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Chemistry for Sustainable Development 13 (2005) 359375 359

Materials for Adsorption Purification of Water

from Petroleum and Oil Products


Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences,

Prospekt Akademicheskiy 3, Tomsk 634021 (Russia)

E-mail: novoselova@i

(Received June 15, 2004; in revised form November 17, 2004)

The most interesting results among those described in literature on the development and application of
the materials for adsorption purification of water from petroleum and oil products are considered and
generalized. Sorbents used both for elimin ation of oil outflow and for purification of oil-containing waste
water are considered. Natural (plant- and mineral based), artificial and synthetic sorbents are described.
Fibrous (non-woven, in the form of chaotically positions fibres, wool, pressed, etc.) materials are considered
along with those used in the dispersed or granulated form. It is stressed that combin ation of materials
differing both in origin and in the state of aggregation, with addition al modifications if necessary (for the
purpose of enhancing the actual properties or imparting new characteristics) leads to a multi ple increase in
the efficiency of purification process.

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
2. Adsorbents for elimination of outflow of petroleum and oil products . . . . . . . . . . . . . . . 361
2.1. Materials used in dispersed and granulated form . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
2.2. Fibrous materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
3. Materials for purification of oil-containing waste water . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
3.1. Purification of oil-containing waste water with the help of filters made of
n atural and artificial materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
3.2. Purification of oil-containing waste water with the help of combined filters . . . . . 371
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373

1. INTRODUCTION As we have already noted above, physical

(mechanical, radioactive, light, noise,
At present, a global problem of preventing electromagnetic, and thermal), biological
environmental degradation during the development (biotic, micro- and macrobiological) and
of natural resources and transformation of natural chemical kinds of pollution of the biosphere
systems is urgent. Pollution is deterioration of the can be distinguished. Classification of chemical
quality of environment, both due to admission pollutants of water depending on the degree
of extrinsic chemical or biological agents and due and features of the action of chemicals on the
to the physical action. With reasonable nature living environments looks as follows:
man agement, environmental pollution is not biologically unstable organic compounds;
heavy; it recovers its quality due to natural self- low-toxic inorganic salts;
regulation and self-purification (passive biogenic compounds;
purification). In the case of non-reason able substances with specific toxic properties,
management, the environment itself is unable to including heavy metals, biologically strict
cope with pollution; active purification is required. (indecomposable) organic synthetic compounds;

oil products, etc. [15]. A decrease in the concentration of

Petroleum and oil products (OP) comprise a petroleum and OP in water due to self-
special group of pollutants of the hydrosphere. purification occurs as a result of their n atural
Water gets polluted with OP during petroleum decomposition, chemical oxidation, evaporation
production, transportation and processing, of low-boiling fractions and biological
when OP are used as a fuel for marine engines, destruction by microorganisms living in water.
when tanks pf oil-tankers are washed, when As we have already stressed, these processes
water flows from OP-polluted lands, etc. [3, 6 are characterized by low rate, which depends
10, 73]. Among the total amount of OP getting mainly on environmental temperature. For
into seas and oceans annually, losses from oil instance, a decrease in oil mass in a film within
transportation account for about 35 %, about the first days after its formation occurs mainly
32 % is brought out by rivers, urban and due to evaporation: within the first three days,
industrial wastes account for 10 %, and the same the loss reaches about 25 % for water
amount comes from the atmosphere and from temperature 2227 oC and 12 % for 25 oC
natural sources [2, p. 19]. (Fig. 1) [13].
The solubility of oil in water is insignificant, At present, various methods are used to
so OP get accumulated first of all on the surface purify water from petroleum and oil products:
and at the bottom of water reservoirs [15, mechanical, physicochemical, chemical,
11]. In the case when the oil film is more than biochemical. Among physicochemical methods,
0.1 mm thick, both oxygen penetration into the absorption is the most interesting procedure;
water and removal of carbon dioxide from it is very efficient and can ensure purification
water slow down. The effect of OP on living to any required level in the case of multi-step
organisms is exhibited as disorders of arrangement of the process. Sorbents may be
physiological activity, diseases caused by either n atural, based on plants or minerals
penetration of hydrocarbons into organisms, (cotton, turf, peat-moss, sawdust, wood
changes in the biological features of shavings, wood flour, hemp, straw, clay,
environment, etc. Water microorganisms pearlite, etc.), or artificial or synthetic materials
gradually destroy oil products but this process based on viscose, hydrated cellulose, synthetic
is slow. Accumulation of oil sediments on the fibres, thermoplastic materials, polyurethane
bottom of water bodies may bring about foam, etc. In order to render hydrophobic
an aerobic conditions and become the source of properties to sorbents, many substances are
secondary pollution of the hydrosphere. used: paraffin, silicon or petroleum oil,
monoalkyl ethers of polyethylene glycol, high-
molecular compounds, etc. The materials are
treated with hydrophobizing agents by
immersing the former into the solutions or melt
of the latter, by spraying over the surface
followed by hardening, etc. A hydrophobizing
agent itself should possess good adhesion to the
material, get uniformly distributed coating the
material completely, be non-washable during
performance and insoluble in OP. The maximal
effect may be achieved by choosing such a
hydrophobizing agent, which would allow one
to exclude the addition of an active substance
providing an increase in oil capacity of the
resulting material.
An adsorbent based on straw treated with
Fig. 1. Changes in the mass of the oil film (M) on water polymers (polyethylene, polypropylene,
surface (13) and at the bottom (46) depending on water polystyrene, polyvinyl chloride, etc.) was
temperature [13], oC: 25 (1, 6), 1015 (2, 5), 2227 (3, 4). proposed for purification of water surface from

petroleum about 25 years ago. The sorbent was both for oil outflow elimin ation and for
manufactured in the form of a mattress; purification of petroleum-containing waste
treatment was carried out either by immersing water (PCW) from oil-mining and oil-processing
straw into the solution of a polymer or by plants, petroleum storage depots, refueling
spraying it over the material [14]. However, this stations, car wash, etc.
sorbent could not be recovered, possessed rather
low adsorption capacity, and was rather difficult
Modern materials are more up-to-date and
technologically reason able. For example, a
Outflow in oil mining (oil blowout at the
method was proposed to purify water from OP
Bravo drilling platform in the North Sea, at
by introducing adsorbents into a layer of OP
the underwater well Istok-1 in Mexico, etc.) and
[15]. Porous materials based on schungite,
during transportation of petroleum and OP
tri poli, pearlite, diatomite, calf (with particle
with the help of oil-pi pe lines, means of river,
size not more than 500 m) and a thermoplastic
sea and trucking delivery services, etc. (pi peline
hydrophobic polymer (with particle size not
breaking in the Persian Gulf, in Louisiana, at
more than 300 m) with the mineral : polymer
the Usinskoye oil field; tanker wreck near the
mass ratio of 100 : (25130) are used as
shores of France in 1999 when more than
adsorbents. The mixture is subjected to thermal
10 000 t of crude oil and the products of its
treatment at a temperature of the melt off
processing got into the sea [11], etc.) causes
the thermoplastic polymer for 540 min. Low-
large-scale losses of the valuable raw material
or high-pressure polyethylene, wastes of
(from several tons to tens thousand tons) and
polyethylene, polystyrene, and polyvinyl
at the same time very dangerous environmental
chloride in the form of powder. After thermal
pollution [16].
treatment, a sorbent is formed into different
The strategy of measures against oil outflow
shapes: discs 515 mm thick with the diameter
events includes localization of the oil patch,
of 1501000 mm; cylinders with the external
collection of the major part of oil spoiled over
diameter of 1501000 mm, length of 2501000
the water surface, and elimin ation of the
mm and wall thickness of 515 mm; a
residual film [16, 17].
continuous ribbon 501000 mm wide and 1.5
In order to localize an oil patch on water
2.0 mm thick. The sorbent ribbon is duplicated
surface and at the same time to absorb spoiled
on one side with a non-woven fabric of the
OP, and in order to remove continuous layers
same width not more than 1 mm thick at a
temperature equal to the melting temperature of OP up to several millimeters thick in small
of the polymer of non-woven fabric. A disc, a water areas, sorbents encapsulated in permeable
cylinder or a ribbon is placed into water polluted shells are often used in the form of harbour
with OP and rotated at a frequency of booms of different design and kinds [18, 19].
1120 rpm. Adsorbed products are continuously Adsorbents are used in different
taken off with knives, brushes or by suction. arrangements to collect spoiled oil and OP. In
This method also involves shaping of the the disperse or granulated form in thin layer,
sorbent as plates of various configuration which adsorbents are mainly used to elimin ate
are immersed into water to be purified and kept separate spots of products on water surface.
there for a time interval necessary for OP In order to remove continuous layers of spoiled
removal to the level of MPC equal to 0.05 mg/l. OP up to several centimeters thick from a small
Recovery is carried out by centrifuging [15]. water area, sorbents made in the form of mats
In the present work we have made an are most frequently used. The use of sorbents
attempt to generalize and an alyze some data in the form of n apkins excludes some
reported in literature on the development and densification of the material, which sometimes
application of materials for adsorption occurs with mat formation and causes a slight
purification of water from petroleum and oil decrease in capacity. In mechanical oil-spill
products. We consider sorbents that can be used boats, sorbents are used in the form of

multilayer units, absorbing shells, etc.; this water areas from OP and to treat oil-containing
provides collection of OP from water surface, water. The material is cheap, technologically
removal of OP from the absorbing material, favourable (filters have a simple design, it is
followed by their export into a collector. The easy to deposit the sorbent onto water surface
above-listed materials for elimin ation of oil and to collect it after sorption) and exhibits
outflow (mats, n apkins, booms, absorbing increased sorption capacity, which is about 8 g/g.
shells, etc.) are manufactured on the basis of In addition, pearlite modified by OSC, after
disperse, granulated and fibrous sorbents working in a filter in the dynamic mode, can
considered in detail below. be used to collect floating oil.
Some synthetic materials, for example
polyurethane foam, absorb petroleum and OP
2.1. Materials used in the disperse in the amount 20 times as large as their own
a nd gra nulated form mass. Such foam plastic can absorb a layer of
petroleum up to 10 mm thick from water
As we have already mentioned, among
surface and decrease the oil content of water
natural sorbents, most frequently used ones are
from 40006000 to 1014 mg/l [13].
turf, bog moss, sawdust, wood chi ppings, etc.
In addition, sorbents based on polyurethane
For instance, 1 kg of bog moss absorbs 8.5 kg
foam allow one to solve the problem of oil
of transformer oil, 9.8 kg of crude oil and
collection with simultaneous prevention of its
12.9 kg of petrol [13].
spread over water. For this purpose, the foam
Artificial sorbents based on natural pearlites,
plastic is obtained directly on water surface by
vermiculite, zeolites, aleurite, silica, silicates,
mixing the components prelimin arily. For
scoria and so on are widely used. Thus, an
example, after mixing polyester, carbamide
adsorbent of interest to collect oil from water is
that based on circulite; the specialists from the solution and toluylenediisocyanate at a bank or
Kiev Polytechnical Institute and Institute of on board the shi p, followed by discharge of the
Colloid Chemistry and Water Chemistry, National resulting mixture to an oil spot on water surface,
Academy of Sciences of the Ukraine, developed foam plastic is formed which prevents oil from
the technology of obtaining this sorbent. The spreading and at the same time absorbs it. Such
sorption capacity of this kind of pearlite is mote a foam plastic may be recovered by mechanical
than 800 % of its own mass and is maximal for streak or by washing with solvent and used many
the fraction size of 0.20.4 mm [13]. times as usual petroleum sorbent [16].
Modification of circulite by organosilicon It was also proposed to use plastic plamilon
compounds (OSC) causes its hydrophobization micro-containers developed at BashNIPIneft as
and an increase in the efficiency of collecting the sorbing material. Plamilons are obtained by
the floating oil (oil capacity increases by a factor spraying a mixture of synthetic thermoreactive
of 34). Another advantage of pearlite modified resin, gas forming agent and a solidifying agent
by OSC in comparison with circulite is the in drying chambers. These materials are
possibility to use the former both to purify open recommended for use when it is necessary to

Parameters of the purification of water surface from petroleum with the help of microballoons with a size of 1 1054 104 m [13]

Resin Sorbent Thickness of petroleum Specific consumption Purification degree, %

for microballoons density, g/cm3 film, mm of microballoons, g/g
Bakelite V 0.150.25 1.5 0.770 92
0.150.25 1.0 0.052 97
0.150.25 0.5 0.040 97
FRV-1A 0.120.20 1.5 0.128 86
0.120.20 1.0 0.095 90
0.120.20 0.5 0.056 91

TABLE 2 These adsorbents are often based on natural

Parameters of the purification of water surface FB, either plant-based (cotton, flax, hemp) or
from petroleum with the help of various materials mineral ones (asbestos, etc.) [18, 20, 21, 2428].
There are sorbents composed of a fibrous
Material Oil capacity, g/g
cellulose material in the form of technological
Bog moss 9.8
wool or wastes of textile works (9397 mass %)
Circulite 8.0
treated with the oxidized ataxic polypropylene
Polyurethane foam 20.0
(OAPP) (37 mass %) [20] or a block copolymer
of butadiene and 1050 % styrene (210
a) based on Bakelite V mass %) [21]. The advantages of these materials
for film thickness, mm: are high sorption capacity with respect to oil
1.0 19.2 (up to 30 g/g) and the ability to survive many
0.5 25.0 recovery cycles, which ensures multi ple use of
b) based on FRV-1A these materials. A shortcoming is the trend to
for film thickness, mm: be prone to microbiolgocial decomposition when
1.5 7.8 stored and used in filters.
1.0 10.5 A sorbent has been proposed which
0.5 17.9 incorporates a fibrous support (93.099.5
mass %), an active organic susbtance (0.45.0
mass %) and a hydrophobic component, in
particular polybutadiene (0.12.0 %) [22, 23]. The
remove petroleum film 0.51.5 mm thick from active substance is a mixture of fractions of
water surface (Table 1) [13]. alkyl carboxylic compounds 1016, 1720,
Comparison of the characteristics of above- 20 25 taken in the ratio of 1 : 3 : 3.
listed sorbents shows that the highest capacity Disadvantages of this material are rather low
with respect to petroleum is exhibited by capacity and the presence of such an expensive
polyurethane foam and micro-containers based and scarce component as alkyl carboxylic acids.
on Bakelite B (Table 2). However, as we have A sorbent has been developed which is
already mentioned, the latter are efficient in obtained by modifying n atural cellulose fibrous
removing oil films not thicker than 1.5 mm. In materials with 1,2-polydienes based on the
addition, similarly to the majority of synthetic monomers with 45 carbon atoms in the
materials, both materials are toxic (especially molecular chain, in syndiotactic form (molecular
in the case of fire), which limits their mass: 100 000300 000) taken in the amount
application. The main advantages of n atural of 0.51.0 mass % [24]. This material is
adsorbents are availability, cheapness, characterized by highly hydrophobic character,
sufficient raw resources, non-toxic character, high sorption capacity, floatation, and admits
etc.; for practical application, these advantages more than 10 recovery cycles (Table 3).
compensate somewhat lower oil capacity. Cellulose was treated with a 33 % aqueous
emulsion of polybutadienes at room temperature
2.2. Fibrous materials and dried to the constant mass. It was established
that when the amount of polybutadienes used
Fibrous materials (FM) are highly efficient for modification is less than 0.5 %, the sorbent
against oil outflow when they are used to collect is characterized by negative floatation, while for
oil and OP from water surface. It is most this amount larger than 1.0 % the sorbent
promising to use various FM (hydrophobized, requires elevated expenses for production and
addition ally treated with an active substance) exhibits lower oil-sorbing capacity. The sorption
in the form of mats, multilayer units, etc. [16 capacity of the proposed material (with respect
18, 2730]. These sorbents may be used many to the commercial mixture of West Siberian
times; they may be recovered at the site by petroleum) is 20.0 g/g [24].
mechanical streak, by treating with solvelnts, Cellulose may be hydrophobized also with
live stream, etc. the help of insoluble aluminium soap by

Results of test of sorbent [24]

Concentration of polydienes, Sorption capacity with respect to Time of full Floatation

mass % petroleum, g/g sorption, s
0.4 23 150
0.5 23 150 +
0.8 20 150 +
1.0 16 120 +
1.3 2 120 +

preci pitating it form the aqueous solution in of spinning are used to manufacture this
the amount of 115 % of cellulose mass using sorbent) shaped as mats with a thin layer of
a water-soluble aluminium salt in equimolar machine or transformer oil sprayed onto their
amount with the sodium soap [25]. outer surface [27]. A layer of cotton-containing
In order to reduce the cost of production sorbent is fixed in a mat between the layers of
of highly efficient fibrous adsorbents for cotton or synthetic sparse cloth or a cotton net.
petroleum and OP collection from water surface The distance between threads in the cloth or
and at the same time to solve the problem of mesh size in the net fixing the sorbent in a mat
efficient utilization of large-scale wastes formed is less than the particle size of cotton-containing
in flax raw processing, the authors of [26] sorbent. The length and width of the mat are
developed adsorbents based on the wastes of 0.51.0 m, the ratio of its thickness to the
flax production. Prelimin ary cottonizing thickness of spoiled petroleum or OP layer is
followed by hydrophobization with OAPP (0.5 : 1.0)(1 : 1).
allowed obtaining sorbents with the capacity On the basis of one of the waste products
with respect to petroleum 1114 g/g, while the of cotton-processing plants, SINTAPEKS
initial material itself possessed oil capacity of sorbent was developed. It is close to sheet
45 g/g. wadding and sintepon in its oil absorbing
Purification of water surface from capacity but it is cheaper [18]. The absorbing
petroleum and OP is possible also with the help capacity of this material towards a broad range
of a cotton-containing sorbent (cotton wastes of OP (from petrol to various kinds of oil) is

Oil capacity of some materials based on cellulose, treated with various hydrophobizing agents

Material Hydrophobizing agent Oil capacity, g/g Ref.

material* OAPP 30 [20]
Block copolymer
of butadiene and styrene [21]
1,2-Polydienes 23 [24]
aluminium soap [25]
or transformer oil [27]
1015 [18]
Flax OAPP 45 [26]
Flax** OAPP 1114 [26]

*In the form of sheet wadding, technical wool or wastes from textile plant.
**Prelimin ary cottonizing of the material.

520 g/g. After collecting OP, the sorbent can solvent and an ali phatic ester of carboxylic
easily be squeezed and can be used many times. acids; then it is dried. Feltproofing elements
The SINTAPEKS sorbent can be used to made of basalt cloth are set onto the dried
remove oil outflow not only in the form of mats layer, then again a layer of impregn ated
but also in the disperse form in a thin layer, as basaltic cloth and fin ally a layer of reinforcing
cylindrical booms, as well as in mechanized oil- elements made of basaltic cloth. For strength,
spill boats providing sorption, extraction and the layers are stitched. Plaits or ribbons made
petroleum withdrawal into a collector. of basalt cloth with the specific surface of 500
An alysis of the data shown in Table 4 700 m 2 /g are imposed on the resulting
indicates that all the materials based on cellulose multilayer cloth (the number of layers depends
exhibit high oil capacity. In this row, a minimal on the required characteristics). The multilayer
(45 g/g) capacity of flax-based sorbent is likely sorbent is cut into charts or stri pes. Purification
to be due to an increased size of flax fibres as of surfaces from petroleum and OP within one
the roughest material. An increase in the capacity working cycle sorption desorption includes
of the flax sorbent can be achieved by contacting with the sorbent (preferably in a
preliminary cottonizing of the raw material [26]. separator), sorbent recovery with live steam,
An increase in the ability of a sorbing addition al introduction of the active substance
material to be used repeatedly in cycles and hydrophobizing agent (about 0.71.4
(especially for collecting stiff petroleum) is mass %) [28]. Disadvantages of this method
ensured when a multilayer sorbent is used [28], include complicated obtaining technology and
which is a material composed of basaltic fibres increased consumption of the modifying agents
impregn ated with an active substance and with (the hydrophobizing agent and active substance)
a hydrophobizing agent; it is equi pped with due to partial washout during operation.
reinforcing, feltproofing, thermo- and steam- At present, increasingly wide application for
resistant elements made of basalt cloth. The adsorption purification of water from petroleum
application of this material ensures many cycles and OP has been won by synthetic fibrous
of purification process (the number of cycles materials [3035].
reaches 20004000 for one sample), high For instance, a material based on
sorption rate (the characteristic sorption time thermoplastic polymer [31] with chaotically
is 1020 s), high oil capacity and mechanical positioned fibres 520 m in diameter with the
strength of the sorbent (the limit may be due density of 0.010.20 g/cm3 is known. Liquids
to a decrease in the strength of basaltic fibres are soaked and retained in this sorbent due to
due to fatigue processes). capillaries formed by the fibres twisted in balls
The sorbent is composed of altern ating and plaits; the content of these capillaries in
layers of the fibrous basis made of basaltic the material reaches 60 %.
fibres 0.22 m in diameter with the specific A sorbent composed of nonwoven fabric was
surface of 7001400 m2/kg (7093 mass %). proposed; the sorbent is impregn ated with a
These layers are impregn ated with the active mixture of alkyl carboxylic acid fractions from
substance belonging to the class of alkyl C9 to C27 and with ali phatic esters of alkyl
carboxylic acids (15 %) and a hydrophobizing carboxylic acids, reinforced with the elements
agent which is an ali phatic ester if alkyl made of polyethylene threads in epoxy resin
carboxylic acids (15 %), then feltproofing or thermofibre in thermoplastic polymers; the
elements made of basalt cloth with the specific sorbent is equi pped with feltproofing elements
surface of 200300 m2/kg (35 %) are imposed; made of glass fibre [29]. The capacity of this
finally, thermo- and steam-proof elements are sorbent is about 4246 kg/kg, number of
placed at the outer side of the sorbent. operation cycles is 2336, and a decrease in
The procedure of sorbent obtaining includes capacity per cycle is 25 %.
several stages. The basaltic fibre with the A material for petroleum and OP sorption
specific surface of 7001400 m2/g) is merged was developed which is a nonmoven fabric
for 1.01.5 h into a solution containing a mixture made of hydrophobic and/or hydrophobized
of alkyl carboxylic acids C 9C27 in organic polymeric fibres attached to each other (the

bulk density 0.010.06 g/cm3) [30]. The sites of

attachment are coated with the fastening
hydrophobizing polymeric film made of
synthetic latex. The content of the polymeric
film counted for the dry residue is about 3 to
15 % of the fibre mass. The ratio of
hydrophobic to hydrophobized fibres in the
material varies depending on operation
conditions (negative or positive temperature
range). The polymeric cloth may also have
crimped structure and reinforcing net.
Disadvantages of this material include
complicated manufacture method and not very
high capacity.
Fig. 2. Sorption capacity (Vg) of polymeric fibre made of
Fibrous sorbents obtained from waste
thermoplastic wastes, with respect to petroleum in the
thermoplastics (polyethylenepolypropylene blotting regime for multi ple cycles (n) of saturation
single-use syringes and plastic bottles made of (sorptionrecovery) [35]: 1 fibre made of the worked
polyethylene terephthalate) [3234] were tested out medical single-use syringes (polypropylene); 2 made
of the used bottles (polyethylene terephthalate); 3 hybrid
with petroleum from the Grushevoe deposit of fibre made of polyethylene and polypropylene wastes
West Siberian region, industrial oil I-20A, (worked out bodies and rods of single-use medical syringes).
summer diesel oil and AI-92 petrol [35]. In the
dynamic mode of determin ation of the sorption
capacity, the performance of filtering load of should be noted that the listed materials
steady waste disposal plant was modeled, and (Pitsorb, Turbosorbjet, etc.) are single-use
in the static mode sorbent performance in the sorbents, while the fibrous products developed
form of mats or booms on water surface was on the basis of thermoplastic wastes can be
modeled for petroleum and op outflow (Table 5). used many times. The dependencies of sorption
The data obtained were compared with the capacity of the samples of polymeric fibrous
characteristics of other sorbents known on the materials on the number of recovery cycles are
world market. For example, the static sorption shown in Fig. 2. One can see that even after 15
capacity Vg of Pitsorb (Can ada) is 67 g/g, performance cycles the capacity of the proposed
Turbosorbjet (France) about 4, Sibsorbent sorbents is conserved at a level of 5070 % of
(France) 89, BTI-1 (Russia) 1215 g/g. It the initial value.

Sorption capacity (Vg) of the samples of polymeric fibre with respect to hydrocarbon liquids, g/g [35]

Sorbent, Dyn amic regime Static regime

material Petroleum Diesel fuel AI-92 I-20A Petroleum Diesel fuel AI-92 I-20A
FN from
the single-use
syringes, PP 6.1 6.9 5.6 6.9 15.6 15.7 10.0
The same,
PE : PP = 1 : 1 5.9 8.5 5.2 8.5 15.0 17.9 10.3
FM based on
the used plastic
bottles, PETP 3.9 5.3 3.7 5.3 12.9 13.2 10.6
Note. FM fibrous material, PP polypropylene, PE polyethylene, PETP polyethylene terephthalate.
*No data for the dyn amic regime; for static regime, sorption capacity is 1325 g/g.
(France), PP*

As a result of investigations, the authors devices, installations in which various processes

of [35] concluded that the fibrous sorbents are carried out starting with filtration,
based on thermoplastic wastes could be coalescence and finishing with adsorption itself)
competitive with the foreign an alogues. in combin ation with multistage purification
technologies. However, many works report on
the data dealing with the investigation of
separate materials for efficient purification of
WW from OP. It is clear that one should
investigate in detail the characteristics of all
As we have already mentioned, in case of
the constituents for the purpose of studying
unpractical maintenance, the environment is
the operation of multicomponent systems. The
unable to cope with pollution; active purification
authors are likely to expect further use of these
is required, including purification of industrial
sorbents either separately (let us call them filters
solutions and gases, waste water (WW), etc.
in this case) and in various combinations with
Purification of WW to the level of industrial
other materials (combined filters).
water supply with utilization of recovery
Materials used in dispersed and granulated
solutions (for example, distribution as the
forms. The most of authors discussing this
commercial product, etc.) is characterized by
subject pay attention not only to the efficiency
high economic efficiency and allows not only
but also on the availability (therefore, low cost)
to prevent waste water discharge into water
of sorbents involved. The requirement of low
bodies but also to solve the problem of
cost is best of all met by the natural materials
supplying the n ation al economy with addition al
and the materials based on various wastes
water resources [25, 73].
(industrial, technological, domestic, etc.). As far
In the general case, in order to choose and
as the degree of purification is concerned, as
optimally combine purification methods [9, 53
a rule, the best sorbents are artificial and
56, 5972], it is necessary to an alyze the
structural chemical and phase disperse synthetic ones.
composition of water to be purified meeting the Let us consider in more detail the application
requirements to the quality of purified water. of n atural and artificial materials used in the
In doing this, one should take into account disperse and granulated forms for purification
changes in the character and phase-disperse state of OWW [3638, 42, 4653, 5558].
of impurities during purification. After choosing Thus, it was proposed to use fine dispersed
the purification chart, either for groups or for clays from the deposits of Bashkortostan to
separate impurities within a group, it is purify WW of various works. The use of these
necessary to choose materials for the process. clays in purification units of some oil-processing
In the present work we will focus on the plants allowed achieving a decrease in OP
problems of OWW (oil-containing waste water) content by a factor of 5.47.3 [36, 37]. In
water from oil-mining and oil-processing addition, investigations aimed at utilization of
plants, petroleum storage depots, filling the worked out clays showed the possibility to
stations, car wash stations, etc. Pollutants most add them into mixtures for the production of
characteristic of OWW include first of all construction materials, which allows us to
petroleum and OP, surface-active substances, consider the mentioned technologies as
heavy metals, etc. However, the subject of ecologically safe and waste-free [38].
investigation chosen for the present study is It is known that such natural sorbents as
OWW purification from petroleum and OP. zeolites can be successfully used to purify
various aqueous media from the pollutants of
3.1. Purification of OWW with filters various kinds [3941]. The authors of [42]
made of natural a nd artificial materials investigated the extraction of OP from water
polluted with petroleum, petrol and oil, with
In view of the complicated character of the the help of n atural zeolites represented by the
process pf WW purification, as a rule, minerals of heulandclinoptilolite group from the
multilayer combined filters are used (materials, Sakhaptinskoye (the Krasnoyarsk Territory) and

Kholinskoye deposits. It was shown that the

application of zeolites allows one to purify
polluted water from emulsified oil products
(EOP) by 100 % and from dissolved oil products
(DOP) by 86 %. The highest OP capacity is
exhibited by the zeolite from the Kholinskoye
deposit for which the Si : Al ratio is 5.5, unlike
the zeolite from the Sakhaptinskoye deposit for
which Si : Al = 5.0. The latter fact confirmed
the assumption that the adsorption activity of
zeolites increases with an increase in Si : Al
ratio. Special attention was paid to the Fig. 3. Curves of filtering for the aqueous solutions of the
mechanisms of pollutant retention by zeolites; Talakan petroleum (1) and its fractions through the initial
khongurine [46]: 2 petrol fraction; 3 diesel fraction.
in the opinion of the authors, these mechanisms
involve either the formation of surface
compounds and complexes with the Carbon-containing sorbents are often used
partici pation of active surface groups (including to purify WW from petroleum and OP at oil-
hydroxyl ones) or absorption of pollutant mining and oil-processing plants, petroleum
particles the size of which is smaller than the storage depots, filling stations [47, 48, 100].
entrance windows of crystal channels [42 For example, it is possible to purify water
45]. systems from OP by adsorption with a carbon-
Investigation of the possibilities to use containing sorbent [47]. The sorbing material is
natural and modified zeolites in the processes recovered after use by washing with a solvent
of water purification from OP was continued at a temperature from 0 to 149 oC.
with the zeolites from the Khonguruu deposit Intercalated graphite obtained from its
(Yakutia) [46]. Maximal sorption of the oxidized forms and containing 0.10.5 mass %
hydrocarbons of the Talakan oil on khongurine of fine dispersed chemically modified
under static conditions was 12 103 mg/g, the amorphous silicon dioxide is used as a sorbent
dyn amic sorption capacity of this material [48]. After saturation, the sorbent is recovered
reached 1.7 mg/g. The results of extraction of by washing with a solvent, followed by drying
the dissolved hydrocarbons in the dyn amic at 120140 oC. The saturation threshold is
regime are presented in Fig. 3. convention ally assigned at a level when the oil
Activation of the zeolite by calcination at to sorbent mass ratio Mo/Ms reaches 20.
350 oC for 2 h resulted in an increase in the The authors of [49] proposed to sorb oil with
specific surface of the material followed by an aluminosilicates (hollow microspheres isolated
increase in its sorption capacity from 30 to 50 % form the ash of coal thermal stations) and then
as a mean. burn oil out with the free access of the air till
Treating it with solvents, life steam, and combustion finishes.
centrifugal separation can perform recovery of Such conventional sorbents as different kinds
the worked out zeolite. It is also possible to utilize of coal (with preliminary activation and without
it by adding into mixtures for the production it) are frequently used to purify OWW.
of construction materials, for example as an Granulated and powdered, decalcified and low-
additive for brick production to improve the ash microporous activated coal (AC) is used, as
structure and increase the porosity of the well as the coal of heat contact coking (CHCC),
resulting material. Zeolites saturated with OP brown coal sorbents like BKZ, ABD, etc. are
can be used as an active reducing flux in ore applied [5053, 55]. The initial raw material to
electrofusion and so on. In the cases when both obtain AC can be any carbon-containing
recovery and utilization of the worked out materials: coal, turf, wood, etc. [54, 55].
materials are hindered till economical Manufacture of high-quality AC is rather
unsuitableness, their single use is possible. complicated and time-consuming, which causes
the high cost of the material and the necessity

of its multi ple use. The kinds of coal most observed for diesel fuel (98 %). An increase in
suitable for water purification are considered the adsorbent to solution ratio under static
to be KAD-iodine, AG-3, BAU, DAK, AGM. conditions leads to an increase in purification
The coal of KAD-iodine, AG-3 and BAU types degree; however, the efficiency of adsorp\bent
possesses high capacity towards the compounds use decreases.
with small molecules; BAU and DAK are The UFP of aluminium oxide obtained under
efficient for OP adsorption, KAD-iodine, AGM different conditions and possessing different
and AG-3 are used for addition al purification specific surface was used to purify water from
of biochemically purified WW [56]. mineral oil [76]. The initial oil content of water
To ensure efficient use of porous carbon was 109 mg/l. Purification was carried out in
materials as sorbents, it is also necessary to two stages. After the first one, the oil content
know the main characteristics of adsorbent of water was about 20 mg/l, after the second
particles and the parameters of larger one (with the fresh portion of sorbent) only
aggregates of particles, for example adsorbent the trace amount of oil was detected in water.
layers. For example, the authors of [52] carried Water to be purified was in contact with the
out densitometric measurements and estimations sorbent for about 30 min, the concentration of
with the help of complexation theory and the sorbent was 5 g/l. As a result of
nomographs to determine porosity of the layers investigations, the authors of [76] concluded
of polydisperse materials. Carbon materials of that the amount of mineral oil sorbed is only
two kinds were studied: those made of AC and slightly dependent on the specific surface of
of the materials obtained by activation of coal sorbents, while purification itself is a layer-
tar pitch by carbon dioxide, and those made by-layer filling of the surface pores of disperse
of intercalation compounds of ferric trichloride materials.
with graphite. The possibilities to use such synthetic and
The authors of [74] studied WW purification n atural microporous materials as the UFP of
processes with aluminium compounds as aluminium oxide, mineral adsorbent ADM-2F
adsorbents. It is known that aluminium oxide is (aluminosilicates polyfunctional adsorbent based
an efficient sorbing material: it is widely used on n atural opal-cristobalite rocks, with total
in chromatography as filler, in the production pore volume 0.7 cm3/g [77]) and natural zeolite
of catalysts, in purification processes, etc. At khongurine were studied by the authors of [78].
present, ultrafine materials attract much The concentration of dissolved OP was
attention. It was established [75, 76, 78, 87 monitored by means of IR spectroscopy, that
89, 91, 92] that synthetic sorbents based on of emulsified OP by means of
ultrafine powder materials (UFP), in particular photocolorimetry with Sudan dye [79, 80].
oxide-hydroxide phases of aluminium (OHA) One can see in the data presented in Table 6
can be used to collect petroleum and oil products and Fig. 4 that the most efficient material among
from aqueous solutions and emulsions. It was those listed above is the adsorbent based on
shown [75] that for adsorption of the dissolved OHA. In the opinion of the authors, high
and emulsified petroleum, diesel fuel and sorption capacity of this UFP is due to the
petrol, the highest water purification degree is nanometer-sized nature of the particles of this

Comparison of the efficiency of purification of model petroleum-containing water with microporous adsorbents [78]

Adsorbent Purification degree, %

Dissolved hydrocarbons Emulsified hydrocarbons
UFP of aluminium oxide 7080 6070
ODM-2F 2040 2540
Khongurine 1015 510

Note. Initial content of oil products in the dissolved and emulsified hydrocarbons is 5.7 and 500 mg/l, respectively.

and synthetic FM for OWW purification are used

very widely and efficiently [3235, 66, 8286].
For instance, good adsorbents are carbon-
containing FM obtained from different kinds of
raw materials under different conditions [83,
84]. The possibility to use carbon fibrous sorbents
based on hydrated cellulose fibre modified with
the compounds of transition metals was shown
[83]. This material was manufactured by the
research-and-production association
Neorganika (Elektrostal city) in the form of
nonwoven cloth of ANM trademark.
Investigation of water purification with this
sorbent was carried out with the help of imitate
solutions of organic compounds. The filter
contained 29 g of ANM material, filtration rate
was 14 m/h, and contact time was 8 s. The
results of experiments showed that this carbon
fibrous material demonstrates high efficiency
in extracting oil hydrocarbons from the aqueous
solutions of kerosene-gas-oil fraction, both for
their high and low content (180 and 5 mg/l).
The fin al content of hydrocarbons in the
imitate solutions purified with ANM sorbent was
about 6 mg/l (for the initial concentration of 180
mg/l) and 0.29 mg/l (for initial 5 mg/l).
In order to elevate the selective sorption
capacity with respect to higher hydrocarbons,
Fig. 4. Sorption of the dissolved (a) and emulsified (b) oil a sorption material based on hydrophobic basalt
products with microporous sorbents [78]: 1 aluminium
fibre was proposed [85]. It was obtained by
oxide; 2 ODM-2F; 3 khongurine.
breaking the hydrated mass of basalt fibre and
the hydrophobizing agent (which was composed
material, which provides an increase in the of 160170 mass parts of water and 0.0250.03
molar surface free energy accompanied by a mass parts of an organosilicon compound per 1
sharp increase in the capacity of the material mass part of the fibre) followed by molding and
[78, 81]. The main advantages of n atural drying. The basalt fibrous material had the density
mineral adsorbents include their availability, of 70150 kg/m3, fibre diameter 0.52.0 m, the
cheapness and the presence of sufficient raw length to diameter ratio 100 to 1000. A decrease in
material resources [78]. the amount of hydrophobizing agent resulted in
Fibrous sorbents for waste water the formation of hydrophilic regions in the material
purification. The data on the application of and subsequent decrease in its sorption capacity.
fibrous materials in the pure form to OWW An increase in the amount of hydrophobizing agent
purification are almost completely absent from above the optimal value decreased the lifetime of
literature. It is clear that, in spite of cheapness, organosilicon emulsions; an increase in its
availability and other advantages of these concentration resulted in coagulation of the
sorbents, the latter have also some shortcomings compositions and hindered uniformity of fibre
preventing their use for this purpose. These treatment. The resulting hydrophobic compacted
shortcomings include low mechanical and material was used as adsorbent for higher
thermal stability, low stability to long-term hydrocarbons from aqueous solutions of
action of humidity and chemical reagents alkanolamines. Under intense operation, the sorbent
(corrosive media). At the same time, artificial did not lose its properties, and the degree of

hydrocarbon recovery even after operation of the sorbents for OWW purification in the dyn amic
material for a long time was 90 % [85]. mode were studied.
An investigation described in [86] deals with
the studies of physicochemical and filtration
3.2. OWW purification with combined filters
characteristics of a number of FM
manufactured at plants in Russia. The subjects Combined adsorbing filters involve various
of investigation were basalt wool, pressed combin ations of materials differing both in the
basalt fibre with the clay-cellulose binder origin (natural, artificial and synthetic) and in
(manufactured by the Federal Research and the aggregate state (powdered, granulated,
Production Centre Altay), nonwoven carbon ground, etc.; fibrous nonwoven in the form
FM VM [84], and polypropylene fibrous of chaotically positions fibres, wool, pressed
nonwoven material. It should be noted that the ones, etc.). In addition, the materials can be
nonwoven carbon FM is based on a carbonized additionally subjected to modification (chemical
composition of polycaproamide and pitch and and/or physical, etc.) for the purpose of
possesses porous fibrillar structure with the enhancing the existing properties or rendering
following characteristics: fibre diameter 0.1 new ones. Such an approach allows one to
3.0 m, total pore volume 23 cm 3 /g. develop new purification technologies including
Investigation showed that the most efficient a large number of materials, and purification
sorbents are pressed basalt fibre and nonwoven flowcharts admitting flexible rearrangement and
carbon material; the use of these materials characterized by high efficiency [88, 89, 93, 94].
allows one to achieve 7080 % purification of Synthetic sorbents based on UFP, in
water from OP. High cost of the fibrous carbon particular OHA, are actively proposed in
material limits its application on the industrial various efficient combin ations with other
scale. Filters based on basalt wool and nonwoven materials [78, 8789, 9193].
PP material demonstrated lower efficiency (50 For example, it was shown in [8789] that
70 % purification degree), possibly due to low the combin ation of the adsorbents of different
porosity of these materials (88 and 84 %, types in one filter results in a multi ple increase
respectively). So, it was established that the in the capacity characteristics of such a filter.
most promising sorbent among the proposed Combin ations of some FM were tested:
number of sorbents is the pressed basalt fibre hydrophobized cellulose, carbon FM
which possesses high adsorption ability with (Viskumak, Mytishchi city, Moscow Region;
respect to petroleum and OP, strength, thermal carbon cloth, Perm) and basalt fibre of various
stability, availability and low cost. In addition, modifications (BSTV-1, Kemerovo), with fine
it was demonstrated that the basalt fibre does aluminium-containing powders [87].
not become caked and consolidated by water Comparative estimation of the efficiency of
flow thus increasing filter restriction, does not fibrous sorbents showed that the best results
require any addition al fixing partitions, etc. [86]. are demonstrated by carbon cloth; however,
We have already mentioned above (see its high cost allows us to recommend it only
Section 2.2) the investigations of synthetic for application in domestic filters to purify
fibrous sorbents made of the wastes of drinking water. Cellulose is distinguished by
thermoplastics (polyethylene-polypropylene instability to putrefaction under humid
single-use medical syringes and plastic bottles conditions. So, hydrophobized basalt fibre is
made of polyethyleneterephthalate) [3235]. It recommended for use in industrial fibres [[89].
should be reminded that the operation of the Investigations of the processes of water
filtering charge of steady purification purification from EDOP and DOP with
constructions was modeled in the dyn amic miltilayer filters containing both UFP based on
mode of determin ation of sorption capacity OHA and fibrous polypropylene and basalt
of these materials with respect to petroleum, sorbents were described in detail in [87]. Some
industrial oil, summer diesel fuel and AI-92 data obtained in these investigations are shown
petrol (see Table 5) [35]. So, the possibilities in Fig. 5.
to use the indicated materials as fibrous It was established that the use of
hydrophilic and hydrophobic adsorbents at the

same time in one filter broadens the range of and decreases the flow-through capacity of the
problems that can be solved with such a filter. devices. Maximal resistance is observed in a thin
Separation of an ultrafine oxide adsorbent layer at the boundary between FM and the
possessing high bulk density into the layers with powder; to decrease this resistance, it is
the help of FM results in a decrease in filter desirable to separate the fibrous and powdered
restriction. In addition, fibrous hydrophobic materials with a layer of a porous material: a
adsorbents operate satisfactorily with high ceramic membrane, nonwoven cloth, etc. As a
concentrations of OP in coalescence regime. result, it is expected to achieve a substantial
With the OP content not higher than 10 mg/l, increase in the filter cycle [91].
FM are inefficient as the collectors of OP [87]. On the basis of a new original adsorption
However, it was noted that the application of technology, the filtration station for WW
polypropylene FM allowed the authors of [90] purification from OP was developed at the
to achieve the maximal OP capacity. It seems Institute of Petroleum Chemistry, SB RAS,
likely that the polypropylene FM obtained on and launched into experimental operation since
the basis of PP wastes (which was studied by 1995 at the Tomsk Petroleum Storage Depot
the authors of [87]) does not provide high of the Tomsknefteprodukt JSC [92]. The
purification degree due to its characteristic filtration-adsorption set-up Sever-3 based on
smooth surface. Either further improvement of multilayer adsorbents (firstly oxide ones) is able
the technology of obtaining this sorbent or its to purify water efficiently if the initial content
special modification is necessary. of OP is 2530 to 300 mg/l and more. The
One of the problems arising with the use degree of purification from suspended and
of multilayer filters based on ultrafine UFP of emulsified OP reaches 100 %, as a rule (with
aluminium oxide, basalt ultrathin fibre, efficient removal of DOP). The OP content of
polyamide FM, etc.) is due to high resistance the purified water is 0.2 to 0.8 mg/l; even after
of adsorbent layers, which hinders filtration the resource of filter operation is exceeded 23
times, this value reaches 1.62 mg/l.
A multilayer filter for water purification
both from DOP and EOP includes an adsorbent
based on pressed basalt fibre and the layers of
adsorbent based on OHA [78]. The major part
of petroleum emulsion is filtered through the
basalt fibre, while DOP and their drops with a
size less than 1 m are sorbed with UFP of
OHA. As a result, the purification degree
increases from 77 (for a single-layer filter made
of pressed basalt fibre) to 97 % (for the
multilayer filter described above).
As we have mentioned above several times,
the combinations of materials for OWW can
be diverse. Let us consider the use of n atural
sorbents in these combined filters [9597].
A set-up for the purification of WW from
car wash units was developed and
recommended for application at the Tomsk
State University of architecture and
construction; the set-up is equi pped with the
cassette-type filters with the combined charge
including granulated turf and FM from PP
Fig. 5. Effect of the initial concentration of emulsified oil wastes. The use of this set-up allows one to pass
products on the degree of purification with the filters:
oxide + basalt fibre (a) and oxide + polypropylene fibre
to the recycling zero-discharge water supply of
(b) [87]: 1 diesel fuel, 2 petroleum, 3 petrol. the dirty cycle with the purification of waste

water from car wash. The use of cassette filters TABLE 8

provides a decrease in the content of Purification of waste water from petroleum and oil
suspensions from 500 to 35 mg/l, OP from 900 products with the help of cotton-containing sorbent [97].
Thickness of sorbent layer: 100 mm, filtration rate:
to 0.55 mg/l. The fibrous filling of the filters
1.5 cm/s, filtration time: 3.5 s
is recovered by centrifuging and used
repeatedly, while the worked out turf is Content Residual content
utilized as fuel briquettes [95]. of oil products, mg/l of oil products, mg/l
At the first stage of a two-stage purification 1 Not detected
procedure for OWW (and also for n atural one), 3 Not detected
the initial water is passed through a two-layer 5 Not detected
filter composed of a layer of coal (fossil coal 10 0.01
with the specific surface of 25150 m2/g) and
a layer of sand, at the second stage it passes
through a one-layer filter made of the same
amount of OP in water ensures the ratio of oil
coal. After saturation, the filter is recovered
to the sorbent mass Mo : Ms = 5 for BR and
by washing at first with water, then with an
Mo : Ms = 24 for the cotton-containing sorbent.
alkaline solution during bubbling. The method
The regime of water passing through the
is characterized by the following efficiency: OP
sorbent layers during purification is important
content of the initial water is 37 mg/l, in the
in achieving the highest purification degree. For
purified water 0.10.2 mg/l [96].
instance, the following conditions were chosen
An increase in the efficiency and a decrease
(or calculated using the known procedures [99]):
in net cost of the process of purification of
the diameter of BR granules, 0.120.5 mm;
petroleum-containing water was achieved due
thickness of sorption layer, 150 mm; height
to the use of a n atural adsorbent (burnt rock)
and diameter of columns: 1m and 10 mm,
and cotton-containing wastes of spinning works
respectively; excess pressure, 0.15 atm;
[97]. Burnt rock (BR) is a metamorphized coal-
filtration time, 32 s; filtration rate, 1.30 cm/s
bearing material composed of carbonaceous and
(Table 7).
weakly carbon aceous argillites, siltstones or
For the second stage (additional purification
sandstone subjected to burning in underground
from petroleum and OP till the maximum
fire. These materials accompany coal and are
permissible concentration which is 0.01 mg/l),
present in all the coal basins [98]. At the first
the following conditions are most suitable: the
stage [97], water to be purified is passed
thickness of sorption layer, 100 mm; height
through a BR adsorbent, at the second stage
and diameter of columns, 1 m; excess pressure,
through a cotton-containing sorbent until the
0.15 atm; filtration time, 3.5 s; filtration rate,
1.50 cm/s (Table 8).
With the indicated filtration conditions,
water with the initial OP content of 100 mg/l
Purification of waste water from oil products with the
help of burnt rock [97]. The content of oil products: is purified to 0.50.9 mg/l (at the first stage
100 mg/l through a layer of BR), with the initial OP
content of 110 mg/l to 0.01 mg/l (at the second
Thickness Filtration Residual content
stage through a layer of cotton-containing
of adsorbent rate, cm/s of oil products, mg/l
sorbent). After 10 cycles of BR sorbent
layer, mm recovery, the residual amount of petroleum in
45 1.3 4.5 water under purification was 8.1 mg/l. Five
75 1.3 1.0 cycles of recovery of the cotton-containing
100 1.3 0.7 sorbent allowed one to purify water to the OP
125 1.3 0.6 content not more than 0.05 mg/l [97].
150 1.3 0.5
100 1.5 0.8
100 2.1 1.5

So, in the present work we made an attempt 5 G. A. Roev, V. A. Yufin, Ochistka stochnykh vod i
to generalize and analyze some reported data vtorichnoye ispolzovaniye nefteproduktov, Nedra,
Moscow, 1987.
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okruzhayushchey sredy pri sooruzhenii i ekspluatatsii
On the basis of an alysis of literature data, gazonefteprovodov, Nedra, Moscow, 1988.
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16 O. S. Mochalova, L. M. Gurvich, N. M. Antonova, Zashchita
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32 Pat. 2093618 RF, 1997.
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