NO782316L - GALVANIC FLOW SYSTEM FOR TOTAL PARTICLE RECOVERY AND LIQUID CLEANING - Google Patents

Description

Galvanic .current nin<g>ss<y>s.tem for. overall, particle recycling'and. liquid cleaning.v"— The requirement for water purification is not only based on the need to treat sewage water and harmful industrial waste, nor does it necessarily have to aim only at obtaining drinking water for humans and animals. Recent environmental control regulations have limited the discharge of water, such as e.g. in general industrial use has had a significantly increased content of dissolved solids (which are usually inorganic or mineral compounds), and has prohibited the discharge of such liquids, which have collected or concentrated particularly toxic components.

E.g. the mass of water, which circulates as a cooling medium in many industrial or chemical plants, is sent back to a heat exchanger, where part of the water is evaporated to lower the temperature of the rest, after which this rest is recycled. This evaporation step in itself causes an increase in the concentration of contained solids only by reducing the liquid volume. However, on its way, the liquid collects deposits or sediments from the pipeline system, and in addition, to reduce corrosion, foaming and scaling (as it is formed by hard water), various inhibitors are added to the circulating stream. Naturally, these inhibitors further contribute to the dissolved solid content, and after the latter has reached the maximum, which is allowed for continued circulation, it becomes necessary to discard part of the liquid mixture and replace it with fresh water (and new additives).

However, this heavily contaminated waste water has now become an illegal pollution factor, if it is discharged into rivers or seas. The problem is therefore to clean it before discharge: and if such a cleaning process is sufficiently successful and completely carried out, the water can be used again and again ad infinitum and does not need to be discharged at all.

A particular polluting component in such a cooling water system is chromium, which is a component of many anticorrosive or biocidal additives.

Hexavalent chromium is thus a toxic substance, which must not be released into the environment. Other toxic components in common cooling water additives are cyanides and phosphates, which must be detoxified before they are released.

„. The purification of contaminated water with a view to re-use, regardless of whether one starts from agricultural or urban waste water or from industrial waste water, has mainly aimed at the extraction of drinking water after the initial separation and removal of solid components in an inert state, which is considered a necessary and preliminary step to any subsequent treatment. The solids may then have been used to a small extent as a planting base or soil filling, but such a product is not the primary purpose of carrying out the separation, and as a rule the undifferentiated sludge is simply separated as a combined mass and obtained by road on

the most convenient way. The purification of the aqueous phase then takes place possibly as a subsequent rather than a parallel process. However, it will be understood that the aqueous effluent from many and probably most water treatment processes (even if it is only a rinse), carries a certain amount of solid and potentially solid constituents with a certain economic value, if these substances could only be recovered in concentrated form without great expense.

Furthermore, the treatment of such masses of polluted water has so far mainly been carried out in batches, with large quantities of water being treated with acids or other reagents in a precipitation basin or even successive chambers, after which the water is allowed to stand for a longer time, until random samples show that the supernatant was done. In short, it has not been made clear that by careful regulation of the parameters of a flowing current, which contains charged particles, separation/purification of an impure aqueous medium could be carried out in a fraction of the time previously required, and that the control could changed to maximize the removal of specific pollutants, which it was desirable to concentrate in a solid state. Some substances may be desirable to destroy, e.g. microorganisms, herbicides, pesticides and inorganic toxins, or to recover e.g. nitrogen compounds, precious metals, etc. Consequently, the control parameters for such a flow treatment can now be adapted to a waste water with a specific composition and with a view to how one wants to get rid of specific pollutants.

It has long been known to purify waste water by oxide ring in the simultaneous presence of iron plus sulfur dioxide or

oxidizing acid. The contamination is then removed by flocculation of the iron in alkaline media. To the extent that this process has been used, solids have necessarily first been removed by filtration, and as regards the remaining

filtrate, so until now treatment has not removed dissolved impurities (e.g. inorganic salts of the NaCl type) or substances that cannot be oxidized (e.g. metal particles). Each of these classes may include such undesirable toxins as arsenic, mercury, cadmium, lead, selenium, boron, etc.

It has now been shown that this double oxidation/ . precipitation step can be built into a complex treatment process, whereby all non-aerobic impurities such as solids can be removed from essentially any liquid, polar liquid medium, which contains finely divided waste as well as soluble salts and non-oxidizable impurities, so that the a sterile, clean, oxygen-containing liquid is formed (e.g. drinking water, which is also able to serve as a medium of existence for fish and other underwater fauna and flora). The precipitated material is also sterile and can possibly be further fractionated for the recovery of substances with economic value, e.g. precious metals, fertilizer-enriched sludge, etc.

In its main features, a self-generated galvanic cell is arranged in a primary reaction vessel or apparatus consisting of several units, all of which are electrically isolated (in the absence of any externally applied electric current), which is formed by "dissolvable" or free electrons, which are formed by acid oxidation of the contents, heavy metal suitable for alkaline flocculation, e.g. iron and/or aluminium, as well as of free electrons produced^ by splitting water (or other nn1fl.r<p>mpd-i al vpiI introduction of g-vnvgl di nyvrl . T.i'IcpTp<Tp<: file - if a minimal suspension of extremely small particles (as defined in the following) is deliberately provided, either by addition or by fractionation of initially occurring solid masses, Such dispersed particles (which preferably make up all of the occurring solid material, apart from the electron-producing metal) has in itself a random motion in the liquid medium (which motion is the -Van der Waal effect originating from an internally generated spin of asymmetric molecules). In connection with the moving electrons, this causes a distribution of charge to other particles and adhesion between charged microparticles and small gas bubbles, which eventually leads to a complete oxidation of all oxidizable material present. This necessary transverse distribution of The random mixing of electrons with both charged and uncharged particles in the insulating cell can be enhanced by allowing gaseous oxygen (air) and/or sulfur dioxide to bubble through the liquid and/or stirring the liquid mass, e.g. using a pump or a stirrer. It is necessary to electrically isolate each reaction vessel to prevent such charge (which is maintained by pH regulation) from grounding through a conductive reaction vessel or liquid line.

Under the stepwise oxidation conditions and the imposed galvanic flow pattern, metal ions agglutinate with particulate matter and are replaced in the aqueous medium by other cations, e.g. hydrogen ions, and at the same time maintains the selected acidity concentration. Among other reactions, such hydrogen ions are combined with existing nitrogen to form NH^. Such ammonium ions then combine with iron ions to form (green) iron ammonium ions.

The successive chemical reactions can be carried out by batch treatment, when there is only sufficient stirring to prevent the constituents from settling before the final and desired flocculation. However, it is generally undesirable to carry out the process as a continuous flow, especially when there is a constant supply of raw material, for example: from a city sewage collection flow or a similar waste water flow from agriculture or industry. Consequently, both the liquid medium and an associated gas stream are moved to and through successive treatment zones or chambers. The amount of reaction gas, which should contain oxygen, is directed so that it is in contact with or flows through the liquid medium, depending on the conditions.

By adapting the size and shape of the reaction containers and the connecting lines are formed there. consequently, a number of dimensionless parameters for both the liquid and gas flows, which result in the treated material being moved in an essentially continuous but stepwise reaction pattern, which prevents phase separation and at the same time enables or favors the electron distribution, until complete oxidation has occurred. The final chemical treatment step is then carried out by alkylation of the medium avoiding a potential phase separation during an initial digestion period followed by electrical grounding of the medium simultaneously with precipitation (flocculation of both the metal ions and the coagulating impurities). Moreover, this grounding of the medium, which can be accomplished by grounding the insulated reaction vessel containing the medium, causes a significantly more tightly packed precipitate than would otherwise be achieved.

If the composite impurity consists of both (a) cellulosic material (e.g., food scraps, waste paper or cardboard, etc.) and (b) suspended minerals or metals and/or soluble salts (e.g., brackish water), the final alkaline flocculation tends to separate "a" and "b" in successive layers with the "b" material deposited first or below the "a" material. The process can thus be used for the concentration of small amounts of precious metals from sludge or the like. If the "a" material is not already mixed with such, the minimal charged particulate matter is added as described.

The separation of all potentially solid components from such a flowing galvanic cell by earth connection and

cessation of movement or stirring in connection with the removal of such impurities from the flocculate, which could previously be expected from the chemical reaction alone, now also draws soluble salts, such as e.g. sodium chloride, out of the solution and bottom traps suspended non-oxidizable particles. For

the participating substances it is only necessary that. the liquid is a polar liquid and that the solid: or potentially solid substance is suitable for the Van der Waal effect. Plus. water comes other polar liquids alcohols, acids, bases and other substances that ionize or conduct, an electric current. The dispersed particulate matter should amount to a minimum of 0.1. weight°a and have a specific particle weight of approx. 1.05 to approx. 2.0 and a size of approx. 30 to approx. 225 micron with a free surface energy of approx. 100 to approx. 500 erg/cm2.

In this connection: it will be understood that the smaller the particles are, the greater the relative surface area and the surface attractive forces (in relation to the weight), so that the relative influence of gravity on the particle is reduced accordingly. In this way, the specific surface energy of a given solid can be increased over 8,000 times, when starting from a diameter of approx. 5 cm to a diameter of 1 micron. At the same time, it is increased. unit surface energy more than 600%. Consequently, the greater the fractionation (maceration) of the solid material into small particles, the greater is the impact of the increased surface energy on the reaction and flow properties. This factor, of course, is the same, whether the material constitutes material, which, in addition to its carrying function, must also be oxidized, or particulate matter, which is only added with a view to its carrying function for a charge in the ongoing galvanic current.

It will be understood, however, that such fractionated particles, which exhibit Brownian motion and increased unit transfer energy, have a strong tendency to agglomerate if they are brought together, i.e. they become a non-free flowing mass instead of to act as independent separate particles. Such a possible coagulation is prevented (1) by pumping action, mechanical agitation and passage of gas currents through the liquid at certain critical locations and (2) by movement of the galvanic liquid flow at a varied and predetermined speed in accordance with Reynolds number and other dimensionless parameters, which is chosen; to prevent phase separation. Thus, when such suspended, galvanically charged particles are finally precipitated in cooperation with a flocculating ion, the cancellation or grounding of the galvanic charge enhances to a very high degree this final desired phase separation. A particularly remarkable and completely unexpected result of this liquid galvanic cell and of the Van der Waal surface effect exhibited by the particle dispersion is that soluble salts, particularly NaCl or other alkali halides, in the liquid of the present process "also leave their state of solution and enters the separated, flock. Such desalination can be partly explained by the continuation of the suspended; flocculate in an oxygen-saturated medium, until reduced; flocculated iron ion itself is completely oxidized to iron ion. •por to recapitulate the present procedure: floating contaminants in a liquid can either be soluble or, solid or both (whereas the solid components are kept suspended by the running current). They may possibly be in a state of lower valence or be capable of detoxification in the presence of oxygen, but in any case the current is subjected to a strong oxidation treatment (initially in a strongly acidic environment, which then changes to a strongly alkaline environment) in an ion exchange medium which is in motion, which peculiarity is achieved by a combination of the Van der Waals surface effect of particulate matter and of a galvanic charge which is applied to such particles. One of the results of this is that gas bubbles (of air and sulfur dioxide) adhere to the particle surface and react with oxidizable particles and are replaced by inert particles (carriers) that transfer similar bubbles to them. The flow is moved through successive treatment units with flow rates, which are determined by dimensionless numbers such as, for example. Reynolds number, Schmidt number, Peclet number, Lehman reaction number, Weber number, Stanten number and certain contact numbers. After alkaline treatment and continued gaseous oxidation, the non-liquid components are flocculated and separated as a sterile solid sludge. This can then be digested and/or fractionated for concentration and recovery of valuable particulate ingredients by known methods.

Whereas up until now there has only been a weak understanding of

that the oxidative reaction with SC^-iron required the presence of free

electrons (which are apparently transferred between the ions), it has now been shown that it is particularly desirable to obtain such a "galvanic exchange" condition everywhere throughout the process and especially in connection with (a) turbulence or agitation and (b) the close- te the presence of gaseous oxygen, which continues one after the other in the following steps, until the flocculating ion itself is oxidized. As already mentioned, the galvanic charge, which is impressed on the particulate material by added electrolytes (acidic and basic reagents), favors or enhances the surface attachment of gas. at the particle and enables the exchange of electrons. Such a reaction state is then maintained, and a phase separation: is prevented! by movement with a suitable flow rate.

Surface-absorbing particulate matter can typically be either oxidizable or non-oxidizable and includes cellulose or other organic material as well as inorganic compounds such as e.g. metal oxides (aluminium, magnesium oxide, calcium oxide, etc.) and especially compounds of atoms that have a Van der Waals packing radius of approx. 1.9 or below. Further examples of particulate matter include i.nfusoria earth, diatomaceous earth, bentonite and siliceous material such as e.g. free-flowing sand, silicones, etc.

The invention is further: explained in the following with reference to the drawing, in which

fig. 1 to 3 semi-schematically illustrate a method and an apparatus according to the present invention, in that the apparatus is intended to be placed next to each other in the specified order with the horizontal flow connections outside each other,

fig. 4. shows a horizontal section, or the line 4-4 .of the soda ash treatment unit in; fig. 1,

fig. 5 is a vertical section, along the line 5-5 of the homogenization tank in; fig. 2, and

fig. 6 shows on a larger scale a section of an end outlet segment in an air supply line for the tanks 70.

and 72.

In the device shown enter esi et; -f lyte capable starting material, such as fresh sewage, through an inlet line 10 into a wet well or a fragmentation chamber 12, where

a hoe pump 14 reduces it. solid matter to the required particle size (30-250 micron).: The liquid level in this chamber is regulated with an automatic control unit 16, which opens and closes a throttle valve 17 in the line. From the wet well, the particle dispersion is moved to a main tank 18 through a line 19 under regulation by means of a liquid level controller 20. If the output <=>capture material does not contain or insufficiently solid matter, the necessary particulate material is added, which can be any inert material, which may be a galvanic charge (e.g. shredded cellulose), to the wet well from a storage container 22 through a line 23.

The finely divided starting material. is then removed from the main tank 18 through a line 24 at a rate determined by a suction pump 25, and is led to a pulsation damping tank 27. A regulated quantity of exhaust gas is emitted from the top of the closed tank 18 through a wet charcoal filter 26 and released odorlessly into the atmosphere. In the main tank 18 there is a submerged transfer pump 28, which is operated to maintain a continuous flow of liquid and suspended particles. The turbulence in the tank 18 is promoted in part by the presence of internal guide plates 29 and by continuous bubbles of a circulating gas mixture from a line 13, which enters through perforations in the pipe system near the bottom of the tank 31. If the liquid medium is clear enough, it can be seen that small gas bubbles here adhere to the surface of the moving solid particles in the liquid, and their gas.sf ormi.ge oxygen content (which originally comes from the air) plus S02. pretreats or conditions oxidizable particles, for the subsequent oxidation. If it concerns highly oxidizable material such as e.g. faecal particles, is a residence time in the antechamber 18 of the order of magnitude approx. 1.5 to approx. 2 hours appropriate.

From the pulsation dampening tank 27, the flow is moved at a speed controlled by a mass flow meter 21 through a line 34 to a mixing tank 35, where it is mixed with a gaseous mixture of sulfur dioxide and air from an inlet 42, which is introduced through downcomers 37 from an overlying gas mixing chamber 36. Recycled gas is introduced into the mixing chamber 36 through a line 38 from a compressor 40, which receives exhaust gas through a line 42, which passes through a silencer unit 43. Both the gas mixer 36 and the flow mixing tank 35 are supplied from time to time other liquid sulfur dioxide through a line 45 from a storage tank 46 (which may be heated) in dependence on a pH meter 44, which maintains the tank 35 at a pH value of approx. 2.0 to approx. 2.5. Instead of or simultaneously with this, sulfur dioxide gas is supplied to the gas mixer 36 from the storage 47 through a line 48 under the control of the pH meter 44 and/or the mass flow meter 21. In the tank 35, the Peclet number is between 9 and 25. The Lehman reaction number in the blower tubes 37 varies from 3.5 to 8, for the drains 25-30.

Outlet gas from a tower 39 is continuously introduced into the iron reaction chamber 50 as a stream of bubbles through lines 49, at the same time that the liquid stream, which contains a certain amount of free gas bubbles, is led through an outlet line 52 and introduced through a line 53 in the reaction chamber 50 below the porous bed. It is very important that the gas inlet valve 49 is partially closed and thus used for a mixture of its flow through with the liquid flowing through the line 53. The gas mixture, which is passed both through the waste iron bed (which emits both ferrous and ferric ions to the medium) and through the flowing liquid, should contain a mixture of both nitrogen and oxygen, i.e. air. A vapor mixture from the iron chamber chimney 51 is passed through a line 54 which separates the non-gaseous components (ie liquid droplets) and returns them to the mixing tank 35 for the main stream through a line 57 or into the outlet from tanks 70 or 72. The gaseous part is recycled through the compressor 40 to the line 57.

The liquid outflow. from reaks ions tank 50 has a pH value of approx. 3.0 to approx. 3.5 and. is led through a line 60 to a blowing tank 62, where air; from a container 63 through a line 64 and a branch pipe 65 is led up through the liquid to separate it and to provide again a liquid system which is saturated with dissolved oxygen. The current is usually red due to its content of ferrous ions. The gas outlet from the chimney 61 through the line 66 and gaseous species from the tanks 70 and 72 through the lines 67, 68 are led through the line 30 back to the main tank 18. From the blowing tank liquid overflow is led to the upper level of the neutralization tank through a line 69. A line 74 connects a mixing nozzle 75 in the outlet line 69 with a sodium hydroxide tank 76, and a line 78 connects a container 79 for slaked lime and a circulation pump 80 with the mixing nozzle 75, the flow of alkali to the neutralization tank 70 being controlled by a pH meter 77. Instead of gradually to neutralize the acidic stream and gradually to bring it up to the required alkalinity of approx. pH 11, it has been found advantageous to introduce through the nozzle 75 at one time substantially the entire amount of alkali necessary to achieve the final pH value for the instantaneous volume of the stream with which it is mixed.

From the air container 63, a number of air supply lines 83 to the neutralization tank 70 and a similar number of lines 88 to the homogenization tank 72 emanate, which different lines are arranged to emit a bubbling cross-cutting air flow from shower nozzles or nozzles with a wedge-shaped opening at the outlet end, so that the swirling or foaming mass of liquid and charged particles is kept in motion, while oxygen and nitrogen are supplied. Consequently, the effluent through conduits 71 and 73 is oxygen saturated, and the adsorbing gas on the particle surface continues to be reactive. Air flow through the various lines 83, 88 is regulated by means of individual hand valves or stop plates, so that it can be set according to the step-by-step advance of the increasing viscous flow and thus constantly prevent agglomeration and sedimentation. A residence time of approx. 15-17 minutes in each tank is typical, in total approx. 30-40 minutes at approx. 16-27°C.

The air container 63 is fed through a line 59 from an air compressor 89, which is connected to a silencer 91. The compressor processes fresh air and can possibly lead it through an ozdniser 98, e.g. of the spark-free, low-voltage

and direct current type with face-separated insulated plates, which is described in US Patent No. 3,948,774. However, the basic procedure is sufficiently effective in most cases without further oxidation by means of ozone.

As shown in particular in fig. 5, the end pieces 100 of the various air ducts 83, 88 are arranged transversely in the tank 70 or 72 at a mutual angle. The end piece has a closed end 101 and an exhaust opening 102, which is cut wedge-shaped into the half-cylinder, which is oriented downwards, when the end piece is placed in the tank at a transverse angle in relation to the vertical longitudinal plane of the chamber. Such a location of the outlet reduces the possibility of liquid backflow and consequent solid deposits or crust formation. The successive segments 100 are arranged criss-cross at different fan-shaped angles, so that their outlet openings are angularly offset in relation to the longitudinal axis of the tank. Functionally, the flow-related series-connected tanks 70, 72 can be considered as forming the same, continuous and accelerated reaction process in tandem aggregates, i.e. that they support the completion of the neutralization process and at the same time keep the formed flocculent in suspension in the increasing , viscous flow, so that a phase separation is counteracted.

If you want to achieve a maximum removal of hard components and silicon dioxide, the outlet line 73 from the homogenization tank 72 receives a sodium ash addition from a storage tank 79 through a line 84 and then proceeds through a heating zone or a heating unit 85, where the flow is heated to a temperature of approx. 32°C to approx. 49°C prior to introduction into the treatment tank 82, where it is stirred by means of a motor-driven stirrer or boat propeller 86. The placement of four spaced vertical impact plates 87 in the tank forces the liquid suspension to circulate in closed paths with a mainly vertical ellipse between the side impact plates lying apart from each other.

From the treatment tank 82, a line 90 leads the flow to a flocculation chamber 92 which may have inclined walls and/or corrugated floor segments, which are separated by vertical impact plates, which form a meandering path for the descent of sediment and liquid. The different floor segments are movable by means of pneumatic drive mechanisms 93, which are fed from air lines 94. Each unit in the apparatus is electrically isolated from earth and from subsequent units, being interconnected by plastic wires, and the chambers preferably being of non-conductive material (concrete, wood, etc.) and in any case is lined with a corrosion-resistant layer, e.g. plastic or fiberglass.

The flow of liquid medium can now be earthed by closing a switch 95 which is connected to an electrode 96, which is in contact with the liquid in the chamber 92. The resulting discharge of the galvanic charge in the particulate material, which at this point should be oxidized to the greatest possible extent, and the cessation of stirring and flow triggers a relatively rapid precipitation of the potentially solid components from the liquid medium. The residence time in the flocculation chamber is of the order of approx. 30 to approx. 90 minutes. At the outlet end, the sludge, which is dark red due to the content of ferric ions, falls into a screw conveyor 97, which passes it through a sorting screen not shown and returns the liquid component to the system.

The liquid in the flocculation chamber 92 passes over an air-locked damper 104 to a tank 106 for decanted water, where a submerged pump 107 moves it through a line 106 to woven screening units 109, 110, which remove colloids,

and from there to the upper inlet in a packed tower 112, where it trickles down through raschig rings or the like in countercurrent with a stream of possibly ozonated air and is then introduced through a line 113 into a collection tank 116. The air from the top of the tower is passed through a line 114 to the tank 106 for decanted water.

The liquid flowing out from the tower 112 passes through a line 115 to a storage and aeration tank 116, which through a line 117 can be connected to a chlorine source for possible use under special conditions, e.g. if required - according to local regulations. A compressor 120 with silencer 121 supplies fresh air through lines 122. 123, 124 to the air tank 116 and to a tank 125. for filtered water through lines 126, 127, 128.

A gas outlet line 129. connects the tank 125. for filtered water with an outlet unit 130 with a charcoal filter. This unit is also connected with a gas line 131 to the air tank 116. The tank 125 contains a submerged pump 132, which leads liquid through a line 133 to a final polishing or collecting tank 134. The air tank 116 is by means of a pump 135 and a liquid line 136 connected with simultaneous or alternately acting tanks 137, 138 with activated charcoal filter and with drain lines 139, 140 which are connected to a line 144, which ends in the storage tank Kl»25. A backwash line 142 collects liquid from the filter tank 134 and delivers it to the tank 106 for decanted water. A return line 146 connects the return flow outlets from them

two filter tanks 137, 138 with tank 106 for decanted water. The pump 132 in the tank 125 emits service water or water for back-flushing through the line 133 to the filters 137, 138 and to the product filter tank 134. A back-flushing line 146 connects the filter tank to the main tank 18.

The solids collected at the bottom of the flocculation tank 9 2 may contain toxins that have not been detoxified by the oxidation. Such toxins can be metals such as mercury, arsenic, boron, lead, iron, gold, silver etc. as well as some biocides. Non-oxidative pyrolysis can be used to remove organic materials, such as petrochemicals. Precipitates, such as carbonates and sulphates, are broken down and removed as carbon dioxide and sulfur dioxide. Nitrogen is removed as an inert gas. The metals can be volatilized and recondensed or removed in a carbon matrix and then calcined/shaken in the presence of oxygen to produce a composition of different metal oxides. The precious metals are recovered as a combined metal concentrate. The special procedure for a specific liquid flow should of course be adapted to the special components, which have been proven by analysis, and which one wants to recover.

Flow chart:

Reynolds number (N Ke) =

E.g. the reaction chamber 50 has the following characteristics: I

A critical factor for such sewage or waste water treatment in the presence of particulate matter and .sulfrt-/ . sulfation or hydroxyl ion is defined as Shape Factor (SF)

— where y = particle concentration factor.

DA = nominal, release area. for air lifting

HFA = hydraulic discharge area. for spilling liquid

An operational SF area is. from approx. 9.5 to approx. 11.3: optimum

10 - 0.5.

Example

City sewage, if. solids content had been reduced in size to the stated particle diameter, was passed through a pre-treatment plant as described above, with the degree of acidity initially set to pH 1.5-2.5 by the addition of liquid and/or gaseous sulfur dioxide.: The liquid flow was then led through the serpentine channels in the tank 35 (form factor 9-10). at NRg of approx. 5000 to approx. 10,000. in contact with the gas flow and approx. 7000 to approx. 18000. without touching the gas flow. The gas mixture of SO 2 and air was moved by

NReca. 40Q to approx. 500.

After approx. After 7.5 to 15 minutes of residence in the iron reaction chamber 50, the flow was passed through the air blowing tank 62 and from there to the neutralization tank 70, where the pH value was increased. from approx. 8.5 to approx. 10.0 in. a period of approx. 15 minutes. It continued through the homogenization tank 72 for approx. 15 minutes, while the pH value increased to a maximum of approx. 11.

If the operation is particularly aimed at removing calcium and magnesium ions ("heat components") and also at reducing the silicate concentration, 15-301 of the sludge that was removed from the sieves after flocculation brought back to the homogenization tank to ■ < increase the particle concentration and contact surface area, i.e.:

Additives of this size include fly ash, carbon black, infusoria soil, etc.

The flow is then moved through a stirring and heating zone 82 at NRg of 30,000 to approx. 40,000. while adding sodium ash. Instead of the use of mechanical propellers, complete agitation with blowing air can be achieved if there is 1.5-3.0 CFM/ft.t2 cross-sectional area.

Finally, the current moves at NRg of approx. 200 to approx. 3700 in approx. 30 to approx. 90 minutes through the flocculation tank or sedimentation zone 92.

The addition of particulate material in the present process differs from various random additions of particles to liquids in known processes in that these particle additions served (a) to remove dispersed colloids by adding charged particles to agglomerate the two substances or (b)

to. removal of a dissolved substance, by adding a substance which reduces the solubility of one or more of the dissolved components. None of these treatments aims at or entails a: continuous reaction (oxidation) between the dispersed particles and a gaseous component, which adheres to the added particles, and/or the interaction of free electrons

are in such surroundings, which electrons take part in the desired ongoing reaction. The known methods also do not aim at maintaining such a dispersion and preventing agglomeration during a necessary reaction period in several steps or at a final precipitation by introducing a flocculating ion. In short, one thus seems to have completely overlooked the importance of provision and utilization

■*of an isolated flowing mass of polar liquid, which constitutes a galvanic or ion exchange module (cell), the contents of which are constantly manipulated both to prevent phase separation (precipitation) and to carry out the desired chemical reactions, which ultimately lead to both liquid purification and separation of solids.

The necessary polar solvent such as mineral oil, kerosene, kerosene, etc., which are not suitable, because they are incapable of transmitting an electric current.

It should be noted that the intended and necessary result of the application of the above-mentioned dimensionless flowless parameters is (1) that sedimentation and agglomeration are prevented and (2) that the dispersed particles by their active surface area maintain the intermolecular attraction, which is often referred to as Van der The Waals effect, which attracts clusters of moving air molecules (bubbles) and brings them to attachment. The result is not only the progressive oxidation of the flowing particles, but also the electric and interatomic field strength, which is thus assumed to be responsible for the removal of the dissolved electrolytes with both positive and negative charge from the solution, such as halide -(chloride) ions and alkali (sodium) ions, which are finally separated. from the medium as a component of the floc.

Besides the Reynolds number which sets the specific<y>ect and the velocity of the fluid in relation to the container design, the following parameters should be taken into account: The heat transfer and energy retention properties of the flowing medium are defined by the Peclet number -

DV pCp/k or Cp S p R2

k+4/3..Dppa T3

where Cp = specific heat, a = surface tension

k = thermal conductivity,

The Peclet number for the tanks 70 and 72 is in the range from 12-32, and the gas escape velocity at the surface is 6-8 cm/sec.

The Schmidt number indicates a relationship between viscosity, specific gravity and container diameter (hydraulic diameter in an irregularly shaped container) Ng_ = u/p. DV.

The Stanton number indicates a relationship between the heat transmission coefficient (h) and specific heat, speed and specific weight.

No = h/CV.

st PP

The Stanton number for the tank 35 to mix of. liquid-flow and gas are 55.50-36.20.. For the neutralization and homogenization tanks 70, 72 the Stanton number is 28.60-10.160.

The Weber number indicates a relationship between the container's shape (length of flow path L), specific weight, velocity and surface tension. N^g = LpV / gc.

The iron tank 50 has within its working area a Schmidt number of 4 x IO-7 to 1.3 x IO<-6>, and the contact number is 228-446.

Reaction gases (air, sulfur dioxide, nitrogen, ozone, etc.) can be introduced into the flow of the particle charge. liquid, by blow-out, spreaders or so-called "b.lase cutting tubes".. Each of these works with a specific Lehman reaction number and Weber number range. The dimensionless Lehman reaction number indicates the relationship between the system's form factor and the mass flow of liquid and gas.

The thermal velocity of spherical and non-spherical droplets of particles deposited in the vapor space will vary from 0.4 to 30 feet/sec. Particles of up to 85 microns are carried along and removed from the gas stream in front of iron; 1" vein 50.

The flow conditions in v: the methane tank 85 are defined

..P-t r_RAynn4,rl.s^.t^-] l- r1^ pq--5 0 . Q Q Q - 4 0 st' f!rac;^ of-prflTif1t1 -

number product in the range 25,600-230,000. for that material consisting of water and particles. Grashof number = (L 3 p 2g/u)(bAT), I where L = length of the reaction chamber, p = specific gravity,

'g = 9.81 m/sec , u = viscosity, b = coefficient of thermal expansion, T = temperature, Prandtl number = Cpy, where C is speci-t K ™

got heat, u is viscosity.

K is thermal conductivity. When removing hardness componentei

- the heating tank is operated at temperatures of 40.6°C - 3.7°C, and the liquid leaves the tank with a temperature between 37.8°C and 43.3°C. The introduction of additional particulate matter through the line

103 to line 73 (outflowing from homogenization tank 72) gives, as discussed above, 30-85% more surface area in the final stage of magnesium conversion to magnesium carbonate and thence to magnesium hydroxide, which is a. solid. Magnesium oxide and magnesium hydroxide also favor the removal of silicates. The sludge reintroduced at this point, which is composed of mechanically formed particulate matter, flocculates and precipitates, assists the sodium ash effectively in the final removal of silicon and magnesium. The electrical charge on the particulate matter also increases the speed and efficiency of silicon removal. Magnesium and calcium chlorides-sulphates and nitrates are converted into solid magnesium hydroxide and calcium carbonate. As Ca and Mg in hard water mainly occur as chloride, bicarbonate and sulphates, they are removed by the present procedure.

The way in which it. the present system treats hexavalent chromium and cyanides, is of particular interest. When the recycled gas stream of oxygen, nitrogen and sulfur dioxide comes into contact with the particulate matter and dissolved salts, the sulphite ion reacts with any metal ion present. Hexavalent chromium is reduced to trivalent chromium in approx. 15 minutes at pH 2.0-2.5. In its capacity as a reducing agent, sulfur dioxide consumes oxygén, but this is continuously replaced. In the iron reaction tank: ferrosylphate is ignited, which also acts as a reducing agent for hexavalent chromium. This ensures complete conversion to trivalent chromium. When this runs into the neutralization tank (with an initial pH of 8.0-8.5), its coupling with hydroxyl ions results in a light and rich precipitate, which is constantly mixed with the ferrous hydroxide, which changes to ferric hydroxide (a heavier precipitate). During a total stay of

about. 30 minutes in the tanks 70 and 72, this reaction is completed, the precipitate continuing to be suspended as a result of the air-driven agitation, which maintains an oxygen-saturated medium, and the pH finally reaches 10.5-10.8 or 11. The outlet line 73 emits finely dispersed, charged particles, which agglomerate quickly in the flocculation/sedimentation zone 9 2.

If cyanides are present, it is necessary to oxidize them to cyanates and then to free carbon dioxide and nitrogen gas (both of which will be freely released). If cyanide ions were oxidized in an acidic medium, cyanide gas would be formed, which requires special safety measures during treatment. If, on the other hand, cyanide is oxidized to cyanate in a strongly basic medium, a long reaction period is required. However, in the presence of the large amount of reactive oxygen, which is carried by the particle dispersion, cyanides can be oxidized to cyanate at pH 8.5 of approx. 5 minutes in the tank 70. If the second cyanate is then exposed to oxygen and iron ions in the iron tank when sent back through the line 105, an iron cyanate complex is formed. After passing through the blowing tank 62, the flow re-enters the neutralization tank 70, where hydroxyl ions react with the cyanate complex and form carbon dioxide and nitrogen. At the same time, ferric sulfates are hydrolyzed to ferrihydrox-I yd, Fe(S04)3<+>6H20 = 2Fe(OH)3+ 3H-S04. When the liquid is grounded, the ferric hydroxide is separated as small plates, which have a cross-sectional dimension of up to 6 mm, are dark red to black and tightly packed in comparison with the fine, greyish, amorphous precipitate formed by ferric hydroxide.

The unexpected benefit of the present heat treatment process with respect to killing and agglomeration of viral and other single-celled life forms must be assumed to derive from the cumulative action or cooperation of a number of individual factors, at least some of which already have a unique effect in themselves. . These factors are: Cl) The wide band shift. from extremely low to extreme ■"high pH (ie 1.5-11) as well as the residence time at each end of the spectrum attack the entire group of organisms, some of which may be resistant to exclusively acidic or basic media, but not to extremes of both pH. (2) In this connection the rapidity (ie, 15-3Q minutes) as well as the extent or strength of the pH change seems to be important. An organism will be better able to acclimate or survive a slow or mild change. (3) The residence time, during which the entire medium or the environment undergoes treatment at each end of the flow process, including gas exchange, continuous suspension/stirring, oxidation and ion exchange, is important. (4) The relative density and composition of the particulate matter in the flow medium compared to the treated water volume is an important parameter .(Total particle surface area 130-13,280 cm<2>/l).(5) The additional effect (attraction to living or recently dead cells) exerted by the galvanic charge carried by the particle e, is efficient. In this connection, it is preferred to achieve the initial low acidity (plus galvanic charge) by introducing sulfur dioxide instead of adding formed acid, as SO 2 produces hydrogen ions and wandering electrons by disassociating water. (6) The detergent effect originates from the sulphonation of fat and oil components in the medium and in particular from such components which may form parts of viral or bacterial capsules or membranes. Proteinaceous components of the membrane can also be degraded. The subsequent salting out of the organic salts then exposes the cell contents to caustic attack or saponification.

(7) Under these critical conditions, lime is particularly effective

effective against certain. viruses.

(8) The rapidity and completeness of the flocculation is important,; e.g. 5-7 minutes after grounding, compared to a minimum of 25-30 minutes or more, which could be needed to "only" clear murky water. flocculation with Al or Fe ions. (9) The total killing is carried out! without the use of chlorine or other toxic agents and without the need to modify the treatment in such a way that it is aimed at a specific organism, the presence of which must first be established. Such a procedure can be used to "harvest" pestilential life forms to identification and study. By taking samples from successive process steps, the cell's sensitivity to each step can be experienced.

Claims (26)

1. Procedure for the removal of dispersed soluble or suspended pollution, from a liquid polar liquid, son solid substance, in which contamination every suspended particle is characterized by the Van der Waals effect, and which contamination is capable of solid existence at the ambient operating temperature and operating pressure, characterized by (a. in the liquid disperses a minimum of approx. 0.1 weight-! of randomly moving!"' rtical substance, which is either •■' Iseted or formed! by "sioning. pollutionc . <;if this is originally present in coarser, shape, and whose -sperged particles have a specific gravity of about 1.05 to about 2.0 and a size of about 30 to about 225 microns with a free surface energy of o about 100 to about 500. erg /cm 2 , and also reduces any further solids present to this particle size, (b) provides an oxidation medium for such of the pre-purification and addition particles, which are capable of oxidation, by making the liquid acidic, and closely disperses gaseous oxygen in the liquid as well as provides a supply of free electrons, e.g. by acidic dissociation of the polar liquid and by oxidation in situ of a heavy metal present therein, which is capable of later forming a flocculated precipitate in an alkaline medium, whereby the mobile particles are imparted with a galvanic charge by random distribution and binding ing of the electrons to these, (c) maintains this charge on the moving particles and limits coagulation and phase separation of particles and soluble contaminants during the successive oxidative reaction periods by agitation, which is carried out at least in part by passing the liquid and its contents through electrically insulated, interconnected flow-connected reaction vessels in intimate mixture with gaseous oxygen and with a varying flow rate, which is determined by dimensionless parameters, which are determined by the internal size qk shape of the respective vessels and their connecting lines, Cd) does. the liquid alkaline and then ceases stirring and grounds the alkaline liquid, whereby flocculating ions of the occupied heavy metal mutually precipitate the charged particles, the metal ions and the soluble impurities, so that an overlying oxygen-containing clean liquid is formed. 2. Method in accordance with claim 1, characterized in that the oxidation medium under (b) comprises sulphite and sulfur ions and is adjusted to a pH of approx. 2 to approx. 2.5, and that the heavy metal includes iron. 3. Method in accordance with claim 1 or 2, characterized in that the liquid under (d) is adjusted to a pH of approx. 10 to approx. 11. 4. Method in accordance with claim 1, 2 or 3, characterized in that the polar liquid is predominantly. water. 5. Method in accordance with claim 1, characterized in that the liquid polar liquid comprises sewage or waste water, which contains solid masses, which are mainly reduced to the particle size specified under (a) cup size. 6. Method in accordance with claim 1 or 5, characterized in that an inorganic salt is a soluble contaminant in the polar liquid and is mainly removed from this, by precipitation according to (d). 7. ' Method in accordance with claim 1, 2 or 5, characterized in that the dimensionless parameters are selected from a group comprising Reynolds number, Peclet number, Lehman reaction number, Shoup factors, Schmidt number, contact number, Weber number , Grashof-Prandtl number and Stanton number. 8. Method in accordance with claim 1, characterized in that the suspended pollution comprises faecal matter, which is reduced in situ to the particle size specified under (a). 9. Method in accordance with claim ^ characterized in that sodium chloride is a soluble contaminant in the polar liquid, which is water. IQ. Method in accordance with claim 1, characterized in that the soluble contamination includes hexavalent chromium and cyanide ions. 11. Method in accordance with claim 2, characterized in that the contamination comprises hexavalent chromium and that the method comprises reduction of the hexavalent chromium to trivalent chromium by reaction with sulphite and ferrous ions in the presence of ferrous sulphate at pH approx. 2.0 to approx. 2.5, and subsequent conversion of trivalent chromium to chromium hydroxide at pH rcra. 10.5 to approx. 11.0 and precipitation of this together with ferric hydroxide. 12. Method in accordance with claim 10, characterized in that the pollution comprises soluble cyanide which is oxidized to cyanate at pH approx. 8.5 in the particle-carrying liquid, which is mainly saturated with gaseous oxygen, after which an iron cyanate complex is formed. by reaction of the cyanate with iron ions, and the liquid is then made alkaline and the complex is converted to carbon dioxide and nitrogen by reaction with hydroxyl ions. 13. Procedure in accordance with claim 1, characterized in that, prior to the flocculation of the charged particles and contaminants, approx. 15 to approx. 30. flocculated sludge together with sodium ash in the liquid, after which the resulting mixture is heated to approx. 37.8°C to approx. 43.3°C under stirring and then flocculated as indicated under (d), as follows. that the removal of silicon, magnesium and calcium from the liquid is increased. 14. Method in accordance with claim 1 or 13, characterized in that the heated liquid stream is passed through a zone, which is arranged to further receive and mix sodium ash and returned sludge with the liquid stream, which is moved in accordance with the dimensionless parameters: Reynolds number 30,000-40,000 and Grashof-Prandtl number product 25,600-230,000. 15. Method in accordance with claim 1 or 2, characterized in that the oxidation medium listed under (b) is moved through a zone, where the heavy metal produces free electrons, at a Reynolds number of approx. 967-2,900, -7 a Shape factor of 9.5-11.3, a Schmidt number of 4 x 10 to 1.3 x 10~ <6> , and a contact tire of 228-446. 16.'Process in accordance with claim 1 or 2, char- a c t e r i s e r t . by the fact that there, polar liquid is moved through a zone, where it mixes with es', gas; in accordance with the dimensionless parameters: Peclet number 9-25, Shape factor 9-10, Reynolds number of 400-500. too gas flow sensitive, 5 . 000-10,000 with gas contact and 7,000-18,000 without gas contact, a Lehman- reaction number of 3.5-8 for blow pipes, which introduce gas into the mentioned zone, and a Stanton number of 35.50-36.20. "Or? Method in accordance with claim 1, 2 or 5, can be characterized in that the alkalization stated under (d) is carried out in a zone of the liquid flow, as agitator with the help of air, which is moved in countercurrent through it, and that the liquid is moved with a Peclet number of 12-32, and the air is introduced into it through diffuser tubes with a Lehman reaction number of 3.4-4.4. el laughs through a "blow cutter tube" with a Lehman reaction number of 6.7-7.7, and a Stanton number of 28.60-10.160. 18. Procedure in accordance with claim 1, 2 or 5, characterized by the one specified under (d); flocculation and precipitation are carried out in a zone, where the current moves with a Reynolds number of 2,000-3,700... 19. Facility for purification of. contaminated liquid and extensive organs for regulation of. liquid-flow-rich, characterized , ved, that it includes the combination of the following successively connected units: (a) a liquid container with associated means for selective separation of solid components of such contaminated liquid and gas supply and venting means. for introducing gas into the intimate area mixing with the contaminated. liquid and the separated components. (b) means for acid treatment, which are flow-connected to the container one, and which comprise means for adjusting the pH value by selectively introducing acidic and gaseous oxidizing reagents into the contaminated liquid, in (c) a reaction vessel, which is in flow communication with the latter, treatment means and comprises a source for soluble heavy metal ions, which shall. mixed with liquid flow, and organs for subsequent aeration of. liquid st the flow by the passage of atmospheric oxygen, (d) neutralization means, which are flow-connected with the latter aeration means and comprise connected means for introducing alkaline reagent into the liquid stream, and a plurality of successive means for intimate mixing of gaseous oxygen.in the alkaline, liquid stream in an amount, which is able to counteract the precipitation of impurities during agitation, (e) organs for flocculation of. separable pollution components from the alkaline liquid stream essentially simultaneously with electrical grounding of this stream, and interrupting means for electrical grounding of the alkaline liquid stream, where each of the mentioned units from (b) and the following are electrically isolated from earth, and the flocculation means (el is electrically isolated from the previous flow-connected unit, whereby the solid particles in the liquid flow can be given an electric charge by pH regulation and electrons from the soluble heavy metal ions, which charge is maintained, until it is discharged by means of the contact means. 20. Installation in accordance with claim 19, characterized in that between the units (d) and (e) it comprises means for simultaneous heating and stirring of the alkaline liquid stream under constant counteraction of precipitation. 21. Installation in accordance with claim 19, characterized in that the unit (d) comprises an elongated chamber, and that the oxygen mixing device, which is located behind the alkali introduction device, counted in the direction of flow, comprises successive gas supply lines, each of which has an outlet dy ser , which is placed transversely in the liquid flow under successively stepped angular displacement from the longitudinal axis of the chamber, which lines have individual flow regulation means, such. that the gas inflow through them can be set to varying turbidity of the liquid flow immediately, at each nozzle. 22. Drinking water, which is produced from. contaminated liquid by the method and apparatus according to any one of the preceding claims. 23. Drinking water in accordance with claim 22, which is produced from brackish water, which was originally. unsuitable for drinking. 24. Drinking water in accordance with claim 22, which is mainly saturated with oxygen as a result of the described procedure. 25. Drinking water and an aggregate of small metal particles, son. each is formed from a liquid suspension containing said particles, and which is formed by the method and apparatus according to any one of the preceding claims. 26. Apparatus for cleaning of. contaminated liquid, essentially as described with reference to the Examples.