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Pasadena, Texas

Pasadena, Texas. Sunoco Eagle Point refinery. Petroleum refining: separation, sorting, reblending, reformulation, cracking and combining individual ,molecules to meet specs. Petroleum chemistry vs petrochemistry. Officially: WWII onward, but: synthetic rubber Bakelite, 1907,

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Pasadena, Texas

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  1. Pasadena, Texas

  2. Sunoco Eagle Point refinery

  3. Petroleum refining: separation, sorting, reblending, reformulation, cracking and combining individual ,molecules to meet specs

  4. Petroleum chemistry vs petrochemistry Officially: WWII onward, but: synthetic rubber Bakelite, 1907, solvents in the 1920s, polystyrene in the 1930s... And it then moved to an incredible variety of areas - from household goods (kitchen appliances, textile, furniture) to medicine (heart pacemakers, transfusion bags), from leisure (running shoes, computers...) to highly specialised fields like archaeology or crime detection. 

  5. Caoutchuck to synthetic rubber 1735 Fresnau (fr), formulated that rubber is a stuff of condensed resinous oil, (in Peru) Hancock: thermal and mechanical treatment “masticator” Macintosh: latex in between clothes, narrow range of flexibile behaviour, benzene to solve rubber 1840: Goodyear discovered vulcanization by chance 1879*1898: Bouchart: polymerized isoprene 1895: Michelin adopted tire to automobiles

  6. Methanol Institute Nonpetrochemical use: denitrification, biochemical processes, Biodiesel and other fuels and fuel cells Here are just some types of materials that are made from methanol: Plastics Synthetic fibers Paints Resins Magnetic film Safety glass laminate Adhesives Solvents Carpeting Insulation Refridgerants Windshield washer fluid Particle board Pigments and dyes

  7. C1-chemistry C1 chemistry coal-based chemistry, consider extents of resources (Rcoal>>Roil), The synthesis of various objective compounds are part of petrochemistry CH4, CH3OH, CO, CO2,HCOH (NATURAL GAS AND COAL BASED SYNGAS AND METHANOL are the major starting materials ,

  8. Technology Advantages Disadvantages Developers/licensors Technology Advantages Disadvantages Developers/licensors POX Feed stock desulfurization not required Very high process operating temperature Texaco Inc. and Royal Dutch/Shell Usually requires oxygen plant SMR Most extensive industrial experience Highest air emissions Haldor Topsoe AS, Foster Wheeler Corp, Oxygen not required, , lowest process operating temperature Lurgi AG, International BV, Kinetics More costly than POX and autothermal reformers Technology and Uhde GmbH Best H2/CO ratio for production of liquid Recycling of CO and removal of the fuels excess hydrogen by means of membranes ATR Lowest process temperature requirement Limited commercial experience Lurgi, Haldor Topsoe than POX, Syngas methane content can be Usually requires oxygen plant tailored by adjusting reformer outlet temperature DRM Green house gas CO2 consumed Formation of coke on catalyst Carbon Sciences Almost 100% of CO2 conversion Additional heat is required as the reaction takes place at 873 K SMR + DRM Best H2/CO ratio for prodn. liquid fuels Separation of unreacted methane from SMR syngas Coke deposition drastically reduced Project Installation cost TRM Directly using flue gases, Usually requires oxygen plant Haldor Topsoe AS Over 95% of methane, 80% CO2 conversion Low H2/CO ratio ratios limit its large-scale application for F-T & MeOH synthesis

  9. Natural gas steam reforming Steam methane reforming (SMR): CH4+H2O↔CO+3H2  ΔH=205.8 kJ/mol Water gas shift (WGSR) CO+H2O↔CO2+H2  ΔH=−41.2 kJ/mol (FT:CO+H2↔”CH”+H2O- especially if Cu is included in catalyst composition) Global/overall SMR CH4+2H2O↔CO2+4H2  ΔH=164.6 kJ/mol Reversible equilibrium shifted by: removing reaction product/byproduct (Gulker, F., 1928. Method of producing hydrogen. GB275273)

  10. CaO (s) + CO2 (g) → CaCO3 (s);  T=  650 - 700 °C  CaCO3 (s) → CaO (s) + CO2 (g);  T > 900 °C  Breakthrough Adsorption capacity time (s) (mg/g) CO2 % in the feed 12 200 24.64 15 220 51.92 18 170 33.01 Adsorption temperature (°C) 35 220 51.92 45 190 33.99 55 160 32.17 Feed flow rate (mL/min) 90 220 51.92 120 120 40.14 150 70 37.64 Amount of adsorbent in the adsorption column (g) 2 80 36.65 4 220 51.92 6 450 54.81

  11. staged-membrane membrane reaction with a regular membrane reactor methane feed 50 m3/h, steam-to-carbon 3.0, pressure 25 bar Variable Unit MR-SMR SSMR-SMR Reaction T C 550 670 700 750 750 780 780 Membrane T C 550 450 450 450 450 450 450 Membr. thickn,μm 25 15 15 15 15 15 15 Membr. area need, m2 5.57 2.90 2.05 1.53 2.10 1.38 1.86 H2/CH4 ratio 2.0 2.0 2.0 2.0 2.4 2.0 2.4 H2 produced, m3/h 100 100 100 100 120 100 120 (Pd–25%Ag) kg 1.255 0.392 0.277 0.207 0.284 0.187 0.252 Pd :MR-SMR – 1.00 0.313 0.221 0.165 0.226 0.149 0.200

  12. Amine treatment 2 RNH2 + CO2 RNH3+-O2CNHR

  13. ALGAE!

  14. Cost of hydrogen production 22

  15. Dry reforming CO2 + CH4 → 2CO + 2H2 Carbon deposition: 2CO → CO2 + C, DH298=-172 KJ/mol, DGo=-39810+40.87T Optimal range to avoid C deposition: optimal range (600–1040 °C) CH4→ 2H2 + C DH298=+75 KJ/mol

  16. Sept 20: here we areSept.27, Oct 4: Maráczi/MOLOct 11: ethylene chemistryOct. 18: propylene chemistryOct 25, Nov 8: possible trips – synthetic lubricants and functional fluids, additive synthesis and testing(lab+seminary)Nov. 15: aromaticsNov 22/29: possible trips/consultation (lab+seminary)Dec 6:Maráczi/MOLDec 13: examination

  17. Methane decomposition Traditional use: carbon nanotube manufacturing, cat: Ni…..Noble metals Catalyst regeneration= combustion, at the end of the day SMR CH4  → C + 2H2   ΔH = 45.0 kJ/mol. CH4 + H2O → CO + 3H2   ΔH = 225.9 kJ/mol.

  18. Partial oxídation of methane CH4 + (1/2)O2 → CO + 2H2

  19. Reverse gas shift reaction CO+H2O CO2+H2

  20. Reaction Formula is CH3OH + 1.5O2 --> CO2 + 2H20
Cathode reaction is 1.5O2 + 6H+ + 6e- --> 3H2O
Anode reaction is CH3OH + H2O --> CO2 + 6H+ + 6e-

  21. Catalyst: Mo(Re)-HZSM-5, T: 950 K MeOH conversion up to 10 %, selectivity: 60%

  22. T:300- 375C CO:H2=1:2,25

  23. Urea-formaldehyde resin

  24. Kérdések? Hozzászólások? Megjegyzések? Köszönöm a figyelmet

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