A new method of the organic waste treatment, concerning waste oil, mixed plastic waste, oil sludge and PCBs waste processing with simultaneous recovery of hydrocarbons

Full text

Petroleum and Coal, Vol. 45, 3-4, 187-192
ANEW METHOD OF THE ORGANIC WASTE TREATMENT,
CONCERNING WASTE OIL, MIXED PLASTICS WASTE, OIL SLUDGE
AND PCBS WASTE PROCESSING WITH SIMULTANEOUS RECOVERY
OF HYDROCARBONS
I. Maïar1 and M. Juriga2
1 Roil Trade s.r.o., Krína 12, 811 07 Bratislava, SK, ima@blowdec.sk
2Department of Chemical Machines and Equipments, Faculty of Mechanical Engineering,
Slovak University of Technology, Nám. Slobody 17, 81231 Bratislava, SK, juriga@sjf.stuba.sk
Abstract. The BLOWDEC® process is a new and original technology developed from Slovak patent No.
279397. The basic goal is the separation of liquids and solids from the original waste material and the
liquefying of the hydrocarbons based polymers by mechanical and thermal degradation of binding forces
with simultaneous cracking of heavier hydrocarbons and inhibition of coke formation. The technology is
proven for the recycling of waste materials with a high content of organic components, primarily waste
mineral oils, oil sludge and waste mixed plastics.
The main principle is the processing of waste organic materials in a hot whirling bed created by solid
particles, for example hot sand, in special equipment - the BLOWDEC® reactor.
The process is also suitable for the treatment of the different types of waste with organic content  refinery
sludge, oil-contaminated earth and similar materials polluted with hydrocarbons. During the BLOWDEC®
process, both physical and chemical activities occur, resulting in almost 100% separation (recovery) of the
hydrocarbons from waste stream.
Key words: whirling bed of hot solid particles, mechano-activating reactions, separation, cracking, organic
waste, waste oil, waste with PCBs content, oil sludge, mixed waste plastics
Introduction
The BLOWDEC® (BLOWing D EComposition) represents
anew and original technology pursuant to the Slovak inven-
tion with a granted patent No. SK 279397 and following name
Process for Thermal and/or Catalytic Depolymerisation or
Decomposition of Low-grade Organic Substances and Device
for Carrying out the Process. The patents granted for inven-
tion abroad are heretofore as follows: U. S. patent No. US
6,165,349; United Kingdom patent No. GB 233 7265 B; Russian
patent RU 218 1126.
The technology taking advantage of the invention has been
proved in the course of recycling of waste materials with a high
content of organic components, first of all in the course of
waste oil recovery and liquefying of waste mixed plastics.
An another application field of the invention that has also
been proved is treatment  extraction of oil from hydrocarbon
sludges resulting from extraction, transport and treatment of
crude oil and utilisation of oil products, as well.
Operational tests have also proved a high effective in the
course of elimination of the oils containing PCBs.
Principle of the invention  technical solution
The basic principle of the regeneration process of wastes,
low-cost organic substances and destruction of complex com-
pounds of PCBs type, herbicides, pesticides and similar sub-
stances consists in their treatment in a hot whirling bed formed
by the solid particles, e. g. hot sand, in a special device  the
BLOWDEC® reactor. Simultaneously with the separation of liq-
uid components in the course of treatment of wastes contain-
ing liquid or solid hydrocarbons, the cracking of hydrocarbons
to an economically attractive product occurs. The chemical re-
actor pursuant to this invention essentially stands for novelty
in the technical field of chemical reactors for cracking and
separation processes.
The core of the device is aspecial processing chamber  the
BLOWDEC® reactor. Its construction reminds of a hammer mill
and radial air fan, as well. To the basic component parts of the
reactor belongs agas proof cylindrical chamber wherein arotor
to which vanes resistant to friction (ceramic) are attached ro-
tates. The rotor is set in circular motion by motor.
The circular motion of rotor vanes in the reaction chamber
brings about an intensive stirring and whirling of the reaction
mass consisting of a solid inorganic substance (sand) and an
organic component (solid/liquid hydrocarbons). As aresult of
the friction of rotor vanes against the reaction mass and effect
of hydrodynamic forces the heat is generated. The particles of
asolid inorganic substance, e. g. sand, form at the same time
afluidised hot whirling bed at the cylindrical face of the cham-
ber (Fig.1).

Petroleum and Coal, Vol. 45, 3-4, 2003188
An immense quantity of intensively whirling fine solid parti-
cles of great kinetic energy has amechano-activation effect on
big hydrocarbon molecules and along with effects of high tem-
perature causes cleaving of molecules. The principal role is
also played by aconsiderable overall surface of the solid parti-
cles having an area of some thousand square meters that repre-
sents aheat-exchanging surface of high efficiency.
Asubstantial part of the chemical reactions and physical
processes takes place in the whirling bed. The most important
chemical reactions going on in afluidised sand bed are crack-
ing reactions of all types  mechano-activation, thermal and
catalytic (SiO2) ones and their combinations, as well. Primary
reaction products of the bigger molecule cleaving enter the
recombination and isomerization reactions. Some plastics are a
subject to an accidental (polyolefins, PE, PP), other ones to
anon random depolymerisation (polystyrene).
An overwhelming part of heavy and solid hydrocarbons
crack in light constituents when being in the whirling fluidised
sand bed and evaporate simultaneously, then leave the reactor
chamber in the form of process gas. At the same time, the sub-
stances of lower boiling point (water) evaporate. With regard to
that all physical and chemical processes in the course of which
the transformation of energy and mass occurs are going on
simultaneously in the only one operational stage, the energetic
efficiency of the process is very high. Minimally depending on
the composition of organic substances entering the BLOW-
DEC® process, the obtained hydrocarbons predominantly do
a c
d
G aseo us pro ducts:
Hydroc arbo ns and water
ef
b
3
2
4
1
Sa nd
41
2
3
Treated Solids
Mk
W hirling Bed
Wa ste
in le t
Figure 1 Principle of the process.
a,b  Basic scheme of the reactors construction
c  Start up (movement of the reactor rotor)
d  Creation of the whiling bed ( Sand filling )
e  Heating of the reactor
f  Process run
Description: 1- process chamber, 2-shaft, 3-arm of the blade, 4-blade, Mk- torque
correspond in their composition to a high-quality energetic
(heating) oil with alow or zero sulphur content. With some
wastes the process is accompanied by production of light liq-
uid hydrocarbons and hydrocarbon gases as well as by asmall
production of coke  an elementary carbon which, however, is
not deposited in a reactor but in the form of aero dispersion
continually taken away by astream of reaction gas.
The BLOWDEC® process results in physical and chemical
activities the consequence of which is besides almost 100%
hydrocarbon recovery also the change in quality of obtained
oil in comparison to original organic substances entering the
process. At the same time an effective decomposition of the
substances forming the original waste material follows where-
by aclean high-quality oil without contaminants is obtained
and waste water and solid fragment (in case they were present)
wherein the particles of inorganic pollutants, e. g. chlorides in
case of PCB treatment are firmly fixed, separated. Oxides of
nitrogen and sulphur are not produced.
An important advantage of the BLOWDEC® technology is
its simple technological equipment and aminimum of devices
and apparatuses used (Fig._2). The very chemical process, as
well as the physical treatment of reaction products is computer-
ised. From the economical point of view it is also profitable to
run adevice of comparatively small production capacity, t. i.
device demanding low investment costs. This advantage is
multiplied by the fact that one device is able to treat different
kinds of wastes of different composition.

Petroleum and Coal, Vol. 45, 3-4, 2003 189
Figure 2. Simplify flow chart. SH - Solid hopper, SC1~2 Screw conveyer, RV- Rotary valve, P1~6 - Pumps,
C1- quench condenser, C2- plate condenser, E1~E3 heat exchanger, CW- Cooling water.
Experimental Station - Operational Experience
The first industrial technological BLOWDEC® unit with
aproposed capacity to treat 3500 tons waste oil ayear and
a200 kW reactor is currently being installed by arecycling fac-
tory of an important waste oil processor in Slovakia  KONZE-
KO Ltd. Markusovce. The unit was built up with the assistance
of agrant by EU - PHARE fund.
The construction of a 200 kW reactor (thermal resistance)
and an overall arrangement of the first unit do not enable to
verify all the prospective fields of application, therefore in the
course of 2002 the second research and development BLOW-
DEC® unit with a45 kW reactor was built up in the vicinity of
Bratislava and set in probation running in January 2003. The
testing of different kinds of real and simulated waste mate-
rials have been carried out in here in the first stage.
The tests have proved that it is possible to treat all the kinds
of wastes taken into consideration under economically favour-
able conditions and obtain valuable, from the commercial view-
point attractive, energetic oil and ahydrocarbon gas. Also the
waste mineral oils, oil - crude oil sludge, clean and waste mixed
plastics have been tested.
The testing of elimination of transformer oils containing dan-
gerous PCBs (polychlorinated biphenyls) currently being ex-
ported out of Slovakia for their liquidation has proved that it is
even possible by means of the BLOWDEC® process to suc-
cessfully and economically eliminate such kinds of dangerous
persistent organic substances.
Figure 3. General view to experimental station (Kuchyòa, Slovakia).

Petroleum and Coal, Vol. 45, 3-4, 2003190
Results of the Experiments.
The testing program applicable to several raw material re-
sources has proved that it is possible to qualify the final prod-
ucts as alight heating oil with alow or zero sulphur content.
The results of aresearch in progress aimed at optimum utilisa-
tion of obtained hydrocarbons as semi finished products for
more refined, e. g. petrochemical treatment seem to be pro-
spective.
Aside product in the process of oil sludge treatment is avery
finely ground inorganic solid fragment containing traces of
hydrocarbons. By means of this product it is possible to re-
place in an advantageous way an important constituent in pro-
duction of road asphalts  so called filler currently replaced by
e.g. finely ground calcite.
The PCBs elimination is characterized by ahigh conversion
whereby a substantial part of chlorine is by means of the pro-
cess bound in chlorides (sodium and calcium) forming apart of
a solid fragment extracted from process.
Waste oil treatment. The EU uses annually approx. 5 mill.
tonnes of oil [6] arising as a waste product of the use of oils in
awide range of industrial and commercial activities, such as en-
gineering, power generation and vehicle maintenance, of which
approx. 2,5 mill. tonnes are recollected, this is cleaned and recy-
cled mostly as heavy heating oil. During use in machines the oil
and pollutants become a stable dispersion system composed of
the hydrocarbon phase of the original oil, solid particles and
water. An adverse feature of such dispersion is its stability and
acceptable physical separation of components cannot be practi-
cally implemented.
The basic goal during the waste oil treatment is the destruc-
tion of additives and their residuals which are responsible for
stability of the dispersion by mechanical and thermal degrada-
tion and a simultaneous inhibition of coke formation.
Additives added to oil are mostly heterogeneous organic
materials, containing, in addition to carbon and hydrogen at-
oms, zinc, phosphorus, calcium, nitrogen, oxygen, etc. Such
materials have a limited heat resistance, which offers a method
for their removal. Technologies operating on the principle of
thermal destruction of additives are well known world-wide,
but not as yet broadly applied. The most frequently used prin-
ciple is delay coking, a version of thermal cracking, which pro-
duces gas oil and coke. The BLOWDEC technology is compet-
itive alternative for waste oil processing. The distribution of
additives elements (Tab.1) demonstrates efficiency of the BLOW-
DEC process for waste black oil treatment executed at the tem-
Oil type SAE 1OW-40 SAE 1OW-40 Waste black oil
"cocktail" BLOWDEC Ash from
sediment
Elements Fresh (ppm) Waste
(ppm) content in oil part
(ppm)
regenerated oil
(ppm)
(% wt.)
Zink (Zn) 879 625 319 2,3 0,41
Calcium (Ca) 1520 1180 833 2,6 3,19
Phosphorus (P) 680 450 350 0,0014 0,56
Water content & light HC 10,8 % wt.
Ash contents 12,71
perature of about 370oC.
The quality liquid fuel and base lubricating oil can be ob-
tained from the regenerated oil by the fractionation of the raw
recovered oil via distillation e.g. in the molecular vacuum thin
film evaporator (Tab.2).
Oil with PCBs treatment. PCBs (polychlorinated biphenyls)
are considered due to their toxicity and persistence as very
dangerous chemicals that come in various forms including oily
liquids, solids and hard resins. PCBs are organochlorines that
were manufactured until the mid-1980s. They are still found in
old electrical equipment. PCBs are very persistent in the envi-
ronment, taking years to degrade. All PCBs from Slovakia are
exported for disposal abroad, while there is no suitable technol-
ogy for destruction of such waste stream. The test (Tab.3) dur-
ing which hot whirling bed of solids was created with strong
alkalic agent showed that at the temperature of about 500oC
could be PCBs oil successfully eliminate.
The oil sludge treatment. The US petroleum-refining indus-
try annually produces more than 2,5 million tonnes of wet haz-
ardous oil sludge, and in addition large quantities of non-haz-
ardous sludge from crude, refined products and intermediate
product tank bottoms. Similar sludge (artificially prepared from
the waste oil, water and the soil) was treated in the BLOWDEC®
unit at the temperate of 390oC. Summary of this test run are in
Table 4.
Mixed waste plastics treatment. The total amount of plastic
wastes generated by our society is growing rapidly. The main
source of plastic waste in Western Europe (18,5 mill. tons/year) is
the municipal solid wastes (MSW) (63,5 wt.%) followed by distri-
bution and large industry (19,5wt.%) [7]. Plastic consumption is
increasing by 4% each year. If this trend continues, we will soon
be swamped by waste plastics. There is a commonly held view
that not all plastics can be recycled. That is not true. All plastics
can be reused, recycled, or have energy recovered from them.
One of the possible ways was proved in BLOWDEC test unit.
The artificially prepared plastics mix was processed at the tem-
perature of 430oC and turned to liquid and gaseous hydrocarbon
product (Tab. 5).
Industrial applicability of the BLOWDEC®
technology
It is possible to apply the BLOWDEC® process and tech-
nology as an advantageous alternative to already known tech-
nologies in several fields. There have been no known econom-
Ta bl e 1 . Additives elements (typical) distribution during the waste black oil cocktail treatment in the BLOWDEC® process

Petroleum and Coal, Vol. 45, 3-4, 2003 191
Table 3. Results of the PCBs in insulation oil destruction test
Material
Parameter
Waste transformer oil
with PCBs
Oil after
the treatment (ppm)
Solids
after treatment (ppm)
Total organic chlorine 3,1% wt. 1048 2,6
PCB content 2790 ppm 1,3 3,2
Chlorides   5990
Ta bl e 4 . Results of the oil sludge treatment in the BLOWDEC® process
Material
Content Oil sludge (% wt.) Separated solids Recovered oil (% wt.)
Hydrocarbons (oil) 18,5 840 ppm 99,8
Solids 75 99,9 % wt. 0,12
Water 6,5 0,1 % wt. 0,08
Table 2. Properties of distillation fractions from the product of the waste black oil regeneration in process BLOWDEC®
fractionated in short way vacuum film evaporator
Raw
Recovered Oil
Distillate No.1 yield
18,5% Bearing oil
Distillate No.2 yield
72,9% NS 150
Parameter Unit Value Value Value
Density at 20oC kg/m3 874 865 878
Viscosity at 40oC mm2/s 29,1  
Viscosity at 20oC mm2/s  5,90 42,4
Viscosity at 100oC mm2/s   6,2
VI (Viscosity index)    95
Diesel index  61 48,7 
Distillation test    
Initial boiling point oC 65 224 
up 250oC recovered % vol. 7 9 
up 350oC recovered % vol. 25 55 
up 360oC recovered % vol. 36 70 
End of distillation / recovered oC / % vol. 385 / 50 385 / 99 
Sulphur content % wt. 0,32 0,246 0,51
Pour point oC  -14 
Freezing point oC -20 -29 -18
Flash point (PM) oC <20 109 210
Acid number mg KOH / g 2,6 0,10 0,07
Determination of ash % wt.  0,001 0,001
Conradson Carb. Residue - 10% % wt.  0,015 0,054
Corrosion Cu 3h/100oC    1a
Corrosion Fe 3h/100oC    negat.
Resins content % wt.   0,53
Colour ISO    4,5
Colour after clay bleaching (5%, 200oC, N2)   3,0
Appearance    B&C
Acid number % wt. 0,03  
Conradson Carbon Residue % wt. 0,05  
Aniline point oC 91,1  
Bromium number g Br/100g 15  
Average molecular weight  312  
Aromatic carbon content
IR method % 13  
Paraffin carbon content
IR method % 61  

Petroleum and Coal, Vol. 45, 3-4, 2003192
ically accepted processing technologies (mixed plastics) in the
world yet in some fields of process utilisation. Very promising
is its application in the sphere of upgrading of the alternative
raw material resources (coal conversion, bitumen sands, and
deserted oil fields).
The two main areas of application of the BLOWDEC® tech-
nology are as follows:
 WASTE MANAGEMENT
 UPGRADING OF HEAVY HYDROCARBONS
WASTE MANAGEMENT  treatment of wastes containing
petroleum substances represents a field the process was devel-
oped for. Acharacteristic feature is ahigh adaptability to the
composition of incoming waste materials.
Amajority of wastes containing hydrocarbons produced in
the course of oil exploitation, transport and treatment as well as
when making use of petroleum products represents amixture of
oil  water  solid substance. The individual kinds of wastes
only differ in different proportion of individual components
and in stability of disperse system the nature of which is often
typical of waste. Out of ahuge spectrum of such wastes, an
extreme example can be given by the waste motor oil on the one
hand and dewatered oil sludge from the refinery waste-water
treatment plant on the other hand. It is possible to successfully
treat both kinds of wastes by means of the BLOWDEC® pro-
cess and at the same time get the oil back. Since there is also the
cracking of the present hydrocarbons in the course of process,
the oil obtained in such way is of attractive economic value.
Aprospective and proved field of application of the BLOW-
DEC® technology within waste management is treatment of
waste plastics, first of all polyolefins (PE, PP), polystyrene (PS)
and other widespread plastics.
THE HEAVY HYDROCARBON CRACKING represents an-
other attractive area of application of the BLOWDEC® technol-
ogy. Cleaving  cracking of the heavy oil fractions is acommon
way of depth oil treatment. The raw materials used for BLOW-
DEC® are heavy residues of atmospheric and vacuum distilla-
tion of crude oil or its chemical treatment.
The utilization of alternative raw material resources such as
heavy crude oils (Kazakhstan), oil-bearing shales and sands
(Athabaska, Canada) or natural bitumens (Trinidad, South
America) represents apromising future field of application of
the BLOWDEC® technology. The already known technologies
enable upgrading of vast fields of such hydrocarbons to
asufficient economic effect, however, the application of the
BLOWDEC® process can make these hydrocarbon resources
much more attractive. Another possible application field con-
sists in reopening of oil exploitation on deserted oil fields where
the oil exploitation was brought to ahalt because of ahigh
sand content in oil.
Final remarks - benefits of the process
The BLOWDEC® technology has many significant benefits
and it enables:
effective, almost 100% recovery of hydrocarbons from wastes
containing petroleum substances such as waste mineral oils,
refinery sludges and sediments, sludge from oil exploitation
and transport, tar sludges
economical conversion of separated as well as waste mixed
plastics to liquid hydrocarbons
extraction of hydrocarbons from alternative sources such as
oil and tar sands, natural bitumens, crude oil with ahigh
sand content
simple and effective elimination of wastes containing PCB
and other troublesome persistent organic substances
flexibility to waste composition and treatment of wastes,
raw material resources within asingle working stage inde-
pendently of a contamination level or composition of an
incoming stream
lack of coke residues formation in adevice
low specific power consumption or high energetic effective-
ness in comparison to other technologies
ecological operation without formation of dangerous wastes
and gaseous emissions  sulphur and nitrogen oxides
compact unit with acomparatively simple technological de-
vice demanding little room
low investment resources requirement.
Reference
[1] Slovak patent No. 279397
[2] USA Patent US 6,165,349
[3] UK patent GB 233726 5B
[4] Russian patent RU 218 1126
[5] Web page: www.blowdec.sk
[6] Vercheval J., International Conference on Waste Oil Management,
Prague, October 2001  Conference materials
[7] Cardona S.C.; Corma A., Applied Catalysis B: Environm. 2000,
25, 151
Ta bl e 5 . Results of the mixed plastics treatment in the BLOWDEC® process
Reference composition
of the mixed plastics Properties of the liquefied oil recovered by the reference mixed plastics conversion at 450o
C
Component Value (% wt.) Parameter Unit Value
HD PE 10 Density at 20oC kg/m3 881
LD PE 38 Viscosity - 40oC mm2/s 29,1
PP 30 Mechanical impurities % wt. 0,14
PS 15 Water content % wt. 0,05
PA 4 Sulphur content ppm 25
PMMA 1 Pour point oC 8
PUR 2 Calorific value MJ/kg 41,8
PVC (!) 0 Distillation test: up 350oC recover. % vol. 26