Us 20100256432

US 20100256432A1
( 12) Patent Application Publication ( 10) Pub. N o. : US 2010/0256432 A1

( 19 ) United States
Arnold et al. ( 43) Pub. D ate: Oct. 7 , 2010
( 54) PROCESS FOR PROD UCIN G ETHYLEN E VIA Publication Clas s i? cation
OXID ATIVE D EHYD ROGEN ATION ( OD H) OF
ETHAN E ( 51) Int. Cl.
C07 C 5/333 ( 2006. 01)
( 7 5) Inv entors : Stephen Craig Arnold, Mountain ( 52) US. Cl. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585/655
Lak es , N ] ( U S) ; Anne Mae
Gaf f ney , W es t Ches ter, PA ( U S) ; ( 57 ) ABSTRACT
Ruozhi s ong: W llm lngtons A proces s f or the ox idativ e dehy drogenation of ethane is
( Us ) ; Chuen Yuan Yeh Edls on, N J dis clos ed. The proces s m ay include: contacting an ethane
( Us ) f eed and an ox y gen- containing gas in the pres ence of an
ox idativ e dehy drogenation cataly s t in an ox idativ e dehy dro
COITeSPPHdeHCe Addres s ? genation reaction Z one under conditions to ox idativ ely dehy
Os ha Llang LLP / Lum m us _ _ drogenate at leas t a portion of the ethane to produce a product
TW O Hous ton Center, 9 09 Fallllllls s ulte 3500 s tream com pris ing ethy lene, carbon ox ides , W ater, and unre
Holls toll, TX 7 7 01 0 ( Us ) acted ox y gen and ethane, W herein an ox y gen concentration in
the product s tream is at leas t 0. 1 m ol %; contacting the prod
( 7 3) ASSigneeI LUMMUS N OVOLEN T uct s tream W ith an ox y gen elim ination cataly s t in an ox y gen
GMBH/LUMMUS elim ination reaction Z one to com bus t at leas t a portion of the
TECHN OLOGY IN C, ox y gen; recov ering f rom the ox y gen elim ination reaction
BlOom ? eld, N J ( US) Z one an ef f luent hav ing a reduced ox y gen content; s eparating
W ater f rom the ef f luent; s eparating carbon ox ides and any
( 21) Appl. N o. : 12/417 , 523 non- condens able gas ( es ) f rom the ethy lene and the unreacted
ethane; and s eparating the ethy lene f rom the unreacted
( 22) Filed: Apr. 2, 2009 ethane.
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US 2010/0256432 A1
PROCESS FOR PROD UCIN G ETHYLEN E VIA
OXID ATIVE D EHYD ROGEN ATION ( OD H) OF
ETHAN E
BACKGROUN D OF D ISCLOSURE
[ 0001] 1. Field of the D is clos ure
[ 0002] Em bodim ents dis clos ed herein relate generally to a
proces s f or the ox idativ e dehy drogenation of hy drocarbons to
f orm ole? ns . More s peci? cally , em bodim ents dis clos ed
herein relate to a proces s f or the ox idativ e dehy drogenation of
ethane to f orm ethy lene. Such proces s es m ay be perf orm ed in
the pres ence of a m ix ed m etal ox ide cataly s t, alloW ing f or
ex ceptionally high s electiv ity to the ole? n at all hy drocarbon
conv ers ion lev els ( f rom <20% to > 9 0%) .
[ 0003] 2. Back ground
[ 0004] Ethy lene is an im portant petrochem ical us ed as a
raW m aterial f or the m anuf acture of poly m ers , ethy lbenZ ene,
s ty rene, and poly s ty rene, am ong other chem ical products .
Ov er 9 0% of currently produced ethy lene is deriv ed f rom
s team crack ing of naphtha and/or ethane and/or propane.
Ethy lene m ay be obtained f rom the non- cataly tic therm al
crack ing of s aturated hy drocarbons , s uch as ethane and pro
pane, and alternativ ely f rom therm al or s team crack ing of
heav ier liq uids s uch as naphtha and gas oil. Steam crack ing
produces a v ariety of other products , including diole? ns and
acety lene. The latter are cos tly to s eparate f rom the ethy lene,
us ually by ex tractiv e dis tillation and/or s electiv e hy drogena
tion to the corres ponding m ono- ole? n, e. g. acety lene to eth
y lene. An ethy lene plant us ing therm al crack ing ty pically
achiev es an ethy lene s electiv ity up to 80- 85 percent calcu
lated on a carbon atom bas is at an ethane conv ers ion of 55- 65
percent. In addition, therm al crack ing proces s es f or ole? n
production are highly endotherm ic. Accordingly , thes e pro
ces s es req uire a large cons um ption of f uel and the cons truc
tion and m aintenance of large, capital- intens iv e and com plex
crack ing f urnaces to s upply the heat.
[ 0005] Ex is ting s team crack ing proces s es generate ethy l
ene by rais ing the f eed ( ethane or other hy drocarbons ) to high
enough tem perature ( 7 00- 1000o C. ) in f urnace tubes to ther
m ally crack the hy drocarbons into ole? ns , es pecially ethy l
ene and s econdarily propy lene, plus a range of other hy dro
carbons , hy drogen and cok e. The res idence tim e m us t be v ery
s hort, at a lev el m eas ured in m illis econds , and the e? Iuent
m us t be q uenched im m ediately , in order to m ax im iZ e the
des ired ole? ns and m inim iZ e the undes ired by - products . The
pres s ure m us t be k ept to a m inim um , s ubs tantial s team dilu
tion is req uired, and des ign f eatures are critical f or obtaining
the bes t perf orm ance. As a res ult, the reaction conditions are
v ery s ens itiv e, and the f um aces are v ery ex pens iv e, W ith high
f uel req uirem ent due to both the high tem perature and the
high endotherm icity of the crack ing reactions . Freq uent
decok ing is als o a m aj or req uirem ent. Furtherm ore, f urnace
tubes m us t be replaced periodically .
[ 0006] Autotherm al crack ing ( ATC ) is a s im ilar proces s ,
but W ith a com bus tion reaction added to s upply the heat, as an
alternativ e to us ing ex pens iv e heat trans f er in f urnaces . The
com bus tion reaction m ay include us e of a cataly s t, f or W hich
the high tem perature and other conditions are a s ev ere env i
ronm ent. There are s till v ery s ens itiv e crack ing reactions and
q uenching, W ith a range of products , and the added com bus
tion reactions create additional by products W hile cons um ing
either a portion of the f eed and product and/or a com bus tible
that is added.
Oct. 7 , 2010
[ 0007 ] An alternativ e is to cataly tically dehy drogenate
ethane in the pres ence of ox y gen to f orm ethy lene. The pro
ces s is called ox idativ e dehy drogenation ( OD H) . In this pro
ces s , the product is largely lim ited to ethy lene W ith s m all
am ounts of carbon m onox ide and carbon diox ide as by prod
ucts . The ef ? uent als o contains W ater ( produced in the reac
tion plus W hatev er enters W ith the f eed) , res idual ethane,
s om e res idual ox y gen, and nitrogen if introduced W ith the
ox y gen ( e. g. , as air) . The ox idativ e dehy drogenation ( OD H)
of ethane is therm ody nam ically f av ored and can be carried
out at loW er reaction tem peratures W ithout cok e f orm ation.
[ 0008] In US. Pat. N o. 4, 250, 346, ethane is cataly tically
ox y dehy drogenated to ethy lene in a gas phas e reaction, in the
pres ence or abs ence of W ater, at tem peratures of les s than
5500 C. The cataly s ts dis clos ed include ox ides of m oly bde
num : MoaXbYc, W here XICr, Mn, N b, Ta, Ti, V and/or W ,
YIBi, Ce, Co, Cu, Fe, K, Mg, N i, P, Pb, Sb, Si, Sn, Tl and/or
U.
[ 0009 ] US. Pat. N o. 4, 524, 236 dis clos es cataly s ts us ef ul
f or the production of ethy lene f rom ethane v ia ox idativ e
dehy drogenation, including ox ides of m oly bdenum : MoaVb
N bcSbdXc, W here XILi, Sc, N a, Be, Mg, Ca, Sr, Ba, Ti, Z r,
Hf , Y, Ta, Cr, Fe, Co, N i, Ce, La, Z n, Cd, Hg, Al, Tl, Pb, As , Bi,
Te, U, and W . The reaction can be carried out in the pres ence
or abs ence of W ater; hoW ev er, s igni? cant am ounts of acetic
acid are f orm ed in the pres ence of W ater, W hich res ults in
reduced ethy lene s electiv ity .
[ 0010] US. Pat. N o. 6, 858, 7 68 dis clos es cataly s ts us ef ul
f or the production of ole? ns f rom alk anes v ia ox idativ e dehy
drogenation, including an ox ide s elected f rom the group con
taining alum ina, Z irconia, titania, y tria, s ilica, niobia, and
v anadia. As dis clos ed, the cataly s ts need s ubs tantially
elev ated tem peratures f or activ ation.
[ 0011] US. Pat. N o. 7 , 319 , 17 9 dis clos es m ix ed m etal
ox ide cataly s ts com pris ing m oly bdenum , v anadium , tellu
rium , and niobium us ef ul as a cataly s t f or OD H of ethane to
ethy lene.
[ 0012] JP 07 - 053414 dis clos es us e of m ix ed m etal ox ide
cataly s ts containing trans ition m etal elem ents W ith m oly bde
num , v anadium , niobium , and tellurium f or the OD H of
ethane to ethy lene. The bes t s electiv ity reported therein is
9 1. 5 C % ethy lene at 56. 7 % conv ers ion at a reaction tem pera
ture of 3600 C.
[ 0013] Other patents dis cus s ing OD H of ethane to ethy lene
include US. Pat. N os . 6, 858, 7 68, 7 , 135, 603, 4, 9 40, 826,
6, 433, 234, and 6, 566, 57 3. Various other ref erences dis cus s
ing OD H include: P. Botella, E. Garcia- GonZ aleZ , A. D ej OZ , J.
M. LopeZ - N ieto, M. I. VaZ q ueZ , and J. GonZ aleZ - Calbet,
Selectiv e ox idativ e dehy drogenation of ethane on
MoVTeN bO m ix ed m etal ox ide cataly s ts , Journal of Calaly
s is 225: 428- 438, 2004; Q. Xie, L. Chen, W . W eng, and H.
W an Preparation of MoVTe( Sb) N b m ix ed ox ide cataly s ts
us ing a s lurry m ethod f or s electiv e ox idativ e dehy drogena
tion of ethane, Journal of Molecular Cataly s is A. 240: 19 1
19 6, 2005; and GraboW s k i, R. Kinetics of ox idativ e dehy
drogenation of C2- C3 alk anes on ox ide cataly s ts , Calal. Rev .
Sci and Eng g. 48: 19 9 - 268, 2006.
[ 0014] D ue to the potential adv antages ov er the prior art,
OD H of ethane to ethy lene has been the obj ect of cons ider
able res earch. Ov er the y ears , m any cataly s t s y s tem s hav e
been inv es tigated, including carbon m olecular s iev es , m etal
phos phates , and m ix ed m etal ox ides . HoW ev er, com m ercial
iZ ation has not been pos s ible due to loW product s electiv ity at
reas onably high ethane conv ers ions . In m any of the prior art
US 2010/0256432 A1
proces s es us ing OD H to f orm ethy lene, the ox y gen has gen
erated ex ces s iv e by products ( prim arily COx ) , W ith s electiv ity
to the des ired ethy lene product reaching no higher than 80- 85
C % at ethane conv ers ion of 55- 65%. At this lev el of s elec
tiv ity and conv ers ion, no adv antage ov er s team crack ing is
realiZ ed, es pecially as the prim ary by - products ( COX) do not
prov ide added v alue, in contras t to s igni? cant v alue f or the
hy drocarbon by products f rom s team crack ing.
[ 0015] Accordingly , there rem ains a need in the art f or
OD H proces s es hav ing high s electiv ity at reas onably high
hy drocarbon conv ers ions .
SUMMARY OF THE D ISCLOSURE
[ 0016] In one as pect, em bodim ents dis clos ed herein relate
to a proces s f or the ox idativ e dehy drogenation of ethane to
ethy lene, including: contacting an ethane f eed and an ox y gen
containing gas in the pres ence of an ox idativ e dehy drogena
tion cataly s t in an ox idativ e dehy drogenation reaction Z one
under conditions to ox idativ ely dehy drogenate at leas t a por
tion of the ethane to produce a product s tream com pris ing
ethy lene, carbon ox ides , W ater, and unreacted ox y gen and
ethane, W herein an ox y gen concentration in the product
s tream is at leas t 0. 1 m ol %; contacting the product s tream
W ith an ox y gen elim ination cataly s t in an ox y gen elim ination
reaction Z one to com bus t at leas t a portion of the ox y gen;
recov ering f rom the ox y gen elim ination reaction Z one an
e? luent hav ing a reduced ox y gen content; s eparating W ater
f rom the e? Iuent; s eparating carbon ox ides and any non
condens able gas ( es ) f rom the ethy lene and the unreacted
ethane; and s eparating the ethy lene f rom the unreacted
ethane.
[ 0017 ] In another as pect, em bodim ents dis clos ed herein
relate to a proces s f or the ox idativ e dehy drogenation of
ethane to ethy lene, including: contacting ethane and an ox y
gen- containing gas in the pres ence of a m ulti m etal- ox ide
cataly s t in an ox idativ e dehy drogenation reactor under con
ditions to ox idativ ely dehy drogenate at leas t a portion of the
ethane to produce a product s tream com pris ing ethy lene,
carbon ox ides , W ater, and unreacted ethane; s eparating W ater
f rom the product s tream to recov er a W ater f raction and a
f raction com pris ing carbon ox ides , ethy lene and unreacted
ethane; s eparating the f raction com pris ing carbon ox ides ,
ethy lene and unreacted ethane to recov er carbon ox ides and
any non- condens able gas ( es ) and a hy drocarbon f raction
com pris ing ethy lene and unreacted ethane; and s eparating the
hy drocarbon f raction com pris ing ethy lene and unreacted
ethane to f orm an ethy lene f raction and an ethane f raction;
W herein the m ulti- m etal- ox ide cataly s t com pris es at leas t one
cataly s t s elected f rom the group cons is ting of :
[ 0018] a) MOaVbN bcTeeOn
[ 0019 ] W herein f or cataly s t a) , a: 1 . 0; b: 0. 05 to 1. 0, c: 0.
001 to 1. 0, e: 0. 001 to 0. 5, and n is determ ined by the
ox idation s tates of the other elem ents ;
[ 0020] b) MOaVbXcYdZ eOn;
[ 0021] W herein f or cataly s t b) , XIat leas t one of N b and
Ta; YIat leas t one of Sb and N i; Z Iat leas t one of the Te,
Ga, Pd, W , Bi and Al; a: 1. 0; b: 0. 05 to 1. 0; c: 0. 001 to
1. 0; d: 0. 001 to 1. 0; e: 0. 001 to 0. 5; and n is determ ined
by the ox idation s tates of the other elem ents ; and
[ 0022] c) MOaVbXcYdZ eM/On,
[ 0023] W herein f or cataly s t c) , XIat leas t one of N b and
Ta; YIat leas t one of Sb and N i; Z Iat leas t of one of Te,
Ga, Pd, W , Bi and Al; M: at leas t one of Fe, Co, Cu, Cr,
Ti, Ce, Z r, Mn, Pb, Mg, Sn, Pt, Si, La, K, Ag and In;
Oct. 7 , 2010
a: 1. 0; b: 0. 05 to 1. 0; c: 0. 001 to 1. 0; d: 0. 001 to 1. 0;
e: 0. 001 to 0. 5; and f : 0. 001 to 0. 3; and n is determ ined
by the ox idation s tates of the other elem ents .
[ 0024] Other as pects and adv antages W ill be apparent f rom
the f olloW ing des cription and the appended claim s .
BRIEF D ESCRIPTION OF D RAW IN GS
[ 0025] FIG. 1 is a s im pli? ed proces s How diagram f or ox i
dativ e dehy drogenation proces s es according to em bodim ents
dis clos ed herein.
dis clos ed herein.
[ 0027 ] FIG. 3 is a s im pli? ed proces s How diagram f or ox i
dis clos ed herein.
dis clos ed herein.
[ 0029 ] FIG. 5 is an X- ray dif f ractogram of a prior art cata
ly s t.
[ 0030] FIG. 6 is an X- ray dif f ractogram of a cataly s t
according to em bodim ents dis clos ed herein.
[ 0031] FIG. 7 is an X- ray dif f ractogram of a cataly s t
according to em bodim ents dis clos ed herein.
D ETAILED D ESCRIPTION
[ 0032] In one as pect, em bodim ents herein relate to a pro
ces s f or the ox idativ e dehy drogenation of hy drocarbons to
f orm ole? ns . More s peci? cally , em bodim ents dis clos ed
herein relate to a proces s f or the ox idativ e dehy drogenation of
ethane to f orm ethy lene. Such proces s es m ay be perf orm ed in
the pres ence of a m ix ed m etal ox ide cataly s t, alloW ing f or
ex ceptionally high s electiv ity to the ole? n at all hy drocarbon
conv ers ion lev els ( e. g. , f rom <20% to > 9 0%) . In s om e
em bodim ents , es s entially no hy drocarbon by products and
m inim al am ounts of carbon ox ides are produced.
[ 0033] Ox idativ e dehy drogenation ( OD H) proces s es
according to em bodim ents dis clos ed herein m ay be per
f orm ed by contacting a hy drocarbon and an ox y gen contain
ing gas in the pres ence of a m ulti- m etal ox ide cataly s t under
conditions to ox idativ ely dehy drogenate at leas t a portion of
the hy drocarbon to produce an ole? n product. The m ulti
m etal- ox ide cataly s ts dis clos ed hereinbeloW and in US.
patent application Ser. N o. 12/417 , 488, titled Proces s f or
Mak ing Cataly s ts Us ef ul f or the Conv ers ion of Paraf ? ns to
Ole? ns , and Ser. N o. 12/417 , 507 , titled Cataly s ts f or the
Conv ers ion of Paraf ? ns to Ole? ns and Us e Thereof , each
? led of ev en date hereW ith, and incorporated herein by ref er
ence, is prepared in a m anner s uch that the res ulting cataly s t
has an ex ceptionally high s electiv ity toW ard ole? n produc
tion, at all hy drocarbon conv ers ion lev els . The cataly s ts
des cribed herein, together W ith the reactor conditions
re? ected herein, res ult in high enough ethy lene s electiv ity
and ethane conv ers ion to prov ide an econom ical proces s f or
OD H of ethane to ethy lene.
[ 0034] OD H proces s es dis clos ed herein, W hen us ed W ith
cataly s ts prepared according to em bodim ents dis clos ed
herein f or OD H of a ethane to ethy lene, m ay hav e an ethy lene
s electiv ity of at leas t 85 m ole % at an ethane conv ers ion of at
leas t 60%. In s om e em bodim ents , proces s es dis clos ed herein
m ay hav e an ethy lene s electiv ity of at leas t 88 m ole % at an
ethane conv ers ion of at leas t 60%; an ethy lene s electiv ity of at
US 2010/0256432 A1
leas t 9 0 m ole % at an ethane conv ers ion of at leas t 60% in
other em bodim ents ; in other em bodim ents , cataly s ts dis
clos ed herein m ay hav e an ethy lene s electiv ity of at leas t 9 0
m ole % at an ethane conv ers ion of at leas t 65%; an ethy lene
s electiv ity of at leas t 9 0 m ole % at an ethane conv ers ion of at
leas t 7 0% in other em bodim ents ; and an ethy lene s electiv ity
of at leas t 9 0 m ole % at an ethane conv ers ion of at leas t 7 5%
in y et other em bodim ents .
[ 0035] For ex am ple, W hen us ed f or the ox idativ e dehy dro
genation of ethane to ethy lene, proces s es dis clos ed herein
m ay hav e an ethy lene s electiv ity of at leas t 9 7 . 5 W t. % carbon
( C % ) at an ethane conv ers ion beloW 20%. In s om e em bodi
m ents , proces s es dis clos ed herein m ay hav e an ethy lene
s electiv ity of at leas t 9 7 C % at an ethane conv ers ion of about
20- 30%; an ethy lene s electiv ity of at leas t 9 6 C % at an ethane
conv ers ion of about 30- 40% in other em bodim ents ; in other
em bodim ents , cataly s ts dis clos ed herein m ay hav e an ethy l
ene s electiv ity of at leas t 9 5 C % at an ethane conv ers ion of
about 40- 50%;
[ 0036] an ethy lene s electiv ity of at leas t 9 3. 5 C % at an
ethane conv ers ion of about 50- 60%. in other em bodim ents ; at
leas t 9 1 C % at an ethane conv ers ion of about 60- 7 0%, at leas t
88 C % at an ethane conv ers ion of about 7 0- 80%, and an
ethy lene s electiv ity of at leas t 84 C % at an ethane conv ers ion
of about 80- 9 0% in y et other em bodim ents . The cataly s ts and
the OD H proces s es of em bodim ents dis clos ed herein are
des cribed in m ore detail beloW .
[ 0037 ] Cataly s t
[ 0038] Cataly s ts us ef ul in OD H proces s es dis clos ed herein
m ay include at leas t one of :
[ 0039 ] a) MoaVbN bcTeeOn;
[ 0040] b) MoaVbXcYdZ eOn; and
[ 0041] c) MOaVbXCYdZ eM/On.
[ 0042] For cataly s t a) , a: 1. 0; b: 0. 05 to 1. 0, c: 0. 001 to 1. 0,
e: 0. 001 to 0. 5, and n is determ ined by the ox idation s tates of
the other elem ents . For cataly s t b) , XIat leas t one of N b and
Ta; YIat leas t one of Sb and N i; Z Iat leas t one of the Te, Ga,
Pd, W , Bi andAl; a: 1. 0 ( norm alized) ; b: 0. 05 to 1. 0; c: 0. 001
to 1. 0; d: 0. 001 to 1. 0; e: 0. 5; and n is determ ined by the
ox idation s tates of the other elem ents . For cataly s t c) , XIat
leas t one of N b and Ta; YIat leas t one of Sb and N i; Z Iat leas t
of one of the Te, Ga, Pd, W , Bi and Al; MIat leas t one of Fe,
Co, Cu, Cr, Ti, Ce, Z r, Mn, Pb, Mg, Sn, Pt, Si, La, K, Ag and
In; a: 1. 0 ( norm alized) ; b: 0. 05 to 1. 0; c: 0. 001 to 1. 0; d: 0.
001 to 1. 0; e: 0. 001 to 0. 5; and f : 0. 001 to 0. 3; and n is
determ ined by the ox idation s tates of the other elem ents .
[ 0043] It has s urpris ingly been f ound by the pres ent inv en
tors that the abov e cataly s ts m ay prov ide f or the des ired
im prov em ents in s electiv ity and conv ers ion W hen prepared in
accordance W ith preparation m ethods dis clos ed herein. Other
cataly s ts com pos itions , s uch as thos e dis clos ed in JP
07 - 053414, US. Pat. N o. 4, 524, 236, and US. Pat. N o. 7 , 319 ,
17 9 , m ay als o be us ed, s o long as the cataly s t com pos itions
are prepared in accordance W ith procedures dis clos ed herein.
Each of thes e is incorporated herein to the ex tent not contra
dictory W ith cataly s t preparation m ethods dis clos ed herein.
[ 0044] The abov e des cribed cataly s ts m ay be prepared by a
proces s including at leas t the f olloW ing s teps . In a ? rs t s tep,
com pounds of the dif f erent m etals , or pure elem ents , or of a
m ix ture of both m ay be adm ix ed. The adm ix ing m ay be
perf orm ed s tarting f rom the com pounds of the dif f erent ele
m ents , s tarting f rom the actual pure elem ents in s olution, or
by hy drotherm al m ethods .
Oct. 7 , 2010
[ 0045] The elem ents Mo, V, N b, Sb, and Te can be incor
porated into the adm ix ing s tep as pure m etallic elem ents , as
s alts , as ox ides , as hy drox ides , as alk ox ides , as acids , or as
m ix tures of tW o or m ore of the abov e- m entioned f orm s . As
s alts , s ulf ates , nitrates , ox alates , halides , or ox y halides m ay
be us ed. For ex am ple, the Mo can be incorporated at the
m ix ing s tage as m oly bdic acid, am m onium heptam oly bdate,
m oly bdenum chlorides , m oly bdenum acetate, m oly bdenum
ethox ide and/or m oly bdenum ox ides . The V can be incorpo
rated at the adm ix ing s tep, f or ex am ple, as am m onium v ana
date, v anadium ox ide, v anady l s ulf ate, v anady l ox alate, v ana
dium chloride or v anady l trichloride. The N b can be
incorporated at the adm ix ing s tep, f or ex am ple, as niobium
pentox ide, niobium ox alate, niobium chloride or N b m etal.
The Sb can be incorporated at the adm ix ing s tep, f or ex am ple,
as antim ony ox alate, antim ony ox ide, antim ony chloride and
antim ony acetate. The Te can be incorporated at the adm ix ing
s tep, f or ex am ple, as telluric acid, tellurium diox ide, tellu
rium ethox ide, tellurium chloride and m etallic tellurium .
[ 0046] The elem ents Ta, N i, Pd, W , Ga, Al, Cu, Bi, Sn, Fe,
Co, rare earth, alk aline m etals or alk aline earth m etals m ay
als o be incorporated at the adm ix ing s tep as s alts , ox ides ,
hy drox ides or alk ox ides , pure or as m ix tures of tW o or m ore
elem ents . In s om e em bodim ents , they m ay be incorporated as
s ulf ates , nitrates , ox alates or halides .
[ 0047 ] The abov e elem ents and com pounds m ay be com
bined to f orm one or m ore s olutions or s lurries , W hich m ay be
s ubs eq uently adm ix ed.
[ 0048] N itric acid is us ed to adj us t the pH of the res ulting
adm ix ture or an initial adm ix ture to be com bined W ith addi
tional s olutions or s lurries to f orm the des ired cataly s t com
pos ition. For ex am ple, in s om e em bodim ents , a s olution
including all des ired com pounds m ay be f orm ed and the pH
adj us ted us ing nitric acid. As another ex am ple, in s om e
em bodim ents , a ? rs t s olution m ay be f orm ed including a
s ubs et of the des ired com pounds , and a s econd s olution m ay
be f orm ed including a s ubs et of the rem aining com pounds ;
the ? rs t or s econd s olution m ay then be m ix ed W ith nitric acid
and the ? rs t and s econd s olutions then adm ix ed to res ult in the
des ired cataly s t com pos ition.
[ 0049 ] The adm ix ing s tep m ay be f olloW ed by a period of
s tatic perm anence in the reactor, or the m ix ing m ay be carried
out W ith s tirring. Both the s tatic perm anence and the s tirring
m ay be done in a norm al reactor or in an autoclav e. The
adm ix ing s tep m ay be carried out in s olution, s uch as in
deioniZ ed W ater, or by m eans of hy drotherm al treatm ent.
[ 0050] The res ulting adm ix ture m ay then be dried. D ry ing
m ay be carried out by conv entional m ethods in a k iln, ev apo
ration W ith s tirring, and ev aporation in a rotav apor, by s pray
dry ing, or by v acuum dry ing, am ong other m ethods .
[ 0051] The dried s olids m ay then be calcined. Calcination
of the dry s olid can be carried out in an inert gas atm os phere,
s uch as f or ex am ple nitrogen, helium , argon or m ix tures , of
air or m ix tures .
[ 0052] An alternativ e em bodim ent of the m ethod is , as
s tated earlier, carried out by em ploy ing hy drotherm al m eth
ods ( containing tW o or m ore elem ents in the s y nthes is , es pe
cially containing Mo, V, Te, Sb, and N b) . The s y nthes is tem
perature and tim e m ay be determ ining conditions us ed during
hy drotherm al m ethods . The s y nthes is tem perature m ay be
W ithin the range f rom about 100 C. to about 250 C. in s om e
em bodim ents , and f rom about 150 C. to about 200 C. in
other em bodim ents . The s y nthes is tim e m ay be W ithin the
US 2010/0256432 A1
range f rom about 6 to about 500 hours in s om e em bodim ents ,
and f rom about 24 to about 200 hours in other em bodim ents .
[ 0053] Calcination m ay be carried out by caus ing a How of
inert gas to pas s ( W ith s patial v elocities betW een 1 and 400
h_ l) or s tatically . Calcination tem peratures m ay range f rom
about 250 C. to about 1000 C. in s om e em bodim ents , and
f rom about 400 C. to about 800 C. in other em bodim ents .
The calcination tim e is not a determ ining f actor, though cal
cination tim es m ay range f rom about 0. 5 hours to about 20
hours . The s peed of heating is not a determ ining f actor,
though betw een 01 C. /m inute to about 10 C. /m inute is
ty pical. The cataly s t m ay als o be initially calcined in an
ox idizing atm os phere at a tem perature up to about 350 C. in
s om e em bodim ents , and W ithin the range f rom about 250 C.
to about 300 C. in other em bodim ents , and later be s ubj ected
to calcination in an inert atm os phere.
[ 0054] Various elem ents , s uch as Ta, N i, Pd, W , Ga, Al, Cu,
Bi, Sn, Fe, Co, rare earth, alk aline m etals or alk aline earth
m etals m ay als o be incorporated af ter the calcination s tage by
im pregnation or precipitation. In this cas e, the res ulting s olid
W ill be s ubj ected to a s econd calcination s tage.
[ 0055] The res ulting s olid f orm ed by the abov e des cribed
m ethods m ay then be s iZ ed and f orm ed into a des ired cataly s t
particle. SiZ ing m ay include grinding of the s olids to f orm a
poW der. The res ulting poW der m ay then be pres s ed and s iZ ed
to f orm , f or ex am ple, granules . In s om e em bodim ents , the
granules are f orm ed to be W ithin the 12- 20 m es h s iZ e range.
[ 0056] Grinding is an im portant s tep in em bodim ents dis
clos ed herein, not only f or f orm ing the des ired cataly s t par
ticle, but als o f or the im prov em ent of cataly s t perf orm ance,
including activ ity and ethy lene s electiv ity . There is no par
ticular res triction as to the grinding m ethod. It can be conv en
tional m ethods , f or ex am ple, dry ing m illing, W et m illing,
cry ogenic m illing and j et m illing. Pref erred BET s urf ace area
af ter grinding is in the range of 5- 30 m 2/ g and 8- 20 m 2/g is
m ore pref erred. The ground cataly s t poW der can be us ed f or
the f olloW ing purpos es :
[ 0057 ] 1. SiZ e to des ired particle f or perf orm ance ev alu
ation in a lab- s cale reactor
[ 0058] 2. Shape to des ired f orm and s iZ e f or com m ercial
application s uch as f orm ing ex trudate, pellet or W as h
coated onto pre- s haped s upports .
[ 0059 ] 3. Us e f or pos t treatm ent s uch as acid treatm ent
f or f urther im prov ed perf orm ance. Af ter acid treatm ent,
the cataly s t poW der can then be s iZ ed f or perf orm ance
ev aluation in lab or s haped to des ired f orm and s iZ e f or
com m ercial application.
[ 0060] In other em bodim ents , the abov e cataly s ts m ay be
f orm ed on a s upport. Suitable s upports f or the cataly s t include
s ilica, alum ina, s ilica- alum inas , alum inos ilicates , Z irconia,
titania, boria, Z irconia toughened alum ina, lithium alum inum
s ilicates , s ilicon carbide, ox ide- bonded s ilicon carbide, and
m ix tures thereof . W hen us ed on a s upport, the s upported
cataly s t us ually com pris es f rom about 10 to 50% by W eight of
the cataly s t com pos ition, W ith the rem ainder being the s up
port. W hen the cataly s t is to be us ed W ith a s upport, in s om e
em bodim ents it is des irable to ? lter the com bined s olution to
rem ov e the ins oluble portion bef ore im pregnating the s up
port.
[ 0061] In other em bodim ents , cataly s ts f orm ed according
to the proces s es des cribed abov e m ay undergo one or m ore
acid treatm ent and/ or annealing s tages . For ex am ple, calcined
cataly s ts or s iZ ed cataly s ts particles m ay be contacted W ith a
carbox y lic acid, s uch as ox alic acid. In s om e em bodim ents ,
Oct. 7 , 2010
the acid treatm ent can be carried out W ith the calcined and
ground poW der and f olloW ed by cataly s t s haping. In other
em bodim ents , the acid us ed f or the treatm ent can be m ineral
acids , s uch as nitric acid, s ulf uric acid and phos phoric acid.
The acid concentration us ed f or treatm ent according to
em bodim ents dis clos ed herein m ay be W ithin the range f rom
about 0. 5% to about 40%; f rom about 1% to about 20% in
other em bodim ents . Acid treatm ent tem peratures m ay be
W ithin the range f rom about 20 to about 150 C. in s om e
em bodim ents , and f rom about 50 to about 120 C. in other
em bodim ents . The res ulting s olids m ay then be dried and
s iZ ed, if neces s ary . If neces s ary , annealing, f or ex am ple, m ay
be perf orm ed by heating the acid- treated cataly s t to a tem
perature in the range of 300 C. to about 500 C. , s uch as
about 400 C. , f or a tim e period of at leas t 1 hour.
[ 0062] PoW der cataly s t obtained as des cribed abov e m ay be
f orm ed into ex trudates in s om e em bodim ents . For ex am ple, a
poW der cataly s t m ay be m ix ed W ith a binder, s uch as s ilica or
other binders k noW n to one s k illed in the art. The m ix ture m ay
then be ex truded, s uch as W ith a Loom is Ram Ex truder or
other s uitable eq uipm ent, to f orm ex trudates of the des ired
s iZ e. The ex trudates m ay then be dried in an ov en at tem pera
tures in the range f rom about 100 C. to about 150 C. , and
m ay then be calcined at tem peratures f rom about 250 C. to
about 7 00 C.
[ 0063] In addition to ex trudates , the cataly s t m ay als o be
f orm ed into other v arious s hapes in com bination W ith a
binder. For ex am ple, cataly s t pellets m ay be prepared by
m ix ing cataly s t poW der W ith a binder and/ or pre- s haped s up
ports by W as hcoating. Other us ef ul cataly s t s hapes m ay
include s pheres , rings , and tri- lobed or other v arious s hapes
k noW n to thos e s k illed in the art. Cataly s ts us ed herein m ay
additionally be s uitably m anuf actured f or us e in ? uidized bed
reactors .
[ 0064] Ox idativ e D ehy drogenation Proces s
[ 0065] The proces s es dis clos ed herein m ay be us ed to con
v ert gas eous hy drocarbons into ole? ns . In s om e em bodi
m ents , gas eous hy drocarbons s uch as ethane, propane, butane
and m ix tures thereof m ay be us ed. Suitably , the hy drocarbon
is a paraf ? n- containing f eed including hy drocarbons hav ing
at leas t tW o carbon atom s . In s om e em bodim ents , proces s es
dis clos ed herein m ay be us ed to conv ert ethane to ethy lene. In
other em bodim ents , proces s es dis clos ed herein m ay be us ed
to conv ert n- butenes to butadienes . In y et other em bodim ents ,
proces s es dis clos ed herein m ay be us ed to conv ert ethy lben
Z ene to s ty rene. Ox idativ e dehy dration of other paraf ? ns and
ole? ns m ay als o be perf orm ed us ing em bodim ents of the
proces s es dis clos ed herein.
[ 0066] Hy drocarbon f eeds including ethane m ay be f rom
any num ber of s ources , including natural gas , prov ided that
im purities are rem ov ed s uf ? ciently to prev ent cataly s t poi
s ons and ev entual product contam inants , and als o to av oid
econom ically ex ces s iv e content of other accom pany ing com
pounds , including hy drocarbons , hy drogen, carbon diox ide,
etc. This can be accom plis hed by conv entional m eans k noW n
to thos e s k illed in the art.
[ 0067 ] Other ethane f eed s ources m ay include ethane
by product f rom a py roly s is plant ( s team crack er, autotherm al
crack er) that m ight otherW is e be recy cled to the py roly s is
plant f or f urther crack ing to ethy lene. Ins tead, this py roly s is
ethane can be f ed to ethane OD H proces s es dis clos ed herein.
Ty pically , this py roly s is ethane is already at a v ery high purity
and is ex cellent f eed to ethane OD H proces s es dis clos ed
herein.
US 2010/0256432 A1
[ 0068] The f eed to the ethane OD H reactor m ay include
f res h ethane, s uch as f rom s ources m entioned abov e, and m ay
als o include recy cle of unreacted ethane recov ered f rom the
OD H reactor ef ? uent.
[ 0069 ] The ox y gen- containing gas m ay include air, ox y
gen, and/or an air/ox y gen m ix ture. Ox y gen m ay be pure
ox y gen or s em i- pure ox y gen f rom an ox y gen plant, e. g. , air
s eparation plant, or any other s uitable s ource. The m olar ratio
of m olecular ox y gen to hy drocarbon ( e. g. , ethane) in the f eed
f or OD H proces s es dis clos ed herein m ay be W ithin the range
f rom about 0. 01: 1 to about 1: 1.
[ 007 0] The ox y gen- containing gas m ay be m ix ed W ith an
inert gas s uch as nitrogen, helium or argon. Additional f eed
com ponents s uch as hy drogen, carbon m onox ide, carbon
diox ide and s team m ay als o be included. The content of inert
com ponents ( nitrogen, etc. ) in the ox y gen- containing gas
need not be beloW any s peci? c lim it. HoW ev er, it m ay be
econom ically adv antageous that the content of inert gas es be
lim ited, s uch as to beloW that repres enting the us e of air
( 3. 7 7 : 1 m olar ratio of inert gas es relativ e to ox y gen) ; beloW a
m olar ratio of inert gas es to ox y gen of 1: 1 in s om e em bodi
m ents ; beloW a m olar ratio of inert gas es to ox y gen of 0. 3: 1 in
other em bodim ents ; and beloW a m olar ratio of inert gas es to
ox y gen of 0. 1 : 1 in y et other em bodim ents . Lim iting inert gas
com ponents m ay reduce cos ts as s ociated W ith ef ? uent s epa
ration s y s tem s that m ay be req uired. In s om e em bodim ents ,
inclus ion of s om e am ount of inert gas com ponents m ay be
adv antageous f or lim iting the ? am m ability of s om e e? iuent
s tream ( s ) that m ay contain res idual ox y gen.
[ 007 1] Steam m ay be prov ided in s u? icient q uantity to act
as a heat diluent, lim iting reaction tem perature ris e, and hot
s pots , and to av oid f orm ation of a ? am m able f eed m ix ture.
[ 007 2] A ty pical f eed com pos ition, f or ex am ple, m ay be 15
m ole % ethane, 8 m ole % ox y gen, and 7 7 m ole % W ater
( s team ) , neglecting contents of m inor cons tituents , or 15
m ole % ethane, 38 m ole % air, and 47 m ole % W ater ( s team ) .
Such a f eed com pos ition is s uitable f or operation W ith a
conv ers ion of about 7 0%; thus , the 15 m ole % f eed ethane
m ay include about 10. 5 m ole % f res h ethane and 4. 5 m ole %
recy cle ethane. For a higher ethane conv ers ion ( e. g. , 80- 9 0%)
and the s am e inlet ox y gen concentration, the f eed ethane
concentration m ay be loW er, e. g. , 12 m ole %, W ith the s team
concentration corres pondingly higher. In the direction of
loW er ethane conv ers ion per pas s , a f eed com pos ition cons is
tent W ith about 60% ethane conv ers ion m ay be 20 m ole %
ethane, 9 m ole % ox y gen, and 7 1 m ole % W ater ( s team ) , or 20
m ole % ethane, 43 m ole % air and 37 m ole % W ater ( s team ) .
At about 50% ethane conv ers ion per pas s , the f eed com pos i
tion m ay be 30 m ole % ethane, 10 m ole % ox y gen, and 60
m ole % W ater ( s team ) , or 30 m ole % ethane, 48 m ole % air
and 22 m ole % W ater ( s team ) . At about 40% ethane conv er
s ion per pas s , the f eed com pos ition m ay be 40 m ole % ethane,
12 m ole % ox y gen, and 48 m ole % W ater ( s team ) , or 40 m ole
% ethane, 57 m ole % air and 3 m ole % W ater ( s team ) . At about
30% ethane conv ers ionperpas s , the f eed com pos ition m ay be
7 0 m ole % ethane, 15 m ole % ox y gen, and 15 m ole % W ater
( s team ) .
[ 007 3] The concentration of ox y gen in the f eed m ay be
lim ited W ith a m argin beloW the m inim um ox y gen f or com
bus tion at the hy drocarbon- rich concentration of the m ix ture
( by us ing s u? icient s team and/or inert gas , e. g. nitrogen,
and/ or high enough hy drocarbon concentration) in order to
hav e a non- ? am m able f eed m ix ture, in particular W hen the
f eed hy drocarbon and ox y gen are prem ix ed prior to entering
Oct. 7 , 2010
the reactor, as W ith the us e of a ? x ed bed reactor. The
ex am ples of elev ated f eed concentration and alloW able f eed
ox y gen ( or air) concentration and corres ponding ethane con
v ers ion per pas s dis clos ed abov e are bas ed on a repres entativ e
m argin relativ e to the ? am m ability diagram of ethane in ox y
gen and inert ( nitrogen and/or s team ) f or a pres s ure and
tem perature lev el that m ay be us ed W hen the hy drocarbon and
ox y gen f eed s tream s are pre- m ix ed, as W hen us ing a ? x ed
bed reactor s y s tem . The v alues are realis tic but illus trativ e.
Som e alteration in the alloW able f eed ox y gen ( or air) concen
tration m ay be incorporated depending on hoW large a s af ety
m argin is prov ided relativ e to the ? am m ability env elope and
on W hat pres s ures and tem peratures are utiliZ ed. W ith s pecial
m ix ing and f eed inlet des igns and s af ety s y s tem s , and pro
v ided that the reactor s y s tem can adeq uately rem ov e the large
heat of reaction, including locally intens e regions ( hot
s pots ) , it m ay be pos s ible to alloW ev en higher f eed ox y gen
( or air) concentration than the ? am m able am ount. This m ay
als o inv olv e s pecial heat rem ov al des ign and/ or cataly s t par
ticles .
[ 007 4] The f eed ratio of ethane to ox y gen m ay be s et appro
priately to obtain the des ired com bination of conv ers ions of
ethane and ox y gen, W hich are inter- related by m aterial bal
ances and reaction s electiv ities . Us e of a large content of
s team as diluent prov ides cons iderable adv antages f or its heat
dilution capacity and als o f or reducing the ? am m ability env e
lope ( increas ing the m inim um ox y gen f or com bus tion) , but
increas es the proces s ing cos ts f or s team its elf . Conv ers ely ,
us e of an elev ated concentration of ethane can alloW reduction
in the s team concentration, reducing the cos ts related to the
s team but increas ing cos ts related to ethane recy cle. An ex tra
im pact of elev ating the ethane concentration is that it can
perm it increas e in the alloW able ox y gen concentration due to
the relations hip of the ? am m ability env elope. This can alloW
f urther loW ering of the req uired s team concentration. Con
s idering adv antages of an elev ated f eed ethane concentration,
it can be econom ical to utiliZ e a loW er ethane conv ers ion, e. g.
doW n to 60%, to 50%, to 40%, ev en to 20- 30%. It can be s een
that, though there is a debit f or increas ed ethane recy cle, there
are bene? ts f or higher concentration of the reactants and
products and corres pondingly loW er diluent ( s team ) req uire
m ent and total v olum etric ? oW rate and eq uipm ent s iZ ing f or
a giv en ethy lene production rate. In addition, there is a s ub
s tantial bene? t f rom higher s electiv ity at the loW er conv ers ion
lev el. The optim um conv ers ion lev el m ay depend on the pric
ing v alues at a s peci? c plant s ite.
[ 007 5] The f eed com ponents , ethane, ox y gen/ air, W ater,
etc. , m ay be v aporiZ ed, preheated and m ix ed to the ex tent
practical prior to f eeding to the OD H reactor. This can be
accom plis hed by m eans k noW n to thos e s k illed in the art.
Preheat techniq ues m ay include, f or ex am ple, heat ex change
f rom s team , a heat trans f er ? uid, reactor e? 1uent, and a f ur
nace.
[ 007 6] The OD H reactor m ay be a ? x edbed reactor W ith
high heat rem ov al, s uch as a m ulti- tube s hell- and- tube reac
tor/heat ex changer W ith cataly s t and proces s ? oW ins ide the
tubes and a heat trans f er ? uid ( or s team generation) circulated
in the s hell s ide.
[ 007 7 ] Another ex am ple is a ? x edbed reactor W ith cataly s t
in the s hell s ide and heat rem ov al tubes ins ide the cataly s t bed.
Yet another ex am ple is a plate- and- f ram e reactor/heat
ex changer, s uch as a D EG Therm oplate Reactor or a Cas ale
Plate Cooled Reactor W ith cataly s t and proces s ? oW in the
channel on one s ide of a plate and a heat trans f er ? uid in the
US 2010/0256432 A1
channel on the other s ide of the plate, hav ing alternating
plates and channels . Another ex am ple of a s uitable reactor
includes a m icro- channel reactor/heat ex changer.
[ 007 8] As an alternativ e, the OD H reactor m ay be a ? uid
iZ edbed reactor W ith high heat rem ov al. A ? uidiZ edbed
reactor m ay res ult in greater is otherm icity , av oidance of hot
s pots , and m ay als o alloW the f eeds to be introduced s epa
rately , W ithout pre- m ix ing. This can elim inate cons traints on
ov erall f eed concentration related to hot s pots and ? am m a
bility , and alloW the us e of a m uch higher concentration of
prim ary reactants ( ethane and ox y gen) , W ith a corres ponding
reduction in s team ( and/or nitrogen) f or dilution. Various
? uidiZ edbed reactor s y s tem s m ay be us ed, including dens e
bed ( f rom gently bubbling up to turbulent bed) , highly
ex panded bed ( f as t ? uid bed or circulating ? uid bed ) ,
entrained ? oW ( ris er or doW ner ) , or com binations . Heat
rem ov al can be to a heat trans f er ? uid or s team generation,
through coils s ubm erged in the bed and/or f reeboard ( abov e
the bed) , through the v es s el W all, f rom a connected v es s el
W ith the cataly s t particles trans f erred f rom one v es s el to the
other, etc. Another ? uidiZ ed bed s y s tem can be a s eparated
red/ox ? uidiZ ed bed s y s tem , W here the ethane is ox idativ ely
dehy drogenated by the ox y gen contained in the cataly s t in
one v es s el, and the [ O]- depleted cataly s t is trans f erred to a
s econd v es s el to replenis h its ox y gen ( plus burn of f any cok e
that has been f orm ed) . Then the ox y gen- rich cataly s t is
returned to the ox y dehy drogenation reactor. The s y s tem als o
has heat rem ov al coils .
[ 007 9 ] Ty pically O2 in the ov erall f eed to the OD H reactor
W ill be greater than about 3%, pref erably the O2 f eed is
greater that 6 m ol %. Ov erall ethane in the f eed to the OD H
reactor s hould be at leas t about 5%, pref erably greater than
about 10 m ol %. The OD H reactor bed tem perature s hould be
betW een about 250 and 4500 C. , pref erably betW een about
300 and 4000 C. The reactor pres s ure s hould be betW een 0. 1
and 20 barg, pref erably betW een 0. 5 and 10 barg.
[ 0080] One or m ore of the f eeds m ay be f ed in s tages ; i. e. ,
a portion at the reactor inlet, a f urther portion at s om e m id
point, etc. This can be done to s om e ex tent W ith ? x edbed
reactors , particularly if s ev eral cataly s t s tages are us ed ( s tage
1, s tage 2, etc. ) . It is es pecially f eas ible in a ? uidiZ edbed
reactor s y s tem .
[ 0081] The reactor s y s tem m ay include a s ingle s tage or
there m ay be s ev eral s tages . The s tages m ay be of the s am e
ty pe ( ? x ed bed, ? uidiZ edbed) or canbe of dif f erent ty pes . The
cataly s t or its concentration ( e. g. , m ix ed W ith s om e s olid
diluent) or s iZ e/s hape contained in each s tage m ay be the
s am e or dif f erent. The tem perature in each reaction s tage m ay
be the s am e or dif f erent. As noted abov e, a portion of one or
m ore f eed com ponent m ay be delay ed to a later s tage. Cata
ly s t and heat rem ov al m ay be dif f erent f rom one s tage to the
nex t, f or ex am ple ( 1) a ? rs t s tage W ith preheat, ( 2) a s econd
s tage, or com bined W ith the ? rs t s tage, W ith high activ ity
cataly s t and W ith m inim al or no heat rem ov al in order to
f acilitate ? nal preheat tak ing adv antage of the reaction ex o
therrn, and pos s ibly W ith les s v oid f raction in order to ens ure
es tablis hm ent of good ? oW dis tribution, ( 3) a third s tage W ith
cataly s t of m oderated activ ity , pos s ibly diluted W ith inert
com ponents , etc. , together W ith m ax im um heat rem ov al
des ign f or that s tage and its cataly s t ( pos s ibly m ore v oid
f raction) , ( 4) a f ourth s tage W ith cataly s t of m ax im um activ ity
and s electiv ity and m os t s uitable tem perature to driv e toW ard
f ull conv ers ions at peak s electiv ity , ( 5) a ? nal s tage that m ay
s erv e as a q uench s tage, e. g. , W ith loW er tem perature or
Oct. 7 , 2010
W ith added W ater/ s team . Conv ers ely , W ith ox y gen or air to the
? rs t reactor s tage pos s ibly lim ited in order to k eep the ox y gen
f eed concentration beloW its ? am m ability lim it and/or to
av oid ex ces s iv e heat generation and hot s pot in the ? rs t s tage
( s ) , additional ox y gen or air m ay be f ed to a later s tage in order
to boos t the ov erall production in a s ingle reaction train and
to m inim iZ e the ov erall dilution of the f ull proces s ? oW
through the s y s tem .
[ 0082] The heat that is rem ov ed f rom the reactor and its
e? luent m ay be trans f erred to reactor f eed heatup or to a heat
trans f er ? uid f or s ubs eq uent f urther heat trans f er. The
rem ov ed heat m ay als o be us ed f or s team generation ( orboiler
f eed W ater preheat) f or us e as an energy s ource, including as
s team its elf or f urther trans f orm ed into poW er. Energy ex port,
f or ex am ple, to an adj acent air s eparation plant that prov ides
the ox y gen f eed m ay be particularly s y nergis tic.
[ 0083] The e? luent f rom the reactor W ill ty pically contain
ethy lene, added W ater, if us ed, and additional W ater f orm ed
by the OD H reaction, CO, C and s m all am ounts of other im pu
rities ( f rom the f eed and f rom additional reactions ) in addition
to res idual am ounts of unreacted ethane and ox y gen. The
e? luent m ay als o contain inert gas es , es pecially W hen air is
us ed to s upply ox y gen to the OD H reactor.
[ 0084] In s om e em bodim ents , the ef ? uent f rom the OD H
reactor m ay contain in ex ces s of 0. 1 m ole % ox y gen; greater
than 0. 2 m ole % ox y gen in other em bodim ents ; greater than
0. 3 m ole % ox y gen in other em bodim ents ; greater than 0. 5
m ole % ox y gen in other em bodim ents ; greater than 1 m ole %
ox y gen in other em bodim ents ; greater than 2 m ole % ox y gen
in other em bodim ents ; greater than 3 m ole % ox y gen in other
em bodim ents ; greater than 4 m ole % ox y gen in other em bodi
m ents ; and greater than 5 m ole % ox y gen in y et other em bodi
m ents .
[ 0085] At the m oderate reactor and ef ? uent conditions , it is
pos s ible to control the e? luent to contain a ? nite optim um
ox y gen partial pres s ure rather than be es s entially abs ent, and
als o im pos e a pro? le of the ox y gen partial pres s ure f rom
reactor inlet to outlet. This prov ides a bene? t f or the cataly s t
in term s of both the cataly s t reactiv e s tate ( ideal ox idation
lev el) f or m os t activ e and s electiv e perf orm ance and als o
long- term , s table perf orm ance by prev enting cok ing and
other ef f ects . The e? luent ox y gen concentration f rom reac
tion s tage( s ) m ay be im portant f or controlling the perf or
m ance ( i. e. , conv ers ions and s electiv ities ) of the OD H s tage
( s ) . The ox y gen conv ers ion is a k ey reaction res ult and m ay be
us ed to s et the res idence tim es and tem peratures .
[ 0086] In s om e em bodim ents , it m ay be adv antageous to
include an ox y gen elim ination reactor doW ns tream of the
ethane OD H reactor in order to reduce the ef ? uent ox y gen
concentration to a loW er lev el than achiev able in the OD H
reactor at either adv antageous or econom ically practical con
ditions , e. g. , res idence tim e or reactor tem perature, or perf or
m ance res ults , e. g. , ethane conv ers ion or ethy lene s electiv ity ,
or cataly s t s tability . W hen an ox y gen elim ination reactor is
included doW ns tream of the OD H reactor, it can be pos s ible to
alloW ev en higher ox y gen concentration ( W ithin a m oderate
range) in the ethane OD H reactor e? luent and thereby obtain
better conditions in the ethane OD H reactor f or the cataly s t
q uantity ( les s cataly s t and res idence tim e s ince loW er ox y gen
conv ers ion is req uired) , perf orm ance, s tability and lif e, and
ov erall optim um ethane conv ers ion and ethy lene s electiv ity
and y ield as W ell. Proces s es us ef ul f or rem ov al of ox y gen
f rom hy drocarbon s tream s m ay include thos e dis clos ed in
Us . Pat. N os . 4, 29 9 , 800, 5, 157 , 204, and 6, 7 47 , 066, am ong
US 2010/0256432 A1
others , f or ex am ple. Cataly s ts us ef ul in an ox y gen elim ina
tion reactor m ay include ox y genation cataly s ts , com bus tion
cataly s ts , and hy drogenation cataly s ts , am ong others .
[ 0087 ] The ethane OD H reactor e? luent ox y gen concentra
tion m ay be in the range of 0. 1- 5 m ole % in s om e em bodi
m ents . The inclus ion of an ox y gen elim ination reactor is
es pecially adv antageous f or ethane OD H reactor e? luent
ox y gen concentrations abov e 0. 5 m ole %, but it m ay be us ed
W hen the reactor e? luent ox y gen concentration is loW er as
W ell.
[ 0088] One ty pe of ox y gen elim ination reactor us es an ox i
dation cataly s t to hav e the ox y gen in the ethane OD H reactor
e? luent com bus t CO plus a portion of the ethy lene and uncon
v erted ethane. The com bus tion of the C2s repres ents y ield
los s , but is not ex ces s iv e W hen the ethane OD H reactor e? lu
ent ox y gen concentration is not higher than 1- 2 m ole %,
cons idering that the cons um ption of ethane and ethy lene dur
ing com plete com bus tion to CO2 and H20 is only 0. 29 and
0. 33 m oles /m ole ox y gen cons um ed, res pectiv ely . The cata
ly s t, conditions , and conv ers ions cited in Us . Pat. N o. 5, 446,
232 are illus trativ e of an appropriate s y s tem . This includes a
reactor tem perature of 200- 3000 C. , thus eq ual to or cooler
than the ethane OD H reactor. Cooling the ethane OD H reac
tor ef ? uent prior to the ox y gen elim ination reactor is highly
appropriate and com patible. Of cours e, it is pref erred f or the
ox y gen elim ination reactor to obtain com plete com bus tion of
CO and W hatev er am ount of C2s to CO2 and H20 rather than
to CO, partially ox y genated hy drocarbon by - products , and
H2. This is to m inim iZ e cons um ption of the C2s in their partial
or f ull com bus tion reactions and als o to m inim iZ e the CO in
the ? nal e? luent.
[ 0089 ] Lik e the ethane OD H reactor, the ox y gen elim ina
tion reactor m ay be any of v arious ty pes of reactors ( ? x ed bed,
? uid bed) . It is pref erable that it als o hav e high heat rem ov al
capability , as the heat releas e can otherW is e produce a large
tem perature ris e, es pecially if the inlet ox y gen concentration
is higher than 0. 5 m ole %. On the other hand, s ince the inlet
ox y gen concentration is m uch loW er than the ov erall inlet to
the ethane OD H reactor, ? am m ability is no longer an is s ue
and the adv antage of a ? uidized bed is not as s trong f or the
ox y gen elim ination reactor f rom that pers pectiv e as f or the
ethane OD H reactor.
[ 009 0] The ox y gen elim ination reactor m ay be in a s eparate
v es s el f rom the ethane OD H reactor, or a pos s ible em bodi
m ent is f or it to be in the s am e v es s el, e. g. , as a ? nal s tage
( es pecially if it us es the s am e ty pe reactor) . An adv antage of
us ing s eparate v es s els is the ability to handle the ox y gen
elim ination cataly s t dif f erently f rom the ethane OD H cata
ly s t, e. g. , if there is a need f or m ore f req uent regenerations or
replacem ents . Additionally , in s om e em bodim ents , there m ay
be m ore than one ox y gen elim ination reactor in parallel,
alloW ing cataly s t in one to be changed W hile the other is
online, W ithout s hutting doW n the ethane OD H reactor.
[ 009 1] An option f or the ox y gen elim ination reactor is to
add a com bus tible to the ox y gen elim ination reactor f eed,
e. g. , H2 or a hy drocarbon, in order to both [ a] f acilitate the
com bus tion cons um ption of the ox y gen and [ b] cons um e the
added com bus tible ins tead of the m ore v aluable ethy lene or
res idual ethane, es pecially to the ex tent that the ox y gen elim i
nation cataly s t and conditions can obtain s electiv e com bus
tion of CO and the added com bus tible relativ e to the C2s .
[ 009 2] Another ty pe of ox y gen elim ination reactor is f or it
to be a ? nal ethane OD H s tage W ith s igni? cantly dif f erent
conditions f rom the m ain ethane OD H s tage( s ) in thes e
Oct. 7 , 2010
em bodim ents , operated to driv e the ox y gen to elim ination,
W hile s till producing m ore ethy lene by OD H. Such dif f erent
operation m ay be W ith the s am e or dif f erent cataly s t and m ay
be in the s am e v es s el or one or m ore s eparate v es s el( s ) , as
des cribed abov e f or the ? rs t ty pe of ox y gen elim ination reac
tor.
[ 009 3] Another option is to us e both a ? nal ethane OD H
s tage W ith its em phas is on driv ing the ox y gen toW ard elim i
nation W hile obtaining additional product ethy lene f olloW ed
by an ox y gen elim ination reactor us ing com bus tion. Again,
thes e s tages or reactors m ay be in s eparate v es s els or s om e
s tages /reactors com bined into a com m on v es s el.
[ 009 4] Yet another ty pe of ox y gen elim ination reactor m ay
incorporate addition of H2 and a hy drogenation cataly s t to
hy drogenate the ox y gen ( rather than ox idation cataly s t to
accom plis h com bus tion) . Such a s y s tem m ay hav e additional
bene? t of hy drogenating v arious by - products to the ex tent
that s om e m ay be pres ent, s uch as acety lene and ox y genates .
[ 009 5] As W ith the OD H reactor, the heat that is rem ov ed
f rom the ox y gen elim ination reactor and its ef ? uent m ay be
trans f erred to OD H reactor f eed heatup or to a heat trans f er
? uid f or s ubs eq uent f urther heat trans f er. The rem ov ed heat
m ay als o be us ed f or s team generation ( or boiler f eed W ater
preheat) f or us e as an energy s ource, including as s team its elf
or f urther trans f orm ed into poW er.
[ 009 6] The e? luent f rom the ethane OD H reactor, and
thereaf ter f rom the ox y gen elim ination reactor, if us ed, W ill
hav e a high content of H20, particularly f or operation at high
OD H conv ers ion if a ? x edbed reactor s y s tem is utiliZ ed
( operation at loW OD H conv ers ion W ith high ethane recy cle
and f eed concentration, or highly concentrated W ith a ? uid
iZ ed bed reactor s y s tem , can hav e a m uch loW er H2O concen
tration) . The e? luent m ay be cooled and m uch of its W ater
content condens ed prior to com pres s ing the gas es . The con
dens ed W ater m ay be recy cled to prov ide s team dilution of the
reactor f eed. N et W ater generated by reaction is purged f rom
the s y s tem . Energy recov ery f rom the condens ing W ater m ay
be accom plis hed by m eans k noW n to thos e s k illed in the art.
[ 009 7 ] The condens ation of the large am ount of e? luent
W ater greatly reduces the ? oW rate of the rem aining v apor
phas e and corres pondingly res ults in a large increas e in the
concentration of the non- condens ing com ponents . This m ay
res ult in a decreas e in the cos t of the s ubs eq uent proces s ing.
HoW ev er, it is im portant to recogniZ e that any ox y gen that
m ight be pres ent ( es pecially if there is no ox y gen elim ination
reactor prior to W ater condens ation, or to the ex tent that the
ox y gen elim ination is les s than 100% com plete) W ill becom e
m uch higher than bef ore the W ater condens ation. This con
centrating ef f ect on the non- condens ing v apor W ill increas e
f urther W ith s ucces s iv e proces s ing, i. e. , com pres s ion and f ur
ther W ater k nock - out, rem ov al of CO2, and ev entually con
dens ation of hy drocarbons ( ethane, ethy lene, and any other
C2+ hy drocarbons ) in the recov ery s y s tem . A s eem ingly loW
concentration of ox y gen in the ef ? uent f rom the ethane OD H
reactor ( or s ubs eq uent to any ox y gen elim ination reactor) can
becom e a high and pos s ibly ? am m able concentration in
doW ns tream proces s ing. This has im portant im pacts f or the
des ign and operation of the recov ery s y s tem , and is a reas on
that it is im portant to accom plis h the ox y gen elim ination to a
high lev el prior to the s teps that condens e and rem ov e the
condens able com ponents .
[ 009 8] If the ox y gen elim ination has been les s than 100%,
it m ay be appropriate to add an ox y gen ads orber f or ? nal
rem ov al prior to the condens ation of hy drocarbons . An alter
US 2010/0256432 A1
nativ e approach m ay be to accept the pres ence of a s m all
res idual am ount of ox y gen in the s tream and add s om e gas
eous diluent ( e. g. , nitrogen or m ethane) at that point to av oid
em ergence of a gas s tream W hich is s elf - ? am m able ( ins ide the
? am m ability env elope W ithout req uiring additional ox y gen
or com bus tible) . If m ethane is us ed, the ? nal of f - gas m ay be
utiliZ ed as a f uel gas . If nitrogen is us ed, the nitrogen m ight be
obtained f rom the s am e air s eparation plant that prov ides the
ox y gen f or the ethane OD H reactor. If air has been us ed in the
OD H reactor, the res idual nitrogen m ay already prov ide s uf
? cient dilution of the ? nal of f - gas . Ev en if the ox y gen- con
taining gas f or the OD H reactor is ox y gen f rom an air s epa
ration plant, it m ay contain a s u? icient content of inert gas
com pounds to prov ide adeq uate dilution of the ? nal of f - gas ,
either as s upplied f rom the air s eparation plant or by us e of
loW er ox y gen purity or by m ix ing W ith a m oderate am ount of
air prior to f eeding to the OD H reactor.
[ 009 9 ] It has been m entioned abov e that the ox y gen elim i
nation reactor m ay accom plis h s om e additional goals related
to elim inating undes irable by products , s uch as CO, acety
lene, and ox y genates . N ev ertheles s , it m ay s till be adv anta
geous or neces s ary to incorporate appropriate proces s ing
s teps at and doW ns tream of the W ater condens ation and com
pres s ion f or the proces s ing, including ultim ate rem ov al of
thes e by products by m eans k noW n to thos e s k illed in the art.
[ 0100] FolloW ing ox y gen elim ination, W ater s eparation,
carbon diox ide recov ery , and nitrogen s eparation, each W here
req uired, the ethy lene product m ay be s eparated f rom the
res idual ethane, any heav y by products , light by products and
res idual gas es , plus im purities that boil clos e to the product
ethy lene and the ethane that is recy cled, by m eans k noW n to
thos e s k illed in the art. In addition, as a bene? t of lim iting the
am ount of the com pounds other than ethy lene and ethane
generated us ing proces s es and cataly s ts dis clos ed herein, the
s eparations m ay be accom plis hed W ith les s inv es tm ent and
operating cos t than f or conv entional s team crack ing of
ethane.
[ 0101] The m aj or com pounds W hos e proces s ing and s epa
ration hav e greates t im pact on the cos t are the unconv erted
ethane f or recy cle and the dilution W ater, als o f or recy cle,
both of W hich are dependent on the conv ers ion per pas s that is
utiliZ ed and the corres ponding appropriate f eed com pos ition.
The ethane recy cle rate and its cos t im pact is at its larges t f or
operation at loW ethane conv ers ion per pas s , W hile the s team
rate and its cos t im pact is at its larges t at the oppos ite condi
tion W hen the ethane f eed concentration is loW , thus at high
ethane conv ers ion per pas s , in conj unction W ith a ? x edbed
ethane OD H s y s tem . The s team rate and its cos t im pact can be
reduced if a ? uidiZ edbed ethane OD H reactor s y s tem is us ed
becaus e the f eeds do not hav e to be pre- m ix ed and it can
theref ore be pos s ible to utiliZ e a highly concentrated ov erall
f eed com pos ition that m ight ev en be ? am m able if pre- m ix ed.
The s tronges t bene? t in s uch a s ituation can be at high ethane
conv ers ion per pas s ( W hich als o has m inim al ethane recy cle
rate and cos t) . A s eparated red/ox ? uidized bed s y s tem can
ev en utiliZ e air and k eep its nitrogen s eparated f rom the m ain
proces s ? oW . On the other hand, f or a ? x edbed reactor s y s
tem req uiring av oidance of ? am m ability W hen the f eeds are
pre- m ix ed, or other s y s tem utiliZ ing f eed pre- m ix , an addi
tional bene? t at high ethane f eed concentration ( and loW
ethane conv ers ion per pas s ) is that s uch a condition on the rich
s ide of the ? am m ability env elope alloW s higher ox y gen con
centration W ithout becom ing ? am m able. This perm its a
higher concentration of reactor f eeds and products , W ith cor
Oct. 7 , 2010
res pondingly loW er v olum etric ? oW rate and higher reactor
productiv ity f or additional cos t bene? ts , together W ith loW er
s team dilution req uirem ent, W hile als o obtaining heightened
s electiv ity .
[ 0102] N itrogen als o has a m aj or im pact on e? luent pro
ces s ing, s eparations and cos ts , if it is a m aj or com ponent of
the f eed, as W hen air is utiliZ ed f or the ox y gen s upply ( unles s
it is k ept s eparate by us e of a s eparated red/ox ? uidiZ ed bed
s y s tem ) . On the bene? cial s ide, W hen pres ent, nitrogen is an
additional inert W ith res pect to hoW concentrated the reaction
m ix ture is and hoW clos e to ? am m ability it is , and als o e? lu
ent and of f gas s tream s as dis cus s ed abov e, etc. N itrogen,
s team and high ethane concentration are alternativ e com
pounds W ith m aj or cos t im pact each of W hich can be cons id
ered and com pared f or an econom ical proces s , including us e
of a com bination.
[ 0103] The OD H cataly s ts des cribed herein enable the us e
of m uch les s s ev ere and s ens itiv e conditions than us ed in the
therm al crack ing and autotherm al crack ing proces s es , and
als o in prev ious OD H dev elopm ent attem pts . The tem pera
tures utiliZ ed are W ithin the ideal range f rom about 200 C. to
about 500 C. , pref erably f rom about 300 C. to about 450 C.
( relativ ely m ild, but s till hot enough f or ex cellent, ef ? cient
recov ery of the large ex otherm ic reaction heat releas e) ; the
s uper? cial res idence tim es are in the practical range of 0. 1 - l0
s econds , pref erably 0. 5- 5 s econds , W ithout a critical need of
q uick q uenching; and the pres s ure is in the m oderate range of
about 0. 1- 30 barG, pref erably 0. 1 to 20 barG. The reaction is
ex otherm ic, s uch that tem perature control is by conv entional
heat rem ov al at the tem perature range m entioned, W ith con
v enient trans f er to inex pens iv e s team cogeneration, W ith s ide
bene? t of its energy f or heat and/or poW er utiliZ ation. W ith
the m oderate conditions ( and the cataly s t characteris tics ) , the
cataly Z ed OD H reaction m ay be accom plis hed W ith es s ential
av oidance of m ultiple s ide reactions .
[ 0104] Eq uipm ent that m ay be us ed in the proces s
des cribed abov e includes conv entional reactors , etc. , at m od
erate conditions . They are am enable and econom ical f or us e
in proces s plants that can be either large or s m all, unlik e
s tandard s team crack ing W ho s e com plex f urnace reactors are
econom ical only W hen built f or v ery large plants .
[ 0105] The OD H ef ? uent res ulting f rom proces s es dis
clos ed herein ty pically req uires s eparate proces s ing through
s om e initial s teps , but m ay als o be integrated W ith py roly s is
plant product gas s eparation and puri? cation s y s tem s in
doW ns tream s teps . This approach m ay be econom ically pre
f erred W hen incorporated into the original des ign of a py roly
s is plant W ith f urther conv ers ion of its py roly s is ethane to
additional ethy lene, due to both higher ov erall s electiv ity /
production of ethy lene and loW er inv es tm ent, than W hen a
py roly s is ethane recy cle crack er is utiliZ ed. Proces s es dis
clos ed herein m ay als o be us ed to retro? t an ex is ting py roly s is
plant and releas e capacity of ex is ting recy cle ethane crack ing
f urnace( s ) and pos s ibly their portion of the ex is ting com pres
s ion train f or thos e to be us ed f or increas ing the f eed rate of
the py roly s is plant and ov erall ethy lene production f or the
retro? tted plant.
[ 0106] Ref erring noW to FIGS. 1- 4, v arious OD H proces s es
according to em bodim ents dis clos ed herein are illus trated,
W here lik e num erals repres ent lik e parts .
[ 0107 ] Ref erring noW to FIG. 1, hy drocarbon s tream 6,
including f res h hy drocarbon 2 and recy cle hy drocarbon 4, if
us ed, m ay be f ed to ox idativ e dehy drogenation reactor 12,
W hich includes ox idativ e dehy drogenation cataly s ts as dis
US 2010/0256432 A1
clos ed herein, s uch as in a pack ed or ? uidized bed, or a
s eparated red/ox ? uidized bed s y s tem . An ox y gen- containing
gas 8, s uch as air, and dilution s team 10 m ay als o be f ed to
ox idativ e dehy drogenation reactor 12. Contact of the hy dro
carbon and ox y gen in the pres ence of the cataly s t at appro
priate reaction conditions , as des cribed abov e, conv erts at
leas t a portion of the hy drocarbons to ole? ns , W ater, and
reaction by products , if any . The reactor e? luent, W hich m ay
include unreacted ox y gen, unreacted hy drocarbons and nitro
gen as W ell as the ole? ns , W ater and reaction by products , m ay
be recov ered v ia ? oW s tream 14.
[ 0108] If neces s ary or des ired, the reactor ef ? uent m ay then
be f ed v ia ? oW s tream 14 to an ox y gen elim ination reactor 18,
prov iding f or cons um ption of part or all of the rem aining
ox y gen by com bus tion reactions . Additionally , added com
bus tible, s uch as hy drogen or hy drocarbons s uch as m ethane,
propane or other, m ay be added v ia ? oW line 16 to be com
bus ted pref erentially ins tead of the ole? n product and f eed
hy drocarbons .
[ 0109 ] Ef ? uent f rom the ox y gen elim ination reactor, or
directly f rom the OD H reactor, m ay be recov ered v ia ? oW line
20 and f ed to q uench unit 22 to reduce the ef ? uent tem pera
ture and als o condens e and s eparate a large portion of the
W ater content, in adv ance of doW ns tream proces s ing. W ater
m ay be recov ered f rom q uench unit 22 v ia ? oW line 24, at
leas t a portion of W hich m ay be recy cled to ox idativ e dehy
drogenation reactor 12 v ia ? oW line 10. W ater not recy cled
m ay be W ithdraW n f rom the s y s tem v ia ? ow line 26, repre
s enting m os t of the W ater generated in the OD H and ox y gen
elim ination reactors .
[ 0110] The hy drocarbons , dilution gas es s uch as nitrogen,
if pres ent, and by product gas es s uch as carbon ox ides and
acety lene, m ay then be f ed v ia ? oW line 28 to com pres s ion
unit 30, W here com pres s ion of the gas es m ay res ult in rem ov al
of additional W ater recov ered v ia ? oW line 32. The res ulting
com pres s ed s tream 34 m ay then be proces s ed to s eparate
carbon diox ide f rom the hy drocarbons in CO2 rem ov al unit
36. The CO2 is W ithdraW n in How line 38, W hich m ay include
additional com pounds as s ociated W ith its rem ov al. The
rem aining com ponents , including unreacted hy drocarbons ,
ole? ns , light and heav y by products , diluent gas es , and any
res idual am ount of W ater, m ay then be f ed v ia ? oW line 40
through dry er 42.
[ 0111] The dried s tream 44 is s ent to gas s eparation unit 46,
W hich rem ov es the of f gas that contains any inert gas , res idual
ox y gen, carbon m onox ide, m ethane if pres ent, and other non
condens ables . The C2+ com pounds leav e in How s tream 50.
Prior to its dis charge, of f gas ? oW s tream 48 m ay hav e pro
ces s ing s tep( s ) to recov er C2+ s o that it can j oin ? oW s tream
50. This is es pecially true the m ore nitrogen or other inert
gas es hav e been f ed into the proces s ( e. g. , in air as the ox y gen
s ource) and ends up in of f gas ? oW s tream 48.
[ 0112] The C2+ com pounds are f ed v ia ? oW line 50 to the
hy drocarbon s eparation and puri? cation s y s tem 52, W here the
product ethy lene s tream 56 is s eparated, puri? ed and deliv
ered. Other hy drocarbon s tream s that are s eparated m ay
include s tream 54 W ith com pounds that are lighter than the
product ethy lene, unreacted f eed ethane 58, and com pounds
heav ier than ethane 60. Stream 54 m ay be recy cled to dis trib
ute its lighter com pounds to the of f gas s tream 48 and recov er
its ethy lene, ev entually to product s tream 56. At leas t a por
tion of the recov ered unreacted ethane 58 m ay be recy cled to
Oct. 7 , 2010
ox idativ e dehy drogenation reactor 12 v ia recy cle line 4, as
m entioned abov e. The heav y com pounds 60 m ay be dis
charged f or f urther us e.
[ 0113] The f res h ethane f eed s tream 2 m ay be pre- f raction
ated in order to rem ov e its lighter and/or heav ier com pounds
prior to being f ed to the OD H reactor. This pre- f ractionation
f ractionation m ay be accom plis hed in conj unction W ith the
e? luent hy drocarbon s eparation and puri? cation s y s tem 52.
[ 0114] The CO2 rem ov al unit 36 and drier 42 m ay be pos i
tioned at a later point in the hy drocarbon s eparation and
puri? cation s y s tem 52. There m ay als o be hy drogenation of
acety lene and pos s ibly other acety lenic com pounds . All of the
proces s ing m ay be in accordance W ith approaches and con
ditions k noW n to thos e s k illed in the art, but incorporating
alterations and s av ings due to greatly loW ered contents of
by products other than CO, C and W ater.
[ 0115] In the em bodim ent illus trated in FIG. 2, in lieu of
recy cling s om e portion of the W ater f rom q uench unit 22, at
leas t a portion of the nitrogen recov ered v ia gas s eparation
unit 46 m ay be recy cled v ia ? oW line 62 as dilution gas to
ox idativ e dehy drogenation reactor 12. N et of f gas is purged
v ia ? oW s tream 64.
[ 0116] In the em bodim ent illus trated in FIG. 3, ox y gen
containing gas s tream 8 m ay contain higher ox y gen concen
tration ( loW er content of inert gas es ) than in air. As a res ult, it
m ay be pos s ible to s im plif y s eparation and puri? cation s y s
tem s 46 and 52 due to m uch loW er content of inert gas es . FIG.
3 depicts the gas s eparation to be incorporated m odes tly into
the hy drocarbon s eparation and puri? cation s y s tem 52, W ith
of f gas purge 48. Various options ex is t f or recov ering C2+
f rom the of f gas plus light hy drocarbons .
[ 0117 ] In the em bodim ent illus trated in FIG. 4, carbon
diox ide pres ent in s tream 28 f olloW ing q uench unit 22, m ay
be s eparated in CO2 rem ov al unit 36 prior to com pres s ing the
m ain ef ? uent gas es in unit 30, as an alternativ e option rather
than rem ov ing the CO2 af ter com pres s ion. Carbon diox ide
m ay be recov ered v ia ? oW s tream 38, and s tream 40 W ith the
hy drocarbons , including ethane and ethy lene, m ay then be
com pres s ed 30, dried 42, and s eparated betW een of f gas and
C2+ hy drocarbons v ia gas s eparation unit 46. The C2+ hy dro
carbon m ix ture, including ethane/ ethy lene, m ay then be s epa
rated and puri? ed in s y s tem 52 as dis cus s ed abov e.
[ 0118] Sev eral pos itions f or CO2 rem ov al hav e been illus
trated in FIGS. 1 and 4 and in the dis cus s ion abov e. Other
pos s ible pos itions include together W ith ( aq ueous s y s tem ) , or
ups tream of ( dry , hot s y s tem ) , the W ater q uench unit 22 prior
to com pres s ion, as des cribed. CO2 rem ov al depends on
W hether it has high concentration and thus s u? icient partial
pres s ure. In addition, as als o applies to other proces s ing s teps ,
tW o or m ore s teps m ay be incorporated f or optim um proces s
ing, including als o the pos s ibility of the ? rs t s tage ups tream of
s om e other proces s ing s tep ( e. g. , com pres s ion) and the s ec
ond s tage doW ns tream .
[ 0119 ] Other us ef ul ? oW s chem es are contem plated v ia
em bodim ents dis clos ed herein.
EXAMPLES
[ 0120] Tes ting Procedures
[ 0121] Ev aluation of cataly s ts f or ethane ox y dedrogenation
( OD H) is carried out in a ? x ed bed ? oW reactor. The f eed
com pos itions are v arious com binations of C2H6/O2/H2O/N 2,
including m olar ratios of : 10/10/10/7 0 ( Feed A) and 15/ 10/
10/65 ( Feed B) . A s uper? cial s pace v elocity of 1200 h- 1 is
us ed, calculated bas ed on v olum etric ? oW rate of the reaction
US 2010/0256432 A1
m ix ture at s tandard conditions of 1 atm os phere and 25 C. ,
together W ith the reactor v olum e occupied by the cataly s t.
The reactor cons is ts of 1. 0 cm ( 0. 4 inch) ID , s tainles s s teel
tube heated in an upright Lindberg f urnace and at tem pera
tures betW een 250 and 500 C. In this tes t the reactor contains
2. 5 cc of the tes t cataly s t of 12- 20 m es h s iZ e. The reactor bed
depth is approx im ately 3. 0 cm ( 1. 2 inches ) . In the tes t W ith
ex trudates , the particle s iZ e is 1. 6 m m diam eter> <2. 0 m m
length, and, again, 2. 5 cc of the particles are charged. All
products are analy Z ed through an online GC s y s tem ( Perk in
Elm er CLARUS 500) . The GC is eq uipped W ith tW o detec
tors , TCD and FID f or tW o s eparate channels . One channel
W ith the TCD is us ed to analy Z e H2, O2, CO, CO2, and light
hy drocarbons and the other channel W ith FID detector is us ed
to analy Z e ox y genates and long- chain or arom atic hy drocar
bons .
Cataly s t Preparation
Com parativ e Ex am ple 1
[ 0122] A cataly s t W ith a nom inal com pos ition Mol_ OVO_
43N bO_ l1SbO_ O7 CaO_ O3O, C is prepared in accordance W ith com
pos ition and preparation as dis clos ed in Ex am ple 1 of Us .
Pat. N o. 4, 524, 236. 9 . 9 7 g of am m onium m etav anadate is
added to 100 m L of W ater and heated to 7 0 C. W ith s tirring
f or ? f teen m inutes to f orm a s olution ( s olution 1) . Am m o
nium niobate ( V) ox alate hy drate ( 20 W t % N b content)
am ounting to 10. 56 g, antim ony ( III) ox alate am ounting to
3. 29 g and calcium nitrate tetrahy drate am ounting to 1. 7 7 g
are added to a s econd 100 m L of W ater and heated to 7 0 C.
W ith s tirring f or ? f teen m inutes and a s lurry is obtained. This
s lurry is com bined W ith s olution 1 to f orm s econd s lurry and
the res ulting s lurry is heated at 7 0 C. W ith s tirring f or ? f teen
m inutes . To a third 100 m L of W ater is added 35. 3 g of
am m onium heptam oly bdate tetrahy drate and the m ix ture is
heated to 7 0 C. W ith s tirring to f orm a s olution ( s olution 2)
and this s olution is added to the abov e s lurry to f orm ? nal
m ix ture. The ? nal m ix ture is als o heated at 7 0 C. f or ? f teen
m inutes W ith s tirring. The W ater is rem ov ed f rom the ? nal
m ix ture on a rotav apor at 50 C. to obtain a s olid. The s olid is
f urther dried in an ov en at 120 C. ov ernight and then ov en
calcined in air at a tem perature of 350 C. f or ? v e hours . The
X- ray dif f ractogram ( XRD ) of the calcined m aterial m ainly
s hoW s am orphous phas e. The calcined m aterial is ground
W ith a m ortar/pes tle to poW der W hich is then pres s ed and
s iZ ed to 12- 20 m es h granules f or reactor ev aluation. The
cataly s t is tes ted according to the abov e des cribed tes t proce
dure and res ults are s hoW n in Table 1.
[ 0123] A cataly s t W ith a nom inal com pos ition Mo l_ OVoO_
43N bO_ 1 1 SbO_ O7 TeO_ O3O, C is prepared in accordance to Ex am ple
1 of Us . Pat. N o. 4, 524, 236 W ith Ca replaced by Te. The
preparation procedure is the s am e as des cribed f or Com para
tiv e Ex am ple 1 ex cept that 1. 40 g of telluric acid is added in
place of the calcium nitrate tetrahy drate.
LoW Tem perature Calcinations
29 N bO_ l7 TeO_ 2lSbO_ O1O, C is prepared us ing a dif f erent prepara
tion procedure f rom Ex am ple 1 of Us . Pat. N o. 4, 524, 236
ex cept f or the calcination conditions . In a beak er 15. 80 g of
Oct. 7 , 2010
am m onium niobate ( V) ox alate hy drate ( 20 W t % N b con
tent) , 0. 5 g of antim ony ox alate and 4. 0 g of ox alic acid
dihy drate are dis s olv ed in 160 m L of D I W ater at room tem
perature and a hom ogeneous s olution ( s olution 1) is obtained.
In a round bottom ? as k , 35. 60 g of am m onium heptam oly b
date tetrahy drate, 6. 7 2 g of am m onium m etav anadate, 9 . 56 g
of telluric acid are dis s olv ed in 200 m L W ater at 7 0 C. to f orm
a s econd s olution ( s olution 2) . 5. 0 m L of concentrated nitric
acid is added to s olution 2 and the res ulting acidi? ed s olution
is then com bined W ith s olution 1, obtaining an orange- col
ored gel. The W ater is rem ov ed f rom the gel on a rotav apor at
50 C. to obtain a s olid. The s olid is f urther dried in an ov en
at 120 C. ov ernight and a portion of the dried s olid is calcined
? v e hours in air at 350 C. The other portion of the dried s olid
is us ed in Ex am ple 1 f or high tem perature calcinations . The
X- ray dif f ractogram @ ( RD ) of the calcined s olid m ainly
s hoW s am orphous phas e as illus trated in FIG. 5. The calcined
m aterial is ground W ith a m ortar/pes tle to poW der W hich is
then pres s ed and s iZ ed to 10- 20 m es h granules f or reactor
ev aluation.
High Tem perature Calcination in the Abs ence of
HN O3
29 N bO_ l7 TeO_ 2lSbO_ OlO, C is prepared in the abs ence of nitric
acid in the f olloW ing m anner: In a beak er 7 . 9 0 g of am m o
nium niobate ( V) ox alate hy drate ( 20 W t % N b content) , 0. 25
g of antim ony ox alate and 2. 0 g of ox alic acid dihy drate are
dis s olv ed in 80 m L of D I W ater at room tem perature and a
hom ogeneous s olution ( s olution 1) is obtained. In a round
bottom ? as k , 17 . 84 g of am m onium heptam oly bdate tetrahy
drate, 3. 36 g of am m onium m etav anadate, 4. 7 8 g of telluric
acid are dis s olv ed in 100 m l W ater at 7 0 C. , obtaining a
s econd s olution ( s olution 2) . Solution 2 is com bined W ith
s olution 1 and an orange- colored gel is f orm ed. The W ater is
rem ov ed f rom the gel on a rotav apor at 50 C. to obtain a s olid.
The s olid is f urther dried in an ov en at 120 C. ov ernight and
then calcined tW o hours in air at 27 5 C. f olloW ed by tW o hour
calcinations at 600 C. in ? oW ing nitrogen. The calcined
m aterial is ground W ith a m ortar/pes tle to poW der W hich is
then pres s ed and s iZ ed to 12- 20 m es h granules f or reactor
ev aluation.
Ex am ple 1
High Tem perature Calcination in the Pres ence of
HN O3
[ 0126] The portion of dried and uncalcined s olid f rom
Com parativ e Ex am ple 3 is ? rs t calcined tW o hours in air at
27 5 C. in an ov en and then calcined tW o hours at 600 C. in
? oW ing nitrogen. X- ray dif f raction ( XRD ) of the calcined
m aterial s hoW s the pres ence of tW o dis tinguis hed cry s talline
phas es ( hex agonal and orthorhom bic phas es ) as illus trated in
FIG. 6. The s olid is ground W ith a m ortar/ pes tle to poW der and
a portion of the poW der is then pres s ed and s iZ ed to 12- 20
m es h granules f or reactor ev aluation. The other portion of the
poW der is us ed f or acid treatm ent as des cribed in Ex am ple 3.
Ex am ple 2
[ 0127 ] The cataly s t of Ex am ple 1 is tes ted W ith dif f erent
f eed com pos ition as s hoW n in Table 1.
Ex am ple 3
[ 0128] In a round bottom ? as k , 10 g of the poW der of
Ex am ple 1 are m ix ed W ith 10 g of ox alic acid dihy drate and 9 0
US 2010/0256432 A1
g of D I W ater. The res ulting m ix ture is heated at 80 C. f or ? v e
hours W ith s tirring and then the s olids is collected by v acuum
? ltration and dried in an ov en at 120 C. ov ernight. The dried
s olid is heated tW o hours at 500 C. in ? oW ing nitrogen. The
X- ray dif f ractogram ( XRD ) of the acid- treated cataly s t s hoW s
the pres ence of m ainly one cry s talline phas e ( orthorhom bic
phas e) as illus trated in FIG. 7 . The acid- treated cataly s t is
then pres s ed and s iZ ed to 12- 20 m es h f or reactor ev aluation.
Ex am ple 4
High Sb
[ 0129 ] A cataly s t W ith a nom inal com pos ition Mol_ OVO_
29 N bO_ l7 TeO_ 2lSbO_ O7 O, C is prepared in the f olloW ing: In a bea
k er, 7 . 9 0 g of am m onium niobate ( V) ox alate hy drate ( 20 W t
% N b content) , 1. 7 0 g of antim ony ox alate and 2. 0 g of ox alic
acid dihy drate are m ix ed W ith 80 m L of D I W ater at room
tem perature and s lurry is obtained. In a round bottom ? as k ,
17 . 84 g of am m onium heptam oly bdate tetrahy drate, 3 . 36 g of
am m onium m etav anadate, 4. 87 g of telluric acid are dis
s olv ed in 100 m L W ater at 7 0 C. and a hom ogeneous s olution
is obtained. 2. 5 m L of concentrated nitric acid is added to the
Oct. 7 , 2010
obtained. 2. 5 m L of concentrated nitric acid is added to s olu
tion 2 and the res ulting acidi? ed s olution is then com bined
W ith s olution 1 and an orange- colored gel is f orm ed. The
W ater is rem ov ed f rom the gel on a rotav apor at 50 C. and a
s olid is obtained. This s olid is f urther dried in an ov en at 120
C. ov ernight and then calcined tW o hours in air at 27 5 C.
f olloW ed by tW o hour calcination at 600 C. in ? oW ing nitro
gen. The calcined m aterial is ground W ith a m ortar/pes tle to
poW der W hich is then pres s ed and s iZ ed to 12- 20 m es h gran
ules f or reactor ev aluation.
Ex am ple 6
LoW Te, 0. 15 Lev el
29 N bO_ l7 SbO_ OlTeO_ 15O, C is prepared f olloW ing the s am e pro
cedure as f or Ex am ple 5 ex cept that the am ount of telluric
acid is increas ed f rom 2. 9 0 g to 3. 41 g.
s olution and the res ulting acidi? ed s olution is then com bined Ex am ple 7
W ith the s lurry and an orange- colored gel is f orm ed. The
W ater is rem ov ed f rom the gel on a rotav apor at 50 C. and a N i in Place of Sb
s olid is obtained. The s olid is f urther dried in an ov en at 120
Ex am ple 5
LoW Te, 0. 125 Lev el
29 N bO_ 17 SbO_ OlTeO_ 125O, C is prepared in the f olloW ing: In a
beak er, 7 . 9 0 g of am m onium niobate ( V) ox alate hy drate ( 20
W t % N b content) , 0. 25 g of antim ony ox alate and 2. 0 g of
ox alic acid dihy drate are m ix ed W ith 80 m L of D I W ater at
room tem perature and hom ogeneous s olution ( s olution 1) is
obtained. In a round bottom ? as k , 17 . 83 g of am m onium
heptam oly bdate tetrahy drate, 3. 43 g of am m onium m eta
v anadate and 2. 9 0 g of telluric acid are dis s olv ed in 100 m L
W ater at 7 0 C. and a hom ogeneous s olution ( s olution 2) is
[ 0132] A cataly s t W ith nom inal com pos ition Mo l_ OVO_
29 N bO_ 17 TeO_ lON iO_ O4O, C is prepared in the f olloW ing m anner:
In a beak er, 7 . 9 0 g of niobium ox alate and 2. 0 g of ox alic acid
dihy drate are dis s olv ed in 80 m L D I W ater ( s olution 1) at
room tem perature and a hom ogeneous s olution ( s olution 1) is
f orm ed. In a round bottom ? as k , 17 . 84 g of am m onium hep
tam oly bdate tetrahy drate, 3. 36 g of am m onium m etav ana
date, 2. 32 g of telluric acid and 1. 21 g of nick el nitrate
hex ahy drate are dis s olv ed in 100 m L of D I W ater at 7 0 C.
( s olution 2) . 2. 5 m L of concentrated nitric acid is added to
s olution 2 and then com bined W ith s olution 1 to f orm a gel.
The W ater is rem ov ed f rom the gel on a rotav apor at 50 C. ,
obtaining a s olid. The s olid is f urther dried in an ov en at 120
TABLE 1
Tes t
Condition Perf orm ance
Tem p C2 C2: C2:
Ex am ple Cataly s t Feed ( C. ) % Conv C % Sel C %Yield
Com p. Mo1_ 0V0_ 43N b0_ 11Sb0_ 07 Ca0_ 03O, C A 400 67 62 42
Ex . 1
Com p. Mo1_ 0V0_ 43N b0_ 11Sb0_ 07 Te0_ 03O, C A 37 5 69 56 39
Ex . 2
Com p. Mo1_ 0V0_ 29 N b0_ 17 Sb0_ 01Te0_ 21O, C A 37 5 44 7 6 33
Ex . 3
Com p. Mo1_ 0V0_ 29 N b0_ 17 Sb0_ 01Te0_ 21O, C A 37 5 57 9 1 52
Ex . 4
Ex . 1 Mo1_ OVO_ 29 N bO_ 17 SbO_ O1TeO_ 21Ox A 380 7 4 89 66
Ex . 2 " B 39 0 7 0 9 1 64
Ex . 3 Mol_ OVO_ 29 N bO_ l7 SbO_ O1TeO_ 2lOx B 380 7 1 9 2 65
US 2010/0256432 A1 Oct. 7 , 2010
1 2
TABLE l- continued
Tes t
Condition Perf orm ance
Tem p C2 C2: C2:
Ex am ple Cataly s t Feed ( C. ) % Conv C % Sel C %Yield
Ex . 5 Mo1_ OVO_ 29 N bO_ 17 SbO_ O1TeO_ 1250K B 360 67 9 3 62
Ex . 6 Mo l_ 0v 0_ 2, N b0_ l7 s b0_ 01Te0_ 150, : B 37 0 7 0 9 1 64
Ex . 7 Mo1_ 0V0_ 29 N b( , _ 17 Te0_ 10N i0_ O42O, C A 39 0 7 1 87 62
Com parativ e Ex am ple 5 gram s . BET analy s is of the ground pow der s how s 16. 2 m 2/ g
s urf ace area. The ground pow der is pres s ed and s ized to 12- 20
Unground Cataly s t m es h f or reactor ev aluation.
[ 0133] The cataly s t of Ex am ple 5 is reproduced in a larger
s cale and als o s ev eral batches are prepared, com bined and
us ed f or grinding, ex trus ion and treatm ent w ith ox alic acid as
des cribed in Ex am ples 8- 18. The preparation procedure is as
f ollow s : In a beak er, 15. 82 g of am m onium niobate ( V)
ox alate hy drate ( 20 w t % N b content) , 0. 50 g of antim ony
ox alate and 4. 0 g of ox alic acid dihy drate are m ix ed w ith 160
m L of D I w ater at room tem perature and hom ogeneous s olu
tion ( s olution 1) is obtained. In a round bottom ? as k , 35. 60 g
of am m onium heptam oly bdate tetrahy drate, 6. 85 g of am m o
nium m etav anadate and 5 . 80 g of telluric acid are dis s olv ed in
200 m L w ater at 7 0 C. and a hom ogeneous s olution ( s olution
2) is obtained. 5. 0 m L of concentrated nitric acid is added to
s olution 2 and the res ulting acidi? ed s olution is then com
bined w ith s olution 1 and an orange- colored gel is f orm ed.
The w ater is rem ov ed f rom the gel on a rotav apor at 50 C. and
a s olid is obtained. This s olid is f urther dried in an ov en at
120 C. ov ernight and then calcined tw o hours in air at 27 5
C. f ollow ed by tw o hour calcination at 600 C. in ? ow ing
nitrogen. A portion of the calcined s olid is pres s ed and s ized
to 12- 20 m es h f or reactor ev aluation. The tes t res ults and BET
s urf ace area are s how n in Table 2.
Ex am ple 8
Analy tical Grinder
[ 0134] 10 g of the calcined s olid of Com parativ e Ex am ple
5 are ground w ith a Tek m ar A- 10 Analy tical Mill: tw o m in
utes f or ev ery ? v e gram s . BET analy s is of the ground pow der
s how s 8. 2 m 2/ g s urf ace area. The pow der is pres s ed and s ized
to 12- 20 m es h f or reactor ev aluation.
Ex am ple 9
Cry ogenic Grinding, 2 m in
5 are ground w ith a Freezer Mill ( m odel # 67 7 0, Spex ) : tw o
m inutes f or ev ery ? v e gram s . BET analy s is of the ground
pow der s how s 9 . 0 m 2/ g s urf ace area. A portion of the ground
pow der is pres s ed and s ized to 12- 20 m es h f or reactor ev alu
ation. The res t of the pow der is us ed f or treatm ent w ith ox alic
acid as des cribed in Ex am ples 14- 18.
Ex am ple 10
5 are ground w ith a f reezer/m ill: ? v e m inutes f or ev ery ? v e
Ex am ple 11
[ 0137 ] 110 g of the calcined s olid of Com parativ e Ex am ple
5 are ground w ith a f reezer/m ill: ten m inutes f or ev ery ? v e
gram s . BET analy s is of the ground pow der s how s 17 . 3 m 2/ g
s urf ace area. A portion of the ground pow der is pres s ed and
s ized to 12- 20 m es h f or reactor ev aluation. The res t of the
pow der is us ed f or ex trus ion as des cribed in Ex am ple 12.
Ex am ple 12
Ex trudate
[ 0138] 100 g of the pow der cataly s t f rom Ex am ple 11 are
m ix ed w ith 28 g of Ludox AS- 40. The m ix ture is w ell m ix ed
to f orm a doll w hich is then ex truded w ith a Loom is Ram
Ex truder ( m odel # 232- 16) and 1. 6 m m ex trudates are
obtained. The ex trudates are dried in an ov en at 120 C.
ov ernight and then calcined in ? ow ing N 2 at 500 C. f or tw o
hours . The calcined m aterials are cut into 2 m m in length f or
reactor ev aluation.
Ex am ple 13
[ 0139 ] Cataly s t is the s am e as f or Ex am ple 12, but is tes ted
at dif f erent tem perature.
[ 0140] Table 2 s um m arizes the tes t res ults and BET s urf ace
areas f or Ex am ples 8- 11 and tes t res ults only f or Ex am ples
12- 13. All the tes ts are carried out under the conditions
des cribed prev ious ly and w ith a f eed of C2H6/O2/H2O/
N 2: 15/10/10/65 m olar.
TABLE 2
Perf orm ance
BET Surf ace Tem p C2 C2: C2:
Ex am ple Area ( m Z /g) ( C. ) % Conv C % Sel C %Yield
Com p. 5. 5 420 7 5 86 65
Ex . 5
Ex . 8 8. 2 37 0 7 6 9 1 69
Ex . 9 9 . 0 355 7 0 9 2 64
Ex . 10 16. 2 350 7 1 9 0 64
Ex . 11 17 . 3 340 67 9 0 60
Ex . 12 380 69 87 60
Ex . 13 37 0 64 9 0 58

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