ISSN 0965-5441, Petroleum Chemistry, 2007, Vol. 47, No. 6, pp. 379–388. © Pleiades Publishing, Ltd., 2007.

Original Russian Text © G.A. Kolmakov, D.F. Grishin, A.D. Zorin, V.F. Zanozina, 2007, published in Neftekhimiya, 2007, Vol. 47, No. 6, pp. 411–421.

Environmental Aspect of Storage of Acid Tars

and Their Utilization in Commercial Petroleum Products
(Review)
G. A. Kolmakov, D. F. Grishin, A. D. Zorin, and V. F. Zanozina
Research Institute of Chemistry, Nizhni Novgorod State University, pr. Gagarina 23/5, Nizhni Novgorod, 603600 Russia
e-mail: kolmakovga@mail.ru
Received December 5, 2006

Abstract—Data on the formation and disposal of acid tars, as well as on the development of ways of their uti-
lization into commercial petroleum products, are summarized. An analysis of the relevant literature over the
past 60 years has made it possible to objectively assess the environmental situation that has developed as a result
of the disposal of acid tars in storage ponds in Russia. The risks of harmful effects of heavy refinery wastes on
humans and animals were estimated.
DOI: 10.1134/S0965544107060011

Acid tars are high-volume wastes from the refining
of petroleum oils by means of sulfuric acid. Their
amount in storage ponds is so great that they may be
considered an industrial feedstock for the manufacture
of commercial petroleum products, in particular, road
asphalt.
Acid Tars, Their Appearance and Properties
During the manufacture of distillate, motor, and
other petroleum oils, refining methods associated with
the use of concentrated sulfuric acid or oleum have
been widely practiced [1]. Unsaturated and aromatic
hydrocarbons, as well as sulfur and nitrogen com-
pounds and resinous substances, which impair the sta-
bility and performance characteristics of commercial
petroleum oils are removed in this case. Acid tars pro-
duced as waste and stored in lagoons or ponds are a
source of environmental pollution [2].
Acid tar is a thick, viscous substance with a pun-
gent, acidic smell; it can contain 10−50% sulfuric acid
and a noticeable amount of oil and resin and is highly
corrosive toward metals [3]. Acid tars are amenable to
oxidation and solidification in air; therefore, their prop-
erties may substantially vary during storage.
Pond acid tars acquire fairly stable properties after
long-term (more than 10–15 years) storage [1]. Soluble
substances (above all, sulfuric acid and sulfonic acids) are
gradually washed out with rainwater, and other com-
pounds present in acid tars enter various chemical reac-
tions (desulfurization, condensation, fusion, etc.) [1].
The composition of acid tars is complex and is not
well understood. As has been mentioned above, it
includes a large number of various sulfur compounds
[4–6]. The primary products that constitute acid tars are
sulfonic acids, as well as acid and normal esters of sul-
furic acid, which are very reactive; therefore, acid tars
can include the products of their interaction with both
initial and newly formed compounds. These products
contain aliphatic, naphthenic, and aromatic or their
polycondensed derivatives as organic moieties.
Chemical reactions occurring in acid tars lead to the
formation of high-molecular-mass resinous products
containing sulfur and oxygen; i.e., petroleum acids
(naphthenic and asphaltic), which get into tar from
petroleum [7] or are produced during petroleum refin-
ing as a result of oxidation of paraffins, naphthenes, and
alkylarenes [1] whose interaction with sulfuric acid or
oleum leads to the formation of mixed sulfocarboxylic
acids [6].
The pond tars are characterized by a large excess of
paraffinic–naphthenic oils and alcohol–benzene-
extractable resins and a high bound-sulfur content (acid
tars contains ≤5 wt % sulfur, whereas straight-run vac-
uum residues contain 0.1–2.0 wt % [5]) and are
depleted in polyaromatic oils and benzene-extractable
resins [3]. Most tars produced as a result of refining of
light products are liquid, and tars from the refining
treatment of lubricating oils are heavy, resinous sub-
stances [8].
Environmental Aspect of Disposal of Acid Tars
to Storage Ponds
A common occurrence at oil refineries and tank
farms is soil pollution with petroleum products that
migrate with ground water, thereby poisoning the envi-
ronment. Refineries produce up to 1.6 million t of liq-
uid and solid wastes per year, of which about 80% are

379
380 KOLMAKOV et al.
processed immediately at these plants and a part is
transferred to other branches of industry [9–11].
The reserves of sulfuric acid wastes that have accu-
mulated in storage ponds are very significant [12]. For
example, about 480 thousand tons of acid tars have
been gathered in 17 storage ponds at the Slafneft’ Men-
deleev refinery. What aggravates the situation is that the
refinery ponds with the hazardous matter are separated
from the Pechegda river, which falls into Volga, by a
dam only a few meters in width. [13].
The Volga basin contains about 450 oil and gas
fields. The production, transportation, and processing
of oil and gas create an incredibly strong technogenic
load and a risk of accidental release of petroleum prod-
ucts and refinery wastes into Volga and its reservoirs
[14].
A similar situation happens in many other regions of
Russia (Nizhni Novgorod and Ivanovo oblasts; the cit-
ies of Ufa, Omsk, Groznyi, etc.) and abroad [13]. Sta-
tistical data [15] indicate that refinery-pond acid tars in
Russia and other former USSR countries amount to
about 2 million tons.
Attempts to utilize acid sludge were made as early
as the late XIX century; sulfuric acid concentrated to
95 wt % was separated upon heating and briquettes
were disposed in pits. However, the problem remains
unresolved. Its complexity is due to the fact that the
acid tar composition is individual in each retention
pond. A wide scatter in the concentration of sulfuric
acid and sulfonic acids, as well as the organic matter,
cause significant difficulties in the creation of a univer-
sal technology for the utilization and processing of tars
into commercial petroleum products.
Toxicological characteristics of tars and asphalts.
Petroleum refinery products have a toxic effect on
humans and animals [16, 17]. For example, when
asphalts produced from Bashkirian, Volga, and Ukrai-
nian crude oils were applied on the skin of white mice,
the animals died of emaciation, pneumonia, etc. within
1−12 months [17]. Note that the lifespan of the white
mouse is 24–36 months under natural conditions [18].
Skin exposure to asphalts from Bashkirian oils leads to
hair loss, epidermis hyperplasia, and papilloma
growths. Similar effects were observed in the skin
exposed to asphalts manufactured from acid tars
[16, 19]. The ability of asphalts made from cracking
residues to cause tumors in 18.4% of mice that lived for
9–10 months, with 10% of the tumors being malignant,
was revealed. Tarry residual fuel oil containing
0.0015−0.0002 wt % benzo(α)pyrene, a carcinogenic
chemical, caused tumors in 7 mice out of 16, with two
mice having malignant tumors [20]. In contrast, asphalt
samples obtained from benzo(α)pyrene-free tars did
not case the formation of tumors, according to [21].
Composition of acid tars. The organic portion of
acid tars includes various sulfur compounds, solid
asphalt-like substances (asphaltenes), carbenes, car-
boids, mineral impurities, and other components, a
composition that allows them to be processed into
asphalt for road building [12]. Elemental analysis
shows that the carbon/hydrogen ratio of acid tars from
different storage ponds is 10 : 1. In addition, they con-
tain nitrogen, oxygen, and sulfur, as well as transition
metals (V, Ni, Fe, Co, Cu, etc.), which are usually coor-
dinated at the center of the polyaromatic core of
asphaltenes [22]. The relative amount of mineral matter
(ash content) varies within the range 0.14–1.50 wt %
depending on the storage time and the occurrence depth
of a particular sample of acid tar. The density of acid tar
at 25°ë is 1.1–1.2 kg/dm3 because of a large amount of
emulsified water.
The isolation of individual substances from residual
petroleum products is a complex, laborious, and expen-
sive process. Therefore, a chemical characteristic of
heavy petroleum residues is the group composition of
components. The separation of vacuum residues and
asphalts in accordance with their group composition
was proposed by Richardson in the early XX century
[23], was perfected later by Marcusson [24], and is used
at present with small revisions [25, 26]. The process
comprises the separation of asphaltenes from
malthenes dissolved in the asphaltenes. Malthenes are
separated into other five groups of compounds: paraf-
finic–naphthenic, monoaromatic, and bicycloaromatic
compounds and toluene- and alcohol–toluene-extract-
able resins, by means of adsorption chromatography
(on silica gel or alumina). In turn, paraffinic–naph-
thenic compounds are separated into normal alkanes,
isoalkanes, and polycycloalkanes (polycyclonaph-
thenes) via complexation with carbamide and thiocar-
bamide [23].
Acid tars are subdurded into two types based on the
amount of base substance; i.e., that with a high acid
content (≤50%) and a that high organic-matter content
(≤50%). When excess spent sulfuric acid is contacted
with the organic component of acid tars during the
refining treatment of petroleum oils, very complex
chemical reactions take place, e.g., oxidation with oxy-
gen produced via the thermal degradation of sulfuric
acid, as well as sulfonation and alkylation [22, 24–28].
As a result, sulfide compounds, which act as bitumen
oxidation inhibitors; flexible asphaltenes; and their
supramolecular structures with small deviations from
the equilibrium state are formed. Thus, the oxidation of
petroleum residues with an excess of spent sulfuric acid
must lead to the formation of organic compounds that
form the basis for asphalts. This possibility makes acid
tars attractive as feedstock for the manufacture of
asphalts and asphaltic compositions with improved
structure and enhanced stability toward aging.
Methods for Acid Tar Management and Processing
into Commercial Petroleum Products
Various methods proposed by Russian and foreign
industrial chemists for the processing of refinery wastes
are capable of rendering harmless only a part of acid
PETROLEUM CHEMISTRY Vol. 47 No. 6 2007
 ENVIRONMENTAL ASPECT OF STORAGE OF ACID TARS
tars. Continuous studies on the improvement in the
technology create new processing methods and, hence,
the possibility of manufacturing new valuable products.
The complexity of the composition of acid tars sug-
gests a variety of ways for their utilization. At present,
the processing of acid tars into commercial products,
such as surfactants (Carpatol, Sulfanol, etc.) [29, 30],
H2SO4 and colloidal sulfur [12, 13, 14, 31–33], desulfu-
rized light liquid hydrocarbons [18, 92, 93], coke [12]
and active carbon [36], boiler and furnace fuel [37–42],
pitches [43], asphalts [44–57] and binders for asphalt
manufacture [58–66], heat-insulation compositions and
antirust mastics [67], commercial ammonium sulfate
[68], gypsum and cement obtainable from wash water
deacidified with calcium oxide or hydroxide [29], and
mixture of acid tars with peat as a high-calorific-value
fuel [69].
During the treatment of acid tars, the upper, easily
movable layer of weak acid organic compounds is uti-
lized, the aqueous layer is neutralized, and the amount
of organic matter in the layer in brought to the level
specified by disposal standards, and the lower (organic)
layer—acid tar—is decontaminated [13, 29].
Oily aromatic compounds from the upper layer are
used for oiling forms in the manufacture of reinforced
concrete and for manufacturing road binder or, together
with fuel oil, for firing kilns in cement manufacture.
The middle aqueous layer is neutralized with lime
materials, simultaneously cleaning water of organic
compounds. The lower layer of high-molecular-mass
hydrocarbons is neutralized with slake lime or anhy-
drous calcium oxide, solidified, and stored under con-
ditions that preclude washout by atmospheric precipita-
tion.
Use of acid tars in oil producing industry. The
manufacture of surfactants from acid tars is based on
the high surface activity of sulfonic acids and sul-
fonates, which are present in the tars. For this purpose,
acid tars are neutralized with ammonia; in this way, the
crude surfactant Carpatol is obtained which is used in
oil recovery [29] as a demulsifier, frothing, lubricant–
coolant, or flotation agent. A large amount of sulfonic
acids in the surfactants called for studying the ways for
their rational use. Investigation into the preparation of
neutralized acid tars showed the feasibility of obtaining
high-performance oil-driving agents—micellar solu-
tions—on their basis [30].
Manufacture of sulfur dioxide. The main process
for utilization of acid tars is high-temperature cracking
based on the reaction of thermal dissociation of sulfuric
acid yielding sulfur(IV) and sulfur(VI) oxides. To reach
the temperature (810–1200°ë) required for the process,
the organic portion of acid tar is incinerated [12, 29]:
O2+C
H 2 SO 4 + H 2 S SO 2 + SO 3 + H 2 O + CO;
O2
SO 3 + CO SO 2 + CO 2 .
PETROLEUM CHEMISTRY Vol. 47 No. 6 2007
381
Sulfur dioxide produced in the process is used for
the manufacture of sodium hydrogen sulfate, anhy-
drous sodium sulfate, or dilute sulfuric acid followed
by its utilization in the manufacture of superphosphate.
Via this process, pure standard sulfuric acid of any con-
centration (up to oleum) can be prepared.
Jianu [31] patented a process for preparing liquid
sulfur dioxide from acid tars. A mixture of tar and a
reducing liquid (its chemical composition was not
specified) obtained from deoiled asphalt or atmospheric
residuum is prepared. The mixture is heated first to
100–130°ë; the gas phase containing SO2 is washed at
30°ë and dried with 95–98% H2SO4; after that, SO2 is
brought to the liquid state under pressure.
A process for the recovery of sulfuric acid proposed
by Schröder and Helmut [32] comprises the following
steps. Acid tars produced during the sulfuric acid or
oleum refining of oils, vaselines, Parex paraffin waxes,
crude benzenes, and other substances are mixed under
vigorous stirring with phenolic solvents and water; phe-
nolic tars remaining after the solvent extraction or dis-
tillation treatment of crude phenols, which has a den-
sity at 20°ë of 1.10–1.25 g/cm3 and a pour point of
20°ë, are especially suitable for this purpose [32].
After a short settling time, the mixture separates into
two phases, forming the inorganic layer consisting of
50–70% sulfuric acid and the organic layer containing
the phenolic solvent, resinous components, and sul-
fonic acids. The process is based on the phenomenon
that the micellar compound of acid tar is destroyed on
one hand, as a result of molecular interaction of water
with the acid, and on the other hand, phenolic and bitu-
minous particles of the phenolic tar. As a result, the
emulsion degrades to make the system separated into
the acid and tar phases [33].
Synthesis of desulfurized light liquid hydrocar-
bons. A process for the treatment of acid tar with the
aim of obtaining liquid hydrocarbons having a low sul-
fur content was designed by Kut’in et al. [34]. Acid tar
is neutralized with quicklime and the oily fraction is
distilled off; then, the fraction is heated and its vapor is
passed through granulated quicklime at 550–700°ë.
Cracking catalyzed by the developed active surface of
calcium oxide leads to the condensation reactions of the
lightest hydrocarbons and to the thermal degradation of
the high-molecular-mass portion, thus effecting an
increase in the proportion of products with a middle
molecular mass useful as boiler fuel. Simultaneously,
the high-temperature reaction of calcium oxide with
sulfonic acids that are distilled off from the oily fraction
takes place, which leads to binding their sulfur in the
form of calcium sulfate, sulfite, and sulfide.
Via a process patented by Nomatsu [35], organic
substances present in acid tar are likewise contacted
with quicklime at a temperature that gradually (in a
stepwise manner) increases from 100 to 600°ë in
accordance with the boiling points of distilled fractions.
As a result, a considerable portion of the feedstock con-
382 KOLMAKOV et al.
tacts with quicklime at a temperature that is insuffi-
ciently high for cracking. It is not until the point when
only the heaviest components remain in the material
subjected to treatment that cracking and the binding of
sulfur compounds along with distillation can occur.
Note that the stepped temperature profile of the distilla-
tion process does not provide optimal conditions
(550−700°ë) and retards noticeable degradation of the
feedstock, yielding sulfur-free liquid fuel components.
Coke manufacture. Units for the low-temperature
decomposition of acid tars with coke as a heat carrier
are most widespread in the industry [12]. These units
can be used for the decomposition of solutions of spent
sulfuric acid as well, providing that the solutions are
preliminarily mixed with organic matter-rich petroleum
residues.
As a result, gas of the following composition is
formed (vol %): SO2, 6.5; H2O, 24.0, CO2, 10.0; and
N2, 59.5. The hot flue gas is used to heat air in furnaces
and a recuperating heat exchanger. Through a cyclone,
the fuel gas is forced by a smoke exhauster into the
atmosphere. The coke yield is 27–30%. It contains
8−12% sulfur, 70–75% fixed carbon, and 17–22% vol-
atile matter. The heating value of this coke is
30.2 MJ/kg.
However, this process is difficult to commercialize,
mainly, because of strong corrosion of certain parts of
equipment.
Granulated active carbon, a more valuable commer-
cial product, can be prepared from acid tars according
to a process proposed in [36]. The process consists of
three steps: manufacture of carbon, granulation, and
activation by steaming. The product is characterized by
high values of the specific surface area, good porosity,
and good adsorption properties and can be used in gas
adsorption and solvent recovery processes.
Boiler and furnace fuel. To prepare organic-matter
enriched solid fuel from acid tars, it was proposed
[37−39] to use an organic admixture (atmospheric res-
idue, heavy oil distillates, topped atmospheric residue,
vacuum residue, and other petroleum residues) in an
amount of 3–25% of feedstock mass. The process is
conducted via pulverization through a nozzle and
simultaneous heating to 200–300°ë. Instantaneous
heating takes place during the pulverization of a mix-
ture of acid tar with an organic additive; as a result, a
solid high-molecular-mass product and volatile organic
compounds are formed.
It was found that the organic matter of acid tar
heated to 200–300°ë is a reducing medium for sulfuric
acid. Upon heating, sulfuric acid enters into the reac-
tion with the organic portion of acid tar, which is oxi-
dized, in that way being converted into a solid organic
product. The reduction products of sulfuric acid are
water and sulfur dioxide, which is used for the manu-
facture of sulfuric acid. The solid organic product is
used as fuel. The sulfur content of the product does not
exceed 2.1 wt %, and sulfuric acid is absent at all.
Lyakhevich and Rudkovskii [40] proposed a process
for the manufacture of boiler fuel using solid and high-
viscosity acid tars, in particular pond tars. Acid tar is
mixed with a straight-run petroleum fraction (its com-
position is not specified). Prior to mixing, the tar is
treated with overheated steam at 120–230°ë. The mix-
ing products are heated in the temperature range
240−430°ë at a pressure of 2.8–12 atm for 10–15 s.
Then, the mixture is cooled, the pressure is reduced,
surfactants (alkylsulfonic acids, alkylarylsulfonic
acids) are simultaneously added, and low-boiling-point
fractions are separated. The yield of boiler fuel accord-
ing to this technology is 92–97.4 wt %.
It is recommended [41] to abandon high-tempera-
ture feedstock treatment; instead, petroleum acid tar is
neutralized at 60–90°ë with an aqueous alkaline solu-
tion of the still residue of a mixture of synthetic fatty
acids from oxidized petroleum waxes with an acid
number of 90–120 mg KOH/g taken in an amount of
10–50% of the feedstock mass.
After neutralization, an ammonia or caustic solution
at pH ≥ 8 is heated to 90°ë, the still residue from pro-
cessing of synthetic fatty acids at a temperature of
60−70°ë is added, and the reaction mixture is thermo-
stated for an hour at 90°ë. The mixture is cooled, and
the product separates within 24 h into two layers; the
upper layer consists of neutralized sulfonic acids in oil
and the lower layer is aqueous. The lower layer is
decanted and the upper layer is used as fuel.
To provide for occupational safety and to improve
the quality of liquid fuel, Zorin et al. [42] designed a
process for the conversion of acid tars into light petro-
leum products with a high yield.
In this process, the thermal cracking of the oily frac-
tion of acid tar occurs at 400–500°ë in an atmosphere
of an inert carrier gas, where the carrier gas is nitrogen
taken in the oily fraction/nitrogen mass ratio of
1 : (0.05–0.1). The sulfuric acid solution produced is
neutralized with an aqueous Ca(OH)2 solution to pH 7.
Under these conditions, the thermal cracking of organic
components of acid tar leads to the formation of gas-
eous hydrocarbons (primarily, ë1–ë4), as well as liquid
hydrocarbons that correspond to boiler or furnace fuel
by composition.
Running the thermal cracking of the oily fraction in
a nitrogen atmosphere leads to a substantial enhance-
ment of the safety of the process [42]. If the amount of
nitrogen in the mixture is below the value specified by
the above ratio, i.e., less than 5 wt %, this quantity is
insufficient for attaining the optimal effect and the yield
of liquid hydrocarbons decreases. The introduction of
nitrogen in amounts above 10 wt % is unreasonable,
since it does not lead to a further increase in the yield of
the liquid fraction.
Pitches. A process for the utilization of acid tars
having pour points of 20°ë to produce pitches was
studied in [43]. For this purpose, acid tars are first
heated to 200–400°ë, and a fine polymeric hydrocar-
PETROLEUM CHEMISTRY Vol. 47 No. 6 2007
 ENVIRONMENTAL ASPECT OF STORAGE OF ACID TARS
bon powder is obtained after the removal of low-boiling
polycondensation products and dry distillation. Thus,
heating 300 g of acid tar of a certain composition at
250°ë for 80 min yields 200 g of black polymeric pow-
der, the pitch.
Asphalts. One of the environmentally friendly tech-
nologies is the conversion of petroleum residues into
high-molecular-mass hydrocarbon systems, asphalts
with good processing, performance, and economic
characteristics: plasticity upon heating, a rapid increase
in viscosity upon cooling, high adhesion to various
materials, hydrophobicity, water impermeability, and
resistance toward corrosive liquids and gases, as well as
insulating and sound-proofing properties, a low density,
a low thermal conductivity, atmospheric resistance, and
low cost [44].
Tars left after refining naphtha, kerosene, and lube
oil distillates are treated with water, air, and steam. As
a result, lighter oil components are concentrated at the
top of the reactor, while the acid accumulates at the bot-
tom, and asphaltenic–resinous substances remain in the
central part. The lighter oils are removed by evapora-
tion, the obtained mixture is washed with water and dis-
tilled with overheated steam until asphalt of the
required viscosity is obtained.
Asphalts can be manufactured from acid tars via
heating the latter to 250°ë in a mixture with an equal
amount of straight-run asphalt of cracking residue or by
admixing 1–5% light gas oil and rosin [45], as well as
via distillation of acid tar diluted with wood tar.
The specific properties of asphalts prepared from
acid tars are sensitivity to temperature, high sulfur and
oxygen contents, a low wax content, an extremely low
concentration of saturated compounds, an increased
concentration of sulfonated residues (unlike pitches), a
noticeable solubility in water, high softening tempera-
tures, and the presence of up to 0.25 wt % lead that gets
into asphalt from lead containers used in the sulfuric
acid treatment process [45].
Asphalts manufactured from acid tars exhibit con-
siderably lower atmospheric resistance than natural
asphalts and air-blown or residual asphalts. The ductil-
ity of asphalts at low temperatures, i.e., the tensile
strain, can be increased by the addition of acid tars to
air-blown and residual asphalts. The product with a
high softening temperature can be obtained via the
treatment of acid tar with propane at 32–46°ë.
Commercial asphalts of the BND-60/90, BND-
90/130, and BND-130/200 brands according to GOST
(State Standard) were prepared via the addition of
20−30 wt % oxidized acid tar to viscous asphalts from
West Siberia petroleum [46, 47].
A process for the manufacture of road asphalts on
the basis of pond acid tars after their single washing
with waiter [48] is worth noting. The asphalt obtained
via this process is then mixed with straight-run vacuum
residue and used in road building.
PETROLEUM CHEMISTRY Vol. 47 No. 6 2007
383
The pond tar : petroleum residue ratio varies from
20 : 80 to 30 : 70. At this ratio of the materials, it is pos-
sible to obtain asphalt with a ring-and-ball (R&B) soft-
ening temperature of 40−50°ë; the greater the amount
of pond acid tar, the higher the softening temperature.
During its processing, the mixture is heated to 200°ë,
with the temperature being elevated by 15–20°ë/h to
110°ë and 30–35°ë/h to 200°ë. The mixture is ready to
use after holding at 200°ë for an hour.
The results of study on the preparation of asphalts
via heating a mixture of straight-run petroleum vacuum
residue with acid tars left after the treatment of motor
and machine oil distillates with 95% sulfuric acid are
reported in [49]. The oxidizing agent for the organic
matter is oxygen produced during the thermal decom-
position of sulfuric acid present in the acid tar. The tem-
perature of the process is 250–350°ë. The asphalt has
the following parameters: the R&B softening tempera-
ture, °ë, 88–96; ductility, cm, 3–8; penetration at 25°ë,
0.1 mm, 5–25. According to [49], the asphalt formation
mechanism consists of the successive steps: evapora-
tion of water, degradation of sulfuric acid and sulfonic
acids, and oxidation of the acid-tar organic matter. As a
result, fusion reactions occur in which oils are partly
converted into resins and resins are converted into
asphaltenes.
A large-scale laboratory unit for the manufacture of
asphalt from shale oil was designed at the Slantsy inte-
grated plant [50]. The process is conducted at 330–
360°ë, and acid tar left after the treatment of aromatic
hydrocarbons, e.g., benzene and toluene, is used as an
oxidizing agent. The reaction mixture is heated at this
temperature for 15–30 min. The oxidation should pref-
erably be carried out under the conditions of recycling
a part of the oxidized product.
Frolov et al. [51] showed the feasibility of the prep-
aration of road asphalt from acid tar. The process com-
prises the following steps: the neutralization of sulfuric
acid by technical-grade calcium oxide, the removal of
water from the reaction mixture by distillation, and the
oxidation of the neutralized mixture with oxygen. The
obtained asphaltic material meets the GOST 22245-76
requirements for BND 60/90 grade asphalt [47] in pen-
etration, softening temperature, flash point, brittleness,
and adhesion to marble parameters and has a relatively
low brittle temperature (–18°ë) and a high penetration
at 0°ë, mm × 10–1, 58. The main disadvantage of the
asphalt derived from acid tar is a low ductility. It was
noticed that petroleum road asphalts have a low adhe-
sion to mineral material. The addition of the acid-tar
derived asphalt to these asphalts considerably improves
this parameter.
The process was further improved with the aim of
reducing its power consumption [52]. As a neutralizing
agent, shale ash in an amount of 1–9 parts per 100 parts
of acid tar was used. Oxidation products are mixed with
asphalt derived by the propane deasphalting of petro-
leum residuum. This process makes it possible to
384 KOLMAKOV et al.
reduce the power consumption by the abandonment of
water addition at the step of neutralization and subse-
quent drying. Moreover, it becomes unnecessary to use
the neutralizing agent Ca(OH)2 (which is expensive and
is always in short supply). The technical result is road
asphalt of a higher quality.
Filippova et al. [53] patented a unique process for
the preparation of asphalt from acid tar, which com-
prises heating, evaporating water, neutralizing the acid,
and subsequent oxidizing the asphalt with ambient oxy-
gen; a disadvantage of the process is a low product
yield. Acid tar is heated by means of electrodes
immersed into the material. Employing the property of
acid tar to conduct electric current, one can substan-
tially reduce power consumption and shorten the time
of heating the tar to the temperature required for the
evaporation of water.
It was shown that building and roofing asphalts
could be manufactured via the oxidation of acid tar with
air oxygen in the presence of an iron-containing cata-
lyst as a fine powder [54]. The feedstock is acid tar hav-
ing an acid number of 30–70 mg KOH/g, and the cata-
lyst is a fine powder obtained upon water treatment or
isolated from air cleaning devices of smelting units and
taken in an amount of 0.9–10.0 wt % of feedstock mass.
The process takes 1.4 h at the most and is run at a tem-
perature below 150°ë, so that the power consumption
is reduced. The product asphalt has a high acid number.
There is a process for the utilization of acid tars for
asphalt manufacture [55] by means of preliminary
removal of free acid via low-temperature decomposi-
tion. For this purpose, a mixture of acid tar with
straight-run petroleum residue is loaded into a vat and
is heated to 280–320°ë. First, the evaporation of water
takes place and, then, free sulfuric acid and sulfonated
compounds decompose and oxidize the organic matter;
thus resulting in resins and asphaltenes. Quality
asphalts can be prepared at a mass ratio of acid tar and
petroleum residue organic matter to sulfuric acid of
7−10.
We have formulated the scientific principles of a
groundbreaking process for the manufacturing of
asphalt composition immediately from acid tar without
any additive [56]. The process consists in running the
thermal degradation of acid tar components, in particu-
lar, sulfonic acids and other organic sulfur compounds,
at 400–480°ë for 10–19 min. Under laboratory condi-
tions, we obtained asphalt samples that meet the GOST
requirements in penetration, ductility, R&B softening
point, flash point, adhesion (to crushed granite), and
some other parameters.
Zorin et al. [57] designed a process for the manufac-
ture of asphalt from acid tars, which includes their dew-
atering and heating. Heating is carried out in a flow
reactor at a cracking temperature below the coking tem-
perature and results in nonvolatile and vapor-phase
hydrocarbon fractions. Components having the boiling
point above 300°C are isolated from the vapor-phase
hydrocarbon fraction and are mixed with the nonvola-
tile hydrocarbon fraction withdrawn from the reactor.
These operations make it possible to prepare high-qual-
ity asphalt in accordance with the GOST standards. It is
reasonable to use acid tars with a sulfuric acid content
that does not exceed 7% of the tar mass.
In the asphalt preparation process, sulfuric acid acts
as an oxidizing and vulcanizing agent. If the amount of
sulfuric acid is greater than 5 wt %, acid tars should be
washed by means of any conventional technique. A
high sulfuric acid content leads to the deterioration of
asphalt quality because of enhanced brittleness. By
varying the temperature conditions and the sulfuric acid
content, it is possible to control the characteristics of
asphalt to comply with the requirements and conditions
of its further use [57]. The simplicity of this process
allows asphalts to be manufactured in mobile devices
immediately at the site of disposal ponds.
Binders for asphalt manufacture. Aleksandrov
et al. [58] proposed a process for the manufacture of a
binder from pond acid tars at 60–90°ë. Upon continu-
ous stirring, 25–30 parts by mass of waste left after the
liming step in the hydroquinone manufacture and
15−50 parts of a plasticizer, the mixture of fatty-acid
pitch with a still residue remaining after fractional dis-
tillation in the manufacture of butyl acrylate, were
added to 100 parts of tar. Fatty-acid pitch, the plasti-
cizer component, is a black pastelike byproduct residue
from manufacturing glycerol at fat-and-oil plants.
Fatty-acid pitches contain polyglycerol (calcium
soaps), aluminocalcium soaps of fatty and insoluble
compounds, calcium compounds, and water. The use of
a mixture of the butyl acrylate distillation residue with
fatty-acid pitches makes it possible to control the prop-
erties of the binder, which should vary depending on
particular climatic conditions of it use.
The quality of the binder was tested in road pave-
ment compositions. It was found that the samples of
asphalt concrete compositions prepared on the basis of
binders made from acidic pond tars do not rank below
standard samples in parameters and are almost two
times superior in some characteristics [58].
According to a procedure patented by Barskov and
Karpov [59], a binder is prepared via dewatering of
pond acid tar and mixing it with deasphalting asphalt in
the reactor. The process in conducted in the presence of
a plasticizer, the butyl acrylate, methyl acrylate, methyl
methacrylate, and methacrylic acid distillation residue,
and the mixture is held at 100–115°ë for 30–40 min.
The components are taken in the following amounts, wt %:
pond acid tar, 70–80; deasphalting asphalt, 15–25; and
still residue, 3–7. The process is characterized by good
practicability, low cost, and improved properties of
asphalt concrete prepared from the binder.
A distinguishing feature of the process described in
[60] is the copolymerization of pond acid tar, organic
byproducts from manufacturing ammonium sulfate,
and petroleum short residue. The ratio between the
PETROLEUM CHEMISTRY Vol. 47 No. 6 2007
 ENVIRONMENTAL ASPECT OF STORAGE OF ACID TARS
components is as follows, wt %: acid tar, 75–80;
(NH4)2SO4 byproduct, 5–15; and petroleum residue,
10–15. The products can be used for the manufacture of
both road and building materials and can repeatedly be
heated without a decline in properties. There are
requirements imposed on the feedstock: acid tar should
be washed to remove sulfuric acid, and the (NH4)2SO4
manufacture byproduct should contain at most 46–47%
methyl methacrylate, 40–42% methyl α-hydroxyisobu-
tyrate, 5–6% methacrylic acid, and trace water and
ammonia.
To improve the quality of the binder, Makhnin et al.
[61] proposed a procedure for the oxidation of atmo-
spheric residue at 180–200°ë in the presence of 5–20%
acid tar. The acid tar used had an acid number of
120−170 mg KOH/g.
Bychkov et al. [62] reported a process for the prep-
aration of a binder to be used in an asphalt concrete
mixture, which makes it possible to reduce the cost of
concrete and power consumption for its manufacture,
as well as to improve transportability. To prepare an
asphalt concrete blend by mixing a bituminous compo-
nent, sulfur, and an elastomer powder (crumb rubber or
green rubber), where the bituminous component is a
tar-sand upgrading product with a bitumen content of
3–7%. A disintegrator is used for mixing. After loosen-
ing and drying, the tar sand is sent to an electrostatic
separator, in which dusty rock particles containing the
major portion of bitumen are separated from sand par-
ticles coated with an extremely thin bitumen layer. In
its group composition, the bitumen of tar sands is closer
to petroleum vacuum residues and contains asphalt-
enes, resins, and oils in the mass ratio of 15 : 25 : 60.
The asphalt concrete meets the GOST requirements.
Makin et al. [63] designed a process for the rapid
manufacturing of a binder based on pond acid tars. A
mixer is charged with fatty-acid pitch and a liming res-
idue in an amount determined by the sulfuric acid con-
tent of the feedstock pond tar. The slurry is loaded into
a reactor at 90°ë. Then, pond acid tar having a water
content of 1 wt % is fed to the reactor. After completion
of neutralization, a butyl acrylate distillation residue is
added to the reactor and the mixture is agitated until it
becomes homogeneous. The time of the process is no
longer than 1.5 h.
In the binder manufacturing process reported in
[64], acid tar is preliminarily dehydrated to a residual
water content of 1–3 wt % and is mixed at 70–90°ë
with deasphalting asphalt. Then, a slurry that has pre-
liminary been prepared from fatty-acid pitch and dolo-
mite powder at 60–70°ë is added to the mixture and the
resulting mixture is heated to 100°ë with the subse-
quent addition of the rest of deasphalting asphalt and
pond atmospheric residue and is homogenized at
120−130°ë.
A binder manufacturing process via oxidation with
air at 220–250°ë of petroleum sludge formed during oil
producing and on-site preparation operations [65] is
PETROLEUM CHEMISTRY Vol. 47 No. 6 2007
385
proposed. Petroleum sludge is a black jellylike material
composed of a mixture of crude oil compounds, water,
and mechanical impurities (clay, sand, iron sulfate).
Upon heating, it converts into a volatile liquid contain-
ing light fractions and water, which are condensed and
collected.
According to this process [65], the binder is
obtained via mixing petroleum sludge with deasphalt-
ing asphalt, subsequent heating to 180–200°ë, and oxi-
dizing with air oxygen. The oxidation process consid-
erably slows down at temperatures below 180°ë and is
uneconomical above 200°ë. As a result, the time of the
binder manufacturing process is reduced by a factor of
3–5 and the yield of the binder increases to
79.1−84.1 wt % with a substantial decrease in power
consumption (by a factor of 2–3).
A process for manufacturing a road building compo-
sition based on petroleum sludge with enhanced
strength and reduced water uptake was proposed in
[66]. Lime or lime dust (byproduct of calcium carbide
manufacture) and petroleum sludge are successively
introduced into soil; then, a still residue from the poly-
urea-based isocyanate synthesis is added and the com-
position is homogenized by mixing. The water uptake
of the material is 0.71–0.8 wt %, and the compressive
strength of water-saturated samples at 20°ë is
18.5−19.5 MPa.
Heat-insulating compositions. Ganyushkin et al.
[67] designed a process for the manufacturing of heat-
insulating compositions that are based on pond acid tars
and are intended for heat insulating of industrial equip-
ment and pipelines operating at contact surface temper-
atures of –60 to +130°C. The process comprises heat-
ing dolomite powder–neutralized pond acid tar to
90−100°ë and the subsequent introduction of deas-
phalting asphalt and butyl acrylate distillation residue
heated to 80–90°ë. After homogenization, the temper-
ature of the mixture is elevated to 150–160°ë; the com-
position is mixed with pearlite sand; and monolithic
sheets, plates, etc. are formed. The material obtained
via this process has low water absorption and a low
thermal conductivity coefficient, and the process itself
completely excludes the consumption of commercial
asphalt.
Manufacture of commercial ammonium sulfate
in the acid tar treatment process. A process for the
manufacture of commercial (NH4)2SO4 upon acid tar
treatment for the removal of sulfuric acid via its extrac-
tion with hot water in a countercurrent rotating-disk
reactor was developed in [68]. Tars cleaned of sulfuric
acid are sent to drying, and the sulfuric acid solution is
subjected to neutralization with ammonia. As a result, a
20–30% (NH4)2SO4 solution is produced, which is used
as a liquid nitrogen fertilizer.
The organic components of acid tars cleaned of sul-
furic acid and water experience temperature-mediated
thermochemical transformations in a desulfonation
reactor into ë5–ë20 high-boiling-points fuel compo-
386 KOLMAKOV et al.
Quality characteristics of solid fuel based on peat with organ-
ic additives [69]
Amount, wt %
Characteristic peat–tar briquette peat–organic solid
(with acid tar admix- fuel (with admixture
ture) of spent oil)
Ash content 5.9–6.5 9.8–10
Sulfur 1.6 0.1
Water 30 25
Heating value, 6694 ± 132 6217 ± 80
kcal/kg
nents (85%), ë1–ë4 gaseous hydrocarbons (5%), and
coke (10%):
RH C + R 1 H + ( CH 4 + C 2 H 6 + C 3 H 8 ).
Sulfonic acids present in organic mixtures are
reduced by the action of temperature to hydrogen sul-
fide, water, and hydrocarbons [68]:
RSO 3 H R 2 H + H 2 S + H 2 O.
The waste gas is cleaned of hydrogen sulfide in an
aqueous ammonia-spray sanitary column in which
hydrogen sulfide is absorbed by the ammonia solution
yielding ammonium sulfide. When iron(II) sulfate is
added, ammonium sulfide reacts with iron sulfate to
form an iron sulfide precipitate [68]. The sulfide precip-
itate is oxidized with air oxygen into sulfate, which is
used in the hydrogen sulfide removal cycle again.
Cement manufacture. It is rational to mix acid tars
having a sulfuric acid content of no more than 3–5 wt %
with fuel oil used at cement works and to burn. Acid
tars with a sulfuric acid content of 40–50% are neutral-
ized with a cement slurry. These tars can be used as
clinkering enhancers in cement manufacture, the best
effect is reached when 9–15 wt % acid tar neutraliza-
tion product is added to the fuel.
Preparation of peat briquettes with acid tars. A
proprietary processes for utilization of acid tars in the
manufacture of peat briquettes useful for burning in
solid fuel–fired boilers is described in [69]. The cost of
the fuel is almost half that of coal. Briquetting is carried
out at a pressure of 10 kg(force)/cm2 to shape cylindri-
cal billets of 40 mm × 18 mm size. The fuel composi-
tion is 50 wt % peat and 50 wt % acid tar (storage pond
at the 497th km of Moscow–Kazan highway M7). The
fuel possesses a required strength and noticeably loses
moisture during holding in air. Water loss for 20 days of
storage in air (16–18°ë) is 10%. For comparison, the
table presents quality characteristics of the proposed
samples of Torfogud (peat–tar) and peat–organic fuel
with an admixture of spent mineral oil. It is evident that
the quality of the fuel containing acid tar is higher than
that of the one with spent oil.
Processes for neutralization of acid tars. Meissner
Grundbau (Germany) [70, 71] designed a process for the
treatment and neutralization of petrochemical wastes.
According to this technology, petroleum sludge, in par-
ticular, acid tar, is delivered onto a flat, compacted soil
ground and is evenly distributed over the surface to form
a layer of a certain thickness. After that, a quicklime-
based reagent is applied on the layer. The product is a
brown powdered material composed of fine grains.
According to the Meissner Grundbau data, the material
is inert to water (the permeability coefficient for water is
10–7–10–9 m/s), has no effect on soil, is frost-resistant,
and possesses a high density, thus being able to with-
stand loads of up to 90 MPa. The product can be used as
a hard pavement building material.
This process was first used for the disposal of acid
soils accumulated at the Dollberg oil plant (Federal
Republic of Germany). The operation was performed in
two stages. First, 8000 t of waste was treated and, then,
on successful completion, another 40000 t of acid soils
was disposed. The decontaminated lands were reme-
died [70].
Minigazimov et al. [71] described the choice of con-
ditions for the thermal cracking processing of acid tars
having an increased concentration of organic com-
pounds. The process characteristics for the conversion
of 1 : 2 and 1 : 3 acid tar mixtures with spent hydrocar-
bon-alkylation H2SO4 were measured. It was found that
a relatively stable temperature regime is ensured in the
latter case; the SO2 concentration in the roast gas
reaches 6.5–7.9 vol %, thus providing for stable opera-
tion of contact reactors. The technology was perfected
and the composition of furnace-compartment roast gas
was determined for the conversion of the 1 : 1 fuel–H2S
mixture.
Bronfin et al. [41] invented a process for the treat-
ment of acid tars via neutralization with an aqueous
alkali solution for the purpose of simplifying the tech-
nology and manufacture of a homogeneous product
that would be stable on storage. The neutralization is
carried out in the presence of the residue remaining
after the distillation of synthetic fatty acids recovered
from oxidized petroleum waxes. The residue is taken in
an amount of 10–15% of the feedstock mass. The
experiment was run on the laboratory scale.
Landfilling acid tars. Albul et al. [72] proposed
that a suspension of 4.85 m3 of CaCO3 in 13.7 m3 of
water should be added per 10 m3 of acid tar to neutral-
ize acid tar produced during the regeneration of spent
oils. To reduce the heating of the mixture, one−third of
the suspension is introduced within 45 min and then the
rest is slowly added within 2–3 h and the mixture is
stirred until the completion of the reaction. To remove
unpleasant odors of the gases released during neutral-
ization, air in the air/exhaust gas ratio of 50 : 1 is sup-
plied to the exhaust duct. To prevent the entrainment of
acid vapor, water is sprayed through a sparger.
PETROLEUM CHEMISTRY Vol. 47 No. 6 2007
 ENVIRONMENTAL ASPECT OF STORAGE OF ACID TARS
It is quite evident that the approaches discussed in
this review do not resolve the problems of refinery
waste management, but only postpone their solution to
a later time. One cannot unequivocally answer the
question of which of the proposed processes for the
treatment of acid tars is most suitable. The demand for
a particular petroleum product, engineering design,
power consumption of the process, waste emissions to
the environment, all these factors determine the pros-
pects for commercialization of a process under particu-
lar conditions. In the view of toughening environmental
standards and requirements, as well as the necessity of
the intensification of research into petroleum resources,
the problem of utilization of acid tars will undoubtedly
remain topical for a rather long period of time.
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