BNL-66589

$qposiu.in inCh@ysi$ on %$vigas CbrwerdonihFwk and Diviiiion of Petroleum Chemistry Spring ACS Meeting, Anaheim, CA March 21-25,1999

C&ntidak

DEVELOPMENT OF ATOM-ECONOMICAL CATALYTIC PATHWAYS FOR CONVERSIONS OF SYNGAS TO ENERGY LIQUIDS D. Mahajan*, JE. Wegrzyn and Z Lee Building 815, Department ofApplied Science,BrookhavenNationalLaboratory,

Uptou New York 11973 M. Guwvich Office of Heavy VehiclesTechnok@q U.S. Depwtm@ of Energy, WashingtorqD.C. 20585 (Keywordx catalysis, syngas convcmiomoxygenatedfhels, methano~&methylether) FAX 516-344-7905
INTRODUCTION

The subject of catalytic syngasconversionsto fiels and chemicalsis wellstudied (l-3). But globally,the recent focus is on dlevelopnxmt of technologiesthat offkran economicalroute to desired products (4). EconornicaIti=rt of naturaigas Ilom remote locationsand within

clathrate hydrates is of continuingrnterestat BrookhavenNational LaboratoV (BNL). Under

this projec~ a Liquid Phase Low Temperature @PLT)concept is beii appliedto attain highly efficienttransformations of natund-gas derived syngasto specifk products. Furthermore,a more precise term Atom Economy has been recentlyintroducedby Trost to describedevelopmentof 9 highlyefficienthomogeneouslycatklyxxl synthesisof organic molecules(5). T~en from rdkrence 5, the term Atom Economyis deiined as mximkhqg the numberof atoms of all raw materialsthat end up in the product with any other reactant required on in catalyticamount. For applicationto methdnetransformationsthat mayrnvolveone or more step%atom economy of each of these steps is critkd We, therefore, oonsideratom-economysynonymouswith overall

energyefficiencyof a pxxxess. Ibispaper descriis potential liquidproducts from catalytic -. ~

syngas conversio~ i.e. gas to liquids(GTL) technologiesand process considerations that are nemxary for economicaltransport of natural gas. As SUCL the present study defines an atorw *nnnm;enl d9nrl~rA tn MW- UW a-h . . . . . . . -A.-W--J

m ~-~. -.. . .

cvwmnAm u CTI
-~.~ V -.

tshnrdn*--W.

-.

NAlUKAIJ

GAS

CUN

Vl!XSIUNS

We consider options to promote natural gas usage that meet the following set-forth criterix l) fitsweIlinthe present dis@MiOn W&tr@me ,2) safe based on public perqtio~ is m harmonywith the environrne@and 4) fklvorable process economics. Equations 1-13, showncollectivelym F= 1, represent availableoptions to harness energy fiorn
. A-IL ----xc-: -. L AA.> CLLC1 gy Ucllvcl y Clllvlmlvy Is ucll.uGu --us

3)

-.-n . .&. g. r.. .-2.... -_-l: --*:--- l%1 UC u VG1all Uwd LUI Varluus appilwuulm

&=&-(&

+b+G+Ql&

(14)

where = .-.-1 Lulul

ET
~

Mum

A-A

Cucrgy

m luuurd

--4

gias al Lb

---

-.

--n -LWGJI NW.

= energy

required

fir exploration drilhng, and refiningi-e., total energy that is required to

bring naturalgastothe surke. ~=_mtitip~*orc_ ~=energyneededto Em= enerw . . ..~ transport.

tal cmnmlimee . ..*__.

tiom~d*ek_tik.

fnr . . . f=mfim~ . ...-

Thedeliveryefficiency(Q

refm to the stored ener~ m natural gas. The following

discussion sets fbrth the direction for the present study 1. The most exothermicprocess is to burn natural gas at the well site. Natural gas

cmnbustion energy is 20,551 BTU/lb(Equation 1). Due to a mismatchbetween source location -md~~
Wimizhg

mmo+~gQ-IIC w

mdmF91 ..

rmc k &w .

6* . . . Kfmdbi -y...-

9A

t_h_

txpmcnartd rv. .

in ..-.-.. ref%omtd X-n

tianbrc ....

energy inputthat is requiredto transport gas is the goai. 2

2.

Natural gas transpbrt either as compressednaturalgas (CNG) or liquefiednatural gas. optionwith deliveredenergy efficiency(E=) of

(LNG) is knowm Here, LNG is the Pref-

-80?!. As shownin Equation 2, this serves as the baselinebecause this physicaltransformation --L. .-* -CI&.*.&n+:..flz \ u E -..1 qh. n AlezG, q Wpuus w * Ullly&yuuea G-s ~ VL Jlquwawwu \qJ.
- -. dt3iveIY d%ihfi)y k d)out . . . . . ----B-J.U/lb. 16,WU taut A =.*.#l+:.. w UqUcablvll 1A lw. pA

3.

Other options to transport natural gas as other liquidsare considered. In conversionof

natural gas to energy liquids(GTL), the totaI energyrequired for chemicaltransformation (l&) determinesdeliveryefficiency. W*
Ithe

available&@ direct methane to metband is considered

a viableprocess (Equation 3). This route is underdevelopment(6, 7).

A -8-. Tn thm a d w afWT nn+kn u A u .puu+ *km t9nn*7cbn+kwil uw WVAX v wubzwusu
*wn-&4an
s w u-m~wy

nwnnativs n#k.e
yxv

VXLWAO

cc v a

a wmda+w AC .Iamm
AwbJ VA WS-

4%.1

AUWL

product options. Here, the Em term inciidex ~=

Em=lE~P+ EST

(15)

whm Ew relates to syngasproduction Step I and E~~relates to Step II m which syngasis

converted to liquids. ~ five product options are considered in two broad categories. These 10-13).
bo+~ Akntathvl
J a

are a) hydrocarbonproducts (Equation 9) andb) oxygenatedprodtis (lUp&ns n...m+e..e 1n-l s9 dvmlA J.#yucuNub7Av-=ether (lJM@ @ ~thy~
in
. .

k -

vhmnarl ;. ihtannntnvt nf Avaww+A lK&U ae w . i&vlcttn& lwaq~. v-w w au UAw w-swab WA w AWvv

fOXIIIW2

(!M-~) can~

(kkd

fio~

~L

~w8uS?

OfIW%W

htterest

dimethylether (DME), this product is consideredseparately. The basis of this paper thus

considersF-T liquids,MeO~ DME as viableoptionsto LNG.. Two guidelinesare considered Criticak 1. hy tiloned
&dOtA.b

natural gas-basedcosts must includepreserving options that allownatural

.

-am,... ana ~a$-aJ#ai

2.

at +ha wdn+ WA UW=. WAJ bWWJS W GLIW ~JUb n#Anlbaw

it is to benoted that ail fivereactions ~-Euations9-iYJ are exothermic. But the overall

GTL transtbrmatbn is a net energy user and overall process efficiencyis dependent on energy re@redfbrc hemicaltransfbrmationsl&
carrkX& mdnking Since both Canal Hatomsrnnaturd gasareenergy

transport of these atoms willminimhe til value loss oftk delivered

product. It is this aspect M the term Atom Economy relates to. From the overall discussio~ it is clear that minkkhqg % % k --~ km i.e. total

maximiz E@ Inthispaper, theem@asis isonminim&@ %tirnm I&termSrn EqUatiOn 14.

relates tothe~and

THE LIQUID STATE OPTIONS

R_tit_~(ti

~t-)_gmmahqtid

k*dhe&, Theemphasis isonatom

&

ongoingBNL R & D effort is directed to mbimizetlw~term

economyof catalytictransforrmtions and this formed the basis for developingnovelcdysts

to

attain these goals. In addition to ongoing work at BNL related to GTL, other promisingsystems under developmentare also considered. These are:
q

Direct methaneto methanol conversionusing Catalytic technobgy (6). Anotheroption is still urder development (7).

The Syntroleumapproach that uses air for partial oxidation of methaneto produce syngas (Step I or Equation 4). The eifect of eliminatingan 0,-sepmtion plant but inmased opressure (to accmnmodateNz m syngas) during F-T synthesis.

The BNL approach utiking the LPLT concept for methanolproduction DME synthesiswith upmming technobgies includingthat based on the BNL LPLT concept.

The BNL one-pot -is

of methylftmnate.

AIIearlier costing study(8) that took the cradle to grave approach m calculatingoverall

,>.

energy efficiencyfor various transformationsis relevant. SpecificaIIy reviewed in the present study m emergingatom-economicalGTL technologies that emphasizesakty and environmental _ ~ ~st ~~~es of *o~s optio~ to _fi ~ti
gas fiornremote locations.

W* presentlypopular LNG option alfdeliveryefficiency- 80??as a baseline,conversionof natural gas to clean liquid fhels m skid-mount~ product flexiile, and economicalGTL plants at the well-siteis the goaL
LIbIRATURE CITED (1) Hutching$ G.J. and Scurre& MS. (eds.), S@e~

Elsevieq CataLToday, 6(3) (1990). A., Catal. Rev.- !%i.Eng. 35 (l), 1

(2) Hind~ (1993).

J.P., Hutching%G.J,, and Kienn~

(3) Dry, M.E., J. Organomet. Chem.:372,117 (1989). (4) Remote Gas Strategies, pp. 4,5 and 13,14,April 1998. (5) Tro% B.M., Angew. Chem Int. Fd. EngL34,259 (1995). (6) P-R-A, (1998). (7)Lh M., HogT., SA., J. Am Cbem. SOC., 119,6048 (1997). Taube, D.J., Gamble,S., Taube, H., Sato4 T., and Fuj& H., Science,280,560

(8) Stodolslcy,F. aud Santir&D.J., C!HEMTEC~ 54, October 1993.

Work at Brookhaven is supported under US DOE Contract No. DE-ACO2-CH1O886.

Figure 1:
Well-site Usage: Physical Transformation: Chemical Transformation: Step h ~+

The Reaction Scheme

20, ~ CO, + 2H,0 (1)
(2) (3)

cH4@)+EL c%) ~+

Em ~ EnergyLquid

Syugas Production cHug)+EsP co+nH2 1. Steam Reforming: q)+H20 ~ CO+3H,

(4) (5)

(6)
ii ~.

C~J+%02(Air)
Step II:

~ CO+2Hz+@Q

m
(8)

Syngas Transformations x CO + y~z + Em ~ Hy&WiKbO~

~ Oxygenates
I. HydrocarbonSJdwsiS (F-TPR=ss)

nCO + 2nH2 - (-CH2-)~ + nHzO

%Mdhanol Synthesis CO+ 2HZ ~ CH~OH 3. DimdhylEher Synthesis

(9)

(lo)
(11)

2C0 + 4 Hz + (cH&o + H~o 4. Methyl Formate $vnthesis 2C0 + 2~ ~ CH@CHO

(12) (13)