Novel Catalytic Process Technology for Utilization of CO for Acrylonitrile

Novel Catalytic Process Technology for Utilization of CO2 for Acrylonitrile Production

DE-FE0030678

Angela Zheng, Aravind V. Rayer, Jian-Ping Shen, Zach Davis-Gilbert, Tim Bellamy, and Marty Lail

Andrew Jones and Jose Figueroa

1 RTI International is a registered trademark and a trade name of Research Triangle Institute. www.rti.org Acknowledgement and Disclaimer

Acknowledgement: This presentation is based on work supported by the Department of Energy under Award Number DE-FE0030678.

Disclaimer: “This presentation was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.”

2 Project Summary

Objective: Develop and optimize novel catalytic process for utilization of CO2 as a feedstock and oxidant for the production of valuable chemicals

Key Metrics U.S. DOE/NETL Office of Fossil Energy Demonstration of CO -ACN catalyst • 2 Project Manager – Andrew Jones RTI International

reactivity showing percent-level production Wayne Holden, Ph.D. ACN RTI International President and CEO RTI International Technology for Energy, Environment, and Engineering • Data from lab-scale testing showing Dennis Gilmore, Ph.D. Dr. Marty Lail 50% yield CO Sr. Director Technology for Energy, PI & Program Director Environment, and Engineering RTI Administration Brian Donovan (Contracts) Specific Challenges Nichole DiPippo (Finance) • Development of catalyst with

required selectivity Catalyst Development Process Development • Cost competitiveness with .Qinghe Zheng, Ph.D. Jian-Ping Shen, Ph.D Aravind V. Rayer commercial ACN Zach-Davis Gilbert Vijay Gupta Tim Bellamy Timeframe: 10/01/2017 to 06/30/2020 Development Team Total Funding: $1,000,000

3 BP2 Tasks

BP2 Tasks

Task 6.0 Evaluation and Optimization of the CO2-Reducing Catalysts for Propylene Ammoxidation Task 7.0 Build Aspen Process Model for ACN Process Task 8.0 ACN Process TEA and LCA Task 9.0 Technology gap analysis

4 Novel Catalytic Process Technology for Utilization of CO2 for Acrylonitrile Production

downstream products

megatons market

5 Acrylonitrile

Opportunity

• $1500-$1700/ton Thermodynamics of CO2 utilization for acrylonitrile • ~10MT/year demand • ~3.5% anticipated growth o PAN o ABS o SAN o Nylon 6,6

Long history of production starting with the SOHIO process using a fluidizable catalyst, propylene, ammonia, and oxygen.

CO2 utilizing route would consume CO2 as a feedstock and produce CO as a second product

6 Competitive Reaction of Propylene Reforming

Favorable Gibb’s energy calculations for utilization of CO2 with propylene to make acrylonitrile (blue circles) or syn gas (red circles)

7 Equilibrium Composition and Kinetic Control

Equilibrium composition calculations for carbon dioxide, ammonia, and propene over the temperature range 0- 1000°C. Left shows full scale, right is magnification of grey circle in left

Thermodynamic control of reaction products compared to kinetic control

8 CO2-AN Path Underway (present status)

• Demonstration of CO2-ACN catalyst reactivity in fixed-bed microreactor using initial catalyst formulations. • Initial data gathering for process model.

• Data from lab-scale testing of CO2-ACN. • Modifying catalyst formulations for improved performance • Study of individual mechanistic steps

9 Experimental Set Up

Reaction Conditions Feed Composition: Stoichiometric Reaction T: 500-800°C Reaction P: 1 atm Catalyst Loading: 0.5 grams Chemical Looping Mode Operation

Renewable ammoxidation of propylene with CO2 as sole oxidant

Propylene ammoxidation (SOHIO process) C H + 3/2 O + NH C H N + 3H O (12) 55% ~83% 3 6 2 3 → molar3 3 yield 2

RTI proposed CL-Ammoxidation process using CO2 as sole oxidant Ammoxidation step:

C H + NH + 3MeO C H N + 3MeO + 3H O (13) 700−800 ℃ 3 6 3 𝑥𝑥 3 3 𝑥𝑥−1 2 CO2 reduction (catalyst oxidation) step:

3MeO + 3CO 3MeO + 3CO (14) 700−800 ℃ 𝑥𝑥−1 2 𝑥𝑥 Chemical looping-ammoxidation with CO2 (CO2-CL-Ammox)

40 NH3 35 8.79 10.75 30 11.19 C3H6 Ammoxidation step 9.27 25 • % conversion NH3 CO2 20 5.88 • % conversion C3H6 7.06 15 27.81 27.93 2.54 24.00 22.21 CO2 Reduction step Conversion Conversion (%/ cycle) 10 16.39 13.57 12.73 • CO is the only oxygen source during 5 2

0 0.84 1.88 1.26 1.24 1.25 0.48 0.95 the redox cycles • X(CO2)= · 100 Total molar amount of O in the product 2 C Total molar amount of O in the CO feed o C C C o o o C o - MCM - 41 C o @ 500 Mo @ 500 @ 500 C @ 600 o @ 500 @ 500 Commercial catalystCommercial 1.5Ru,3Mo,3Mn / 1.5Ru,3Mo,3Mn MCM41 @ 500 1.5Ru,3Mo,3Mn / 1.5Ru,3Mo,3Mn MCM41 1.5Ru,3Mo,3Bi / MCM41 / MCM41 1.5Ru,3Mo,3Bi 1.5Ru,3Mo,3Mn,3Bi / MCM411.5Ru,3Mo,3Mn,3Bi

11 / MCM41 1.5Ru,3Mo,3Mn,3Bi,Na,W Chemical looping-ammoxidation with CO2 (CO2-CL-Ammox)

35 Acrylic acid O 30 O H3C CH3 H2C CH2 Propanenitrle H2C 25 OH Acrylonitrile acrylic acid ethylene oxide ethane ethylene 20 Acetonitrile 15 Ethylene H2C H3C H C product yield product 10 oxide 3 -

C C2H6 N N 5 N C2H4 0 propane nitrile acrylonitrile acetonitrile C o C C o C o C o o C o C - MCM - 41 o @ 500 @ 500 Mo @ 500 @ 600 @ 500 @ 500 a , a : C atom amount in product i and feed respectively; @ 500 Coomercial catalystCoomercial i 0

1.5Ru,3Mo,3Mn / 1.5Ru,3Mo,3Mn MCM41 n , n : Molar flow rate of product i and feed, mol/min. 1.5Ru,3Mo,3Bi / MCM41 / MCM41 1.5Ru,3Mo,3Bi 1.5Ru,3Mo,3Mn / 1.5Ru,3Mo,3Mn MCM41 i 0 1.5Ru,3Mo,3Mn,3Bi / MCM411.5Ru,3Mo,3Mn,3Bi

1.5Ru,3Mo,3Mn,3Bi,Na,W / MCM41 1.5Ru,3Mo,3Mn,3Bi,Na,W a n C yield = i i × 100 % a0n0 9 ∑ Chemical looping-ammoxidation with CO2 (CO2-CL-Ammox)

25 Acrylonitrile • Target product 20 Acetonitrile 15 Propanenitrle • Known byproduct Acrylonitrile 10 • Minimization will improve acrylonitrile N N product yield (%) Acetonitrile yield 5 Propanitrile 0 • H2 produced with current catalyst formulations C C o C C o o o C C o o - MCM - 41 @ 500 @ 500 @ 500 @ 600 Mo @ 500 @ 500 ai, a0: N atom amount in product i and feed respectively; Commercial catalystCommercial ni, n0: Molar flow rate of product i and feed, mol/min. 1.5Ru,3Mo,3Mn / 1.5Ru,3Mo,3Mn MCM41 1.5Ru,3Mo,3Mn / 1.5Ru,3Mo,3Mn MCM41 1.5Ru,3Mo,3Bi / MCM41 / MCM41 1.5Ru,3Mo,3Bi 1.5Ru,3Mo,3Mn,3Bi / MCM411.5Ru,3Mo,3Mn,3Bi a n N yield = i i × 100 a0n0 9 ∑ NH3 oxidation- CO2 reduction cycle test in AutoChem reactor

3 redox cycles, in each cycle:

Step 1: Reduction of metal (oxide) species with NH3 (10% NH3 in He) at 500 oC. NH g 1.5H g + 0.5N g = 45.9 kJ mol NH g + 0.5M O H g + 0.5N g + 0.5H0 O g + 0.5M O−1 3 → 2 2 ∆𝐻𝐻298 3 x y → 2 2 2 x y−1 o Step 2: TPO of metal oxides with CO2 (20% CO2 in He) from 200 C to 700 oC at 10 oC/min. M O + CO M O + CO

x y−1 2 → x y

• He purge in between Step 1 and 2 and during temperature ramp.

• Step 1 in prep mode (to avoid potential corrosion of TCD detector with moist NH3. • Step 2 in analysis mode and its TCD signals were recorded. NH3 oxidation- CO2 reduction cycle test in AutoChem reactor

0.51 (a) Blank reactor

TCD_Cycle 1 0.505

0.5 TCD signal (a.u.)

0.495 200 300 400 500 600 700 Temperature (oC) 0.51 (b) 12111-20_3% Mo/gamma Al2O3 TCD_Cycle 1 TCD_Cycle 2 0.505 TCD_Cycle 3

0.5 TCD signal (a.u.) 300~325 oC 600~640 oC 0.495 200 300 400 500 600 700 Temperature (oC) M O + CO M O + CO

x y−1 2 → x y Future Work

• Optimization of the CO2-Reducing Catalysts for acrylonitrile and minimization of propylene reforming • Build Aspen Process Model for ACN Process • ACN Process TEA and LCA • Technology gap analysis

17 Summary

• Conversion of CO2 to acrylonitrile underway • Initial test results show production of acrylonitrile • Several other nitriles produced • Catalyst can be improved for selectivity for acrylonitrile to achieve project goals • Autochem results consistent with mechanism Thanks for your attention! Marty Lail, Ph.D. Senior Director, Carbon Capture and Conversion Technology for Energy, Environment, and Engineering RTI International 3040 Cornwallis Rd. Research Triangle Park, NC 27709 919-485-5703 (o) 919-809-2204 (l) 18