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Activation of Natural Gas Using Nontraditional Oxidants: Eric McFarland, University of California, Santa Barbara

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(1)

March 2016 NAS Workshop 

The Changing Landscape of Hydrocarbon 

 Feedstocks for Chemical Produc<on – Implica<ons for Catalysis 

•  Today’s prac<ces, challenges, and opportuni<es 

•  Why not oxygen 

•  Lots of interes<ng fundamental and prac<cal ques<ons. 

•  Combining reac<on engineering and catalysis         to make wise use of our methane resources. 

 

 

Ac3va3on of Natural Gas Using Nontradi3onal Oxidants 

 

(2)

The 

Changing Landscape 

of Hydrocarbon 

 Feedstocks for Chemical Produc<on – Implica<ons for Catalysis 

What’s Changing ?   

Vola<lity in price ?  

           

Or  

 

(3)
(4)

Natural Gas 2016 

~ 0.5‐1 ton CO2/ton C 

O= C =O 

C

‐4 

O

‐2 

It has not proven possible to parVally oxidize   alkanes with oxygen at high rates and low cost 

without producing CO2. 

(5)

The Future of Methane Conversion ? 

Our challenge

:  

low CO

2

 release in electricity and transporta3on

 

 and …………  more sustainable chemical produc6on  

 get value from our resources 

HC’s + Cx + H2 

 catalysis 

Need New Catalysts for  

DecarbonizaVon of our Shale Gas ! 

NH

3

 

(6)

SelecVve ParVal OxidaVon and OxidaVve Coupling  

of Methane:  free energy and enthalpy of reacVon 

Oxidant 

Reac<on 

ΔG

r

° 

ΔH

r

° 

O

2

 

2CH

4

 + O

2

 

 C

2

H

4

 + 2H

2

O 

‐295 

‐281 

NO

2

 

2CH

4

 + 2NO

2

 

 C

2

H

4

 + 2H

2

O + 2NO 

‐221 

‐165 

Cl

2

 

2CH

4

 + 2Cl

2

 

 C

2

H

4

 + 4HCl 

‐219 

‐169 

SO

3

 

2CH

4

 + 2SO

3

 

 C

2

H

4

 + 2H

2

O +2SO

2

 

‐153 

‐83 

Br

2

 

2CH

4

 + 2Br

2

 

 C

2

H

4

 + 4HBr 

‐57 

‐3 

NO/N

2

 

2CH

4

 + ½ NO+ ¼ N

2

 

C

2

H

4

+ ½ H

2

O +NH

3

 

‐8 

‐31 

I

2

 

2CH

4

 + 2I

2

 

 C

2

H

4

 + 4HI 

131 

183 

heat 

2CH

4

  

 C

2

H

4

 + 2H

2

  

170 

202 

CO

2

 

2CH

4

 + 2CO

2

 

 C

2

H

4

 + 2H

2

O + 2CO 

219 

287 

S

2

 

2CH

4

 + S

2

 

 C

2

H

4

 + 2H

2

S 

235  

332 

(7)

2CH4 + 4 S2  2CS2 + 4H2S 

(8)
(9)
(10)

2CH

4

 +2CO

2 

 4CO + 4H

2

 

2CO + 4H

2

 C

2

H

4

 + 2H

2

O 

2CH

4

 + 2CO

2 

 C

2

H

4

 + 2H

2

O + 2CO 

 

(11)

Andrussow Process 

Andrussow Process 

CH4 + NH3 + 1.5 O2 → HCN + 3 H2O 

300 microsecond residence Vme,  Pt catalyst  or else,  COx 

(12)

NO2 

(13)

Hg (III)  Pt (IVII) 

(14)
(15)

ΔH/ΔG 400 C  H2O + ½ C2H4  

I

2  (94/36kJ/M) 

H2 + ½ C2H4  

(106/60kJ/M) 

Heat

 

Par<al Oxida<on of CH

4

 Without CO

2 

2H2 + C 

2HBr +2HI+ C 

(‐34/‐128kJ/M) 

I

2 

4HI + C  (60/‐34 kJ/M) 

2HCl+2HI + C 

I2 

Benchmark SMR + CCS 

O

2 

(16)
(17)

BUT To Suppress Complete OxidaVon 

Halogens

:  flame retardants:

  

      1) Oxida6ve dehydrogena6on +   

 2) Suppresses oxycombus6on

 

‐CH

2

‐CH

Br

‐CH

2

‐ ‐ ‐ ‐ ‐‐‐ ‐ ‐ CH

2

‐CH

2

‐CH

2

‐ 

(18)

Fredrick Rust, Industrial & engineering chemistry    1949 vol:41 iss:11 pg:2595 

This is well known 

Oxyhalogena6on/Dehydrohalogena6on for Par6al Oxida6on 

(19)

Oxychlorina<on (OCL) almost on parity  with SMDS for methane 

Oxyhalogena<on and  

dehydrohalogena<on in one step with I

2

  

Well Known Process (many fundamental ques<ons) 

(20)

Cl  

 Polychlorides,  CO

x 

Front. Chem Sci Eng    2013,  Vol. 7 Issue (3) : 279‐288 

(21)
(22)

       AlF3~ 1000 C  200 kta faciliVes 

MgCl2~750 C 

(23)
(24)

Heat, MX

z

,X

2

,XY

 

  XY= I, Cl, Br

 

+  

H

X/Y

 

Our Approach Preserva<on of Methane Chemical Poten<al in 

an Op<mally Efficient Chemical Processing Plaoorm 

C

H

4 

 

‐(C

H

2

)‐ 

 

C

 

H

2  

Q/eV

  

H

2

O + 

Q

/

eV

  

O

2

,Ox

 

(25)

React for Show, Separate for Dough 

CH

4  

+ XY 

     H

3

C‐X/H

n

C

m

 

  

   +     HY

    

XY 

HY 

O

2    

 

CH

4 

  N

2

, CO

x   

CH

y

O

x 

 

H

2

O 

S 

CH

4   

CH

3

SH

   

CS

2 

 

H

2

S 

NO

x 

CH

4   

N

2

, NO, CO

x 

 

H

2

O 

SO

x 

CH

4   

 SO

2

 CH

3

SO

3

H 

H

2

O   SO

2

 H

2

SO

4

 

(26)

1981 Jack Kilby, Texas Instruments 

HI/HBr/O2 Fuel Cells 

HBr 

Br2 out 

HBr  Br2 

H

X

 has a carrier role in “an electron world”; 

it has value! 

 

(27)

Cataly<c Oxida<on HBr + O

2  

less well studied academically (than HCl, Deacon) 

but proven in lab and pilot studies  

(excess water equilibrium limit at high temp)

 

 

Can Make Heat or Electricity 

2HX + ½ O

2

 

  H

2

O +

 

X

2 

(28)

Bromination

T~400 C

Catalytic Coupling

T~ 400 C

Br

2

 

  

2H

Br

  

  

Solid Oxide

Chem. Com. 2004, 2100 

Catalysis Today 2004, 98, 317 

Chem.Com. 2004, 566, 658 

Phys. Chem.Chem.Phys. 2011, 13,2550 

Bromine Mediated Dehydrogena6on in Two‐Phase Reactor System

 

keep HC away from O

2 

(29)

29 

Clarence Chang and Tony Silvetsri, Mobil 1970’s

CH3OH

-HBr -HBr -HBr -HBr

CH3Br

CH3Br CH3Br CH3Br CH3Br

(30)

Methane

Ethane

!

Propane

!

C6+

!

Methanol/DME"

Olefins! BTX+!

Ethanol" Glycol"

Ethylene!

BTX+!

Olefins"

Ethoxylates"

Propanol"

Propylene!

BTX!

O2/Electricity/Photons  H2O / H2 

GRT/UCSB Demonstrated Br

2

/HBr Plaoorm 

Ethylbromide  ethylene (99.5% selecVvity)  Propylbromide  propylene (99.2% selecVvity) 

Butylbromide  butene (99.1 % selecVvity)   

(31)

Ac<va<on: 

Methane

Aromatics

Light Olefins

2002: Bromine Mediated DehydrogenaVon 

Regenerable Solid Reactant (Br carrier)  NiBr2 



 NiO

 

•

 

Bromine Containing Components 

Remain at Temperature 

(32)

Unsolved (Unsolvable?) Issues 

‐

 

Regenerability of solid reactants 

 sintering 

‐

 

Capacity of supported solids 

‐

 

Hydrocarbon stability over solids 

(33)

Bromination

T~400 C

Catalytic Coupling

T~ 400 C

Br

2

 

  

2H

Br

  

  

Catalytic Oxidation

In The Absence Of A Regenerable Solid,

More Conventional Separations Were Used

(34)

34

Methane

Aromatics

Light Olefins Alkanes

Where Prior Methane/Br Work Stopped 

Major Issues (that made capital too high):

 

(35)

0.0% 5.0% 10.0% 15.0% 20.0% 25.0% 30.0% 35.0%

Cost (ISBL) by Equipment Type

For Propane Dehydrobromination

Cost Dominated By Indirect Heat Exchange  

(36)

Change Our Approach:   

separa<on in molten salt: MO(H

2

O)/MOH + HBr 

MBr

2 

Halogens Remain Hot 

(37)
(38)

Hydrogen as the ul<mate  sustainable electron 

acceptor   CH

4 

 C + 2H

2 

 

CH4 + 2O2  CO2 + 2H2O 

CH4  C + 2H2  2H2 + O2  2H2O 

(39)

Hydrogen as the ul<mate  sustainable electron 

acceptor   CH

4 

 C + 2H

2 

 

(40)

Barriers and Opportuni<es 

~ 0.5‐1 ton CO2/ton HC 

@$100/ton CO2  ~ 10% inc feed 

Enable New low C Fuels, H2, NH3  New routes to fix C 

Process IntegraVon/Cost reducVon   IntegraVon OpportuniVes (C e‐) 

Referensi

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Activation of Natural Gas Using Nontraditional Oxidants: Eric McFarland, University of California, Santa Barbara

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