[PPT] - A LOW CO 2 HYBRID IN-SITU SHALE LIQUID PRODUCTION PROCESS Jacob PowerPoint Presentation

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30th Oil Shale Symposium

Colorado School of Mines

A LOW CO2 HYBRID IN-SITU SHALE LIQUID PRODUCTION PROCESS Jacob Bauman, Prashanth Mandalaparty, Pankaj Tiwari and

Milind Deo

Department of Chemical Engineering, University of Utah, Salt Lake City, UT

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OIL SHALE CHALLENGES

Ò Oil shale pyrolysis is an energy intensive process. Ò Heating rate is typically slow. Ò Initial permeability is low. Ò Heating requirements, hydrocarbon products, and

carbonate decomposition contribute to CO2 and other emissions.

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CONCEPT

Step 1:Pyrolysis - Heating wells rapidly heat the formation near the

well. Products are generated, including coke. Permeability is

increased in “hot” zones according to a model relating fluid porosity and permeability. kmul = 5 in these simulations. Step 2: In-situ combustion - After initial pyrolysis period air is injected into the formation. Coke combustion supplies heat to formation far from heating wells. Step 3: CO2 injection - CO2 is injected to drive out remaining oil, and for CO2 storage

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SI SIMULATI TION N

50 ft thickness. 26.5 ft between Injector 1 and Injector 2.

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ENERGY S SAVINGS W WITH I IN-SITU C COMBUSTION

112 MBTU savings with in-situ combustion switching at 600 days.

0.00E+00 5.00E+07 1.00E+08 1.50E+08 2.00E+08 2.50E+08 3.00E+08 3.50E+08 4.00E+08 4.50E+08 5.00E+08 500 1000 1500 2000 2500 3000 3500 4000

Ene nergy S y Suppli lied b by H y Heaters ( (BTU) U) Time me ( (days ys)

Pyrolysis followed by combustion Pyrolysis

nly

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PRODUCTION C COMPAR ARISON

157 bbl more oil is produced when pyrolysis is followed by combustion although products could be consumed during the combustion stage.

50 100 150 200 250 300 350 400 450 500 500 1000 1500 2000 2500 3000 3500 4000

Cumu mula lative O Oil P l Produced ( (bbl) l) Time me ( (days ys)

Oil Production with combustion Pyrolysis only

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PRODUCTION COMPARISON

50000 100000 150000 200000 250000 300000 350000 400000 450000 500000 500 1000 1500 2000 2500 3000 3500 4000

Ga Gas p produced ( (scf) Time me ( (days ys)

Gas production with combustion Pyrolysis only

Gas production is also significantly improved with combustion

period. This is somewhat counterintuitive.

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OBSERVATION

Product mobility is an issue in the “cold zone” at the bottom

f the resource. This causes oil to pool.

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OB OBSER ERVATION ION

0.00E+00 1.00E+08 2.00E+08 3.00E+08 4.00E+08 5.00E+08 6.00E+08 7.00E+08 500 1000 1500 2000 2500 3000 3500 4000

Ene nergy S y Suppli lied b by H y Heaters ( (BTU) U)

Time me ( (days ys)

Pyrolysis followed by combustion Pyrolysis only Pyrolysis only (higher heating rate)

With higher heating rate 373 bbl oil are produced compared to 280 bbl with lower heating rate. With pyrolysis only there is a tradeoff between recovery and heating requirement.

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CO2 BALANCE

Ò Pyrolysis followed by CO2 injection

É Net CO2 injected = 8040 ft3

Ð Most CO2 injected is produced. Oil pools at the bottom of the

resource.

Ð No carbonate decomposition reactions included.

Ò Pyrolysis followed by In-situ combustion and CO2

injection

É Net CO2 injected = - 597,000 ft3

Ð 600,000 ft3 CO2 are generated from combustion Ð Only a small fraction of the generated CO2 is injected.

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Ø To study the geochemical implications of injecting CO2 into the spent shale formation Ø Most of the organic content is driven out as oil and gas Ø The subsurface has the geochemical complexity to drive the sequestration reactions Ø Current effort focuses on

ü Understanding the fate of CO2 in the spent shale formation ü Studying the basic reactivity of CO2-brine mixtures with rocks in the formation. ü The mineralogical changes in the rock ü The changes in brine chemistry

GEOCHEMICAL STUDY

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SPENT S SHAL ALE U USED F FOR G GEOCHEMICAL AL S STUDY

Green River formation – Oil shale

u Core sample- ¾” diameter

ü Pyrolysis (N2) - 60ml/min ü Temperature -350C ü Duration - 24 hrs ü Weight loss 12.61% ü Oil yield 4.84%

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Ø High temperature, high pressure experiments Ø 316 stainless steel reactors Ø Feed samples – spent shale

Ø Brine composition: 3-5 weight% Ø Temperature: 2000C Ø Feed gas composition: CO2 Ø Reaction period: 7-35 Days Ø Analysis

Rock Chemistry:
XR

XRD, (X-ray Diffraction)

SEM

SEM, (Scanning Electron Microscope )

EDS

DS, (Energy Dispersive X-ray analysis)

Brine Chemistry:
IC

ICP-M

MS, (Inductively coupled plasma-mass spectrography)

Conditions

SEQUESTRATION EXPERIMENTS

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CO2 N2

P P

Te Temperature Cont ntrolle ller

Pump P P

SO SO2, N , NH3

3 , H

, H2S S as f feed g gases with C h CO2

2

SO SO2, N , NH3

3 , H

, H2S S as f feed g gases with C h CO2

2

N2 for leak test Single cylinder positive displacement pump Supercritical CO2

EXPERIMENTAL SETUP

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INITIAL XRD ANALYSIS

Illite 3.8% Dolomite 69% Quartz 8.0% Albite 10.8% Orthoclase 6.4% Analcime 2.1% Interlayered chlorite/smectite (or C/S) also observed, but is below the detection limit (~1*) for the bulk analysis.

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METHODOLOGY

v The reactors fed with the sample and brine- allowed to

equilibrate

v CO2 is fed into the reactors and the reactors are isolated and

allowed to cook at temperature

v Each reactor is cooled and degassed in time intervals of 7 days

to analyze the reaction progress

v After the experiment reactor is degassed and products

analyzed

v The results compared with the initial XRD analyses and the

products identified through XRD and SEM analyses

v The correlation of the rock chemistry with changes in brine

chemistry is identified

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CO2 (g) CO2 (aq) H2O + CO2 H2CO3 H2CO3 H+ + HCO3

CaCO3 +H+ Ca2+ + HCO3
Ca2+ + CO3

2- CaCO3 2H+ + CaAl2Si2O8 + H2O Ca2+ + Al2Si2O5(OH)4

CaAl2Si2O8 + H2CO3 + H2O CaCO3 + Al2Si2O5(OH)4 NaAlSi3O8 + 3 H2O NaAlSi2O6.H2O + H4SiO4 2KAlSi3O8 + 9H2O + 2H+ Al2Si2O5(OH)4 + 2 K+ + 4H4SiO4

PRINCIPAL REACTIONS

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Omni-present woody fragments

RESULTS AFTER 2 WEEKS

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Signs ns o

f C

Ca-z

zeoli

lites p precipitation n

RESULTS AFTER 2 WEEKS

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Hollo llow p prism o m of C Ca-z

zeoli

lite growing ng o

n w

n weathe hering ng

rtho

hocla lase

RESULTS AFTER 3 WEEKS

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EDS DS a ana nalys lysis o

f C

Ca-z

zeoli

lite

RESULTS AFTER 3 WEEKS

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Ano nothe her ho hollo llow Z Zeoli lite c crys ystal l growing ng o

n a

Etche hed o

rtho

hocla lase feld ldspar w with t h traces o

f

Ion Na Mg Al K Ca Fe Ba Si Cl Conc (mg/l) 10675 0.0009 0.10 <0.005 0.8 <6 0.003 <8 19060

Brine prepared from laboratory grade NaCl
3 g of brine in 30 cc DI water

BRINE CHEMISTRY

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10 20 30 40 50 60 0 weeks 2 weeks 3 weeks 4 weeks 5 weeks Conc ncent ntration mg n mg/l l Time me Mg K Al Fe Si

0.0 20.0 40.0 60.0 80.0 100.0 120.0 140.0 160.0 180.0 0 weeks 2 weeks 3 weeks 4 weeks 5 weeks Conc ncent ntration mg n mg/l l Time me Ca Si

BRINE CHEMISTRY

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² Energy requirements of the conventional pyrolysis process can be reduced significantly by utilizing the coke formed during pyrolysis ² Ensuing combustion process does produce CO2 which needs to be managed ² CO2 EOR in oil shale reservoir is feasible, but needs to be

ptimized in consideration of where the oil is

² The spent shale formation has the required complicated geochemistry to initiate and sustain sequential sequestration reactions ² Ca-zeolite, dolomite and kaolinite precipitates are observed when CO2 and brine react with spent hot shale ² Changes in brine composition are consistent with

bservations of changes in mineralogy