MEthane activation via integrated MEmbrane REactors MEMERE

Transcription

1 MEthane activation via integrated MEmbrane REactors MEMERE Fausto Gallucci, Solomon Wassie, Jose Medrano This project has received funding from the European Union s Horizon 2020 research and innovation programme under grant agreement No Duration: 4 years. Starting date: 01-October-2015 Contact: f.gallucci@tue.nl The present publication reflects only the author s views and the European Union is not (Disclosure liable for or any reproduction use that without may be prior made permission of the of information MEMERE is contained prohibited). therein.

2 Outline Introduction (Membranes, MRs, MEMERE) Why MEMERE Highlights of the results Technoeconomic evaluation Next steps

3 Possible membrane functions

4 Membrane reactor concept Combination of reaction and separation steps Reaction carried out on a catalyst Separation carried out via a membrane

5 Project objectives The key objective of the MEMERE project is the design, scale-up and validation of a novel membrane reactor for the direct conversion of methane into ethylene with integrated air separation. The focus of the project will be on the air separation through novel MIEC membranes integrated within a reactor operated at high temperature for OCM allowing integration of different process steps in a single multifunctional unit and achieving significantly higher yields in comparison with the conventional reactor technologies, combined with improved energy efficiency.

6 Consortium The MEMERE consortium bring together 11 partners from 8 different countries

7 Work Packages The MEMERE concept will start from catalyst and membrane material, and design a new reactor for C 2 production

8 C 2 H 4 economy Ethylene is a very important product for the petrochemical industry high impact process and large market share The primary raw material for the C 2 H 4 production are Naphtha and Ethane (especially in Middle East and US) interest in feedstock cost reduction and diversification From an environmentally point of view, naphtha steam cracking results in 2-3 t CO2 /t olef reduce the environmental impact

9 C 3 - separation HE-05 C 2 - separation Cryogenic Cooler dryers NaOH Primary fractionator stripper NAPHTHA STEAM CRACKING Cracker and Furnace Gas stack P06 EX01 P07 Naphtha P01 A01 Air to furnace P26 S03 P05 steam to process quench U02 P02 P04 P P08 IP steam dirty water P09 Oil (C 9+ ) S02 S01 CO 2, H 2 S, etc HP steam A02 Cracked Naphtha P03 Fuel to Furnace P10 C 2 H 2 hydrogenation Ethylene P17 H2-1 Fuel to Boiler P18 P19 U01 Propylene P16 P15 P11 P22 P12 C 3 H 4 hydrogenation De-Methanizer H2.2 P20 De-Ethanizer P23 P21 P13 P24 De-Propanizer BTX P14 P25 9

10 C 2 selectivity Oxidative Coupling of Methane 2CH 4 + O 2 C 2 H 4 + 2H 2 O 100% 80% 60% 40% 20% 0% 0% 20% 40% 60% 80% 100% CH 4 conversion Main reactions 2CH 4 + O 2 C 2 H 4 +2H 2 O C 2 H O 2 C 2 H 4 +H 2 O Side reactions CH 4 + 2O 2 CO 2 +2H 2 O CH 4 + O 2 CO +H 2 +H 2 O 2CH O 2 C 2 H 6 +H 2 O CO + 0.5O 2 CO 2 C 2 H 4 + 2O 2 2CO+2H 2 O C 2 H 6 C 2 H 4 +H 2 C 2 H 4 + 2H 2 O 2CO+4H 2 O CO + H 2 O CO 2 +H 2 The CH 4 /O 2 ratio strongly influences the selectivity towards C 2 H 4 /C 2 H 6 Very exothermic reactions Low pressure and low temperature favor the C 2 yield

11 Oxidative Coupling of Methane Schematic representation of OCM packed-bed membrane reactor concept Methane conversion and C 2 selectivity and yield for a membrane reactor

12 Project Work Packages

13 Powders development

14 Catalyst development Over a hundred metal oxide/promoter/support combinations reported as catalytically active for OCM JM is performing high throughput screening to select the benchmark catalyst for lab and pilot scale testing

15 Novel Reactors Current incarnation Future incarnations Randomly dispersed catalyst aggregates Orthogonal scaffolds Helix-loop scaffolds Microspheres

16 Membrane development Supports Manufacturing of porous ceramic supports Development of dense tubes fitting to porous supports Joining technology between porous supports and dense tubes Analysis of porous tubes

17 Oxygen membranes for OCM Objectives: Development of MIEC capillary membranes. Development of pore-filled supported membranes Improvement of sealing procedure to integrate the membranes in the catalytic membrane reactors Membrane characterization under realistic reforming conditions in labscale units prior to application of the optimal membranes in the pilot prototypes Manufacturing of membranes for the prototype reactor (scaling-up of the membrane length and number per batch).

18 Oxygen membranes for OCM Development of MIEC powders for capillary and pore-filled membranes A-site B-site O 2- Development of MIEC capillary membranes Self-supported membranes

19 Oxygen membranes for OCM Development of supported membranes A) Capillary and supported tubular membrane B) Pore-filled membranes Asymmetric structure

20 Oxygen flux (sccm/cm 2 ) Why asymmetric membranes Motivation are employed for oxygen separation? 10 Kinetics-controlled Air Oxygen deprived Air Diffusion-controlled 2- Oxygen Oxygen ion Membran e layer Porous support Thickness (µm) Electron (Thorogood et. al, 1993) Higher permeability without sacrificing mechanical strength High purity oxygen Favorable multilayer membranes Good connection Free of defects No reaction Stable in operating conditions CGO, BSCF and SFSO powders MgO and Al2O3 tubes

21 Oxygen membranes for OCM Ceramic Slurry preparation Automatic Dip-coater Dip-coating Al2O3 support tube Al2O3 tube coated with ceramic slurries Sintering 350mm Membrane after sintering High quality on-side closed tubes are employed for the dip-coating process

22 Oxygen membranes for OCM BSCF self-supported single phase membrane BSCF-CGO dual phase self-supported membrane Dense membrane with low chemical stability Porous membrane because of the different sintering temperature

23 Parallel and Integrated Reactors Fluidized bed membrane reactor Dual membrane reactor Integrated parallel reactor Network of reactors O 2 CH 4 Godini et al., Chemical Engineering and Processing 74 (2013) Godini et al., Fuel Processing Technology, 106 (2013)

24 Operando experiments

25 Operando experiments

26 C 3 - separation HE-05 C 2 - separation Cryogenic Cooler dryers NaOH Primary fractionator stripper NAPHTHA STEAM CRACKING Cracker and Furnace Gas stack P06 EX01 P07 Naphtha P01 A01 Air to furnace P26 S03 P05 steam to process quench U02 P02 P04 P P08 IP steam dirty water P09 Oil (C 9+ ) S02 S01 CO 2, H 2 S, etc HP steam A02 Cracked Naphtha P03 Fuel to Furnace P10 C 2 H 2 hydrogenation Ethylene P17 H2-1 Fuel to Boiler P18 P19 U01 Propylene P16 P15 P11 P22 P12 C 3 H 4 hydrogenation De-Methanizer H2.2 P20 De-Ethanizer P23 P21 P13 P24 De-Propanizer BTX P14 P25 26

27 Oxidative Coupling of Methane ASU W02 P09 SYNGAS FAN quench quench syngas syngas ACID GAS REMOVAL W04 W03 P10 P W11 P04 P05 SYNGAS COOLERS P06 P STEAM CYCLE W01 P07 P07 P08 W09 W08 W07 W10 EX01 P O 2 O(95% 2 pure) pure) A02 A02 N 2 N(+CO and H 2 O) O) BOILER Fuel fuel to to boiler boiler Air Air to ASU A01 A04 Air to to boiler A03 P H 2 2 O for for OCM dilution COMP CO SYNGAS COMP CO 2 for 2 for OCM OCM dilution PUMP-0 OCM P19 CRYOG. CRYOG. COOLER P11 Fuel fuel to boiler to boiler Ethylene P20 P16 P14 P03 CH CH 4, N 4, 2, Ar, H 2 Ar, H 2, 2, CO CO P13 W06 EXPN P02 P17 P18 R-01 D-01 W05 METHANATOR P01 Natural Gas Gas Ethane Ethane DE-METHANIZER P12 P15 DE-ETHANIZER P P21 Pure CO 2 COMP-03 40% CAPEX 45% OPEX AIR FAN ton CO2 /ton C2H4 = 3.26 Cost of C 2 H 4 = 1450 /ton C2H4

28 Air to ASU Acid Gas Removal OCM classic and OCM porous quench syngas P P H 2 O for OCM dilution P CO 2 for OCM dilution O 2 (95% pure) P fuel to boiler Ethylene N 2 (+CO 2 and H 2 O) CH 4, N 2, Ar, H 2, CO P Pure CO 2 fuel to boiler OCM plant Classic and Porous Air to boiler Natural Gas Ethane

29 OCM reactor configurations O 2 -depleted air porous membranes MIEC membranes Air Oxygen (95% purity) Oxygen (95% purity) Natural Gas Natural Gas Natural Gas

30 MIEC + OCM plant Acid Gas Removal O 2 -depleted air quench syngas P air H 2 O for OCM dilution P CO 2 for OCM dilution fuel to combustor Ethylene CH 4, N 2, Ar, H 2, CO P Pure CO 2 P Natural Gas Ethane

31 Target: 1MTPY ethylene Thermodynamic comparison feedstock naphta steam cracking OCM reference OCM porous OCM MEMERE naphtha kg/s natural gas kg/s thermal input MW LHV chemical products ethylene kg/s purity % 99.87% 99.40% 99.88% 99.87% propylene kg/s purity % 99.43% BTX kg/s other kg/s fuel-to-chemicals %, LHV 65.7% 37.91% 68.91% 68.28% carbon conversion % 70.1% 45.23% 82.22% 81.46% Electricity Steam cycle MW Gas turbine MW expander MW gas compressor MW refrigeration cycle MW O 2 production MW CO 2 sep. & cond. MW air fans MW heat rejection MW net electricity MW fuel-to-electricity %, LHV 1.5% -15.5% -8.1% -1.6% overall energy %, LHV 67.2% 22.4% 60.8% 66.7% CH 4 -O 2 contact strategy has a major influence on the amount of feedstock required In the NSC technology, the byproducts increase the fuel to olefins efficiency The classic OCM produces more electricity than the other technologies because of low carbon conversions No ASU in the MEMERE concept NSC and MEMERE achieve similar efficiencies

32 Thermodynamic comparison feedstock naphta steam cracking OCM reference OCM porous OCM MEMERE olefins production operating temperature C operating pressure bar CH 4 -to-o 2 ratio mol. basis X CH4,ss, conversion % y C2H4 yield % reactor volume m C 2 H %vol. 39.5% 5.6% 19.6% 22.1% H 2 O-to-fuel ratio kg/kg CO 2 emissions direct CO 2 emissions t CO2 /t C2H CO 2 -from-electricity t CO2/ t C2H total CO 2 emissions t CO2/ t C2H CO 2 capture rate % 0.0% 38.3% 9.2% 9.9% NSC and OCM MEMERE achieve similar overall efficiencies NSC produces enough electricity for the plant, while the OCMs need to import it The yield of the process largely increases by distributing the oxygen The fraction of ethylene before the distillation columns influences the refrigeration unit CO 2 emissions by the MEMERE concept are just 17% of the NSC CO 2 emissions Large reactor volumes in MEMERE The bottleneck of the process Only the use of membranes has an impact on the CO 2 emissions

33 Cost comparison naphta steam cracking OCM reference OCM porous OCM MEMERE turbomachines + steam cycle 34.2% 17.4% 19.2% 17.1% reactors 29.5% 25.4% 24.2% 43.7% HE+cond+rebs 8.4% 2.6% 2.9% 2.6% % of BEC refrigeration units 21.4% 35.2% 28.7% 23.4% distillation columns 6.5% 2.0% 5.0% 4.9% Air Separation Unit 7.9% 9.6% 0.0% CO2 separation 9.6% 10.4% 8.3% BEC M TOC M specific cost M /(ton/h C2H4 ) Operating Costs Need of 60 reactors in the MEMERE concept Refrigeration cycle costs depend on the fraction of C 2 H 4 at the inlet feedstock electricity/by-products /ton C2H O&M cost of C 2 H 4 /ton C2H Similar BEC for NSC and OCM with membranes No costs for oxygen separation in the MEMERE concept, neither in NSC Naphtha is a more expensive feedstock material compared to NG NSC is the only process with a net production of electricity OCM technology with membranes is an interesting alternative to NSC based on the economics of the process

34 Next Steps Prototype is being constructed (tests to start in 2019) Finalize the business case for large scale and small scale Improve sealing and stability of the tubular membranes Scale up (next project)

35 MEthane activation via integrated MEmbrane REactors MEMERE Thank you for your attention Contact: This project has received funding from the European Union s Horizon 2020 research and innovation programme under grant agreement No Duration: 4 years. Starting date: 01-October-2015 Contact: f.gallucci@tue.nl

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