The extraction tube, i.e. test tube, may have an inner diameter of about 0.1-2 mm. The narrow inlet passage used to feed solvents into the extraction tube can be constructed, as previously mentioned, in many different ways, but should be advantageous if it has a circular inner diameter of approx. 5 - 20 mm. In addition, it is advantageous if the narrow inlet passage is made as short as possible to avoid a need for excessive pressure to inject solvents into the inlet. Only very short capillary nozzles or short inserts with small aperture should not be used to unnecessarily increase the pressure drop. Narrow inlet passages made directly in the side wall of the extraction tube may be funnel-shaped and tapered towards the extraction tube.

•: By injecting the extractant at high speed into the sample stream, the extractant is atomized into small micro-droplets, which are effectively involved in the sample stream, thus leading to an efficient extraction process. The formed microdrops • have a high kinetic energy, 1/2 mv2, comparable e.g.

«·> * ·; With the effect of a jet of water in a high-pressure washer, used 35.: to clean hardened surfaces. The high kinetic energy leads to forced collisions and an efficient contact between the solvent microdroplets and the colloidal or other particles in the sample flow.

The pressure needed to achieve the purpose of this invention may vary within a wide range depending on the specific sample flow, specific extraction agent, and depending on the apparatus used. However, for one skilled in the art, it is not difficult to determine what pressure is needed to atomize the extractant in an appropriate manner.

The high pressure injection of extractant results in an efficient and almost instantaneous extraction of colloidal and suspended substances. A balance between dissolved substances in the sample flow and the extractant is also achieved simultaneously. Eventually, a coalescence of the microdroplets builds up into larger droplets and segments of extractant will arise in the extraction tube downstream from the injection point. The extractant may be separated as a continuous stream from the sample stream in a phase separator. Various types of phase separators described in the literature can be used to separate the two phases. E.g. a pressure optimized porous PTFE membrane separator in which only organic solvent was allowed to pass through the pores of the membranes unlike the aqueous phase, which does not wet the membrane. In a settler basin "settler", different phases are easily separated on the base by their different density.

k. . In an extraction device, two or more narrow inlet passages can be arranged in series or in parallel. In a * · * <30 device with several narrow inlet passages in series happens! : * repeated extraction processes, which will increase the f *** in the effect of the extraction process and further increase, the extraction yield.Of course, one can inject different types of extractants, solvents, through the various passages. , if different components are to be extracted in consecutive steps. It is advantageous to inject solvents through a plurality of parallel inlet passages where larger sample flows are to be analyzed as this increases the capacity of the extraction process.

The narrow inlet passage (s), e.g. The capillary nozzle (s) are advantageously arranged so as to direct the inlet flow of extractant, e.g. organic solvent, perpendicular to the sample flow. Injectors are injected perpendicularly, the atomization to microdroplets 10 is further enhanced due to the strong impact of the microdroplets jet on the opposing side wall of the extraction tube.

The new method and apparatus may be used to extract components which are permanently or only momentarily in a liquid in a lost, colloidal or suspended form. A suspension of water and a solid or liquid medium containing the component to be extracted can, e.g. In some applications, the solid particles in the water are first prepared just before the extractant is injected into the water. A suspension prepared in this way may remain stable only for so long as extraction is allowed to take place.

The new method and device may e.g. can be used, not only for the analysis of components, but also for the extraction of components from colloidal or suspended particles, with the intention of producing a product which t: * ·· contains these components.

* <· * 301: The new process and device may further be applied to the separation of solid components from the surface of * 1 · solid particles suspended in a liquid. The 'medium jet, which has a very high velocity, i.e. high' 3.5 'kinetic energy, can be used to "scale" away certain layers of solids from solids suspended in, for example, water.

The invention will now be described in more detail with reference to the accompanying drawings, in which: FIG. 1 shows a schematic cross-section of a tube with a T-coupling used for injecting extractant into a sample flow to be analyzed according to a conventional flow extraction system; FIG. 2 shows a schematic cross-section of a tube with a T-coupling for the injection of extractant according to this invention; FIG. 3 shows a schematic cross-section of another device according to this invention; FIG. 4 shows a cross section of the device of FIG. 3 along the line AA ', FIG. 5 shows a schematic cross-section of yet another device according to this invention; FIG. 6 shows an enlargement of the encircled area of FIG. 5, FIG. 7 is a schematic cross-sectional view of yet another device according to this invention; FIG. 8 shows a cross section of device of FIG. 7 along the line BB 'and' li! FIG. 9 shows the device of FIG. 7 seen from above.

FIG. 1 shows a schematic cross-section of a tube 10 with T-t '' coupling for injecting extractant into a sample flow, * · 3.0 'to be analyzed, in a conventional flow extract. .tion system (FIA). The tube with the T-connection consists of a /:.

} "", main pipe 12 and a side pipe 14. A sample flow 16 to be analyzed is pumped or sucked through the main pipe 12 in the direction of the arrow. The extraction means 18 is measured into the main pipe through a side pipe 14 connected to an opening 20 in the main pipe. s 12 sidewall 22.

11 100859

The extractant, which is not miscible with the sample to be analyzed or extracted, flows through the side tube 14 into the main tube 12 and forms large segments 24. The extraction agent, e.g. a hydrocarbon, and the sample, e.g. an aqueous solution, forms on. successive segments flowing downstream of a phase separator, not shown. Substances that are soluble in the solvent in the sample are extracted at an acceptable rate to the extractant.

10 In FIG. 2 shows a tube 10 with T-coupling, for use in an extraction device according to this invention. The device comprises a main tube 12, e.g. an extraction tube, with a continuous sample stream, and a side tube or capillary tube 14, i.e. the solvent inlet pipe, which pipe is directly and perpendicularly connected to the side wall 22. of the main pipe 12 The side wall has a very small inlet opening 26, ie. a narrow inlet passage joining the side tube 14 with the main tube 12.

20

A high pressure pump, not shown, is coupled to the side tube 14 to force the extractant at high speed through the small inlet opening 26, a jet of high speed extractant being attached to the main pipe 12. The direction of the jet 25 is perpendicular to the flow direction in the main pipe.

• ♦ ·

The extractant beam is immediately atomized into a large number of microdroplets 28 and thereby blended very well. . sample flow. An efficient and almost instantaneous extraction 'occurs. The microdroplets 28 coalesce downstream of the injection point 30 into larger droplets 28 'and even further downstream. to larger segment 28 ''. The large segments 28 '' are separated from the sample flow in a phase separator, not shown.

• * «

The main tube 12 and the side tube 14 can be made of metal, glass,

Silicon or some other suitable material. In FIG. 2 is a side tube connected perpendicular to the side wall of the main tube. IN

In other applications of this invention, it may be convenient to insert multiple side tubes in series or to use other types of side tube fittings, such as Y-fittings or W fittings known per se.

5 FIG. 3 and FIG. 4 shows another variant of the tube with T-connection. In this construction, a section 32 of the main pipe 12, which has a narrow inlet opening 34, coaxially surrounded by another pipe 36, is of a somewhat larger diameter. The outer tube is gas tightly welded to the main tube 12, so that an annular space 38 is formed between the tubes 12 and 36.

The annular gap 38 is pressurized with extractant via a side tube 14 which is coupled to a gas space through an opening 40 in the side wall 42 of the outer tube 38. The opening 40 between the tube 14 and the annular gap 38 may be of ordinary size. The inlet opening 34, made in the side wall of the main pipe and which joins the annular gap 38 with the inside of the main pipe 12, is a heel 20 with a very small diameter, a diameter of about 5-10 mm.

A high pressure pump, not shown, is coupled to the side tube and is used to force an extractant flow through the narrow inlet opening 34 into the main tube 12 at a flow rate of e.g. 0.5 - 1 ml / min. The sample is pumped through the main tube 12 at a flow rate of e.g. 2 ml / min.

The construction of FIG. 3 and 4 utilize as a test or .30 main tube 12 a thin-walled adjusting tube having a material, ···. thickness of 0.1 mm. The heel or inlet opening 34, having a small diameter, can be drilled into the thin-walled adjusting tube 12 t · 1 · with laser, the heel forming a nozzle of very small length.

FIG. 5 and 6 show another extraction device according to the invention. A thin-walled capillary tube 14 of glass or quartz glass, which tube has an inner diameter of about 150 - 250 μτα, is connected to the main tube 12 of glass, which tube has an inner diameter of about 1 mm. Capillary tube 14 has been glued to glass tube 12 with silicone glue or with some other solvent resistant glue.

A card, e.g. 500 μη, inner capillary portion 46 of glass or quartz glass, has been inserted into the end 48 hp capillary tube 14 before it is connected to the main tube to roin the cross-sectional area pk inlet opening between the glass tube and capillary tube 14 of quartz. The outer diameter of the inserted capillary portion 46 corresponds to the inner diameter of the outer capillary tube 14.

The inner capillary portion is glued, with a polyimidine adhesive 50 or other solvent-resistant adhesive, at the end 48 of the outer capillary tube 14. The inner diameter 44 of the separately inserted inner portion 46 forming a narrow inlet passage between the solvent inlet tube 14 and the extraction tube. 12 may be very small e.g. about 5-10 μτα.

20

The combined capillary structure 14 and 46 are glued with silicone adhesive 52 on a previously drilled aperture 44 in the glass tube 12. The end 48 of the combined capillary tube is coupled to inject solvent perpendicular to the flow direction in the glass tube 12.

• · ·. In use, the quartz glass tube 14 is pressurized with extraction agents, e.g. by means of a high performance liquid chromatograph pump (HPLC), at a pressure of advantageously 50 ° C - 400 bar. At the same time, the sample flow through the glass tube 12 is guided by a low pressure pump, such as a peristaltic pump, at 0.5-1 bar.

In FIG. Figures 7, 8 and 9 show a further construction of an extraction device according to the invention. This construction leads to a very small / minimal flow extraction device which can be applied e.g. in clinical biochemistry or to determine drugs in pharmaceutical preparations.

The extraction tube, i.e. the main channel 54, is formed between two plates 56 and 58 of silicon. The channel can be made extremely small suitable for very small sample flows. The main channel 54, which in this embodiment has a non-circular cross-section, is formed between the plates 56 and 58 by etching a channel on the surface of one plate 58. In addition, a small narrow inlet opening 60 is formed in channel 54 by etching an opening, e.g. a square heel or slot, in plate 56. It is possible to make extremely narrow channels and openings, with high accuracy, by etching in monocrystalline silicon. The silicon plates 56 and 58 may be joined together by bonding, anodic compound, heating, or by any other suitable method known per se.

A covering plate is provided over the inlet opening 60 on the outer side of plate 56. A gas-tight space 64 is thus formed between the covering plate 62 and the plate 56. A capillary tube 14, not shown, is connected to an opening 66 in the covering plate for input of extractant into the space 64.

In use, the gas-tight space 64 is pressurized with 4 · · * extractants, which are fed with a high-pressure pump through aperture 66. Extraction means is forced under high pressure from the space 64 through the aperture 60 into the sample flow in channel 54.

• · • · 15 100859

The most important advantage of using a silicon structure is high accuracy, as well as an extremely narrow inlet passage for extractants. A lower feed pressure is required to force a high speed jet extractant through the narrow inlet passage than in other cases due to the lower pressure drop in the extremely short inlet passage. A further advantage is the possibility of producing identical identical extraction units on a large scale, similar to the manufacture of electronic components, which results in very low manufacturing costs per piece.

The following is an experimental evaluation of this invention. Samples of thermomechanical (TMP) pulp suspension diluted with water to a concentration of 1%, freed from coarse fibers or other particles and prepared with pH 3.0 - 3.5. The TMP suspension contained both dissolved and colloidal substances (DCS).

A manual extraction of a DCS sample was performed to obtain a reference value. A 4.00 ml DCS sample was measured in a test tube and then 2.00 ml methyl tert-butyl ether (MTBE) was added. The sample was shaken vigorously by hand for 2 minutes and then centrifuged at 1500 rpm for 25 minutes. The clear MTBE layer was then pipetted carefully. This extraction was performed two times with two. ml portions of pure MTBE. The MTBE solution portions were pooled and evaporated in a stream of nitrogen. The dried residue was then analyzed in a gas chromatograph (GC).

: 3 * 0

Mi · t '“' Two on-line flow extractions were also performed on the sample. First. ' . a conventional (FIA) extraction was done on the sample in one

• · I

*; / apparatus shown in FIG. l. The FIA extraction apparatus consisted of a glass capillary tube 14, with an inner diameter of pk 150µπι, which was glued to the pk side wall 22 of a glass tube 12, with a diameter of 1 mm.

Second, a high pressure flow extraction (HPFE) was made on the sample according to the invention in an apparatus shown in FIG. 5. The HPFE apparatus had the same construction as the FIA apparatus, except that a capillary insert 46, consisting of a short piece of glass or quartz glass with a small aperture, diameter of 10 mm, was glued with polyimide resin on the inner side of one end of the capillary tube 14. which originally had a diameter of about 150 mm. The capillary insert was approximately 500 mm long.

In the peripherals, both Examples 2 and 3 included an HPLC pump, which fed 1.05 ml / min of pure MTBE into capillary tube 14 (150 m®). At the FIA extraction, the pressure drop in the capillary tube was approx. 2 bar. At HPFE, the pressure drop was approx. 285 bar.

The DCS sample was pumped at a rate of 0.70 ml / min into the glass tube 12 (1 mm) with a peristaltic pump. A 1 meter long Teflon tube with an inner diameter of 0.70 was connected to the outlet of the glass tube, in which the phases could form 20 larger segments. The apparatus was run several minutes before taking the first test. Ca. 10 ml of clear aqueous phase was pipetted and centrifuged so that the entire organic phase was safely separated. The aqueous phase was then manually extracted to determine residual DCS.

25 »· ·

At each extraction, 80 βΐ BSTFA (bis-trimethylsilyl-trifluoroacetamide) and 40 μΐ TMCS (trimethylchlorosilane) were added.

To the dried rest of the MTBE solutions. The solution * was inserted into a furnace at 70 ° C for 20 minutes and was then ready for analysis in gas chromatograph. The GC analysis was done as follows. that it directly gave the concentration in mg / 1 for the different «·.

. *. extractable components and component groups in the sample.

Each extraction, manual, FIA and HPFE was repeated three times and an average was taken to ensure reproducibility. The results given in Table 1 show the relative extraction yields for each major component group analyzed.

Table 1. Yield (%) of various component groups in extraction of TMP in water.

Manuelite FIA HPFE

fatty and resin acids 84% 65% 68% lignans 61% 81% 86% 10 sterols 79% 40% 88% steryl esters 77% 28% 72% triglycerides 84% <4% 82%

The results show that the lignans dissolved in the aqueous phase as well as the fatty and resin acids, which are partially dissolved in water, are very well extracted with a conventional flow injection system (FIA). The triglycerides, which are not soluble in water and therefore present in colloidal form, are practically not extracted at all in a conventional FIA system. * However, the triglycerides are very well extracted with the new HPFE system of the invention.

The test results thus confirm that a dramatic improvement can be achieved with the new high-pressure extraction system.

Although the invention has been described herein with reference to. . such applications, which in this are now considered to be the most practical and advantageous, it should be understood that one does not intend to limit the invention to these described conditions. The object of the present invention is, on the contrary, to cover the invention with different modes of application and equivalent solutions, which are encompassed. of the appended claims.

* ·· Thus, one should e.g. understand that the invention can be applied to a very large number of extractable components and solutions, although in the aforementioned examples, mainly the extraction of hydrophobic substances with organic solvents has been discussed. It is, for example, It is possible to apply the invention pk extraction of inorganic substances, such as metal chelates, from aqueous solutions. It is also possible to use this invention to extract water from solvent-based solutions.

«. .

• «· * ·« t · • 1 · • e • · 4 • · «« • · «• · · · · *»

Claims (19)

A method for directly extracting extractable components in liquids, such as solutes, colloidal and / or suspended particles, from a stream, the method comprising the sequential steps of: (a) feeding a first liquid stream (16) containing extractable components; (b) feeding a second liquid (18) that is substantially immiscible to the first liquid stream to the first liquid stream to extract at least a portion of the extractables from the first liquid to the second liquid, and (c) separating the second liquid containing at least a portion of the extractables. from a combined flow of the first and second liquids, characterized in that the second liquid is injected into the first liquid flow as a high velocity jet, immediately dividing the second liquid into very fine droplets (28) and dividing said droplets into the first liquid. Method according to Claim 1, characterized in that. v that the second liquid is divided into fine droplets with a ..li '25 diameter of about 0.1 - 10 Mm. »» »···· A method according to claim 1, characterized in that the second liquid is pressurized to a pressure of about 25 to 400 bar to inject this liquid as a high-velocity jet into the first liquid. • ♦ ♦ • ·: A method according to claim 1, characterized in that. that the second liquid is injected into the first liquid: through a narrow passage (26, 34, 44, 60) through which. 35 diameter or width <20 mm 24 100859 A method according to claim 1, characterized in that - the first liquid is fed in a continuous flow through a first main branch (12) of a tube made of glass, quartz or metal with a T-joint, said first branch having a diameter of <2 mm , and - the second liquid is injected at a high pressure, preferably 25 to 400 bar, at a pressure perpendicular to the first liquid through a second capillary branch (14) 10 of the tube with a T-joint, the diameter of the narrow passage (26, 44) connecting the capillary branch to the main branch being <20 μιη. A method according to claim 1, characterized in that the first liquid is pumped or sucked in a continuous flow through the first tube (12) and the second liquid is injected into the first liquid through one or more small openings (34) in the septum of the first tube. A method for on-line analysis of materials according to claim 1, characterized in that the first liquid is a colloidal aqueous suspension, such as process or wastewater from a paper or pulp mill, a drug, milk or blood containing hydrophobic .... components to be analyzed and that the second liquid is an organic solvent such as hexane or MTBE. * · · • · · • »· 8. An apparatus for extracting extractable components in liquids, such as solutes, colloidal or suspended particles, directly from a stream, the apparatus comprising: • · • «·: - an extraction tube (12, 54) through which flow a first liquid (16) comprising extractable components which are: to be analyzed or to be treated in another way, - a second liquid (18) of the supply pipe (14) which is substantially immiscible with the first liquid , for extracting the extractant or solvent, into the first tube, characterized in that the device comprises a narrow passage (26, 34, 44, 60) which connects the second tube (14) directly or indirectly to the first tube (12, 54), whereby the passage (26) , 34, 44, 60. diameter or width is <20 Mm. Device according to Claim 8, characterized in that. 10 that the supply pipe (14) is connected to a high-pressure pump which supplies a pressure of> 25 bar, preferably 25 to 400 bar, for injecting the extractant as a high-speed spray jet into the extraction pipe (12, 54). Device according to Claim 8, characterized in that the inner diameter of the extraction tube made of metal, glass or quartz glass is between 0.1 and 2 mm and in that the diameter of the supply tube (14) made of metal, glass or quartz glass is <300 mm. Device according to Claim 8, characterized in that - one or more supply pipes (14) are connected directly to the extraction pipe (12) and in that at least one of the supply pipes forms a T-connection with the extraction pipe. • · · • · t Device according to Claim 11, characterized in that:. that two or more supply pipes are connected in series • · ·. ···. 30 extraction tubes. Device according to Claim 8, characterized in that. : that the supply pipe (14) is indirectly connected to the extraction pipe: (12) via a gas - tight chamber (38) between the pipes. 26 100859 Device according to claim 8, characterized in that the narrow passage (26, 34, 60) connecting the supply pipe (14) directly or indirectly to the extraction pipe (12) is a narrow opening formed in the wall of the extraction pipe, such as a circular hole or slot. Device according to Claim 8, characterized in that. that a pipe piece (46) 10 is arranged inside the outlet end (48) of the feed pipe (14) connected directly to the extraction pipe (12) to form a narrow inlet channel (44). Device according to Claim 8, characterized in that. that - the outer tube (36) is arranged concentrically around the extraction tube 15 (12) to form a gas-tight space (38) around the extraction tube, - the supply tube (14) is connected to an opening (40) in the side wall (42) of the outer tube to supply extractant (18) to the gas-tight space (38), and that a narrow opening (34) forming the inlet channel 20 is formed in the side wall of the extraction tube (12) for injecting extractant from the gas space into the extraction tube. Device according to Claim 8, characterized in that. 25 that • ·· · ———— ··· - a first channel (54) forming an extraction tube * · ** is formed between the two plates (56, 58), and that - a narrow opening is formed in at least one of the plates (56); ·. (60) for injecting the extractant under high pressure into the channel * · 1 * ... 3 0. Device according to Claim 17, characterized in that. that the plates (56, 58) are made of silicon and that the first-X; channel (54) is formed by etching the recess at least! ! 35 to one of the plates (58). 27 100859 Device according to Claim 8, characterized in that one or more supply pipes (14) are connected to the extraction pipe (12) in order to increase the process capacity in order to achieve parallel operation. • ·· · ♦ · «« • * · »• · · • 0 0 · ·« • «• · • t« • · · · · · · · I · ·