US 20200002165A1

IN
(19) United States
(12 ) Patent Application Publication ((4310)) Pub
DESAI et al.
Pub..No .: US 2020/0002165 A1
Date : Jan. 2 , 2020
(54 ) HIGH THROUGHPUT METHANE B01J 38/48 (2006.01)
PYROLYSIS REACTOR FOR LOW -COST C07C 5/32 ( 2006.01)
HYDROGEN PRODUCTION (52) U.S. CI.
CPC COIB 3/26 (2013.01); BOIJ 21/18
(71) Applicant: PALO ALTO RESEARCH CENTER (2013.01); B01J 35/12 (2013.01 ); B01J 38/48
INCORPORATED , Palo Alto , CA (2013.01); B01J 2203/06 (2013.01 ); COIB
(US) 2203/1241 (2013.01 ); COIB 2203/1041
(72) Inventors: DIVYARAJ DESAI, HAYWARD , CA
(2013.01 ); COIB 2203/1005 (2013.01); C07C
(US); TODD KARIN , FAIRFIELD , 5/321 ( 2013.01)
CA (US ) ; JESSICA LOUIS BAKER (57) ABSTRACT
RIVEST, PALO ALTO , CA (US) A system for hydrocarbon decomposition comprising a
( 21) Appl. No.: 16 /394,041
reactor volume, a mechanism to distribute the liquid catalyst
as a liquid mist, a distributor to distribute a hydrocarbon
reactant, a heat source , a separator to separate the solid
( 22 ) Filed : Apr. 25 , 2019 product from the liquid catalyst, a re - circulation path and
mechanism to re-circulate the liquid catalyst, and an outlet
Related U.S. Application Data for at least one gaseous product. A system to distribute a
(60 ) Provisional application No.62/692,558 , filed on Jun . liquid to an enclosed volume as a mist has a plurality of
29, 2018 . orifices designed to break the liquid into a mist. A method to
decompose a hydrocarbon reactant includes generating a
Publication Classification mist of a liquid catalyst, heating the reactor volume, intro
ducing a hydrocarbon reactant into the reactor volume to
(51) Int. Cl. produce a solid product and a gaseous product, separating
COIB 3/26 ( 2006.01) the solid product from the liquid catalyst, removing the solid
B01J 21/18 ( 2006.01 ) and gaseous products from the reactor volume, and recircu
B01J 35/12 ( 2006.01 ) lating the liquid catalyst to the reactor volume.
30

34 P HIGH -PURITY
H2
IT-36
Heat
COMPRESSOR -55
38 40
41
42 PSA -54

33 14 CHA
Heat

44

02000:
49
0

-35
32
46 48
Patent Application Publication Jan. 2 , 2020 Sheet 1 of 6 US 2020/0002165 A1

10

12 {
141 17 !
O O
O
O
25
TERNARY CARBON ALLOY
18 CHA 2H2
20

24
-22
-23
PHASE
SEPARATED
26 = CARBON
-
-

FIG . 1
Patent Application Publication Jan. 2 , 2020 Sheet 2 of 6 US 2020/00022165 A1

30

34 . HIGH -PURITY
8
H2

Heat
COMPRESSOR -55
38 40
4

42 PSA 54
33. CH4\\
Heat

44

35 5
48
-32

FIG . 2
Patent Application Publication Jan. 2 , 2020 Sheet 3 of 6 US 2020/0002165 A1

CH2OMPRES OR
55

ELCTRIC ORHEAT
54

GAS
TAIL PSA2 PSA
EL CTRIC ORHEAT -41
52
48
FILTER
2
HeatExchanger FCOLUINDG Water
(
or
)
Air
3
.
FIG
50
LRMECITHUNLAEIO
46 FILTER
1 Storage
C

H2
C.
.

32
RECH4ACTOR
CHA

EL CTRICHEAT
Patent Application Publication Jan. 2 , 2020 Sheet 4 of 6 US 2020/0002165 A1

44
H2 + C + CH4 out
58
METAL IN

40 40
Molten
42

Heater
32
CHE ? 51 C
-56

49
MOLTEN FIG . 4
METAL
RECIRCULATION
Patent Application Publication Jan. 2 , 2020 Sheet 5 of 6 US 2020/0002165 A1

GENERATE A LIQUID 60
CATALYST MISTINA
REACTION CHAMBER

REACT A HYDROCARBON -62

GAS WITH THE LIQUID
CATALYST

REMOVE REACTION 64
PRODUCTS FROM THE
CHAMBER

SEPARATE REACTION -66

PRODUCTS

FIG . 5
Patent Application Publication Jan. 2 , 2020 Sheet 6 of 6 US 2020/0002165 A1

100 %
20 bar
1 bar 1400 °C
75 % 1000 °C
1

Yield
H2
)
%
(
50 %

25 %

0% 1

1.E +0.0 1.E +0.3 1.E + 0.6 1.E +0.9

GHSV (h1

FIG . 6
US 2020/0002165 A1 Jan. 2 , 2020

HIGH THROUGHPUTMETHANE TABLE 1

PYROLYSIS REACTOR FOR LOW -COST
HYDROGEN PRODUCTION Comparison of proposed technology with the steam -reforming ,
water electrolysis using solid oxide electrolyzers and methane pyrolysis .
Natural Gas
RELATED APPLICATIONS Steam Water Pyrolysis
Metric Reforming Electrolysis (Molten Metal)
[ 0001] This application is a continuation of and claims Enthalpy of reaction 63 143 37
priority to U.S. Provisional Patent Application No.62/692 , (kJ/mol H2)
558, filed Jun . 29, 2018 , which is incorporated herein by Process CO2 Emissions 7.5 0-1.1
reference in its entirety (kg/kg H2)
Operating temperature (° C.) 700-1100 600-800 650-1400
Pressure of CH4 (bar) 3-25 Ambient 1-20
TECHNICAL FIELD Conversion efficiency ( % ) 95 95 > 90
Capital cost > 1800 > 2700 < 900
($ /ton per year H2)
[0002 ] This disclosure relates to hydrogen production , H2 production cost 1.25 $ 3.16 1.25 (no C
more particularly to methane pyrolysis for hydrogen pro ( $/kg H2) revenue)
duction .
[0006 ] Methane pyrolysis , CH4 > C +H2, has long prom
BACKGROUND ised an energy -efficient approach to emission - free hydrogen
production and techno -economic models predict the feasi
[0003 ] Fracking has unlocked an abundance of low cost bility of achieving cost-parity with steam reforming through
methane , over 21 trillion proven reserves. This methane will revenue from carbon production. However, achieving cost
be combusted or converted into hydrogen (H2), which parity in the absence of carbon revenue is challenging due to
releases greenhouse gas emissions, unless new technologies the unfavorable stoichiometry compared to steam methane
are developed . In the US , almost all 10 million tons ofH2per reforming , CH4+ 2H20CO2+ 4H2. This overall exergy bal
annum (Mtpa ) results from steam methane reforming (SMR ) stock ance results in methane pyrolysis requiring more CH4 feed
and produces 100 Mtpa CO2. The energy content of the achieve , on the order of 30 % , requiring low capital costs to
produced H , represents approximately 1 % of US energy [0007 ] cost Non
parity.
-catalytic methane pyrolysis needs to over
consumption and 2 % of domestic CO2 emissions. The H2 come a high activation energy barrier of approximately 400
market is growing at a compound annual growth (CAGR ) of kJ/mol. The high operating temperatures results in increased
over 6 % motivating a shift towards low -carbon production reactor fabrication costs. Past efforts at methane pyrolysis
methods such as water electrolysis or carbon capture . using high melting point, solid -phase catalysts such as
[0004 ] Steam reforming of natural gas is the current state nickel (Ni), iron (Fe ), molybdenum (Mo ) or cobalt (Co )
of the art in hydrogen production . As an alternative have lowered activation energy barriers ( < 300 kJ per mole
approach , water electrolysis is energy intensive and depen hydrocarbon feedstock ), but are rapidly deactivated because
dent upon low electricity prices to maintain price parity with of carbon buildup ,or coking . The use ofmolten metals could
steam reforming. Similarly, carbon capture approaches suf potentially enable carbon separation, but existing methods
fer from the absence of carbon credits and geological [suffers 0008 ]
from poor catalytic activity for methane pyrolysis.
The use of catalytically active molten alloys for
restraints for carbon sequestration and storage systems.
[0005 ] Steam reforming of natural gas involves reacting it achievingpyrolysis
methane
cost
has been recently reported . However,
parity is unlikely due to the extremely low
with steam in the presence of a metal catalytic , such as gas hourly space velocity
nickel (Ni), in a catalytic reactor at high temperatures in the volatile molten metal. The(GHSV ) and high loss rate of the
reactor design approaches cur
range of 700-1100 ° C., and modest pressure, in the range of rently reported , including bubble column, slug, and capillary
3-25 bar. The overall reaction produces 4 moles of H2 per reactors all have a continuous gas phase with a size -depen
mole of CH4 but the user of natural gas for process heat dent bubble rise velocity . Since the gas residence time is
reduces the hydrogen yield by 60-75 % and is associated constrained by the low bubble rise velocity , all of these
with CO2 emissions, in the range of 10 kg CO2 per kg Hz. methods suffer from low throughput on account of slow
The product gases are cooled and passed onto a pressure bubble rise velocity
swing absorber (PSA ) vessel to yield high purity H2, greater [0009 ] Currently, .no commercially mature technology
than 99.9 % . However, the presence of CO contaminant is exists that can produce emissions-free hydrogen at cost
incompatible for use in electromechanical applications , par parity with steam reforming .
ticular fuel cells , necessitating additional expensive purifi
cation steps . Partial oxidation (PDX ) and coal gasification SUMMARY
( CG ) are alternative approaches to use fossil fuels for H2
production . The addition of a CO , capture and sequestration [0010 ] According to aspects illustrated here , there is pro
system results in increased H2 production costs being com vided a system to decompose a hydrocarbon reactant into a
parable to that of energetically -intensive water electrolysis. gaseous product and a solid producthaving a reactor volume
Water electrolysis has been touted as a method of producing containing liquid catalyst, a mechanism to distribute the
emission - free H2, but projections continue to put it far out of liquid catalyst into the reactor volume as a liquid mist
reach of economic competition with SMR . Table 1 shows a through a first inlet, a distributor to distribute a hydrocarbon
comparison of the embodiments to steam reforming and reactant through a second inlet into the reactor volume, a
water electrolysis. heat source positioned to maintain a temperature between
US 2020/0002165 A1 Jan. 2 , 2020
2

1100 ° C. and 1400 ° C. in the reactor volume, a separator to catalyst 12. As will be discussed in more detail further , the
separate the solid product from the liquid catalyst , a re catalyst may reside inside a reservoir inside the reactor, or
circulation path to re -circulate the liquid catalyst back to the external to the reactor and later introduced into the reactor.
reaction chamber, and an outlet to allow at least one output The liquid may be converted into a mist using a set of
gas to be removed from the reactor volume. misting nozzles 14. In various embodiments, either a single
[0011 ] According to aspects illustrate here, there is pro nozzle or a plurality ofnozzle designsmay be used to ensure
vided a system to distribute a liquid to an enclosed volume that the liquid fill fraction within the reactor volume is
in the form of a mist , comprising a plurality of orifices between 1 percent and 5 percent, or between 5 and 30
designed to break up the liquid into a mist, the mist having percent by volume. The mist of liquid catalyst droplets such
droplets with a liquid fraction within the enclosed volume as 24 enters the reaction chamber into which is introduced
greater than five percent. methane (CH4) through an inlet 18 that may have a co
[0012] According to aspects illustrated here, there is pro current, countercurrent, cross -current or an arbitrary posi
tion relative to the nozzles 14. The entrance of the mist of
vided a method to decompose a hydrocarbon reactant into a liquid catalyst could be at the top of the reactor, as shown,
gaseous product and a solid product that includes generating from either side, or from the bottom .
a mist of a liquid catalyst within a reactor volume, heating [0021] As the hydrocarbon interacts with the liquid cata
the reactor volume to a temperature between 1100 ° C. and lyst , the reaction results in the production of H , or alkane,
1400 ° C., introducing a hydrocarbon reactant into the reactor alkene or alkyne -based gases 20 , solid carbon outputs 22 ,
volume to produce a solid product and a gaseous product, and a ternary carbon alloy 25. Some of the carbon may be
separating the solid product from the liquid catalyst, remov entrained in the hydrogen gas, which may require further
ing the solid product and gaseous product from the reactor process to harvest and some may exit the reactor as phase
volume, and recirculating the liquid catalyst be re - intro separated carbon 23. Similarly , the carbon may mix with the
duced to the reactor volume. liquid catalyst and may need further separation . The liquid
catalystmistmay pool at the bottom of the chamber such as
BRIEF DESCRIPTION OF THE DRAWINGS at 26 and can be recycled and reused , possibly after sepa
ration from the solid product of the reaction . As used here ,
[ 0013 ] FIG . 1 shows an embodiment of a liquid mist the terms“ reaction chamber," " reactor” and “ vessel” may be
catalyst methane pyrolysis reactor. used interchangeably to refer to the volume in which the
[0014 ] FIG . 2 shows another embodiment of a liquid mist reaction between the gas and the catalyst takes place . Table
catalyst methane pyrolysis reactor. 2 shows a comparison of embodiments using this approach
[0015 ] FIG . 3 shows an embodiment of a piping diagram and the current state of the art.
for a liquid mist catalysis methane pyrolysis reactor.
[0016 ] FIG . 4 shows an embodiment of a liquid mist TABLE 2
catalyst methane pyrolysis reactor. Comparison of methane pyrolysis states of the art and the embodiments
[0017 ] FIG . 5 shows a flowchart of an embodiment of a
method to perform methane pyrolysis . Metric
Bubble
Column Liquid Mist Reactor
[ 0018 ] FIG . 6 shows a graph of an expected range of
performance for a methane pyrolysis reactor. Reactor fill fraction ( % ) 25 1-5 , 5-30
Reactor SA: V (cm² catalyst/cmº reactor) 1.5 > 0.6-18,000
DETAILED DESCRIPTION OF THE Reaction rate (umol CHA/cm². s) 0.79 >2
EMBODIMENTS Operating temperature (° C.) 1065 650-1400
Pressure of CH4 (bar) 1.6 1-20
[ 0019 ] The embodiments here involve a liquid mist reactor Conversion efficiency ( % ) 95 80-99.999
Space velocity (l/h ) < 10 100-107
that decomposes natural gas or any hydrocarbon to produce H2production cost ($ /kg ) > 3.00 < 1.5
hydrogen gas and solid carbon , longer chain hydrocarbons
(for example : 2CH_C2H4+ 2H2), shorter chain hydrocar [0022 ] The use of molten metal in pyrolysis reactor
bons (for example: C4H10 -> 2CH4 + C2H2) or any combina designs are in the early stages of development, and usually
tions of those . The embodiments enables low -cost H2 pro take the form of bubble column, capillary, packed bed , and
duction through a combination of a catalytically active falling film reactors. However , all these designs suffer from
liquid to improve pyrolysis kinetics and a liquid mist reactor low throughput on account of low bubble rise velocity in
designed to improve catalyst surface area . The catalytic slug and bubble column reactors , or low surface area to
liquid allows for high production flux , and the mist reactor volumeratio in packed bed and fluid wall flow reactors . The
design allows for a high surface area on which the reaction differential reactor conversion ( DX ) can be explained in
occurs. These use of liquid mist catalysts provides a very terms of the design equation to predict the conversion in
high catalyst surface per unit reactor volume, enable terms of differential residence time (dt ), reaction flux (rcht)
extremely high reactor vessel utilization to be achieved and specific surface area (a ):
( 100-107 h-?). The terms mist , aerosol and spray are used
interchangeably , and unless specified otherwise , refer to a d (X )=rch * a *dt.
fine suspension of liquid droplets or solidified particles in a In bubble column reactors, the residence time( t« VD ) and
gas . The size of the produced droplets or solids in the mist specific surface area
may vary from 0.1 to 1000 microns in diameter. In case the
droplets are non -spherical, the droplet size is defined as the
mass -averaged equivalent diameter of the non -spherical
droplet DD
[0020 ] FIG . 1 shows a diagram of an approach set forth in
the embodiments. The liquid mist reactor 10 has a liquid
US 2020/0002165 A1 Jan. 2 , 2020
3

are simultaneously depending upon bubble size (Dj). bon gas is methane and is heated by heater 40 prior to
Achieving high conversion rates necessitates high specific entering the chamber and there is a hydrocarbon recircula
surface area, usually meaning small bubble size. However, tion channel 41. The reaction in the chamber between the
small bubble size unfortunately also reduces bubble buoy liquid catalyst mist and the hydrocarbon gas results in a
ancy and thereby reactor throughput. To reduce reactor separation of hydrogen and carbon from the gas . Some of the
capital costs , the process needs reactor designs that circum carbon ,which will typically comprise a solid , will fall to the
vent this constraint. The use of mist reactors along with bottom of the chamber, mixed in with the unreacted liquid
liquid catalysts at high temperature enables extremely high catalyst. The chamber 32 may have a liner 35 , such as a
reactor throughput to be achieved . In practice , the expected ceramic or other type of liner, which is a barrier between the
throughput, or gas hourly space velocity (GHSV ) required liquid catalyst and material of construction of reaction vessel
for 90 percent hydrogen yield can vary from approximately 32. The catalyst is subsequently recovered through recircu
100 h -1 (1000 ° C., PCH4 = 1 bar) to approximately 107h -1 lation line 33 , which also includes the use of an appropriate
( 20 bar, 1400 ° C.). The expected range of performance is high - temperature pump 49 to recirculate the liquid catalyst.
summarized in FIG . 6. These reactor throughput values are [0028 ] Some of the carbon may also be entrained in the
far higher than reportedly achievable using existing reactor hydrogen gas that exits the chamber through the outlet 44 .
designs. This may be captured using a filter , such as a knock out pot
[0023 ] The embodiments here include a reactor design , a 46 , and a second filter 48. These allow extraction of the solid
liquid catalyst composition of matter and a nozzle design to carbon from the hydrogen gas. In this particular embodi
form a mist of the liquid catalyst. FIGS. 2-5 show alternative ment, the gas may go through a pressure swing adsorber
embodiments of the reactor design . Components that are (PSA ) 54 and a compressor 55 to output high - purity product
similar between the various embodiments will be identified gas. In one embodiment, the output hydrogen may be
using the same reference numbers . 99.999 % pure at 10 bar of pressure .
[0024 ] In general, the system will include a reactor vol [0029 ] FIG . 3 shows a piping diagram for an embodiment
ume containing liquid catalyst ,where “ containing” includes making a bubble column reactor 32. The reactor 32 receives
a pre- loaded catalyst or where the catalyst is added into the the electric heat and the methane or other hydrocarbon gas.
vessel from an external source . The system will also include Typically, the liquid catalyst will enter the chamber from the
a mechanism to distribute the liquid catalyst, a distributor to top of the reactor. The outlet transfers the hydrogen with
distribute a hydrocarbon gas through an inlet into the reactor entrained carbon and any unreacted hydrocarbon gas to a
volume, a heat- transfer source positioned to uniformly dis first filter. For example , the first filter 46 may comprise a
tribute the temperature by either adding or removing heat, a cyclone filter or a knock -out pot. The cyclone filter 46 may
separator to separate out the solid pyrolysis from the liquid be attached to a carbon storage 50. After going through the
catalyst and a way to remove the output gas from the cyclone filter, a further filter 48 , such as a cartridge filter,
volume. The heat sources may exchange heat between may catch any remaining solid carbon . The hydrogen may
streams of the hydrocarbon reactant and the solid pyrolysis then be cooled at 52 and sent to a to an optional pressure
product to maintain a process energy efficiency of at least 25 swing adsorber (PSA ) bed 54 for purification to yield up to
percent. In one embodiment, the reactor may operate at a 99.999 % pure H2. The unconverted methane is recirculated
temperature of less than 1400 ° C. and pressures of up to 20 to the reactor feed stream , and residual tail gas composed of
bar. H2, natural gas and inerts may pass through a second PSA
[0025 ] The hydrocarbon gas, also referred to as the hydro 57 may be used for process heating value . The H2 may
carbon reactant, may comprise at least one selected from the optionally be compressed using a compressor 55 and then
group consisting of: natural gas ; liquefied petroleum gas ; output .
gasoline ; diesel; kerosene; naphtha; JP -8 ; methane ; ethane; [0030 ] FIG . 4 shows an alternative embodiment of a
propane; butane; pentane ; hexane ; benzene; xylene; toluene ; reactor. In this embodiment the liquid catalyst may already
and any combination thereof. Further, the hydrocarbon may reside inside the reactor vessel in the reservoir 32. In
also refer to all alkanes, akenes, alkynes and arenes with a addition to the nozzle 14 , the liquid catalyst is continuously
boiling point less than 600 ° C. recirculated through inlet 58 and converted into a mist
[ 0026 ] In the system 30 of FIG . 2 , the reactor vessel 32 has within the chamber 32. Additional pressure may be added
an inlet 34 through which a liquid catalyst loads into the through the use of a diaphragm located outside the heated
vessel. In this embodiment, a pre -heating chamber 40 heats zone , such that the gas is not in contact with the liquid
the catalyst to make it easier to turn it into a mist or it is catalyst. External heaters 40 operate to keep the reactor
heated in the internal reservoir 42. For somematerials , this vessel at a uniform temperature, typically between 600 ° C.
may involve melting the material into a liquid catalyst . The and 1100 ° C., or between 1100 ° C. and 1400 ° C. The
liquid catalyst is transferred into the reactor chamber 32 methane or other hydrocarbon gas enters the chamber
through a series of nozzles or orifices such as 14 that convert through the second inlet 51 and upon generation of the
the liquid catalyst into a mist. The use of a mist increases the output gas , which may include entrained solid carbon, some
available surface area for reactions, resulting in a higher of the carbon exits the system through the outlet 44. The
conversion efficiency . Pressuremay be added at 36 to assist output product may include unreacted methane , which is
with this process . In one embodiment, the average diameter captured in the PSA bed and recirculated through inlet 51.
of the particulate in the mist is between 1 and 1000 microns, [0031] In one embodiment, the liquid catalyst and hydro
and the droplet fill fraction is between 1 and 25 percent. carbon inlets and ports may be positioned to achieve a
[0027 ] The hydrocarbon gas is also introduced into the co -current flow in which the liquid catalyst and hydrocarbon
chamber 32 through the inlet or port 38. As mentioned flow in the same direction , counter-current flow in which
before , the hydrocarbon gas inlet may be located at any spot they flow in opposite directions , or cross -current flow , in
on the vessel. In this particular embodiment, the hydrocar which they flow orthogonal to each other, within the reactor
US 2020/0002165 A1 Jan. 2 , 2020
4

volume. These reactor configurations are intended to [0037 ] In experiments, a TGA furnace was used as a
achieve uniform heat transfer; higher conversion ; higher model reactor. Diluted methane at 5 % volume was flowed
reactant throughput; improved carbon - liquid separation or past a single Nio 2Gaos catalyst bead (251 mg) and pyro
improved carbon - gas separation within the reactor volume. lyzed at 850 ° C. and near-complete initial conversion was
In the same embodiment, the position of liquid catalyst and achieved at 95 % . The high conversion efficiency and com
gas inlet ports may be located at the top , bottom or side of parable GHSV are particularly remarkable since the SA : V
the reactor. The liquid catalyst and reactant may be injected ratio and operating conditions used in this un -optimized
through the same port in at least one embodiment. setup could easily be improved to meet our higher GHSV
[0032 ] In one embodiment, the reactormay be constructed milestone .
of stainless steel and high nickel and stainless steel alloys . [0038 ] The carbon produced in the TGA experiments was
In one embodiment, the reactor may have a liner of quartz characterized using scanning electron microscopy and
and alumina that will allow recapture and recycling of the energy dispersive spectroscopy (EDS). The results suggest
liquid catalyst . The selection of the liner material may be that physical morphology of the carbon phase is highly
made dependent upon the material used in the liquid cata depending upon the catalyst used and varies from fibers (Ga
lyst. and Ni_Ga), graphitic ( Cu ), and aggregated (Ni). This
[ 0033 ] In one embodiment, the reactor may have a top and dependency encourages the possibility for control over the
a bottom , with the top arranged and configured to allow a control properties and the ability to tailor the properties for
batch -type atomized or misting spray of the liquid catalyst use in various applications. Carbon fibers with aspect ratio
down into the reactor volume from above . In one embodi up to 150 :1 and up to 250 micrometers length were
ment, the reactor vessel will be pre-charged with the liquid observed , and contained up to 12 weight % metal. SEM
catalyst before operation , and brought up to melt/ liquid micrographs support the feasibility of complete de -wetting
temperatures with reactor wall heaters , such as those shown and separation of metal and carbon phases.
in FIG . 4 . [0039 ] As mentioned previously, in addition to the reactor
design , the embodiments may include a misting nozzle that
[0034 ] In one embodiment, the reactor may include facilitates the break -up of the liquid catalyst. In one embodi
augers , rotary or gravimetric separators to remove the car ment, the liquid catalyst droplet size ranged from 150-500
bon product layer that gravimetrically settles on top of the micrometers, or microns . In one embodiment, the nozzles
pool of liquid catalyst 56. The carbon would be removed have a diameter of 250 micrometers. In one embodiment, the
through outlet 53 and the system include high temperature misting nozzle comprises an array of misting nozzles that
ceramic gear pumps or electromagnetic pumps to recirculate generate a mist that has a surface area to volume ratio greater
liquid catalyst at 49. The temperature of operation ofmolten than 1 cm² per 1 cm of reactor volume. A device may be
metals is intended to be maintained between 650 ° C. and attached to the plurality of orifices to increase the hydro
1400 ° C. static pressure of the liquid upstream of the plurality of
[0035 ] FIG . 5 shows a flowchart of an embodiment of a orifice ejectors. In one embodiment, the device operates at a
method of performing hydrocarbon pyrolysis . At 60 , the pressure head ofless than 10 bar. In one embodiment the size
process generates a mist of liquid catalyst into a reaction of liquid droplets produced by the nozzles has a mass
chamber ,which may occur before or during the introduction averaged diameter of less than 10 micrometers . Additional
of the hydrocarbon gas. At62 the hydrocarbon gas reacts in nozzle modifications are included embodiments that would
the chamber with the liquid catalyst. The process 64 allow controlled production of liquid droplets with a mass
removes the reaction products from the chamber, wherein averaged diameter between 0.1 micrometers and 1000
the reaction products will include at least hydrogen gas and micrometers .
solid carbon , as well as the possibility of other byproducts. [0040 ] An experiment was conducted using such a nozzle
For example , if a gas is used to atomize the catalyst, it may to spray molten gallium (Ga) into droplets using a misting
also become one of the products that exits the chamber. The nozzle . The experiment resulted in 150-500 micrometer
separation of the reaction products 66 may occur from diameters droplets under an applied pressure of 3 bar.
within the vessel, such as by harvesting the solid carbon [0041] Using fill fraction modeling correlations were
from the bottom of the vessel, or after the products exit the developed for the breakup of viscous liquid jets to develop
vessel. The gaseous product removed from the system may relationships between the characteristic nozzle pitch ,median
include at least one ofhydrogen , ethane, ethylene, acetylene, drop size , and break -up length . The median jet width (D.),
propylene , benzene or any combination of those. The liquid drop diameter (Dp), drop breakup length (L ) can be esti
catalyst may also be separated from the solid product to mated from the equations below :
allow it to be re -used . This increases catalyst longevity and
may reduce operating costs .
[0036 ] The system may operate such that a difference Do = AP / Y ;
between enthalpy of the hydrocarbon reactant and solid Dp 2.1D
pyrolysis product is no higher than enthalpy of fusion of the
liquid catalyst contained within the reactor volume. This is Do
achieved by ensuring that the enthalpy of reaction within the L = 4.9034 + 4.559D .
reactor volume is at least higher than the enthalpy of fusion
of the molten alloy . This maintains the gas temperature in
case of an endothermic reaction such as methane pyrolysis. [0042 ] These calculations suggest that stable fill fraction
Mathematically , this is stated as below : of 15.4 % can be expected if a nozzle pitch comparable to the
AHR< AH fusion drop diameter ( 1.25 D ) and drop spacing is comparable to
US 2020/0002165 A1 Jan. 2. 2020
5

the jet breakup that occurs at length . Using helical grooves confirmatory measure of H2 production . Control experi
in misting nozzles creates a rotating jet and corresponds to ments were performed on a gallium sample in an argon
a fill fraction of 25 % . atmosphere and demonstrated negligible weight gain . This
[ 0043 ] In one embodiment, the array of orifices has a pitch indicates the possibility of sample oxidation . The pyrolysis
of greater than 1.25 times a diameter of the orifice opening . rate was measured across a wide temperature range (600
In one embodiment the 950 ° C.) using a thermogravimetric analyzer ( TGA ) coupled
[0044 ] In addition to the nozzle design , the composition of and limited feed partialpressure (PcH4< 0.1 bar ). The control
a novel liquid catalyst to facilitate the catalysis of the experimentperformed using methane (0.05 bar CHA) at 800 °
hydrocarbon gas. In one embodiment, the liquid catalyst C. demonstrated that less than 5 % could be attributed to
here comprises a composition of matter having a melting non -catalytic methane pyrolysis. The demonstrated H2 pro
point of less than 1100 degrees Celsius, and an activation duction fluxes (summarized in Table 3 ) are in agreement
energy of less than 300 kJ per mol for hydrocarbon pyroly with existing reports of methane pyrolysis catalysts .
sis . In another embodiment, the composition ofmatter has
the above two characteristics and also has a carbon solubility TABLE 3
of at least 1 atomic percent. Comparison of H2 flux using molten catalysts at 800 ° C.
[0045 ] In one embodiment, the liquid catalyst may com and PcH4 = 0.05 bar.
prises a multi -component alloy made up of at least two
different components, one with a relatively low melting Catalyst H2 Flux (mol cm-? s =1)
point, and the other that is catalytically active . In another Nio.2G20.8 2.24 x 10-7
embodiment, one catalyst may have both of those properties , Nio.2Sn0.8 1.60 x 10-7
such as a eutectic material. In another embodiment, there Nio.2Bio.8 1.47 x 10-7
may be a second or third component that has carbon solu
bility of at least 1 atomic percent. [0052 ] The expected activation energy for methane
[0046 ] In one embodiment, the liquid catalyst includes at pyrolysis using these catalyst materials is expected to be
least one of the group consisting of lithium ; sodium ; cal between 50 and 300 kJ/mol. The choice of liquid catalyst
cium ; potassium ; cadmium ; aluminum ; antimony ; bismuth ; materials includes molten pure elements, binary alloys,
cerium ; copper gallium ; indium ; lanthanum ; lead ; magne ternary alloys, quaternary alloys othermulticomponent ( >4
sium ; mercury ; silver ; tin ;and zinc. The total atomic percent elements ) alloys.
composition of the abovementioned elements in the catalyst
phase is at least 50 percent and at most 90 percent. [0053 ] One of the criteria for selection of liquid catalyst
[0047] In one embodiment, the liquid catalyst includes at materials also includes the use of materials with high
least one of the group consisting of: nickel; iron ; cobalt; and solubility for carbon produced through pyrolysis. In this
manganese. The total atomic percent composition of the case , the produced carbon is intended to form a liquid
abovementioned elements in the liquid catalyst phase is at solution in the molten phase to enable ease of carbon
least ten percent and at most 50 percent separation. The dissolution of carbon enables its removal as
[0048] In one embodiment, the liquid catalyst includes at a homogenous liquid , and the carbon is subsequently phase
least one of the group consisting of chromium scandium ; separated and removed from the liquid catalyst . The carbon
titanium ; vanadium ; molybdenum ; silicon ; tantalum ; tech solubility is expected to range from 1 to 25 atomic percent
netium ; tungsten ; ruthenium ; and palladium . carbon, and is comprised of the one or more of the materials
[0049 ] In one embodiment, the liquid catalyst is com listed in Table 4.However, this is not an exhaustive list the
prised of a first element having a concentration of at least 0 choice of liquid catalyst materials is also expected to include
but not more than 90 weight percent, the first element molten salts such as alkali metal acetylides.
selected from the group consisting of lithium ; sodium ; TABLE 4
calcium ; potassium ; cadmium ; aluminum ; antimony; bis
muth ; cerium ; copper gallium ; indium ; lanthanum ; lead ; Comparison of carbon solubility in liquid metal phase at the eutectic point.
magnesium ; mercury ; silver; tin zinc . The liquid catalyst is
comprised of a second element having a concentration of at Low solubility
Intermediate
solubility High solubility
least 11 but not more than 90 weight percent, the second
element selected from the group consisting of nickel; iron ; C content C content C content
cobalt ; manganese; chromium ; scandium ; titanium ; vana Element (atomic % ) Element (atomic % ) Element (atomic % )
dium ; molybdenum ; silicon ; tantalum ; technetium ; tungsten ; Zn 1.00 Ni 6.93 Rh 15.5
ruthenium ; and palladium . Sc 1.11 Hf 6.95 Pt 16.5
[0050 ] The system may include a liquid catalyst reservoir Si 1.16 Y 6.96 Fe 16.9
integrated with the heat-transfer source to maintain a reser Li
B
1.17
1.35
Nb
Ce, Pr
10.5
10.6
Mo, Re
Os
17.0
17.5
voir temperature of up to 1400° C. In one embodiment the U 1.95 Mn 11.1 Tc 20.2
reservoir temperature may be at the melting point of the Ti 1.96 Co 11.9 Pd 20.3
catalyst of 900 ° C., 1000 ° C., or 1100 ° C. In another Zr 2.96 Th 12.0 La 20.6
embodiment the reservoir may have a temperature ofat least Cu
Au
4.00
4.70
Ru
Cr
13.4
13.9
Ir
W
20.7
22.9
500 ° C. 15.0 Ta 23.5
[0051] In experiments, the liquid catalyst was loaded into
a reactor and heated to a desired temperature under a
controlled methane partial pressure. Carbon deposition was [0054 ] Removal of the solid pyrolysis product, typically a
recorded as a mass gain , and the product gas was fed was fed carbon -based substance , may involve a multiphase separa
to a gas analyzer to detect impurities and to serve as a tion unit having at least one of a particulate filter , an
US 2020/0002165 A1 Jan. 2 , 2020
6

electrostatic precipitator, a cyclone filter, a knock -outpot, or a liquid jet wherein the mist has a surface area to
a cartridge filter. The carbon product produced may include volume ratio greater than 1 cm² per 1 cm of reactor
at least one of: carbon black , carbon fiber, carbon nanofiber, volume; or
carbon nanotubes, carbon nanocage, fullerene , graphite, a plurality of mechanisms to produce the mist , the mist
amorphous carbon , needle coke, coke or diamond. The having of size of liquid droplets with a mass-averaged
selection of the liquid catalyst may affect which carbon diameter between 0.1 and 1,000 microns.
product is produced . 6. The system as claimed in claim 1 , where the mecha
[0055 ] It will be appreciated that variants of the above nism comprises one of:
disclosed and other features and functions, or alternatives a plurality of mechanisms to produce a mist of the liquid
thereof, may be combined into many other different systems catalyst into the reactor volume;
or applications. Various presently unforeseen or unantici a plurality of misting nozzles to produce a mist of liquid
pated alternatives, modifications , variations, or improve catalyst in the reactor volume through breakup of a
ments therein may be subsequently made by those skilled in liquid jet; or
the art which are also intended to be encompassed by the a plurality ofmisting nozzles to accelerate the breakup of
following claims. a liquid jet through patterned grooves within the mist
What is claimed is : ing nozzles.
1. A system to decompose a hydrocarbon reactant into a 7. The system as claimed in claim 1 , wherein the reactor
gaseous product and a solid product comprising : volume is configured to process one of co -current, counter
a reactor volume containing liquid catalyst; current, or cross -current flows of hydrocarbon reactant and
a mechanism to distribute the liquid catalyst into the liquid catalystmist.
reactor volume as a liquid mist; 8. The system as claimed in claim 1 , wherein the liquid
a distributor to distribute a hydrocarbon reactant into the catalyst is introduced into the reactor volume through an
reactor volume; outlet at the top, side, or bottom of the reactor volume.
a heat source positioned to maintain a temperature 9. The system as claimed in claim 1, wherein the hydro
between 1100 ° C. and 1400 ° C. in the reactor volume; carbon reactant comprises at least one selected from group
a separator to separate the solid product from the liquid consisting of: natural gas ; liquefied petroleum gas; gasoline ;
catalyst; diesel; kerosene; naphtha ; JP -8 ; methane ; ethane; propane ;
a re-circulation path to re-circulate the liquid catalyst back butane; pentane ; hexane; benzene ; xylene; toluene; and any
to the reactor volume; combination thereof; alkynes; alkenes ; alkanes ; arenes ;
and
cyclic compounds and any combination thereof having a
boiling point less than 600 ° C.
an outlet to allow at least one output gas to be removed 10. The system as claimed in claim 1, wherein the system
from the reactor volume. operates such that a difference between enthalpy of the
2. The system as claimed in claim 1, wherein the liquid hydrocarbon reactant and solid product is no higher than
catalyst has a melting point between -40° C. and 1400° C. enthalpy of fusion of the liquid catalyst contained within the
and comprises: reactor volume.
a first element of a concentration of up to 90 weight 11. A system to distribute a liquid to an enclosed volume
percent, the first element selected from the group in the form of a mist, comprising a plurality of orifices
consisting of lithium ; sodium ; calcium ; potassium ; designed to break up the liquid into a mist, the mist having
cadmium ; aluminum ; antimony; bismuth ; cerium ; cop droplets with a liquid fraction within the enclosed volume
per gallium ; indium ; lanthanum ; lead ; magnesium ; greater than five percent.
mercury; silver ; tin zinc ; and 12. The system as claimed in claim 11 , wherein the
a second element of a concentration of at least 11 weight orifices are configured to break up the liquid into the mist are
percent, the second element selected from the group configured to produce a size of a mass -averaged diameter
consisting of nickel; iron ; cobalt; manganese ; chro between 0.1 and 1,000 microns.
mium scandium ; titanium ; vanadium ; molybdenum ; 13. A method to decompose a hydrocarbon reactant into
silicon ; tantalum ; technetium ; tungsten ; ruthenium ; and a gaseous product and a solid product comprising:
palladium generating a mist of a liquid catalyst within a reactor
3. The system as claimed in claim 1, wherein the liquid volume;
catalyst comprises one or more components: heating the reactor volume to a temperature between
wherein the one or more component has an activation 1100 ° C. and 1400 ° C .;
energy barrier for hydrocarbon pyrolysis of less than introducing a hydrocarbon reactant into the reactor vol
300 kJ per mole ; or umeto produce a solid product and a gaseous product;
wherein the one or more component has a carbon solu separating the solid product from the liquid catalyst;
bility of at least 1 atomic percent. removing the solid product and gaseous product from the
4. The system as claimed in claim 1 , further comprising reactor volume; and
a liquid catalyst reservoir integrated with the heat source to recirculating the liquid catalyst be re - introduced to the
maintain a reservoir temperature of between -40 ° C. and reactor volume.
1400 ° C. 14. The method as claimed in claim 13 , wherein gener
5. The system as claimed in claim 1, wherein the mecha ating the mist of liquid catalyst comprises at least one of:
nism to distribute the liquid catalyst comprises one of either: using a plurality of mechanisms to produce the mist of
a plurality of mechanisms to produce the mist of liquid liquid catalyst into the reactor volume through a hydro
catalyst into the reactor volume through the breakup of carbon feed ;
US 2020/0002165 A1 Jan. 2 , 2020
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using a plurality of misting nozzles to produce the mist of nanocage , fullerene, graphite , amorphous carbon , coke ,
liquid catalyst into the reactor volume through breakup needle coke, or diamond as the solid product .
of a liquid jet ; and 18. The method as claimed in claim 13 , wherein the
a plurality ofmisting nozzles to accelerate the breakup of gaseous product contains at least one of hydrogen , ethane,
a liquid jet through patterned of grooves within the ethylene , acetylene ,propylene, benzene , or any combination
misting nozzles . thereof.
15. The method as claimed in claim 13 , wherein separat 19. The method as claimed in claim 13 , wherein the
ing the liquid catalyst from the solid product comprises reactor volume operates at temperatures of less than 1400 °
using one of a rotary scraper , an auger, ladle or a screw C. and pressures up to 20 bar.
separator.
16. The method as claimed in claim 13 ,wherein removing 20. The method as claimed in claim 13 , wherein the
the solid product and gaseous product from the reactor hydrocarbon reactant comprises at least one selected from
volume comprises at least one of using a multiphase sepa group consisting of: natural gas; liquefied petroleum gas;
ration unit comprising one of a particulate filter or an gasoline; diesel; kerosene; naphtha; JP -8 ; methane; ethane ;
electrostatic precipitator to separate suspended solids, or a propane; butane; pentane; hexane; benzene; xylene; toluene;
knock - out pot attached to an outlet of the reactor volume. and any combination thereof; alkynes , alkenes, alkanes,
17. The method as claimed in claim 13 ,wherein the liquid arenes, cyclic compounds, and any combination thereof
catalyst is selected to produce at least one of carbon black , having a boiling point less than 600 ° C.
carbon fiber , carbon nanofiber , carbon nanotube, carbon