Stepwise Liquefaction Technology for Fossil Fuels

Transcription

1 Stepwise Liquefaction Technology for Fossil Fuels Slurry-bed ydrocracking Qiang Guo Synfuels hina Technology o., Ltd. 我们的事业能源的未来 ur expertise Energy in future

2 ontents 1. Background 2. Project planning 3. Research of slurry-bed hydrocracking oals structure and pyrolysis properties Recycling solvents Fe based catalyst X to liquids reaction 4. Pilot tests 我们的事业能源的未来 ur expertise Energy in future

3 1. Background Development of SF F-T technologies LAB 1.0L PP Φ 0.3m DEM Φ 5.Xm Industrialization Φ 10.Xm

4 1. Background Technology improvement Energy efficiency Product quality Stepwise liquefaction Recycling solvent AL 2 DL Residues SEP&YDR hemicals Gasoline Kerosene 2 / 2 PRDUTS UP-GRADING Diesel Solvent GASIFATIN ITL Slurry-bed hydrocracking

5 1. Background Features of slurry-bed hydrocracking reaction 1. Feedstocks Low-rank coals eavy crude oil oal tar Biomass 2. perating pressure bar 3. hemical structure of products Straight-chain alkanes Aromatics ycloalkanes Isoparaffins 4. Process:Recycling solvent balance

6 2. Project planning Fundamental research Feedstocks structure and prolysis properties ydrogen transfer from solvents to coals Structure and performance of Fe-based catalyst Formation and stabilization of free radicals Technologies Preparation of high-activity Fe based catalyst Selective hydrogenation process for 2 -donor solvent oal slurry pretreating technology Slurry-bed hydrocracking reaction Pilot plant (10000 t/a) ommercialization!

7 oal structure-wiser Model S N S S S S N N N S N S Stabilized by hydrogen Products: Gases ( 4, 2 S, LPG ) Liquids ( 2, Naphtha ) Large molecules (Asphaltene, Solids ) oal structure and pyrolysis properties

8 oal structure and pyrolysis properties In-situ electron paramagnetic resonance (EPR) analysis 60 Spins (*10 18 ) /g AUS coal MT coal YZ coal Temperature/ o Free radicals capture Temperature/ o In-situ EPR Spins *10 18 /g Spins capture Spins *10 21 /g

9 oal structure and pyrolysis properties oal Pyrolysis Spin capture Gases Dry gas LPG + Water + hemicals + (small molecules) Ash

10 Recycling solvent oal swelling and hydrogen donor hemical structure

11 Recycling solvent - ydrogen transfer mechanism Solvents Dissociation energy (KJ/mol) - bonds Transition states Tetralin Decalin Dihydroanthracene Tetrahydroanthracene exahydroanthracene ctahydroanthracene Perhydroanthracene Dihydrophenanthrene Tetrahydrophenanthrene ctahydro-phenanthrene Perhydrophenanthrene Dihydropyrene Tetrahydropyrene exahydropyrene Decahydropyrene Perhydropyrene

12 Recycling solvent -ydrogen donating ability Solvents A B D E F Group composition Alkanes Naphthenes Aromatics: monocyclics Dicyclics tricyclics oal liquefaction oal conversion % il yield % >150 o o o yield %

13 atalyst structure 14 Particle size distribution /% Paritcle size /µm

14 atalyst performance naphthalene conversion /% onsumption (t/100t coal ) 0 A B atalyst D 0.0 a b atalyst c d

15 New coal-slurry pretreatment technology Samples MT-coal M-152 M-255 M-296 M-325 Real density Particle size(μm) dv/dlog(w) Pore Volume (cm3/g) Average Width (nm) MT-coal M-152 M-255 M-296 M-325 DTG (%/min) Temperature ( o ) MT-coal M-152 M-255 M-296 M

16 New coal-slurry pretreatment technology oal conversion (%) oal conversion il yield il yield (%) 72 As-prepared M-123 M-152 M-255 M-269 M-325 Pretreatment time (s) 56 Influence of pretreatment of coal liquefaction

17 X to liquid reaction Low-rank coals Samples AUS YL M MT Industrial analysis M ad % A ad % V ad % Test results(pressure:30bar) onversion daf (%) il yield daf (%) yield daf (%) LPG daf (%) <150 o daf (%) o daf (%) o daf (%) >520 o daf (%)

18 X to liquid reaction eavy crude oil Analysis and test results of heavy oil API gravity 11 arbon residue wt% /wt% /wt% / /mol 1.53 N /wt % S /wt% IBP o o % o % o % 63.6 Dry gas (%) 4.79 LPG (%) 3.83 <150 o (%) o (%) o (%) <520 o (%) 水产率 (%) 2.30 Asphaltene yield (%) 2.79

19 X to liquid reaction oal tars Samples YD M JN Z DB Analysis Density (20 o,g/cm 3 ) oal dust % Asphaltene % / mol /S/N wt% <520 o oil % Test results LPG (%) <150 o (%) o (%) o (%) <520 o (%) Asphaltene yield (%)

20 X to liquid reaction Products Samples Naphtha Diesel Density (20 o ), g/cm distillation range: 5% 91.2 o o 50% o o 95% o o S, ppm N, ppm ctane value(rn) 82.6 group composition, m% Alkanes Naphthenes Aromatics: Monocyclics Dicyclics tricyclics 0 0

21 4. Pilot tests 20,000 t/a pilot plant

22 4. Pilot tests Pilot test results Feedstocks eavy crude oil oal tar apacity 1.7t/h 2.0t/h perating conditions Temperature 445 o 435 o Pressure 4.5MPa 4.5MPa Main Products LPG 5.04% 1.70% Naphtha 17.23% 15.93% Diesel 59.39% 69.94% Total 81.66% 87.57% Fe catalyst consumption 1.0% 0.9% 2 consumption 2.14% 3.82%

23 TANK YU ur Expertise, Energy in Future