US011124466B2

( 12) United States Patent ( 10) Patent No .: US 11,124,466 B2

Tanimu et al . (45) Date of Patent : Sep. 21 , 2021
( 54 ) PRODUCTION OF LIGHT ALKENES FROM ( 56 ) References Cited
ALKANE
U.S. PATENT DOCUMENTS
( 71 ) Applicant: King Fahd University of Petroleum 3,745,194 A 7/1973 Bertus et al .
and Minerals , Dhahran ( SA) 5,639,929 A * 6/1997 Bharadwaj C07C 5/48
585/654
( 72 ) Inventors: Gazali Tanimu, Dhahran ( SA) ; 8,088,962 B2 * 1/2012 Klanner C07C 5/3337
585/325
Ziyauddin S. Qureshi , Dhahran ( SA) ; 10,125,061 B2 11/2018 Aljundi
Sachio Asaoka , Dhahran ( SA)
FOREIGN PATENT DOCUMENTS
( 73 ) Assignee : KING FAHD UNIVERSITY OF
PETROLEUM AND MINERALS , CA 2 428 200 5/2002
Dhahran (SA) CN 1308075 C 4/2007
CN 01734987 B 11/2012
( * ) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS
patent is extended or adjusted under 35
U.S.C. 154 (b ) by 0 days. Tanimu et al . ( Effect of support in Ni - Bi- / support catalyst on
oxidative dehydrogenation of n -butane to butadiene, Jun . 16 , 2017 ,
( 21 ) Appl. No .: 16 /564,762 Molecular Catalysis, vol . 438 , pp . 245-255 ) . ( Year: 2017 ) . *
Tanimu, et al . ; Effect of support in Ni - Bi_0 / support catalyst on
Sep. 9, 2019 oxidative dehydrogenation of n -butane to butadiene ; Molecular
(22) Filed : Catalysis, vol . 438 ; pp . 245-255 ; Sep. 2017 ; Abstract Only ; 2
Pages .
( 65 ) Prior Publication Data Maia, et al . ; Isobutane and n -butane cracking on Ni -ZSM - 5
catalyst: Effect on light olefin formation ; Applied Catalysis A :
US 2021/0070674 A1 Mar. 11 , 2021 General 403 ; pp . 58-64 ; Jun . 17 , 2011 ; 7 Pages .
* cited by examiner
(51 ) Int . Cl . Primary Examiner Youngsul Jeong
C07C 5/48 ( 2006.01 )
? 01? 23/84 ( 2006.01 ) (74 ) Attorney, Agent, or Firm Oblon , McClelland,
C07C 11/08 ( 2006.01 ) Maier & Neustadt, L.L.P.
B01J 23/843 ( 2006.01 ) (57 ) ABSTRACT
B01J 35/02 ( 2006.01 ) A method of oxidative dehydrogenating of butane stream
? 01? 37/08 ( 2006.01 ) comprises contacting the same with a bimetallic catalyst in
( 52 ) U.S. CI . the presence of oxygen , wherein the bimetallic catalyst
CPC C07C 5/48 (2013.01 ) ; BOIJ 23/8437 containing nickel and bismuth or oxides thereof supported
( 2013.01 ) ; B01J 35/023 (2013.01 ) ; B01J on solid support such as zirconium oxide, low aluminum
37/08 (2013.01 ) ; C07C 11/08 (2013.01 ) MFI zeolite , and mesoporous silica foam . Various embodi
(58) Field of Classification Search ments of the method of oxidative dehydrogenating the
CPC .. C07C 5/48 ; C07C 5/42 ; B01J 23/843 ; B01J butane- containing hydrocarbon stream and the bimetallic
37/08 ; B01J 35/02 catalyst are also provided.
See application file for complete search history . 19 Claims , No Drawings
 US 11,124,466 B2
1 2
PRODUCTION OF LIGHT ALKENES FROM stocks using steam to produce different products such as
ALKANE alkenes, alkanes and molecular hydrogen [ Al-Ghamdi, S. A.
" Oxygen - Free Propane Oxidative Dehydrogenation Over
BACKGROUND OF THE INVENTION Vanadium Oxide Catalysts: Reactivity and Kinetic Model
5 ling ” December, 2013 , Ph . D. Thesis, University of Western
Field of the Invention Ontario, Canada — incorporated herein by reference in its
entirety. Fluid catalytic cracking ( FCC ) is used for upgrad
The present invention relates to a method of producing ing streams from refineries. It produces higher value prod
alkene from alkane by oxidative dehydrogenation . ucts such as gasoline from vacuum gas oil and de-asphalted
10 oil . Ethylene is mainly produced by naphtha steam cracking
Description of the Related Art in addition to other feedstocks such as ethane and liquefied
petroleum gas (LPG) . Propylene is obtained as byproduct of
The " background " description provided herein is for the FCC and naphtha steam cracking. By varying the operating
purpose of generally presenting the context of the disclo- conditions and additives , the yield of propylene can be
sure. All references cited herein are incorporated by refer- 15 enhanced . Also , propylene can be produced from propane
ence . Work of the presently named inventors, to the extent dehydrogenation. These processes produce high purity ole
it is described in this background section , as well as aspects fins in an acceptable yield at relatively high energy cost due
of the description which may not otherwise qualify as prior to the endothermic nature of the reactions involved . Also ,
art at the time of filing, are neither expressly or impliedly they produce coke which deactivates the catalyst used in the
admitted as prior art against the present disclosure . 20 processes . In addition , selectivity is difficult to control at
Increased demand for light olefins which are widely used such temperatures [ Rodriguez et al . “ Dehydrogenation of
in the polymer and petrochemical industries has provided n -butane over PdGa / Al2O3 catalysts ” Appl. Catal. A Gen. ,
motivation for identifying new production methods that are vol . 373 , pp . 66-70 , 2010 ; and Mamedov and Corberan,
more efficient and economical than conventional methods, “ Oxidative dehydrogenation of lower alkanes on vanadium
in particular, methods utilizing alkanes as starting materials. 25 oxide -based catalysts . The present state of the art and
Olefins such as ethylene and propylene are considered as the outlooks ” Appl. Catal. A , Gen., vol . 127 , pp . 1-40 , 1995 ,
backbone of the petrochemical industry. Light alkanes hav- each incorporated herein by reference in their entirety ]. The
ing 2-6 carbon atoms are available and are relatively less current methodologies for producing alkenes are believed to
expensive compared to alkenes having the same number of have reached their full potential and cannot accommodate
carbon atoms . That provides an economic motivation to 30 the ever - increasing demands of the petrochemical industry.
develop efficient methods for converting alkanes to alkenes . Catalytic oxidative conversion of alkanes has been uti
Such methods have the added advantage of being considered lized as an alternative process for the production of alkenes
more environmentally friendly than other methods currently including ethylene, propylene , and butene isomers as well as
in use , and hence , alkanes have been widely used as a raw butadiene . The process has relatively low operating cost and
material in the production of petrochemicals [ Nieto , J. L. 35 reduced environmental impact. The catalytic oxidative con
“ The selective oxidative activation of light alkanes . From version of alkanes is an exothermic process producing
supported vanadia to multicomponent bulk V - containing alkenes at lower temperature . Catalytic oxidative catalysts
catalysts ” Top . Catal., vol . 41 , pp . 3-15 , 2006 ; and Téllez et are auto - activated by oxygen provided in the feed stream
al . “ Oxidative Dehydrogenation of Butane over VMgo and do not require an additional re -oxidation step . Thus, the
Catalysts , ” J. Catal ., vol . 195 , pp . 113-124 , 2000 ) . Among 40 presence of oxygen within the hydrocarbon feed stream not
all alkenes, ethylene and propylene are the most used only reduces coking but also extends the catalyst life time
petrochemicals for the production of polymers such as [Malaika et al . “ Chemically Modified Activated Carbons as
polyethylene, polypropylene, polystyrene, polyacrylonitrile , Catalysts of Oxidative Dehydrogenation of n -Butane,” Acta
and polyethylene oxide. About 60 % of propylene produced Phys. Pol. A , vol . 118 , pp . 459-464 , 2010 , incorporated
worldwide is used in the production of thermoplastic poly- 45 herein by reference in its entirety ]. In addition , the formation
propylene. The global production capacity of ethylene and of water as a byproduct provides additional advantage by
propylene is forecasted to reach 385 million tons in 2030 continuously removing the hydrogen gas produced in the
increasing from 240 million tons in 2016 [ Fagg , L. “ Long- reaction mixture, and thereby avoids the thermodynamic
term Sustainability in Commodity Petrochemicals: An out- limitations associated with conventional methods [Heracle
look for olefins and aromatics ” , Asia Petrochemical Industry 50 ous et al . “ Oxidative dehydrogenation of ethane and propane
Conference (APIC ), Amghizar, I. , Vandewalle, L. , Van over vanadia and molybdena supported catalysts” J. Mol.
Geem , K. , Marin , G. New Trends in Olefin Production, Catal. A Chem ., vol . 232 , pp . 29-39 , 2005 , incorporated
Engineering , vol 3 , pp . 171-178 , 2017 ] . herein by reference in its entirety ].
Butadiene is used mainly as a monomer in the manufac- Jermy and co - workers investigated the catalytic oxidative
ture of polymers such as synthetic rubbers including styrene 55 conversion of alkanes targeted mainly at producing butadi
butadiene rubber ( SBR) , polybutadiene rubber (PBR) , and ene as a second step dehydrogenation product [ Jermy et al
nitrile rubber. Such polymers are durable and / or elastic “ Oxidative dehydrogenation of n - butane to butadiene over
[ Vasilev and Galich " Catalysts for the oxidative dehydro- Bi — Ni– O / y - alumina catalyst” J. Mol. Catal. A Chem ., vol .
genation of butenes and butane to butadiene” Chem . Tech- 400 , pp . 121-131 , 2015 ; Jermy et al . “ Influence of calcina
nol. Fuels Oils, vol . 33 , pp . 185-192 , 1997 ; and Veldurthi et 60 tion on performance of Bi— Ni – O /gamma -alumina catalyst
al . “ Promotional effects of Cu on Pt/ Al2O3 and Pd / Al2O3 for n - butane oxidative dehydrogenation to butadiene,"
catalysts during n -butane dehydrogenation ,” Catal. Today, Catal. Sci. Technol., vol . 5 , pp . 4622-4635 , 2015 ; and
vol . 185 , pp . 88-93 , 2012 ] . Tanimu et al . “ Composition effect of metal species in (Ni,
Commercial methods for alkene production include steam Fe , Co ) Bi – O / gamma - alumina catalyst on oxidative
cracking which a gaseous one-phase homogeneous reaction 65 dehydrogenation of n - butane to butadiene , " J. Ind . Eng.
is occurring at temperatures greater than 800 ° C. Steam Chem ., vol . 45 , pp . 111-120 , 2017 , each incorporated herein
cracking involves the decomposition of hydrocarbon feed- by reference in their entirety ]. Several metal oxide catalysts
 US 11,124,466 B2
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including monometallic , bimetallic and ternary metallic In view of the foregoing discussions , one of the objectives
combinations were evaluated . The role of the support in of the present invention is to provide a process for the
dispersing the metal oxides and the influence of calcination catalytic oxidative conversion of a hydrocarbon stream
temperature on the catalytic activities were also evaluated . comprising butane to ethylene and propylene using a sup
The results showed that both ethylene and propylene were 5 ported bimetallic catalyst at relatively low pressure and
coproduced at lower yields , which was highly dependent on temperature in comparison to those of conventional pro
the nature of active oxygen species and the acid- base cesses to provide improved yield and product selectivity.
character of the catalyst .
CN101734987B discloses a method for preparing ethyl SUMMARY OF THE INVENTION
ene and propylene from C4 hydrocarbons. The method 10
comprises introducing a C4 hydrocarbon into a reactor According to a first aspect , the present disclosure relates
comprising a dehydrogenation catalyst to produce an alkene to a method of dehydrogenating a butane-containing hydro
followed by introducing the resulting alkene to a second carbon stream comprises contacting a mixture of the butane
reactor containing a cracking catalyst to obtain ethylene and containing hydrocarbon stream and oxygen with a bimetallic
propylene. The dehydrogenation catalysts are platinum , pal- 15 catalyst supported on a solid support selected from the group
ladium , nickel , cobalt , and chromium supported on silicon consisting of zirconium oxide , low aluminum MFI zeolite ,
dioxide , diatomite , or pumice . The cracking catalysts are and mesoporous silica foam to form a product stream
acidic natural or synthetic molecular sieve , silicon oxide, comprising one or more oxygenated products, ethylene and
and alumina . The method disclosed in CN101734987B is a propylene, wherein the bimetallic catalyst consists of nickel
two - step method carried out in sequence. 20 oxide and bismuth oxide .
CN1308075C discloses a catalyst system for converting In one embodiment, the method further comprises sepa
alkanes to alkenes and to their corresponding oxygenated rating the ethylene and the propylene product from the
products. The catalyst system comprises at least one element oxygenated products.
such as gold , silver, iridium , nickel, palladium , platinum , In one embodiment, the hydrocarbon stream comprises
rhodium , ruthenium and at least one modifier metal oxide 25 butane, isobutene, rafinate , or combination thereof.
such as bismuth , indium , magnesium , phosphorous, anti- In one embodiment, the butane is n -butane .
mony, and zirconium . In one embodiment, the raffinate is one or more of
U.S. Pat. No. 3,745,194A discloses a dehydrogenation raffinate - 1, raffinate - II, rafinate - III, rafinate - IV , or a combi
catalyst consisting of tin associated with at least one metal nation thereof.
such as bismuth , cobalt , or nickel to convert C4 to C10 30 In one embodiment, the bimetallic catalyst is prepared by
alkane to alkene in the presence of oxygen . The ratio of tin impregnating un- calcined solid support with nickel oxide
to bismuth , cobalt , or nickel is in the range of 3: 1 to 1 : 3 . The and bismuth oxide .
catalyst may be supported on ilica , alumina , or silica- In one embodiment, the un - calcined solid support zirco
alumina . The main product of the method disclosed in U.S. nium oxide , zirconium hydroxide or combination thereof.
Pat . No. 3,745,194A patent is 1,3 -butadiene obtained 35 In one embodiment, the mixture comprises oxygen and
through oxidative dehydrogenation alkanes. butane in an oxygen /butane molar ratio in the range of 1 to
U.S. Ser. No. 10/ 125,061B2 ( incorporated herein by ref- 6 .
erence in its entirety ) discloses a butane dehydrogenation In one embodiment, the solid support is modified with Fe ,
method comprising passing a stream of butane on nickel Co , Ga , Mo and /or W.
oxide and bismuth oxide catalyst supported on titanium 40 In one embodiment, the catalyst comprises a weight
carbide in the presence of oxygen at a temperature in the percent of nickel in the bimetallic catalyst is within a range
range of 400 ° C. to 500 ° C. The U.S. Ser. No. 10 / 125,061B2 of 15 wt % to 25 wt % , relative to the total weight of the
method is mainly concerned about the production of bimetallic catalyst.
1 -butene, cis- and trans - 2 -butene as well as butadiene . In one embodiment, the catalyst comprises a weight
CA2428200A1 discloses an electrochemical method for 45 percent of bismuth in the bimetallic catalyst is within a range
the conversion of alkane to at least one corresponding of 25 wt % to 35 wt % , relative to the total weight of the
alkene. The method is carried out in an electrochemical cell bimetallic catalyst.
comprising an anode chamber containing the alkane, a In one embodiment, the bimetallic catalyst supported on
cathode chamber comprising oxygen, and comprises passing solid support is subjected to calcination at 250-400 ° C. for
a proton through a medium from the cathode chamber to the 50 at least 0.5 h and 560-640 ° C. for at least 1 h prior to the
anode chamber. The disclosed method in the CA2428200A1 contacting
is directed to a method for producing propylene, butanes , In one embodiment, the butane -containing hydrocarbon
and styrene. stream is contacted with the bimetallic catalyst supported on
Tanimu et al . [ Mol . Cat . ( 2017 ) 438 , 245-255 ] examine the solid support at a temperature of 400 to 600 ° C.
the effect of the catalyst support on the activity and selec- 55 In one embodiment, the bimetallic catalyst has an average
tivity of oxidative dehydrogenation of n - butane to butadiene particle size in the range of 0.1 to 2 mm .
catalyzed by NiO / Bi_03 . The order of selectivity for buta- In one embodiment, the method further comprising treat
diene is a catalyst supported on Al2O3 > SiO2 > ZrO2>>None. ing the bimetallic catalyst supported on the solid support
Maia et al . [ Appl. Catal . A : General 403 (2011 ) 58-64 ] with an inert gas having a temperature in a range of 300 to
disclose Ni - ZSM - 5 as a catalyst to obtain light olefin from 60 600 ° C. prior to the contacting.
isobutene and n -butane . Nickel ( 0.4-6 wt % ) was introduced In one embodiment, the butane -containing hydrocarbon
into H - ZSM - 5 zeolite by dry impregnation and ionic stream is at a pressure in the range of 1-10 bars during
exchange methods. Also , Maia et al . disclose a method of contacting
converting the alkanes to propylene and ethylene at a In one embodiment, wherein the product stream com
temperature of 500 ° C. and comprises heating the catalyst 65 prises the ethylene and propylene molar in a molar ratio of
under nitrogen and introducing isobutane or n - butane with (moles of ethylene and moles of propylene ):(all other com
nitrogen gas as a carrier. pounds in the product stream ) at least 0.6 .
 US 11,124,466 B2
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In one embodiment, a conversion of butane to ethylene It will be further understood that the terms " comprises ”
and propylene is in a range of 5 to 30 mol % , and wherein and / or " comprising," when used in this specification, specify
a combined yield of ethylene and propene is in the range of the presence of stated features, steps , operations, elements,
3 to 25 mol % based on the conversion of butane . and / or components, but do not preclude the presence or
In one embodiment, the method further comprises mixing 5 addition of one or more other features, steps , operations,
the mixture of butane- containing hydrocarbon stream and elements , components , and / or groups thereof.
As used herein , the term “ and/ or ” includes any and all
oxygen with an inert gas prior to the contacting , wherein a
volume fraction of the butane - containing hydrocarbon combinations of one or more of the associated listed items.
stream is within a range of 0.01 to 0.1 . Links are disabled by deletion of http: or by insertion of
In one embodiment, the butane - containing hydrocarbon 10 the
a space or underlined space before www. In some instances,
text available via the link on the “ last accessed ” date may
stream is contacted with the bimetallic catalyst at a tem
perature of 450 to 550 ° C. , and wherein a molar ratio of be As incorporated by reference .
used herein in the specification and claims , including
oxygen to butane is in a range of 1 : 1 to 6 : 1 . as used in the examples and unless otherwise expressly
In one embodiment, a method of dehydrogenating a 15 specified , all numbers may be read as if prefaced by the word
butane -containing hydrocarbon stream , comprising: " substantially ” , “ about” or “ approximately , ” even if the term
contacting a mixture of the butane -containing hydrocar- does not expressly appear. As used herein , the term “ about”
bon stream and oxygen at a pressure in the range of 1-10 bar refers to an approximate number within 20 % of a stated
with a bimetallic catalyst supported on a solid support value , preferably within 15 % of a stated value , more pref
selected from the group consisting of zirconium oxide , low 20 erably within 10% of a stated value, and most preferably
aluminum MFI zeolite , and mesoporous silica foam to form within 5 % of a stated value . For example, if a stated value
a product stream comprising ethylene and propylene, is about 8.0 , the value may vary in the range of 8-1.6 , +1.0 ,
wherein the butane - containing hydrocarbon stream is con- +0.8 , +0.5 , +0.4 , +0.3 , +0.2 , or +0.1 .
tacted with the bimetallic catalyst at a temperature of 450 to Disclosure of values and ranges of values for specific
550 ° C. 25 parameters ( such as temperatures, molecular weights,
In one embodiment, a molar ratio of oxygen to butane is weight percentages, etc. ) are not exclusive of other values
in a range of 1 : 1 to 6 : 1 . and ranges of values useful herein . It is envisioned that two
or more specific exemplified values for a given parameter
DETAILED DESCRIPTION may define endpoints for a range of values that may be
30 claimed for the parameter. For example, if Parameter X is
Embodiments of the present disclosure will now be exemplified herein to have value A and also exemplified to
described more fully hereinafter with reference to the have value Z , it is envisioned that parameter X may have a
accompanying drawings, in which some , but not all embodi- range of values from about A to about Z. Similarly, it is
ments of the disclosure are shown . The present disclosure envisioned that disclosure of two or more ranges of values
will be better understood with reference to the following 35 for a parameter (whether such ranges are nested, overlapping
definitions. or distinct) subsume all possible combination of ranges for
All publications mentioned herein are incorporated herein the value that might be claimed using endpoints of the
by reference in full for the purpose of describing and disclosed ranges . For example, if parameter X is exemplified
disclosing the methodologies, which are described in the herein to have values in the range of 1-10 it also describes
publications, which might be used in connection with the 40 subranges for Parameter X including 1-9 , 1-8 , 1-7 , 2-9 , 2-8 ,
description herein . Nothing herein is to be construed as an 2-7 , 3-9 , 3-8 , 3-7,2-8 , 3-7 , 4-6 , or 7-10,8-10 or 9-10 as mere
admission that the inventors are not entitled to antedate such examples. A range encompasses its endpoints as well as
disclosure by virtue of prior disclosure . Also , the use of “ or ” values inside of an endpoint, for example, the range 0-5
means “ and /or” unless stated otherwise . Similarly, “ com- includes 0 , >0 , 1 , 2 , 3 , 4 , < 5 and 5 .
prise," " comprises," " comprising " " include," " includes , 22
As used herein , the words “ preferred ” and “ preferably ”
and “ including ” are interchangeable and not intended to be refer to embodiments of the technology that afford certain
limiting . benefits , under certain circumstances. However, other
Unless otherwise specified, “ a” or “ an ” means “ one or embodiments may also be preferred, under the same or other
more ” . circumstances. Furthermore, the recitation of one or more
Terminology used herein is for the purpose of describing 50 preferred embodiments does not imply that other embodi
particular embodiments only and is not intended to be ments are not useful, and is not intended to exclude other
limiting of the invention . embodiments from the scope of the technology.
The headings ( such as “ Background” and “ Summary ” ) As referred to herein , all compositional percentages are by
and sub -headings used herein are intended only for general weight of the total composition , unless otherwise specified.
organization of topics within the present invention, and are 55 As used herein, the word “ include,” and its variants, is
not intended to limit the disclosure of the present invention intended to be non - limiting, such that recitation of items in
or any aspect thereof. In particular, subject matter disclosed a list is not to the exclusion of other like items that may also
in the “ Background ” may include novel technology and may be useful in the materials, compositions, devices, and meth
not constitute a recitation of prior art . Subject matter dis- ods of this technology. Similarly, the terms “ can ” and “ may ”
closed in the “ Summary ” is not an exhaustive or complete 60 and their variants are intended to be non - limiting , such that
disclosure of the entire scope of the technology or any recitation that an embodiment can or may comprise certain
embodiments thereof. Classification or discussion of a mate- elements or features does not exclude other embodiments of
rial within a section of this specification as having a par- the present invention that do not contain those elements or
ticular utility is made for convenience , and no inference features.
should be drawn that the material must necessarily or solely 65 The description and specific examples, while indicating
function in accordance with its classification herein when it embodiments of the technology, are intended for purposes of
is used in any given composition . illustration only and are not intended to limit the scope of the
 US 11,124,466 B2
7 8
technology. Moreover, recitation of multiple embodiments more than 0.05 , preferably no more than 0.02 . Exemplary
having stated features is not intended to exclude other non - butane compounds that may be present in the butane
embodiments having additional features, or other embodi- containing hydrocarbon stream include , but are not limited
ments incorporating different combinations of the stated to , methane, ethane, propane , pentane, hexane , ethylene,
features . Specific examples are provided for illustrative 5 propylene, pentene, hexane , propadiene , butadiene, penta
purposes of how to make and use the compositions and diene , tert - butanol, methyl tert-butyl ether, methanol, etha
methods of this technology and , unless explicitly stated nol , acetic acid , acetaldehyde, water, and the like . The
otherwise, are not intended to be a representation that given
butane -containing hydrocarbon stream may be an effluent
embodiments of this technology have , or have not, been from a debutanizer, a fluid catalytic cracker, a steam cracker,
made or tested . 10 a separation column, or a combination thereof. In an alter
A first aspect of the invention is directed to a method of native embodiment, at least a portion of the alkane present
oxidative and dehydrogenation of a butane - containing in the butane - containing hydrocarbon stream is oxidatively
hydrocarbon stream to produce ethylene and propylene. dehydrogenated in the presence of the bimetallic catalyst
As used herein the term " dehydrogenation ” refers to a and the oxidant, via an oxidative dehydrogenation reaction
chemical reaction that involves removal of hydrogen from 15 to produce alkenes and oxygenated products
an organic molecule . In addition , " oxidative dehydrogena- In one embodiment, the butane -containing hydrocarbon
tion ” refers to a chemical reaction that involves the removal stream is in a gaseous state when contacted with the bime
of hydrogen from an organic molecule in the presence of an tallic catalyst. In another embodiment, the butane-contain
oxidant such as molecular oxygen . Accordingly, in aspects ing hydrocarbon stream is in a liquid /gaseous state , wherein
of the present disclosure a butane - containing hydrocarbon 20 liquid reactants present in the butane - containing hydrocar
stream is contacted with a bimetallic catalyst in the presence bon stream may be vaporized by methods and devices
of an oxidant such as oxygen gas , wherein at least a portion known in the art prior to be contacted with the bimetallic
of butane present in the butane - containing hydrocarbon catalyst . Alternatively, the butane- containing hydrocarbon
stream is oxidatively dehydrogenated accompanied by the stream may be in a liquid state .
loss of at least one carbon and one hydrogen molecule . As 25 In some embodiments, the butane -containing hydrocar
a result, a product stream that includes ethylene and pro- bon stream may contain any gaseous or low boiling fraction
pylene in addition to one more compounds other than distillate obtained from petroleum refinery processes; such
ethylene and propylene such as but not limited to butene, as but not limited to : normal butane, isobutene, light petro
cis- and trans- isobutene , butadiene, propane , carbon diox- leum gas , butane - butene mixtures , and raffinate . Raffinates
ide , and carbon monoxide may form . 30 are light petroleum gas or liquefied petroleum gas mixtures
In one embodiment, the butane - containing hydrocarbon (LPG or LP gas ) that are flammable mixtures of hydrocarbon
stream includes butane and one or more hydrocarbon com- gases , mostly a mixture of propane and butane. They are
pounds selected from the group consisting of alkanes, alk- often formed as byproduct fractions of a naphtha cracking
enes , dienes, aromatics, and mixtures thereof. The term process. Raffinate - I (C4R1 ) refers to C4 residual compounds
“ alkane” as used herein refers to saturated straight -chain , 35 obtained after separating 1,3 - butadiene from a C4 raffinate
saturated branched , or saturated cyclic hydrocarbons having stream and which, mainly contain isobutylene 40-50 wt %
a carbon number in the range of 1 to 12 , preferably 2 to 6 , and cis- or trans - 2 - butene 30–35 wt % . Raffinate - II (C4R2 )
such as methane, ethane, propane, pentane, hexane, heptane, refers to C4 residual obtained after separation of 1,3 -buta
octane , nonane, decane, and the like . The terms " alkene ” and diene and isobutylene from C4 a raffinate stream and which
“ olefin ” are used herein interchangeably having the same 40 mainly consists of cis- or trans - 2 - butene 50–60 wt % ,
meaning and refer to a hydrocarbon compound comprising 1 - butene 10–15 wt % , and n -butane ~ 20 wt % . Raffinate - III
at least one double bond such as ethylene, propylene, (C4R3 ) refers to C4 residual obtained after separation of
1 -butene, cis- or trans - 2 -butene, pentene, cyclopentene, 1,3 -butadiene, isobutylene, and 1 -butene from a C4 raffinate
hexane, cyclohexene, butadiene , and the like . Also , the stream which mainly contains cis- or trans- 2 -butene, n -bu
terms “ diolefin ” and “ diene ” as used herein interchangeably 45 tane , and unseparated 1 -butene. Raffinate - 4 ( C4R4 ) refers to
to refer to hydrocarbon compounds having two conjugated C4 residual obtained after separation of 1,3 -butadiene,
or unconjugated double bonds that may be present in the isobutylene, 1 -butene, and cis- or trans - 2 -butene from a C4
butane - containing hydrocarbon stream or the resulting prod- raffinate stream which mainly contains n -butane .
uct stream . These include, but are not limited to propadiene, The oxidant is preferably a gaseous oxidant, but may also
butadiene, isoprene, pentadiene, cyclopentadiene, hexadi- 50 include a liquid oxidant or a solid - state oxidant. The gaseous
ene , and the like . Additionally, exemplary oxygenated com- oxidant is preferably molecular oxygen , and may be present
pounds that may be present in the butane - containing hydro- as an oxygen stream or as an oxygen -containing stream . The
carbon stream and / or the resulting product stream include , oxygen -containing stream may be air, or an oxygen stream
but are not limited to water, tert -butanol, methyl tert -butyl that has been diluted with one or more inert gases such as
ether, methanol, ethanol, acetic acid, acetaldehyde, acetone, 55 nitrogen, argon , helium, and the like. Other gaseous oxi
and the like . In one embodiment, a volume fraction ofbutane dants , such as , but not limited to N2O , NO , or NO , may also
in the butane - containing hydrocarbon stream is at least 0.4 , be used for oxidatively dehydrogenating the butane -contain
at least 0.5 , at least 0.6 , at least 0.7 , at least 0.8 , at least 0.9 , ing hydrocarbon stream . In embodiments wherein a solid
preferably at least 0.92 , preferably at least 0.95 , preferably state oxidant is used , the oxidant may be periodically
at least 0.98 , preferably at least 0.99 . In some embodiments, 60 regenerated . In a preferred embodiment, the oxidant is an
the butane - containing hydrocarbon stream is in liquid oxygen -containing stream which is mixed with the butane
state , and a mass fraction of butane in the butane -containing containing hydrocarbon stream such that a molar ratio of
hydrocarbon stream is at least 0.5 , at least 0.6 , preferably at oxygen to butane is in the range of 1 : 1 to 1 : 8 , preferably 1 : 1
least 0.7 , preferably at least 0.8 , preferably at least 0.9 . to 1 : 7 , preferably 1 : 1 to 1 : 6 , preferably 1 : 1 to 1 : 5 , and
Preferably, a volume fraction of non - butane compounds 65 preferably 1 : 1 to 1 : 4 .
present in the butane -containing hydrocarbon stream is no The bimetallic catalyst used in the invention comprises
more than 0.1 , preferably no more than 0.08 , preferably no nickel and bismuth supported on any solid support such as
 US 11,124,466 B2
9 10
but not limited to zirconium oxide , low - aluminum zeolite , % , preferably less than 8 wt % , preferably less than 5 wt % ,
mesoporous silica foam . In a preferred embodiment, nickel and down to 0.01 wt % , preferably down to 0.05 wt % ,
is used in the bimetallic catalyst , Nickel , as the term is used preferably down to 0.1 wt % relative to the total weight of
herein , refers to elemental nickel , although in some embodi- the bimetallic catalyst . Alternatively, the third element may
ments, nickel as used in the bimetallic catalyst is present in 5 be an alkali metal , an alkaline earth metal, an oxide thereof,
the form of a nickel oxide, a nickel salt , or mixtures thereof. a salt thereof, or a mixture of such elements or compounds.
Additionally, in a preferred embodiment, bismuth used in For example, in one embodiment, the third element is
the bimetallic catalyst refers to elemental bismuth , although selected from the group consisting of Ca , K , Mg , Sr, Ba , Li ,
in some embodiments the bismuth may be present in the and Na , most preferably Ca , K and Mg , and in either case ,
form of a bismuth oxide , a bismuth salt , or mixtures thereof. 10 oxides thereof and salts thereof, or mixtures of such ele
Furthermore, in some embodiments , the bimetallic catalyst ments or compounds. In one embodiment, the third element
includes elemental nickel and one or more of a nickel oxide is a basic metal oxide to adjust an acidity of the bimetallic
and a nickel salt ; and elemental bismuth and one or more of catalyst. An oxide of an element is an oxide thereof where
a bismuth oxide and a bismuth salt . In an alternative the respective element is in an oxidation state other than the
embodiment, nickel and bismuth are present in the bimetal- 15 fully -reduced state , and includes oxides having an oxidation
lic catalyst as a form of a bimetallic alloy of NiBi and / or states corresponding to known stable valence numbers, as
Ni Biy , wherein x and y are integers in the range of 1 to 10 , well as to oxides in partially reduced oxidation states . In
preferably 1 to 5 , preferably 1 to 3 . addition, a salt of an element can be any stable salt thereof,
In one embodiment, a weight percent of nickel ( present as including, for example, nitrates, carbonates, and acetates .
elemental nickel , a nickel oxide, and / or a nickel salt) in the 20 Preferably, other metals that are not listed above may not be
bimetallic catalyst is within the range of 15 wt % to 25 wt present in the bimetallic catalyst .
% , preferably 16 wt % to 24 wt % , preferably 17 wt % to 23 In a preferred embodiment, the support may be any
wt % , preferably 18 wt % to 22 wt % , preferably 19 wt % suitable porous solid support with a pore size ranging from
to 21 wt % , preferably about 20 wt % , relative to the total 2 nm to 100 nm , preferably 5 nm to 80 nm , preferably 10 nm
weight of the bimetallic catalyst . In another embodiment, a 25 to 60 nm , preferably 15 nm to 50 nm , preferably 20 nm to
weight percent of bismuth ( present as elemental bismuth , a 40 nm . Additionally, the catalyst support may have a surface
bismuth oxide , and / or a bismuth salt) in the bimetallic area ranging from 0.5 m-/ g to 300 m?lg , preferably 5 m² /g
catalyst is within the range of 25 wt % to 35 wt % , preferably to 250 mº /g, preferably 15 m-/ g to 200 m- /g , preferably 20
26 wt % to 34 wt % , preferably 27 wt % to 33 wt % , m²/ g to 150 m /g, preferably 25 m-/g to 100 mg . In view
preferably 28 wt % to 32 wt % , preferably 29 wt % to 31 wt 30 of this embodiment, nickel, bismuth , and / or the third ele
% , preferably about 30 wt % , relative to the total weight of ment ( if present) may be present on a surface of the catalyst
the bimetallic catalyst. In an alternative embodiment, a support, or inside the pores . Examples of suitable supports
weight ratio of bismuth to nickel in the bimetallic catalyst is include but limited to silica , alumina, zeolite , activated
in the range of 1 : 1 to 3 : 1 , preferably 1.1 : 1 to 2 : 1 , preferably carbon , titania , zirconia, and magnesia . In some embodi
1.2 : 1 to 1.8 : 1 , preferably 1.3 : 1 to 1.5 : 1 , preferably about 35 ments, a second catalyst support may be used in the com
1.4 : 1 . In some embodiments, nickel and bismuth as used in position of the bimetallic catalyst to modify porosity and / or
the bimetallic catalyst are nanoparticles with an average a surface area of the primary support of the bimetallic
particle size in the range of 5 to 50 nm , preferably 8 to 30 catalyst. In view of that, a weight percent of the second
nm , preferably 10 to 15 nm that are deposited on a surface catalyst support relative to the weight of the primary support
of a support such as but not limited to zirconium oxide or 40 is no more than 20% , preferably no more than 15 % , pref
low -aluminum zeolite or mesoporous silica foam . erably no more than 10% . In the embodiments, where the
The term “ bimetallic catalyst " as used herein refers to a second catalyst support contains a catalytically active ele
catalyst that includes nickel and bismuth as major metallic ment (e.g. , Al2O3 that contains aluminum ), the second cata
elements ( i.e. having a weight percent of at least 15 wt % , lyst support may catalyze the oxidative dehydrogenation
preferably at least 18 wt % , preferably at least 20 wt % , 45 reactions. In some other embodiments , the second catalyst
relative to the total weight of the bimetallic catalyst ), and support is inert, and does not participate in the oxidative
thus provide a major contribution to catalyze the oxidative dehydrogenation reactions.
dehydrogenation reactions. However, a catalyst support may In some embodiments, the bimetallic catalyst is supported
also be a catalytically active in the oxidative dehydrogena- on one or more supports such as zirconia , low aluminum
tion reaction . 50 zeolite , preferably low aluminum zeolite MFI , or mes
The term “bimetallic" is not meant to be limiting to two oporous silica , preferably mesoporous silica foam .
metallic elements, and thus more than two metallic elements As used herein the terms " zirconia " and " zirconium
may also be present in a composition of the bimetallic oxide” have the same meaning referring to zirconium diox
catalyst. However, metallic elements other than nickel and ide . The porous zirconia may be obtained from a commercial
bismuth may also be present as minor elements, i.e. , having 55 source or prepared by well -known method in the art such as
a weight percent of up to 10 wt % , preferably up to 8 wt % , described by any of U.S. Pat . Nos . 4,203,772 ; 5,128,291 ;
preferably up to 5 wt % , and down to 0.01 wt % , preferably 5,275,759 ; 7,642,210 ; 7,927699 ; and 9,956,543 each of
down to 0.05 wt % , preferably down to 0.1 wt % , relative to which incorporated herein by reference in its entirety. The
the total weight of the bimetallic catalyst . Accordingly, in porous zirconia catalyst support preferably has a BET sur
one embodiment, the bimetallic catalyst includes a third 60 face area of 20-500 m²/ g , for example a BET surface area of
element selected from titanium (Ti ) , tantalum ( Ta ), niobium at least 20 , at least 50 , at least 100 , at least 150 and at least
(Nb ), iron (Fe ) , cobalt ( Co ) , gallium (Ga ) , molybdenum 350 m²/ g . In preferred embodiments , the zirconia has sur
( Mo ) , hafnium (Hf), tungsten ( W) , yttrium ( Y ), zinc ( Zn ), face area in the range of 150 to 250 m´/ g , or about 200 to
zirconium ( Zr ), aluminum (Al ) , and / or a compound contain- 220 m² /g . The zirconia -based porous support has a pore
ing one or more of such element ( s) for example oxides or 65 diameter of at least 20 nm , preferably at least 30 nm , at least
salts of such elements, or mixtures thereof. Preferably, a 40 nm , at least 50 nm , at least 60 nm , at least 70 nm , at least
weight percent of the third element may be less than 10 wt 80 nm , at least 90 , at least 100 nm or more , and a total pore
 US 11,124,466 B2
11 12
volume of at least 0.1 mL / g, preferably at least 0.2 mL / g , at filled with a regular arrangement of pores . The template can
least 0.4 mL/ g , 0.5 mL / g, 0.6 mL/g , at least 0.7 mL/ g , at least then be removed by washing with aqueous solution adjusted
0.8 mL/ g , at least 0.9 mL/g , at least 1.0 mL / g or more . to a proper pH or by calcination at a temperature in the range
Zeolites are the aluminosilicate members of a family of of 300-600 ° C. Also , mesoporous particles may be synthe
microporous solids known as “ molecular sieves ” , and 5 sized by a sol - gel method , or a spray drying method . A more
mainly contain Si , Al , O , and other metals including but not effective precursor for the synthesis of the mesoporous silica
limited to Ti , Sn , and Zn . The term molecular sieve refers to is ( 3 -mercaptopropyl )trimethoxysilane (MPTMS ). The use
a particular property of zeolite , i.e. , the ability to selectively MPTMS as precursor is reported to reduce aggregation and
sort molecules based primarily on a size exclusion process . ensures more uniform spheres.
This is due to a very regular pore structure of molecular 10 In some preferred embodiments, the bimetallic catalyst is
dimensions . The maximum size of the molecular or ionic supported mesoporous foam . As used in herein , “ mes
species that can enter the pores of a zeolite is controlled by oporous silica foam ” means an amorphous mesoporous
the dimensions of the channels, which are conventionally silica foam , i.e. , a silica support with a non - ordered structure
defined by the ring size of the aperture . For example, the and a narrow pore size distribution . The non - ordered struc
term “ 8 - ring ” refers to a closed loop that is built from eight 15 ture may be random and thus , different than the other
tetrahedrally coordinated silicon and / or aluminum atoms mesoporous silica which have hexagonal or cubic structures.
and 8 oxygen atoms . The rings are not always perfectly Specifically, the mesoporous silica foam has a narrow pore
symmetrical for variety of reasons that include strain size distribution of at least 3 nm to about 40 nm and a total
induced by the bonding between units needed to produce the porevolume ofat least 0.500 cm® /g , preferably 0.600 cm® /g ,
overall structure, or coordination of some of the oxygen 20 preferably, 0.700 cm /g , 0.800 cm°/g, preferably 0.900
atoms of the rings to cations within the structure. Therefore , cm /g, preferably 1.0 cm /g, preferably 1.50 cm / g , prefer
the pores in many zeolites are not cylindrical. Zeolites may ably 2.0 cm° /g , preferably 2.50 cm° /g . Without being bound
be natural or synthetic material and their pore structure can by theory, the present pore size distribution and pore volume
accommodate a wide variety of cations, such as , but not are sized to achieve better catalytic activity and reduced
limited to Na + , K+ , Ca2 + , and Mg2 + . The positive ions are 25 blocking of pores by metal oxides, whereas smaller pore
loosely held in the zeolite matrix and can readily be volume and pore size support are susceptible to pore block
exchanged for others in a contact solution . Some of the more ing and thereby reduced catalytic activity of the bimetallic
common mineral zeolites are analcime, chabazite, clinop- catalyst . Reducing the blocking of the pores leads to higher
tilolite , heulandite , natrolite, phillipsite , and stilbite . An dispersion of Ni-Bi catalytic species on the amorphous
example of the mineral formula of a zeolite is : 30 mesoporous silica foam . Higher NiBi dispersion leads to
Na Al Si2010-2H2O , the formula for natrolite . The cation higher catalytic activity and thus, higher ethylene and pro
exchanged zeolites have different acidity and therefore, have pylene yield .
catalytic activity. In some preferred emb nent, the zeolite In one or more embodiments, the pore size distribution of
support of the bimetallic catalyst is synthetic . the mesoporous silica foam impregnated with bimetallic
In some preferred embodiments, the bimetallic catalyst is 35 catalyst may range from at least 3 nm to about 40 nm , or
supported on a zeolite having an MFI structure such as from about 3 nm to about 20 nm , or from about 4 nm to
ZSM - 5 and the like . Further, the zeolite may contain an about 10 nm , or from about 4 nm to about 8 nm , or from
oxide other than silica and alumina in the crystal structure . about 4 nm to about 6 nm . Moreover, mesoporous silica
The zeolite support used to support the bimetallic catalyst foam impregnated with bimetallic catalyst may have a total
preferably has low aluminum content. As used herein the 40 acidity in the range of 0.125 mmol/ g to 0.500 mmol/ g. In
term “ low aluminum content ” refers to a zeolite having an further embodiments, the amorphous mesoporous silica
atomic ratio of silicon to aluminum ( Si/Al ) of at least 50 , foam impregnated with the bimetallic catalyst may have a
preferably 100 , preferably 150 , preferably 200 , preferably total acidity from about 0.125 mmol/ g to about 0.250
250 , preferably 300, preferably 350. Further, the zeolite mmol / g, or from about 0.125 mmol/ g to about 0.150 mmol/
catalyst used in the present invention preferably contains an 45 g . While various surface areas are contemplated, the bime
alkaline earth metal ( AEM ) such as calcium , strontium and tallic catalyst may, in one or more embodiments , have a
the like , and it has an atomic ratio of the AEM to aluminum surface area of at least about 400 m² /g , or in the range of 400
( AEM / Al) in the catalyst of 0.5 or more , preferably 0.75 to m?lg to about 800 m²/ g , preferably 400 m²/ g to about 500
15 and more preferably 2 to 8. The zeolite catalyst contain- m²/g, preferably 400 m² / g to about 450 m´/g, preferably 425
ing such an AEM may be prepared by well- known methods 50 m²/g to about 450 m?lg .
in the art. Here, the atomic ratio , Si/Al and AEM / A1 may be The bimetallic catalyst may be prepared by any well
determined by a conventional analytical method, for known method in the art from metal precursors which are
example , such as atomic absorption spectrometry, induc- generally metal salts . Examples of suitable metal salts
tively coupled plasma emission spectrometry and the like , or include but are not limited to metal alkoxides, chlorides ,
either by the stoichiometric ratio of the silicon -containing 55 bromides, iodides , nitrates, and carboxylates. Typically, the
compound to the aluminum - containing compound used for metal precursors of nickel and bismuth are added to an
the synthesis of the zeolite or the stoichiometric ratio of a aqueous medium which may contain a water miscible sol
compound containing an AEM to the aluminum -containing vent such as , but not limited to methanol, ethanol, propanol ,
compound . In one embodiment, the bimetallic catalyst is isopropanol , and ethylene glycol to form a reaction mixture.
supported on law aluminum zeolite MFI . 60 The reaction mixture may be acidic at a pH in the range of
Another preferred support for the bimetallic catalyst is 3-6 , neutral pH about 7 , or basic at pH in the range of 8-13 ,
mesoporous silica such as , but not limited to mesoporous and may be stirred and/ or heated at a temperature in the
nanoparticles MCM - 41 and SBA - 15 . Mesoporous silica range of 45-95 ° C. , preferably 50-85 ° C. , preferably 55-75 °
nanoparticles are synthesized by reacting tetraethyl ortho- C. for at least 0.5 h , preferably 1.0 , preferably 1.5 h ,
silicate ( TEOS ) with a template such as but not limited to 65 preferably 2 h , preferably 3 h , preferably 4 h , preferably 5
micelles or polymers, preferably rod shaped micelles . The h , preferably 6 h . A calcined or un -calcined support may be
result is a collection of nano -sized spheres or rods that are added to the reaction mixture before heating or after heating
 US 11,124,466 B2
13 14
to form a suspension. The amount of solid support in the preferably about 0.04 . Preferably, the inert gas may be at
catalyst is at least 50 wt . % , preferably at least 55 wt . % , least one gas selected from nitrogen, argon , and carbon
preferably at least 60 wt . % , preferably, preferably 70 % of dioxide .
the total weight of the catalyst . The suspension is generally In one embodiment, the butane -containing hydrocarbon
cooled to ambient temperature and stirred for at least 5 h , 5 stream , the oxidant, and the bimetallic catalyst may be
preferably 7 h, preferably 8 h , preferably 9 h , preferably 12 contacted by passing a mixture of the butane -containing
h to impregnate the support with the metals or their oxides hydrocarbon stream and the oxidant through a fixed - bed
or salt. reactor packed with the bimetallic catalyst, or by passing
In a preferred embodiment, the bimetallic catalyst is said mixture over an exposed surface of the bimetallic
prepared by impregnating an un - calcined or calcined solid 10 catalyst. The contact time ( or residence tune) may vary,
however, preferably the contact time may range from about
support such as , but not limited to zirconium oxide , alumi 0.1 seconds to about 10 seconds , preferably from about 0.5
num MFI zeolite or mesoporous silica foam with the catalyst seconds to about 8 seconds, preferably from about 1 seconds
material. to about 5 seconds. In another embodiment, the butane
In one embodiment, the bimetallic catalyst may be mixed 15 containing hydrocarbon stream and the oxidant are in a
with binders and /or diluents , which are known to those of gaseous state , wherein a gas space velocity may range from
skilled in the art to reduce a concentration and an acidity of about 100 / hr to about 10,000 /hr, preferably from about
the bimetallic catalyst. Diluents may be added to the catalyst 300 /hr to about 6,000 /hr, and more preferably from about
in the range of 0 to 30 vol % , preferably 5 to 25 vol % , 300 /hr to about 2,000/ hr . In one embodiment, the inert gas
preferably 10 to 20 vol % , relative to the total volume of a 20 is used to adjust the gas space velocity. In another embodi
catalyst bed that houses the catalyst and the diluents. The ment, the butane -containing hydrocarbon stream and the
diluents may improve the heat removal or heat transfer of the oxidant are contacted with the bimetallic catalyst at a
bimetallic catalyst to help avoid hot spots or to modify hot temperature that ranges from about 300 ° C. to about 600 ° C. ,
spots . Additionally, binders may provide mechanical more preferably from about 320 ° C. to about 550 ° C. , even
strength to the catalyst and may be added to the bimetallic 25 more preferably from about 350 ° C. to about 520 ° C. , still
catalyst in the range of 0 to 30 vol % , preferably 5 to 25 vol more preferably from about 375 ° C. to about 500 ° C. , and
% , preferably 10 to 20 vol % , relative to the total volume of yet more preferably from about 390 ° C. to about 475 ° C. ,
the catalyst/binder. Preferable binders include silica sol, and most preferably from about 400 ° C. to about 470 ° C. In
silica , alumina , diatomaceous earth , hydrated zirconia , silica another embodiment, the butane -containing hydrocarbon
aluminas, alumina phosphates, naturally occurring materi- 30 stream and the oxidant are contacted with the bimetallic
als , cements and combinations thereof. Preferable diluents catalyst at a pressure that ranges from atmospheric pressure
(i.e. 1 atm ) to about 20 bars , preferably from about 1.5 bars
include , for example, quartz chips, sands, clay and / or to about 10 preferably from about 2 bars to about 8
cement.
Preferably, the bimetallic catalyst may be pressed to form 35 bars , preferably from about 2.5 bars to about 5 bars .
in disc - shape pellets having a diameter in the range of 0.1-2 or The
more
product stream includes ethylene and propylene, one
non - ethylene compounds, one or more non- propyl
min, preferably 0.2-1.5 mm , more preferably about 1 mm . ene compounds , and water. The non -ethylene and non
The bimetallic catalyst may also be pressed to form a propylene compounds which may be present in the product
powder, granules , pellets , extrudates, or a shaped catalyst . stream include one or more of 1 - butene, cis - 2 -butene , trans
Accordingly, the bimetallic catalyst may have a cylindrical 40 2 -butene, 1,3 -butadiene, and isobutylene produced from
( solid or hollow cylindrical ), a spherical, a rectilinear, a n - butane or isobutane . In one embodiment, one or more
star- shape, a ring - shape, a conical, a pyramidal, a rectangu- other products may be formed such as methane, ethane and
lar, or a cubical geometry with an average particle size in the butadiene . The product stream has a combined molar ratio of
range of 0.1-2 mm , preferably 0.2-1.5 mm , more preferably the ethylene and propylene to other compounds of at least
about 1 mm . Shaping of the bimetallic catalyst may be 45 0.5 , preferably 0.6 , preferably 0.7 , preferably 0.8 , preferably
carried out by compaction ( for example tableting or extru- 0.9 . In one embodiment, halide - substituted alkanes (prefer
sion ) of a solid catalyst mixture with or without a prior ably having a carbon number of 2 to 5 ) are oxidatively
kneading step , if necessary with addition of conventional dehydrogenated using the bimetallic catalyst to form vinyl
auxiliaries (e.g. , graphite or stearic acid or its salts as halides . For example, ethyl chloride may be oxidatively
lubricants ). In some embodiments, the solid catalyst mixture 50 dehydrogenated using the bimetallic catalyst and methods
may be shaped either before or after calcining the catalyst , described herein to form vinyl chloride. In addition, the
for example, by grinding the solid catalyst mixture before or product stream may further include unreacted alkanes, an
after calcination . unreacted oxidant, as well as side -products ( e.g. , CO2 ) .
In one embodiment, the bimetallic catalyst is housed in a Ethylene and propylene may be separated from the product
catalyst bed of a reactor, and the butane - containing hydro- 55 stream by well -known method in the art including but not
carbon stream and the oxidant are delivered to the reactor limited to cryogenic separation , by pressure - swing adsorp
either together as a mixed gas through a common feed line, tion ( e.g. , on zeolites ) , by selective absorption, and the like .
or separately but simultaneously via different feed lines . The In an alternative embodiment, the product stream may be
reactor may preferably be a fixed -bed reactor, although other used , without further separation or with partial separation
reactors such as a batch reactor or a fluidized bed reactor 60 (e.g. , with a removal of CO2 and / or H2O ) as a feed stream
may also be employed . to a downstream reactor, where the alkene product can be
In one embodiment, the butane -containing hydrocarbon reacted further.
stream is mixed with an inert gas to form a gaseous mixture In some embodiments, the ethylene produced via oxida
prior to contacting with the bimetallic catalyst . A volume tive dehydrogenation of n -butane using the bimetallic cata
fraction of the butane - containing hydrocarbon stream in the 65 lyst may be further reacted to form polyethylene, styrene,
gaseous mixture is preferably within the range of 0.01to 0.1 , ethanol, acetaldehyde, acetic acid , vinyl chloride, ethylene
more preferably 0.02 to 0.08 , preferably 0.03 to 0.05 , oxide, ethylene glycol , ethylene carbonate, ethyl acetate , and
 US 11,124,466 B2
15 16
vinyl acetate . For example, ethylene may be polymerized to in the art. Vinyl acetate may also be prepared by vapor -phase
form polyethylene according to methods known in the art reaction of ethylene, acetic acid and oxygen over a Pd
using a catalyst having activity for polymerizing ethylene to catalyst.
polyethylene. Exemplary polymerization approaches In some embodiments, propylene produced via oxidative
include free radical polymerization and polymerization over 5 dehydrogenation of propane using the bimetallic catalyst
Ziegler -Natta (i.e. , metal alkyl) catalysts. Ethylene may also may be further reacted to form polypropylene , acrolein ,
be reacted with benzene in the presence of acid catalysts acrylic acid , acetone, propylene oxide , and propylene car
such as aluminum chloride or zeolites to form ethylbenzene, bonate . Propylene may be optionally purified , and then
which may further be catalytically dehydrogenated (using further reacted according to one or more of the following
the bimetallic catalyst of the invention or known dehydro- 10 schemes. For example, in one embodiment, propylene can
genation catalysts ) to form styrene. Styrene may also be be polymerized to form polypropylene according to methods
formed directly from a reaction of ethylene and benzene . known in the art using a catalyst having activity for polym
Moreover, ethylene may be hydrated to form ethanol accord- erizing propylene to polypropylene ( e.g. aluminum alkyl
ing to methods known in the art using a catalyst comprising catalysts ). In another embodiment, propylene is oxidized to
an element or compound having activity for hydrating 15 form acrolein according to methods known in the art using
ethylene to ethanol (e.g. catalysts that include oxides of B , a catalyst comprising an element or compound having
Ga , Al , Sn , Sb or Zn, or mixtures of such oxides ) , along with activity for oxidizing propylene to acrolein (e.g. catalysts
a water stream that is preferably co - fed to a reaction zone that include an oxide of Bi , Mo , Te or W , or mixtures of such
during the hydration reaction . Acetaldehyde may also be oxides ). In another embodiment, propylene is oxidized to
formed from ethylene according to methods known in the art 20 form acrylic acid according to methods known in the art
either directly or through an ethanol intermediate . Accord- using a catalyst comprising an element or compound having
ingly, ethylene can be oxidized to acetaldehyde using a activity for oxidizing propylene to acrylic acid (e.g. catalysts
catalyst comprising an element or a compound having that include an oxide of Mo , V or W , or mixtures of such
activity for oxidizing ethylene to acetaldehyde ( e.g. catalysts oxides ). Acetone may be produced from propylene by oxi
that include oxides of Pd , Cu , V or Co , or mixtures of such 25 dation of propylene . Propylene may also be oxidized to form
oxides ). Alternatively, ethylene may be hydrated to form propylene oxide according to methods known in the art
ethanol and ethanol is then oxidized to form acetaldehyde in using a catalyst comprising an element or compound having
the presence of a catalyst having activity for oxidizing activity for oxidizing propylene to propylene oxide ( e.g.
ethanol to acetaldehyde ( e.g. catalysts that include metals catalysts that include TiSi oxide or PdTiSi oxide) . In one
and / or metal oxides of Cu , Co , Ag , Re , Ru, Pt, Bi , Ce , Sb , 30 embodiment, propylene carbonate is formed by preparing
In, Pd , Rh, Ir, V , Cr or Mn, or mixtures of such oxides ) . propylene oxide as described above , and by reacting the
Furthermore, ethylene may be oxidized to form acetic acid propylene oxide with carbon dioxide . Propylene can also be
according to methods known in the art using a catalyst directly converted to propylene carbonate in a single - step
comprising an element or compound having activity for process.
oxidizing ethylene to acetic acid (e.g. catalysts that include 35 In other embodiments, non - ethylene and non - propylene
a noble metal or an oxide thereof, preferably Pd or Pt or compounds /olefins such as n - butene or isobutene are formed
oxides thereof ), along with a water stream that is preferably in the product stream which may be purified, and then
co - fed to a reaction zone during the ethylene oxidation further reacted to form useful products. For example ,
reaction . Besides , ethylene may be chlorinated or oxychlo- isobutene may be oxidized to form methacrylic acid accord
rinated to form vinyl chloride according to methods known 40 ing to methods known in the art using a catalyst comprising
in the art. In a chlorination reaction , chlorine or other an element or compound having activity for oxidizing
chlorinating agent may be preferably co - fed to the reaction isobutene to methacrylic acid (e.g. catalysts that include
zone , and ethylene is chlorinated in the presence of a catalyst polyoxometallate (POM) , preferably PVMo- or PVW -con
having activity for chlorinating ethylene to vinyl chloride taining POM ). Butanol may be prepared by hydrating
( e.g. catalysts that include a metal halide or a metal oxyha- 45 n -butene to form butanol. Alternatively, n - butene may be
lide , and preferably a halide or an oxyhalide of Cu , Fe , or oxidatively dehydrogenated to form butadiene according to
Cr) , or alternatively in the absence of a catalyst. In an methods known in the art using a catalyst comprising an
oxychlorination reaction , a gaseous oxidant and HCl or element or compound having activity for oxidatively dehy
other chlorinating agent may preferably be co - fed to the drogenating n -butene to butadiene ( e.g. catalysts that include
reaction zone, and ethylene is oxychlorinated in the presence 50 elements or compounds selected from the group consisting
of a catalyst having activity for oxychlorinating ethylene to of Ni , Ti, Ta, Nb , Hf, W , Y , Zn , Zr, Al , oxides thereof, and
vinyl chloride ( e.g. catalysts that include a metal halide or a salts thereof, or mixtures of such elements or compounds ).
metal oxyhalide, preferably a halide or an oxyhalide of Cu , Butanediol may also be prepared by forming butadiene , as
Fe , or Cr ). Yet, ethylene may be oxidized to form ethylene described above and then hydrating butadiene to form
oxide according to methods known in the art using a catalyst 55 butanediol. Moreover, n - butene may be oxidatively dehy
comprising an element or compound having activity for drogenated to form butadiene , and butadiene can be oxi
oxidizing ethylene to ethylene oxide (e.g. catalysts that dized to form methylethylketone ( MEK) according to the
include Ag , a halide thereof, an oxide thereof or a salt methods known in the art using a catalyst comprising an
thereof). Ethylene glycol may be produced by oxidizing element or compound having activity for oxidation of buta
ethylene to ethylene oxide as described above , and hydrating 60 diene to MEK (e.g. catalysts that include Bi/ Mo , Mo /V / W ,
ethylene oxide to form ethylene glycol . Ethylene carbonate VPO or a polyoxometallate ). Alternatively, n - butene may be
may be produced from ethylene by reacting ethylene with oxidatively dehydrogenated to form butadiene (as described
carbon dioxide or carbon monoxide to form ethylene car- above) , and butadiene can be oxidized to form methylvi
bonate, or alternatively by forming ethylene glycol as nylketone (MVK ) according to the methods known in the art
described above and then reacting the ethylene glycol with 65 using a catalyst comprising an element or compound having
phosgene . Ethyl acetate may be formed from acetic acid , activity for oxidation of butadiene to MVK (e.g. catalysts
prepared as described above , according to methods known that include Bi /Mo , Mo /V / W , VPO or a polyoxometallate ).
 US 11,124,466 B2
17 18
In one embodiment, furan is prepared by oxidizing n - butene . result a butane conversion of about 15 % to 20 % and a
Crotonaldehyde can also be prepared by forming butadiene, selectivity of about 60% to 90 % , compared to a butane
as described above and oxidizing butadiene to form croton- conversion of about 5 % and a selectivity of about 90% for
aldehyde. conventional catalysts.
In a preferred embodiment, the butane -containing hydro- 5 In one embodiment, the bimetallic catalyst of the present
carbon stream , the oxidant, the bimetallic catalyst loading, disclosure is stable with respect to a dehydrogenation activ
and reaction conditions are controlled to achieve a reaction ity and performance characteristics . Stability of the bime
performance that is suitable for industrial applications. tallic catalyst can be demonstrated by a lifetime testing ,
Accordingly , in one embodiment, the butane-containing wherein the butane - containing hydrocarbon stream and the
hydrocarbon stream , the oxidant, the bimetallic catalyst 10 oxidant are co - fed to a reaction zone of a reactor containing
loading , and reaction conditions are controlled such that the bimetallic catalyst , while maintaining the reaction zone
butane is dehydrogenated to ethylene and propylene with a (and the bimetallic catalyst) at a temperature that ranges
butane conversion of at least about 5 % by mole , preferably from about 200 ° C. to about 600 ° C. , preferably from about
at least about 10 % by mole , preferably at least about 15 % by 300 ° C. to about 550 ° C. , preferably from about 350 ° C. to
mole , preferably at least about 20 % by mole , preferably at 15 about 520 ° C. , preferably from about 375 ° C. to about 500 °
least about 25 % by mole , but no more than 30 % by mole , C. , preferably from about 390 ° C. to about 475 ° C. , prefer
and a selectivity of at least about 70 % by mole , preferably ably from about 400 ° C. to about 470 ° C. The butane
at least about 75 % by mole , preferably at least about 80% by containing hydrocarbon stream is contacted continuously
mole , preferably at least about 85 % by mole , preferably at with the bimetallic catalyst in the presence of the oxidant to
least about 90 % by mole . In another embodiment, the 20 dehydrogenate butane (and other alkanes present in the
butane -containing hydrocarbon stream , the oxidant, the butane - containing hydrocarbon stream ) and to form ethyl
bimetallic catalyst loading , and reaction conditions are con- ene and propylene as well as other corresponding alkenes .
trolled such that butane is dehydrogenated to ethylene and The ethylene, propylene, other alkenes, unreacted alkanes
propylene with a butane conversion in the range of 5 % to and unreacted oxidants are contentiously exhausted or oth
30 % by mole , preferably 8 % to 25 % by mole , preferably 25 erwise removed from the reaction zone . In a preferred
10 % to 22 % by mole , preferably 11 % to 20% by mole , embodiment, the steps of contacting the butane -containing
preferably 15 % to 20 % by mole , and a selectivity of hydrocarbon stream and the oxidant with the catalyst , dehy
ethylene and propylene compounds in the range of 80% to drogenating the alkanes, and exhausting the alkenes and
95 % by mole, preferably 82 % to 92 % by mole , preferably unreacted reactants are carried out in a continuous cumula
85 % to 90 % by mole . In some embodiments, a selectivity of 30 tive period of not less than about 200 hours , preferably not
ethylene is in the range of 3 % to 60 % by mole , preferably less than about 400 hours , more preferably not less than
5 % to 55 % by mole , preferably 20 % to 55 % by mole , about 600 hours , even more preferably not less than about
preferably 30 % to 45 % by mole . In other embodiments, a 1000 hours, and most preferably not less than about 2000
selectivity of propylene is in the range of 1 % to 30 % by hours . Accordingly, the bimetallic catalyst may preferably
mole , preferably 3 % to 25 % by mole , preferably 5 % to 20 % 35 be stable for at least about 5000 hours, and more preferably
by mole , preferably 7 % to 15 % by mole . at least about 8000 hours .
As used herein , the term “ butane conversion ” refers to the In one embodiment, the bimetallic catalyst is treated with
percentage of the amount (by mole ) of butane provided to a an inert gas before contacting the butane -containing hydro
reaction zone of a reactor via the butane - containing hydro- carbon stream and the oxidant with the catalyst. The inert
carbon stream , which is converted to carbon products. 40 gas is preferably at least one selected from nitrogen , argon ,
As used herein , the term “ selectivity” refers to the per- helium and carbon dioxide . Treating the bimetallic catalyst
centage of the amount (by mole) of butane that is converted is performed to bring a temperature of the catalyst to a
to ethylene and / or propylene . In addition , the selectivity of preferable temperature, in which oxidative dehydrogenation
oxygenation and cracking reactions refers to the amount (by is carried out . In view of that, the inert gas may have a
mole ) of butane that is converted via oxygenation and 45 temperature from about 200 ° C. to about 600 ° C. , preferably
cracking reactions, and the selectivity of partial oxidation from about 300 ° C. to about 550 ° C. , preferably from about
reactions refers to the amount (by mole) of butane that is 350 ° C. to about 520 ° C. , preferably from about 375 ° C. to
converted via partial oxidation reactions. Alternatively, the about 500 ° C. , preferably from about 390 ° C. to about 475 °
" selectivity ” is defined as a molar ratio of the combined C. , preferably from about 400 ° C. to about 470 ° C. In
molar amount of ethylene and propylene to the other com- 50 another embodiment, at least a portion of the product stream
pounds present in the product stream . In one embodiment, is recycled to be contacted with the bimetallic catalyst .
the selectivity is substantially independent of the butane Recycling at least a portion of the product stream may result
conversion .
In view of the above definitions of the butane conversion
inselectivity
an overall improvement in the butane conversion and the
. For example, in one embodiment, recycling at
and the selectivity, a yield of ethylene and propylene based 55 least a portion of the product stream may increase the butane
on the butane conversion may be defined as a multiplication conversion by at least 5 % , preferably at least 10 % , but no
of the butane conversion and the selectivity. Accordingly, in more than 30 % . In a preferred embodiment, unreacted
one embodiment, the yield of the ethylene and propylene is alkanes of the product stream are first separated from
in the range of 2 % to 20% , preferably 3 % to 15 % , preferably ethylene, propylene , and other alkenes, and then the unre
4 % to 12 % , based on the butane conversion , which is in the 60 acted alkanes are recycled to be contacted with the bime
range of 5 % to 30% , preferably 8 % to 25 % , preferably 10 % tallic catalyst.
to 22 % , preferably 11 % to 20 % , preferably 15 % to 20 % . Although the present invention is described and exempli
The bimetallic catalyst of the present invention offers fied primarily in connection with oxidative dehydrogenation
significant performance advantages as compared to cur- of butane, dehydrogenation of other alkanes using the bime
rently used catalysts for oxidative dehydrogenation of 65 tallic catalyst and the method disclosed herein may also be
butane such as VMo, MgO / ZrO2, or VMgO /MgO / ZrO2 contemplated, and is within the scope of the invention . For
catalysts . For example, the catalysts of the invention may example, cyclohexane may be oxidatively dehydrogenated
 US 11,124,466 B2
19 20
over the bimetallic catalyst of the invention to form benzene. least 8 hours, preferably at least 12 hours , preferably at least
Moreover, the bimetallic catalyst of the invention may be 24 hours , during which nickel and bismuth are deposited on
used for dehydrogenating alkenes to one or more dehydro- a surface a support particles . Any suitable porous catalyst
genation products, e.g. dienes or alkynes. Similarly, butenes support known in the art may be used in the preparation of
may be dehydrogenated to form ethylene, butylene, butadi- 5 the catalyst of the invention such as but not limited to porous
ene , and isoamylene may be dehydrogenated to form iso- carbon , silica , metal oxides such as , but not limited zinc
prene . oxide, vanadium oxide , magnesium oxide , magnesium
Another aspect of the invention relates to a method of oxide, and the like , zeolite , and the like . In preferred
producing the bimetallic catalyst . The method involves embodiment, the support is at least one of at least zirconium
dissolving a nickel precursor and a bismuth precursor in 10 oxide , low aluminum MFI zeolite , and mesoporous silica
water, preferably deionized water, to form a Ni - Bi solu- foam . The ability of the zirconium oxide , low aluminum
tion . In a preferred embodiment, the nickel precursor is a zeolite , or mesoporous silica foam to improve the dispersion
metal salt of nickel and a counter ion selected from nitrate, of the active metal oxide system coupled with the availabil
acetate , oxalate , and halide . For example, in one embodi- ity of lattice oxygen species selective for oxygenate and
ment, the nickel precursor is nickel nitrate, preferably nickel 15 cracking products have a major positive impact on the
nitrate hexahydrate. In another preferred embodiment, the oxidative dehydrogenation reaction . The support may be
bismuth precursor is a metal salt of bismuth and a counter calcined or un - calcined when added to the solution com
ion selected from nitrate, acetate , oxalate , and halide . For prising Ni — Bi precursor. In a preferred embodiment , the
example , in one embodiment, the bismuth precursor is support is un - calcined as it produces a catalyst that is more
bismuth nitrate , preferably bismuth nitrate pentahydrate. 20 uniformly dispersed on the surface of the support. In a
The nickel and the bismuth precursors may be in the form preferred embodiment, a weight ratio of bismuth to nickel in
of a sol - gel that include nickel or bismuth along with one or the suspension is in the range of 1 : 1 to 2 : 1 , preferably in the
more counter ions selected from nitrate , acetate , oxalate , a range of 1.2 : 1 to 1.5 : 1 , preferably about 1.4 : 1 . In a preferred
halide , and an alkoxide . Additionally, the nickel and the embodiment, a ratio of the amount of the support particles
bismuth precursors may be dissolved in a solvent such as 25 to a volume of the NiBi solution depends on a pore
water, aqueous organic solvent, or organic solvent (e.g. volume of the support particles, and may range from about
methanol, toluene, tetrahydrofuran, ethylene glycol , etc. ). 50 to about 150 , preferably from about 70 to about 90 times
When a halide is used as a counter ion, a resulting bimetallic the pore volume of the support particles . For example, in one
catalyst is preferably rinsed with water to remove halide. For embodiment, 1.5 to 2.5 g , preferably 2 g of support particles
example, in one embodiment, the nickel precursor is nickel 30 are used for 140 to 180 ml , preferably 150 to 170 ml ,
nitrate along with potassium bromide , wherein a resulting preferably 160 ml of the Ni-Bi solution , wherein the
bimetallic catalyst is preferably rinsed with water to remove support particles have a specific pore volume in the range of
potassium bromide . In one embodiment, the Ni—Bi solution 0.5 to 3 ml /g , preferably about 1.5 ml/ g . In one embodiment,
further includes a third precursor to provide the third ele- a pH of the suspension is maintained at about 2 to about 6.5 ,
ment to the bimetallic catalyst. The third precursor may 35 preferably about 3 to about 6 , preferably about 4 to about 6 .
preferably be a salt of Ti , Nb, Ta, and Zr, for example, The method further involves drying the suspension .
titanium oxalate, niobium oxalate, tantalum oxalate, or Accordingly, the suspension may be dried preferably at a
zirconium oxalate . reduced pressure ( i.e. a sub atmospheric pressure of less than
In one embodiment, a concentration of nickel in the 0.9 atm , preferably less than 0.5 atm ), and at a temperature
Ni - Bi solution is in the range of 5 to 7 g /L , preferably 5.2 40 ranging from about 80 ° C. to about 150 ° C. , preferably from
to 6.8 g / L , preferably 5.5 to 6.7 g/L , preferably 5.8 to 6.5 about 100 ° C. to about 140 ° C. , preferably about 120 ° C. , for
g/L , preferably about 6.2 g / L . In another embodiment, a a period of time ranging from about 1 hour to about 5 hours,
concentration of bismuth in the Ni - Bi solution is in the preferably 2 to 4 hours , preferably about 3 hours .
range of 7 to 9 g / L , preferably 7.5 to 8.9 g/L , preferably 8 Alternatively, the suspension may be dried by other
to 8.8 g/L , preferably 8.5 to 8.7 g/L , preferably about 8.65 45 methods known in the art such as lyophilization, precipita
g/L . To achieve the Ni—Bi solution having the aforemen- tion , and / or evaporation. Lyophilization refers to freezing
tioned concentration of nickel and bismuth , in one embodi- the suspension ( e.g. , under liquid nitrogen ), and then placing
ment, 0.75 to 1.25 g , preferably 0.95 to 1.05 g , preferably a frozen suspension in a vacuum so that water (i.e. ice )
about 1 g of the nickel precursor is dissolved in 140 to 180 sublimes , leaving behind a solid pre -calcination composition
ml , preferably 150 to 170 ml , preferably 160 ml of water, 50 that includes the bimetallic catalyst . Precipitation refers to a
preferably distilled water. Then , 1.3 to 1.5 g , preferably 1.35 method of separating a solute from a solvent via adding one
to 1.45 g , preferably about 1.39 g of the bismuth precursor or more chemical reagents that can selectively precipitate
is mixed with the resulting solution to form the Ni-Bi the solute (i.e. the bimetallic catalyst) from the solvent ( i.e.
solution . Preferably, the Ni — Bi solution may be stirred at an water ). The chemical reagents may provide ions that shift
elevated temperature of 30 to 70 ° C. , preferably 40 to 65° C. , 55 ionic equilibrium to favor formation of insoluble metal salts,
preferably 50 to 60 ° C. , preferably about 55 ° C. to dissolve or may bind with bismuth , nickel , or other elements present
the nickel and the bismuth precursor in water. In the embodi- on the catalyst support to form uncharged and water
ments where a third precursor is present to provide the third insoluble coordination compounds. The chemical reagents
element to the composition of the bimetallic catalyst, a may also oxidize or reduce bismuth , nickel , or other ele
concentration of the third element in the Ni—Bi solution is 60 ments present on the catalyst support to form ionic species
no more than 2 g/L , preferably no more than 1 g / L , prefer- that produce water insoluble salts . Regardless of a precipi
ably no more than 0.5 g/L . tation mechanism used, precipitated compounds (i.e. the
The method further involves mixing and a catalyst sup- bimetallic catalyst ) may be separated from the remaining
port with the Ni-Bi solution to form a suspension. The suspension by first centrifuging the suspension and then
suspension is maintained at a temperature in the range of 20 65 decanting a supernatant. Residual water present in the solid
to 60 ° C. , preferably 24 to 50 ° C. , preferably 26 to 40 ° C. , pre -calcination composition may be removed by evapora
preferably about 25 ° C. , for at least 6 hours , preferably at tion via heating and / or under vacuum . Preferably, the solid
 US 11,124,466 B2
21 22
pre -calcination composition may be achieved in a form of a Taking into account the exothermic nature of oxy-dehy
powder that includes the bimetallic catalyst . drogenation reaction, the catalyst bed temperature was
In some embodiments, the method further involves press- monitored by a thermocouple, which inserted into thermo
ing the powder to form pellets of the bimetallic catalyst with couple well . The products and reactants were analyzed by an
an average pellet particle size in the range of 0.1 to 2 mm , 5 Agilent 7890N gas chromatograph equipped with flame
preferably 0.2-1.5 mm , more preferably 0.4 to 1 mm , even ionization detector ( FID ) and GC - Gas Pro capillary column
more preferably 0.5 to 0.9 mm . The pellets may further be (L : 60 m and ID : 0.032 mm ) analyzing the hydrocarbons and
crushed to form bimetallic catalyst granules, and said gran oxygenates. The thermal conductivity detector (TCD ) , Shin
ules may further be sieved to form finer granules with an Carbon 80/100 mesh SS Column (Helium as a carrier gas )
average particle size in the range of 0.1 to 1 mm , preferably 10 and MSSA 60/80 mesh SS Column ( Argon as a carrier gas )
0.2-0.8 mm . Having the bimetallic catalyst in the form of were also attached with the GC system for detection of gases
pellets or granules may provide a consistent bulk density of including CO , CO2 , 02 , N2 and H2 . The effluents were
the catalyst and /or a consistent pressure drop across a identified by comparing with authentic samples. The con
catalyst bed of a reactor that houses the bimetallic catalyst . version of n - butane and selectivity of products were deter
In a preferred embodiment, the bimetallic catalyst gran- 15 mined on the basis of carbon balance.
ules is calcined via a two - step calcining process , wherein the Example 3
bimetallic catalyst granules is first calcined at a temperature
in the range of 300 to 400 ° C. , preferably 320 to 380 ° C. , The catalytic oxidative conversion of n -butane using
preferably 340 to 360 ° C. , preferably about 350 ° C. , for no
more than 2 hours , preferably no more than 1 hour. Next, the 20 unsupported metal oxides of Ni and Bi ( Ni - Bi – O ) catalyst
was studied at Oz/n - C4H10 ratios of 2.0 and 4.0 mole /mole,
already calcined catalyst is calcined for a second time at a and temperatures of 400 and 500 ° C. The product distribu
temperature in the range of 500 to 900 ° C. , preferably 550 tion is presented in Table 1. The catalytic conversion of
to 700 ° C. , preferably 570 to 620 ° C. , preferably about 590 ° n - butane by Ni- Bi O catalyst was 13.1 % at 500 ° C. The
C. , for no more than 3 hours , preferably no more than 2
hours. Preferably, the two -step calcining process is carried 25 selectivity of ethylene and propylene from the oxidative
out in an inert atmosphere, for example, under a constant cracking were 30 and 11.6 % , respectively. The unsupported
flow of an inert gas (e.g. argon , helium , nitrogen, etc. ) . catalyst showed high selectivity towards dehydrogenation
The examples below are intended to further illustrate ( butenes ) and partial oxidation ( CO ) products. The selectiv
protocols for the method of dehydrogenating the butane ity of butenes and CO decreased with increase in tempera
containing hydrocarbon stream and the method ofproducing 30 ture. The result indicates that a suitable catalyst support is
needed to disperse the active metal oxides for effective
the bimetallic catalyst , and are not intended to limit the performance .
scope of the claims .
Example 1 TABLE 1
35
Catalyst Preparation: n - Butane conversion & product
selectivity over unsupported Ni- Bi – O catalyst
Bi — Ni oxide based catalysts were prepared using co Catalyst
impregnation technique, using Ni(NO3 )2.6H2O ( 99 % , Temperature
Ni - Bi - 0
400 ° C.
Ni - Bi - O
500 ° C.
Fisher -Scientific ) and Bi (NO3 ) 3.5H2O ( 98 % , Fluka-Garan " Oz/nC4H10 4.0 2.0
tie ) as precursors for metals . In a typical preparation of 40 nC4H10 conversion 1.3 13.1
supported 30 wt % Bi - 20 wt % Ni catalyst, to a solution of bSelectivity mole % mole %
0.99 g of nickel nitrate hexahydrate in 160 ml of distilled
water, 1.392 g of bismuth nitrate pentahydrate and 2.0 g of CO 22.3 1.8
solid support were added and the mixture stirred at 55 ° C. CO2 9.5 33.8
about 2 h . The resulting suspension was left overnight for 45 C 0.0 0.0
impregnation. After drying the suspension for 3 h at 120 ° C. , C2
0.0
6.9
0.0
30.0
the resulting powder was pressed into pellets form , crushed C3 0.0 0.0
to break up the crumbs and then sieved into 500-850 mesh C31 7.7 11.6
granules. t- 2 - C45 11.5 3.7
50 1 -C4 31.4 12.3
Example 2 c - 2-C4 10.7 3.1
BD 0.0 3.6

Conversion of Butane to Alkenes Sum 100.0 100.0

The catalytic oxidative conversion of n -butane was car C2 yield 0.09 3.9
ried out in an automated fixed bed fixed bed reactor with 55 C3 yield 0.10 1.5
continuous flow system purchased from Microtrac Bel Com- mole /mole,
pany, Japan . The reactor comprises quartz tubular reactor, @abbreviation: C? methane, C2 ethane, C2 ethylene, C3 propane, C3 propene , t-2 -C4
placed inside stainless steel furnace which passes through trans- 2 -butene, 1 -C4 1 -butene, c - 2 -C4 cis - 2 - butene , and BD butadiene.
the reactor furnace thermo well wall . Typically 300 mg of
the as - synthesized catalyst was placed into the quartz reac- 60 Example 4
tion tube ( length of heating zone = 18 cm , inner diameter = 8
mm ). Prior to the reaction , the catalyst was pretreated at high Active metal oxides of Ni and Bi were supported on a
temperature under flowing nitrogen. After which the catalyst calcined zirconium oxide . The calcination was carried out at
was cooled down to the reaction temperature using nitrogen . a temperature of 550 ° C. for 3 h . Products distribution of
The reactions were carried out at temperature in the range of 65 n - butane conversion over Ni—Bi/ZrO2 catalyst is presented
350-550 ° C. with reactant feed ratio of Oz/ n -butane in the in Table 2. The supported catalyst showed higher conversion
range of 1.0 mole /mole to 6 mole /mole . compared with the unsupported Ni- Bi— catalyst . Ethyl
 US 11,124,466 B2
23 24
ene yield increased from 3.9 C % with unsupported Ni TABLE 3 - continued
Bi- 0 to 6.4 C % with supported catalyst. The Ni—Bi/ZrO2
catalyst showed enhanced dehydrogenation product selec n - Butane conversion & selectivities over Ni - Bi - O /Zirconia
tivity especially butadiene ( 2nd dehydrogenation product) as support at reactions temperature of 400 and 500 ° C.
it increased from 3.6 % with NiBi O catalyst to 29.2 % 5 Selectivity
with Ni-Bi/ZrO2 at reaction temperature of 500 ° C. The
catalyst showed low selectivity towards partial oxidation CO 0.0 0.0
products. Lower olefins yields increased at lower reaction CO2
C
40.9
0.9
38.6
2.3
temperature of 400 ° C. Ethylene yield increased from 6.4 C C2 0.3 0.6
% to 9.5 C % when the reaction temperature was reduced 10 38.8 35.7
from 500 ° C. to 400 ° C. 0.0 0.4
C3 6.3 8.8
t- 2 -C4 1.9 1.7
TABLE 2
1 -C4 6.8 3.5
n - Butane conversion & product C - 2-C4 1.4 1.1
selectivity over calcined Ni - Bi - O /Zirconia 15 BD 2.8 7.3

Ni — Bi – O /Zirconia support catalyst Sum 100.0 100.0

Cz yield 15.7 10.1
Temperature 400 ° C. 500 ° C. C3 yield 2.6 2.5
" Oz/nC4H10 4.0 2.0
nC4H10 conversion 41.4 29.4 20 mole /mole,
bSelectivity babbreviation: C , methane, C2 ethane, C. ethylene, C3 propane, C3 propene , t-2- C4
trans- 2 - butene, 1 -C4 1 -butene, c-2 - C4 cis - 2 -butene, and BD butadiene.
CO 0.2 0.2
CO2 24.4 23.6
0.7 3.2
0.0 0.2 Example 6
25
88
-
????
-
C3
22.9
0.0
21.9
0.2
C31 3.8 5.0 The catalyst used in this example comprises of the active
t- 2 -C4 6.6 5.2 metal oxides of Ni and Bi deposited on low - aluminum
1 -C4
C - 2-C4
19.1
5.8
7.7
3.8
zeolite , Silicalite - I or Ge - MFI silicate. The product distri
BD 16.8 29.2 30 bution is presented in Table 4. The low - aluminum zeolite
showed dispersion ability and increased the active lattice
Sum 100.0 100.0 oxygen species selective towards cracking products (pro
C2 yield 9.5 6.4
pylene and ethylene ). The low - aluminum supported catalyst
C3 yield 1.6 1.5
gave 4.7 C % and 1.9 C % as the yields of ethylene and
mole /mole ,
babbreviation : C? methane, C2 ethane, C2 . ethylene, C3 propane, C3 . propene, t- 2 - C4"
35 propylene, respectively at reaction temperature of 500 ° C.
trans- 2 -butene, 1 - C4" 1 -butene, c -2 -C4 cis - 2 -butene, and BD butadiene. The low -aluminum zeolite supported catalyst showed a
decreased in dehydrogenation product yields . These cata
Example 5 lysts also showed low selectivity toward partial oxidation
products. Light olefins yields of 6.2 C % for ethylene and 2.7
Active metal oxides of Ni and Bi were deposited on an Cof %500for° C.propylene
40
with the
were obtained at a reaction temperature
Ge -MFI silicate supported catalyst.
uncalcined zirconium oxide (zirconium hydroxide ) support.
Products distribution of n - butane conversion over the cata TABLE 4
lyst is presented in Table 3. The un - calcined zirconium oxide
support showed improved the dispersion of the catalyst 45 n -Butane conversion & product selectivities over
leading to increase in the active lattice oxygen species Ni — Bi– O /Zeolite support at reaction temperature 500 ° C.
selective towards cracking products ( propylene and ethyl Low - aluminum Ge -silicate
ene ). Compared with the calcined zirconia supported cata
lyst , the catalyst showed a high increase in the yields of both Zeolite support species MFI zeolite Silicalite - I MFI zeolite
ethylene and propylene from 6.4 C % and 1.5 C % to 10.1 50 nC4H10 conversion 16.1 16.9 37.0
C % and 2.5 C % , respectively at reaction temperature of Selectivity
500 ° C. The un - calcined zirconium oxide supported catalyst CO 9.0 5.8 5.3
showed a decreased in dehydrogenation product yields . 32.9 12.6 19.2
Also , the catalyst showed no selectivity toward partial 0.0

88
stunt
5.3 4.1
oxidation products (CO ) . A substantial increase in the yield 55
0.7
29.0
0.0
10.1
0.0
16.7
of 15.7 % ethylene and 2.6 % propylene was observed at a 0.0 0.7 0.3
low reaction temperature of 400 ° C. with the instant catalyst 11.7 7.6 7.4
compare to that of the catalyst of example 4 . t- 2 -C4 4.4 10.9 8.2
1 -C4 2.9 26.4 19.1
C - 2 -C4 3.3 9.6 5.9
TABLE 3 60 BD 0.8 16.3 13.8
n -Butane conversion & selectivities over Ni — Bi – O /Zirconia Sum 100.0 100.0 100.0
support at reactions temperature of 400 and 500 ° C. Cz yield 4.7 1.7 6.2
Zirconia support species Zro , sol Zro , sol C3 yield 1.9 1.3 2.7
Temperature 400 500
65 " Oz /n -butane = 2.0 mol/mol,
Oz /nC4H10 4.0 2.0
babbreviation: C , methane, C2 ethane, C2 ethylene, C3 propane, C3 propene , t- 2 - C47
nC4H10 conversion 40.5 28.2 trans- 2 - butene, 1- C4" 1 -butene, c- 2 -C4 cis - 2 -butene, and BD butadiene.
 US 11,124,466 B2
25 26
Example 7 TABLE 6 - continued
n - Butane conversion & selectivities over Ni - Bi - O /
Active metal oxides of Ni and Bi were modified with Fe , Silica foam support at reactions temperature 500 ° C.
Co , Mo and / or W. The product distribution is presented in 5 Metal species Ni—Bi Ni - Ga - Bi
Table 5. The Fe/Co , Mo and /or W modified Ni - Bi oxide
catalysts showed improved dispersion ability and increased Selectivity
the active lattice oxygen species selective towards cracking CO 1.6 22.6
products, i.e. , propylene and ethylene. The Ni - Bi - W CO2 32.3 23.9
catalyst showed 3.7 C % and 1.1 C % as the yields of 10 0.2 2.5
ethylene and propylene, respectively at 500 ° C. The modi 0.0
8.6
0.2
15.3
fied metal oxide catalysts showed an increased in dehydro C3 0.3 0.1
genation and partial oxidation product yields . Light olefins C3 1.7 3.0
yields of 10.7 C % for ethylene and 0.4 C % for propylene t- 2 -C4 5.8
6.9
4.2
4.2
were obtained at a reaction temperature of 500 ° C. with the 15 1 -C4
c - 2 - C45 4.1 3.1
Ni- Fe Co Bi catalysts . BD 38.5 20.9

TABLE 5 Sum 100.0 100.0

C2 yield 3.2 6.0
n - Butane conversion & product selectivities over 20
C3 yield 0.6 1.2
modified Ni— Bi – O /alumina at reaction temperature 500 ° C.“
" Oz/ n -butane 2.0 mol/mol,
=

Metal oxide system Ni - Fe - Co - Bi Ni - Bi - Mo Ni — Bi — W babbreviation: C1 methane, C2 ethane , C2 ethylene, C3 propane, C3 . propene, t- 2 - C4

trans- 2 - butene, 1 -C4 1 -butene, c - 2 - C4. cis - 2 -butene, and BD butadiene.
nC4H10 conversion
Selectivity
39.6 28.3 30.1 One objective of the present invention is to provide a
25 catalytic oxidative process for direct conversion of n -butane
CO 0.3 17.2 20.4 to light olefins, mainly ethylene and propylene. The catalyst
CO2 27.6 10.9 13.5 used in the oxidative cracking reaction includes one ore
C
C2
1.5
0.0
2.4
0.0
4.3
0.0
more metal oxides of Ni and Bi supported on zirconium
27.3 10.2 12.2
oxide, low aluminum zeolite and / or mesoporous silica foam
C3 0.0 0.4 0.0 30 to enhance the production of light olefins. Generally, the
C3 1.0 2.0 3.7 method of the invention involves co -feeding a stream of
t- 2 -C4 4.9 6.1 4.1 hydrocarbon containing butanes, air as a source of oxygen
1 -C4 6.4 5.9 3.1 and inert gas into a fixed bed reactor. The oxidative cracking
C - 2 -C4 3.8
27.3
4.8
40.1
3.1
35.7
of feedstock hydrocarbon resulted in production of ethylene
BD
and propylene at lower temperature compared to steam or
Sum 100.0 100.0 100.0 35 catalytic cracking without oxygen . The degraded catalyst
Cz yield 10.7 2.9 3.7 can be regenerated in - situ by an oxidizing atmosphere .
C3 . yield 0.4 0.6 1.1 The invention claimed is :
1. A method of dehydrogenating a butane- containing
" Oz/ n -butane= 2.0 mol/mol,
babbreviation : C , methane, C2 ethane, C2 . ethylene, Cz propane, Cz propene, t- 2 - C41 hydrocarbon stream , comprising :
trans - 2 - butene, 1 -C4 1 -butene, c-2 - C4 cis - 2 -butene, and BD butadiene. 40 contacting a mixture of the butane -containing hydrocar
bon stream and oxygen with a bimetallic catalyst
supported on a solid support of low aluminum MFI
Example 8 zeolite to form a product stream comprising one or
more oxygenated products, ethylene, and propylene ,
The active metal oxides of Ni and Bi were modified with
45 wherein the bimetallic catalyst consists of nickel oxide
Ga and deposited on mesoporous silica foam (MSF ) . Prod and bismuth oxide ,
ucts distribution of n - butane conversion over Ni—Bi/MSF wherein the bimetallic catalyst has an average particle
catalyst is presented in Table 6. The Ga modified catalyst size in a range of 0.1 to 2 mm ,
showed enhanced dispersion ability and increased the active wherein the low aluminum MFI zeolite comprises alumi
lattice oxygen species selective towards cracking products,
50 num and has a silicon to aluminum atomic ratio of at
i.e. , propylene and ethylene. Compared with the unmodified least 250 , and
catalyst, this catalyst showed doubled the yields of both wherein the solid support of low aluminum MFI zeolite is
ethylene and propylene from 3.2 and 0.6 to 6.0 and 1.2 modified with Fe , Co , Ga , Mo and /or W.
2. The method of claim 1 , further comprising separating
respectively at reaction temperature of 500° C. The Ga 55 the ethylene and the propylene from the oxygenated prod
modified catalyst showed a decreased in dehydrogenation ucts .
product yields . Also , Ga -modified catalyst showed high 3. The method of claim 1 , wherein the butane- containing
selectivity toward partial oxidation products ( syngas ). hydrocarbon stream comprises butane, isobutene, raffinate - I,
TABLE 6
raffinate -II, rafinate - III, rafinate - IV , or a combination
60 thereof.
n - Butane conversion & selectivities over Ni Bi – Ol 4. The method of claim 1 , wherein the butane is n -butane.
Silica foam support at reactions temperature 500 ° C.“ 5. The method of claim 3 , wherein the nickel oxide and
Metal species Ni — Bi Ni - Ga - Bi
bismuth oxide is prepared by impregnating un - calcined solid
support.
Temp -Oz/nC4H10 500-2 500-2 65 6. The method of claim 1 , wherein a weight percent of
nC4H10 conversion 40.5 28.2 nickel in the bimetallic catalyst is within a range of 15 wt %
to 25 wt % , and
 US 11,124,466 B2
27 28
wherein a weight percent of bismuth in the bimetallic wherein the butane -containing hydrocarbon stream is
catalyst is within a range of 25 wt % to 35 wt % , each contacted with the bimetallic catalyst at a temperature
relative to the total weight of the bimetallic catalyst . of 450 to 550 ° C. ,
7. The method of claim 1 , wherein the bimetallic catalyst wherein the bimetallic catalyst consists of nickel oxide
supported on the solid support is subjected to calcination at 5 and bismuth oxide,
250-400 ° C. for at least 0.5 hours and at 560-640 ° C. for at wherein the bimetallic catalyst has an average particle
least 1 hour prior to the contacting. size in a range of 0.1 to 2 mm ,
8. The method of claim 1 , wherein the butane -containing wherein the low aluminum MFI zeolite comprises alumi
hydrocarbon stream is contacted with the bimetallic catalyst num and has a silicon to aluminum atomic ratio of at
supported on the solid support at a temperature of 400 to 10 least 250 , and
600 ° C. , and wherein the solid support of low aluminum MFI zeolite is
wherein a molar ratio of oxygen to butane in the mixture modified with Fe , Co , Ga , Mo and / or W.
is in a range of 1 : 1 to 6 : 1 . 14. The method of claim 1 , wherein the solid support
9. The method of claim 1 , further comprising:
treating the bimetallic catalyst supported on the solid is comprises strontium , and
wherein the solid support has a strontium to aluminum
support with an inert gas having a temperature in a
range of 300 to 600 ° C. prior to the contacting. atomic ratio in a range of 2-8 .
10. The method of claim 1 , wherein the butane -containing 15. The method of claim 1 , wherein the solid support is
hydrocarbon stream is at a pressure in a range of 1-10 bars modified with Ga .
during the contacting. 20 16. The method of claim 1 , wherein the solid support is
11. The method of claim 1 , wherein the product stream modified with W.
comprises the ethylene and propylene in a molar ratio of 17. The method of claim 1 , wherein the solid support is
(moles of ethylene and moles of propylene ) :(all other com- modified with Fe and Co.
pounds in the product stream ) at least 0.6 . 18. The method of claim 17 , wherein the solid support
12. The method of claim 1 , wherein a conversion of 25 further comprises strontium , and
butane to ethylene and propylene is in a range of 5 to 30 mol wherein the solid support has a strontium to aluminum
% , and atomic ratio in a range of 2-8 .
wherein a combined yield of ethylene and propene is in a 19. The method of claim 18 , wherein the low aluminum
range of 3 to 25 mol % based on the conversion of MFI zeolite has a silicon to aluminum atomic ratio of 250 to
butane. 30
300 ,
13. A method of dehydrogenating a butane - containing wherein a weight percent of nickel in the bimetallic
hydrocarbon stream , comprising: catalyst is within a range of 19 wt % to 21 wt % , and
contacting a mixture of the butane -containing hydrocar wherein a weight percent of bismuth in the bimetallic
bon stream and oxygen at a pressure in a range of 1-10 catalyst is within a range of 29 wt % to 31 wt % , each
bars with a bimetallic catalyst supported on a solid 35 relative to the total weight of the bimetallic catalyst .
support of low aluminum MFI zeolite to form a product
stream comprising ethylene and propylene,