GB2471320A

GB2471320A - Removing oil contaminants from aqueous liquids

Info

Publication number: GB2471320A
Application number: GB0911041A
Authority: GB
Inventors: Nigel Willis Brown; Edward P L Roberts
Original assignee: Arvia Technology Ltd
Current assignee: Arvia Technology Ltd
Priority date: 2009-06-25
Filing date: 2009-06-25
Publication date: 2010-12-29
Anticipated expiration: 2029-06-25
Also published as: GB201204885D0; GB2486130A; CA2766071A1; GB0911041D0; WO2010149982A1; CA2766071C; GB2471320B; GB2486130B

Abstract

A method of removing oil contaminants from aqueous liquids involves contacting the liquid with particles of a carbon-based adsorbent material to form a layer of the oil contaminant on each particle. The adsorbent particles are then electrochemically regenerated and recycled in the liquid to form an additional layer of oil contaminant on each particle. Subsequently, the particles are removed from the liquid and are regenerated by electrochemical oxidation. The method may comprise the delivery of contaminated liquid to a treatment reservoir 2 containing the adsorbent particles in the form of a bed of particles at the base of the reservoir. The bed of particles is then, preferably, agitated or fluidised to distribute the adsorbent material in the liquid and adsorb the contaminant therefrom. After ceasing the agitation and allowing the bed to settle, the adsorbent may be regenerated by passing an electric current through the bed which releases carbonaceous gases and water. The decontaminated water can then be removed from the tank. Preferably, the adsorbent material comprises unexpanded intercalated graphite. At least one of the oil contaminant and the aqueous liquid may be radioactive.

Description

TREATMENT OF LIQUID WITH OILY CONTAMINANTS

This invention relates to products for the treatment of contaminated liquid by contact with an adsorbent material. It has particular application in the treatment of liquids to remove oily contaminants. It uses technology disclosed in our International Patent Publication Nos: WO 2007/125334 and WO 2008/047,132; unpublished International Patent Application No: GB 07/20429.0; and unpublished British Patent Application Nos: 0823165.6, 0907813.0 and 0907812.2. The entire disclosure of these published and unpublished applications are incorporated herein by reference.

Adsorbent materials are commonly used in liquid treatment apparatus.

Carbon-based such materials are particularly useful, and are capable of regeneration by the passage of an electric current therethrough. The use of carbon-based adsorbents in the treatment of contaminated water is described in the following papers published by The University of Manchester Institute of Science and Technology (now the University of Manchester) in 2004, incorporated herein by reference: Electrochemical regeneration of a carbon-based adsorbent loaded with crystal violet dye by N W Brown, B P L Roberts, A A Garforth andRAWDryfe Electrachemica Acta 49 (2004) 3269-3281 Atrazine removal using adsorption and electrochemical regeneration by N W Brown, E P L Roberts, A Chasiotis, T Cherdron and N Sanghrajka Water Research 39 (2004) 3067-3 074 The present invention adapts the techniques disclosed in the Patent Publications and Applications referred to above to remove oil contaminants from aqueous liquids. So contaminated liquids appear in many fields of activity, one of which is the nuclear industry where the disposal of radioactive oils and oily wastewaters is a major problem. According to the invention a method of removing oil contaminants from aqueous liquids comprises contacting the liquid with particles of a carbon-based adsorbent material to form a layer of the oil contaminant on each particle; electrochemically regenerating the adsorbent particles and recycling the particles in the liquid to form an additional layer of the oil contaminant on each particle; removing the particles and regenerating the particles by electrochemical oxidation. In the practice of the method the particles bearing the oil contaminant layers can be allowed to coalesce in the liquid into one or more solid bodies with voids between the particles into which bodies further oily contaminant is absorbed.

To treat a neat oil or a concentrated oily wastewater, it can be desirable to dilute the oil with water. Since oils are usually not miscible with water, it is necessary to treat the oil with an emulsifying agent. Of course, soluble oils which mix readily with water will not need such an addition. The emulsifying agent is likely to be an organic polymer of some description, but any organic emulsifying agent could be used. An organic emulsifying agent is recommended as this will be destroyed in the regeneration process.

In one particular application of the invention, the process can be used to treat radioactive contaminated waste oil or oily wastewater. In this application, the aim is to destroy the oil whilst leaving the radioactive particles in the aqueous phase. The generation of radioactive oils and oily wastewaters is an issue for the nuclear industry for which there is currently no satisfactory treatment solution. Existing cementation or vitrification processes are unable to produce stable matrices when oil is present in anything other than low quantities. By using adsorption coupled with electrochemical regeneration, it is possible to destroy the oil component leaving the radioactive particles in the water. Radioactive particles present in water can be treated using existing technologies.

The method of the present invention is well suited to the treatment of individual quantities of liquid in a batch rather than in a continuous treatment process.

When so practised the contaminated liquid is delivered to a treatment reservoir containing the carbon based adsorbent material in the form of a bed of material at the base of the reservoir. The bed is agitated for a period to distribute the adsorbent material in the liquid and adsorb contaminant therefrom, at the end of which period the agitation ceases, allowing the bed of material to settle. During this settlement period the adsorbent will separate from the liquid. The degree of separation depends upon the length of time allowed. It is possible to adjust the time scale according to the nature of the liquid being treated. The adsorbent is then regenerated, during or after settlement, by passing an electric current through the bed to release from the adsorbent gaseous products derived from the contaminant in bubbles rising through the decontaminated liquid in the reservoir, which is then removed. The liquid can of course be removed before the adsorbent is finally regenerated. At different stages of the regeneration period, the current can be adjusted. For example, at the beginning of the regeneration period, only a very thin layer of the adsorbent will have settled so a smaller current is required than later in the regeneration period when substantial settlement has occurred.

In the above described method adsorption occurs within the regeneration zone as well as the adsorption zone, facilitating a compact and potentially mobile apparatus. It also allows for a larger regeneration zone. An increase in the size of the electrodes would be beneficial for treatment liquid containing a high concentration of contaminant.

Particular advantages of the above method are that it allows a treatment cycle to be selected for the particular liquid to be treated. The method allows the steps of agitating the bed and allowing it to settle, and of regenerating the adsorbent, to be repeated to remove further contaminant from the liquid prior to its removal. Put another way, the degree of decontamination of the liquid can be monitored, and the method adapted accordingly. It will also be appreciated that the relative sizes of the regeneration and adsorption zones can be varied according to the treatment required.

The quantity of adsorbent that is added to the tank can be adapted to type and load of contamination present in the liquid. The ability to modif' the method, the quantity of adsorbent and the relative sizes of adsorption and regeneration zones gives a process with significant flexibility.

Preferred adsorbent materials for use in the method of the invention comprise unexpanded intercalated graphite, preferably in powder or flake form. The material may consist only of unexpanded intercalated graphite, or a mixture of such graphite with one or more other adsorbent materials, as described in our Application No. 0907812.2 referred to above. Individual particles of the adsorbent can themselves comprise a mixture of more than one adsorbent material.

In this preferred method, the bed of adsorbent material is normally agitated by the delivery of fluid to the base of the bed. The fluid will normally be a gas, such as air, but in some circumstances a liquid can be used. The liquid may be neutral such as water, or may be the contaminated liquid itself as or as part of its delivery to the reservoir. In other words, the contaminated liquid can be delivered to the treatment reservoir as part of the agitating process, at least in an initial decontamination stage.

If a subsequent decontamination stage is required, a different agitator fluid, such as air, can be used. The agitating fluid can itself include a treatment component or a component to be treated if required.

Apparatus for carrying out the preferred method can be simply designed to enable the method steps to be carried out. The apparatus comprises a reservoir for the liquid having an upper and a lower section. The reservoir will contain a particulate adsorbent material, preferably of the kind referred to above, capable of electrochemical regeneration, and in the form of a bed supported in the lower section at the base of the reservoir. An agitator is installed for agitating the bed to distribute the particles in liquid contained in the reservoir including the upper section, and electrodes are disposed from opposite sides of the lower section for delivery of an electric current to pass through the bed of particles. The agitator will normally comprise a chamber under the bed with discharge orifices directed upwardly therefrom into the bed, and means will be provided for delivering fluid under pressure through the orifices into the bed to distribute the bed particles. Typically, the agitator will comprise a plurality of nozzles, for example in the form of a manifold, for directing fluid under pressure upwards into the bed of particles. It could be in the form of a chamber with a porous plate above. The agitator can be provided with means for connecting it to an external source of pressurised fluid, but could be quite independent with a source of pressurised fluid being installed in the agitator itself.

This provides for the possibility of the agitator being installed in an existing reservoir to treat contaminated liquid on site. Provided the agitator dimensions are compatible with those of the reservoir, the agitator can be installed and the bed of particles formed thereover, prior to delivery of the contaminated liquid, from above or below the bed of particles.

An additional means for agitation of the content of the reservoir can be included in the form of a mechanical mixer with the extra function of preventing coagulation of the adsorbent material and treatment liquid in the upper section of the reservoir. Coagulation can prove a problem as it entraps the agitation bubbles, reducing the density of the adsorbent material and therefore causing it to float. This reduces the efficiency of adsorption and can cause incomplete separation. This can be a problem associated with the presence of, for example, a surfactant or oil in the liquid to be treated. However, with oil contaminants coagulated particles can create bodies with voids which absorb, rather than adsorb, further contaminant from the liquid. In a preferred embodiment of the experiment, the mixer is positioned within an upper section of the reservoir and attached to a lid or cover if used, but it could be incorporated anywhere in the adsorption section of the chamber. A mechanical mixer can also be used to fluidise the bed as an alternative to the use of pressurised fluid.

This could be necessary when the contaminated liquid is of a nature that should not be exposed to bubbles; for example, foaming agents or highly volatile agents.

Generally, the reservoir in apparatus for use with the invention will have a substantially uniform horizontal cross-section, with the bed of adsorbent particles extending across the entirety of that cross-section. However, the cross-sections of the upper and lower reservoir sections do not have to be the same, and particularly for relatively small quantities of contaminated liquid, the bed of adsorbent material can be defined in a lower section of smaller cross-section than the upper section, and into which the adsorbent material flows as it settles. In this embodiment, the reservoir can then take the form of a hopper with an intermediate section between the upper and lower sections around which the reservoir wall or walls converge towards the lower section in which the adsorbent bed is formed.

The reservoir may be closed by a lid or cover (not shown), to increase the pressure under which the agitation process is performed, increasing the efficiency of adsorption. In order to maintain the desired pressure within the reaction chamber one or more valves will be needed to provide controlled release of the gases generated or used in the process.

In the practice of the method using the above apparatus, when the agitated adsorbent bed material has been allowed to settle, it is regenerated by passing an electric current through the bed. This current is created by the application of a voltage between electrodes on opposite sides of the bed. Normally, the cross-section of the bed or lower section of the reservoir will be square or rectangular, with the electrodes disposed on opposite sides of the lower section. A plurality of electrodes can be disposed along each of these sides. For example, in a reservoir having a uniform rectangular cross-section of 200 x 100cm, 30 electrodes might be disposed along each of the longer opposite sides. Multiple electrodes can be installed horizontally to allow different currents to be applied at different heights in the bed during regeneration.

The above and further features of the invention will be apparent from the following description given by way of example, of apparatus in which the method may be practised. Reference will be made to the accompanying schematic drawings wherein: Figure 1 is a perspective view of the apparatus; Figure 2 is a top plan view of the base of the reservoir in Figure 1, upon which a bed of adsorbent is supported; Figure 3 is a perspective view of a device for supporting a fluidized bed in apparatus for use in the practice of the invention; Figure 4 is a perspective view of an alternative form of apparatus for use in the practice of the invention; Figure 5 is a top plan view of an alternative base of the reservoir of Figure 1, below the level of the distribution plate, and showing an alternative arrangement of regeneration electrodes; and Figures 6 and 7 illustrate the use of multiple cells in the base of apparatus for use in the practice of the invention.

Figure 1 illustrates a simple tank 2 of rectangular horizontal cross-section. In the lower section 4 of the tank a bed of particulate adsorbent material is supported on a plate 6. Beneath the plate 6 is a chamber 8 for receiving a fluidising medium, such as air, from inlet pipe 10.

Figure 2 is a horizontal cross-sectional view of the lower section 4 of the tank 2, specifically showing the plate 6 and the inlet pipe 10. Figure 2 also shows the openings 12 in the plate for the passage of fluidising medium from the chamber 8 below. On the opposite longer sides of the plate 6, and extending upwardly therefrom, are two banks 14 of electrodes 16. The bed of adsorbent material is supported on the plate 6 within the walls of the container 2, between the banks 14 of electrodes 16.

The adsorbent material used in the practice of the present invention is carbon based, and provided in particulate form that can be readily fluidised within a body of liquid. Preferred adsorbents are those disclosed in the Patent Publications and Applications referred to above. In use of the apparatus of Figures 1 and 2, contaminated liquid is delivered to the tank 2 which is normally open at the top. The adsorbent material is then fluidised by delivery of a suitable medium through input 10 to distribute the adsorbent material within the body of contaminated liquid then contained in the tank. The adsorbent takes contaminants from the liquid which attach to the surfaces of the adsorbent particles. After a predetermined period of time, the flow of fluidizing medium is stopped with the consequence that the adsorbent material settles on the plate 6 between the banks 14 of electrodes 16. At this point the decontaminated liquid can be removed through discharge 18 but its removal may be deferred. Its degree of decontamination can be measured, and if this is now acceptable then it may be removed. If further decontamination is required, it is retained in the tank 2.

If required, additional agitation of the liquid in the upper section of the tank 2 can be provided by a mechanical mixer indicated at 19. This can be a simple paddle, which will normally be sufficient if it is to function in conjunction with the fluidising medium delivered through the plate 6. If it is to be the only agitating mechanism, then it can be installed within or under the bed to urge the adsorbent material into the upper section, but it can be installed in the upper section itself Particularly if disposed at the surface of liquid of the reservoir it can be used to coagulated particles.

Whether or not the decontaminated liquid has been removed, the adsorbent material in the bed supported on the plate 6 can now be regenerated. This is accomplished by passing an electric current through the material of the bed between the electrodes 16. This releases the adsorbed contaminants in the form of carbonaceous gases and water. The gases are released either through the open top of the tank 2, or if the top is closed, through a separate exhaust duct 20, possibly for subsequent treatment. If the decontaminated liquid remains in the tank, the released gases merely bubble through it. Contaminated liquid retained in the tank after regeneration of the adsorbent material can of course now be further decontaminated by re-fluidization of the bed to distribute the particulate adsorbent once more within the liquid. This sequence can be repeated, with the degree of decontamination of the liquid being monitored after each treatment.

In the treatment of oils, oils in water or oily wastes at least two adsorption stages are normally required. In the first a single layer of oil forms on the adsorbent particles. However on regeneration, the capacity for adsorption remains similar, even if insufficient charge is passed to achieve 100% electrochemical regeneration of the adsorbent material. After a charge has been passed through the adsorbent during regeneration, the surface of the adsorbentloil is suitable for subsequent layers of oil to be adsorbed. Hence multi-layer adsorption appears to occur under these conditions when there is a high liquid phase concentration. In addition the presence of oil causes the adsorbent particles to stick together to create solid bodies or "balls". These have spaces between the particles which can then fill due to absorption, probably caused by capillary condensation. Oil concentrations on the adsorbent can at this stage reach 60% by weight.

After the treatment is concluded the adsorbent is removed and regenerated by electrochemical oxidation. This removes the oil adsorbed on the surface of the material; any "balls" are destroyed; and the original particles are recovered. After this is achieved the particles can be reused.

In the apparatus of Figure 1 the bed of adsorbent material; the means for fluidizing the bed to distribute the material within liquid in the tank; and the electrodes for regenerating the adsorbent after a decontamination treatment, are all integrated in the tank construction. However, it will be appreciated then, that the tank is a mobile decontamination unit that can be moved between sites where one or more batches of liquid must be contaminated, but where a permanent installation is not required. If a suitable tank is already on site, then it is the decontamination system; the bed of adsorbent and fluidizing mechanism that can be delivered separately. Such a system is illustrated in Figure 3 which, as can be seen, includes the same elements as are present in the lower section of the tank 2 in Figure 1, with the exception of the input 10 for the fluidizing medium. This is replaced by a pipe 22, which can extend through the top of an on-site container for connection to a source of fluidizing medium. In use, the system shown in Figure 3 will be installed in the lower section of a tank, with suitable seals between the end boundaries 24 and the electrode banks 14 with the walls of the container, and the adsorbent material then delivered to rest on the plate 6 between the electrode banks 14. Contaminated liquid is then delivered to the tank and the treatment followed, as described above. When the treatment is complete, the respective tank can be drained and the system removed together with or separate from the adsorbent material on the plate 6.

Figure 4 shows an alternative apparatus according to the invention which is suitable for smaller quantities of contaminated liquid; for example, for experimental use. The elements of the apparatus are essentially similar to those of the apparatus of Figures 1 and 2, but the cross-section of the lower section 26 of the tank 28 is smaller than that of the upper section 30. In the treatment process, the adsorbent material on the plate 6 is fluidized in the same way by delivery of a simple medium through input 10, and when delivery of the fluidizing medium is halted, the adsorbent material is directed back into the lower section 26 by the converging container walls 30.

Additional mixing may be required within the expanded upper zone if it is significantly larger than the lower section and this can be provided by additional agitators.

Figure 5 illustrates another embodiment of the invention in which a multiplicity of electrodes can be closely aligned in a cell in a parallel arrangement.

Application of a voltage across the outer electrodes 28 and 30 polarises the intermediate electrodes 32, so effectively a series of alternate cathodes and anodes are present between the outermost cathode 28 and anode 30. The use of bipolar electrodes in this way facilitates one current to be generated a number of times with a proportional increase in voltage. This has the advantage of increasing the voltage to obtain a larger current in the adsorbent material in sections of the bed between the electrodes than would be achieved by the simple application of a larger voltage across the bed as a whole. The distance between the electrodes can be up to about 25 mm; this is sufficient to allow cell voltage to be kept at an acceptable level, without creating blockages of the adsorbent material, and to allow the released contaminants to escape in the form of bubbles.

In the regeneration zone of apparatus of the invention the cathode will normally be housed in a separate compartment defined by a porous membrane or filter cloth to protect it from direct contact with the adsorbent material. A porous membrane enables a catholyte to be pumped through the compartment, serving both to provide a means for controlling the pH level and as a coolant for removing heat from the regeneration zone.

Apparatus of the invention may contain a single cell, or a plurality of cells. Figure 6 illustrates an arrangement of cells in an adjacent arrangement to one another with equal polarity. Figure 7 shows cells arranged in a continuous line, with opposite polarities in order to prevent unnecessary consumption of current. In each of the arrangements shown in Figures 6 and 7, the respective outermost electrodes must be connected in parallel.

EXAMPLES

1. Neat Oil treatment waste A 25% oil water emulsion was created by mixing oil with water in the presence of an organic polymer to stabilise the emulsion. This was used to make a SOOml solution of 5% oil. This was mixed with 1 OOg of unexpanded intercalated graphite particles as the adsorbent. After mixing for 30 minutes, 1 OOml of sample was removed for analysis and 100 ml of 25% emulsified oil solution added. Between each adsorption cycle the adsorbent was electrochemicaily regenerated. After adsorption cycle 8 a further lOOml sample was removed and 100 ml of 25% emulsified oil added. Table 1 below gives the Total Organic Carbon (TOC) figures before and after adsorption.

TOC Before TOC After Adsorption adsorption Adsorption Cycle (mg/i) (mg/i) 1 15669 4536 2 12380 8669 3 8669 5102 4 5102 2601 2601 1301 6 1301 895 7 895 701 8 701 584 9 7333 1680 1107 1107 11 1107 1125 12 1125 615 13 615 446 14 446 314 314 274 16 274 248 17 248 401 18 401 292 19 292 223 223 212 Table 1 -Treatment of neat oils over a number of adsorption cycles (with electrochemical treatment between cycles) Adsorptive/absorption capacity can be calculated as approximately 60% on a weight for weight basis.

2. Synthetic and semi synthetic cutting oils Two samples of cutting oil solution were made up as 0.1% solutions and then used in the adsorption/regeneration system. Table 2 shows the Chemical Oxygen Demand (COD) data before and after adsorption.

Cutting Oil COD before COD after (mg/i) (mg/I) Synthetic 1,524 0 Semi-synthetic 1,650 0 Table 2 -COD before and after adsorption with electrochemical treatment 3. Adsorption with and without electrochemical treatment In order to demonstrate the effect of electrochemical treatment, a 1 litre emulsified sample of 1% neat oil was mixed with 200g of unexpanded intercalated graphite particles for 30 minutes. After mixing the mixture was allowed to stand and the 750ml of supernatant decanted. 750m1 of fresh emulsified 1% oil was added and the solution was mixed for a further 30 mins. This sequence was repeated.

In one series of experiments the adsorbent was electrochemically treated prior to a second adsorption and in the other there was no eiectrochemical treatment.

Adsorption No Treatment Electrochemical cycle _______________ Treatment 1 100 100 2 0 86.83 3 0 90.99 4 3.33 91.32 ______________ 80.82 Table 3 -Adsorptive capacity compared with fresh adsorbent with and without electrochemical treatment

Claims

CLAIMS1. A method of removing oil contaminants from aqueous liquids comprising contacting the liquid with particles of a carbon-based adsorbent material to form a layer of the oil contaminant on each particle; electrochemically regenerating the adsorbent particles arid recycling the particles in the liquid to form an additional layer of the oil contaminant on each particle; removing the particles and regenerating the particles by electrochemical oxidation.
2. A method according to Claim 1 wherein the particles bearing the oil contaminant layers are allowed to coalesce in the liquid into one or more solid bodies with voids between the particles into which bodies further oily contaminant is absorbed.
3. A method according to Claim 1 or Claim 2 wherein the concentration of oil contaminant in the liquid is reduced by dilution.
4. A method according to Claim 3 wherein the dilution is assisted by adding an emulsifying agent.
5. A method according to Claim 4 wherein the emulsifying agent is organic.
6. A method according to any preceding Claim wherein at least one of the oil contaminant and the aqueous liquid is radioactive.
7. A method according to any preceding Claim wherein the adsorbent material comprises unexpanded intercalated graphite.
8. A method according to any preceding Claims including the steps of: delivering the contaminated liquid to a treatment reservoir containing the adsorbent material particles in the form of a bed of particles at the base of the reservoir; agitating the bed to distribute the adsorbent material particles in the liquid and adsorb contaminant therefrom; ceasing the agitation, and allowing the bed of particles to settle; regenerating the adsorbent by passing an electric current through the bed to release from the adsorbent gaseous products derived from the contaminant in bubbles rising through the liquid in the reservoir; and removing the decontaminated liquid from the tank.
9. A method according to Claim 1 wherein the steps of agitating the bed and allowing it to settle, and of regenerating the adsorbent, are repeated to remove further contaminant from the liquid prior to its removal.
10. A method according to Claim 8 or Claim 9 wherein the bed of adsorbent material is agitated by the delivery of a fluid to the base of the bed of adsorbent.