(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

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(43)1ntemationalPublicationDate __..... WO 2021/152109 Al
05 August 2021 (05.08.2021) WI PO I PCT

(51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every
CJ0G 1/10 (2006.01) Cl0L 1/04 (2006.01) kind of national protection available): AE, AG, AL, AM,
AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ,
(21) International Application Number:
CA, CH, CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM, DO,
PCT/EP202l/052134
DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN,
(22) International Filing Date: HR, HU, ID, IL, IN, IR, IS, IT, JO, JP, KE, KG, KH, KN,
29 Januaiy 2021 (29.01.2021) KP, KR. KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA. MD,
ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO,
(25) Filing Language: English
NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW,
(26) Publication Language: English SA, SC, SD, SE, SG, SK, SL, ST, SV, SY, TH, TJ, TM, TN,
TR, TT, TZ, UA, UG, US, UZ, VC, VN, WS, ZA, ZM, ZW.
(30) Priority Data:
20154706.4 30 Januaiy 2020 (30.0 l.2020) EP (84) Designated States (unless otherwise indicated, for eve1:v
kind of regional protection available): ARIPO (BW, GH,
(71) Applicant: YANCHEP TECHNOLOGY LIMITED GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ,
[GB/GB]; 5 Taplins Court, Taplins Farm Lane, Hartley UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,
Wintney Hampshire RG27 8:XU (GB). TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
(72) Inventors: HARPER, Robert David; urb. Apts Tenis, Blq EE, ES, FL FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV,
24, Apt A6, Sotogrande, ll3 IO Cadiz (ES). TIMPANY, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM,
Edward Allen; Hazeley House, Hazeley Heath Hampshire TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,
RG27 SL T (GB). KM, ML, MR, l\'E, SN, TD, TG).

(74) Agent: MATHISEN & MACARA LLP; Communica- Declarations under Rule 4.17:
tions House, South Street, Staines-upon-Thames Middlesex as to applicant's entitlement to app(v for and be granted a
;;;;;;;;;;;;;;;
TW18 4PR (GB). patent (Rule 4. I 7(ii))
;;;;;;;;;;;;;;;
;;;;;;;;;;;;;;; ofinventorship (Rule 4.17(iv))

-- (54) Title: PRODUCTION OF FUEL PRODUCTS FROM WASTE RUBBER MATERIAL

-
;;;;;;;;;;;;;;; Fig 1
(57) Abstract: A process for extracting fuel products from waste rub-
ber, comprising the steps of subjecting the waste rubber to pyrolysis to
produce a pyrolysis vapour, subjecting the pyrolysis vapour to a con-
densation step to produce a pyrolytic oil having a boiling point range of
Chip hopper 45-400°C and a flash point below 25 °C, and then subjecting the pyrolytic
oil to a vacuum steam stripping step so as to recover a fraction having
a flash point of at least 40°C but no higher than 55°C, a boiling point

-- range starting at l00°C or higher. a density at 15°C ofless than 990 kg/
m3 , a total acid number TAN of up to 12, a styrene content of less than

-
;;;;;;;;;;;;;;;
;;;;;;;;;;;;;;;
C-a-fbon
char
7000ppm, and an organic halogen (as Cl) content of less than 50ppm.

To
a!mosp,ere
RawoH

Steam Multi-stage
Solids
C8'1(fifuge

Naphtha Fluxan!
product product

[Continued on next pageJ

 WO 2021/152109 A 1 Illlll llllllll 1111111111111 lllll lllll 111111111111111111111111111111 lllll 11111111111111111111111
Published:
- with international search report (Art. 21 (3))
 WO 2021/152109 PCT/EP2021/052134

PRODUCTION OF FUEL PRODUCTS FROM WASTE RUBBER MATERIAL

The present invention relates to compositions obtained from the pyrolysis of waste
rubber such as tyres, to fuel products comprising such compositions and also to a process
comprising the pyrolysis of waste rubber and subsequent separation of the resulting oil to
produce fuel products.
Many methods are known for preparing gasoline and diesel from waste carbonaceous
material such as rubber and plastics. For example, US 5744668 discloses a method for
producing gasoline, diesel and carbon black from waste rubber and/or waste plastics which
involves the sequential steps of pyrolysis, removal of residual sulphur nitrogen and chlorine,
catalytic cracking and then fractionation of a portion of the catalytically cracked reaction
product to separate gasoline, diesel and a heavy residue fraction. The heavy residue fraction
is recycled into the pyrolysis step in this case, but ultimately a significant proportion will
remain at the end of the process; furthermore the proportion of the residue fraction will be
much greater in processes that do not run the (generally uneconomical) catalytic cracking
step described in US 5744668. WO 90/14409 discloses a method of extracting chemicals
from tyre-derived pyrolytic oils which comprises subjecting the oils to a fractional distillation
and recovering a fraction boiling in the range 43-204°C, and then subjecting this fraction to
further fractional distillation in order to isolate and extract specific chemical products.
We have discovered that waste rubber products such as tyres can be treated so as to
obtain products which have a particularly valuable combination of properties. Our copending
application PCT/EP2019/070266 discloses a composition obtained from the pyrolysis of
waste rubber and subsequent separation having:
a flash point above 55°C determined according to ASTM D93 procedure B,
a boiling point range starting at 140°C or higher under atmospheric pressure
determined according to ASTM D86,
a density at 15°C of less than 990 kg/m 3 determined according to ASTM D4052,
a total acid number (TAN) ofup to 12 determined according to ASTM D664,
a styrene content ofless than 3000ppm,
and an organic halogen (as Cl) content of less than 50 mg/kg determined according to
IP510.
The above compositions are stated to have utility as marine fuel products. Similar
compositions having lower flash points would not be considered for use as marine fuel

1
 WO 2021/152109 PCT/EP2021/052134

products for safety reasons. However we have now further discovered it is possible to make
such compositions and to use them as part of a blend with a further marine fuel component.
Accordingly in a first aspect the present invention provides a composition obtained
from the pyrolysis of waste rubber including natural rubber and subsequent separation
having:
a flash point of at least 40°C but no higher than 55°C determined according to ASTM
D93 procedure B,
a boiling point range starting at 140°C or higher under atmospheric pressure
determined according to ASTM D86,
a density at 15°C ofless than 990 kg/m 3 determined according to ASTM D4052,
a total acid number (TAN) ofup to 12 determined according to ASTM D664,
a styrene content of less than 7000ppm,
and an organic halogen (as Cl) content of less than 50 mg/kg determined according to
IP510.
The composition of this first aspect of the invention has a particular combination of
features which allow its use as a component in a fuel product, and in particular as a marine
fuel component. Accordingly a further aspect of the invention comprises the use of the above
composition as a component in a fuel product, preferably a marine fuel component.
Due to the presence of the heavy black components, conventional rubber pyrolysis oils
are black in colour. They also have a low flash point, which necessitates the use of storage
and transportation equipment of a suitable low flash point class. However tanks, transporters
and vessels that have the required safety status to carry low flash point class materials are
generally dedicated to clear-coloured products, as the majority of products in the low flash
point class are clear coloured. If a black product is placed in any receptacle designed for clear
fuels, then an expensive cleaning process is required once the product is discharged, so as to
avoid contamination of subsequently used clear products. As a result it is uneconomical to
use a black product with a low flash point in the majority of tanks, transporters and vessels
that service the petrochemical and industries. The marine fuels sector does have tanks,
transporters and vessels which accept black coloured materials without the need for
expensive post-use cleaning, but these generally do not comply with the onerous additional
safety requirements for low flashpoint class fuels, and so are not generally capable of
accepting low flashpoint class products.
An advantage of this composition is that its styrene content is sufficiently low to permit
its use in a marine fuel: high levels of styrene are not permitted in marine fuels due to the risk

2
 WO 2021/152109 PCT/EP2021/052134

of polymerisation, which can result in line blockages. Its Total Acid Number (TAN) is also
low enough make it suitable for use in a marine fuel. Compositions which have high Total
Acid Numbers can be corrosive which is undesirable in engines, and subsequent
neutralisation can produce salts, which is undesirable in fuels due to the risk of sediment
formation. A low level of halogen, particularly chlorine, is also important because chlorine is
undesirable and strictly regulated in fuel products.
A further feature of the composition of the invention is the low percent recovery level
under the distillation conditions of ASTM D86. The composition preferably has a percent
recovery ofless than 90vol% when subjected to a distillation test according to ASTM D86;
more preferably the recovery is less than 80vol%, and more preferably still it is less than
70vol% and most preferably it is less than 60vol%. Conventional diesel fuels usually have
higher recovery levels, typically around 97vol% or greater.
It is particularly surprising that it is possible to produce a fuel component which is
suitable for commercial use as in a fuel and simultaneously satisfies all of the above
requirements, whilst at the same time containing high levels of black products which are
normally oflittle commercial value.
Although the composition itself is wholly obtained from the pyrolysis of waste rubber
and subsequent separation, in use it is blended in an amount of no more than 10% with
conventional marine fuel derived from fossil fuel sources.
Accordingly a second aspect of the invention comprises a marine fuel comprising from
0.01 to 10%, preferably 0.1 to 5%, of the composition of the first aspect of the invention.
The marine fuel may be classified as a residual marine fuel rather than distillate marine fuel.
All residual marine fuels are manufactured by combining blends of heavy fractions from
crude oil refining, such as residual fuel oil or vacuum gasoil, with additional fuel components
which are added to give the fuel desirable properties such as improved viscosity, reduced
sulphur content or improved stability. The composition of the first aspect of the invention is
particularly useful as a blend component as it can improve the stability of marine fuels due to
its aromatic hydrocarbon content.
The waste rubber from which the composition of the invention is derived via pyrolysis
preferably contains at least 10wt%, more preferably at least 20wt% and most preferably at
least 30wt% of natural rubber. As a result of the presence of natural rubber, the composition
of the invention contains biogenic carbon, and preferably has a biogenic carbon content of at
least 15%, more preferably at least 20%, most preferably at least 30% and particularly
preferably at least 40%, as determined according to ASTM D6866 Method B (AMS). The

3
 WO 2021/152109 PCT/EP2021/052134

biogenic carbon content is the percentage carbon from "renewable" (biomass or animal by-
product) sources versus petroleum (or otherwise fossil) sources. For reference, 100%
biogenic carbon indicates that a material is entirely sourced from plants or animal by-
products and 0% biogenic carbon indicates that a material did not contain any carbon from
plants or animal by-products: an intermediate value represents a mixture of natural and fossil
sources of carbon.
As a result of it being derived from waste rubber, the composition of the invention also
contains aromatic hydrocarbons (organic compounds with benzene-like rings). Typically the
total aromatic hydrocarbon content is at least 20% m/m, preferably at least 35% m/m and
more preferably at least 50% m/m, as measured according to the IP391 test method.
The composition of the invention may have a flash point of at least 40°C, preferably at
least 45°C, but less than 55°C determined according to ASTM D93 procedure B. In one
embodiment the flash point ranges from 40°C, preferably 45°C, to 54°C. In another
embodiment it ranges from 40°C preferably 45°C, to 53°C.
The composition of the invention may have a density at 15°C ofless than 980 kg/m 3 .
Density is determined according to ASTM D4052.
The composition of the invention may have a boiling point range starting at l 10°C or
higher under atmospheric pressure, and this may optionally be 120°C or higher, 130°C or
higher or even l 40°C or higher.
The boiling point range of the composition of the invention may start at a temperature
not exceeding 220°C under atmospheric pressure. Alternatively it may start at a temperature
not exceeding 2 l 0°C, or 200°C, or l 90°C, or l 80°C, or I 70°C, or l 60°C, or even not
exceeding l 50°C.
The composition of the invention preferably has a TAN no higher than 10, more
preferably no higher than 8, and most preferably no higher than 7. TAN is determined
according to ASTM D664.
The composition of the invention preferably has a styrene content of less than
5000ppm, more preferably less than 4000ppm, and most preferably less than 3500ppm.
Styrene content is determined by gas chromatography.
The composition of the invention preferably has an organic halogen content (as Cl)
below 40 mg/kg, more preferably below 30 mg/kg. Organic halogen content is determined
according to IP510.
A further aspect of the invention provides a process for extracting fuel products from
waste rubber, comprising the steps of:

4
 WO 2021/152109 PCT/EP2021/052134

(a) subjecting waste rubber to pyrolysis to produce a pyrolysis vapour;

(b) subjecting the pyrolysis vapour to a condensation step to produce a pyrolytic oil having a
boiling point range of 45-400°C and a flash point below 25°C, preferably below 18°C;
(c) subjecting the pyrolytic oil to a vacuum steam stripping step at a pressure ofless than 0.85
bar a and with a temperature of less than 120°C at the top of the column, and recovering a
first component having an initial boiling point not exceeding 75°C under atmospheric
pressure and a second component which has a boiling point range starting from 100°C under
atmospheric pressure or higher and possesses the properties defined above for the
composition of the invention.
Preferably the waste rubber which is used in the process of the invention and from
which the compositions of the invention are derived comprises waste tyres, the rubber in
which is generally at least 25wt% and more commonly at least 40wt% natural rubber. Typical
waste tyres comprise approximately equal quantities of synthetic rubber and natural rubber,
as well as other components such as plasticisers and carbon black. The waste tyres are usually
chipped or shredded prior to use.
Regarding the pyrolysis step (a), such processes are well known in the art. A preferred
process is operated at a temperature of 400-550°C, preferably 450-500°C and more
preferably 460-480°C. The process is preferably operated at a negative pressure relative to
atmosphere of up to 0.1 bar, more preferably up to 0.02 bar. The residence time in the reactor
is typically 1-4 hours, preferably 2-3 hours. Carbonaceous solids are evacuated from the base
of the pyrolysis reactor, and the remaining pyrolysis product comprising gas and hydrocarbon
vapour is passed onto the next condensation stage.
In the condensation stage (b) any suitable method may be used. In one preferred
method, in a first stage the raw pyrolysis oil product is cooled, preferably to below 80°C,
before being sprayed as an oil shower through a vertical condenser unit in which the hot
pyrolysis gas and vapour products flow upwards through the descending oil shower. Oil
condenses from the vapour stream, and the remaining vapour and gas is passed through a
second condenser to condense the remaining oil. The condensed oil streams are combined to
form a pyrolysis oil having a boiling point range of 45-400°C and a flash point below l 8°C,
which may then be separated into the two compositions of the invention.
The pyrolytic oil typically contains 3-5% of suspended solid particles, which comprise
principally carbon black. Prior to the separation stage, it is preferred that the solid level in the
pyrolytic oil is reduced to no more than 0.2wt%, preferably no more than O. lw1%. This is to
reduce the risk of a stable Pickering emulsion forming around carbon particles during the

5
 WO 2021/152109 PCT/EP2021/052134

subsequent separation stage. Techniques for removing suspended solids are well known in
the art, and any process which is capable of reducing the solids to the required level may be
used.
If it is required to reduce the level of suspended solids, they may be removed in one or
more separate steps, with two or more steps being preferred. In a preferred solids removal
stage, in a first step the pyrolytic oil is passed through a centrifuge to reduce the solids level
to below l.5wt%, preferably below l.2w1%. The resultant stream is then subjected to a
further solids removal step to reduce the solids level to no more than 0.5wt%, and preferably
no more than 0.2wt%. The reason for the preferred use of two or more solids removal steps is
that separators suitable for obtaining the very lowest levels of solids typically function most
efficiently if the starting solids level is already low.
The separation step (c) utilises a vacuum steam stripping column: in this method, it is
preferred that the pyrolytic oil contains no more than 0.2wt% solids, and therefore it is
preferred that prior to the separation step the pyrolytic oil has been subjected to a solids
removal stage such as described above. In the vacuum steam stripping column, the pyrolytic
oil flows down a packed vertical column and steam is pumped upwards. Oil and steam
flowrates and the column pressure are adjusted to ensure that the correct components are
separated. The column pressure is preferably less than 0.85 bar a, more preferably less than
0.5 bar a (where atmospheric pressure is defined as 1 bar a). The light components are carried
away by the steam, and this stream is condensed before being separated. The heavier
component comprising the remaining liquid oil, which is the composition of the invention
and is usually referred to as the fluxant product, is collected in a holding tank. The light
components and fluxant product together comprise at least 98vol%, preferably at least
99vol% of the total product obtained from this vacuum steam stripping step (c).
The fluxant product has a boiling point range starting at 100°C or higher. The absence
of any high temperature cut-off means that it contains large, complex hydrocarbon molecules
and is typically black in colour.
A preferred embodiment of the invention is described below with reference to Figure 1,
which is a schematic view of this preferred embodiment of the process of the invention.
In this preferred embodiment of this invention, the waste rubber material used as a
feedstock comprises waste tyres, which are first chipped to a size of no more than 40mm x
40mm. The rubber feedstock may be pre-treated in any known manner to remove impurities.
The chipped rubber feedstock is fed from the chip hopper into a pyrolysis reactor via an
airlock to prevent oxygen from entering the reactor vessel. The reactor is a horizontal round

6
 WO 2021/152109 PCT/EP2021/052134

vessel with a slowly rotating shaft carrying paddles to move the rubber through the reactor.
Burners provide heat to the reactor so as to control the temperature therein to about 470°C.
The reactor operates at a slight negative pressure of -14mb so as to prevent gas leakage. As
the rubber passes through the reactor and is pyrolysed, the solid components form
carbonaceous solids, which are evacuated from the reactor by means of an archimedes screw
with an air lock on the exit purged with inert gas. The hydrocarbon gas and vapour is
extracted from the reactor using the slight negative pressure, and transferred to the next
condensation stage.
In the condensation stage the hot hydrocarbon gas and vapour flows upwardly through
a vertical condenser unit containing packing, down through which is sprayed a shower of
previously condensed crude pyrolytic oil which has been cooled to 70°C. The passage of the
cooled oil through the packing causes about 90% of the vapour flowing upwards to condense.
This condensed oil is passed through a water-to-oil heat exchanger where it is cooled to
70°C. From there it may either be recirculated into the condenser to form part of the oil
shower, or transferred to a mixing tank for the next stage. The remaining vapour and gas
exiting the condenser at 70°C is passed through a second condenser to remove further
condensables. In the second condenser the gas and vapour is bubbled through a chilled bath
(15°C) containing a lighter fraction of the condensed pyrolytic oil in order to further
condense the vapour, as well as removing very light carbon particles. The remaining gas
stream is then passed through a glycol heat exchanger (7°C) to condense out any final liquid
fractions. The dried gas which remains is condensed in syngas tanks, and is typically filtered
and then used to fuel the burners heating the pyrolysis reactor, as shown in Fig 1.
In this preferred embodiment of the invention, prior to separation the condensed
pyrolytic oil is passed through a solids removal stage in order to reduce its solids content. The
oil is first centrifuged through a decanter centrifuge to reduce the solids content to
approximately 1wt%, and then centrifuged further in a second step to reduce the solids
content to below 0.2wt%.
The filtered pyrolytic oil is then passed to a vacuum steam stripping column. The oil
flows down the packed vertical column as an oil shower with steam flowing up the column.
The temperature at the top of the column is maintained at less than 120°C. The column
operates at below 0.85 bar a, preferably below 0.5 bar a and the oil and steam flowrates and
pressure are adjusted to ensure that the lighter component (initial boiling point not exceeding
75°C under atmospheric pressure), usually known as the naphtha stream, is carried away by
the steam. This naphtha stream is condensed in a heat exchanger, and the naphtha phase then

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 WO 2021/152109 PCT/EP2021/052134

separated from the water. The fluxant product boiling above 100°C is collected in a holding
tank.

EXAMPLE
A composition according to the invention was obtained by performing pyrolysis of a
feedstock of chipped tyres followed by condensation, solids removal and vacuum steam
stripping as described above. In this case the fluxant product had a boiling point range
starting at 141 °C.
The collected products were subjected to a distillation according to ASTM D86. The
results are shown in the Table below.

TABLE 1
Distillation test according to ASTM D86

Fluxant
REC
Initial boiling pt oc 141.0
5% oc 160.0
10% oc 199.5
30% oc 270.0
50% oc 319.0
70% oc --
90% oc --
95% oc --
Final boiling pt oc 319.0
Recovery vol% 50.0
Residue vol% 49.0
Loss vol% 1.0
3
Density at l 5°C kg/m 949.0
REC = recovered
Density was determined according to ASTM D4052.

It can be seen that the fluxant product had a percent recovery of just 50vol% in this test.
By contrast the standard automotive and marine diesel products, which are middle distillates,
had a percent recovery exceeding 97vol%.
The recovered fluxant product was found to have the following properties:
Flash Point (ASTM D93B) - 49°C

8
 WO 2021/152109 PCT/EP2021/052134

TAN (ASTM D664) - 4.48 mg KOH/kg

Styrene content (gas chromatography method)- 1376 ppm
Organic halogen as Cl (IP510)- 14 mg/kg
Density at 15°C (ASTM D4052)- 949.0 kg/m 3
Biogenic carbon content (ASTM D6866B)- 51%
Total aromatic content (IP 391) - 47.0vol¾

The above data shows that the fluxant product recovered has properties which permit its
use as a component of marine fuels, as well as having a flash point high enough to permit its
transportation without additional safety restrictions. Furthermore it makes use of high boiling
point black components, which otherwise need to be further processed or disposed of
separately, as they are regarded as being of little commercial value, since black colouration is
incompatible with most transportation fuel products.

9
 WO 2021/152109 PCT/EP2021/052134

CLAIMS

1. Composition obtained from the pyrolysis of waste rubber including natural rubber and
subsequent separation of the resulting oil, which has:
a flash point of at least 40°C but no higher than 55°C determined according to ASTM
D93 procedure B,
a boiling point range starting at 100°C or higher under atmospheric pressure
determined according to ASTM D86,
a density at 15°C ofless than 990 kg/m 3 determined according to ASTM D4052,
a total acid number (TAN) ofup to 12 determined according to ASTM D664,
a styrene content of less than 7000ppm determined according to gas chromatography,
and an organic halogen (as Cl) content of less than 50 mg/kg determined according to
IP510.

2. Composition according to claim 1, which has a flash point of at least 40°C, preferably
at least 45°C, but less than 55°C, and more preferably which has a flash point ranging from
40°C, preferably 45°C, to 54°C, and most preferably from 40°C preferably 45°C, to 53°C.

3. Composition according to claim 1 or 2 which contains biogenic carbon, preferably

having a biogenic carbon content of at least 15%, preferably at least 20%, more preferably at
least 30%, and most preferably at least 40%, as determined according to ASTM D6866
Method B (AMS).

4. Composition according to any preceding claim which contains aromatic

hydrocarbons, preferably having a total aromatic hydrocarbon content of at least 20%m/m,
more preferably at least 35%m/m and most preferably at least 50%m/m, as measured
according to IP3 91.

5. Composition according to any preceding claim, having a boiling point range starting
at l 10°C or higher, preferably 120°C or higher, more preferably130°C or higher and most
preferably l 40°C or higher.

10
 WO 2021/152109 PCT/EP2021/052134

6. Composition according to any preceding claim, having a boiling point range starting
no higher than 220°C, preferably no higher than 210°C, more preferably no higher than
200°C and most preferably no higher than l 90°C.

7. Composition according to any preceding claim, having a flash point ranging from
40°C, preferably 45°C, to less than 55°C, preferably ranging from 40°C, preferably 45°C, to
54°C, and more preferably ranging from 40°C, preferably 45°C, to 53°C.

8. Composition according to any preceding claim, wherein the waste rubber from which
the composition is derived comprises waste tyres.

9. Marine fuel, preferably a residual marine fuel, comprising from 0.01 to 10%,
preferably 0.1 to 5%, of a composition as defined in any preceding claim.

10. Use of a composition as defined in any of claims 1 to 8 as a component in a fuel

product, preferably as a marine fuel component and more preferably as a component in a
residual marine fuel.

11. Process for extracting fuel products from waste rubber, comprising the steps of:
(a) subjecting waste rubber to pyrolysis to produce a pyrolysis vapour;
(b) subjecting the pyrolysis vapour to a condensation step to produce a pyrolytic oil
having a boiling point range of 45-400°C and a flash point below 25°C, preferably below
18°C;
(c) subjecting the pyrolytic oil to a vacuum steam stripping step at a pressure ofless than
0.85 bar a and with a temperature ofless than 120°C at the top of the column, and recovering
a first component having an initial boiling point not exceeding 75°C under atmospheric
pressure and a second component which has a boiling point range starting from 100°C under
atmospheric pressure or higher and which possesses the properties defined in any of claims 1
to 7.

12. Process according to claim 11, wherein said first and second components together
comprise at least 98vol%, preferably at least 99vol% of the total product obtained from this
vacuum steam stripping step ( c).

11
 WO 2021/152109 PCT/EP2021/052134

13. Process according to claim 11 or 12, wherein prior to the vacuum steam stripping step
(c) the condensed pyrolytic oil is passed through a solids removal stage in order to reduce its
solids content.

14. Process according to claim 13, wherein the solids content of the pyrolytic oil is
reduced to less than 0.5wt%.

12
 WO 2021/152109 PCT/EP2021/052134

Fig 1

Chip hopper

Reactor 1-----a.{; Condensation

units

Compressors
Carbon
char
Syngas tanks

To 4 Emissions .,..._-1 Balance burners

atmosphere1---1 control
Raw oil

Steam----- Stripping column Multi-stage

Solids
centrifuge

Water Water
• separation separation

Technica1
water
Naphtha Fluxant
product product

1/1
 INTERNATIONAL SEARCH REPORT International application No

PCT/EP2021/052134
A. CLASSIFICATION OF SUBJECT MATTER
INV. C10Gl/10 C10Ll/04
ADD.
According to International Patent Classification (IPC) or to both national classification and IPC

B. FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
C10G C10L

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO-Internal, WPI Data

C. DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

X US 2013/144090 Al (PANSARE SOURABH S [US] 1-8,10

ET AL) 6 June 2013 (2013-06-06)
table 8
X Exxonmobil: "Marine fuel oil ISO 9
8217:2012 11
,

•
10 June 2017 (2017-06-10), pages 1-1,
XP055526652,
Retrieved from the Internet:
URL:https://www.scribd.com/document/350883
689/Exxonmobil-Marine-Fuel-Oil
[retrieved on 2018-11-23]
table 1
-/--

[K) Further documents are listed in the continuation of Box C. [] See patent family annex.

* Special categories of cited documents :

"T' later document published after the international filing date or priority
date and not in conflict with the application but cited to understand
'A" document defining the general state of the art which is not considered the principle or theory underlying the invention
to be of particular relevance
"E" earlier application or patent but published on or after the international "X" document of particular relevance; the claimed invention cannot be
filing date considered novel or cannot be considered to involve an inventive
"L" document which may throw doubts on priority claim(s) or which is step when the document is taken alone
cited to establish the publication date of another citation or other "Y" document of particular relevance; the claimed invention cannot be
special reason (as specified) considered to involve an inventive step when the document is
•o• document referring to an oral disclosure, use, exhibition or other combined with one or more other such documents, such combination
means being obvious to a person skilled in the art
'P" document published prior to the international filing date but later than
the priority date claimed "&" document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

26 February 2021 09/03/2021

Name and mailing address of the ISA/ Authorized officer
European Patent Office, P.B. 5818 Patentlaan 2
NL - 2280 HV Rijswijk
Tel. (+31-70) 340-2040,
1 Fax: (+31-70) 340-3016 Deurinck, Patricia
Form PCT/ISA/210 (second sheet) (April 2005)

page 1 of 2
 INTERNATIONAL SEARCH REPORT International application No

PCT/EP2021/052134
C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

X ROBINSONS: "WAVE GOODBYE TO SCRAP 11-14

TYRES",
EUROPEAN RUBBER JOURNAL, XX, XX,
vol. 171, no. 8,
1 September 1989 (1989-09-01), page 32/33,
XP008061526,
ISSN: 0305-2222
figure 1
X EP 3 312 223 Al (SIA GREEN CLARITY [LV]) 11-14
25 April 2018 (2018-04-25)
paragraph [0031] - paragraph [0033]; claim
1; figure 1
X US 2003/114722 Al (BRADLEY WILLIAM D [US]) 11-14
19 June 2003 (2003-06-19)
paragraph [0019] - paragraph [0022]; claim
1; figures 1,2

1
Form PCT/ISA/210 (continuation of second sheet) (April 2005)

page 2 of 2
 INTERNATIONAL SEARCH REPORT International application No
Information on patent family members
PCT/EP2021/052134

us
Patent document
cited in search report

2013144090 Al
I Publication
date

06-06-2013
I us Patent family
member(s)

2013144090 Al
I Publication
date

06-06-2013
us 2013144091 Al 06-06-2013
us 2013144094 Al 06-06-2013
us 2013144098 Al 06-06-2013
WO 2013085944 Al 13-06-2013
WO 2013085980 Al 13-06-2013
WO 2013085994 Al 13-06-2013
WO 2013086001 Al 13-06-2013

EP 3312223 Al 25-04-2018 NONE

us 2003114722 Al 19-06-2003 NONE

Form PCT/ISA/210 (patent family annex) (April 2005)