(19)

*EP003759047B1*
(11) EP 3 759 047 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) International Patent Classification (IPC):
of the grant of the patent: C01B 3/38 (2006.01)
25.10.2023 Bulletin 2023/43
(52) Cooperative Patent Classification (CPC):
(21) Application number: 19705658.3 C01B 3/382; C01B 2203/0244; Y02P 20/129

(22) Date of filing: 31.01.2019 (86) International application number:

PCT/US2019/015989

(87) International publication number:

WO 2019/164649 (29.08.2019 Gazette 2019/35)

(54) INTEGRATION OF A HOT OXYGEN BURNER WITH AN AUTO THERMAL REFORMER

INTEGRATION EINES HEISSGASBRENNERS MIT EINEM AUTOTHERMEN REFORMER
INTÉGRATION D’UN BRÛLEUR À OXYGÈNE CHAUD AVEC UN REFORMEUR AUTOTHERMIQUE

(84) Designated Contracting States: (72) Inventors:

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB • SHAH, Minish Mahendra
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Amherst, NY 14051 (US)
PL PT RO RS SE SI SK SM TR • BOOL, Lawrence
East Aurora, NY 14052 (US)
(30) Priority: 26.02.2018 US 201815905292
(74) Representative: Novagraaf Group
(43) Date of publication of application: Chemin de l’Echo 3
06.01.2021 Bulletin 2021/01 1213 Onex / Geneva (CH)

(73) Proprietor: Praxair Technology, Inc. (56) References cited:

Danbury, CT 06473 (US) WO-A1-2004/062788 WO-A1-2008/009250
WO-A2-2005/058751 DE-A1-102006 033 441
US-A1- 2005 188 615
EP 3 759 047 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Processed by Luminess, 75001 PARIS (FR)

 EP 3 759 047 B1

Description

BACKGROUND OF THE INVENTION

5 Field of the Invention

[0001] The present invention relates to a novel system and process for integrating a hot oxygen burner with an auto
thermal reformer for reducing capital expenditure as compared to existing partial oxidation and autothermal reformer
systems. The system also reduces oxygen utilization and soot formation as compared to existing partial oxidation system
10 and keeps soot formation to at or below the levels in existing autothermal reformer system. Specifically, the system
reduces the sizes of pre-reformer and fired heater or eliminates the need for pre-reformers and/or fired heater entirely.
The system further enables the use of ’opportunity fuels’ (as defined below) in the ATR.

Description of Related Art

15
[0002] Hydrocarbons such as natural gas, naphtha, or liquefied petroleum gas (LPG) can be catalytically converted
with steam to obtain a synthesis gas (i.e., a mixture of hydrogen (H2) and carbon monoxide (CO), commonly referred
to as synthesis gas or syngas. This reforming process could be done through the use of a so-called steam methane
reforming, or alternatively, partial oxidation and auto thermal reforming processes. These generation systems are known,
20 and are typically utilized to obtain syngas which may be ultimately utilized in the production of hydrogen, methanol,
ammonia, or other chemicals. These partial oxidation ("POx") and auto thermal reforming ("ATR") systems typically
generating syngas with a low H2:CO ratio in the range of about 1.5 to 2.5. The ATR system requires multiple process
steps and pieces of equipment to carry out reforming resulting in capital intensive processes. The POx system, on the
other hand, requires single process step for reforming. However, the POx system consumes ~20 - 30% more oxygen
25 than the ATR system per unit volume of syngas and it requires more expensive specialized boiler due to higher temper-
ature of syngas exiting the POx reactor (1371 - 1482 °C vs. 982 - 1038 °C (2500 - 2700 °F vs. 1800 - 1900 °F) for ATR)
and soot formation within the reactor.
[0003] For instance, employees of the assignee developed a hot oxygen burner based POx technology that drives
rapid mixing in the POx reactor using a hot oxygen jet and a patented technique to minimize soot within the POx reactor.
30 This is shown in U.S. Patent No. 9,540,240. However, HOB-based POx systems exhibit the same disadvantages inherent
to conventional POx systems (i.e., high oxygen consumption in comparison to an ATR and higher capital expenditures
in the form of expensive boilers, and the like.
[0004] With reference to Figure 1, a related art ATR system for generating syngas is shown. Hydrocarbon feedstock
stream (1) is mixed with hydrogen (2) and then pre-heated to a temperature ranging from 316 - 385 °C (600 - 725 °F)
35 in heating coils (102) and then preheated hydrocarbon stream (5) is fed to desulfurizer (105). Amount of hydrogen mixed
with hydrocarbon is generally in 2 - 3% of hydrocarbon feed on a volumetric basis and it is used for aiding reactions
within desulfurizer. Desulfurized hydrocarbon stream (8) is mixed with steam (35) and a mixed feed (10) is preheated
to 371 to 510 °C (700 to 950 °F) in heating coils (107). The ratio of steam to hydrocarbon (by volume) could vary from
0.4 to 1.5 (i.e., steam/carbon ratio). Pre-heated mixed feed (12) is fed to a pre-reformer (110), where any C2+ hydrocarbons
40 are reacted with steam so as to convert them into mixture of H2, CO and CH4. Pre-reformed feed stream (14) is further
heated to 538 - 649 °C (1000 - 1200 °F) in heating coils (112) within fired heater (100) and then fed to ATR (120) as
pre-heated pre-reformed feed (16). Oxygen needed in the ATR is produced by air separation unit ("ASU") (130). Air
feedstock stream (21) is separated into oxygen stream (24) and nitrogen (31) in ASU (130). Oxygen is pre-heated to a
temperature ranging from 93 to 204 °C (200 to 400 °F) in oxygen preheater (135) and preheated oxygen (25) is also
45 fed to the ATR (120). At the heart of the autothermal reforming process is an ATR unit operation (120) that combines a
partial oxidation (POx) step and a catalytic reforming step. Within ATR (120), preheated pre-reformed feed (16) and
oxygen (25) react to produce a syngas mixture (20) comprising H2, CO, CO2, steam, any unconverted CH 4 and other
trace components. Specifically, the feed (16) first reacts with oxygen (25) in a POx step to consume all the oxygen and
release heat. The remaining hydrocarbons in the feed are then reformed autothermally (not catalytically) with CO2 and
50 H2O present in the mixture. Since the reforming reactions are endothermic this non-catalytic reforming results in a
reduction in gas temperature. As the reaction cools, the rates of reaction ("kinetics") slow down causing a kinetic limit
to the achievable hydrocarbon conversion. To overcome this kinetic constraint, the still hot, reactive, mixture is fed to a
catalyst which promotes reforming to achieve a near equilibrium degree of reforming. Due to the nature of the catalyst
bed, it is critical that soot not enter the catalyst as it could cause fouling. Therefore, the conditions in the non-catalytic
55 zone of the reactor must be maintained to prevent soot at the entrance to the catalyst. This can be accomplished by
preventing soot from forming in the first place, or by promoting soot gasification reactions that would consume any soot
formed before the gas reaches the catalyst. For this reason a conventional ATR requires a pre-reformer (110) to convert
higher hydrocarbons, which may be prone to sooting in the POx step, to methane. Further the ATR may use steam

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 EP 3 759 047 B1

injection at higher levels than needed in the catalytic reforming step just to reduce soot formation and enhance soot
oxidation.
[0005] Syngas (20) exits the ATR at a temperature of 982 - 1038 °C (1800 - 1900 °F) and at pressure ranging from
2413 - 3792 kPa (350 - 550 psia). Syngas (20) is then passed through process gas boiler (150) boiler feed water heater
5 (155) and water heater (160) in sequence to recover thermal energy contained in syngas for steam generation. Tem-
perature of syngas exiting the process gas boiler ranges from 288 to 371 °C (550 to 700 °F). Steam is typically generated
at 2413 - 5171 kPa (350 to 750 psia), however, it can be generated at higher pressure if desired. Finally, syngas is
cooled to 27 to 43 °C (80 to 110 °F) in a cooler (165) and sent to a condensate separator (170) to separate any condensate.
Syngas (32) is then routed to a downstream process for either making chemicals such as methanol or Fischer Trope
10 liquids or sent to a purification process for separating syngas into hydrogen and carbon monoxide. Any residual fuel
stream from the downstream process is combined with make-up hydrocarbon fuel stream to form a fuel stream for the
fired heater. Burning of fuel in the fired heater provides heat for various heating coils disposed within the fired heater.
Process water (50) is combined with condensate (52) and heated in water heater (160) to a temperature of 93 - 99 °C
(200 - 210 °F). Heated water is fed to deaerator (140) to remove any dissolved gases. Boiler feed water (55) from
15 deaerator (140) is pumped to desired pressure (generally >3103 kPa (450 psia)) and heated to temperature that is 5.6
to 27.8 °C (10 to 50 °F) below the boiling point of water and sent to steam drum (125). Hot boiler feed water stream (60)
from steam drum (125) is circulated through process gas boiler (150) to generate steam. A portion of saturated steam
(62) from steam drum is superheated in heating coils (114). The superheated steam (35) is used in the reforming process.
The remainder of saturated steam (70) is exported.
20 [0006] Turning to Figure 2, a related art partial oxidation process for generating syngas is depicted. Hydrocarbon
feedstock stream (1) is mixed with hydrogen (2) and pre-heated to 232 - 385 °C (450 - 725 °F) in hydrocarbon heating
device (104) and the preheated hydrocarbon stream (5) is fed to desulfurizer device (105). Desulfurized hydrocarbon
stream (8) along with oxygen stream (24) from the ASU (130) is fed to the POx reactor (115). Syngas (20) from the POx
reactor exits at a temperature of 1371 to 1482 °C (2500 to 2700 °F) and at pressure ranging from 2413 - 3792 kPa (350
25 - 550 psia). Syngas stream (20) may contain some soot due to cracking of hydrocarbons within the POx reactor. Due
to high temperature and potential presence of soot, a specialized boiler called syngas cooler (152) is required to cool
syngas and generate steam. If steam has no value, syngas cooler can be replaced by quench vessel (not shown) to
cool syngas using direct contact with water. Partially cooled syngas (22) at 288 to 399 °C (550 to 750 °F) from syngas
cooler (152) is used to preheat hydrocarbon feedstock in the hydrocarbon heating device (104). Syngas stream (23) is
30 then routed and processed in a soot scrubber (154). The soot scrubber includes a venturi scrubber for contacting syngas
with large quantity of water, a contact tower for additional scrubbing section to remove residual soot from syngas and
separating soot containing water from syngas and pump for circulating water. Soot free syngas (26) at 135 to 177 °C
(275 to 350 °F) is then routed through a water heater (160) and cooler (165) to cool the syngas (30) to 26.7 to 43.3 °C
(80 - 110 °F) and sent to the condensate separator (170). The syngas product (32) from condensate separator is sent
35 to the downstream process. Process water (50) is combined with condensate (52) and heated in water heater device
(160) to a temperature ranging from 93.3 - 98.9 °C (200 - 210 °F). Heated water is fed to deaerator (140) to remove any
dissolved gases. Boiler feed water (55) is pumped to desired pressure (generally > 3103 kPa (450 psia)) and sent to
syngas cooler (152) to generate steam. Optionally, boiler feed water can be heated (not shown) close to its boiling point
against partially cooled syngas prior to feeding it to syngas cooler.
40 [0007] While the partial oxidation system also produces syngas with low H2:CO ratio in the range of about 1.5 to 2.5,
the oxygen consumption in the POx reactor is about 25% higher than the ATR system for a comparable quantity of
syngas. High grade heat at the exit of the POx reactor is either used for steam generation or rejected to atmosphere via
quench cooling. Therefore, in order to take advantage of the high temperatures (~ 1427 °C (2600 °F)) at the exit of the
POx reactor, an expensive boiler (i.e., syngas cooler) is necessary.
45 [0008] In a conventional ATR the burner is designed to rapidly mix the feed(s) and oxygen, often using swirl and other
mixing enhancement strategies. These strategies make staging the burner difficult, if not impossible. In other words, in
the related art designs all the feed streams are rapidly mixed with the oxygen without the ability to feed different streams
into different parts of the flame. For instance, in the related art U.S. Patent No. 7,255,840 owned by the assignee of the
present invention, this rapid mixing was used to mix the hot oxygen-containing gas with the hydrocarbon feed to reduce
50 the mixture temperature below the ignition temperature without igniting the mixture, thereby feeding an oxygen and
hydrocarbon containing mixture to the catalyst bed. WO 2004/062788 A1 discloses an ATR process with another burner’s
design.
[0009] In contrast, the HOB/ATR reactor of the integrated system of the invention uses a different mixing strategy. A
portion of the fuel is burned in an oxygen stream upstream of a nozzle. The resulting ’hot oxygen’ stream exits the nozzle
55 and mixes quickly with surroundings. Since the mixing method is that of a simple reacting jet, it is possible to control
how different streams get mixed into the reactive portion. In the present invention, the HOB/ATR reactor ignites the
oxygen and hydrocarbon containing mixture to perform partial oxidation reactions prior to the mixture entering the catalyst
bed. Therefore, the HOB is designed to mix the streams more slowly than that in the related art to ensure ignition and

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 EP 3 759 047 B1

avoid soot formation.

[0010] To overcome the disadvantages of the related art, such as soot formation, high oxygen consumption and the
need for expensive boilers (e.g., syngas coolers), it is an object of the present invention to integrate an HOB with an
ATR reactor in the syngas generation system. It is another object of the invention, to eliminate the pre-reformer and the
5 fired heater. By using a catalyst bed to reform a portion of natural gas by using high grade heat, oxygen consumption
per unit volume of syngas will be reduced. In addition, exit temperature from such a reactor will be below a temperature
of ~1093 °C (2000 °F) and will make it possible to use less expensive process gas boiler. It is yet another object of the
invention, to improve the conventional ATR process by replacing the burner in the ATR by HOB and enable reduction
in pre-reformer and fired heater sizes. Further object of the invention is to enable use of unconventional fuels in a
10 conventional ATR process by employing HOB in the ATR reactor.
[0011] Other objects and aspects of the present invention will become apparent to one of ordinary skill in the art upon
review of the specification, drawings and claims appended hereto.

SUMMARY OF THE INVENTION

15
[0012] In one aspect the invention is a method for generating syngas, comprising:

providing a hydrocarbon feed stream without pre-reforming and/or heating said hydrocabon feed stream;
splitting said hydrocarbon feed stream between a fuel stream directed to the hot oxygen burner assembly integrated
20 with an auto thermal reactor and a hydrocarbon feed stream where said fuel stream is combusted with oxygen in
the hot oxygen burner assembly of an autothermal reactor to form a hot oxygen jet;
mixing the hydrocarbon feed stream with steam, and introducing said mixture of hydrocarbon feed in a non-catalytic
region of the auto thermal reactor wherein the mixture of hydrocarbon feed is substantially entrained in the hot
oxygen jet; igniting the hydrocarbon stream with hot oxygen to create a reactive jet, thereby performing partial
25 reforming of the hydrocarbon in a non-catalytic zone of the auto thermal reactor; and
further reforming the hydrocarbon in a catalyst bed of the auto thermal reactor to generate syngas.

[0013] In a further aspect the invention is amethod for generating syngas comprising:

30 providing a main desulfurized hydrocarbon feed stream split into at least two hydrocarbon streams wherein a first
hydrocarbon stream is routed to the hot oxygen burner and utilized therein as a fuel which is mixed with oxygen to
combust said fuel and generate a hot oxygen jet;
routing the second hydrocarbon stream to a fired heater and pre-reforming the second hydrocarbon stream into a
heated pre-reformed hydrocarbon stream;
35 routing the heated pre-reformed hydrocarbon stream through the fired heater to increase the temperature further,
and thereafter introducing the heated pre-reformed hydrocarbon stream in close proximity to the hot oxygen burner
wherein heated pre-reformed hydrocarbon feed is substantially entrained in the hot oxygen jet to create a reactive
jet, thereby performing partial reforming of the hydrocarbon in a non-catalytic zone of the auto thermal reactor; and
completing the reforming in a catalytic reaction zones of the of the auto thermal reactor, thereby forming a syngas.
40
BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The objects and advantages of the invention will be better understood from the following detailed description
of the preferred embodiments thereof in connection with the accompanying figures wherein like numbers denote same
45 features throughout and wherein:

Figure 1 is a process flow diagram for a related art ATR reactor based system for generating syngas;
Figure 2 process flow diagram for a related art POx reactor based system for generating syngas; and
Figure 3 depicts a process flow diagram of the present invention where an HOB is integrated with the ATR based
50 reactor system for generating syngas. The system generates syngas without employing pre-reformers and fired
heater.
Figure 3A depicts a sketch of an HOB/ATR reactor used for the process shown in Figure 3.
Figure 4 depicts a process flow diagram of another embodiment of the present invention where an HOB is integrated
with the ATR based reactor system for generating syngas. The system generates syngas without employing pre-
55 reformers and fired heater and two hydrocarbon containing streams are introduced in two different locations of an
HOB/ATR reactor.
Figure 4A depicts a sketch of an HOB/ATR reactor used for the process shown in Figure 4.
Figure 5 depicts a process flow diagram of another embodiment of the present invention where an HOB is integrated

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 EP 3 759 047 B1

with the ATR based reactor system for generating syngas, wherein fuel for HOB bypasses pre-reformer and fired
heater.
Figure 5A depicts a sketch of an HOB/ATR reactor used for the process shown in Figure 5.
Figure 6 depicts a process flow diagram of another embodiment of the present invention where an HOB is integrated
5 with the ATR based reactor system for generating syngas, wherein fuel for HOB and first hydrocarbon feed bypass
pre-reformer and fired heater.
Figure 6A depicts a sketch of an HOB/ATR reactor used for the process shown in Figure 6.
Figure 7 depicts a process flow diagram of another embodiment of the present invention where an HOB is integrated
with the ATR based reactor system for generating syngas, wherein fuel for HOB and first hydrocarbon feed bypass
10 pre-reformer and fired heater and pre-reformed second feed for an HOB/ATR reactor bypasses fired heater.

DETAILED DESCRIPTION

[0015] The present invention provides for a system and method of integrating an HOB, such as the one developed by
15 the assignee of the current invention, into an ATR reactor to design a syngas generation system that minimizes capital
expenditure by either eliminating some of the process units or by reducing the sizing thereof. The "HOB/ATR," as utilized
herein, will be understood to be a single unit operation, which is at times referred to as a hot oxygen burner assembly
integrated with an auto thermal reformer or simply as an HOB-based reactor. The HOB’s ability to control mixing in the
ATR reactor such that ignition of the oxygen-containing and hydrocarbon containing streams and subsequent partial
20 oxidation reactions are achieved and soot formation is minimized is leveraged by integrating it into the ATR reactor. In
addition, the system developed does not require a pre-reformer and a fired heater, thereby simplifying the syngas
generation system. The utilization of a catalyst bed to reform a portion of hydrocarbon feed by employing high grade
heat results in a reduction of oxygen consumption per unit volume of syngas generated compared to the related art POx
system. As utilized herein, hydrocarbon shall be understood to mean a natural gas feed, or a refinery-off gas containing
25 various hydrocarbons as well as hydrogen, CO and CO2 or the like. Further, the exit temperature from an HOB/ATR
reactor is below ~1093 °C (2000 °F) and advantageously the syngas generation system utilizes a far less expensive
process gas boiler.
[0016] In the present invention, various streams, process conditions, and unit operations in common to the exemplary
embodiments (and denoted by the same numerals) will be omitted for the sake of simplicity. In addition, the following
30 terms shall be defined as follows: "total stoichiometric ratio" or ("total SR") shall mean moles of oxygen supplied to
process/moles of oxygen required to completely combust hydrocarbons supplied for syngas conversion. It should be
noted that in calculation of total SR, only those hydrocarbons that are supplied for syngas conversion are accounted
and any hydrocarbons that are used as fuel in fired heater are not counted; "burner stoichiometric ratio" or "burner SR"
shall mean moles of oxygen supplied to burner/moles of oxygen required to completely combust hydrocarbons supplied
35 to the burner.
[0017] Now with reference to Figure 3, an exemplary embodiment of the invention where the HOB-based ATR system
is presented. Figure 3A shows a sketch of an HOB/ATR reactor (118) to show non-catalytic and catalytic reaction zones
of the reactor and entry locations of various feeds to the reactor. This embodiment has several advantages over the
related art discussed above. Compared to the system of Figure 2 wherein the integrated system includes either a
40 conventional or an HOB-based partial oxidation unit, the design of process gas boiler is simplified due to lower inlet
temperature (∼1038 °C (1900 °F) vs. 1427 °C (2600 °F)) and minimization of soot in the syngas. The soot scrubber is
not needed due to minimization of soot formation. Compared to the system of Figure 1 wherein an autothermal reformer
is employed, the fired heater and pre-reformer are not needed due to unique design of burner used in the HOB/ATR
reactor that minimizes soot formation without the use of pre-reforming.
45 [0018] Specifically, in the exemplary embodiment of Figure 3, hydrocarbon feedstock stream (1) is pre-heated to 232
- 385 °C (450 - 725 °F) in hydrocarbon heating device (104) and the preheated hydrocarbon stream (5) is routed to
desulfurizer device (105) to form hydrocarbon feed stream (8). In this exemplary embodiment of the invention main
hydrocarbon feed stream (8) is split into two separate streams referred to as fuel stream (9) and feed stream (11). Fuel
stream (9), usually amounting to about 5 - 10% of main feed stream (8), is combusted with oxygen (24) by HOB (180)
50 to generate a reactive hot oxygen jet. The amount of fuel (9) fed to HOB is such that burner SR value is between 3 and
6. The combustion product from HOB is a hot oxygen jet that contains mainly oxygen, CO2 and H2O. The feed stream
(11) is combined with a steam stream (68) from the steam drum (125) and the combined mixed feed (15) is introduced
in close proximity to the HOB (180). One way to ensure that mixed feed (15) is introduced in close proximity to the HOB
is by providing an annular section around HOB as shown in Figure 3A. Other option is to provide feed ports in the
55 HOB/ATR reactor close to where HOB penetrates the reactor (not shown). The amount of oxygen is adjusted such that
total SR for the reactor is between 0.28 and 0.33. Thus, oxygen supplied is 0.28 to 0.33 times the amount needed for
complete combustion of stream 8. The reaction between hot oxygen jet and combined mixed feed (15) in a non-catalytic
zone of the reactor generates syngas. Mixing the streams in the non-catalytic zone in this manner, the streams (9) and

5
 EP 3 759 047 B1

(15) are mixed sufficiently quick to avoid soot formation by the hydrocarbons in the reactor, but sufficiently slow to avoid
soot formation by cracking of the hydrocarbons in the hot gas stream. The syngas than enters the catalyst bed where
further reforming takes place. The syngas (20) exits the reactor at about 982 to 1038 °C (1800 to 1900 °F) and at about
2413 - 3792 kPa (350 to 550 psia). The syngas composition depends on relative amounts of hydrocarbon feed stream
5 (8), oxygen (24) and steam stream (68) are supplied in the system. Generally, the range of concentrations of various
components on a molar basis could be ranging from 40 to 60% for hydrogen, 20 to 35% for CO, 10 to 25% for H2O, 1
to 7% for CO2, 0 to 2% of CH4 and <1 % other components including nitrogen, argon, NH3, and HCN. The lower exit
temperature from the reactor (118), enables use of a steam generation system comprising process gas reboiler (150)
and steam drum (125) that is similar to that in embodiment of Figure 1 and significantly less expensive compared to
10 more expensive syngas cooler (152) of the embodiment of the related art shown in Figure 2. In addition, it eliminates
the need of pre-reformer (110) or the fired heater (100) of the related art embodiments in Figure 1 or the soot scrubber
(154) in the related art embodiment of Figure 2, thereby reducing capital expenditure. Partially cooled syngas (22) at
288 to 399 °C (550 to 750 °F), from process gas boiler (150) is used to preheat hydrocarbon feed in the hydrocarbon
heating device (104). Syngas stream (27) is then routed to a boiler feed water heater (155) to preheat boiler feed water
15 to about 5.6 to 27.8 °C (10 to 50 °F) below its boiling point. Syngas is further cooled through water heater (160) and
cooler (165). The cooled syngas (30) is separated in a condensate separator to generate syngas product (32) for further
use in a downstream process.
[0019] Figure 4 depicts an alternative exemplary embodiment, in which main hydrocarbon feed stream (8) is split into
three fractions. One fraction forms first fuel stream (9) with flow ranging from about 5 - 10% of the main hydrocarbon
20 feed flow of stream (8). Separately, a second fraction forms a first feed stream (11) for reactor with flow of 50 to 85% of
main hydrocarbon feed stream (8). The third fraction forms a second feed stream (18) with flow of sufficient quantity to
achieve the total SR desired by the operator. This second feed is combined with steam (68) to form a second feed stream
(15) for the reactor. First fuel stream (9) is introduced into the HOB along with oxygen (24) to form a hot oxygen stream
and first feed stream (11) is introduced into a section closest to the nozzle of the HOB (180) in reactor (118) such that
25 this first feed stream (11) is preferentially entrained into the hot gas jet over second feed stream (15). The first feed
stream (11) is ignited by the hot oxygen stream to create a reactive jet, partially reforming the hydrocarbon in a non-
catalytic zone of the auto thermal reactor. The second feed stream (15) is introduced after first feed stream (11) has
been predominantly entrained into the reactive jet. One option for introducing second feed stream (15) is just upstream
of catalyst bed in the HOB/ATR reactor (118) as shown in Figure 4A. In this manner, the total SR value in the non-
30 catalytic reaction zone of the reactor would be similar to a conventional HOB reactor at 0.35 to 0.37 and syngas exiting
the non-catalytic reaction zone would contain minimal soot. Thus, the soot is minimized by mixing the streams sufficiently
quick to avoid soot formation by hydrocarbons in the reactor, but slow enough to avoid soot formation by cracking of the
hydrocarbons in the hot gas stream, as described in detail in U.S. Patent No. 9,540,240 B2, which is incorporated herein
in its entirety.
35 [0020] The syngas temperature toward the end of the non-catalytic zone (i.e., in proximity to the non-catalytic and
catalytic zone interface) would be 1371 to 1482 °C (2500 to 2700 °F). This syngas and second feed stream (18) are
mixed just upstream of the catalyst bed and temperature of the syngas decreases to below 1149 °C (2100 °F) as a
result. This syngas then enters the catalyst zone, where thermal energy from the syngas aids in endothermic reforming
of hydrocarbons in the second feed (18). The syngas exiting the reactor (118) is similar in temperature, pressure and
40 composition to those described earlier for Figure 3. The total SR value for the entire reactor (non-catalytic and catalytic
zones) when all the hydrocarbon containing stream (9), (11) and (18) are considered would be similar to that of embod-
iment of Figure 3 at 0.28 to 0.33.
[0021] In the event that steam has no other use in the system, the embodiments of Figures 3 and 4 are envisioned
where the system configuration for the embodiments of Figures 3 and 4, steam generation equipment process gas boiler
45 (150) and steam drum (125) are replaced by a quench vessel (not shown), which utilizes direct contact with water.
Partially cooled syngas (22) at 288 to 399 °C (550 to 750 °F), from process gas boiler (150) is used to preheat hydrocarbon
feed in the hydrocarbon heating device (104). Syngas stream (27) is then routed to a boiler feed water heater (155) to
preheat boiler feed water to about 5.6 to 27.8 °C (10 to 50 °F) below its boiling point. Syngas is further cooled through
water heater (160) and cooler (165). The cooled syngas (30) is separated in a condensate separator to generate syngas
50 product (32) for further use in a downstream process.
[0022] While Figures 3 and 4 shows embodiments with significant simplifications in systems of prior art, the HOB/ATR
reactor can be deployed in a conventional ATR like system of Figure 1 to achieve improvements over the related art.
[0023] As illustrated in Figure 5, an alternative exemplary embodiment depicts a system/process configuration change
to that of related art system of Figure 1. With reference to Figure 5A, a sketch of an HOB/ATR reactor (118) including
55 HOB assembly (180) is depicted. Since the ’fuel’ fed to the HOB (180) is completely combusted before it enters HOB/ATR
(118) it is possible to use non-pre-reformed feed, or opportunity fuels as a fuel stream in HOB. As utilized herein,
"opportunity fuels" will be understood to mean any hydrocarbon that can provide an economic advantage, including but
not limited to refinery off-gases, tail gases, and other associated gases. As shown in Figure 5, a portion of desulfurized

6
 EP 3 759 047 B1

NG (8) is split as a slip stream of hydrocarbon fuel (9), which bypasses pre-reformer (110) and is fed directly to HOB/ATR
(118), specifically into HOB assembly (180). This would reduce the need for prereforming this portion of the total feed
and associated heating duty within fired heater.
[0024] In the exemplary embodiment of Figure 6 a variation in the system of Figure 5 is provided. Starting from the
5 detailed showing of the HOB assembly (180) and the HOB/ATR reactor (118) in Figure 6A the mixing can be carefully
controlled within HOB assembly (180), it is possible to introduce a specific portion of the feed as first feed stream (19)
a hydrocarbon gas split from the hydrocarbon main stream (8) is routed near the burner such that this feed is entrained
into the jet prior to introducing the second feed stream (16) which consists of pre-reformed natural gas. Since reactions
in this portion of the jet are fuel lean enough to avoid soot formation, it can be possible to feed unreformed feed into this
10 region without forming soot. The remaining feed can then be mixed into the later part of the jet, after the first feed stream
(19) is predominantly entrained in the jet, and take the mixture down to the final stoichiometric ratio. Specifically, with
reference to Figures 6, in this embodiment, desulfurized hydrocarbon main stream (8) is split into three fractions: hydro-
carbon fuel stream (9) which is fed to HOB/ATR (118) to support the fuel lean combustion, specifically into HOB assembly
(180); stream of hydrocarbon (19) which is fed as first feed to HOB/ATR (118), specifically into close proximity of HOB
15 assembly (180) and a stream of desulfurized hydrocarbon (18), which is first routed through fired heater (100). Desul-
furized hydrocarbon feedstock stream (18) is mixed with steam stream (35) and processed through pre-reformer (110)
and fired heater (100) as described with respect to the embodiment of Figure 1 to generate pre-heated pre-reformed
feed stream (16), which is fed to HOB/ATR (118) as second feed stream. In this embodiment the reaction of the hydro-
carbon fuel stream (9) and the fuel lean combustion product from the HOB assembly (180) are not likely to form soot.
20 Therefore, the pre-reformer duty can be reduced, and in some situations alternative fuels from within or outside the
integrated system could be used, in essence reducing the size of the fired heater and/or the pre-reformer and enabling
use of lower cost fuel and/or refinery off-gas streams.
[0025] In yet another exemplary embodiment and with reference to Figure 7 in this configuration it is not necessary
to preheat pre-reformed feed (14) prior to feeding it to HOB/ATR (118). Therefore, in this embodiment, pre-reformed
25 hydrocarbon feed (14) is directly fed to HOB/ATR (118) a second feed. Thus, eliminating the preheating of this steam
reduces the duty of the fired heater. In addition, the total SR is increased, thereby reducing the soot forming potential.
[0026] The invention is further explained through the following examples, which compare the related art embodiments
with the various ones of the present invention , and those based on various embodiments of the invention, which are
not to be construed as limiting the present invention.
30
EXAMPLES

[0027] Process simulations were carried out for various embodiments described above. Main feed and product streams
conditions used in all simulations are listed in Table 1. Natural gas was used as a hydrocarbon feed in all the simulations.
35 All the embodiments were compared for a fixed flow of 20 MMscfd for H 2+CO content in syngas product (32). Amounts
of feed and product streams per unit volume of syngas varied between various embodiments as indicated in Table 2.
Also, syngas compositions were somewhat different for different embodiments as indicated by H2/CO ratios in Table 2.

Table 1.
40
HC feed (1) Oxygen (24) Syngas (32) Export steam (65)
Temperature [°C (F)] 21.1 (70.0) 37.8 (100.0) 37.8 (100.0) 263.2 (505.7)
Pressure [kPa (psia)] 4229.9 (613.5) 4033.4 (585.0) 3181.9 (461.5) 4941.5 (716.7)

45 Mole Fractions
Methane 0.905900
Ethane 0.036100
Propane 0.007800
50
i-Butane 0.003100
n-Butane 0.004500
Nitrogen 0.012595

55 CO2 0.030000
H2S=mercaptans 0.000005
Oxygen 0.996

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(continued)

HC feed (1) Oxygen (24) Syngas (32) Export steam (65)

Argon 0.004
5
H2O 1.000

[0028] Table 2 summarizes key comparative parameters of syngas generation systems in the embodiments of Figures
1 through 7, detailed above. All the embodiments of this invention (Figures 3 through 7) achieves H2/CO ratio of between
10 2.2 to 2.4. Embodiments of Figures 3 and 4 consume about the same NG while consuming ~10 % less oxygen in
comparison to relate art embodiment of Figure 2. This improved performance is achieved by embodiments of Figures
3 and 4 while simultaneously reducing process complexity by eliminating soot scrubber and using a lower cost boiler
when compared to Figure 2. When compared to the related art embodiments of Figure 1, the embodiments described
with respect to Figures 3 and 4 consume slightly less NG and --22% more oxygen while significantly lowering process
15 complexity by eliminating fired heater and pre-reformer.

Table 2.
Figure 1 Figure 2
(related (related
20
Embodiment art) art) Figure 3 Figure 4 Figure 5 Figure 6 Figure 7
H2+CO in SG,
MMm 3 per day
(MMscfd) 0.566 (20) 0.566 (20) 0.566 (20) 0.566 (20) 0.566 (20) 0.566 (20) 0.566 (20)
25
NG/(H2+CO) 0.388 0.380 0.377 0.382 0.391 0.396 0.395
O2/(H2+CO) 0.200 0.272 0.245 0.246 0.204 0.209 0.226
H2/CO ratio 2.4 1.6 2.2 2.2 2.4 2.4 2.4

30 Steam export, 12512 20086 13911 14092 29921 13489 13422

kg/hr (lb/hr) (27584) (44281) (30668) (31068) (29921) (29738) (29589)
Prereformer size 1 n/a n/a n/a 0.95 0.68 0.68
Fired heater size 1 n/a n/a n/a 0.98 0.89 0.56
35 Steam generation
equipment PGB SG cooler PGB PGB PGB PGB PGB
Soot scrubber
required? No Yes No No No No No

40
[0029] Embodiments of Figures 5, 6 and 7 consumes slightly more NG and oxygen compared to the related art
embodiment of Figure 1 while achieving size reduction for the fired heater between 5% and 32% and that for the pre-
reformer between 2% and 44%.
[0030] While the invention has been described in detail with reference to specific embodiments thereof, it will become
45 apparent to one skilled in the art that various changes and modifications can be made, and equivalents employed, without
departing from the scope of the appended claims.

Claims
50
1. A method for generating syngas, comprising:

providing a hydrocarbon feed stream (1) without pre-reforming and/or heating said hydrocarbon feed stream;
splitting said hydrocarbon feed stream between a fuel stream (9) directed to the hot oxygen burner assembly
55 (180) integrated with an auto thermal reactor (118) and a hydrocarbon feed stream (11) where said fuel stream
is combusted with oxygen in the hot oxygen burner assembly (180) of an autothermal reactor to form a hot
oxygen jet;
mixing the hydrocarbon feed stream with steam, and introducing said mixture of hydrocarbon feed in a non-

8
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catalytic region of the auto thermal reactor (118) wherein the mixture of hydrocarbon feed is substantially
entrained in the hot oxygen jet; igniting the hydrocarbon stream with hot oxygen to create a reactive jet, thereby
performing partial reforming of the hydrocarbon in a non-catalytic zone of the auto thermal reactor (118); and
further reforming the hydrocarbon in a catalyst bed of the auto thermal reactor (118) to generate syngas.
5
2. The method of claim 1, wherein the fuel stream (9) is a refinery off-gas or a tail gas,.

3. The method of claim 1, wherein the syngas (20) exiting the auto thermal reactor (118) at a temperature below 815,6
°C (2000° F) and at 2,41 to 3,79 MPa (350 to 550 psia).
10
4. The method of claim 1, wherein the fuel stream (9) is about 5-10% by volume of the hydrocarbon feed stream.

5. The method of claim 1, wherein the syngas generated is routed to a process gas reboiler (150) and further downstream
unit operations.
15
6. A method for generating syngas, comprising:

(a) providing a main desulfurized hydrocarbon feed stream (8) split into at least two hydrocarbon streams wherein
a first hydrocarbon stream (9) is routed to the hot oxygen burner (180) and utilized therein as a fuel which is
20 mixed with oxygen to combust said fuel and generate a hot oxygen jet;
(b) routing the second hydrocarbon stream (19) to a fired heater (100) and pre-reforming the second hydrocarbon
stream into a heated pre-reformed hydrocarbon stream (16);
(c) routing the heated pre-reformed hydrocarbon stream through the fired heater (100) to increase the temper-
ature further, and thereafter introducing the heated pre-reformed hydrocarbon stream in close proximity to the
25 hot oxygen burner (180) wherein heated pre-reformed hydrocarbon feed is substantially entrained in the hot
oxygen jet to create a reactive jet, thereby performing partial reforming of the hydrocarbon in a non-catalytic
zone of the auto thermal reactor (118); and
(d) completing the reforming in a catalytic reaction zones of the of the auto thermal reactor (118), thereby forming
a syngas.
30
7. The method of claim 6, wherein the first hydrocarbon feed stream is a refinery off-gas or a tail gas.

8. The method of claim 6, further comprising:

splitting a third hydrocarbon stream (18) from the desulfurized hydrocarbon feed stream (8) and introducing said
35 third hydrocarbon stream in close proximity to the hot oxygen burner (180) disposed in the auto thermal reactor
(118) and introducing said heated pre-reformed hydrocarbon feed, such that the heated pre-reformed hydrocarbon
feed is entrained into the reactive jet after the second hydrocarbon stream is predominantly entrained.

9. The method of claim 6, wherein the heated pre-reformed hydrocarbon stream of step (b) is introduced directly in
40 close proximity the hot oxygen burner (180) thereby performing partial reforming of the hydrocarbon through partial
oxidation reactions in the non-catalytic zone of the auto thermal reactor (118).

Patentansprüche
45
1. Verfahren zum Erzeugen von Synthesegas, umfassend:

Bereitstellen eines Kohlenwasserstoffzufuhrstroms (1) ohne ein Vorreformieren und/oder ein Erhitzen des Koh-
lenwasserstoffzufuhrstroms;
50 Aufteilen des Kohlenwasserstoffzufuhrstroms zwischen einem Brennstoffstrom (9), der auf die Heißsauerstoff-
brenneranordnung (180) gerichtet ist, die mit einem autothermischen Reaktor (118) integriert ist, und einem
Kohlenwasserstoffzufuhrstrom (11), wobei der Brennstoffstrom in der Heißsauerstoffbrenneranordnung (180)
eines autothermischen Reaktors mit Sauerstoff verbrannt wird, um einen Heißsauerstoffstrahl auszubilden;
Mischen des Kohlenwasserstoffzufuhrstroms mit Dampf und Einführen der Mischung aus Kohlenwasserstoff-
55 zufuhr in einem nicht katalytischen Bereich des autothermischen Reaktors (118), wobei die Mischung aus
Kohlenwasserstoffzufuhr im Wesentlichen in dem Heißsauerstoffstrahl mitgerissen wird; Zünden des Kohlen-
wasserstoffstroms mit Heißsauerstoff, um einen reaktiven Strahl zu herzustellen, wobei dadurch ein partielles
Reformieren des Kohlenwasserstoffs in einer nicht katalytischen Zone des autothermischen Reaktors (118)

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durchgeführt wird; und

weiteres Reformieren des Kohlenwasserstoffs in einem Katalysatorbett des autothermischen Reaktors (118),
um Synthesegas zu erzeugen.

5 2. Verfahren nach Anspruch 1, wobei der Brennstoffstrom (9) ein Raffinerieabgas oder ein Endgas ist.

3. Verfahren nach Anspruch 1, wobei das Synthesegas (20), das den autothermischen Reaktor (118) bei einer Tem-
peratur unter 815,6 °C (2000 °F) und bei 2,41 bis 3,79 MPa (350 bis 550 psia) verlässt.

10 4. Verfahren nach Anspruch 1, wobei der Brennstoffstrom (9) etwa 5-10 Vol.-% des Kohlenwasserstoffzufuhrstroms
beträgt.

5. Verfahren nach Anspruch 1, wobei das erzeugte Synthesegas zu einem Prozessgas-Reboiler (150) und weiteren
stromabwärtigen Einheitsoperationen geleitet wird.
15
6. Verfahren zum Erzeugen von Synthesegas, umfassend:

(a) Bereitstellen eines entschwefelten Hauptkohlenwasserstoffzufuhrstroms (8), der in mindestens zwei Koh-
lenwasserstoffzufuhrströme aufgeteilt ist, wobei ein erster Kohlenwasserstoffstrom (9) zu dem ersten Heißsau-
20 erstoffbrenner (180) geleitet wird und darin als ein Brennstoff genutzt wird, der mit einem Sauerstoff gemischt
wird, um den Brennstoff zu verbrennen und einen Heißsauerstoffstrahl zu erzeugen;
(b) Leiten des zweiten Kohlenwasserstoffzufuhrstroms (19) zu einer befeuerten Heizeinrichtung (100) und Vor-
reformieren des zweiten Kohlenwasserstoffstroms in einen erhitzten vorreformierten Kohlenwasserstoffstrom
(16);
25 (c) Leiten des erhitzten vorreformierten Kohlenwasserstoffstroms durch eine befeuerte Heizeinrichtung (100),
um die Temperatur weiter zu erhöhen, und danach Einführen des erhitzten vorreformierten Kohlenwasser-
stoffstroms in unmittelbarer Nähe zu dem Heißsauerstoffbrenner (180), wobei die erhitzte vorreformierte Koh-
lenwasserstoffzufuhr im Wesentlichen in dem Heißsauerstoffstrahl mitgerissen wird, um einen reaktiven Strahl
herzustellen, wobei dadurch das partielle Reformieren des Kohlenwasserstoffs in einer nicht katalytischen Zone
30 des autothermischen Reaktors (118) durchgeführt wird; und
(d) Abschließen des Reformierens in einer katalytischen Reaktionszone des autothermischen Reaktors (118),
wobei dadurch ein Synthesegas ausgebildet wird.

7. Verfahren nach Anspruch 6, wobei der erste Kohlenwasserstoffzufuhrstrom ein Raffinerieabgas oder ein Endgas ist.
35
8. Verfahren nach Anspruch 6, ferner umfassend:
Aufteilen eines dritten Kohlenwasserstoffstroms (18) aus dem entschwefelten Kohlenwasserstoffzufuhrstrom (8)
und Einführen des dritten Kohlenwasserstoffstroms in unmittelbarer Nähe zu dem Heißsauerstoffbrenner (180), der
in dem autothermischen Reaktor (118) angeordnet ist, und Einführen des erhitzten vorreformierten Kohlenwasser-
40 stoffzustroms derart, dass die erhitzte vorreformierte Kohlenwasserstoffzufuhr in den reaktiven Strahl mitgerissen
wird, nachdem der zweite Kohlenwasserstoffstrom vorwiegend mitgerissen wird.

9. Verfahren nach Anspruch 6, wobei der erhitzte vorreformierte Kohlenwasserstoffstrom von Schritt (b) in unmittelbarer
Nähe des Heißsauerstoffbrenners (180) direkt eingeführt wird, wobei dadurch das partielle Reformieren des Koh-
45 lenwasserstoffs durch partielle Oxidationsreaktionen in der nicht katalytischen Zone des autothermischen Reaktors
(118) durchgeführt wird.

Revendications
50
1. Procédé de génération de gaz de synthèse, comprenant :

la fourniture d’un courant d’alimentation d’hydrocarbures (1) sans préreformage et/ou chauffage dudit courant
d’alimentation en hydrocarbures ;
55 la division dudit courant d’alimentation d’hydrocarbures entre un courant de combustible (9) dirigé vers l’en-
semble brûleur à oxygène chaud (180) intégré à un réacteur autothermique (118) et un courant d’alimentation
d’hydrocarbures (11) où ledit courant de combustible est brûlé avec de l’oxygène dans l’ensemble brûleur à
oxygène chaud (180) d’un réacteur autothermique pour former un jet d’oxygène chaud ;

10
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le mélange du courant d’alimentation d’hydrocarbures avec de la vapeur, et l’introduction dudit mélange d’ali-
mentation d’hydrocarbures dans une région non catalytique du réacteur autothermique (118), le mélange d’ali-
mentation d’hydrocarbure étant sensiblement entraîné dans le jet d’oxygène chaud ; l’allumage du courant
d’hydrocarbures avec de l’oxygène chaud pour créer un jet réactif, réalisant ainsi un reformage partiel de
5 l’hydrocarbure dans une zone non catalytique du réacteur autothermique (118) ; et
le reformage supplémentaire de l’hydrocarbure dans un lit de catalyseur du réacteur autothermique (118) pour
générer du gaz de synthèse.

2. Procédé selon la revendication 1, dans lequel le courant de combustible (9) est un effluent gazeux de raffinerie ou
10 un gaz résiduaire.

3. Procédé selon la revendication 1, dans lequel le gaz de synthèse (20) sort du réacteur autothermique (118) à une
température inférieure à 815,6 °C (2 000 °F) et à 2,41 à 3,79 MPa (350 à 550 psia).

15 4. Procédé selon la revendication 1, dans lequel le courant de combustible (9) est d’environ 5 à 10 % en volume du
courant d’alimentation d’hydrocarbures.

5. Procédé selon la revendication 1, dans lequel le gaz de synthèse généré est acheminé vers un rebouilleur de gaz
de traitement (150) et d’autres opérations unitaires en aval.
20
6. Procédé de génération de gaz de synthèse, comprenant :

(a) la fourniture d’un courant d’alimentation d’hydrocarbures désulfuré principal (8) divisé en au moins deux
courants d’hydrocarbures, un premier courant d’hydrocarbures (9) étant acheminé vers le brûleur à oxygène
25 chaud (180) et utilisé dans celui-ci en tant que combustible qui est mélangé à de l’oxygène pour brûler ledit
combustible et générer un jet d’oxygène chaud ;
(b) l’acheminement du second courant d’hydrocarbures (19) vers un dispositif de chauffage (100) et le prére-
formage du deuxième courant d’hydrocarbures en un courant d’hydrocarbures pré-reformé chauffé (16) ;
(c) l’acheminement du courant d’hydrocarbures pré-reformé chauffé à travers le dispositif de chauffage (100)
30 pour augmenter davantage la température, puis l’introduction du courant d’hydrocarbures pré-reformé chauffé
à proximité immédiate du brûleur à oxygène chaud (180), la charge d’hydrocarbures pré-reformé chauffée étant
sensiblement entraînée dans le jet d’oxygène chaud pour créer un jet réactif, réalisant ainsi un reformage partiel
de l’hydrocarbure dans une zone non catalytique du réacteur autothermique (118) ; et
(d) l’achèvement du reformage dans une zone de réaction catalytique du réacteur autothermique (118), formant
35 ainsi un gaz de synthèse.

7. Procédé selon la revendication 6, dans lequel le premier courant d’alimentation d’hydrocarbures est un effluent
gazeux de raffinerie ou un gaz résiduaire.

40 8. Procédé selon la revendication 6, comprenant en outre :

la division d’un troisième courant d’hydrocarbures (18) à partir du courant d’alimentation d’hydrocarbure désulfuré
(8) et l’introduction dudit troisième courant d’hydrocarbure à proximité immédiate du brûleur à oxygène chaud (180)
disposé dans le réacteur autothermique (118) et l’introduction de ladite charge d’hydrocarbure pré-reformée chauf-
fée, de telle sorte que la charge d’hydrocarbures pré-reformée chauffée est entraînée dans le jet réactif après que
45 le deuxième courant d’hydrocarbures est principalement entraîné.

9. Procédé selon la revendication 6, dans lequel le courant d’hydrocarbures pré-reformé chauffé de l’étape (b) est
introduit directement dans la proximité immédiate du brûleur à oxygène chaud (180) réalisant ainsi un reformage
partiel de l’hydrocarbure à travers des réactions d’oxydation partielles dans la zone non catalytique du réacteur
50 autothermique (118).

55

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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 9540240 B [0003] • WO 2004062788 A1 [0008]

• US 7255840 B [0008] • US 9540240 B2 [0019]

23