CA2251923C - Cleansing contaminants from a heterogeneous material using a sorption agent - Google Patents

Cleansing contaminants from a heterogeneous material using a sorption agent Download PDF

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Publication number
CA2251923C
CA2251923C CA002251923A CA2251923A CA2251923C CA 2251923 C CA2251923 C CA 2251923C CA 002251923 A CA002251923 A CA 002251923A CA 2251923 A CA2251923 A CA 2251923A CA 2251923 C CA2251923 C CA 2251923C
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accordance
sorption agent
solvent
oil
mixture
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CA002251923A
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CA2251923A1 (en
Inventor
Oyvind Bones
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Sphagnum AS
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Sphagnum AS
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Priority claimed from NO961511A external-priority patent/NO961511D0/en
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Abstract

There is described a process for cleansing contaminants, such as oil, PCB, PAH, heavy metals and the like, from a heterogeneous material, such as sand, gravel, earth, oil gravel, asphalt, drill borings ("kaks") and the like. More specifically the invention relates to a process comprising the steps: i) that a sorption agent is added to the material, and that the material and the sorption agent are mixed/kneaded sufficiently for a considerable portion of the contamination to be extracted from the material and absorbed by the sorption agent, and that ii) thereafter the sorption agent is separated from the material on the basis of specific gravity/particle size by means of an applied flow of gas, so that the sorption agent is led with the flow and can be collected in a separate fraction.

Description

CLEANSING CONTAMINANTS FROM A IiETEROGENEOUS MATERTAL USING A SORPTION
AGENT
The present invention relates to a process for cleansing contaminants, such as oil, PCB, PAH, heavy metals, lipids and the like from a heterogeneous material, such as sand, gravel, earth, oil gravel, asphalt, drill borings ("kaks"), sewage sludge and the like.
Contamination of dissimilar materials for example in connection with industrial equipment, dump locations or beaches which are contaminated by for example an oil spill, is a well known and increasing problem, and large resources are employed to find solutions to purifying such masses. The solutions must be able to be carried out practically and economically. Several reports describe big environmental problems connected with such contaminated materials. In this connection various hydrocarbon com-pounds are often mentioned such as oil-like compounds, hydrocarbons which either have coupled on chlorine or bromine groups (PCB), or dissimilar types of aromatic com-pounds (PAH). The said compounds are all soluble in non-polar solvents. That is to say they are dissolved slightly in water, and in an association that will be energetically favourable to exclude water. By virtue of the water-re-pelling property these media will readily adhere to solid surfaces, such as stone, gravel and earth. Furthermore
2 water which runs through these materials will not wash away or dilute these hydrophobic solvents.
s A number of locations are mapped where such contaminated materials constitute a significant environmental problem.
In addition to the materials consisting of hydrophobic contaminants they will also consist of various heavy metals, which because of their toxicity also represent an 1o environmental problem.
To-day it is usual to "clean" such dump materials by combusting the contamination of the stone materials. However this is very expensive since the costs of such burning off is related to the weight of the materials and to the combustion s5 value, that is to say how much energy which can be utilised by such a combustion. Materials from industrial sites or dumps consist mainly of stone/gravel, that is to say the weight is high and the combustion value low.
There is therefore a need for alternative solutions.
2o Such a solution is described in WO 97/04623 which relates to a sorption agent comprising the plant family Sphagnum for the sorption of hydrophobic compounds where the sphagnum plant is substantially wholly or partially dried. The publication also describes the application of the plant 25 material for removing hydrophobic compounds from solutions and emulsions, together with it being employed directly on materials which are contaminated with hydrophobic compounds by being rubbed against the material. For example it is mentioned t$at the plant material can be rubbed directly 3o against an oil spill for example in a workshop hall.
However there are other problems which must be solved in order to cleanse contaminants from a heterogeneous material, such as stone and earth. In such materials the oil is an integrated part of the material, that is to say it envelops 35 and sticks together with the dissimilar components of the material so that it becomes a relatively
3 viscous, tacky material. Furthermore the material is formed of particles of relatively small size so that one cannot apply the moss for example to "dry" the particles as one for example can dry off a workshop floor.
The present invention aims therefore to produce a solution for cleansing such materials. When an effective absorptive or adsorptive material is added to a material, and the material and the sorption material are kneaded and tumbled together a certain time, the contaminants will, whether they are hydrophobic compounds or for example heavy metals, be transferred from the material to the sorption agent, assuming that the sorption agent has stronger ad- and/or absorptive properties than the material, and that the compounds are detached from the material by the friction which is created during the kneading/tumbling process, or by means of water/solvents.
Even for an effective sorption agent this will not be added if the contaminants are solidified and very strongly fixed to particles of the material. Also this problem is aimed to be solved with the present invention.
A further problem in the cleaning of such materials is that the material, such as sand, gravel and earth, with respect to the size of the particles constitutes a hetero-geneous mixture, and often comprising a significant pro-portion of smaller particles, right down to a size of only some few microns in diameter. A problem which cannot be solved with the afore-mentioned invention is therefore separating the sorption agent from these in part very small particles. The present invention therefore aims to solve this problem also.
The present invention describes therefore a process for cleaning various types of materials, such as for example fill materials, gravel, earth and the like by removing the dissimilar contaminants, such as hydrophobic contaminants as for example oil, PCB and PAH, and heavy metals from the materials.
4 By the term "material" is designated any type of material, such as fill material, oil gravel, asphalt, drill cake, sewage sludge, gravel, sand, earth and the like.
The term "sorption agent" designates an agent which has absorptive and/or absorptive properties, that is to say properties for absorbing a compound or adhering to the surface, and/or integrated in the structure of the agent.
The term "solid contaminants" designates contaminants which are relatively strongly adhered to the material.
Typically such solid contaminants must be dissolved from the material by applying a non-polar and/or polar solvent.
The present invention describes a process which is characterised by the steps:
c) that a sorption agent is added to the material, and that the material and the sorption agent are mixed/kneaded sufficiently for a considerable portion of the contaminant to be extracted from the material and absorbed by the sorption agent, and that e) the sorption agent is thereafter separated from the material on the basis of specific gravity/particle size by means of an applied gas flow, such as a stream of air, so that the sorption agent is led with the flow and can be collected in a separate fraction.
Further modifications of the invention are evident from the steps:
a) which consists in adding to the material a non-polar solvent, which dissolves "solid" contaminants in the material and makes them soluble in the fluid fraction, and that thereafter the fluid fraction is separated from the material, for example by filtration, decanting, centri-fuging and the like, and b) which consists in adding to the material a polar solvent, such a water, added to one or more detergents, which dissolve "solid" contaminants so that these are made soluble in the fluid fraction, and that thereafter the fluid fraction is separated from the material, for example by filtering, decanting, centrifuging gad the'like and d)' which consists in drying the material for example by applying an air flow, a~/or that the material is: heated.
In one embodiment the above process is characterized in
5 that the kneading/mixing consists in interacting the material and the agent (solvent or sorption agent) in-a rotating drum having a speed and a time period which is adapted to. the contaminated material which is to be cleansed, and the solvent and/or sorption agent which is utilized. The drum may rotate with a speed in the range of 5-100 revolutions per minute, preferably 20-40 revolutions per minute, and that the drum time is (roan 1-600 minutes, preferably 5-20 minutes.
In yet another embodiment the process of the invention may be characterized in that the non-polar solvent can be any _polar liquid solvent, or a mixture of several non-polar , solvents, such as diesel, paraffin, white spirit, alkaaes, alkenes, alkyaes, alcohols, organic acids, aromatic compounds and the like. A mixture~comprising material and non-polar solvent may be heated to a temperature which depends on the boiling point of the solvent, the temperature being chosen to be in the range of 0°C to just below the boiling point of the solvent.
In yet a further embodiment of the present invention the grocers is characterized in that the polar solvent can be preferably any polar liquid solvent, such as water, comprising one or more detergents, such as mixtures like soap, washing agents and the like, or more characterized detergents such as cationic, anionic, zwitterionic or non-polar detergents. The process is further characterized in that the material and solvent may be heated to a temperature in the range of 0-98°C, preferably in the range of 30-50°C.
In yet a further embodiment of the present invention the above process may be characterized in that the sorption agent comprises.chemical and/or biological agents, a sorption agent having a specific gravity which is sufficiently leas than the specific gravity of the material so that the sorption agent including the contaminant can be blown off, and is separated 5a from the material, with a flow of gas, and that the strength of the gas flow can be adjusted and adapted according to the agent and the properties of the material so that an effective separation is achieved. Furthermore the sorption agent may be biologically degradable and/or combustible and may also comprise bark, moss or peat which is in advance partially dried.
In yet a further embodiment of the present invention the process may be characterized in that the sorption agent comprises Sphagnum plants and/or peat. The sorption agent of the present invention may be processed so that it consists of particles having a size in the range of 0-20 mm, preferably 0.1-0.5 mm.
A preferred embodiment is therefore to mix together the sorption agent and a contaminated material so that the contaminants are transferred to the sorption agent.
Preferably this is carried out in a rotating drum. For the mixing/kneading to be effective it is an advantage, but not a necessity, that the drum is equipped with a number of blades, so that the material and the agent are thoroughly mixed. When a sufficient quantity of the contaminant is transferred to the sorption agent these two fractions must be separated from each other. According to the invention this is carried out by blowing a current of air through the mixture. One way this can be carried out is that the drum with blades rotate during the blowing operation. The blades will then lift the material so that separation is made more efficient. Alternatively the current of air can for example be blown directly through the mixture. The strength of the air current is adapted to the two fractions which are to be separated.
Various types of sorption agents, such as chemical or biological, can be utilised. A preferred solution is to employ bark, peat or moss since these are materials which have a low specific gravity, and are both combustible and biologically degradable. The greater the difference is between the specific gravity of the particles in the 5b material and the specific gravity of the garticl,e~ of the sorption agent, the more effective is the separation pro-cess, that is to say the smaller the strength of the air flow that is required for blowing off the sorption agent, and the smaller the proportion of the smallest particles in the material that will be transferred to the sorption agent fraction. In addition to specific gravity the par-ticle size is an important parameter in the separation
6 process, and it has been found that if the sorption agent particles are of small size so the separation is more effective. If the sorption agent is for example moss so it will be more favourable to cut this up into small par-titles.
In addition to the direct mixing of material with sorption agent it will be favourable in a number of cases to add a solvent to the material to dissolve and remove a portion of the contaminants before the sorption agent is added. Both non-polar and/or polar solvents can be utilised, and the sequence is determined from the type of contaminant which is to be cleansed from the material.
When the solvent has taken effect for a time on the material, generally during the tumbling/kneading where length depends on the type of contaminant and solvent, the fluid fraction is separated from the solid particles with filtering, centrifuging, decanting or in another manner.
In order to increase the solubility of the cont-aminants it is often favourable to heat the mixture of 20. material and solvent. This is tarried out in a known manner, not indicated further.
After the material is treated with solvent, one or more times, so the sorption agent is added. The mixture is kneaded/tumbled so that the sorption agent absorbs the contaminant, and possibly residues of solvent. Thereafter it can be favourable to reduce the moisture content of the sorption agent before the separation process starts. This can be carried out either by air drying, for example by blowing an air current into the mixture, or by heating the mixture, for example due to the drum being equipped with a heating element, possibly a combination of these methods.
The cleansing process according to the invention is specified in some illustrating examples.
Example 1 7962 grams of a black, viscous and sticky oil gravel, consisting of particles of an order of magnitude of 5 - 50
7 mm are kneaded/mixed in a drum (about 150 litres) together with 1952 grams of diesel oil. The type of oil gravel which is used includes about 10 weight per cent of oil. The object is s to remove the oil from the stone/gravel particles. The material and diesel are tumbled together for 5 minutes at a speed of 27 revolutions per minute. The fluid fraction (1598 grams) is strained off (run off time 3 minutes). Thereafter a water solution consisting of 102 grams washing agent/detergent so (ZaloTM) and 985 grams of water is added. The mixture is tumbled for 5 minutes, and the water fraction (1152 grams) is strained from the gravel fraction (run off time 3 minutes).
In these two steps large portions of the oil are now removed. However the gravel particles are coated with a film s5 consisting of detergent/oil/water. If this mixture is dried by evaporating the water the oil will continue to remain as a film on the gravel particles, and thus the problem will not be satisfactorily solved.
To this mixture (detergent/oil gravel/water), where 2o the amount of water is now 1265 grams there is added 1109 grams, dried Sphagnum moss. The moss is cut up and consists of particles having a size in the range of 0.1 - 10 mm. The mixture is tumbled for 15 minutes. Thereafter the moss is blown away, that is to say separated from the gravel fraction 25 with an applied current of air, and a visual characterization of the gravel particles shows that nearly all the oil has gone. Residues of the oil cannot be seen on the gravel particles.
Example 2 3o Ditch gravel (10026 grams), which is gravel/sand particles having a size in the range of 0.1 - 10 mm, and a moisture content of about 10%, is added to Troll - crude oil (956 grams). To this mixture of oil and gravel is added Sphagnum moss (735 grams) in particulate form (0.1 - 10 mm).
35 The mixture is tumbled for 15 minutes. The moss particles are blown off, and the gravel fraction appears
8 completely clean, free from oil and moss, while the moss fraction is free of gravel particles. However there is a slight odour of oil from the gravel particle fraction.
Example 3 Ditch gravel (10832 grams), of the same type as above, is added to Trolls crude oil (699 grams). To this mixture there is added a mixture of water (1056 grams) and washing agent, of the Zalo type, (101 grams). The mixture is so mixed/kneaded in a rotating drum for 10 minutes. Thereafter the water is removed. Run off 5 minutes. To the mixture is added 684 grams moss; and it is tumbled for 10 minutes. The moss fraction is blown off. The gravel mixture appears completely clean, and no odour of oil is observed from this i5 fraction now. The moss is free of gravel particles.
In relation to Example 2 the extra washing step which is introduced has caused the moss to become somewhat cleaner. The reason for this is that the detergent/water mixture which is employed dissolves, that is to say makes water- soluble, the 20 oil fraction which is most strongly adhered to the gravel particles.
Example 4 Brown earth (11312 grams) having a particle size in 25 the range of from 0.1 - 10 mm, and having a moisture content of about 15o is added to Troll' - crude oil (953 grams). To this mixture is added 794 grams moss in particulate form.
There is tumbling for 20 minutes, after which the moss is blown off. The earth fraction appears completely clean, only 3o a slight odour of oil, and consists of spherical particles (0.2 - 1 cm). The moss fraction does not contain earth particles.
The Example with earth is conducted in order to illustrate how for example sewage sludge can be treated in 35 order to cleanse this for example of heavy metals. The Examples show that a process in accordance with the
9 present invention can clean a material which is cont-aminated by various types of compounds. Very often such materials consist however of various oil-like compounds, and the Examples are therefore carried out by utilising oil. By a visual characterization it is assumed that the gravel/earth fractions include less than 0.1% oil, that is to say that more than 99% of the oil is removed. By a correct adaptation of the air pressure during the separation the moss fraction is not contaminated by stone/earth particles.
There is in progress now a chemical characterization of the various fractions. The effect which is achieved with the method is very surprising, and makes a parti-cularly important contribution to the possibility of taking care of the environment in a better manner by effectively clearing it of contaminated materials.
Dried Sphagnum moss is a material of very low specific gravity, and relative to stone/gravel the speci-fic gravity of the moss is considerably less. Even after the moss has absorbed the oil contamination the specific gravity is considerably lower than for stone/gravel. This fact is employed in order to separate the oil-containing moss from the gravel particles.
Since the quantity of water in the sorption agent will be reduced during drying an effect is obtained pro-portionate to composting and/or combustion of the sorption agent in that the weight of the contaminant-containing fraction is reduced. Costs of composting and combustion are related to the weight of material. In addition the costs are related to the combustion value of the material, and this will also increase as the moisture content of the material is reduced.
By utilising the separation technique according to the present invention the gravel fraction which is left in the drum after the cleaning process will be nearly completely clean, both with respect to oil, diesel, water and sorbent. The sorbent has correspondingly absorbed nearly all the oil, the diesel and the water, except that this fraction is not significantly contaminated with gravel particles to a particular degree.
In this way there are two fractions which can be 5 treated in a dissimilar manner. The gravel fraction can be employed as if it were free of contamination. The moss fraction can be either composted or burned. The big gain lies in the contamination being transferred to a much lighter fraction, which can be processed much more simply,
10 cheaply and better than the contaminated gravel fraction.
The process according to the invention will also be able to be employed for cleansing heavy metals and oil from the gravel fractions in drill borings ("kaks"). Drill borings is a collective term for the fraction which is taken up in the boring of new bore holes and consists largely of stone/gravel particles released in a fraction of drill sludge. The sludge is separated from the borings by known methods, but the problem is that the borings include a coating of oil-type compounds and heavy metals.
By mixing these drill borings with a sorption agent and by using the process according to the invention these cont-aminants can be removed from the borings. On cleansing bore drillings the process can also include the step (b) so that the heavy metals are dissolved in a watery fraction, in order thereafter to be absorbed by the sor-bent together with the water. Thereafter the water is dried off by heating/air flow so that the heavy metals are concentrated in the sorbent. In this way the heavy metals and the oil compounds are separated from the borings, and cleansing of such borings is therefore comprised by the scope and idea of the invention.

Claims (17)

The embodiments of the invention for which an exclusive property or privilege is claimed are defined as follows:
1. A process for cleansing contaminants from a heterogeneous material characterised in that the process comprises the steps:
c) that a sorption agent comprising sphagnum plants is added to the material, and that the material and sorption agent are mixed sufficiently for a considerable portion of the contaminant to be extracted from the material and absorbed by the sorption agent, and that e) the sorption agent is thereafter separated from the material on the basis of specific gravity and particle size by means of an applied gas flow so that the sorption agent is led with the flow and can be collected in a separate fraction.
2. The process in accordance with claim 1, characterised in that the process further comprises a step (a) which is carried out before the steps (c) and (e), in which:
(a) consists in adding to the material a non-polar solvent, which dissolves solid contaminants in the material and makes the solid contaminants soluble in a fluid fraction, and that the fluid fraction is thereafter separated from the material.
3. The process in accordance with claim 2, characterised in that the process further comprises that the mixture of material and added solvent is heated so as to increase the solubility of the solid contaminants.
4. The process in accordance with claim 1, characterised in that the process further comprises, before the steps (c) and (e), a step (b), in which:
(b) consists in adding to the material a polar solvent, such as water, preferably comprising one or more detergents , which dissolve solid contaminants so that the solid contaminants become soluble in a fluid fraction, and the fluid fraction is thereafter separated from the material.
5. The process in accordance with claim 4, characterised in that the process further comprises that the mixture of material and added solvent is heated so as to increase the solubility of the solid contaminants.
6. The process in accordance with claim 1, characterised in that the process comprises the steps (a), (b), (c) and (e), where the sequence of the steps (a) and (e) is arbitrary.
7. The process in accordance with claim 6, characterised in that the mixture of material and added solvent in one of the steps (a), (b), or both, is heated so as to increase the solubility of solid contaminants.
8. The process in accordance with one of the claims 1 -7, characterised in that the process further comprises, after the steps (a), (b) and (c), but before the step (e), a step (d), in which:
(d) consists in drying the material and the sorption agent for example by applying a stream of air, or that the material is heated.
9. The process in accordance with one of the claims 1 -8, characterised in that the mixing consists in interacting the material and the agent (solvent or sorption agent) in a rotating drum having a speed and a time period which is adapted to the contaminated material which is to be cleansed, and the solvent or sorption agent which is utilised.
10. The process in accordance with claim 9, characterised in that the drum rotates with a speed in the range of 5 - 100 revolutions per minute, preferably 20 - 40 revolutions per minute, and that the drum time is from 1 -600 minutes, preferably 5 - 20 minutes.
11. The process in accordance with one of the claims 1 characterised in that the non-polar solvent can be any non-polar liquid solvent, or a mixture of several non-polar solvents, selected from the group consisting of diesel, paraffin, white spirit, alkanes, alkenes, alkynes, alcohols, organic acids and aromatic compounds.
12. The process in accordance with claim 11, characterised in that the mixture comprising material and non-polar solvent is heated to a temperature which depends on the boiling point of the solvent, the temperature being chosen to be in the range of 0°C to just below the boiling point of the solvent.
13. The process in accordance with one of the claims 1 - 8, characterised in that the polar solvent comprises water and a detergent selected from the group of conventional washing agents, cationic detergents, anionic detergents, zwitterionic detergents and non-polar detergents.
14. The process in accordance with claim 13, characterised in that the material and solvent are heated to a temperature in the range of 0 - 98°C, preferably in the range 30 - 50°C.
15. The process in accordance with claim 1, characterised in that the contaminants are selected from the group consisting of oil, PCB, PAH, heavy metals and lipids.
16. The process in accordance with claim 1, characterised in that the heterogeneous material is selected from the group consisting of sand, gravel, earth, oil gavel, asphalt, drill borings and sewage
17. The process in accordance with claim 1, characterized in that the applied gas flow is a stream of air.
CA002251923A 1996-04-17 1997-04-16 Cleansing contaminants from a heterogeneous material using a sorption agent Expired - Fee Related CA2251923C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NO961511A NO961511D0 (en) 1996-04-17 1996-04-17 Contaminated pulp cleaning method
NO961511 1996-04-17
PCT/NO1997/000099 WO1997038805A1 (en) 1996-04-17 1997-04-16 Cleansing contaminants from a heterogeneous material using a sorption agent

Publications (2)

Publication Number Publication Date
CA2251923A1 CA2251923A1 (en) 1997-10-23
CA2251923C true CA2251923C (en) 2006-07-04

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CA002251923A Expired - Fee Related CA2251923C (en) 1996-04-17 1997-04-16 Cleansing contaminants from a heterogeneous material using a sorption agent

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